Crompton1998 PDF

MANUAL OF PLASTICS ANALYSIS
MANUAL OF PLASTICS ANALYSIS
T. R. CROMPTON
Formerly of Shell Research Co.
Cheshire, United Kingdom
Springer Science+Business Media, LLC

Library of Congress Cataloging-in-Publication Data
On file
ISBN 978-1-4899-1405-7 ISBN 978-1-4899-1403-3 (eBook)

DOI 10.1007/978-1-4899-1403-3
© 1998 Springer Science+Business Media New York

Originally published by Plenum Press, New York in 1998
Softcover reprint of the hardcover 1st edition 1998
10987654321
All rights reserved
No part of this book may be reproduced, stored in a retrieval system, or transmitted in any form or by any
means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written
permission from the Publisher
PREFACE
The book aims to cover all analytical aspects using both chemical and physical
methods. Its contents derive from the author's experience as previous Head of the
Analytical Research Department concerned with plastics at a major plastic producer and
are also based on a complete review of world literature on the subject.
The subject matter is broken down into six chapters, each dealing with a particular
aspect of polymer analysis as shown below. The book offers the student and general
reader a complete picture of all aspects of polymer analysis, including not only the
polymer itself, but also deliberately added non-polymeric processing chemicals used during
manufacture, chemicals added to improve the polymer properties during service life and
impurities such as water and processing solvents, unreacted monomers etc.
Chapters 1 and 2 deal, respectively with the analysis of a wide range of polymers
and copolymers, and under each polymer discusses the determination of volatiles, water
and various types of polymer additives. Numerous detailed methods, many previously
unpublished, are included for carrying out these analyses. Also included in Chapter 2 is a
discussion of the available methods for determining total unsaturation, ester groups,
amide and amino groups, sulphonyl groups, carbonyl groups, nitrile groups, alkyl groups,
hydroxyl, alkoxyl, carboxyl, epoxy and anhydride groups. This is supported by examples
of results obtained in this type of analysis. The chapter concludes with a section on the
occurrence of end-groups in polymers and their determination.
In Chapter 3 are discussed the detelmination in polymers and copolymers of non-
metallic and metallic elements whether these be major constituents of the polymer,
catalyst residues, adventicious impurities or pigments. A wide variety of chemical and
physical methods of analysis are discussed in detail. Chapter 4 is devoted entirely to
copolymers and discusses chemical and physical methods available for the determination
of comonomer ratios in those materials.
Methods discussed in Chapters I and 2 for the determination of additives are
usually concerned with the determination of a single additive, e.g. an antioxidant. Many
polymer formulations contain several additives which it may be required to determine. In
these cases, as discussed in Chapter 5, in order to avoid interference effects it is usually
a
necessary to apply a chromatographic procedure to solvent extract of the polymer in
order to obtain fractions containing the different additives which are then separately
determined without interference by appropriate chemical or physical methods.
Methods are discussed utilising thin-layer chromatography, high performance
liquid chromatography and gas chromatography, used in conjunction with an infrared or
ultraviolet spectroscopic or mass spectroscopic finish.
Frequently, the identification of an unknown plastic can be made on the basis of
simple physical tests such as solubility in solvents, odours produced on ignition, etc.
Such tests will be discussed in as much as they provide a simple practical means of
identification. In Chapter 6 the principles of infrared spectroscopy and pyrolysis - gas
chromatography will be discussed and infrared and pyrograms presented for a wide range
v
of polymers and copolymers showing how they may be used to identify unknown
polymers by the fingerprint approach.
Detailed analytical methods are presented in Chapter 7.
The book aims to cover all analytical aspects using both chemical and physical
methods and is intended as a manual for use in the laboratory.
The book offers the student and general reader a complete picture of all aspects of
polymer analysis, including not only the polymer itself, but also deliberately added non-
polymeric processing chemicals used during manufacture, chemicals added to improve
polymer properties during service life, and impurities such as water and processing
solvents, unreacted monomers etc.
vi
ACKNOWLEDGEMENTS
The author wishes to express his gratitude to the publishers of various journals for
permission to reproduce the following illustrations.
Figure 1.2 L, Ho.F.F. Analytical Chemistry 45 603 (1973). American Chemical

Society.
Figures 5.1 - 5.3 Squirrell, D.C.M. Analyst (London) 106 1042 (1981). Royal Society
of Chemistry, London.
Figure 6.4 Dennig, R. Kunststoffe 758 (1985). Carol Hauser Verlag. Munich.
Figure 6.5 May, R.W. Pearson, E.F. Porter, J. Scothem, M.D. Analyst
(London) 98 364 (1973). Royal Society of Chemistry, London.
Figures 6.6 and Folmer, O.F. Analytical Chemistry 43 1057 (1971). American
7.45 Chemical Society.
Figure 7.4 Soncek, J. lelinkova, E. Analyst (London) 107 623 (1982). Royal
Society of Chemistry, London.
Figure 7.10 Allen, BJ. Elsea, G.M. Keller, K.P. Kinder, H.D. Analytical
Chemistry 49 741 (1977). American Chemical Society.
Figure 7.11 Frankoski, S. P. Siggia, S. Analytical Chemistry 44507 (1972) .

Ainerican Chemical Society.
Figure 7.15 Anderson, D.G. Isakson, K.E. Snow, D.L. Tessari, DJ.
Vandeberg, IT. Analytical Chemistry 43894 (1971). American
Chemical Society.
Figure 7.16 Korenaga, T. Analyst (London) 10640 (1981). Royal

Figure 7.17 Tittareli, P. Zerlia, T. Calli, A. Ferrari, G. Analytical

Chemistry 55 220 (1983). American Chemical Society.
Figure 7.27 Krishen, A. Analytical Chemistry 44 494 (1972). American

Chemical Society.
Figure 7.28 Johnson, D.E. Lyeria, lR. Horikawa, T.T. Pederson, LA

Analytical Chemistry 49 77 (1977). American Chemical Society.
Figures 7.29 Blackwell, J.T. Analytical Chemistry 48 1883 (1976). American

and 7.30 Chemical Society.
vii
Figures 7.34 - Majors, R.E. J. Chromatographic Science ~ 338 (1970). Preston
7.36 Publications Inc, New York.
Figures 7.38 - Juvet, R.S. Smith, L.S. Li, K P. Analytical Chemistry

7.40 4449 (1972). American Chemical Society.
Figure 7.6 Crompton, T.R. Myers, L.W. Plastics and Polymers

p205 June (1968). Pergamon Press, Oxford.
Figures 7.7 - 7.9 Udris, J. Analyst (London) 96130 (1971). Royal Society of
Che~istry, London.
Figure 7.37 Rudewicz, P. Munson, B. Analytical Chemistry 58 358 (1986).

American Chemical Society.
Figures 7.41 - 7.44 Anderson, D.M.W. Analyst (London) 84 50 (1959). Royal Society of
Chemistry, London.
viii
CONTENTS
PART 1, REVIEW OF METHODOLOGY

CHAPTER 1 POLYMER ANALYSIS
1.1 Polyethylene and polypropylene 1

1.1.1 Volatiles and water 1
1.1.2 Additives 3
1.1.2.1 General discussion 3
1.1.2.2 Phenolic antioxidants 5
1.1.2.3 Amine antioxidants 8
1.1.2.4 Diorganosulphide (and tertiary phospite) antioxidants 9
1.1.2.5 Ultraviolet absorbers and optical brighteners 9
1.1.3 Fractionation 10
1.2 Polystyrene 11
1.2.1.1 Monomers and aromatic volatiles 11
1.2.1.2 Aliphatic expanding agents 13
1.2.2 Oligomers 15
1.2.3 Impurities in styrene monomer 15
1.2.4 Additives 16
1.2.4.2 Ultraviolet absorbers 16
1.2.4.3 Organic peroxide residues 16
1.2.4.4 Inhibitors in styrene monomer 17
1.2.5 Fractionation and molecular weight 17
1.3 Poly(vinyl chloride) 18
1.3.1 Water, volatiles, monomers and chlorohydrocarbons 18
1.3.2 Additives 19
1.3.2.1 Phenolic and amine antioxidants 19
1.3.2.2 Plasticizers 20
1.3.2.3 Organotin stabilizers 21
1.3.2.4 Other types of stabilizers 21
1.4 Vulcanized and non-vulcanized rubber (polyisoprene) 22
1.4.1 Volatiles 22
1.4.2 Additives 22
1.4.2.1 Accelerators and antioxidants 22
1.4.2.2 Antioxidants and antiozonants 22
1.5 Polyesters and polyamides 23
ix
1.5.1 Functional groups 23
1.5.1.1 Hydroxyl 23
1.5.1.2 Alkene and vinyl esters 25
1.5.1.3 Carboxyl 25
1.5.1.4 C-O-C groups 26
1.5.1.5 Amino groups 26
1.5.1.6 Acidic and glycol repeat units 27
1.5.3 Oligomers 28
1.5.4 Additives 29
1.5.4.1 Flame retardants 29
1.5.4.2 Residual organic peroxides 29
1.5.4.3 Unreacted starting materials 29
1.6 Polyacrylates 29
1.6.2 Monomers and water 29
1.6.3 Oligomers 30
1.6.4 Additives 30
1.7 Poly(ethylene glycol) and Poly(propylene glycol) 30
1.7.1 Oligomers 30
1.7.2.1 Hydroxy groups 30
1.7.2.2 Ether linkages 32
1.8 Polybutadiene 33
1.8.1 Additives 33
1.8.1.1 Amine antioxidants and antiozonants 33
1.9 Cellulose 34
1.9.1 Water 34
1.10 Polyamides, polyimides and polyamides-imides 35
1.10.1.1 Amino 35
1.10.1.2 Carboxyl 35
1.11 Polyacrylamides 35
1.11.1 Monomers 35
1.12 Polyurethanes 36
1.12.1 Volatiles 36
1.12.2 Characterisation 36
1.13 Polyvinyl alcohol 36
1.13.1.1 Hydroxy 36
1.14 Silicones and siloxanes 36
1.14.1.1 Alkyl and aryl 36
1.14.1.2 Si OH and Si H groups 37
1.14.2 Oligomers 37
x
1.15 Phenol formaldehyde resins 37
1.15.1 Oligomers 37
1.16 Polyoxymethylene glycol 37
1.16.1 Oligomers 37
1.17 Poly(styrene sulphonates) 38
1.18 Fluoropolymers 38
1.18.1 Oligomers 38
1.19 Polycarbonates 39
1.19.1 Composition 39
1.19.2 Oligomers 39
1.20 Polyvinylpyridine 39
1.21 Alkyl ketenes 39
1.21.1 Oligomers 39
References 55
CHAPTER 2 COPOLYMERS AND CONDENSATION PRODUCTS
2.1 Styrene-butadiene 67
2.1.1.1 Unsaturation 67
2.1.2 Monomers and other volatiles 69
2.1.3 Additives 70
2.1.3.1 Stearic acid and sodium stearate 70
2.1.3.2 Tertiary phosphite antioxidants 70
2.1.3.3 Antioxidants and stabilisers 71
2.2 Styrene-acrylonitrile 71
2.2.1 Characterization 71
2.2.2 Monomers 71
2.3 Vinyl chloride, butadiene, acrylonitrile, 2-ethyl-hexylacrylate 72
copolymers and terpolymers
2.3.1 Characterization 72
2.3.2 Monomers 72
2.4 Ethylene oxide - propylene oxide - glycerol condensates 73
2.4.1.1 Hydroxyl 73
2.4.1.2 Alkoxyl 74
2.5 Ethylene oxide - propylene oxide - polyhydric alcohol and ethylene oxide -
propylene oxide - amine condensates 75
2.5.1.1 Oxyethylene and oxypropylene 75
2.6 Ethylene - propylene - diene terpolymers 77
2.6.1.1 Unsaturation 77
2.7 Acrylate copolymers 78
xi
2.7.1.1 Carboxyl 78
2.7.1.2 Ester 79
2.7.1.3 Epoxy 82
2.8 Acrylamide copolymers 82
2.8.1.1 Alkoxy 82
2.9 Octadecene - maleic anhydride copolymers 83
2.9.1.1 Anhydride groups 83
2.10 Epoxy resins 84
2.10.1 Volatiles 84
2.10.2.1 Epoxy 84
2.11 Tert-octyl phenol ethylene oxide condensates 84
2.11.1 Oligomers 84
2.11.2 Molecular weight 84
References 88
CHAPTER 3 DETERMINATION OF ELEMENTS
3.1 Minor metallic constituents 92

3.1.1 Catalyst residues 92
3.1.1.1 Iron, aluminium and titanium 92
3.1.1.2 Zinc 92
3.1.1.3 Aluminium 92
3.1.1.4 Aluminium and vanadium 92
3.1.1.5 Chromium 93
3.1.1.6 Silica 93
3.1.1.7 Sodium and lithium 93
3.1.2 Adventitious metal impurities 93
3.2 Metal-containing additives 94
3.2.1 Antimony 94
3.2.2 Arsenic 94
3.2.3 Tin 95
3.2.4 Zinc 95
3.3 Organic and inorganic pigments 95
3.4 Non-metallic elements 95
3.4.1 Halogens 96
3.4.2 Sulphur 96
3.4.3 Nitrogen 97
3.4.4 Phosphorus 97
References 98
CHAPTER 4 COMPOSITIONAL ANALYSIS
4.1 Styrene - butadiene copolymers 100

4.2 Acrylonitrile - butadiene - styrene terpolymers 100
4.3 Natural rubber, styrene - butadiene rubber and ethylene-propylene
terpolymer in cured stocks 101
xii
4.4 Styrene isoprene copolymer 101
4.5 Alkene copolymers 101
4.5.1 Ethylene - propylene copolymers 101
4.5.2 Ethylene-butene copolymers 102
4.5.3 Ethylene - alpha olefin copolymers 104
4.6 Other ethylene copolymers 104
4.6.1 Ethylene-vinyl acetate copolymers 104
4.6.2 Ethylene-tetrafluoroethylene copolymers 104
4.7 Acrylic copolymers 104
4.7.1 Styrene-acrylate copolymers 104
4.7.2 Styrene-methacrylate copolymers 105
4.7.3 Methyl methacrylate - methacrylic acid copolymers 105
4.7.4 Butyl methacrylate-methyl methacrylate copolymers 106
4.7.5 Acrylic and methacrylic and copolymers 106
4.7.6 Functional groups in acrylics 106
4.7.7 Vinyl chloride - vinylidene chloride copolymers 106
4.8 Hexa fluoropropylene - vinylidene fluoride copolymers 106
4.8.1 19FNMR 106
4.8.2 Pyrolysis gas chromatography 107
References 109
CHAPTER 5 ADDITIVE MIXTURES
5.1 Separation methods for additive mixtures 112

5.1.1 Solvent extraction methods 112
5.1.2 Solution - precipitation methods 115
5.1.3 Vacuum thermal displacement - extraction methods 1lS
5.2 Chromatographic methods 115
5.2.1 Gas chromatography 115
5.2.2 Thin-layer chromatography 117
5.2.3 High performance liquid chromatography 119
5.2.4 Supercritical flow chromatography 121
5.3 Mass spectrometry 121
5.3.1 Secondary ion mass spectrometry 122
5.3.2 Liquid chromatographY - mass spectrometry 123
5.3.3 Gas chromatography - mass spectrometry 123
5.4 Additive degradation techniques 124
5.4.1 Photolytic degradation - gas chromatography 124
5.4.2 Pyrolysis - gas chromatography - mass spectrometry 124
5.5 Infrared spectroscopy 125
5.5.1 Infrared laser Raman spectroscopy 125
5.5.2 Laser desorption - Fourier transform techniques 125
5.5.3 Gas chromatography - infrared spectroscopy 125
References 128
CHAPTER 6 PRELIMINARY QUALITATIVE IDENTIFICATION
6.1 Preliminary removal of additives from polymers 131

6.2 Classification of polymers 133
6.2.1 By elements 133
xiii
6.2.2 By solubility 134
6.2.3 By colour reactions 136
6.2.4 By burning and heating tests 139
6.3 Qualitative identification by pyrolysis - gas chromatography 141
6.3.1 Filament (orcoil)pyrolysers 141
6.3.2 Combustion furnace pyrolysers 142
6.4 Laser pyrolysis - gas chromatography 145
6.5 Photolysis - gas chromatography 145
6.6 Pyrolysis - mass spectrometry 146
6.7 Typical polymer pyrograms 148
6.7.1 Filament and furnace pyrolysis 148
6.7.2 Curie point pyrolysis 149
6.7.3 Laser pyrolysis 149
6.8 Polymer identification by infrared spectroscopy 149
6.9 Polymer identification by laser desorption - ion mobility spectrometry 152
6.10 Other mass spectrometric techniques 154
6.11 Examination of polymer surfaces 158
References 160
xiv
PART 2, ANALYTICAL METHODS
7.1 POLYMER ANALYSIS
Method Number
1 Detennination of water and volatiles in polyalkenes, polyacrylics and polyvinyls
1.1 Summary 164
1.2 Apparatus
1.3 Method
1.4 Experimental procedure
1.5 Discussion of results
2 Determination of water in polyalkenes. Semi-automated Karl Fischer

titration method 168
2.1 Summary
2.2 Apparatus
3 Determination of Santonox R phenolic antioxidant in polyethylene.

2,2' - dipyridyl spectrophotometric method 169
3.1 Summary
3.2 Apparatus
3.3 Reagents
3.4 Method
3.6 Typical results
4 Detennination of phenolic antioxidants in polyethylene. p-nitroaniline

coupling - spectrophotometric method 174
4.1 Summary
4.2 Apparatus
4.3 Reagents
4.4 Method
5 Determination of lonol phenolic antioxidant in polyethylene. Ultraviolet

spectroscopy 176
5.1 Summary
5.2 Apparatus
5.3 Reagents
5.4 Method
6 Determination of Santonox R phenolic antioxidant in polyethylene.

Ultraviolet spectroscopy 177
6.1 Summary
6.2 Apparatus
xv
6.3 Reagents
6.4 Method
7 Determination of2,6-di-tert-butyI4-methylphenol and 4-substituted

2,6-xylenol phenolic antioxidants in polypropylene. Derivative
ultraviolet spectroscopy 179
7.1 Summary
7.2 Apparatus
7.3 Reagents
7.4 Method
8 Determination of Topanol OC, Binox M and Ionox 330 phenolic

antioxidants in polyethylene. Ultraviolet shift method 183
8.1 Summary
8.2 Apparatus
8.3 Reagents
8.4 Method
9 Determination of Santonox R phenolic antioxidant in polyolefins.

Thin layer chromatography 184
9.1 Summary
9.2 Apparatus
9.3 Reagents
9.4 Method
10 Determination of phenolic antioxidants in polyalkenes. Thin layer

chromatography 186
10.1 Summary
10.2 Apparatus
10.3 Reagents
10.4 Method
10.6 Typical results
11 Determination of phenolic and amine antioxidants, ultra-violet

absorbers and organotin stabilizers in polyalkenes and other polymers.
11.1 Summary
11.2 Apparatus
11.3 Reagents
11.4 Method
xvi
12 Determination ofIrganox 1076, Irganox 10to and butylated

hydroxytoluene phenolic antioxidants in polyethylene. High
performance liquid chromatography 191
12.1 Summary
12.2 Apparatus
12.3 Reagents
12.4 Method
13 Detennination of Nonox CI amine antioxidant in polyalkenes. Acid

hydrogen peroxide spectrophotometric method 193
13.1 Summary
13.2 Apparatus
13.3 Reagents
13.4 Method
14 Detennination of amine antioxidants in polyalkenes and other

polymers. p-nitro aniline coupling - spectrophotometric procedure 196
14.1 Summary
14.2 Apparatus
14.3 Reagents
14.4 Method
15 Detennination of diorganosulphide and tertiary phosphite antioxidants

in polyethylene. Chloroperoxybenzoic acid - oxidation method 198
15.1 Summary
15.2 Apparatus
15.3 Reagents
15.4 Method
16 Detennination of diorganosulphide antioxidants in polyalkenes. Gas

chromatography 200
16.1 Summary
16.2 Apparatus
16.3 Reagents
16.4 Method
xvii
17 Determination of Cyasorb UV531 ultraviolet absorber in polyethylene.

Infrared spectroscopy 202
17.1 Summary
17.2 Apparatus
18 Determination of Cyasorb UV 531 ultraviolet absorber in polyalkenes.

18.1 Summary
18.2 Apparatus
18.3 Reagents
19 Determination ofTinuvin 326 ultraviolet absorber in polypropylene.

Ultraviolet spectroscopy 205
19.1 Summary
19.2 Apparatus
19.3 Reagents
19.4 ~ethod
20 Determination of aromatic volatiles in polystyrene. Gas chromatography 206

20.1 Summary
20.2 Apparatus
20.3 Reagents
21 Determination of aromatic volatiles in polystyrene. Head-space analysis 209

21.1 Summary
21.2 Apparatus
21.3 ~ethod
22 Determination of volatiles in polystyrene. Head-space analysis 212

22.1 Summary
22.2 Apparatus
22.3 Reagents
22.4 ~ethod
xviii
23 Determination of residual isobutane in expandable and expanded
polystyrene. Gas chromatography 213
23.1 Summary
23.2 Apparatus
23.3 Reagents
23.4 Method
24 Determination of residual iso-hexane in expandable and expanded

24.1 Summary
24.2 Apparatus
24.3 Reagents
24.4 Method
25 Determination of residual n- and isopentane in expandable and expanded

25.1 Summary
25.2 Apparatus
25.3 Reagents
25.4 Method
26 Determination of residual neo-hexane in expanded and expandable

26.1 Summary
26.2 Apparatus
26.3 Reagents
26.4 Method
27 Solvent-free procedure for the determination of residual n- and isopentane

in expandable and expanded polystyrene. Gas chromatography 220
27.1 Summary
27.2 Apparatus
27.3 Method
28 Determination of down to 5 ppm hydrocarbon impurities in styrene

monomers. Gas chromatography 220
28.1 Summary
xix
28.2 Apparatus
28.3 Reagents
28.4 Method
29 Determination of hydrocarbon impurities in styrene monomers.

Temperature programmed gas chromatography 223
29.1 Summary
29.2 Apparatus
29.3 Method
30 Determination of benzaldehyde in styrene monomer. Gas chromatogmphy 229

30.1 Summary
30.2 Appamtus
30.3 Method
31 Determination of phenolic antioxidants in polystyrene. p-nitro-aniline

coupling - spectrophotometric procedure 231
31.1 Summary
31.2 Apparatus
31.3 Reagents
31.4 Method
32 Determination of Uvitex UB ultraviolet absorber in polystyrene.

Fluorirnetric procedure 232
32.1 Summary
32.2 Apparatus
32.3 Reagents
32.4 Method
33 Determination ofp-tert-butyl perbenzoate in polystyrene. Cathode-ray

polarography 233
33.1 Summary
33.2 Apparatus
33.3 Reagents
33.4 Method
xx
34 Detection and determination ofp-tert-butyl perbenzoate and benzoyl
peroxide residues in expandable polystyrene. Thin-layer chromatography 236
34.1 Summary
34.2 Apparatus
34.3 Reagents
34.4 Method
35 Rapid semi-quantitative tests for inhibitors in styrene monomer 238

35.1 Summary
35.2 Apparatus
35.3 Method
36 Determination ofhydroquinone, p-tert-butyl catechol and p-methoxy

phenol inhibitors in monomers. Spectrophotometric method 240
36.1 Summary
36.2 Apparatus
36.3 Reagents
36.4 Method
37 Determination ofhydroquinone inhibitor in monomers. Cathode-ray

polarography 241
37.1 Summary
37.2 Apparatus
37.3 Reagents
37.4 Method
38 Determination ofp-tert-butyl catechol inhibitor in styrene monomer.

Spectrophotometric method 244
38.1 Summary
38.2 Apparatus
38.3 Reagents
38.4 Method
39 Identification of dialkyltin stabilizers in PVC 246

39.1 Summary
39.2 Apparatus
39.3 Reagents
39.4 Method
xxi
40 Identification of dialkyltin carboxylated and hemiester stabilizers in PVC 251
40.1 Summary
40.2 Apparatus
40.3 Reagents
40.4 Method
41 Identification of accelerators in nonwlcanized rubber compounds.

Thin-layer chromatography 253
41.1 Summary
41.2 Apparatus
41.3 Reagents
41.4 Method
42 Determination of additives in rubber vulcanizates. Mass spectrometry 256

42.1 Summary
42.2 Apparatus
42.3 Method
43 Determination of acid and glycol units in terylene and other polyesters.

Hydrolysis-gas chromatography 260
43.1 Summary
43.2 Apparatus
43.3 Reagents
43.4 Method
44 Determination of water in polyesters. Derivativization-gas chromatography 262

44.1 Summary
44.2 Apparatus
44.3 Reagents
44.4 Method
45 Determination of acrylic acid monomer in polyacrylates. High

performance liquid chromatography 265
45.1 Summary
45.2 Apparatus
45.3 Reagents
45.4 Method
xxii
46 Determination of hydroxyl groups in polyethylene glycol. Silation-gas
chromatography 266
46.1 Summary
46.2 Apparatus
46.3 Reagents
46.4 Method
47 Determination of amine antioxidants and antidegradants in rubbers. Gel

permeation chromatography 269
47.1 Summary
47.2 Apparatus
47.3 Reagents
47.4 Method
48 Determination of water in celluloses. Karl Fischer titration 270

48.1 Summary
48.2 Apparatus
48.3 Reagents
48.4 Method
49 Determination of amino groups in aromatic polyamides, polyimides and

poly(amides-imides). Sodium hydroxide fusion-gas chromatography 274
49.1 Summary
49.2 Apparatus
49.3 Reagents
49.4 Method
50 Determination of acrylamide monomer in polyacrylamide.

Differential pulse polarography 279
50.1 Summary
50.2 Apparatus
50.3 Reagents
50.4 Method
51 Determination of acrylonitrile and methacrylonitrile monomers in
polyacrylamide. High performance liquid chromatography 281
51.1 Summary
xxiii
51.2 Apparatus
51.3 Reagents
51.4 Method
52 Determination of2,4- and 2,6-diaminotoluenes in flexible polyurethane

foams. Fluorimetric method 283
52.1 Summary
52.2 Apparatus
52.3 Reagents
52.4 Method
7.2 COPOLYMERS AND CONDENSATION PRODUCTS
53 Determination of styrene monomer and other volatiles in conventional

polystyrene and styrene-butadiene copolymers. Gas chromatography 286
53.1 Summary
53.2 Apparatus
53.3 Reagents
53.4 Method
54 Determination of stearic acid and sodium stearate in styrene-butadiene

rubber solutions. Titrimetric procedure 289
54.1 Summary
54.2 Apparatus
54.3 Reagents
54.4 Method
55 Determination of styrene and acrylonitrile monomers in styrene-

acrylonitrile copolymers. Cathode-ray polarography 291
55.1 Summary
55.2 Apparatus
55.3 Reagents
55.4 Method
56 Determination of styrene and acrylonitrile monomers in styrene-

acrylonitrile copolymers. Bromination procedure 294
56.1 Summary
xxiv
56.2 Apparatus
56.3 Reagents
56.4 Method
57 Determination of vinyl chloride, butadiene, acrylonitrile, styrene and

2-ethylhexyl acrylate monomers in polymers. Head-space analysis 297
57.1 Summary
57.2 Apparatus
57.3 Reagents
57.4 Method
58 Determination of hydroxyl number of glycerol-alkylene oxide polyethers

and butane 1,4-diol adipic acid polyesters. Direct injection enthalpiJnetry 300
58.1 Summary
58.2 Apparatus
58.3 Reagents
59 Determination of primary and secondary hydroxyl groups in ethylene oxide-

tipped glycerol propylene oxide condensates. Phenyl isocyanate kinetic method
59.1 Summary 302
59.2 Apparatus
59.3 Reagents
59.4 Method
60 Determination of oxyalkylene and polyether bases in polyurethane

polymers. Mixed anhydride cleavage-gas chromatography 313
60.1 Summary
60.2 Apparatus
60.3 Reagents
60.4 Method
61 Identification of acrylic acid and methacrylic acid in acrylic copolymers.

Propylation-pyrolysis-gas chromatography 315
61.1 Summary
61.2 Apparatus
61.3 Reagents
61.4 Method
xxv
62 Determination of acrylic ester groups in copolymers. Hydriodic

reduction-gas chromatography 318
62.1 Summary
62.2 Apparatus
62.3 Reagents
62.4 Method
63 Determination of combined vinyl acetate in vinyl acetate - vinyl chloride

copolymers. Isotopic dilution-derivative method 321
63.1 Summary
63.2 Apparatus
63.3 Reagents
63.4 Method
64 Determination of etherification levels in acrylamide interpolymers.

Alcohol exchange-gas chromatography 324
64.1 Summary
64.2 Apparatus
64.3 Reagents
64.4 Method
7.3 DETERMINAnON OF ELEMENTS
65 Determination of iron, titanium and aluminium catalyst residues in poly-

alkenes and polyalkene copolymers. Ashing-spectrophotometric procedure 329
65.1 Summary
65.2 Apparatus
65.3 Reagents
65.4 Method
66 Determination of aluminium and vanadium catalyst residues in polyalkenes

and polyalkene copolymers. Ashing-spectrophotometric procedure 333
66.1 Summary
66.2 Apparatus
66.3 Reagents
66.4 Method
xxvi
67 Detennination of vanadium catalyst residues in ethylene-propylene rubber.
Ashing-spectrophotometric procedure 335
67.1 Summary
67.2 Apparatus
67.3 Reagents
67.4 Method
68 Determination of silica catalyst support in high density polyethylene.

Infrared spectroscopy and NMR spectroscopy 336
68.1 Summary
68.2 Apparatus
68.3 Method
69 Determination of sodium neutralizing aid in high density polyethylene and

polypropylene. Emission spectrography and flame photometry 338
69.1 Summary
69.2 Apparatus
69.3 Reagents
69.4 Method
70 Determination of lithium in polyalkenes and copolymers. Ashing-flame

photometry 341
70.1 Summary
70.2 Apparatus
70.3 Reagents
70.4 Method
71 Determination oftraces of nickel, copper, zinc, iron, manganese, lead,

cadmium and chromium in polymers. Ashing-atomic absorption
spectrometry 343
71.1 Summary
71.2 Apparatus
71.3 Reagents
71.4 Method
71.6 Typical results and discussion
72 Determination of traces of copper in polyalkenes. Matrix ashing-

spectrophotometric procedure 344
72.1 Summary
72.2 Apparatus
xxvii
72.3 Reagents
72.4 Method
73 Determination of traces of arsenic in acrylic fibres containing antimony

trioxide. Acid digestion-atomic absorption spectrometry 349
73.1 Summary
73.2 Apparatus
73.3 Reagents
73.4 Method
74 Identification of pigments in polymers. Thermal ultraviolet absorption

spectroscopy 351
74.1 Summary
74.2 Apparatus
74.3 Method
75 Determination of traces of chlorine in polyalkenes and polyalkene

copolymers. Sodium carbonate fusion-titration procedure 353
75.1 Summary
75.2 Apparatus
75.3 Reagents
75.4 Method
76 Determination of up to 1% of chlorine in chlorobutyl and other chlorine-

containing polymers. Oxygen flask combustion-turbidimetry 358
76.1 Summary
76.2 Apparatus
76.3 Reagents
76.4 Method
77 Determination of up to 80010 of chlorine, bromine and iodine in polymers.

Oxygen flask combustion-titration procedure 359
77.1 Summary
77.2 Apparatus
77.3 Reagents
77.4 Method
xxviii
78 Determination of chlorine in polymers containing chlorine and sulphur and/or

phosphorus and/or fluorine. Oxygen flask combustion - mercurimetric titration
78.1 Summary 362
78.2 Apparatus
78.3 Reagents
78.4 Method
79 Determination of fluorine in polymers. Oxygen flask combustion 365

spectrophotometric procedure
79.1 Summary
79.2 Apparatus
79.3 Reagents
79.4 Method
80 Determination of traces of sulphur in polyalkenes. Oxygen flask

combustion-titration procedure 367
80.1 Summary
80.2 Apparatus
80.3 Reagents
80.4 Method
81 Determination of macro amounts of sulphur in polymers. Sodium fusion-

titration procedure 369
81.1 Summary
81.2 Apparatus
81.3 Reagents
81.4 Method
82 Determination of sulphur in polymers. Oxygen flask combustion-titration

procedure 371
82.1 Summary
82.2 Apparatus
82.3 Reagents
82.4 Method
xxix
83 Determination of traces of organic nitrogen in polymers, Kjeldahl
digestion-boric acid titration method 375
83.1 Summary
83.2 Apparatus
83.3 Reagents
83.4 Method
84 Determination of I to 90% organic nitrogen in polymers. Kjeldahl

digestion-boric acid titration method 377
84.1 Summary
84.2 Apparatus
84.3 Reagents
84.4 Method
85 Determination of 0.002 - 75% organic nitrogen in polymers. Kjeldahl

digestion-spectrophotometric indophenol blue procedure 385
85.1 Summary
85.2 Apparatus
85.3 Reagents
85.4 Method
86 Determination of 1 - 5% organic nitrogen in polymers. Micro Dumas

combustion procedure 392
86.1 Summary
86.2 Apparatus
86.3 Reagents
86.4 Method
87 Determination of 0.01 to 2% phosphorus in polymers. Oxygen flask

combustion-spectrophotometric procedure 398
87.1 Summary
87.2 Apparatus
87.3 Reagents
87.4 Method
88 Determination of 2 - 15% phosphorus in polymers. Oxygen flask

combustion-spectrophotometric procedure 401
88.1 Summary
88.2 Apparatus
88.3 Reagents
xxx
88.4 Method
89 Microdetennination of phosphorus in polymers. Digestion-

spectrophotometric procedure 403
89.1 Summary
89.2 Apparatus
89.3 Reagents
89.4 Method
7.4 COMPOSITIONAL ANALYSIS
90 Determination of natural rubber, styrene butadiene rubber and ethylene-

propylene-diene terpolymer in compounded rubber stocks. Pyrolysis-gas
chromatography 405
90.1 Summary
90.2 Apparatus
90.3 Reagents
90.4 Method
91 Determination of bound ethylene in ethylene-propylene copolymers

containing greater than 95% bound propylene. Infrared spectroscopy 408
91.1 Summary
91.2 Apparatus
91.3 Method
92 Detennination of bound ethylene in ethylene propylene copolymers,

(up to 95% propylene). NMR spectroscopy 409
92.1 Summary
92.2 Apparatus
92.3 Reagents
92.4 Method
93 Determination of bound styrene in styrenated alkyd resins. Infrared

spectroscopy 411
93.1 Summary
93.2 Apparatus
93.3 Reagents
93.4 Method
xxxi
94 Determination of styrene and methacrylate units in styrene-methyl methacrylate

and styrene - n-butyl methacrylate copolymers. NMR spectroscopy 412
94.1 Summary
94.2 Apparatus
94.3 Reagents
94.4 Method
95 Determination of styrene and methacrylate units in styrene-methyl methacrylate

and styrene n-butyl methacrylate copolymers. Pyrolysis-gas chromatography 415
95.1 Summary
95.2 Apparatus
95.3 Reagents
95.4 Method
96 Determination of compositional analysis of methyl methacrylate-methacrylic

acid copolymers. Fourier transform Be NMR spectroscopy 416
96.1 Summary
96.2 Apparatus
96.3 Reagents
96.4 Method
97 Determination ofhexafluoropropylene and vinylidene fluoride units in

polyhexafluoropropylene - vinylidene fluoride copolymers. Pyrolysis-gas
chromatography 418
97.1 Summary
97.2 Apparatus
97.3 Reagents
97.4 Method
7.5 ADDITIVE MIXTURES
98 Determination of mixtures of additives in polymers. Thin-layer

chromatography-infrared/ultraviolet spectroscopy 424
98.1 Summary
98.2 Apparatus
98.3 Reagents
98.4 Method
xxxii
99 Determination of additives in polyethylene and PVC. High performance

liquid chromatography 436
99.1 Summary
99.2 Apparatus and experimental procedure
100 Determination of additives in polypropylene. Chemical ionization mass

spectrometry 439
100.1 Summary
100.2 Apparatus
100.3 Reagents
100.4 Method
101 Determination of additives in polypropylene. Liquid chromatography-mass

spectrometry 442
101.1 Summary
10 1.2 Apparatus
10 1.3 Reagents
101.4 Method
102 Identification and determination of additives in polymers. Photolytic degradation

102.1 Summary 444
102.2 Apparatus
102.3 Method
103 Identification of additives in polymers. Gas chromatography-infrared

spectoscopy 449
103.1 Summary
103.2 Apparatus
103.3 Method
7.6 PRELIMINARY QUALITATIVE IDENTIFICATION
104 Qualitative detection of elements in polymers 455

104.1 Summary
xxxiii
104.2 Apparatus
104.3 Reagents
104.4 Method
105 Identification of polymer films. Thermal method 459

105.1 Summary
105.2 Apparatus
106 Pyrolysis-gas chromatography of polymers. Curie point filament

pyro1yser technique . 464
106.1 Summary
106.2 Apparatus
106.3 Method
t 06.4 Experimental procedure
107 Pyrolysis-gas chromatography of polymers. Platinum ribbon or coil

procedures 465
107.1 Summary
107.2 Apparatus
107.3 Method
lOS Pyrolysis-gas chromatography of polymers. Laser pyrolysis technique 467

10S.1 Summary
lOS.2 Apparatus
10S.3 Method
10S.4 Experimental procedure
References
INDEX 475
xxxiv
CHAPTER 1
POLYMER ANALYSIS
1.1. POLYETHYLENE AND POLYPROPYLENE
1.1.1. Residual Volatiles and Water
The solid polymer head space analysis technique developed by Crompton and
Myers' has been applied to the identification and determination of residual poly-
merization solvent residues in polyethylene and polypropylene.
Polyethylene is not appreciably soluble in organic solvents and the determination
of existing volatile impurities cannot be conveniently carried out by the analysis of
solutions of the polymer. Many organic solvents will extract such volatiles from
polyethylene, but these are likely to be lost during the solvent removal stage prior to gas
chromatographic analysis. A further problem is that extraction procedures cannot be used
for investigating those volatiles that are not inherently present but are produced only
when the polymer is heated. The following examples illustrate the use of this method for
examining both types of volatiles released from polyethylene.
The technique was used to study the effect of temperature on the nature of the
volatiles released. To investigate this, polyethylene was heated for 15 min in air at 125°,
150°, 175° and 200°C and the volatiles were examined by gas chromatography. Figure
1.1 shows the chromatograms of the volatiles released at 125° and 200°C and Table l.l
gives the peak height ratios of the major components (I - 7) released at four temperatures.
Replicate runs indicated good reproducibility.
The results in Table 1.1 show that the only significant variation of peak height
ratios with temperature occurs when component 1 is compared with components 2 - 7 and
component 2 is compared with components 4 - 7. As the temperature increases to 200°C
components 1 and 2 increase while components 3 - 7 decrease (Fig 1.1). Components 1
and 2 were eluted in the C2 - C4 hydrocarbon region and components 3 - 7 were eluted
coincident with the major components of the polymerization solvent known to be used in
this polyethylene manufacturing process. These observations suggest that between 125°C
and 200°C there is some thermal degradation of the polymerization solvent to C2 - C4
hydrocarbons.
Food and drink containers extruded or moulded from polyethylene may
occasionally possess unpleasant odours which are likely to taint the packaged product and
are unacceptable to the consumer. In one such case it was found that by heating a sample
of an odour-producing polyethylene for 15 min at 200°C under helium the chromatogram
of the liberated volatiles contained certain peaks which were absent from the
corresponding chromatogram from a polyethylene which produced non-odourous food
containers. The temperature of 200°C was chosen to simulate the extrusion temperature.
Method 1 at the end of this chapter has been used2 for determining water and
volatiles in polyolefins in which the solid sample is placed in a gas chromatograph
sample loop which is then heated under controlled conditions and the volatiles swept by
helium carrier gas on to a gas chromatographic column prior to estimation.
(1 )
Heated II 200'C
(3)
Healed It 12S'C
(3)
(6)
Figure 1.1. Chromatograms of volatiles liberated from polyethylene healed at different temperatures for 15
minutes in air. Chromatographed on 200 ft x 1116 ID dibutyl-phthalate-coated copper column at 30·C and
100 mllmin helium flow, with flame ionization detection.
Table 1.1 - Peak Height Ratios of Volatiles Liberated by Polyethylene at Various

Tempemtures
Peak Height Ratio
Component Number 12S·C IS0·C 17S·C 200·C

Ratio
1:2 4.4 5.4 3.1 3.1

1:3 0.3 0.3 0.3 1.7
1:4 2.1 3.2 2.4 14.6
1:5 0.7 1.0 0.8 4.7
1:6 0.5 0.8 0.6 3.5
1:7 0.9 1.2 1.0 5.9
2:3 0.06 0.06 0.08 0.06
2:4 0.5 0.6 0.8 4.6
2:5 0.2 0.2 0.3 1.9
2:6 0.1 0.1 0.2 1.1
2:7 0.2 0.2 0.3 1.9
3:4 8.1 9.6 9.1 8.3
3:5 2.9 3.1 3.1 2.7
3:6 2.1 2.3 2.3 2.0
3:7 3.4 3.7 3.8 3.4
4:5 0.4 0.3 0.3 0.3
4:6 0.3 0.2 0.3 0.2
4:7 0.4 0.4 0.4 0.4
5:6 0.7 0.7 0.7 0.8
5:7 1.2 1.2 1.2 1.3
6:7 1.7 1.6 1.6 1.7
2
Conventional weight loss methods for determining water in polymers have several
disadvantages not the least of which is that any other volatile constituents of the polymer
such as solvents, dissolved gases, volatile substances produced by decomposition of the
polymer or additives therein are included in the determination. The Karl Fischer method
described in method 2 for the determination of water in polyalkenes has the advantage
that it is absolutely specific for water. In addition, by controlling the temperature of the
sample, for example, by temperature programming the sample, information can be
obtained regarding the rate of release of water from the polymer and its dependence on
sample temperature.
Evolved gas analysis 372 - 374 has been evolved to study the chemical nature of the
volatiles produced by breakdown of a polymer when it is heated to various controlled
temperatures. The polymer is heated in a thermogravimetric analyser and the volatiles
lead into a gas chromatograph for identification and determination.
1.1.2. - Additives
1.1.2.1 General Discussion
In order to appreciate fully the techniques which have been developed for the
analysis of additives in polymers, it is necessary to be familiar with the difficulties
involved in such an undertaking and also with the chemical and physical properties of the
additives themselves.
Most of the analytical problems arise from three factors; the situation of the
additive in a more or less insoluble polymer matrix, the high reactivity and low stability
of many types of additives, especially antioxidants, and the low concentrations of
additives present in many instances in the polymer matrix. The first factor severely limits
the choice of analytical techniques that can be applied to the sample without prior
separation of the additive from polymer, a procedure which is itself hindered by the
nature of the polymer matrix. In addi.tion, any extract of the polymer is liable to
contamination by low molecular weight polymer "wax" which may interfere with
subsequent analysis and is difficult to remove.
The second and third factors mentioned above combine to make the handling of
extracts an exacting job if quantitative ·information is required. Antioxidants,
particularly, are labile unstable compounds, forming complex decomposition products;
this considerably complicates interpretation of analytical data and any loss of material by
decomposition is liable to be a significant since the quantities present are initially so low.
It is recommended that polymer extracts are kept in actinic glassware and used for
subsequent analysis without delay. If any storage of solutions is necessary, this should be
done under nitrogen, in the dark and in a refrigerator to minimize the effects of oxygen,
light and heat on any labile compounds present. Lorenz et al3 have published data on
sample changes during handling of antioxidant extracts, including losses during
concentration by evaporation. Generally, however, this aspect of additive analysis does
not seem to have received the consideration it deserves.
Apart from these factors which complicates the processing of the sample, there are
others which complicate the interpretation of the data obtained, the principle ones being
the wide range of additives used nowadays in polymer technology, which make positive
identification difficult by all but the most sophisticated analytical techniques, the
presence of several types of additives in a single polymer formulation, e.g. plasticizers,
ultraviolet stabilizers, slip agents and possibly two antioxidants, one for processing and
one for service, may all be present in a single formulation and, finally, depending on
processing history and age of the polymer, the possibility that additive decomposition
3
products may also be present to complicate the analytical problem in hand. The latter
type of additive decomposition should be distinguished from that occurring during
analytical processing. For example, a particular type of polymer additive may undergo
partial thermal degradation during extrusion operations involved in its manufacture and
then during analysis may degrade by another route under the influence of light.
To summarise then, the determination of additives in polymers presents the
analyst with some difficult problems. Only small concentrations are present, complex
mixtures may be involved and, moreover, frequently the mixture is of compounds of
completely unknown type. Most methods for the determination of additives in plastics
come under one of three categories:
i. Direct examination of polymer, ie. non-destructive testing

ii. Examination of solvent extracts of polymers
iii. Examination of volatiles released upon heating the polymer.
An example of direct examination is the examination of the polymer film by

infrared or ultra-violet spectroscopy or of thicker sections of polymer by attenuated total
reflectance (ATR) infrared spectroscopy.375 Such techniques have severe limitations in
that, because the additive is in effect heavily diluted with polymer, detection limits are
usually well above the low concentration of additive present and this method is only
applicable if the additive has distinct sharp absorption bands in regions where the
polymer itself shows little or no absorption. In-situ spectroscopic techniques are not
likely to be of value, then, in the analysis of samples of unknown composition. If known
amounts of additive can be incorporated into additive-free polymer, however, these
techniques are likely to be extremely useful in the study of solvent extraction procedures,
and the study of additive ageing processes (ie. the effects of heat, light, sterilization,
radiation, etc.), since the rate of disappearance of or decay can be measured directly by
the decrease in absorbance of the sample at a suitable wave-length.
The direct analysis of additives in polyethylene film by means of ultraviolet
spectroscopy is limited by excessive beam dispersion due to light scattering from the
polymer crystalline regions. Additives at low concentrations (0.1%) require sample
thickness such that analysis must be performed in the presence of a high level of light
scattering which may change unpredictably with wavelength. At lower levels of
concentration and corresponding greater sample thickness, unacceptable signal to noise
ratios exist. Nevertheless, ultraviolet spectroscopy remains an attractive method for
analysis for many additives; principal advantages over infrared spectroscopy include
greater sensitivity arising from higher extinction coefficients and a lack of interfering
absorptions from the polymer matrix. These advantages can be realised, however, only if
background scattering from the polymer can be reduced.
Solvent extraction procedures are commonly used in additive analysis. In these
procedures the polymer is refluxed with a solvent which either dissolves the polymer or
softens it so that additives dissolve into the solvent phase. A non-solvent for the polymer
is then added to reprecipitate the polymer, leaving the additives in solution. A good
example of this is the extraction of additives from polyethylene in which the polymer is
refluxed with toluene which partly dissolves the polymer. Upon the addition of absolute
ethanol the polymer is reprecipitated leaving the additives in solution in the toluene -
ethanol solvent mixtures which is then tiltered off and carefully evaporated to dryness to
provide the additive extract which is essentially free from polymer. Such extracts when
prepared quantitatively are extremely useful for either direct analysis for known additives
or for subsequent separation of their components by one of a number of chromatographic
4
techniques prior to examination of the individual separated compounds by spectroscopy
for identification and for quantitation.
A list of soluble solvent extraction procedures for various types of polymers is
given in Table 1.2.
i.i.2.2 Phenolic Antioxidants
Generally, methods are based on solvent extraction of the additive followed by

analysis for the extracted additive by a suitable physical technique such as visible
spectrophotometry of the coupled antioxidant, redox spectrophotometric methods, ultra-
violet spectroscopy, infrared spectroscopy, gas chromatography, thin-layer chromato-
graphy or column chromatography. In general, direct chemical methods of analysis have
not found favour. These include potentiometric titration with standard sodium
isopropoxide in pyridine medium26 or reaction of the antioxidant with excess standard
potassium bromide-potassium bromate (ie. free bromine) and estimation of the unused
bromine by addition of potassium iodide and determination of the iodine produced by
titration with sodium thiosulphate to the starch end_point. 27
i.i.2.2a Visible Spectrophotometric Method Metcalf and Tomlinson8 have

described a very useful general colorimetric procedure for the determination of phenolic
and other types of antioxidant in polyethylenes (method 3). This procedure involves
oxidation of the antioxidant (A) under controlled conditions with an absolute ethanol
solution of ferric chlorid~:
A reduced + Fe3+ = A oxidized + Fe2+
followed by reaction of the ferrous iron produced with 2,2'- dipyridyl to form a coloured
complex, the intensity of which is proportional to the concentration of antioxidant
present.
The procedure has been applied to various phenolic and amine type antioxidants,
viz. Succanox 18, butylated hydroxy toluene, lonol (2,6-di-tert-butyl-p-cresol) and Nonox
CI (N-N-di-2-napthyl-p-phenylenediamine)
Coupling with diazotized sulphanilic acid has also been used as the basis of a
method for determining phenolic antioxidants in polyethylene. 29
Hilton28 published a method (method 4) for the determination of phenolic
antioxidants in polymers based on the preparation of a methanol or ethanol extract of the
polymer, followed by coupling the extracted phenol with diazotized p-nitroaniline in
strongly acidic medium. The solution is then made alkaline and the visible absorption
spectrum determined.
i.i.2.2b Ultraviolet Spectroscopy. Ultraviolet spectroscopy is liable to be in

error owing to interference by other highly absorbing impurities that may be present in
the sample.3o - 33 However, within prescribed limits, ultraviolet spectroscopy is of use
and, as an example,34 - 37 two procedures are discussed (methods 5 and 6) for the
determination of lonol (2,6-di-tert-butyl-p-cresol) and of Santonox R (4,4' -thio-bis-6-tert-
butyl-m-cresol) in polyolefins.
In an attempt to overcome the difficulty of interference effects by other polymer
additives in the ultraviolet spectroscopic determination of phenolic antioxidants, Wexler
38 makes use of the bathochromic shift exhibited by phenols on changing from a neutral
or acidic medium to an alkaline one. This shift is due to the change of absorbing species
s
Table 1.2 - Solvent Extraction Methods of Additive Extraction from Polymers
Polymer Type Substances Extracting Comments References Type of

Extracted Solvent Extraction
Polyethylene cresolic and chloroform heat at 50°C for 4 fractional

phenolic 3 h in a closed extraction
antioxidants container
Polyethylene cresolic antioxidants hexane heat at 50°C for 5 fractional
24h extraction
Polyethylene cresolic antioxidants ether in the dark at 6 fractional
20°C extraction
Polyethylene phenolic chloroform 7 fractional
antioxidants extraction
Polyethylene antioxidants toluene reflux to dis- 8 fractional
solve polymer in precipitation
precipitate with
methanol
Polyethylene antioxidants water at 70°C under 9 fractional
nitrogen extraction
Polyethylene phenolic carbon 10
antioxidants disulphide
iso-octane
Polyolefins 2,6 di-t-butyl p- cydo- reflux 30 min 11
cresol hexane
PVC diphenyl thio-urea methanol
2-phenylindole or ether
dicyandiamide
PVC Stabilizers, ether 12
lubricants,
plasticizers
Rubbers amine and phenolic ethanoll reflux, then 13,14
antioxidants HCI steam-distil
amines from
extract
Rubbers phenyl salicylate, ether
resorcinol benzoate
Rubbers antioxidants acetone 15,16
Rubbers ketone-amine acetone 17
condensates phenols
2-mercaptobenz-
imidazole
General p-Phenylen- 95% reflux 16 h in an 18
ediamine- methanol extraction cup
derivatives or ethanol
Polypropylene antioxidants tetrahydrof 19
uran
Polyethylene antioxidants chloroform 20
Polyolefins antioxidants methylene 21
dichloride
Polyethylene antioxidants ground 22
polymer
chloroform
extraction
on soxhlet
Polypropylene antioxidants tetrahydrof 23
(8 mesh) uran for 24
6
Table 1.2 continued
Polyethylene antioxidants dekalin at 24,25

and 1I0·for 30
Polypropylene mins
because of solute-solvent interaction. Using a double-beam recording spectrophotometer,

he measured a difference spectrum by placing an alkaline solution of the polymer extract
in the sample beam, and an identical concentration of sample in acid solution in the
reference beam. The resulting difference spectrum is a characteristic and useful
indication of the concentration and chemical identity of the phenolic substance. Possible
interference due to non-ionizing, non-phenolic species are usually cancelled out in the
difference spectrum which should make the technique of interest to the polymer analyst.
Soncek and Jelinkova39 have also used this differential principle to determine in
polypropylene two antioxidants (2,6-ditert-butyl-4-methylphenol and 4-substituted 2,6-
xylenol) which have virtually identical ultraviolet absorption spectra in the absence of
alkali (method 7). The antioxidants can be distinguished in alkaline medium, where 4
substituted 2,6-xylenol forms phenolate readily, thus allowing the utilisation of the
bathochromic shift for its determination. The use of derivative spectroscopy reduces light
scattering and matrix interferences when extracts from polypropylene samples are
measured.
Ruddle and Wilson34 used observed shifts in the ultraviolet following treatment of
polymer extracts with alkali and nickel peroxide as the basis of a low interference method
for determining Topanol OC, Binox M and Ionox 330 in polyethylene (Method 8).
1.1.2.2c Infrared Spectroscopy. Spell and Eddy 41 have described infrared

spectroscopic procedures for the determination of up to 500 ppm of various additives in
polyethylene pellets following solvent extraction of additives at room temperature. They
showed that Ionol (2,6-di-tert-butyl-p-cresol) and Santonox R (4,4-thio-bis-(6-tert-butyl-
m-cresol) are extracted quantitatively from polyethylene pellets by carbon disulphide in 2
- 3 h and by iso-octane in 50 - 75 h.
Miller and Willis42 obtained infrared spectra of antioxidants from polymer films.
They compensated with additive free polymer in the reference beam. Infrared
spectroscopy is more specific than ultraviolet spectroscopy, but some workers 43 find that
the antioxidant level in polymers is too low to give suitable spectra. In-situ spectroscopic
techniques are not likely to be of value then, in the analysis of samples of unknown
composition.
Luongo44 and Drushel and Sommers4S described methods for incorporating
known amounts of additives into polymer.
1.1.2.2d Thin Layer Chromatography. This technique comes into its own when
dealing with known mixtures of antioxidants in polymer extracts as discussed in more
detail in Chapter 5.
In Method 9 is described a quantitative thin-layer procedure for determining a
single additive, namely Santonox R (4,4' -thio-bis-6-tert-butyl-m-cresol) in polyethylene.
Dobies46 has described detailed thin-layer procedures for determining 0.02 - 0.2%
of various antioxidants in polyethylene and polypropylene films (method 10). Simpson
and CurreU47 use thin-layer chromatography in the determination of additives such as
7
antioxidants, ultraviolet absorbers and organotin stabilizers in polyolefins and other
polymers (Method II)
1.1.2.2e Direct Ultraviolet Spectroscopy Of Polyalkene Films. Albarino 48 stated

that analysis of polyalkene additives by means of direct ultraviolet spectroscopy of the
polymer film is limited by excessive beam dispersion due to light scattering from the
polymer crystalline regions. Additives at low concentrations (0.1%) require sample
thicknesses such that analysis must be performed in the presence of a high level of
scattering which may change unpredictably with wave-length. At lower levels of
concentration and correspondingly greater sample thicknesses, unacceptable signal-to-
noise ratios exist. Nevertheless, ultraviolet spectroscopy remains an attractive method for
analysis of many additives. Principal advantages over infrared analysis include greater
sensitivity arising from higher extinction coefficients and a lack of interfering absorptions
from the polyalkene matrix. These advantages can be realized however, only if
background scattering from the polymer can be reduced.
Albarino48 demonstrated the feasibility of quantitative ultraviolet analysis of
Irganox 1010 antioxidant in polyethylene film at temperatures above the polymer melting
point where the crystallites, which account for much of the scattering, are eliminated.
1.1.2.2f High Performance Liquid Chromatography. Schabon and Fenska24 have

described a rapid extraction procedure (method 12) followed by high performance liquid
chromatography for the determination in polyethylene of down to 10 ppm of Irganox
1076 (octadecyl 3,5-di-tert-4-hydroxy hydrocinnamate), Irganox 1010 (tetrakis
(methylene(3,5-di-tert-butyl-4-hydroxhydrocinnamate» methane), and butylated
hydroxytoluene (2,6-di-tert-butyl-4-methyl-phehol).
Vargo and Olsen 377 used absorbance and mass spectrometric detectors to detect
antioxidant, and UV stabilizers leaving an hplc column in acetonitrile extracts of poly-
propylene.
Selective mass spectrometry. Rudewicz and Munson 376 used selective mass
spectrometry (SIMS) for the determination of additives in polypropylene without the
need for prior solvent extraction of additives.
1.1.2.3 Amine Antioxidants
1.1.2.3a Spectrophotometric Method In a procedure recommended by the

British Standards Institutionso for determining Nonox CI (N,N'-di-2 napthyl-p-
phenylene-diamine) in low density and high density polyethylene, the polymer is refluxed
with toluene, reprecipitated with ethanol and filtered to provide a clear extract. The
antioxidant content of the filtrate is determined colorimetrically by oxidation with
hydrogen peroxide, in the presence of sulphuric acid. This reagent produces a green
colour with Nonox CI which gradually reaches a maximum intensity. The colour is
evaluated at 430 nm when the maximum depth of colour is reached.
CromptonSI has described a modification to this procedure (method 13) for the
determination of Nonox CI in high density polyethylene which, compared to low density
polymer, has only a small solubility in toluene. He has also extended the procedure to the
determination of oxidized Nonox CI, and a further product which he calls degraded
Nonox CI.
The procedure described under phenolic antioxidants involving oxidation of the
antioxidant with ferric iron followed by spectrophotometric estimation of the ferrous iron
produced using 2,2'-dipyridyl is also applicable to the determination of amine
8
antioxidants. Other chromogenic reagents that have been used for the determination of
amine antioxidants include p-diazobenzene sulphonic acid,52 diphenyl-6-picrylhydrazyl
and benzothiazolin-2-onehydrazone. 54
The Hilton 35,56 diazotization procedure has been used for the determination of
amine antioxidants in polyolefins and other polymers (Method 14).
1.1.2.4 Diorganosulphide (and Tertiary Phosphite) Types ofAntioxidants in Polyolefins
1.1.2.4a Selective Oxidation Procedure. Kellum57 has described a method

(Method 15) based on selective oxidation, for the determination of diorganosulphide and
tertiary phosphite types of secondary antioxidants in polyolefms. These two classes of
compounds were selectively determined in the presence of each other by oxidation using
m-chloro-peroxy-benzoic acid to sulphones and phosphates. In this method, a heptane
extract of the polyolefins containing the antioxidants is treated with a two-fold excess of
the oxidant and allowed to react before the unreacted oxidant is decomposed with sodium
iodide to produce iodine which is estimated by sodium thiosulphate titration. This
method has the advantage of being free from interference by hindered phenolic
antioxidants, benzophenones and substituted hydroxy phenyl benzotriazole type light
stabilizers, triazoles, fatty acid amides and stearate salts, all of which might be present in
the polymer extract.
i.i.2.4b Gas Chromatographic Procedure. Gas chromatography has been

employed to determine diorganosulphide antioxidant, such as dilauryl 6,6' thiodi-
propionic acid in polyolefins (method 16). This method has the advantage of being less
subject to interference than the selective oxidation procedure described above.
1.1.2.4c Thin Layer Chromatography. Thin layer procedures have been

described2s2 for the determination of dilauryl 8,6' - thiodipropionate antioxidant in
polyalkenes. In this procedure the total additives are first extracted from the polymer by
extraction under nitrogen with a I: 1:4 mixture of chloroform, ethanol and n-hexane. To
separate dilauryl 6,6' thiodipropionate from its own oxidation products and from other
additives, the extract was subject to thin layer chromatography on a silica gel coated
plate. The spot containing dilauryl B,8' thiodipropionate is refluxed for 30 minutes at
80°C with 5N methanolic potassium hydroxide to hydrolyse the ester to lauryl alcohol
which is then extracted from the aqueous alcoholic phase with chloroform containing n-
octadecene internal standard. This extract is gas chromatographed on an isothermal
column packed with 1.5% fluor-silicone oil FS 1265 on 60 to 100 mesh Chromosorb W
operated at 300°C and utilizing a flame ionization detector. Suitable reference solutions
of dilauryl 8,B' - thiodiproprionate run in parallel through the whole procedures gave a
recovery of 97%.
1.1.2.5 Ultraviolet Absorbers and Optical Brighteners in Polyalkenes
Among the numerous additives commonly used in plastic materials, the ultra-
violet absorbers are increasing in importance because they are often used in food pack-
aging materials to protect the plastic material as well as the foodstuff packaged from the
actinic action of ultraviolet radiation. Actinic effects may cause discolouration of both
the plastic material and the foodstuff and, on occasion, also changes in taste and loss of
vitamins in the food.
9
The ultraviolet absorbers can be divided in different groups (Table 1.3)
(a) Benzophenone derivatives

(b) Salicylic acid esters
(c) Resorcinol esters
(d) Benzotriazole compounds
(e) Coumarin derivatives
Methods 17 and 18, respectively, determine Cyasorb UV 531 (2-hydroxy-4-n-

octoxybenzophenone) in polyolefins by direct infrared spectroscopy and thin-layer
chromatography. Phenolic and organophosphorus type antioxidants do not interfere in
these procedures. Method 19 describes an ultraviolet spectroscopic method for the
determination ofTinuvin 326 ultraviolet absorber in polypropylene.
The fluorescence emitted by optical brighteners under ultraviolet light on a thin-
layer plate has been utilized as a means of estimating these compoundss9 (method 19).
To estimate Tinuvin 326 7(6-butoxy-5-methyl-benzotriazol-2-yl) 3-phenyl-coumarin) in
polymer granules, the sample is extracted from the polymer with chloroform. The extract
is applied to two Kieselgel G plates and chromatograms are developed with benzene-
chloroform (2:3) and benzene, respectively; the spots being detected by their fluorescence
in ultraviolet radiation.
1.1.2.50 Gas Chromatographic Procedure. Lappin and Zannucci60 showed that a

number of ultraviolet light absorbers as well as antioxidants could be quantitatively
determined on an SE-30 column. SE-30 has a maximum operating tempemture of about
350°C. This high temperature permits elution of some high molecular weight additives.
When the polymer was dissolved in p-xylene and reprecipitated with an equal volume of
p-dioxane a relatively clean chromatogram was obtained from the filtrate. The position
of decomposition peaks from unstable compounds, such as dilauryl B,B' -thiodipropionate
and distearyl pentaerythritol diphosphite, are predictable and do not interfere with the
determination of those additives studied by Lappin and Zannucci. 60
Lappin and Zannucdo determined 4-(dodecyloxy)2-hydroxybenzophenone
(DOBP) and 2,6-di-tert-butyl-p-cresol (BHT) in polypropylene by this technique (Table
1.4). The precision of the BHT determination is good but the quantity found (0.02%) was
less than the amount added (0.05%) possibly due to some losses of volatile BHT during
polymer compounding. DOBP determinations ranged from 0.20 to 0.35% for a sample
originally containing 0.30% of the additive.
Denning and Marshal1 61 devised a method in which toluene extracts of
polyethylene are examined for ultraviolet absorbers (and antioxidants) at two column
temperatures in order to overcome the problem that whereas some compounds have a
relatively low retention time, others of higher molecular weight have very long retention
time at 250°C. Relative retention data obtained for ultraviolet absorbers, are given in
Table 1.5.
1.1.3 Fractionation
Low molecular weight high density polyethylene has been fractionated by supercritical
fluid chromatography usinc!i carbon dioxide, propane and propane modified carbon
dioxide as eluting agents. 4
10
Table 1.3 - Some Ultraviolet Absorbers Used in Plastic Materials
Chemical Formula Trade Name Manufacturer
2-hydroxy-4-methoxy- UvinalM40 General Aniline Co

benzophenone Uvistat24 Ward & Blenkinsop
CyasorbUV 9 Cyanamid
2. 2,4-dihydroxy-benzophenone Uvistat 12 Ward & Blenkinsop
Uninul400 General Aniline Co
3. 2-hydroxy-4-methoxy-4- Uvistat 2211 Ward & Blenkinsop
methyl-benzophenone
4. 2,4,5-trihYdroxy Inhibitor THBP Eastman
butyrophenone
5. 4-dodecyloxy-2-hydroxy Inhibitor DOBP Eastman
benzophenone
6. 2-hydroxy-5-n-octoxy- Cyasorb UV 531 Cyanamid
benzophenone
7. 2,2' dihydroxy-4-methoxy Cyasorb UV 24 Cyanamid
benzophenone
8. 2,2'dihydroxy-4,4' dimethoxy Uvinul049 General Aniline Co
benzophenone
9. p-tert-butylpheny\salicilate
10. resorcinol mono benzoate Inhibitor RMB Eastman
II. hydroxyphenylbenzo-triazole TinuvinP Geigy
12. 7-diethylamin0-4-methyl Ward
coumarin
Table 1.4 - Analyses of Polypropylene for BHT and DOBP

Additive found (%)
Sample Composition Run 1 Run 2 Run 3 Run 4
0.05% 2,6-di-tert-butyl-p-cresol 0.02 0.02 0.03 0.02

0.30% 4(dodecyloxy) 2-hydroxy-benzophenone 0.25 0.32 0.20 0.35
From Lapin and Zanncdo with permission. American Chemical Society.
1.2 POLYSTYRENE
1.2.1 Volatiles and Water
1.2.1.1 Monomers and Aromatic Volatiles
1.2.1.1a Gas Chromatography. The styrene monomer used in the manufacture of

polystyrene generally contains low concentrations of aromatic impurities. These fall into
two categories (a) saturated compounds such as benzene, toluene, ethyl benzene, xylenes,
propyl benzene, butyl benzene, ethyl toluenes, diethyl benzenes, traces of which remain
in the final polymer and (b) unsaturated impurities such as methyl styrenes which either
wholly or partially copolymarize with the styrene. The presence of all these substances in
addition to residual styrene monomer in the final polymer has implications from the
points of view of the mechanical properties of the final polymer and toxicity in the case
11
Table 1.5 - Separation of Ultraviolet Absorbers
Ultra violet absorber Class of compound Relative retention time Column Temp-
(relative to Santonox R) erature (0C)
Tinuvin P Benzotriazole 0.20 250

Tinuvin 326 Benzotriazole 0.64 250
Tinuvin 327 Benzotriazole 0.85 250
Cyasorb UV 531 Aromatic ketone 1.0 250
Tinuvin P 2-(2'-Hydroxy-5'-methylphenyl benzotriazole)
Tinuvin 326 2-(2'Hydroxy-3'-t-butyl-5'methyl ethyl phenyl-3-)chlorobenzo triazole
Cyasorb UV 531 2-Hydroxy-4-n-octoxybenzophenone
From Denning and Marshall with permissionY American Chemical Society
of foodstuff packing grades of polystyrene. Method 20 is capable of determining all

these aromatics in amounts down to 0.001% w/w in polystyrene.
A further apparatus for carrying out solid polymer head space analysis of
polystyrene for styrene monomer and aromatic volatiles has been described by Crompton
and Myers. 1 In this apparatus the polymer is heated up to 300°C in the absence of
solvents, prior to their examination by gas chromatography. The technique (Method 21)
avoids the disadvantages resulting from the use of extraction or solution procedures.
Davies and Bishop62 have developed a further head space analysis technique
(Method 22) in which the polystyrene film or sheet, together with internal standard, is
placed in a 250 cm3 sealed container and heated at 100°C for 90 min. This method has
been used to determine many different solvents in several different substrates. The
solvents include ethanol, ethyl acetate, ethyl methyl ketone, 2-ethoxyethanol, propan-I-ol
and toluene. The substrates include polyethylene, polypropylene and cellophane, which
occur individually, coated with saran or combined in laminates.
Roper63 has discussed the problem of determining very low concentrations of
volatiles in polymers. To achieve this Roper63 employed a trap-tube. The capillary
portion of the tube is packed with a gas chromatographic column packing consisting of
20 to 30% of a suitable liquid phase on a granular diatomaceous type support. The tube
is fitted with a suitable hypodermic needle so that it can be connected to the gas
chromatograph through the injection port. The polymer sample to be analysed is weighed
into the trap-tube and the tube is connected to an inert-gas stream and heated to the
appropriate temperature while the gas stream sweeps the volatile material into the packed
section of the tube, which is usually cooled with dry ice. Melting the polymer is often
necessary to rid it of volatiles. After the volatiles have been absorbed in its packed
section, the trap-tube is disconnected and moved to the chromatograph. The heater,
already at temperature, is then moved to the capillary portion of the tube-trap where the
heat and carrier gas flow sweeps the volatiles from the packing through the hypodermic
needle and into the gas chromatograph.
Various other workers have described procedures for the determination of vola-
tl'1'
es In po IyethyIene 1..264 and poIypropy Iene. 66
1.2.1.1 Ultraviolet Spectroscopic Procedure. An alternate procedure for

determining styrene monomer in polystyrene is based on ultraviolet spectroscopy.
Styrene monomer has a strong absorption maximum of 292 nm. Unfortunately, this is
subject to interference by aromatic additives, ego antioxidants, which are often present in
12
the polymer at a concentration similar to that of the monomer. Methods which handle
this interference are discussed below.
The baseline correction technique can obviously be applied to the determination
of styrene monomer in polystyrene only if any other ultraviolet absorbing constituents in
the polymer extract (eg. lubricant, antioxidants) absorb linearly in the wavelength range
288 - 300 nm). If the polymer extract contains polymer constituents other than styrene
with non-linear absorptions in this region, then incorrect styrene monomer contents will
be obtained.
1.2.1.1c Distillation Ultraviolet Absorption Procedure. In the distillation tech-

nique64 the polystyrene (0.5g) is dissolved in chloroform or ethylene dichloride (20 ml) in
a stoppered flask and the solution is poured into an excess of methyl alcohol (110 ml) to
reprecipitate dissolved polymer. The polymer is filtered off and washed with methanol
(120 ml) and the combined filtrate and washings gently distilled to provide 200 ml of a
distillate containing only styrene monomer and any other distillable component of the
original polystyrene sample. Non-volatile polymer components (viz. stabilizers,
lubricants and low molecular weight polymer) remain in the distillation residue.
The optical density of the distillate is measured at 292 nm or by the baseline
method against the distillate obtained in a polymer-free blank distillation. Calibration is
performed by applying the distillation procedure to solutions of known weights of pure
styrene monomer in the appropriate quantities of methyl alcohol and the chlorinated
solvent.
Tables 1.6 and 1.7 show results obtained for styrene monomer determinations
carried out on samples of polystyrene by the direct ultraviolet method and by the
distillation modification of this method. It is seen that the distillation method gives
results that are consistently higher than those obtained by direct spectroscopy.
Similar effects to these were also observed with polystyrene containing other
ultraviolet absorbing additives. Thus, the influence of a mixture of 0.4% w/w tris-
(nonylated phenyl phosphite (Polygard) and 0.2% w/w 2,6-di-tert-butyl-p-cresol (lonol
CP) on the determination of styrene monomer is shown in Table 1.8.
1.2.1.1d Mass Spectrometry. Peltonen378 applied mass spectrometry to the

identification of volatile breakdown products of heated polystyrene. Evolved gas analysis
involving the coupling of a gas chromatograph to a mass srsictrometer has been used to
identify volatile products formed on heating polystyrene.379- 82
1.2.1.1e Thermogravimetric Analysis. Thermogravimetric analysis has been used

to determine the concentration of solvents in polymers and in neat polymer additives and
to determine the temperatures of which additives in polymers start to degrade. 383
1.2.1.1/ Supersonic Jet Spectrometry. Imasaki et al409 carried out supersonic jet
spectrometry of chemical species resulting from the thermal decomposition of poly-
styrene at 400°C. Styrene monomer and its dimer and trimer, also toluene were identified
in the decomposition products.
1.2.1.2 Aliphatic expanding agents
Expandable grades of polystyrene are manufactured by steeping volatile

polystyrene granules in a low boiling hydrocarbon solvent until the polymer becomes
saturated with the solvent. When the granules are put in a mould and are treated with
stearn, they undergo an expansion to many times their original volume and the expanded
13
Table 1.6 - Comparison of Direct Ultraviolet and DistilIationlUltraviolet Methods for the
Determination of Styrene Monomer
Styrene Monomer (%w/w) in Polystyrene Sample
Method Solvent No.1 No.2
Direct UV Method Chloroforml <0.05 0.13

carbon tetrachloride <0.05 0.13 0.14 0.16 0.18
Ethyl acetate <0.05 0.14 0.12 0.14
0.14 0.15
DistillationlUV Ethylene di 0.16 0.18 0.27 0.29
chloride! 0.16 0.18 0.260.29
methanol 0.20 0.29
Table 1.7 - Influence of Phenolic Antioxidant· on the Determination of Styrene

Monomer by Direct Ultraviolet and by DistiIlationlUltraviolet Methods
Styrene Found (% w/w)
Direct UV Method" DistillationlUV Method
Styrene added No phenolic anti- 0.5% phenolic anti- No phenolic anti- 0.5% phenolic anti-
to polystyrene oxidant- addition oxidant· added oxidant· addition oxidant· added
(%w/w) on polymer on polymer
0.11 0.11 0.11 0.040.08 0.12 0.12

0.22 0.22 0.11
0.27 0.26 0.18 0.29 0.26
0.41 0.41 0.40 0.300.27 0.40 0.40
• Wingstay T. " Chloroform used as a sample solvent
Table 1.8 - Influence ofPolygard/lonol CP Mixture on Determination of Styrene

Monomer by Direct Ultraviolet and by DistillationlUltraviolet Methods
Styrene Found (% w/w)
Direct UV Method" Distillation/UV Method6
Styrene added No additive 0.4% w/w Polygard No additive 0.4% w/w Polygard
to polystyrene and 0.2% w/w lonol and 0.2% w/w lonol
(%w/w) CP added on polymer CP added on polymer
0.10 0.10 0.10 0.11 0.11 0.09

0.26 0.25 0.26 0.160.16 0.26 0.27 0.25
0.41 0.42 0.41 0.290.29 0.41 0.400.42
• Chloroform used as a sample solvent. 6 Not measurable due to strong interference by additives
14
granules coalesce. This process is used for the manufacture of insulating polystyrene
board and insulated hot beverage vending vessels. It is important to be able to determine
the concentration of residual volatiles in the original and the expanded polymer and gas
chromatographic methods for carrying out the analysis of several expanding agents are
discussed in Methods 23 to 26.
1.2.1.20 Solid Polymer Head Space Analysis Techniques. A further method

which does not involve the use of solvents is available for the determination of expanding
agents in polystyrene (method 27). This method involves heating the polymer, without
solvent, in a heated copper block and, using the carrier gas, sweeping the released
volatiles from the expanded polymer into the gas chromatograph for quantiative analysis.
An advantage of this procedure is that no sample solvents are present which could
interfere in the interpretation of the gas chromatogram.
1.2.2. Oligomers
High Rerformance liquid chromatography on silica gel columns and 13C NMR
spectroscopy 87 have been employed to determine polystyrene oligomers in the molecular
weight range up to 4800 in polystyrene. Typical elution gradient solvents used in hplc
are n-hexane-tetrahydrofuran or n-hexane-methylene dichloride.
Particle beam liquid chromatograph.r. mass spectrometry has been used to
determine up to n 18 oligomers in polystyrene. 10
Petro et al431 used a molded monolithic rod of macroporous polystyrene divinyl
benzene copolymer as a separation medium for the high performance liquid
chromatography of styrene oligomers and copolymers ego styrene - 2 naphthyl
(methacrylate). "On column" precipitation redissolution chromatography is an altern-
ative to size exclusion chromatography. The solvent gradient used comprises a poor
solvent (water, methanol or acetonitrile) and increasing amounts of a good solvent such
as tetrahydrofuran. Excellent separations of oligomers were achieved by this technique.
1.2.3. Impurities in styrene monomers
All the non-polymerisable volatile impurities which occur in styrene monomer

used in polystyrene manufacture will also be present in the fmished polymer. Analysis of
the monomer is therefore important. Gas chromatographic methods, for determining up
to 40 impurities in styrene monomer are discussed in methods 28 to 30.
In Method 28 the sample was first analysed on the squalene column in the
presence of an added internal standard (eg. n-butyl benzene) to determine down to 5 ppm
n-propyl benzene, butyl benzenes, diethyl benzenes, ethyl toluenes, methyl styrenes, ethyl
styrenes and divinyl benzenes. The sample was then re-analysed on the Carbowax
column to determine benzene, toluene, xylenes, ethyl benzene, cumene, n-propyl benzene
and m-/p-ethyl toluenes. By temperature programming it is possible to reduce the
analysis time to about one hour using a single gas chromatographic column (Carbowax
15 - 20 M-Celite) and to separate up to 40 hydrocarbons up to the divinyl benzenes and
benzaldehyde. Experimental conditions are given in Method 29 (hydrocarbons) and
Method 30 (benzaldehyde).
15
1.2.4. Additives
1.2.4.1 Phenolic Antioxidants
1.2.4.1a Coupling Visible Spectrophotometric Methods. In one such procedure28

described in Method 31 the polymer is extracted with ethanol and the extracted phenolic
antioxidant coupled with diazotized p-nitroaniline in strongly acidic medium. The
solution is then made alkaline and the visible absorption spectrum determined.
1.2.4.2 Ultraviolet Absorbers
1.2.4.2a Ultraviolet Spectroscopic Procedure. By their nature, many of these

types of compounds are amenable to analysis by fluorimetric analysis, thus Uvitex OB
has an intense ultraviolet absorption at a wavelength of 378 nm which is high enough to
be outside the region where many potentially interfering substances present in the
polymer extract would be excited to fluoresce. This is illustrated in the fluorimetric
procedure described in Method 32 for the determination of down to 10 ppm Uvitex OB in
polystyrene.
1.2.4.3 Organic Peroxide Residues
Organic peroxides can occur in small amounts in some types of polymers such as
polystyrenes as a result of the fact that a peroxide has been used as a polymerization
catalyst in polymer manufacture. Also, stable organic peroxides such as dicumyl per-
oxide has been used as synergists, in conjunction with bromine and or phosphorus
containing additives, to impart fire resistance to cellular expanded polystyrene and other
types of plastics
1.2.4.3a Polarographic Procedure. A polarographic procedure for the determ-

ination ofp-tert-butyl perbenzoate in polystyrene is described in method 33.
1.2.4.3b Thin Layer Chromatographic Procedure. Certain types of peroxides

used in polymer formulations are extremely stable and unreactive. This applies to
substances such as dicumyl peroxide used as an ingredient of some self-extinguishing
grades of polymers.
1.1
CH 3 CH 3
I I
CH 3 - C - 0 - 0 - C - CH
I I 3
Ph Ph
This substance cannot be determined by polarography and will not react with
many of the reagent normally used for determining organic peroxides.
Brammer et al 68 have described a method for determining dicumyl peroxide in
polystyrene, which is not subject to interference by other organic peroxides or additives
that may be present in the polymer. The dicumyl peroxide is extracted from the polymer
with acetone and then separated from any other additives present by thin-layer
chromatography on silica gel. The gel in the area of the plate containing dicumyl
16
peroxide is then isolated and digested with potassium iodide in glacial acetic acid
followed by titration of the liberated iodine with dilute sodium thiosulphate solution.
This procedure has a precision of ±12% of the determined value with polymers
containing 0.25 to 0.5% dicumyl peroxide. It is a rather time~consuming procedure but
has the advantage of avoiding all risk of interference from other types of peroxides
present in the sample.
Thin layer chromatography has also been applied to reactive organic peroxide
residues such as tertiary butyl perbenzoate and benzyl peroxide in polystyrene (Method
34).
1.2.4.3c Gas Chromatographic Procedures. Gas chromatography has also been

used to determine certain types of organic peroxides. Bukata et al69 for example, describe
procedures involving chromatography of heptane solutions of peroxide (Table 1.9) on
phthalateldistomaceous earth or silicone/diatomaceous earth columns and using helium as
the carrier gas. No doubt, this type of procedure could be easily adapted to the
examination of solvent extracts of polymers.
Hyden70 describes a gas chromatographic procedure for the determination of di~
tert~butyl peroxide. This is based on the thermal decomposition of the peroxide in
benzene solution into acetone and ethane when the solution is injected into the gas
chromatographic column at 310°C. The technique is calibrated against standard solutions
of pure di~tert-butyl peroxide of known concentration.
1.2.4.4 Inhibitors in Styrene Monomer
Many monomers used in polymer manufacture must be stabilised with a low

concentration of an inhibitor, such as hydroquinone in order to prevent oxidation of the
monomer during storage and consequent effects on its polymerization qualities. As the
inhibitor would, itself, interfere in the polymerization, it is usually stripped from the
monomer imm~diately prior to use by processes such as flash distillation or washing with
aqueous alkali solution.
General methods are described in Methods 35 - 38 for the determination of
inhibitors in monomers.
1.2.5. Fractionation and Molecular Weight
Flow field - flow fractionation has been used40s to fractionate polystyrene and
Kirkland and Rementer411 used thermal field flow fractionation using Mark Houweq
constants to determine the molecular weight distribution of polystyrene and poly
methylstyrene.
Desorption chemical ionization mass spectrometry has been used to determine the
molecular weight distribution of polystyrene. 412 .The liquid chromatographic behaviour
has been studied of polystyrene homopolymers on a C4 pore diameter reversed phase
column. Separation was achieved on a molecular weight basis using a tetrahydrofuran-
acrylonitrile eluting solvent system. 413
Hancock and Synovec414 have carried out rapid characterization of linear and star
branched polystyrene by gradient detection using methylene dichloride solutions of the
polymers. This technique measures weight average molecular weights and is more
specific than results obtained using a refractive index detector.
Time of flight secondary ion mass spectrometry has been used to determine the
molecular weight distribution ofpolystyrene.~t9
17
Table 1.9 - Gas Chromatography Retention Times for Organic Peroxides
Compound Column' TempoC Helium b Retention time

pressure psi min
tert-Butyl hydroperoxide 2m-A 80 20 22.7

tert-Pentyl hydroperoxide I m-A 80 IS 19.9
tert-Butyl peracetate I m-A 100 20 6.5
tert-Butyl peroxyisobutrate I m-A 100 20 15.3
Di-tert-butyl peroxide 2m-A 80 20 8.1
Di-tert-pentyl peroxide Im-A 80 IS 15.4
2,S-Dimethyl-2, S-di (tert-butyl
peroxy)-3-hexyne Im-o 138 IS 4.9
2,S-Dimethyl-2, S-di(tert-butyl
peroxy) hexane 1 moO 138 IS 6.9
n-Heptane 2m-A 80 20 6.1
n-Dodecane 1 moO 138 IS 3.1
n-Pentane 1 m-A 100 20 0.4
n-Nonane I m-A 100 20 4.9
'Length (metres) and type of column used.

b Inlet pressure.
A, didecyl phthalate on diatomaceous earth.
0, silicon grease on diatomaceous earth.
From Buketa et aI.M American Chemical Society
Schriemer and Lim used matrix assisted laser desorbtionlionization (MALDI)

mass spectrometry to detect high molecular weight narrow polydisperse polystyrene with
molecular weights up to 1.5 x 106 Daltons. The method is rapid and agrees well with
results obtained by chemical methods. Retinoic acid was used as the organic matrix for
the laser absorption procedure and the samples were analysed as their silver cation
adducts.
1.3. POLYVINYL CHLORIDE
1.3.1. Water and Volatiles (Monomers, Chlorohydrocarbons) in Vinyls and Acrylics
1.3.1.1 Gas Chromatography Procedures.
The difference between Method 1 for the determination of water and volatiles in
polyalkenes and that described below for the determination of water and volatiles in
vinyls and acrylics, is that in the latter method, the polymer is heated in the presence of
the residual air in the sample tube, and in the first method (polyalkenes) the residual air in
the sample tube is replaced with inert carrier gas, helium, before the sample is heated.
With the non-olefinic polymers the same results for water content are obtained by both
methods, ie. it is not necessary to replace the air with inert gas. Polyalkenes, however,
are oxidized if heated in the presence of air, thus producing additional amounts of water.
Jeffs2 recommends that before carrying out any quantitative work on the volatile
constituents obtained from a polymer powder, a preliminary gas-chromatographic
investigation should be carried out, of their complexity. For example, one polymer
showed nine components other than air, water and the original monomer. These
18
components are chlorinated hydrocarbons, such as 1,1- and 1,2- dichloromethane and cis-
and trans-dichloroethylene, that are present as impurities in the original monomer.
Having chosen a suitable column, the temperature at which a given polymer
liberates all of the moisture has to be found. This is determined by keeping the gas
chromatographic conditions constant and heating known amounts of polymer at various
split-heater temperatures. The peak height (or peak area) per gram of sample is then
plotted against the sample temperature.
Jeffs2 showed that a plot of water liberated against temperature for PVC indicated
a constant amount of water was evolved at temperatures between 115° and 160°C. A
heater temperature of 125°C and the following gas chromatographic conditions are,
therefore, recommended - column, 10 foot (114 inch o.d.) stainless steel tubing, packed
with 10 per cent w/w poly(ethylene glycol) 400 on "Floon" CD4; oven temperature,
90°C; and helium inlet pressure, 10p.s.i. A blank determination is carried out in a similar
manner with an "empty" glass tube containing only two quartz-wool plugs, and any blank
subtracted from the water in the sample.
The major volatile constituents in vinyl chloride - vinyl acetate copolymers is
unpolymerised vinyl acetate, and this monomer is difficult to eliminate from the polymer
by ordinary drying methods. The plot of volatile constituents (water, vinyl chloride
monomer and vinyl acetate) against the sample temperature shows that the maximum
amount of vinyl acetate is eliminated from the sample under the test conditions, only in
the temperature range 130° to 145°C. Above this temperature the amount of vinyl acetate
detected starts to decrease. A similar effect is found for water. At the same time, another
peak begins to appear in the chromatogram. This peak corresponds, in retention time, to
acetaldehyde. This is consistent with the hydrolysis of the vinyl acetate monomer by
water at the elevated temperatures, to ~ive the unstable vinyl alcohol and, hence,
acetaldehyde. A heater temperature of 135 C is recommended for these copolymers.
In the case of acrylic mouldings powders based on methyl methacrylate, the
method described above for vinyl and acrylic polymers is again used. The chromato-
graphic conditions used were similar to those described above for poly(vinyl chloride)
polymer but, if the chromatogram is less complex, a shorter column (4 feet long) of the
same packing can be used. A plot of moisture liberated against sample temperature
indicates that 160°C is the most useful temperature to operate the split heater. A peak due
to unpolymerised methyl methacrylate is also obtained and, at first sight, this also appears
to be a method for determining residual monomer as well as moisture. Unlike vinyl
chloride and vinyl acetate, however, the unchanged methyl methacrylate in the polymer
appears to undergo further polymerisation during the 5 min heating period, as the results
obtained by the gas chromatographic method are low.
A method involving head space analysis gas chromatography has been described
for the determination of monomers and volatiles in pVC.90,91
Residual vinylchloride monomer from 0.02 to 0.1 ppm in PVC has been
determined by gas chromatographic - mass spectrometric monitoring. on,93
The volatiles produced during PVC degradation has been monitored using Raman
microline focus spectrometry. Modalgolyene chains containing 11-12 or 13-14 double
bonds occur in the polymer backbone.4 5
1.3.2 Additives
1.3.2.1 Phenolic and Amine Antioxidants
Vasil'eva et ae l described a method for the determination of lonol and 4,4'-

isopropylidenediphenol in PVC by anodic voltammetry. The sample is dissolved in
19
dimethylformamide and methanol added to precipitate PVC. It is then diluted with 105M
aqueous sodium acetate. A polarogram of an aliquot of the clear solution is recorded
(graphite rod indicator - electrode and 0.5 M cadmium sulphate - cadmium reference-
electrode) to include the steps for 2,6-di-tert-butyl-p-cresol at 0.21 V vs the S.C.E. and
for 4,4'-isopropylidene diphenol at 0.53 V vs the S.C.E. The application ofvoltammetry
to the determination of antioxidants has also been discussed by Barendrecht. 72
Other procedures which have been described include the conversion of an
antioxidant into a polarographically reducible form 73 and a general method for
antioxidants which involved measuring a decrease in the height of the wave, due to the
reduction of dissolved oxygen by antioxidants. 7s Ward74 has discussed the determination
of phenolic and amine types of antioxidants and antiozonants in PVC by the
chronopotentiometric technique, using a paraffin wax impregnated graphite indicating
electrode76 and solutions of lithium chloride and lithium perchlorate and acetonitrile in
95% ethanol as supporting electrolytes. Precision obtainable for repeated chrono-
potentiometric runs in acetonitrile was found to be better than + 1.0% in cases in which
electrode fouling did not occur.
Phenolic (and amine) antioxidants in extracts of PVC have been titrated
electrometrically with lithium aluminium hydride, using platinum or silver electrodes. 78
Small amounts of water in the sample or analysis solvent have an influence on the results
obtained by these procedures.
Electrophoresis is a technique worthy of further consideration for the analysis of
antioxidants79 in PVC. Sawada et al80 report successful separations by coupling the
antioxidants with p-diazobenzene sulphonic acid before electrophoresis. Amine anti-
oxidants are coupled in acetic acid and phenolic antioxidants in sodium hydroxide-
ethanol. Electrophoresis was carried out in 1% w/v methanolic sodium borate.
Procedures involving solvent extraction followed by thin-layer chromatograph.h
have been described for the determination of phenolic and amine types of antioxidants 7
and optical whiteners in PVC.
1.3.2.2 Plasticizers
Due to their volatility the esters used as plasticizers in polymers such as flexible
PVC can be determined by gas chromatographic analysis of a solvent extract of the
polymer. Most published methods of analysis are based on this technique and this is the
favoured technique for determining such substances (see Table 1.10)
The identification and determination of plasticizers is discussed further in Chapter
4.
Wideline nuclear magnetic resonance spectroscopy has been used (Mansfield94)
for the determination of the di-iso-octyl phthalate content of PVC. The principle of the
method is that the narrow line liquid-type NMR signal of the plasticizer is easily separ-
ated from the very broad signal due to the resin; integration of the narrow line signal
permits determination of the plasticizer. A Newport Quantity Analyser Mk I low-
resolution NMR instrument, equipped with a 40 cm3 sample assembly and digital read-
out, has been used to determine 20 to 50% of plasticizer in poly(vinyl chloride) A
curvilinear relationship exists between the signal per g and the percentage by weight of
the plasticizer. For highest precision, it is necessary to know the type of plasticizer
present; use of the appropriate calibration graph gives a precision of 1:0.5%.
20
Table 1.10 - Gas Chromatographic Methods for the Determination of Plasticizers in PVC
Polymer Extraction Analysis of Extract Reference
Extraction of polymer with carbon tetra- Weighing and gas chromatography 82

chloride-methanol azeotrope for IS h
Extraction of polymer with diethyl ether Gas chromatography 83 - 86, 88
for 12h
Extraction of polymer with methanol Gas chromatography 87
Solution of polymer in tetrahydrofuran, Gas chromatography ofTHF- 89

precipitation of polymer with methanol, methanol extract
filtration of clear phase
1.3.2.3 Organotin Heat Stabilizers
Organotin compounds are widely used in the plastics industry as stabilizers for
poly(vinyl chloride) compositions. The most important compounds used for this purpose
are based on dialkyltin groups R2 8n<, especially where R = butyl or octyl.
For analytical considerations it is convenient to divide tin stabilizers into those
containing sulphur and those without sulphur. To the first group belong compounds like
dialkyltin mercaptides, mercaptoesters and mercapto carboxylates (see method 39) to the
second, dialkyltin carboxylates and their esters (see method 40). The identification of
acids and alcohols present in tin stabilizers containing no sUlphur and the identification of
alcohols from stabilizers containing mercaptoesters presents little or no difficulty.
However, the identification of the thioacid and of the alkyl groups attached directly to tin
can prove more difficult, especially if long-chain acids form part of the compound or if
the stabilizer is not pure, ego if it contains plasticisers. The thioacid may also tend to
decompose during hydrolysis procedures. 9s
Methods based on titration and thin-layer chromatography have also been used to
determine organotin compounds in solvent extracts of PVC (Table 1.11).
1.3.2 4 Other Types of Heat Stabilizers
Other types of non-tin organometallic stabilizers have been used in the

formulation of PVC. Mal'kova et al99 described an alternating current polarographic
method for the determination of cadmium, zinc and barium stearates or laurates in PVC.
The samples are prepared for analysis by being ashed in a muffle-furnace at 500°C, a
solution of the ash in hydrochloric acid being made molar in lithium chloride and
adjusted to pH 4.0 ± 0.2. The solution obtained is de-aerated by passage of argon and the
polarogram is recorded. Cadmium, zinc and barium give sharp peaks at - 0.65, -1.01 and
-1.90V respectively, vs the mercury-pool anode.
Other techniques that have been used for the examination of organometallic
stabilizers extracted from PVC include column chromatography (barium, cadmium and
zinc salts offatty acids 1oo), paper chromatography (cadmium, lead and zinc salts offatty
acids)lol and polarography (cadmium, lead and zinc saltS)I02.
21
Table 1.11 - Other Techniques for the Determination ofOrganotin Compounds in PVC
Extracts
Compounds Detennined Method Reference
Organotin heat stabilizers Potentrometric titration of organotin in 95, 96

polymer extract with standard sodium
methoxide in pyridine using antimony
and calomel electrodes
Dialkyltin thiol compounds Titration in benzene methanol extract 95
with standard silver nitrate (in IPA water
medium) using sulphide coated wire
electrode
Organotin thioacids and thiols TLC on kielselgel G, elution with hexane 97
- glacial acetic acid and detection with
catechol violet
Organotin stabilizers TLC on kieselgel GF 254, elution with 47
butanol-glacial acetic acid, detection with
catechol violet and UV irradiation
Kirkland and Rementer411 determined the molecular weight distribution of poly-

vinyl chloride by thermal field flow fractionation using Mark Houweg constants.
1.4. VULCANIZED AND UNVULCANIZED RUBBERS
1.4.1. Volatiles
Thermal degradation and volatilization of chloroprene rubbers and blends thereof

have been studied using thermogravimetric analysis416.
1.4.2. Additives
1.4.2.1 Accelerators
Millingen 103 has described a thin-layer chromatographic method for the identi-
fication of accelerators and antioxidants in nonvulcanized (natural) rubber compounds
(Method 41). This procedure discusses interference from other compounding ingredients
and describes, in detail, means for overcoming this.
1.4.2.2 Antioxidants and Antiozonants
Lattimer et ae 04 have very successfully applied mass spectrometry to the

determination and identification of organic additives (antioxidants and antiozonants) in
rubber vulcanizates (Method 42). A wide variety of components are involved - polymers,
fillers, solvents and organic and inorganic additives. Field desorption/ionization (FDIFI)
is the most efficient for identifying typical organic additives in rubber vulcanizates.
22
Kirkland and Rementer411 studied the molecular weight distribution of poly-

isoprene using thermal field flow fractionation using Mark Houweg constants.
1.5. POLYESTERS AND POLYAMIDES
1.5.1. Functional Groups
1.5.1.1 Hydroxyl Groups
Houwelingenl05.106 have described a procedure for the determination of hydroxyl

groups in the following types of polyesters:
o
@
0
1.2
HO [- (CH 2 )x - 0 - C -
/I
0 - II
C - 0(CH 2 >n - 0 -] n H
with n = 1-100 and x = 2 (polyethylene ter.ephthalate) or 4 (polybutylene

terephthalatel and ester-interchange elastomers of 4-polybutylene
terephthalate and polypropylene glycol.
The hydroxyl groups in these products are determined by acetylation with an

excess of dichloroacetic anhydride in dichloroacetic acid at 60°C and measurement of the
amount of acetylation by a chlorine determination either by potentiometric titration with
silver ions after combustion or by X-ray fluorescence spectroscopy of a compressed disc
of the polymer. The suitability of this method for a number of samples is demonstrated in
Table 1.12. The standard deviation of the method for high relative molecular weight
polymers is 0.7 mmol kg· l whereas for the low relative molecular weight materials, it is
about 10 mmol kg· l .
In an alternate method for hydroxy groups described by these workers, the
polyester is reacted with a dimethyl formamide - monochlorobenzene solution of
vanadium 8-hydroxyquinolinate (V8HQ). According to Tanaka and Kojima l07 a coloured
complex with the following structure is formed:
o o 1.3
II ..
Q - V - Q + ROH ... Q - U - V + H20
I I
OH OR
V=@N
\'0-0
23
Table 1,12 - Hydroxyl End Group Content of Several PETP, PBTP and PBTP-PPG
Samples
Sample Viscosity Hydroxyl Remarks

ratio· End
Groups/mmol
kg'l
PETPA 1.80 30.9-29.8 Total end groups" 76.6 mmol kg'l

30.6-30.4
PETPB 1.82 14.4-14.8 Total end groups 79.1 mmol kg-I
PBTPA 2.07 70.7-70.6 Total end groups 95.2 mmol kg-I
PBTPB 2.08 50.6-49.3 Total end groups 92.6 mmol kg-I
PBTPC 1.24 664-653
PBTP-PPGA 1.25 742-729 MN (calc)·" 2700; MN (measured) 2400 ....
PBTP-PPGB 1.34 329-345
PBTP-PPGC 1.50 229-212 MN (calc) 9000; MN (measured) 10100
PBTP-PPGD 2.38 51-47 MN (calc) 35000; MN (measured) 44800
• Measured for a 1% m/m solution in m-cresol at 25°C (PETP and PBTP). or for a 1% mN solution in
chlorophenol at 25°C (PBTP-PPG)
.. Total end groups in sum of OH + COOH + methyl ester end groups
... MN measured by gel-permeation chromatography in m-cresol as a solvent
.... Calculated from OH + COOH content
From Van Houwelingen. 1os Royal Society of Chemistry, London
Table 1.13 - Comparison of the V8HQ Method with the Acetylation Method
OH contentlmmol kg-I
Sample V8HQ Acetylation
41-9-47.6 50-70
43-1-46.8
II 35.5-34.9 35-50
III 130-1-126.7 170-120
IV 73.8-74.9 50-70
From Tanaka and Kojima. i07 Elsevier Science Publishers. Netherlands
After removal of the excess of reagent by extraction, the complex is acidified with
dichloroacetic acid and the blue colour formed is measured at 620 nm. Calibration is
carried out with an alcohol as internal standard,
The application of this method to some esters of new types of acids showed that a
precise determination is possible (Table 1.13). The standard deviation of this method is
1.5 mmol kg-I which is about ten times more precise than that of the classical acetylation
procedure.
Groom and co-workers 108 employed trichloroacetyl isocyanate and trifluoroacetic
anhydride acetylations to determine hydroxy end-groups in polyester polyols. The
isocyanate reagent was best suited for samples having molecular weights of less than
4500; this anhydride method was more sensitive and applicable to higher molecular
weight polymers than is a 19F NMR method.
24
1.5.1.2 Alkene Groups And Vinyl Esters
Chemical methods for the determination of alkene groups are often based on
halogenation or hydrogenation.
A survey of applications has been given by Hirozawa et al 109 • Von
Houwelingen 105 have used coulometric bromination to determine vinyl ester end-groups
in poly(ethylene terephthalate) formed by thermal chain scission.
1.4
Polyethylene terephthalate
The constant-current generation of bromine is carried out in a medium of

dichloroacetic acid, water, potassium bromide and mercury II chloride. To this medium
an amount of the polymer, previously dissolved in hexafluoroisopropanol and diluted
with anhydrous dichloroacetic acid, is added and bromine is generated. The end of the
reaction is detected biamperometrically. The suitability of this method was tested against
methyl vinyl terephthalate.
1.5
o
II@II
<:) - C - 0 - CI =
0 H
CH 3 - 0 - C -
Methyl vinyl terephthalate
Additions of 14.2 and 1.0 umol of methyl vinyl terephthalate (corresponding to 30

and 2 mmol of vinyl ester end-groups per kilogram of polymer) were recovered quanti-
tatively (recoveries of99.8 and 98.5% respectively).
1.5.1.3 Carboxyl Groups
The determination of these groups in high relative molecular weight polyesters

and polyamides gives, in combination with other data, important information about the
degree ofpolymerisation, chain branching, degradation and thermal stability. The choice
of the method depends on the solubility of the polymer. Most methods are based on
titration in non-aqueous media with visual, potentiometric or photometric indication of
the end-point.
A very convenient technique for the determination of carboxyl groups in
polyethylene and nylon-6 is photometric titration. The sample is dissolved in o-cresol at
125°C, cooled, diluted with chloroform and, after addition of bromophenolblue or bromo-
cresol green, the titration is carried out in a spectrophotometer with tetrabutyl ammonium
25
hydroxide. The change in absorbance is recorded continuously and the end-point is
determined graphically. A detailed description has been given by Van Lingen. III
Table 1.14 compares applications of the photometric titration method together
with a comparison with a potentiometric titration with tetrabutyl ammonium hydroxide in
aniline of low molecular weight poly(ethylene terephthalate) and nylon 6. Generally the
agreement is very satisfactory.
An attractive method for determining carboxyl groups is based on the Schmidt
reaction, in which the carboxyl group is subjected to reaction with sodium azide in sulp-
huric acid. 112
The acylazide formed rearranges to an amine with the liberation of nitrogen and
carbon dioxide
1.6
The carbon dioxide evolved is measured quantitatively by an automatic non-

aqueous titration. This method is applicable to poly(m-phenylene isophthalamide) which
is soluble in dimethylformamide, but is not applicable to poly (p-phenylene tereph-
thalamide) for which no organic solvent could be found.
1.5.1.4 C-O-C Groups In Polyesters
Simak388 investigated absorptions of the C-O-C group in polyethylene

terephthalate in the infrared at 632, 640 and 380 cm· l .
1.5.1.5 Amino Groups
Heterogeneous derivitivisation with I-fluoro,2,4-dinitrobenzene has been used to

determine amino groups in polyethylene terephthalate. lOS
NO N0 2
_@- NH,+ F@NO,- -@-/ -@-NO, HF + 1.7
Polyethylene terephthalate
The polymer is treated for 4 h at 80°C with I-fluoro,2,4-dinitrobenzene in an

ethanol hydrogen carbonate medium. After washing out the excess of reagent, the
dinitrophenyl group introduced is measured spectrophotometrically at 430 nm after
dissolution of the derivatised polymer in methane sulphonic acid.
The spectrophotometric method was calibrated with the I-fluoro,2,4-dinitro-
benzene derivative of the model compound NN' -bis(p-amino-phenyl) terephthalamide:
26
Table 1.14 - Application of the Photometric Titration Method to Various Samples
Content of Carboxyl Groups/mmol kg,i
Photometric Titration Potentiometric Titration
Sample a standard a standard

x deviation x deviation
PETP(MNlow C 4.3 0.25 4.0b 0.10

D 12.0 0.34 12.0b 0.30
E 17.4 0.56 17.5b 0.49
PETP (MN high F 36.8 0.32 35.2 0.9
G 68.3 0.29 68.2 1.2
H 113.4 0.52 112.8 1.8
Nylon 6 I 73.3 0.31 72.4· 1.0
J 53.2 0.22 52.5· 0.37
K 35.3 0.45 36.2· 0.32
• Mean of four independent determinations.

b Titration in aniline at 40·C.
• Titration in benzyl alcohol-methanol-water.
From Van Lingen. 111 Springer Verlag Heidelberg.
I-fluoro,2,4 dinitro benzene derivative ofN,N'-bis (p-amino-phenyl) terephthalamide
1.5.1.6 Acidic And Glycol Repeal Units In Terylene (Dacron)
Terylene is manufactured from terephthalic acid and ethylene glycol as follows:
COOH 1.9
~ - [- CH 2 - CH 200C -<Q)- CO~ n

COOH
Synthesis of Terylene
Such polymers contain repeat units based on ethylene glycol and indeed other
glycols such as l,4-butane diol, and terephthalic acid and proportions of isophthalic acid.
Allen et all\3 developed a precise quantitative method (method 43) for determining such
units in terylene. The sample is subject to an alkaline hydrolysis and glycol and acidic
27
products after conversion to the trimethylsilyl derivatives are analysed by gas
chromatography.
It has been observed that in the preparation of polyester for compositional analysis
by NMR spectroscopy much higher rates of hydrolysis are achieved by refluxing
polyethylene terephthalate with a mixture of sodium hydroxide, an alcohol (methanol)
and a protic solvent (dimethyl sulphoxide) than is achieved with the usual alcoholic alkali
reagents. 417
i.s.2. Volatiles and Water

1.5.2.1 Water In Polyesters.
Hoffinan ll4 has described a procedure (Method 44) for the determination of water
in polyesters. In this method, water is allowed to react quickly with a mixture of hexa-
methyldisiloxane and trimethylchlorosilane (2:1) in the presence of pyridine to form
hexamethyldisiloxane.
1.10
The hexamethyldisiloxane is separated from other silanized active hydrogen com-

pounds and determined by gas chromatography.
1.5.2.2 Water In Poly(Ethylene Terephthalate).
Squirrelll5 has also reported on the fact that with some polymers, in addition to the
initial free water content of the polymer, water is produced during heating. He observed
this in the case of polyethylene terephthalate and for this reason, prefers to determine
water by Karl Fischer titration.
1.5.2.3 Volatiles.
Gas chromatographic methods have been described for the determination of

volatile constituents in polyester coated film ll6 and in polyesters. 1I6
Welsch et al ll6 used gas chromatography combined with accumulated dosage to
determine volatiles. Volatiles from a heated sample are transferred in a carrier gas stream
to a cooled initial part of the GC column and are subsequently discharged onto the
column by heating. The products were identified by mass spectrometry.
Urbanski ll7 measured small amounts of propylene oxide and epichlorohydrin in
polyesters colorimetrically after reaction with a chloroform solution of 2,4-dinitro-
sulphonic acid.
1.5.3. Oligomers
Supercritical fluid extraction and chromatography418 and comparative compli-

mentary phasing desorption mass spectrometry secondary ion mass spectrometry have
been used to determine oligomers in polyethylene terephthalate.420
28
1.5.4. Additives
1.5.4.1 Flame Retardants.
Surface tris (2,3-dibromopropyl) phosphate has been determined on the surface of

flame retardant polyester fabrics 11 8. The technique used to determine the surface TDP
levels involved extraction of the fabric with an organic solvent followed by analysis of
the solvent by x-ray fluorescence for surface bromine and by high pressure liquid
chromatograv:hy for molecular tris (2,3-dibromopropyl) phosphate.
Cope 21 has described a pyrolysis - gas chromatographic procedure for the
determination of tetrakis(hydroxymethyl)phosphonium hydroxide and tris (2,3-dibromo-
propyl)phosphate flame retardants on polyesters and cotton.
1.5.4.2 Residual Organic Peroxides.
Iodometric methods have been described ll9 for the determination of organic
peroxides in polyesters.
1.5.4.3 Unreacted Starting Materials.
Tengler and Von Falkai l20 determined diols, adipic acid and volatiles cyclomono-
diol adipates qualitatively and quantitatively in aliphatic polyesters based on adipic acid.
The identification of the cyclic mon-esters is accomplished with the help of coupling a
gas chromatograph with a mass spectrometer, the diols were classified by gas
chromatographic retention volume.
1.6. POLYACRYLATES
1.6.1.1 Hydroxy Groups.
Dickie et ae 89 derivitivized surface hydroxy groups on acrylic copolymers with

ammonia then characterized them by x-ray photoelectron microscopy.
Kim et a1390 examined the strong infrared band at 3450cm-1 of tetrahydrofuran
associated hydroxy groups in dinitropropyl acrylate prepolymer in order to determine
hydroxy groups.
1.6.2 Monomers and Water
Polyacrylates are used extensively as dispersants for emulsion paints and as

boiler-scale inhibitors and copolymers of acrylic acid and acrylamide are used to aid
water clarification at water treatment works and for the treatment of coal tailings. The
manufacture of such polyeiectrolytes could leave a small residue of unpolymerised
acrylic acid monomer in the polymer.
Brown l22 has described a high performance liquid chromatographic method for
the determination of acrylic acid monomer in polyacrylates (method 45).
A method for the determination of water in polyacrylate is discussed in section
1.1 under polyethylene.
29
1.6.3. Oligomers
Comparative complimentary plasma desorption mass spectrometry/secondary ion

mass spectrometry has been used to determine oligomers in polyacrylates.42o
1.6.4. Additives
1.6.4.1 Phenolic Antioxidants
Budylina et al 123 have described methods based on anodic voltammetry for the
determination of lanai (2,6-di-tert-butyl-p-cresol) and quinol in polyester acrylates. To
determine lonol the sample is dissolved in acetone:methanol (1:2 v/v) and an aliquot
diluted with a solution of lithium chloride (O.lM) and sodium tetraborate (O.02M). A
polarogram is recorded with a graphite-rod indicator-electrode. To determine quinol, the
sample is dissolved in methanol or methanol:acetone (1:1 v/v) and diluted to 100 ml with
the lithium chloride-sodium tetraborate solution. A polarogram is recorded under the
same conditions. The Ey, values (vs. the S.C.E.) are 0.2SV for lonol and O.l6V for
quinol.
Kirkland and Rementer411 determined the molecular weight distribution of

polyacrylates using thermal field flow fractionation using Mark Houweg constants.
Jackson et alm compared the most probable peak values as measured for polymer
distributions by matrix assisted laser desorption/ionization (MALDI) mass spectrometry
and by size exclusion chromatography (SEC). MALDI provided the most probable peak
(Mp) values for polymethyl methacrylate polymers that are low reletive to Mp values
supplied by the polymer manufacturers which were obtained by SEC. The reasons for
this discrepancy are discussed.
1.7. POLYETHYLENE GLYCOL AND POLYPROPYLENE GLYCOL
1.7.1.0Iigomers
Comparative complimentary plasma absorption mass spectrometry has been used

to determine oligomers in polyethylene glycol. 420
Thirty p<llyethylene glycol oligomers have been separated on K+ - form cation
exchange resin.423
Time of flight secondary ion mass spectrometry has been used to determine the
molecular weight distribution of polyethylene glycol oligomers. 421
1.7.2.1 Hydroxyl Groups.
Earlier methods for the determination of hydroxyl groups in polyethylene and

polypropylene ~lycols were based on reaction with p-toluene sulphonic acid catalrsed
acetyl chloride I 4.126, phthalic anhydride l26, perchloric acid catalysed acetylationl26.12 ,129,
B-nitro phthalic anhlsdrlde129, pyromelliticanhydrlde l3l , phenyl isocyanate l29,132 and
potassium periodate. I S
30
Stetzler and Smullinl26 found that for poly(propylene glycols) the classical
phthalation procedure gave consistently low results as did the perchloric acid catalysed
acetylation procedure, developed by Fritz and Shlenkl27. In addition to its greater
intrinsic accuracy, the advantages claimed for the Stelzer and Smullinl26 toluene p-
sulphonic acid catalyzed procedure over phthalation include shorter reaction time and
lower reaction temperature also good reproducibility, indicating no reaction with the ether
groups. In Table I.IS are compared hydroxy values obtained by three methods. It is seen
that in every case the acid catalyzed acetylation method gives a higher result than that
obtained by phthalation, the average difference between the two methods being 2.S% of
the determined value. The agreement between the p-toluenesulphonic acid method and
the phenyl isocyanate method is good.
Kaduji and Rees l34 have described a direct injection enthalpimetric method to
measure the hydroxy value of glycerol alkylene oxide condensates and butane-l,4-diol-
adipic acid polyesters.
Smith and Dawson l3S determined traces of poly(ethylene glycol) by fission with
hydrogen bromide to produce dibromomethane and dibromo-propane followed by gas
chromatographic determination of these two substances.
A method (Method 46) for the determination of hydroxy group in polyethylene
glycols has been described by Fritz et al 133. The method consists of substituting the
hydroxyl group with a chromophoric siloxy group, purification of the silylated polymer,
and a photometric determination of the chromophor concentration. The silanization of
the primary hydroxyls with dimethylaminosilanes proceeds quantitatively under very
mild conditions and elimination of the excess reagent by precipitation is easy. The
precision of the method is ± 4.5% (9S% confidence level) down to S x 10"" mol kg· l. The
method has about the same precision as acylation methods but yields a 1000 fold gain in
sensitivity.
Most of the chemical methods for determining hydroxy groups in polymers do not
distinguish between primary, secondary or tertiary hydroxy groups. An exception to this
is a kinetic approach to the determination of primary and secondary hydroxy groups as
will be discussed under copolymers (Chapter 2.4) under ethylene oxide polyglycol
condensates.
A further method for distinguishing between different types of hydroxy groups in
polymers is the NMR method described by L'HoI36. This procedure is based on the
reaction of the hydroxy compound with hexafluoroacetone to form an adduct which is
amenable to F-19 NMR spectroscopy.
1.11
A fluorine resonance spectrum of a mixture of several hexalfuoroacetone adducts

is shown in Figure 1.2. There are two interesting features in this spectrum. First, it illus-
trates clearly the high resolution and the information on structural aspects of the mole-
cules one can obtain by this method. The hydroxyl adduct from each alcohol gives a
sharp resonance, with the tertiary adducts at high field, followed by secondary and then
primary. The chemical shift of the hexafluoroacetone alcohol adduct is determined by the
structural environment of the hydroxyl. For example, the gradual upfield shift observed
in the series methanol, ethanol, isopropanol and tert-butanol, results from the increase in
shielding caused by replacing a hydrogen atom with a methyl group. The high degree of
resolution under fig. 1.2 was also observed for polymeric materials. Therefore, not only
can the total hydroxyl concentration be determined but also the type or types present in
the polymer.
31
Table 1.15 - Comparison of Results Obtained on Polypropylene-glycol by Catalyzed
Acetylation, Phthalation and Phenyl Isocyanate Reaction
Stetzler and Smullin 126 Phthalation Method Reaction with phenyl
PTSA Method Average isocyanate
OH No. mglKOHJg Average OH No. Average OH No.
MOlwt mgIKOHJg mgIKOHJg
760 353 346

260 276 265
2000 34.9 34.0 34.9
3000 34.3 33.8 35.1
3390 58.3 57.0
From Stelzer and Smullin. 126 American Chemical Society
.. ::. .
,
o 'i' :::
o ::
f . ..
0 0
:: l
.....
'f.
..
~
..... ...
0. .
!!
.... ..... 1-".
~
"'0 ~
::! c
I _.... E ~
N
~
,
...
N
0'"
~
- I ....
"'I ~
:
,
Q)
'"C ...~
..
..".
100 HI
...
0
.: . i
. ~
.
~
Q.
~ ~
. ..... .
w
0 0
!.
.. ~
I
0 0
':...
:z ... ~
.."
'tl .
;:!
......
~
0 ~ 'i'
(J
eo ;.
..
Q)
'" :
..
~
... " ...

~
~ '" ~I"J"TT" .... I""""""
0 II
" .,H 1- -, I
Figure 1.2. Fluorine-19 NMR spectra of several HFA adducts. From left: HFA (free); Butyl
trifluoroacetate; trifluoroacetic acid; HFA dimethyl glyoxime); HFA (benzyl alcohol); HFA (methanol);
HFA (ethanol); HFA (isopropanol); HFA (tert-butanol) and HFA HP). The numbers on top are Hz
down field from CsFslock. From L'Ho with permission. 136 American Chemical Society.
The quantitative aspect of hydroxyl determination is illustrated in Table 1.16 for

the analysis of hydroxyl in some polymeric materials.
1.7.2.2 Ether Linkages.
Smith and Dawson13S determined traces of polyethylene glycol and polypropylene

glycol by reacting the sample with hydrobromic acid then determining the dibromoethane
and dibromopropane fission products by gas chromatography.
32
Various workers have discussed the fractionation of polyethylene glycols using

laser desorption / Fourier transfonn ion cyclotron resonance mass spectrometry403,404 and
flow field - flow fractionation405 techniques.
Kirkland et al420 determined the molecular weight distribution of polyethylene
oxide in the 104 to 2 x 106 molecular weight range by field flow fractionation.
Vincenti et al4l2 used chemical ionization mass spectrometry to determine the
molecular weight distribution of polyethylene glycol.
Polyethylene glycols have been detected using an indirect conductiometric
detector following chromatographic separation.422
Dey et al434 used matrix assisted laser desorption/ionization (MALDI) Fourier Transfonn
mass spectrometry (FTMS) to detennine the molecular weight distribution of
polyethylene glycol samples containing oligomers. This combination of techniques
create a powerful tool for the characterisation of polymers. MALDI permits the creation
of intact, singly charged, high mass (mlz 103-10) ions of polar and non-polar analytes,
whilst FTMS gives high resolution and mass accuracy. The technique was applied to
polyethylene glycols containing oligomers with masses covering the 10k Dalton mass
range.
1.S POLYBUTADIENE
1.S.1 Additives
1.8.1.1 Amine Antioxidants And Antiozonants.
Protivova and Pospisil 137 have reported on the behaviour of some amine
antioxidants and antiozonants and some model substances (phenols, aromatic
hydrocarbons and amines) during gel permeation chromatography and have applied this
technique (method 47) to the analysis of rubber extracts.
The diazotized p-nitroaniline procedure has been applied to the determination of
amine antioxidants in ethanol extracts of thin films of rubber. 56
Gaeta et al146 have described a gas chromatographic method for detennining a
number of commercial antioxidants such as N-phenyl-2-naphthylamine and N,N'-sec-
heptyl phenyl phenylene diamine in oil-extended synthetic polymers such as poly-
butadiene or styrene-butadiene rubber. This involves extracting the antioxidant from the
polymer with ethanol, taking up the concentrated extract with the appropriate solvent and
analysing the resulting solution by gas chromatography. They found by the use of
standard solutions of the antioxidants in carbon tetrachloride, acetone or carbon disulfide
and by the careful choice of chromatographic conditions that the elution of these
materials had little or no interference from the extending -oil present. In addition, the oil
was completely soluble in the solvent and all but the heaviest fractions eluted prior to that
of the antioxidant.
High temperature gas chromatography has been used l44 ,14S for the analysis of
mixtures of amine type antidegradants in rubber. These workers used a separation
column constructed of aluminium packed with 20% Apiezon L on 30 - 60 mesh
Chromasorb W. Analysis was carried out on an acetone extract of the rubber sample,
employing diphenylamine as an internal standard. Using column temperatures up to
310DC they were able to separate a range of antidegradants including 1,2-dihydroxy-2-
33
Table 1.16 - Quantitative Determination of Hydroxyls in Several Commercial Polymers
Polymers Hydroxyls
Found Expected
Aliphatic polyethers
Polyethylene glycol
Carbowax200 17.40 16.2-17.9"
Carbowax 1000 3.54 3.24-3.S8b
Polypropylene glycol
Varonol PIOIO 3.46 3.37d
Voranol P4000 0.85 0.85"
Polyepichlorohydrinf 0.84 0.85
Aromatic polyethers
Bakelite phenoxy resin PKHC 5.8 6.0'
Monosanto R, J-100 resin 5.4 5.4-6.0
Polyesters
Atlac 382E 0.92 0.93
Aromatic ester resin No. 1h 8.20 8.30
Aromatic ester resin No. 2h 12.20 12.35
1 Based on literature molecular weight of 190 to 210.

b Based on literature molecular weight of 950 to 1050'
"Determined after addition of 4.7 molar equivalent oftrifluroacetic acid and 7.6 molar equivalent of water.
d Based on an average molecular weight of 1010.
" Based on an average molecular weight of 4000.
f Polyepichlorihydrin 2000 from Shell Chemical Co.
B Calculated from the idealized molecular structure with a unit weight of284.
hExperimental resin from Hercules Incorporated.
From L'Ho. 06 American Chemical Society
2,4-tri-methyl-6-ethoxy-quinaline, N-isopropyl-NI-phenyl-p-phenylenediamine, N-phenyl,

-2-2naphthalamine,N,N'-di-2-octyl-p-phenylene-diamine and N,N'-diphenyl-p-phenyl-
enediamine. Near quantitative determinations were obtained for all these substances.
Apiezon L was found to be distinctly superior to other substances tried as column
packings.
Solvent extraction gas chromatographic methods have been described 146 for
determining alkylated cresols (2,6-di-tert-butyl-p-cresol) and amine antioxidants (N-
phenyl-2-naphthylamine, p-phenylene diamine type) and Santoflex (NN'sec-heptyl phenyl-
p-phenylene diamine) in polybutadiene.
1.9 CELLULOSE
1.9.1 Water
Details of a Karl Fischer titration procedure which is suitable for polymers such as
cellulose are given in Method 48.
34
1.10 POLYAMIDES AND POLYIMIDES AND POLY(AMIDES-IMIDES) (SEE
ALSO SECTION 1.5)
1.10.1 Functional groups
1.10.1.1 Amino Groups In Aromatic Polyamides. Polyimides And Poly(Amides-Imides)
Schleuter and Siggia147.148 and Frankoski and SiggialSO used the technique of
alkali fusion reaction gas chromatography for the analysis of imide monomers and
aromatic polyimides, polyamides and poly(amide-imides) (Method 49).
Two indirect titration procedures have been described for the determination of
amino end-groups in aromatic polyamides. One method involves the reaction of the
amine with salicyladehyde to form the Schiff base. After precipitation of the polymer,
the excess, unreacted aldehyde is titrated with potassium hydroxide. lSI
Amino groups have also been acetylated with acetic anhydride in
dimethylacetamide. Diethylamine was added, and the excess amine was titrated
potentiometricallyls2. The sequence distribution of an aromatic polyamide terpolymer
prepared under various reaction conditions was determined by nuclear mr,etic
resonance spectrometrylS3. Infrared speCtroscopylS4,ISS and mass spectrometrylS have
been used to estimate the degree of conversion of polyimides, ie. the extent of polyamic
acid ring closure.
Gomoryova lS7 hydrolyzed amide and imide linkages with hydrochloric acid and
identified the diamines using paper or thin-layer chromatography. The diamine portion
of polyamides has also been determined by fusing the sample with an alkali reagent and
separating the products by thin-layer chromatographylS8 Acidification of the melt allowed
the separation and identification of the diacid components. Polyimides have been
decomposed with hydrazine hydrate and the diamine products identified by gas
chromatography lS9. Polyamides and poly(amide-imides) required a prehydrolysis step.
The di, tri- or tetracarboxylic acid segments were determined by reaction of the polymer
with a 10% aqueous solution of tetramethylammonium hydroxide, pyrolysis of the
resulting salt and identification of the volatile methyl ester by gas chromatography.ls9
Kalinina and Doroshinal60 have reviewed qualitative and quantitative methods for
the analysis of polyamides and polyimides.
1.10.1.2 Carboxyl Groups.
A method for the determination of carboxyl groups is discussed in section 1.5.1.

Carboxyl end-groups in poly(m-phenyleneisophthalamide) have been titrated
potentiometrically in dimethylformamide using a non-aqueous potassium hydroxide
solution. lSI
1.11 POLYACRYLAMIDES
1.11.1 Monomers
Due to its toxicity, very sensitive methods are required to determine acrylamide
monomer in polyacrylamide.
Betso and McLean l61 have described a differential pulse polarographic method for
carrying out this determination (method 50). A measurement of the acrylamide
35
electrochemical reduction peak current at -2V v, seE is used to quantitate the acrylamide
concentration.
High performance liquid chromatography, using the reverse phase mode has been
used l62 to determine acrylonitrile monomer and related compounds, including meth-
acrylonitrile in polyacrylamide (Method 51).
1.12 POLYURETHANES
1.12.1 Volatiles
Guthrie and McKinney l64 have described a thin-layer chromatography - fluori-

metric method (Method 52) for the determination of 2,4 and 2,6-diaminotoluene in
flexible polyurethane foams.
High performance liquid chromatography has been used391 to determine methyl-
ene bis aniline volatiles in po~urethanes.
Joseph and Browner3 2 studied the types of volatiles produced upon the comb-
ustion of polyurethane foams.
1.12.2 Characterization
Time of flight secondary ion mass spectrometry (SIMS) has been used406 to carry
out structure characterizations on polyurethanes based on diols (ethylene glycol, 1,4
butane diol, 1.6-hexanediol) and diisocyanates, (methylene disocyanate, toluene
diisocyanate, dicyclohexylmethane diisocyanate). Fragments and oligomers produced in
the mlz range 500 - 3200 enabled characterizations to be carried out.
1.13 POLYVINYL ALCOHOL
1.13.1.1 Hydroxy.
Baumgartner371 has shown that the solution absorbance of a PVA-iodine-boric

acid complex depends on the concentration of cadmium in ions in solution.
1.14 SILICONES AND SILOXANES
1.14.1.1 Alkyl and Aryl Groups.
The technique of alkali fusion reaction gas chromatography has been applied to
the determination of alkyl and aryl groups in polysiloxanes. The method involves the
quantitative cleavage of all organic substituents bonded to silicon, producing the
corresponding hydrocarbons. Reactions are driven to completion, with no apparent
decomposition, in less than 10 minutes by fusing the sample with potassium hydroxide in
an inert atmosphere. After concentration of the volatile products, they are separated and
determined by gas chromatography. The structure of the silicone can be elucidiated from
the nature and concentrations of the decomposition products. Fluids, gum rubbers and
36
resins are handled with equal ease. The percent relative standard deviation of the method
is 1.0%; the average deviation between experimental and theoretical or check method
results is 0.5% absolute. This technique for carrying out the potassium hydroxide fusion
procedure is the same as the analysis described in method 49, in the previous section, 147
for the analysis of polyamides and polyimides. Various other reagents have been used for
the determination of organic substituents bonded to silicon in organosilicon polymers
(fable 1.17).
1.14.1.2 Si OH and Si HGroups.
Dubiel et al l71 described methods for determining these reactive components in

room temperature vulcanized silicone foams. Total SiOH and SiH are determined by
Fourier transform infrared (FTIR) spectrometry, the SiOH peak at 3687 cm· 1 and the SiH
peak at 2168 cm'1 were used for quantitation. The tetrapropoxysilane content was
determined by gas chromatography using a solid capillary open tubular (SCOT) column
and linear programmed temperature control. The diphenylmethylsilanol content was
determined by gel permeation chromatography using the tetrahydrofuran solvent.
1.14.20Iigomers

mass spectrometry has been used to determine oligomers in siloxanes.42o
Supercritical fluid chromatography combined with time of flight mass
spectrometry has been used to determine the molecular weight distribution of
poly(dimethylsiloxane) oligomers in the mass range 103 to 104•
1.14.3 Fractionation and Molecular Weight
Vincenti et al412 determined the molecular weight distribution of polysiloxanes by

desorption chemical ionization mass spectrometry.
Supercritical fluid chromatography coupled with time of flight mass spectrometry
has been used to determine the molecular weight distribution of poly(dimethyl siloxane)
oligomers in the mass range 103 to 104 •
1.15 PHENOL FORMALDEHYDE RESINS
1.15.1 OIigomers
Ludwig393 used high performance liquid chromatography to determine oligomers

in p-alkyl phenol-formaldehyde resins.
1.16 POLYOXYMETHYLENE GLYCOLS
1.16 Oligomers
To determine formaldehyde oligomers in polyoxymethylene glycols and the

corresponding polyoxymethylene ethers Utterback et al394 first derivitivized them with
ammonia then determined the oligomers by capillary column gas chromatography.
Polyoxymethylene oligomers have been separated by temperature programmed
gas chromatography.42S
37
Table 1.17 • Reaction Methods for the Quantitative Determination of Organic Subtituents
Bonded to Silicon
Group Reagent Reaction Product Analysis Ref.

Determined Conditions
Phenyl 60% aqueous KOH in 2 h at 120·C Benzene GC 166
DMSO
Phenyl Bromine in glacial Boiling solution Bromo- Titration of 167
acetic acid benzene excess
bromine
Ethyl and Phosphorus pentoxide 30-S80·C over 4S Ethane and GC-FID 168
Phenyl and water min benzene
Methyl and Powdered potassium 2 h at 2S0-270·C Methane and Gas buret 169
Ethyl hydroxide ethane
Methyl Sulphuric acid 20 min at 280- Methane Gas buret 170,171
300·C
Phenyl Ethyl bromide in the Hexaethyl Gravimetric 172
presence of aluminium benzene
chloride
Vinyl Phosphorus pentoxide 80-600·C over 40 Ethylene GC-FID 173
and water min
Vinyl Phosphorus pentoxide Ambient to SOO·C Ethylene GC-FID 174
Vinyl 90% sulfuric acid 7S-250·C at Ethylene GC-TC 175
10·C/min and I h
at 2S0·C
Vinyl Sodium hydroxide 300·C for IS min Ethylene Colorimetric 176
Vinyl Potassium hydroxide Heat with Meker Ethylene GC-FID 177
pellets burner
1.17 POLY(STYRENE SULPHONATES)
Poli and Schure407 used capiIlery electrophoresis to fractionate poly(styrene

sulphonates) over a wide molecular weight range. The technique was superior to size
exclusion chromatography in terms of resolution, efficiency and fractionating power.
Field flow fractionation has been used to fractionate and determine the molecular
weight of sodium polystyrene sulphonate426.427 and polystyrene sulphonate (molecular
weight range 6.6 x 103 to 6.9 x 10\
Thielking and Kuliche435 used a combination of flow field flow fractionation and
multiple laser light scattering for the characterization of a sulphonated polystyrene
solutions. These workers examined seven sulphonated polystyrene standards (1800 • 3 x
106 g mole-\ which were taken as model substances for macromolecular poly·
electrolytes. The technique was applied to O.lM sodium nitrate solutions of the
polyelectrolytes.
1.18 FLUOROPOLYMERS
1.lS.1 Oligomers
Comparative complimentary plasma desorption mass spectrometry/second~ ion

mass spectrometry has been used to determine oligomers in polytetrafluoroethylene. 20
38
Davidson et al436 characterized perflurotetradecahydrophenanthroline oligomers
using a combination of nuclear magnetic resonance spectroscopy, electron spin resonance
spectroscopy for chemical analysis and time of flight secondary ion mass spectrometry,
infrared spectroscopy and ultraviolet-visible spectroscopy.
They determined the following distribution of groups in this polymer;
Olefin carbon 8%, CF 3 8%, CF2 51%, CF 33%
A structure C 14 F23 (C 14F22)n C 14H23 is proposed where n = 0,1 or 2 corresponding

to dimer, trimer and tetramer.
The molecular weight and composition of a perfluorinated polyether has been

determined from fragment intensities using time of flight secondary ion mass
spectrometry428. Continuose flow fast atom bombardment and field desorption mass
spectrometry of 3,3,3 trifluorophenyl propyne oligomers determined chain length,
molecular weight range and identities of end-groups429.
1.19 POLYCARBONATE
1.19.1 Composition
Supersonic jet spectrometry of the chemical species resulting from the thermal
decomposition of polycarbonate at temperatures up to 400°C showed that p-cresol is the
' decomposltlon
major .. pro duct. 409
1.19.2 Oligomers

mass spectrometry has been used to determine oligomers in polycarbonate. 42o
1.20 POLYVINYLPYRIDINE
Field flow fractionation has been used to fractionate and determine the number
average molecular weight distribution of polyvinylpyridine. 43o
1.21 POLYALKYLKETENES
1.21.1 Dimers
Zimmermann et al437 used time of flight secondary ion mass spectrometry to

determine alkylketene dimer in kraft papers.
Further methods for the determination of functional groups, volatiles and additives in
polymers are reviewed in Tables 1.18 to 1.21.
39
Table 1.18 - Functional Groups in Polymers
Group Polymer Principle of Method Ref.
Primary amino Amino containing polymers Fluorescence 179

Primary amino Amino containing polymers Spectrofiuorimetric, (p-dimethyl- 180
aminobenzaldehyde)
6-caprolactam Poly(ethylene terephthalate) Spectrophotometry (ninhydrin) 181
Carbonyl Vinyl chloride-vinyl-acetate Spectrophotometric, (2:4 182
copolymer dinitrophenyl hydrazine)
Amino Amino containing polymers Spectrophotometry of 4,4' 395
dimethoxytrityl chloride derivative
at 498 nm
Carboxyl Polyacrylic acid Titration with standard organic base 183,184
in non-aqueous medium
Carboxyl Carboxy terminated Infrared spectroscopy 185
polybutadiene
Carboxyl Carboxyl methyl cellulose Precipitation as copper or uranyl 186,187
salt
Chloro groups Polystyrene 13CNMR 188
Epoxy groups Epoxy resins Titration with halogen acid 189
spectrophotometric
Epoxy groups Epoxy resins (2,4 dinitrobenzene sulphonic acid) 190
Ester Methacrylate copolymers Pyrolysis to alkyl iodides-gas 191,192
chromatography
Ester Alkyd resins, polyesters Saponification in alcoholic 193,195
potassium hydroxide
Ester Cellulose, polyvinyl esters, Saponification in ethanolic or glycol 196-198
polyacrylates polymethacrylates solution of potassium hydroxide
Ether Cellulose, polyvinyl ethers Zeisel method 199
Ethylene Polyethylene oxides NMR 200
Hydroxyl Epoxy resins Reaction with lithium aluminium 201
hydride
Hydroxyl Polycarbonates Spectrophotometric (ceric 202
ammonium nitrate)
Hydroxyl Hydroxypolybutadienes 185
Nitric ester groups Nitrocellulose Saponification, reduction with 204
devades alloy determination of
ammonia
Nitrile Styrene-acrylonitrile copolymer Infrared spectroscopy 205,206
Oxirane rings Epoxy resins Ringcleavage with pyriding-HC1, 207,208
glacial acetic acid HBr, dioxan-HCI
Unsaturation Di and polyolefins Halogen addition 210,211
Unsaturation Poly(methylmethacrylate) Bromination 212
Unsaturation Butyl rubber Chlorination with radio chlorine 213,214
Unsaturation 1,2-polybutadiene NMR 215
Table 1.19 - Residual Volatiles in Polymers
Volatile Polymer Method Reference
Styrene o-xylene Polystyrene Head-space analysis, gle 216

Styrene Polystyrene Head-space analysis, gle 217,218
Dichloromethane Polycarbonate Head-space analysis 216,
Styrene ethyl benzene Polystyrene Solution, glc 219-224
40
Table 1.19 continued
Styrene Polystyrene Solution in o-dichlorobenzene or 225

methylene di-chloride, glc
Styrene Polystyrene Solution in DMF, glc 226
Styrene, o-methyl styrene Polystyrene Solution in propylene oxide, glc 64,228
Benzene, toluene, ethyl benzene, Polystyrene Solution in THF, glc, methanol 224-231
xylene, cumene, propyl precipitation of polymer,
benzenes, ethyl toluenes, butyl ultraviolet spectroscopy 237
benzenes, styrene
Styrene Polystyrene Polarography 232,233
Alpha o-methylstyrene Polystyrene Polarography 232
Methylmethacrylate Poly(methyl- Infrared spectroscopy 235
methacrylates)
Methylmethacrylate and Poly(methyl- Gas chromatography 236
methacrylic acid methacrylate)
Plasticizers Polyacrylates Ziesel reaction - gas 192
chromatography
Hexane, trldecane, butylated Polypropylene Head-space analysis 396
hydroxy toluene
Ethyl acetate, ethanol Ziegler-Natta FnR attenuated total reflectance 397
catalyst support spectroscopy
Table 1.20 - Determination of Water in Polymers
Polymer Procedure Reference
PVC Devolatilization - gas chromatography 238

Polypropylene Heating under nitrogen - Karl Fischer titration 66
Anionic resins Oven-drying - Karl Fischer titration 240,243
Polyamide and polyethane diol 245
terephthalate
Polypropylene Removal of water in vacuo or a stream of 244
nitrogen then Karl Fischer titration
Several polymers 241,242
Table 1.21 - Detennination of Additives in Polymers
(a) Antioxidants in Polyethylene Reference

Gas Chromatography
Antioxidants, uv absorbers, lubricants, solvent extraction, glc 246,247

antistatic agents, optical brighteners
2,6 di-t-butyl-4-methylphenol solvent extraction, glc 248
butylated hydroxy anisole solvent extraction, glc 249
butylated hydroxy toluene solvent extraction, glc 249
2,6-butyl-4-methylphenol 2,6 di-tert-butyI-4- solvent extraction, glc 7
methylphenol, p-tert-butylphenol
antioxidants solvent extraction glc 60,61
antioxidants solvent extraction, gle 61
Antioxidants, amine and phenolic solvent extraction, gas chromatography 254
2,6 di-tert-butyl p-cresol solvent extraction, glc 255,256
hydroxy-5-methyl phenyl benzotriazole solvent extraction, glc 255,254
41
2,6 di-tert-butyl phenol, diphenylamine solvent extraction, glc 256

phenyl-2 napthylamine solvent extraction, glc 258
Halogenated bisphenols solvent extraction, glc 254
Antioxidants solvent extraction, glc 360
lonox 330 solvent extraction, glc hydrolysis to lauryl 261
dilaurylthiodipropionate secondary alcohol, extraction with chloroform- 262
antioxidant ethanol-hexane and thin-layer
chromatography, then glc
2,6 ditert butyl-4-methyl-phenol thermal analysis/gas chromatography 263
TopanolO C, 2,6 di-tert-butyl-p-cresol toluene extraction, glc 61
Topanol CA (I, I 3 tris(2-methyl-4 hydroxy-
5-tert butylphenyl) butane)
Polygard, (tris(nonyl phenyl) phosphite)
lrganox 1010 (pentaerythritol tetra-3(3,5-di-
tert-butyl-4-hydroxypheny I propionate)
Irganox 1076 (Octadecyl 3(3,5 di-t-butyl-4-
hydroxyphenyl)propionate)
Santonox R (4,4 thiobis (6-t-butyl-m-cresol»
Annulex PBA 15 (I, I di (3-tert-butyl-4-
hydroxy-6-methylphenyl)butane)
Nonox DCP (2,2 bis (3-methyl-4-hydroxy-
phenyl) - (propane)
Nonox-WSP (bis (2-hydroxy-5-methyl-3-
(methyl-cyclohexyl)phenyl methane)
lonox 330 (1,3,5 trimethyl-2,4,6-tris (3,5 di-
tert-butyl-4 hydroxybenzyl) benzene)
Visible Spectrophotometric Methods
butylated hydroxytoluene solvent extraction, spectrophotometric 265

finish using 2,6 di-chloro-p-
benzoquinone-4-chlorimine
Antioxidants solvent extraction, spectrophotometric 53,267
finish using diphenyl-beta-picryl-hydrazyl
bis-(3,5-di-tert-butyl-4-hydroxy phenol) solvent extraction, oxidation of alkaline 268
methane solution and spectrophotometric
evaluation
lonol (2,6 di-tert-butyl-o-cresol) cyclohexane extraction, visible \0
spectrophotometric finish (low levels)
Phenolic antioxidants including dicresylol toluene extraction, coupling with 29
propane and Santonox R ( (4-4, -thio-bis-(3- sulphanilic acid spectrophotometric finish
napthyl-6-tert butyl phenol (low levels)
Phenolic antioxidants including Succonox solvent extraction, reaction with ethanolic 271
18, butylated hydroxy toluene, lonol, (2,6-di- FeCll to produce Fe2+ which is estimated
tert butyl-p-cresol), Nonox CI (N-N di-beta spectrophotometrically using 2-2'
napthyl-p-phenylenediamine, Santonox R dipyridyl (low levels)
(4,4' thio-bis-3 methyl-6-tert-butylphenol)
Phenolic antioxidants including Agerite Alba methanol or ethanol extraction coupling 28
«hydroquinone monobenzyl ether), Agerite with diazolized p-nitroanaline-
Spar (styrenated phenol), spectrophotometric finish
Agerite Superlite (polyalkyl polyphenol)
Antioxidant 425, ie. (2,2' methyl-bis (6-tert
butyl-4-methyl phenol»
Antioxidant 2246, ie. (2,2'-methylene-bis (6-
tert butyl-4-methyl phenol»
Deenax, (2,6, Di-tert--butyl-p-cresol
I-naphthol
2-naphthol
42
Naugawhite, (alkylated phenol)

Nevastain A, (not disclosed)
Nevastain B, (not disclosed
nonyl phenol
p-Phenyl phenol
Polygard, (Tris (nonylated phenyl)-
phosphite)
Santovar A, (2,5-Di-tert-amyl-hydroquinone
Santovar 0, (2,3-Di-tert-butyl hydroquinone)
Santowhite crystals, (4,4'-Thio-bis-(6-tert-
butyl-m-cresol and SCI:z)
Santowhite powder, (4,4'-Butylidene-bis (3-
methyl-6-tert-butylphenol»
Solux, (N-p-Hydroxyphenyl-morpholine)
Stabilite white powder, (not disclosed)
Styphen I, (Styrenated phenol)
Wingstay S, (Styrenated phenol)
Wingstay T, (a hindered phenol)
Amine antioxidants ego solvent extraction spectrophotometric 271

Nonox CI (N,N' di-2-naphthyl-p-phenylene finish using dipyridyl
diamine)
Succonox 18 (N-stearoyl-p-aminophenyl) toluene extraction, methanol precipitation 50,51
Nonox Cl of polymer, spectrophotometric
determination after reaction with hydrogen
peroxide
Ultraviolet Methods
Phenolic type solvent extraction, thin-layer 34

Topanol OC (2,6 di-tert-butyl-4- chromatography then ultra violet
methylphenol) spectroscopy
Borox M (bis-(3,5-di-tert-butyl-4-hydroxy
phenyl methane»
lonox 330 (1,3,5, trimethyl-2, 4, 6 tris (3,5 solvent extraction oxidation in Pb02 or 34,276
di-tert-butyl-4-hydroxy benzyl) benzene) nickel peroxide - ultra violet spectroscopy
in neutral and alkaline solution
p-methoxyphenol 4,4' methylene bis-(2,6-di- solvent extraction, ultraviolet 38
tert-butyl-phenol) and Santonox R, (4,4'- spectroscopy (using bathochromic shift in
thio-bis-( 6-tert-buty I-m -creso I» sodium hydroxide solution)
lonol (2,6 di-tert-butyl-p-cresol) chloroform extraction 34,35
Santonox R, (4,4' -thio-bis-6-tert-butyl-m- ultraviolet spectroscopy 37
cresol
lrganox 10 10 ultraviolet spectroscopy 41
lonol (2,6 di-tert-butyl-p-cresol) solvent extraction
Santonox R, (4,4'-thio-bis (t-tert-butyl-m- ultraviolet spectroscopy, solvent
cresol) extraction
Fluorescence and Phosphorescence Methods
phenyl-napthylamines solvent extractions, fluorescence method 283

Agerite D (polymeric dihydroxy)-quinone solvent extractions, fluorescence method 45
phenyl-2-napthylamine
Santonox R, (4,4'-thio-bis-(6-tert-butyl-m- solvent extractions, phosphorescence 45
cresol» method
phenyl-2-naphthylamine
Spectroscopic Techniques
dilaurylthio-dipropionate infrared spectroscopy of polymer film 285
43
lonol (2,6 di-tert-butyl-p-cresol) iso-octane extraction 41

Santonox R (4,4'-thio bis-(6'-tert-butyl-m- infrared spectroscopy 35,287
cresol)
Phenolic antioxidant solvent extraction, various fmishes 36,45,291,
including spectrophotometry, NMR 292,293
analysis and mass spectrometry 5
antioxidants extraction with chloroform or hexane or 6,7
diethyl ether or toluene or carbon 299,271
disolphide-iso octane mixtures or 29,50
cyclohexane or water followed by various 9,10
instrumental finishes
Thin Layer and Paper Chromatography

antioxidant solvent extraction, paper chromatography 304,305
using chromogenic reagents 306,307
308,309
Amine antioxidant solvent extraction, thin-layer 310,311
chromatography 312,6,299
antioxidants solvent extraction, thin-layer 47,317
chromatography
lonol (2,6 di-t-butyl-p-cresol) hexane extraction, ethanol solution of 318
Santonox R (4,4'-thio-bis-(6' -t-butyl-m- residue examined by thin-layer
cresol) chromatography 299,319
lonol (2,6 di-t-butyl-p-cresol 2,4,6 tri-t-butyl solvent extraction, thin-layer 27,322
phenol) chromatography
Nonox range of antioxidants (amine and solvent extraction, thin-layer 47
phenolic types) chromatography
Butylated hydroxy toluene "2246"
Santoflex range, (hydroquinone type)
Superlite
Polygard tris (2,3 trinonylphenyl) phosphite
Irganox 1076 n-heptane extraction thin-layer 46
4,4' butylidene, (2-t-butyl-5-methyl) phenol chromatography
4,4' thio bis (6-t-butyl-m-cresol)
pentaerythritol tetrabis 3,5, di-t-butyl-4-
hydroxyhydrocinnamate
2,2' methylene bis(4-methyl-6-t butyl
phenol)
octadecyl (3,5-di-t-butyl-4-hydroxyphenyl)
acetate
lonol (2,6 di-t-butyl-p-cresol)
Column Chromatography
antioxidants solvent extraction, column 29,40
chromatography on silica gel using a 49
range of solvents and various detectors
Phenolic and amine antioxidants solvent extraction, high performance 55
liquid chromatography
dilaurylthiodipropioate gel permeation chromatography 58
Santowhite, (4,4' butylidene-bis-(6-t-butyl- chloroform extraction, column 294
m-cresol) chromatography
butylated hydroxy toluene chloroform (removes BHn I: 10 aqueous
Santonox R, (4,4' thio bis (6-6-butyl-m- methanol (removes Santowhite and
cresol) Santonox R) Eluates analysed by
ultraviolet spectroscopy
butylated hydroxytoluene freeze grinding, diethyl ether extraction, 55
Santonox R (4,4' thio bis (6-t-butyl-m-cresol) column chromatography with refractive
Irganox 1076 index and ultraviolet detectors at column
44
CAO 14 outlet
antioxidants solvent extraction, column 65
chromatography
Miscellaneous Methods
2-t-butyl-4-methylphenol solvent extraction, bromometric 7
2,6 di-t-butyl-4-methylphenol estimation
2,2'-bis (4-methyl-(butylphenyl)
methane
Santonox R (4,4' thio bis (6-t-butyl-m-cresol) ditto 67
dilaurylthio-dipropionate solvent extraction, polarography 77
diorgano-sulphide oxidation with m-chlorophenoxybenzoic 81
Tert phosphite types acid, unreacted oxidant estimated
distearyl thiodipropionate
diJauryl thiodipropionate estimated iodimetrically 3
4,4' thio bis (6-tert butyl-m-cresol )
l' 1' thio bis (2-naphthol)
triphenyl phosphite
triethylphosphite
tri-p-tolyl phosphite
tris (dinonyl phenyl) phosphite
2,2' thio bis (6-tert-butyl-p-cresol)
triisopropylphosphite
Laser Desorption/Ionization F.T. Mass
Spectrometry
(a) Sterically hindred phenols, thioethers, direct analysis of polymer 398

phosphite, phosphonite and hindered amine
types
18 antioxidants analysis of ether extract of polymer 399
(b) Antiozonants in Polyethylene
antiozonants thin-layer chromatography 328,332,7,

67,77,81,
310,311,
312,98,
110,128,
47
(c) Ultraviolet Absorbers in Polyethylene
Thin-Layer Chromatography
benzophenone and salicylic acid types solvent extraction, thin-layer 317
chromatography
benzophenone type solvent extraction, thin-layer 47
salicylate type chromatography
benzotriazole type for quantitative estimation
salicylate type solvent extraction, thin-layer 130,142,
substituted acryonitriles chromatography 143,149,
onganonickel type 163,165,
ultraviolet absorbers and optical brighteners 14,203,318,
246,227
optical whiteners solvent extraction, thin-layer 237
chromatography
45
Tinuvin P (2 'hydroxy S'- toluene extraction, glc 61

methylphenylbenzo-triazole»
Tinuvin 326 (2-(2' hydroxy-3'-tert-butyIS'
methylethylphenyl-3 chlorobenzotriazole»
Tinuvin 327 (2-(2' hydroxy-3' -S' -di-6-
butyl(phenyl)-3-chlorobenzotriazole»
Cyasorb UVS31 (2-hydroxy-4-n octoxy
benzophenone)
benzophenone type solvent extraction, potentiometric titration 239
with sodium methoxide in
dimethylformamide
antioxidants solvent extraction, column 6S
chromatography
7 UV absorbers ether extraction-laser desorption FT ion 399
cyclotron resonance mass spectrometry
(d) Antioxidants in Polypropylene
Gas Chromatography
Ionox 330 (trimethyl2,4,6 tri(3,S di-tert- solvent extraction, glc 2S0,2S1

butyI4-hydroxybenzyl) benzene)
antioxidants solvent extraction, glc 61
2,6, di-tert-butyl-p-cresol p-xylene extraction, glc 60
laurylthiodipropionate
2,4' methylene bis(2,6 di-tert-butylphenol)
2,2 1methylene bis(6-C I -methylcyclphexyl)-
p-cresol)
4,41 thio bis(6-tert-butyl-m-cresol)
4,4 1butylidene bis)6-tert-butyl-m-cresol)
Ionox 330 (l3S trimethyl-2,4,6,tris (3,S, di-
tert-butyl-4-hydroxyphenyl)phosphate
octadecyl3,5 di-tert-butyl-4-
hydroxyhydrocinnamate
2-hydroxy 4-(octyloxy)benzophenone
2,hydroxy-4-methoxybenzophenone
4-dedecyloxy)-2-hydroxybenzophenone
2-(24 benzotriazol- 2 yl)-p-cresol
2,4 di-tert-butyl-6-(S-chloro-2 4
benzotriazol-2yl phenol
Thin Layer Chromatography
diJauryl thio hydrolysis to lauryl alcohol, chloroform- 2S2

dipropionate ethanol-alcohol-hexane extraction.
Thin-layer chromatography then glc
4,4' butylidene antioxidants n-heptane extraction 46
(2-tert-butyl-S-methyl) phenol thin-layer chromatography for quantitative
4,4' thio bis (6-tert-butyl-m-cresol) analysis
penterithitol tetra bis 3,S,di-t-butyl
4-hydroxyhydrocinnamate
2,2' methylene bis(4 methyl-6-tert-butyl
phenol)
octadecyl (3,S di-tert-butyl-4-
hydroxyphenyl)acetate
2,6 di-tert-butyl-p-cresol
46
alkyl phenol and bis phenol antioxidants volatile preconcentration, mass 253
spectrometry
diorgano sulphides and tert phosphites heptaneexttaction. 57
ego distearylthiodipropionate oxidation with m-chloro-peroxy-benzoic
dilaurylthiodipropionate acid.
triphenylphosphite unreacted oxidant estimated iodimetrically
triethylphosphite
didecylphosphite
phosphite antioxidants and their oxidation laser desorption/electron ionization FT ion 400
products cyclotron mass spectrometry
Hydroperoxides in Polypropylene
hydroperoxides iodometric method 260
(e) Antioxidants and Optical Brighteners in Polystyrene
antioxidants solvent extraction, thin-layer 47

phenolic acid chromatography for quantitative analysis
amine type
lonol (2,6 di-tert-butyl-p-cresol) methylene dichloride solution, glc 255
optical brightener methylene dichloride solution, glc 255
Tinuvin P (hydroxybenzyl-benzotriazole
lonol, Tinuvin P methylene dichloride solution, glc 255
(f) Organic Peroxide Residues in Polystyrene Gas Chromatography
tert-butylhydroperoxide solvent extraction, glc 69

tert-pentylhydroperoxide
tert-butylperoxyisobutyrate
di-tert-butylperoxide
di-tert-pentylhydroperoxide
di-tert-butylhydroperoxide thermal decomposition of benzene 70
soiution, gie estimation of acetone and
ethane produced
Thin-layer Chromatography
dicumylperoxide acetone extraction, thin-layer separation 68

and iodometric estimation
Polarography
benzoyl peroxide toluene extraction, polarography 264

succinic acid peroxide
lauroyl peroxide
acetyl peroxide
peroxyacetic acid
methyl ethyl ketone peroxide
phenyl cyclohexane peroxide
di-tert-butyl perphthalate
p-tert-perbenzoate
47
Stearic acid in Polystyrene
surface and internal stearic acid FTIR spectroscopy 401
(g) Organotin Type Stabilizers in Poly(vinylchloride)
solvent extraction, thin-layer 47
dibutyltin-dilaurate chromatography for identification of
dioctyltin-dilaurate organotin compounds
butyltintrichloride
dimethyltindichloride
diphenyltin dichloride
hexabutylditin
tributyltin laurate
dibutyltin bis-(2-ethyl-hexylthioglycollate)
dibutyltin bis(2-ethylhexyl) thioglycollate solvent extraction, thin-layer 47
chromatography
di-n-octyltin maleate solvent extraction, thin-layer 10
chromatography
stabilizers various methods 266,269,
270,272-
274
dibenzyltin bis(isooctyl-mercaptoacetate) solvent extraction, hydrolysis to glycol, 275
dibenzyltin bis(butyl-mercaptoacetate) thin-layer chromatography of 3,5
dibenzyltin bis(cyclohexylmer-captoacetate) dinitrobenzoates
Titration methods
stabilizers titration of carboxylate end-groups with 95,96

sodium methoxide in pyridine
stabilizers determination of sulphur by potentiometric 277
titration with potassium periodate in
glacial acetic acid
dialkyltin thio compounds potentiometric titration with silver nitrate 95
in aqueous iso-propanol. Also,
identification by infrared spectroscopy
Miscellaneous methods
stabilizers heptane-acetic acid extraction various 278

dialkyltin types identification by infrared spectroscopy and 95
dialkylthioglcollates chemical methods
dialkyltin lauryJmercaptides ego dibutyltin
oxide, di-octyltin oxide, dibutyltin maleate
dioctyltin laurate, dioctyltin thioglycollate
(h) Non-tin Type Stabilizers in Poly(vinylchloride)
3 amino crotonic ester of2,2' thiodiethanol mascerate with water, acetic acid-ethanol 279
or heptane, then thin-layer
chromatography
phenylamine solvent extraction, thin-layer 280-282,
2 phenylindal dicyandiamide chromatography 284
48
aminocrotonic esters
stabilizers solvent extraction, thin-layer 47
chromatography
epoxy types methanol extraction, thin-layer 288,289
epoxidized soyabean oil chromatography
epoxidized linseed oil
isooctylepoxystearate
2-ethylhexylepoxystallate
butyl epoxy tallate
butyl ester of epoxy linseed oil
di(isoamyl)4,4,epoxytetrahydro-phthalate
246,290,
stabilizers solvent extraction, glc 247
stabilizers diethyl ether extraction, various 12
diphenylthioureas methanol or diethyl ether extraction, 11
2-phenylindole spectrophotometric finish
(1) Metal Stearate Stabilizers in Poly(vinylchloride)
metal stearates solvent extraction, thin-layer 246

chromatography
Ba solvent extraction, column 100
Cd stearates chromatography
Zn
Cd solvent extraction, paper chromatography 101
Pb stearates
Zn
Cd solvent extraction or ashing, polarography 102
Pb stearates
Zn
Cd solvent extraction, infrared spectroscopy 295
Pb stearates
Zn
"Na solvent extraction, chemioluminescence 296
K stearates techniques
Ba
Cd ashing and elemental analysis by 99
Zn stearates and laurates polarography
Ba
Na ashing, flame photometry 297
K
Ba stearates
Cd
Pb
G) Plasticizers in PVC
Solvent extraction methods

ego dioctylphthalate diethyl ether extraction, weighing 83,298
tritolylphthalate
plasticizers solvent extraction, weighing 82
poJy(propylene adipate) diethyl ether then methanol extraction, 86
dioctylphthalate weighing
49
tritolylphthalate
poly(propylene sebacate) methanol extraction 292
poly(propylene adipate)
Gas chromatography
plasticizers solvent extraction, glc 290,247

alkyl adipate solvent extraction, glc 300,246,
alkyl phthalate 301,302
benzylbutylphthalate solvent extraction, glc 303
alkyl phthalates solvent extraction, glc 313
fatty acid esters
dimethylphthalate dichloromethane extraction, glc 314
dimethyl sebacate
triacetin
diacetin
diethylphthalate
adipate and phthalate type mild pyrolysis-gas chromatography 315
plasticizers solvent extraction, gas chromatography 316
dibutylphthalate pyrolysis-gas chromatography 321,322
diisobutylphthalate
bis(2-ethylhexyl)phthalate
di-n-octyl phthalate
alkyl phthalates tetrahydrofuran extraction, glc (includes 89
alkyl adipates determination of alcohol degradation
aJky I azealates products)
alkyl citrates
alkyl sebacates
alkyl glycollates
alkyl phosphates
plasticizers pyrolysis-gas chromatography of polymer 43
Thin-layer chromatography
plasticizers dimethoxymethane extraction, thin-layer 323

chromatography
phthalic acid esters solvent extraction, thin-layer 324-340,
sebacic acid esters chromatography for identification and 279,286,
phosphoric acid esters determination 289
epoxy esters
amino crotonic esters
diphenylthio
adipic acid type
chlorinated paraffin waxes solvent extraction, glc 43
tricresyl phosphate
dibutyl succinate
di-n-octylphthalate
bis(2-ethylhexyl)phthalate
tributyl phosphate
esters and carboxylic acids and
dicarboxyJic acids
diethyl phthalate
dimethylsebacate
phthalate type solvent extraction, thin-layer 95
chromatography and infrared identification
Infrared and NMR spectroscopy
50
polypropylene adipate extraction diethyl ether then carbon 82

polypropylene sebacate tetrachloride then with methanol followed
tritolylphosphate by infrared spectroscopy
bisoflex 791
bisoflex 220
bisoflex 795
tricresylphosphate solvent extraction, infrared spectroscopy 43
dibutyl succinate
di-n-octylphthalate
bis(2 ethylhexyl)phthalate
tributylphosphate
esters of carboxylic acids
dicarboxylic acids
diethylphthalate
dimethylsebacate
diiso-octylphthalate solvent extraction, NMR spectroscopy 341
plasticizers benzene extraction, measurement of 342

saponification value
plasticizers diethy I ether extraction, various 12
phthalate plasticizers extraction with boiling hydrochloric acid, 343,344
polargraphy
(k) Antioxidants, Antiozonants, Plasticizers and Accelerators in Rubbers and Polyisoprenes
Spectroscopic Methods
amine and phenolic antioxidants ethanolic hydrochloric acid extraction, 13

spectroscopy
phenyl salicylate resorcinol benzoate diethylether extraction, spectroscopy 14,345,16
antioxidants acetone extraction, spectroscopy 16
ketone-amine condensates acetone, extraction, spectroscopy 17
2-mercapto-benzinidazole
antioxidants solvent extraction, fluorescence 346,353
phenylnapthyl amines spectroscopy
rubber accelerators solvent extraction, polarography 347-353
polygard (tris-nonylated phenyl) phosphate solvent extraction, hydrolysis to nonyl 354
phenol, diazotrization and
spectrophotometric evaluation
Column chromatography
amine solvent extraction, gel permeation 137,138-141

types of antioxidants and antiozonants chromatography using tetrahydrofuran 329,355-358
dilution solvent
antioxidant, plasticizers carbon tetrachloride solution of sample put 31
accelerators through column chromatography, ultra-
violet monitoring of effluent successive
elution with various solvents
antioxidants freeze grinding, diethyl ether extraction, 328
N-N' diethyl aniline column chromatography with refractive
N-ethylaniline index and ultraviolet detectors
diphenylamine
N-phenyl-2-napthylamine
51
Gas chromatography
antioxidants solvent extraction, glc 144,145,405

amine type acetone extraction, glc 83
1,2 dibydroxy-2,2,4
trimethyl-6-ethoxy quinoline
N-isopropyl-N' -phenyl-p-phenylenediamine
N,phenyl-2-napthylamine
N,N'di-2-octyl-p-phenylene diamine
N,N' diphenyl-p-phenylene diamine
di-2-napthyl-p-phenylene diamine solvent extraction, glc 145
poly(trimethyl-dibydroquinoline)
(I) Antioxidants, Antiozonants, Accelerators in Rubber Vulcanizates Antioxidants
Gas chromatography
amine and phenolic type solvent extraction, acetylation glc 359
Column chromatography
antioxidants and accelerators, solvent extraction, column 360-362

guanidine type, chromatography. column streaked with
thiocarbanilide mercaptobenz-thiazole-2- detection reagents, UV and IR examination
disulphide of extracts
2-benzthiazolyl-N' cyclohexyl sulphonamide
phenyl napthylamines
sym-di-beta-napthyl-p-phenylene diamine
zinc dialkyldithiocarbamates
formaldehyde-aniline condensation products
aldol napthylamine condensation products
polymerized trimethyl dihydroquinone
amine and phenolic types N- solvent extraction, TLC for identification 311
phenylnapthylamine
acylated diphenylamines
4,4' dimethyoxydiphenylamine
phenolic and amine solvent extraction, TLC 311
antioxidants solvent extraction, TLC 363
Paper chromatography
antioxidants solvent extraction, paper chromatography 305

phenolic and amine 364
antioxidants 365
Spectroscopy
agerite range of antioxidants acetonitrile extraction - then mass 293

stabilite alba (di-o-tolyl ethylene diamine) spectrometry, infrared spectroscopy and
Santoflex 66 (N-phenyl-N'-eyclohexyl-p- NMR
phenylene diamine)
Santoflex DD (6-dodecyl-1 ,2-dihydro-2,2,4-
trimethyl-quinoline)
Santoflex 13
52
N-phenyl beta-napthylamine
Wingstay S (styrenated phenol)
2,6, di-tertbutyl-p-cresol
N,N' diphenyl-p-phenylene diamine
(m) Antiozonants
solvent extraction, TLC 311
antiozonants
antiozonants solvent extraction, paper chromatography 365,366,

for identification 305,66
(n) Accelerators
accelerators solvent extraction, TLC 367,368

guanidines, thiuram type carbonate type ego solvent extraction, TLC for identification 311
tetramethylthiuram monosulphide,
dipentamethylene thiuram-tetrasulphide
cyclic thiuram
piperidinium pentamethylene-
dithiocarbamate
zinc (bismuth and cadmium)-
dimethylthiocarbamate
2-benzothiazyl N,N' diethyl-ethiocarbonyl
sulphide
2-mercaptobenzthiazole
benzothiazyl disulphide
accelerators solvent extraction, paper chromatography 365,293,

305,364
Mass spectrometry
2-mercapto-benzothiazole accelerator volatile preconcentration/mass 369

sulphenamide types spectrometry down to 0.2%
ego N-tertbutyl-2-benzothiazole
sulphenamide
2-(4 morpholinothio)benzothiazole
2-(2,6-dimethyl
morpholinothio)benzothiazole
N,N-diisopropyl-2-sulphenamide
N,N-dicyclohexyl-2-benzothiazole-
sulphenamide
(0) Phenolic Antioxidants in Polycarbonate
p-tert-butyl phenol diazotization with p-nitro-aniline 370,375
53
(p) Toluene Diisocyanate in Polyurethane Foam
toluene diisocyanate derivativization with pentafluoropropionic 402

anhydride· gas chromatography
S4
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66
CHAPTER 2
COPOLYMERS AND CONDENSATION PRODUCTS
2.1 STYRENE-BUTADIENE
2.1.1 Functional Groups
Most of the published work on the determination of functional groups, not unex-
pectedly, has been carried out on copolymers. This is because the determination of a
functional group that is specific to one of the copolymer constituents is the key to the
determination of the monomer ratios in the copolymer.
2.1.1.1 Unsaturation
2.1.1.1a Iodine Monochloride Procedure. Crompton and Reid' have described

procedures for the separation of high impact polystyrene, ie. styrene-butadiene
copolymer, into a solvent soluble function, ie. free rubber plus rubber grafted polystyrene
plus copolymerized rubber and a gel fraction and for estimating total unsaturation in the
two separated fractions. To separate a sample into gel and soluble fractions it was first
dissolved in toluene. Only gel remains undissolved. Methanol is then added, which
precipitates the polystyrene-rubber graft, ungrafted rubber and polystyrene. Any styrene
monomer, soap or lubricant remain in the liquid phase, which is separated from the solids
and rejected. The addition of toluene to the solids dissolve all the polymeric material
with the exception of the gel. The toluene solubles are separated from the solid gel by
centrifuging and made up to a standard volume with toluene. The gel is then dried in
vacuo and weighed.
Both the gel and toluene soluble fractions are reserved for determination of
unsaturation by the iodine monochloride method. To determine unsaturation in styrene-
butadiene rubbers with good accuracy using the iodine monochloride procedure it was
found necessary to contact the sample with chloroform for 15 hours before reaction with
iodine monochloride. Even with a 30 hour reaction period, a constant iodine value (ca.
20) is obtained only when the sample size is 0.05g or less, ie. a five-fold excess of iodine
monochloride reagent. The solid gel, separated from a high impact polystyrene by the
solvent extraction procedure, is completely insoluble in chloroform and in the iodine
monochloride reagent solution. A contact time with chloroform of 90 hours with a 75
hour reaction period with reagent is required.
Crompton and Reid' used these procedure to study the distribution of rubber
added in several laboratory preparations of high impact polystyrene containing 6% of a
styrene-butadiene rubber and 94% styrene, ie. theoretical 4.1% butadiene. The results in
Table 2.1 show the way in which the added unsaturation of 4.1 % butadiene distributes
between the gel and soluble fractions: the butadiene content of the separated gel remains
fairly constant, in the 20 - 25% region, regardless of the quantity of gel present in the
sample. As the gel content increases, therefore, so more of the rubber becomes
incorporated into the gel and less remains as free rubber or soluble graft. The recovered
67
Table 2.1 - Distribution of butadiene between soluble and gel fractions obtained from
polystyrenes containing different amounts of gel
Gel content Butadiene Soluble Gel Total Amount of

of sample content graft butadiene butadiene original
isolated butadiene contentB content rubber un-
gel content A (calculated (A+B) saturation
(calculated on original (calculated in the
on original sample) on original sample
sample) sample) C=(A+B) x 100
4.1
(wt".4) (wt".4) (wt%) (wt%) (wt".4) %
3.5 3.5 85
4.7 19.5 2.8 0.0 3.7 90
5.6 16.2 2.9 0.9 3.8 93
8.9 23.3 1.5 2.1 3.6 88
11.8 20.0 1.5 2.4 3.9 95
From Crompton and Reid) Iohn Wiley, New York
unsaturation lies mainly in the 90 - 95% region, indicating that loss of unsaturation due to
grafting or cross-linking reactions occurs only to the extent of some 5 - 10%.
The iodine monochloride method has been used for a variety of polymers. These
polymers include those which are highly unsaturated, such as polybutadiene and
polyisopreneJ -6 and polymers having low unsaturation such as butyl rubber' and ethylene
propylene diene terpolymer. Considerable work has been done investigating the side
reactions of iodine monochloride with different polymers'. These side reactions are
substitution and splitting out rather than the desired addition reaction.
2.1.1.1b Infrared Spectroscopy. Albert2 has compared determinations of buta-

diene in high impact polystyrene by an infrared method and by the iodine monochloride
method described by Crompton. 1 The infrared method is based on a characteristic
absorbance in the infrared spectrum associated with the trans configuration in
polybutadiene. Since different grades of high impact polystyrene may contain elastomers
with different trans contents, calibration curves based on the standard rubber are not
always suitable for analyzing these products. The results obtained by the two methods
for several high impact grades are compared in Table 2.2. The rubber content of high
impact polystyrene (sample I) determined by titration is lower than the value obtained by
the infrared method. This is expected in inter-polymerized polymers because of cross-
linking which reduces the unsaturation of the rubber. The other polymers (except sample
3) appear to contain Diene 55 type rubber since reasonable agreement was obtained
between the iodine monochloride and infrared methods. High impact polystyrene 3,
however, must contain a polybutadiene of high cis content to explain the low (1.2% w)
amount of rubber found by the infrared method compared to the 9.0% found by the
titration method.
It is seen that the infrared and iodometric methods are complimentary to each
other.
Near infrared spectroscopy has been used to determine the microstructure and
composition (cis I :4, trans 1.4 and 1.2 butadiene contents) of polybutadiene and styrene
butadiene copolymers. 12'
68
Table 2.2 - Rubber content of high-impact polystyrenes (based on PBD)
Sample Polybutadiene %w Polybutadiene %w

(iodine monochloride (IRmethod)
method)
Standard: 6.0%w diene 55 6.2

Standard: 12%w diene 55 12.2
Standard: 15%w diene 55 14.8
High-impact polystyrene 1 8.6 9.7
2.1.2 Monomers and Other Volatiles
Gas chromatography is used extensively for the determination of residual

monomers and other volatiles in copolymers. In this technique the polymer is dissolved
in a suitable, non-interfering solvent, and the solution to which a suitable internal
standard is added, injected directly into the gas chromatograph. Head space analysis
techniques, discussed later in section 2.3.2 (method 57)2S have also been applied to the
determination of monomers in copolymers.
In a variant of the direct gas chromatographic technique, the polymer containing
an internal standard is dissolved in a suitable solvent, the polymer is precipitated by the
addition of water and the aqueous solvent phase is injected into the gas chromatograph.
However, in general, direct injection of a solvent solution of the polymer is to be
preferred. This technique has the disadvantage of leading to deposition of polymeric
material in the injection port of the gas chromatograph which would lead eventually to
blockage and necessitate frequent cleaning. To overcome this the injection port can be
fitted with a replaceable glass liner loosely packed with glass fibre as illustrated in Fig.
2.1. When a solutiori of polystyrene is injected into the liner, polymer is retained by the
glass fibre and volatile components are swept on to the chromatographic column by the
carrier gas.
Using this technique, Crompton and Myers8 have described a technique (Method
53) for determining styrene monomer and a wide range of other volatiles in conventional
polystyrene and styrene-butadiene copolymers. IS
Shanks9 has determined residual butadiene and styrene in polymers with an
analytical sensitivity of 0.05 to 5 ppm by analysis of the equilibrated headspace over
polymer solutions and determined acrylonitrile, alpha-methyl styrene and styrene
monomers by headspace analysis over heated solid polymer samples.
69
Gloss liner
- T o column Sample injection

septum
Corrier Injection port chamber

oas
Figure 2.1. Injection port glass liner fitted to F. & M. Model 1609 gas chromatograph. The glass liner
measures 60 mm x 40 mm o.d x 2 mm and is very loosely packed with glass fibre.
2.1.3. Additives
Many of the procedures described in Chapter 2 for the determination of additives

in polymers can be applied without modification to the analysis of copolymers (Methods
31 - 33).
2.1.3.1 Stearic Acid and Sodium Stearate.
A method is described in Method 54 for the determination of stearic acid and

sodium stearate in styrene butadiene.
2.1.3.2 Tertiary Phosphite Antioxidants.
Nawakowski lO has described a colorimetric method for determining Polygard

(trisnonyJphenylphosphite) based on hydrolysis to nonyl phenol, followed by coupling
with p-nitro benzene-diazonium fluoroborate and colorimetric estimation at 550 nm.
l
-@-O_]3PNaOH/ROH_@_OH
C9H19 hydrolysis C9H19

2.1
ND2@- N = N + -
OH
~N=N-©N02
C9H19 ~ N~OH/EtOH
Vlolet dye
absorption
maximum 550 nm
Various other phenolic antioxidants produced dyes under these conditions, viz.
Wingstay S, A~erite Superlite and Nevastain A.
Brandt has described an alternate method for the determination of Polygard in
styrene butadiene latices which utilizes the bathochromic shift in the spectrum of phenols
70
resulting from the formation of phenolate ions in alkaline solution. The latex is
flocculated by the addition of acid and the antioxidant extracted with iso-octane.
Polygard in iso-octane has an ultraviolet spectrum with a peak at 273 run in neutral
solution. By adding a strong base (tetrabutylammonium hydroxide) the Polygard is
hydrolysed and the peak is shifted to 296 run. The difference in absorbance at 299 run
between the neutral and alkaline solutions is directly proportional to the amount of
Polygard present. By use of this bathochromic shift, interference of nonphenolic
impurities is eliminated and a background correction factor is not required.
The bathochromic shift method has the advantage of being more specific than the
diazotization method. Results obtained by this procedure agree well with these based on
direct determination of elemental phosphorus (Table 2.3).
2.1.3.3 Antioxidants and Stabilizers.
Hilton and Altenau 12 and Hayes and Altenau 13 used mass spectrometry to
qualitatively identify volatile antioxidants in sheet samples of synthetic styrene-butadiene
rubbers and rubber type vulcanizates. They extracted the polymer with acetone in a
Sohxlet apparatus, removed excess solvent and dissolved the residue in benzene.
Substances identified and determined by this procedure include N-phenyl-J3-
napthylamine, 6-dodecyl-2,2,4-trimethyl 1,2-dihydroquinolines, trisnonyl-phenyl-
phosphite, isobutylene - bisphenol A reaction product, 2-mercaptobenzothiazole sulphen-
amide (accelerator) N-cyclohexyl-2-benzothiazole sulphenamide, N-tert-butyl-2-benzo-
thiazole sulphenamide, 2-(4-morpolinothio) benzothiazole, 2-(2,6-dimethyl-morphal-
inothio) benzothiazole, N ,N' -diisopropyl 2-benzothiazoles, 2-mercaptobenzo-thiazole and
N,N' -dicyclohexyl-2-benzothiazole sulphamide.
2.1.4 Fractionation
Styrene-butadiene copolymers have been fractionated by high performance liquid chrom-

atography.54,72
2.2 STYRENE-ACRYLONITRILE
Cortes et al l3l have described an on-line coupled microcolumn size exclusion

chromatographic - pyrolysis - gas chromatographic system for the characterization of
styrene-acrylonitrile copolymers.
2.2.2 Monomers
Residual amounts of styrene and acrylonitrile monomers usually remain in

manufactured batches of styrene-acrylonitrile copolymers. As these copolymers have a
potential use in the food packaging field, it is necessary to ensure that the content of both
of these monomers in the finished copolymer is below a stipUlated level.
In a polarographic procedure14 for determining acrylonitrile (down to 2 ppm) and styrene
(down to 20 ppm) monomers in styrene-acrylonitrile copolymer, the sample is dissolved
in 0.2 M tetramethyl ammonium iodide in dimethyl formamide base electrolyte
71
Table 2.3 - Determination ofPolygard: comparison of ultraviolet with perchloric acid
methods
Percentage
SBRlatex Perchloric acid (phosphorus) Ultraviolet method

type 6101 method
Sample I 1.31 1.30 1.18 1.30

Sample 2 1.26 1.28 1.24 1.36
Sample 3 1.23 1.24 1.36 1.32
Sheet rubber
Type 1019 1.25 1.28 1.04 1.06
Type 1503 1.62 1.63 1.53 1.60
Type 1018 1.59 1.56 1.57 1.58
Type 1022 1.27 1.31 1.16 1.14
From Brandel American Chemical Society
and polarographed at start potentials of -1.7 v and -2.0 v respectively for the two mono-
mers (Method 55).
Titrimetric methods l6 (Method 56) have been described for the determination of
styrene and acrylonitrile monomers in styrene-acrylonitrile. These methods unfortunately
have the disadvantage of being more subject to interference than the polorographic
method described above.
Methods have been described for determining styrene and acrylonitrile (dimethyl
formamide extraction-polarography)17and styrene, acrylonitrile and butadiene monomers
(solution in dimethyl formamide-gas chromatography).18 Acrylonitrile has been
determined by polarographyl9 and by ias chromatography200f a dimethyl formamide
solution. The polarographic method I also determines methacrylonitrile. Styrene
monomer has been determined by a polarographic method. 17
2.2.3 Fractionation
Styrene acrylonitrile copolymers have been fractionated by high performance

liquid chromatography using the precipitation technique. 76
2.3 VINYLCHLORIDE BUTADIENE ACRYLONITRILE STYRENE 2-

ETHYLHEXYLACRYLATECOPOLYMERS
13CNMR spectroscopy has been used to elucidate structural detail of vinyl

copolymers. 89
2.3.2 Monomers
In head space procedures a solution of the polymer in a suitable solvent is placed

in a closed container and allowed to equilibriate at a controlled temperature so that
volatile monomers or other impurities dissolved in the polymer solution partition between
72
the solution and the gas phase. Subsequent analysis of the gas phase enables the
concentration of monomers to be calculated. In a variant of this method, the solid
polymer is allowed to equilibriate with the head space gas.
Although the solid head space method discussed later provides about IO-fold
more sensitivity than the solution head space method (assuming a 10% sample solution)
the solid method may be applied only to sample systems where equilibration with the
head space is rapid and complete. For example, residual styrene monomer in polystyrene
does not reach equilibrium with the head space after 20 hours21 •22 and thus may not be
determined by the solid head space method. Furthermore, even if equilibrium between
the solid and head space is obtained, the partition coefficient must also be determined for
the component of interest in each type of sample matrix. The solution head space
approach is applicable to a much wider range of samples than the solid approach. When
working with sample solutions, head space equilibrium is more readily attained and the
calibration procedure is simplified.
Greater sensitivites and shorter analysis times were obtained using the head space
analysis methods than were possible by the direct injection of polymer solutions into a
gas chromatograph (Table 2.4).
Various methods have been described for the determination of styrene monomer
in polystyrene b~ solution head space analysis. 23•24
Steichen S has discussed a modified solution approach for the gas chrom-
atographic determination of residual vinyl chloride, butadiene, acrylonitrile, styrene and
2-ethylhexyl acrylate monomers in their associated polymers by head space analysis
(Method 57).
2.4 ETHYLENE OXIDE-PROPYLENE OXIDE-GLYCEROL CONDENSATES
2.4.1.1 Hydroxy Groups by Direct Injection Enthalpimetry.
This technique involves the reaction of a small portion of sample with a large
excess of acetic anhydride under conditions where reaction is rapid (less than 1 s), the
change in temperature associated with the reaction, dT, is recorded using a thermistor
bridge. Under conditions of constant heat capacity, dT should be directly proportional to
the number of reactive groups per unit mass of the sample. The main advantages of the
technique are, firstly, that it is relatively simple to operate and secondly, that only a few
minutes are required in order to perform an analysis.
Kaduji and Rees26 and others27 employed direct injection enthalpimetry to
determine the hydroxy value of glycerol - alkylene oxide polyethers and butane-I, 4-diol-
adipic acid polyesters (Method 58).
Direct injection enthalpimetry has great potential as a method for determining the
hydroxyl values of polyethers and polyesters. The method is rapid, the temperature rises
for two samples and a standard being recorded in duplicate in about 10 minutes.
The methods described above determine total hydroxy groups and are applicable
to many types of hydroxy containing polymers including polyethylene glycol,
polypropylene glycol and glycol/alkylene oxide condensates.
In many pratical situations, it is necessary to be able to distinguish between prim-
ary and secondary hydroxyl groups in polymers. Thus, the reaction product of a glycerol
73
Table 2.4 - Comparison of Quantitation Limited* for Residual Monomers Using
Conventional and Head-Space GC Methods
Monomer Boiling Direct Solution Modified

point solution head-space solution
injection" head-space
Vinylchloride _13°C 1-2 ppm 0.05 ppm

Butadiene _4°C 5 ppm 0.05 ppm
Acrylontirile 76°C 10 ppm 0.50 ppm
Styrene 145°C 10 ppm 20.00 ppm 1 ppm
2-ethylhexyl
acrylate 214°C 200 ppm 1000.00 ppm 5 ppm
*The quantitation limit is defined as the monomer concentration necessary to produce a peak at least three
times the baseline noise or 3% of full scale .
• Injection of a 10% polymer solution into a gas chromatograph.
b A 2- to 3-fold increase in monomer peak height resulted from the injection of water into the polymer
solution. A baseline disturbance due to elution of water negated any real improvement in detection limit
for these monomers. From Pfab and Noffz22 American Chemical Society
-ethylene oxide condensate with propylene oxide would contain both types of hydroxy
group.
2.2
-secondary hydroxy, • • primary hydroxy
Reaction rate differences of primary and secondary hydroxy groups with phenyl
isocyanate are the basis of a kinetic method for carrying out this determination28 (Method
59).
2.4.1.2 Alkoxy Groups.
A method for determining alkoxy groups is based on thermal degradation of

alkoxy groups to the corresponding olefin which is determined by gas chromatography.
This latter method is typified by a procedure29,30,31 for the determination of ethoxy groups
in ethylene oxide-propylene oxide condensates in which the sample is pyrolysed in an
evacuated vial at 360 - 410°C and the resulting olefin mixture analysed by gas
chromatography.
14
2.3
A curve relating per cent ethylene as a function of the ethylene oxide content of
ethylene oxide-propylene oxide condensate is linear up to about 50% ethylene oxide, then
turns sharply upward to an ethylene content of 38.6% for pure polyethylene glycol.
The relative contents of ethylene oxide and propylene oxide in polyethylene -
polypropylene glycols has been detennined using combined pyrolysis - gas chrom-
atography calibrated with polyethylene glycol and polypropylene glycol standards. 32
2.5 ETHYLENE OXIDE - PROPYLENE OXIDE - POLYHYDRIC ALCOHOL

AND ETHYLENE OXIDE - PROPYLENE OXIDE AMINE CONDENSATES
2.5.1.1 Oxyethylene and Oxypropyiene
Ethylene oxide and propylene oxide adducts of polyhydric alcohols and amines
are widely used as polyethers in the production of polyurethane foams by reaction with
diisocyanate. The physical properties of the foams depend to a certain extent on the
chemical structure of these polyethers, so it is very important to establish a method for
the identification of the base compounds and for the detennination of the proportions of
their oxyethylene and oxypropylene groups.
Mathias and Mellor32 split the polyethers with hydrobromic acid - acetic acid to
give bromo compounds, which were analysed by gas chromatography.
2.4
In this way, the content of oxyethylene groups, and therefore, the original
polyhydric alcohols, can be detennined. Stead and Hindley33 modified this method and
obtained good results for the detennination of the oxyethylene group contents of ethylene
oxide-propylene oxide copolymers. The detennination of the content of oxyethylene
groups in these copolymers can also easily be carried out by nuclear magnetic resonance
spectrometry32,34 without chemical splitting of the ether linkage. However, it is difficult
to identify the base compounds by this method. A number of methods for the cleavage of
ethers have been studied but few were applied to the identification of the base compounds
of the polyurethane polyethers.
Dowie and CampbeU44 pryolysed alcohol-polyethylene oxide condensates in the
presence of hydrogen bromide and examined the products by gas chromatography.
Several mixed anhydrides of carboxylic and sulphonic acids, as proposed by Karger and
Mazur35 act as reagents for the cleavage of ether linkages. This is particularly true of
acetic anhydride toluene-p-sulphonic acids, which is not only a powerful reagent for the
cleavage of ether linkages but is also an active acetylating agent. For example, when the
propylene oxide adduct of glycerol is treated with this reagent, the polyether is split, thus
giving glycerol triacetate and propylene glycol diacetates, which are easily identified by
gas chromatography.
75
r 2 -(CH 3 CHCH 2 0' nOH
2.5
CH-(CH 3 CHCH 2 0l nOH + 6(CH 3 COI 2 0 =
I
CH 2 -{CH 3 CHCH 2 0l nOH
rzOOCCH3
CHOOCCH 3 + 6CH 3COOCHCH 3-CH ZOOCCH 3 + 3CH 3COOH
I
CH 2 00CCH3
Cervenka and Merrale 7 have investigated the application of acidic dehydration of

ethylene oxide-propylene oxide condensates in bromonapthalene in the presence of p-
toluene sulphonic acid to the elucidation of the molecular structure and monomer
sequence of these polymers. Gas chromatography was used to determine dehydration
products.
Studies on poly(ethylene glycol) and poly(propylene glycol) homopolymers
showed that dioxane and its derivatives (eg. methyl dioxone 1.4) are not the only reaction
products. Dehydration of poly(ethylene glycol) gave three products; that of poly(prop-
ylene glycol) six products. The majority of them were identified.
Cervenka and Merrale 7 conclude that results on homopolymers, their blends and
model copolymers of different chain architectures demonstrate that acidic dehydration is
capable of distinguishing ethylene oxide-propylene oxide copolymers of different
structures, giving correct absolute values of overall monomer contents and also ranking
polyols according to their depees of randomness.
Tsuji and Kounishe extended this method to the identification of base compo-
unds and the determination of their oxyethylene and oxypropylene group contents
(Method 60).
76
2.6 ETHYLENE PROPYLENE-DIENE TERPOLYMERS
2.6.1.1 Trace Unsaturation.
Polymerization of ethylene and propylene results in a saturated copolymer. In

order to vulcanize this rubber, some unsaturation has to be introduced. This is commonly
done by adding a few percent of non-conjugated diene (termonomer) such as
dicyclopentadiene, l,4-hexadiene, or ethylidene norborene during the polymerization.
Since only one of the double bonds of the diene reacts during polymerization, the other is
free for vulcanization. The amount of unsaturation left in the ethylene propylene diene
terpolymer is of great interest because the vulcanization properties will be affected.
Sewell and Skidmore38 used time averaged NMR spectroscopy at 60 Me/sec to
identify low concentrations of nonconjugated dienes introduced into ethylene-propylene
copolymers to permit vulcanization. Although infrared spectroscopl9 and iodine
monochloride unsaturation methods40 have been used to determine or detect such dienes,
these two methods can present difficulties. Identification of the incorporated third
monomer is not always practical in infrared spectroscopy at the low concentrations
involved and in the high-resolution NMR spectra of these terpolymers the presence of
unsaturation is not usually detected, since the signals from the olefinic protons are of such
low intensity that they become lost in the background noise. The spectra obtained by
time averaged NMR are usually sufficiently characteristic to allow identification of the
particular third monomer incorporated in the terpolymer. Moreover, as the third
monomer initially contains two double bonds, differing in structure and reactivity, the
one used up in copolymerisation may be distinguished from the one remaining for
subsequent use in vulcanization. Therefore, information concerning the structure of the
remaining unsaturated entity may be obtained. Table 2.5 shows the chemical shifts of
olefinic protons of a number of different third monomers in the copolymers.
The cyclooctadiene and dicyclopentadiene terpolymers have olofmic protons with
the same chemical shift, 4.55 ppm and so these cannot be differentiated by this technique
but may be distinguished by the use of iodine monochloride. The hexadiene type of
terpolymer may be identified by its olefinic resonance at 4.7 ppm. These three monomers
have what appears as a single olefinic resonance in the terpolymer. On the other hand,
the two norbomadiene types of monomer each show two characteristic resonances. In the
methylene norbomene terpolymer the olefinic resonances arise from two protons, each
giving a separate signal, whereas in the ethylidene norbonene terpolymer there is only
one proton, the signal of which appears as a doublet. In view of these considerations it is
more difficult to detect the olefinic resonance in the latter instance.
Altenau et al41 applied time averaging NMR to the determination of low
percentages of termonomers such as 1:4 hexadiene, dicyclopentadiene and ethylidene
norbomene in ethylene-propylene termonomers. They compared results obtained by
NMR and the iodine monochloride procedure of Lee et al. 42 The chemical shifts and
splitting pattern of the olefinic response were used to identify the termonomer.
Table 2.6 compares the amount of termonomer found by the NMR method of
Altenau et al41 and by iodine IUonochloride procedures.42•4s The termonomers were
identified by NMR and intrarl!d.
77
Table 2.5 - N.M.R. detennination of non-confugated olienes in ethylene propylene
copolymers
Third Monomer Chemical Shift

ppm
Cyclooctadiene 1,5 4.55

Dicyclopentadiene 4.55
1:4 hexadiene 4.7
Methylene norbomene 5.25 and 5.5
Ethylidene norbomene 4.8 and 4.9
From Sewell and Skidmore38• John Wiley, New York
Table 2.6 - Detennination oftennonomer in ethylene-propylene diene terpolymers-

comparison of methods (data shown as weight % terpolymer)
NMR Lee42 Kemp and Termonomer

KoltotTand Peters45
Johnson
7.3 3.0 dicyclopentadiene

1.1 1.6 1,4-hexadiene
5.7 5.9 9.0 ethylidene norbomene
From Altenai l American Chemical Society
Table 2.6 shows that the data obtained by the NMR method agrees more closely
with the Lee et al iodine monochloride method42 than with the iodine monochloride
method of Kemp and Peters. 45 The difference between the latter two methods is best
explained on the basis of side reactions occurring between the iodine monchloride and
polymer because of branching near the double bond. 42 The reason for the difference
between the NMR and the Lee et al42 methods is not clear. The reproducibility of the
NMR method was 10 ± to 15%.
Infrared spectroscopy has been used for the detennination of trace unsaturation in
ethylene-propylene-diene terpolymers. 46 Detennination of extinction coefficients for the
various terpolymers is required if quantitative work is to be done.
2.7 ACRYLATE COPOLYMERS
2.7.1.1 Carboxyl Groups.
Most methods for the detennination of carboxyl groups in polymers are based on
titration techniques. The following copolymers, acrylic acid-itaconic acid,47 acrylic acid-
ethyl acrylate48 and maleic acid-styrene49 have been studied. High frequency titration has
78
been appliedso to the analysis of itaconic acid-styrene copolymers. High frequency
titration gives a precise location of the inflection points related to the polymer carboxyl
groups and is a sensitive method for the detennination of the freedom of the copolymer
samples from monobasic acid impurities (comonomer acids), since mixtures of
copolymer acids with monobasic and dibasic acids show definite inflection points that
can be related to the individual carboxylate species present.
Johnson et al SI found that in titrating copolymers of methylacrylate and meth-
acrylic acid with standard base to determine carboxyl groups, a number of deficiences
were encountered (eg. the presence of up to 5% water and unreacted monomers both lead
to underestimations of the acid content, also titration was not applicable to polymers of
molecular weight over one million or high acid content because of a tendency to
reprecipitate during the titration). For this reason they investigated the application of
proton NMR by using the integral of the ester methoxy protons and combining this result
with the total integral for CH2 and CH3 protons (the overlap between CH2 and CH3
resonances was enough at 100 MHz to prevent separate determination of these integrals),
the copolymer composition could be ascertained. A problem was that the reaction
solvents (toluene and hexane) and comonomers had resonances that overlapped those of
the CH2 and CH3 protons of the copolymers introducing considerable inaccuracy in the
total CH2 CH3 integral. For this reason they investigated the applicability of 13C NMR.
Because of the greater spectral dispersion and narrower resonance lines obtained with l3 C
NMR relative to proton NMR problems associated with resonance overlap can be
resolved. Excellent agreement was obtained between carboxyl values obtained by this
procedure and conventional titration in 1:1 ethanol:water with standard potassium hydr-
oxide to the phenol phthalein end-point over in the acid content range 13% to lOoolo.
Sharp and PatersonS2 have described a pyrolysis - gas chromatographic - mass
spectrometric procedure (Method 61) for the determination of I - 10% of copolymerized
acrylic acid and methacrylic acid in acrylic polymers.
Nissen et alS3 have described a method for carboxyl groups in poly(ethylene
terephthalate). Hydrazinolysis led to formation of terephthalomonohydrazide from
carboxylated terephthalyl residues to provide a selective analysis for carboxyl group viz
ultraviolet absorbance at 240 nm.
Titrimetry, NMR spectroscopy and pyrolysis gas chromatography each give
different information in the analysis of carboxyl groups. Frequently more than one
technique has to be applied to obtain the required information.
2.7.1.2 Ester Groups.
Most methods for the determination of ester groups in polymers are based on the
following procedures:
(a) Saponification
(b) Zeisel procedures, based on hydriodic acid
(c) Pyrolysis - gas chromatography
(d) Physical methods, ego infrared spectroscopy and nuclear magnetic
resonance spectroscopy.
2.7.1.2a Ester Groups Saponification Methods. Ester groups occur in a wide

range of polymers, ego poly(ethylene terephthalate) and in copolymers such as, for ex-
ample, ethylene-vinyl acetate, acrylic acid-vinyl ester, methyl acrylate vinyl ester and
poly(methyl acrylate). The classical chemical method for the determination of ester
79
groups, namely, saponification, can be applied to some types of polymers. For example,
copolymers of vinyl esters and esters of acrylic acid can be saponified in a sealed tube
with 2 M sodium hydroxide. The free acids from the vinyl esters were determined by
potentiometric titration or gas chromatography. The alcohols formed by the hydrolysis of
the acrylate esters can be determined by gas chromatography. Vinyl acetate-ethylene
copolymers can be determined by saponification with I M ethanolic potassium hydroxide
at 80°C for 3 hours and back titration with standard acid55,70,71 or by saponification with
.l2-toluene sulphonic acid and back titration with standard acetic acid. 58,59
Poly(methyl acrylate) can be hydrolyzed rapidly and completely under alkaline
conditions, on the other hand the monomer units in poly(methyl methacrylate) are
resistant to hydrolysis 56 although benzoate end-groups react readily.57 Only about 9% of
the ester groups in poly(methyl methacrylate) react even during prolonged hydrolysis;
hydrolysis of polymethyl acrylate was complete in 30 minutes. Although only about 9%
of the ester groups in polymethyl methacrylate homopolymers are hydrolyzed by
alcoholic sodium hydroxide, this proportion is increased by the introduction of
comonomer units into the polymer chain. Thus, saponification techniques should be
applied with caution to polymeric materials.
2.7.1.2b Ester Groups Zeisel Procedures. Hydrolysis using hydriodic acid has
been used for the determination of the methyl, ethyl, propyl and butyl esters of acrylates,
methacrylates or maieates 60 and the determination of polyethyl esters in methyl
methacrylate copolymers. 62 ,63 First the total alcohol content is determined using a
modified Zeisel hydriodic acid hydrolysis. 61 Secondly, the various alcohols after being
converted to the corresponding alkyl iodides are collected in a cold trap and then
separated and determined by gas chromatography. Owing to the low volatility of the
higher alkyl iodides the hydriodic acid hydrolysis technique is not suitable for the
determination of alcohol groups higher than butyl alcohol. This technique has also been
applied to the determination of alkoxy groups in acrylate esters. 60
Anderson et al64 have used combined Zeisel reaction - gas chromatography to
analyse acrylic copolymers. Acrylic esters were cleaved with hydriodic acid and gas
chromatography was used for analysing the alkyl iodides so formed (Method 62).
2.7.1.2c Ester Groups Pyrolysis - Gas Chromatography. Barrall et al65 have

described a pyrolysis-gas chromatographic procedure for the analysis of polyethylene-
ethyl acrylate and polyethylene-vinyl acetate copolymers and physical mixtures thereof.
They used a specially constructed pyrolysis chanber as described by Porter et al. 66 The
pyrolysis chromatogram of poly(ethylene-vinyl acetate) contains two principal peaks.
The first is methane and the second acetic acid. The pyrolysis chromatogram of
poly(ethylene-ethyl acrylate) at 475°C shows one principal peak due to ethanol. Table
2.7 shows the analysis of 0.05 gram samples of poly(ethylene-ethyl acrylate) and
poly(ethylene-vinyl acetate) obtained at a pyrolysis temperature of 475°C.
Pyrolysis - gas chromatography - mass spectrometry has been used to identify
. acryl'IC copoIymers. 68
ester groups In
Ziesel reduction followed by gas chromatography or pyrolysis followed by gas
chromatography have the advantage of being more specific for the determination of ester
groups than standard saponification procedures.
2. 7.1. 2d Ester Groups Physical Methods. Infrared spectroscopy has been applied
to the determination of free and combined vinyl acetate in vinyl chloride-vinyl acetate
copolymers. 67 This method is based upon the quantitative measurement of the intensity
80
Table 2.7 - Pyrolysis results on physical mixtures of poly (ethylene-ethyl acrylate) and
poly (ethylene-vinyl acetate)
Mixture Acetic wt"10 Ethylene wt"10 Oxygen wt"10

acid calcd found caled' found calcd
found
50%PEEA-l
and 50%
PEVA-2 9.10 9.05 2.65 2.62 7.88 8.25
33.3% PEEA-2
and 66.6%
PEEVA-3 12.15 12.33 0.75 0.70 7.33 7.49
'Calculated from results for acetic acid and ethylene content for individual samples on weight per cent
basis. From BlackweU6s, American Chemical Society
of absorption bands in the near infrared spectral region arising from vinyl acetate. A
band at 1,613 cm-! (6.20 u) vinyl group enables the free vinyl acetate content of the
sample to be determined. A band at 4651 cm-! (2.15 u) is characteristic for the acetate
group and arises from both free and combined vinyl acetate. Thus, the free vinyl acetate
content may be determined by difference at 2.15 u. Polymerized vinyl chloride does not
influence either measurement.
The vinyl acetate content of films of ethylene-vinyl acetate copolymers can be
determined by methods based on the measurement ofabsorbances at 1639 and 1389 cm-!
(6.10 and 7.20 U)70 and at 1245 cm-! (8.03 u) and 1743 cm-! (5.73 U).71,74 The acrylate
salt in acrylate salt-ethylene ionomers has been determined from the ratio of absorbances
at 1560 cm-! (6.41 u) (asymmetric vibration of the carboxylate ion) and 1380 cm-! (7.25
) 69
U.
Anderson et al64 have described an infrared procedure for distinguishing between
copolymerised acrylic and methacrylic acids in acrylic polymers containing more than
10% of the acid. This method is based on precise measurement of the wavelength of the
carboxylic acid absorption maximwn at about 1700 cm- l (5.88 u). The identification of
the acid in compositions containing less than 10% of acid was hitherto not possible,
except when un~lymerised acid residues can be separated from the polymer. 73
Haslam 4 has discussed infrared methods for the determination of ester groups in
acrylic copolymers. NMR spectroscopy has been used for the determination of
isophthalate in poly(ethylene terephthalate isophthalate) dissolved in 5% trichloroacetic
acid. The NMR spectra of these polymers were measured on a high resolution NMR
spectrometer at 80°C. A singlet at 7.74 ppm is due to the four equivalent protons
attached to the nucleus of the terephthalate unit. The complicated signals which appear to
8.21, 7.90, 7.80, 7.35, 7.22 and 7.10 ppm are due to the four protons attached to the
nucleus of the isophthalate unit. The content of the isophthalate unit can be calculated
from the integrated intensities of these peaks.
NMR has also been used to determine ethyl acrylate in ethyl acrylate-ethylene and
vinyl acetate-ethylene copolymers. 7s Measurements were made on 10% solutions in
diphenyl ether at an elevated temperature. Resolution improved with increasing
temperature and lower polymer concentration in the solvent. This technique has also
been used to identify ester groups in acrylic copolymers74 and copolymers.
81
Campbell77 has described an isotope dilution derivative method for the deter-
mination of vinyl acetate in vinyl acetate - vinyl chloride copolymers.
2.7.1.3 Epoxy Groups.
Swaraj and Ranby79 used infrared spectroscopy to determine epoxy groups in

methylmethacrylate - glycidyl methacrylate copolymers. The analysis was performed on
dried potassium bromide pellets containing 0.5 mg sample in 200 mg potassium bromide.
The peaks at the wavenumbers 907 (11.02 u) and 1717 cm'l (5.82 u) are the most suitable
ones for analysis of epoxy and carbonyl groups respectively. Using the "base line
density" method the values of the absorbances at 907 and 1717 cm'l wavenumbers were
determined. The average values of the absorbances, their ratio and the glycidylmethyl-
acrylate mole fraction determined chemically are presented in Table 2.8.
The absorbance ratio at 907 cm'l vs 1717 cm'l is linearly related to the glycidyl
methylacrylate content in the copolymer and can be expressed by the following equation:
R = 0.250 Xo + 0.033
where R is the absorbance ratio at 907 and 1717 cm'l and Xo is the mole fraction of
glycidylmethacrylate containing the epoxy group in the copolymer.
High performance li~uid chromatography has been applied to the fractionation of

styrene-methyl methacrylate 8,95,107,109,113 and styrene n-butyl methacrylate 116 copolymers.
Separations were achieved on silica leI using 1,2 dichloroethane-chloroform as eluting
solvents and an ultraviolet detector. 12
The chemical composition and molecular weight distribution of high conversion
polystyrene - methyl methacrylate (54 - 85% methyl methacrylate) has been determined
by liquid adsorption and size exclusion chromatography.l30
2.8 ACRYLAMIDE COPOLYMERS
2.8.1.1 Alkoxy Groups.
The Ziesel reaction has been extensively studied and has been used successfully
for the determination of alkoxy groups in cellulosic materials.80-82 Quantitative cleavage
of the alkoxy groups in polymers is routinely obtained. However, as discussed in section
2.7.1.2 on the determination of ester groups, hydriodic acid also cleaves any ester link-
ages on the polymer backbone, giving a positive interference.
Anderson et alB3 identified and determined the etherifying alcohols present in
thermosetting acrylamide interpolymers of the type shown below via alcohol exchange
when interfering ester linkages are present in the polymer backbone (Method 64). No
interference is encountered from alkyl esters present in the sample.
82
-(CHrCHCONHR")x - (CHz-CRCOOR!)y-(CHz-CHPh)z 2.6
where R' = H,CH3,C2Hs,C4H9 or CSH!7 and R" = H,
CH20C4H9 or CH20H
Table 2.8 - Analytically determined mole fraction of GMA in the MMA-GMA

copolymers and the infrared absorbanced at 907 (11.02 micron) and 1717 cm-! (5.82
micron)
Expt.no. Mole fraction of A,S.82 A,I1.02 Absorbance ratio
GMA in the co- micron micron A, 11.02 micron
polymer deter- A, S.82 micron
mined chemically
RSO 0.218 1.366 0.128 0.093

RSI 0.394 0.911 0.120 0.131
RS2 0.S84 0.629 0.1 IS 0.182
R61 0.623 0.921 0.177 0.192
RS3 0.706 0.9SS 0.204 0.213
From Swarej and Ranby79. American Chemical Society
2.9 OCTADECANE-MALEIC ANHYDRIDE COPOLYMERS
2.9.1.1 Anhydride Groups.
Van HouwelingenS4 discussed the determination of anhydride groups in a resin

derived from octadecene-l and maleic anhydride.
-r- -r-r-1
CHz 2.7
163,y\
C H C C
n
The common method for anhydride groups involving reaction with an excess of
aniline and subsequent backtitration of the excessss is unsuitable, as the reactivity of the
anhydride group is low. Even after hydrolysis with aqueous pyridine (containing 40%
v/v of water) in a Parr bomb at 150°C for 4 hours, anhydride groups are still seen in the
infrared spectra.
A suitable method for determining the anhydride group is titration with aqueous
potassium hydroxide in pyridine after previous esterification of the carboxyl group with
diazomethane. This esterification is carried out in diethyl ether methanol (9 + I). After
methylation, which takes about 10 m for O.5g of sample, the solvents are removed by
evaporation and a portion of the derivatised polymer is dissolved in pyridine and titrated.
In the infrared spectra of the resin before and after methylation it can be seen that the
absorption band of the acid group at 1710 cm-! (S.84u) disappears and a carbonyl band of
the ester at 1740 em-I (S.74u) is formed. The acid content of the sample is found from
the difference in titres of an unmethylated and a methylated product.
83
2.10 EPOXY RESINS
2.10.1 Volatiles
Thennogravimetric analysis coupled with gas chromatography and mass

spectrometry has been used to study the nature of the volatiles produced during the curing
of epoxy resins.1I7
2.10.2.1 Epoxy Groups.
Peltonen et al 120 used infrared spectroscopy to detennine epoxy resins and their
degradation products.
Further methods for the detennination of functional groups, volatiles and
additives in copolymers are reviewed in Tables 2.9 - 2.11.
2.11 TERTOCTYLPHENOL - ETHYLENE OXIDE CONDENSATES
2.11.1 Oligomers
Wallingford 132 carried out an oligomeric separation of ionic and non-ionic

ethoxylated polymers by capillery gel electrophoresis. The oligomeric distribution of
several sulphated and phosphated alkyl phenol ethoxylate surfactants was detennined on
commercial grade cross linked polyacrylamide gel columns. Non-ionic detergents and
polyethylene glycol oligomers reacted with phthalic anhydride to provide a charge to the
molecule thereby facilitating the detection of polyethylene glycol oligomers from
ethylene glycol to species with 120 monomer units. A linear relationship was found
between molecular weight and migration time.
2.11.2 Molecular Weight
The molecular weight distribution of tert octyl phenol - ethylene oxide

condensates has been detennined by a combination of high perfonnance liquid
chromatography and laser desorption Fourier Transfonn ion cyclotron resonance mass
spectrometry. 128
84
Table 2.9 - Functional Groups in Copolymers
Ref
Nitrile Polystyrene Dye partition method 86
Unsaturation styrene-butadiene Raman spectroscopy 87
methylmethacrylate
terpolymer
Unsaturation acrylonitrile-butadiene NMR 88
styrene terpolymers
Unsaturation ethylene-propylenediene NMR 38
terpolymer
Vinyl vinylchloride- NMR 90,91
vinylidene chloride
Vinyl styrene-divinyl benzene Pyrolysis-mass 92
spectrometry
Table 2.10 - Monomers and Volatiles in Copolymers
Monomer Copolymer Method Ref

or volatile
Divinylbenzene Styrene-divinylbenzene Pyrolysis - mass 93

spectrometry
Styrene Polyester laminates Polarographic 94
Styrene butadiene acrylics
Styrene and Styrene-butadiene Head space analysis and 18,96
butadiene gas chromatography of
DMF solution
Benzene and Rubber adhesives Gas chromatography 97
toluene
Styrene Latex Gas chromatography 98,99
Styrene, dialkyl Polyester resin mOUldings Gas chromatography 100,101
phthalate, mouldings
d-limonene Plasticized vinyl chloride Permeability of polymer 126
benzaldehyde copolymers films to organic vapours
methyl acetate, mass spectrometry
toluene
Styrene, ethyl Styrene ethyl acrylate Radioactive tracer methods 102, 103
acrylate
Styrene, Styrene methacrylic acid Mercurimetric 104, 105
methacrylic acid
Ethylene glycol, Isophthalic acid- Gas chromatography 106
dimethyl tereph- terephthalic acid-
thalate, dimethyl ethylene glycol
isophthalate,
dimethyl adipate
Ethyl acrylate, Styrene - ethyl Distill in presence of 103
styrene, vinyl acrylate toluene, glc
acetate
Methyl acrylate, Mixed polyacrylates solution, glc 108
ethyl acrylate,
2-ethylhexyl
acrylate, butyl
85
Table 2.1 0 continued
acrylate, ethyl
acrylate, vinyl
propionate
2-ethylhexyl Mixed polyacrylates Solution in propyl acetate- 110, III
acrylate, vinyl cyclohexanol, glc. Solution
acetate, butyl in isopropanol-glc
acrylate, methyl
acrylate, meth-
acrylic acid
Methyl meth- Styrene - acrylate and Solution, glc 112
acrylate, ethyl styrene methacrilate
acrylate, styrene
Vinyl acetate, Vinylacetate - Solution in propyl acetate, 108
2-ethyl hexyl 2-ethylhexyl- glc
acrylate acrylate
Table 2.11 - Determination of Additives in Copolymers
Additive Copolymer Method Ref
Dilauryl Ethylene - vinyl acetate Hydrolysis to lauryl alcohol 121

thiodipropionate and acrylonitrile - hydrolysis with chloroform-
butadiene-styrene ethanol-hexane then
TLCorGLC
Santonox Tetramethylene glycol- High performance 114
dimethyl acrylate liquid chromatography
Polygard (tris- Styrene butadiene Methanol or ethanol 115
nonylated phenyl) extraction, coupling with
phosphite diazotized-p-nitro-aniline,
spectrophotometric finish
Polygard (tris- Styrene-butadiene Solvent extraction, 10
nonylated phenyl) hydrolysis to nonyl phenol,
phosphite, Agerite diazotization and spectro-
Supealite NevastainA photometric evaluation
Polygard (tris- Styrene-butadiene Solvent extraction - II
nonylated phenyl) addition of sodium hydroxide
phosphite and measurement ofbatho
chromic shift spectrometry
Various types Styrene-butadiene Solvent extraction 118
Phenyl B napthylamine Colormetric tests
WingstayS (styrenated
phenols), Polygard
Amine acid Solvent extraction, thin 118,
phenolic types layer chromatography for 119
quantitative analysis
N-phenyl-B Volatile preconcentration 17
napthylamine mass spectrometry
6 dodecyl-2,2,4-tri Hydrolysis to lauryl alcohol, 121
methyl 1,2 dihydro- chloroform-ethanol-hexane
quinaline, trisnonyl extraction and thin-layer
phenyl phosphate, chromatography then glc
dilaurylthio dipropionate
Alkylated cresols Ethanol extraction, glc 122
(2,6-di-t-butyl-p-cresol),
amine type (N-phenyl-2
86
napthylamene),
Subst'd p-phenylene
diamine type, Santoflex
13 sec heptyl phenyl-p-
phenylene diamine
Additives and low Solvent extraction - 123
molecular weight column chromatography
compounds
Accelerators and Rubbers Infrared spectroscopy 124
antioxidants
Amine antide- Rubbers Gas chromatography
gradients
Accelerators and Rubbers Column chromatography 43
antioxidants
Antioxidants Acrylonitrile-butadiene- Laser desorption electron 125
phosphite type, (bis styrene terpolymer impact IT ioncyclotron
(2,4 di-tert butyl and polyethylene mass spectrometry
phenol), pentaery terephthalate
thritol diphosphite)
and its diphosphate
oxidation product
also distearylpent-
&erythritol diphosphite
87
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91
CHAPTER 3
DETERMINATION OF ELEMENTS
As many of the methods for determining elements are applicable to various

types of polymers and copolymers, they are grouped in this chapter and not listed
separately under the polymer type listed in chapters 1 and 2.
In addition to carbon and hydrogen and possibly oxygen, many polymers
contain other metallic and non-metallic elements in concentrations ranging from less
than one part per million up to several tens of percentage.
3.1 MINOR METALLIC CONSTITUENTS
3.1.1 Catalyst Residues
These are usually either residues left in the polymer after manufacture, such as
aluminium, titanium or vanadium in low pressure polyolefins, or are adventicious
metallic impurities left in the polymer after manufacture. As in many cases, trace
metals can adversly effect the chemical properties such as oxidative stability of the
polymer, it is important to control the level of such materials left in the fmal polymer.
Methods are reviewed below.
3.1.1.1 Iron, Aluminium and Titanium. see Method 65
3.1.1.2 Zinc.
The zinc content of chlorinated polymers has been determined by fusing the
sample with sodium peroxide followed by a standard complexometric titration of the
resulting solution. I
3.1.1.3 Aluminium.
Trace amounts of aluminium in polyethylene have been determined by gas

chromatography of volatile aluminium complexes with trifluoroacetone or pivaloy-
Itrifluoroacetone.2
3.1.1.4 Aluminium and Vanadium.
In Methods 66 and 67 are described procedures for ashing polyolefin samples

and ethylene propylene rubbers3 and the determination of aluminium and vanadium.
92
3.1.1.5 Chromium.
Traces of chromium in polyolefins originating from Phillips type polymerization

catalysts have been determined by spectrophotometric, atomic absorption
spectrometric and neutron activation analysis procedures.3'
3.1.1.6 Silica.
Commonly, nowadays, the active catalyst (based on chromium, titanium or

vanadium) used in high density polyethylene manufacture is adsorbed on to a highly
porous silica ,support. Determination of the silica catalyst support content of the final
polymer gives an assessment of the economic productivity of the reactor, ie. its output
of polyethylene per g of catalyst and also enables the very low concentration of active
catalyst metal in the polymer to be calculated
Battiste et al4 have described three methods for the determination of silica
catalyst supports in polyethylene, (Method 68).
3.1.1.7 Sodium and Lithium.
Another source of traces of metals in polymers are neutralizing chemicals

added to the final stages of manufacture to eliminate the effects of acidic catalyst
remnants on polymer processing properties (eg. mold corrosion) and on polymer
physical properties, (eg. hygroscopicity due to residual chloride ion).
Procedures for the determination of sodium and lithium in polyolefins are described in
Methods 69 and 70.
3.1.2 Adventicious Metallic Impurities
Atomic absorption spectrometry is a useful technique for the determination of

traces of heavy metals in polymers. Generally, the polymer is ashed at a maximum
temperature of 450°C to avoid losses of elements by volatilization, then the ash is
digested with warm nitric acid prior to spectrometric analysis, (Method 71).
Deacon et al36 have described a high performance liquid chromatographic
method for determining down to 30 ppm of eight divalent metals in polymeric
sealants.
Henn' has reported on a flameless atomic absorption technique with solid
sampling for determining trace amounts of iron, copper and chromium in polymers
such as polyacrylamide with a detection limit of approximately 0.0 I part per million.
The advantages of atomic absorption techniques as opposed to spectrophoto-
metric analysis for the determination of metals are that the former are amenable to
multielement analysis and can be automated. There is some evidence6•7 that ashing
polymers in silica crucibles rather than platinum can lead to up to 10% losses of
elements such as copper by adsorption within the silica matrix to produce a compound
that is not extractible by subsequent acid leaching. This does not occur when ashing
is carried out in platinum. If silica crucibles are used then a magnesium oxide ashing
aid should be employed as is demonstrated in the method for determining down to 0.1
ppm of copper in polyolefins, (Method 72).
93
Another method for avoiding losses of metals during ashing is the low
temperature controlled decomposition technique using active oxygen. This method
bas been studied in connection with the determination of trace metals in PVC,
polypropylene and polyethylene terephthalate.8
X-ray fluorescence spectrometry has several advantages over other methods.
The analysis is non-destructive, specimen preparation is simple, measurement time is
usually less than for other methods and x-rays interact with elements as such, ie. the
intensity measurement of a constituent element is independent of its state of chemical
combination. However, the technique does have some drawbacks, ego absorption
effects of other elements present, for instance, the carbon and hydrogen of the
polyethylene matrix and excitation of one element by x-rays from another, ego
cadmium and selenium mutually affect one another.
Cook et al9 studied the determination of chromium, manganese, iron, cobalt,
nickel, copper and zinc in polybutadiene, polyisoprene and polyester resins. The
samples were ashed and the ash dissolved in nitric acid prior to x-ray analysis. No
separation schemes are necessary and concentrations as low as 10 ppm can be
determined without inter-element interference. Many investigators have obtained
much higher recoveries using various ashing aids such as sulphuric acid, 7 elemental
sulphur1o•1I magnesium nitrate7•14 and benzene and xylene sulphonic acids l2 than by dry
ashing.
Leyden l5 used x-ray fluorescence spectrometry to determine metals in acid
digests of polymers. The aqueous solutions were applied to filter paper discs. He
found that recoveries of metals by the x-ray technique was 101 - 110% compared to
89 - 94% by chemical methods of analysis.
3.2 METAL CONTAINING ADDITIVES
In addition to traces of metals due to catalyst remnants, metal containing

processing chemicals and adventicious impurities, polymers might also contain higher
concentrations of metals. Examples of this include metallic stearate heat stabilizers in
PVC and fire retardant additives such as antimony trioxide in acrylics and polyolefins.
Such elements can be determined by atomic absorption procedures such as that
described in Method 71.
3.2.1 Antimony
Ogure l6 bas described a method for the determination of antimony trioxide in

polypropylene powder by extraction with aqueous hydrochloric acid followed by
atomic absorption spectrometry.
3.2.2 Arsenic.
Korenaga l7 has described an atomic absorption method for the determination

of trace amounts of arsenic in acrylic fibres containing antimony oxide fire retarding
agent, (Method 73).
94
3.2.3 Tin
Udris l8 and Belpaire l9 described various procedures for the quantitative

analysis of organotin stabilizers.
Tin can be also determined in PVC by polarography and atomic absorption
spectrometry30 and in PVC foils by x-ray fluorescence analysis. 31
3.2.4 Zinc.
Radovici et at2° reported on a polarographic method for the micro-

determination of zinc in polyesters.
3.3 ORGANIC AND INORGANIC PIGMENTS
Organic and inorganic pigments are used for colouration of polymers, polymer
films and polymer coatings. Vapour phase ultraviolet absorption spectrometry at 200
nm has been used21 to identify such pigments. In this method powdered samples are
directly vaporized in the heated graphite atomizer. Thermal ultraviolet profiles of
organic pigments show absorption bands between 300 and 900°C, while profiles of
inorganic pigments are characterized by absorption bands at temperatures above
900°C. Temperature, relative intensity and width of the bands allow the identification
of the pigments. The technique shows fast acquisition of thermal ultraviolet profiles
(2 - 3 min for each run) good repeatability and wide thermal range (from 150 to
2300°C). The method has been applied to a variety of polymers, (Method 74).
Hsu and Marshall 32 identified dyes in solid poly(methylmethylacrylate) by laser
desorption Fourier Transform Ion Cyclotron Resonance Mass Spectrometry. Accurate
mass measurements identified several red and orange dyes in untreated
poly(methmethacrylate) at an order of magnitude lower (0.1%) than obtained by
infrared attenuated total reflectance spectroscopy (1 - 2%).
3.4 NON-METALLIC ELEMENTS
As in the case of metals, non-metallic constituents such as halogens, nitrogen

and sulphur can occur in polymers in amounts ranging from a few parts per million
(eg. traces of chlorine catalyst remnants in polyolefins) up to tens of percent (eg.
chlorine in PVC, nitrogen in polyamides).
A variety of techniques have been used for the determination of non-metallic
elements, ranging from modem non-destructive techniques such as x-ray fluorescence
spectroscopy to more classical techniques based on digestion of the sample followed
by an appropriate analytical finish. Generally, the modem techniques have the
advantages of speed of analysis, specificity and sensitivity but are costly to purchase.
For many applications the classical techniques will suffice. A particularly interesting
and rapid technique is that based on oxygen flask combustion. In this, a small
weighed portion of polymer wrapped in a paper container is supported in a platinum
holder and burnt in a sealed flask in pure oxygen. An absorbing solution in the flask
collects the combustion products which are then subsequently analysed by an
appropriate spectrophotometric or titrimetric technique.
9S
3.4.1 Halogens
Three basic types of methods exist for the determination of chlorine and other
halogens in polymers. These are based (i) on fusion of the polymer in a ground form
with sodium carbonate, followed by subsequent determination of the sodium halide
(Method 75), (ii) combustion of the polymer in an oxygen flask containing an
absorbing solution followed by determination of halide ion (Methods 76 - 78)2 and
(iii) non-destructive methods based on x-ray fluorescence spectrometry of the poly-
mer.
Both silver nitrate (Methods 75 and 77) and mercuric nitrate (Method 78) have
been used to titrate halides following sample digestion.
Mittenberger and Gross24 determined chlorine in PVC by fusion with sodium
peroxide followed by silver nitrate titration of the chloride produced. Tanaka and
Morikawa2s described a semimicro technique for the determination of total chlorine in
PVC using a semimicro method based on the Schoniger oxygen flask and Fajans
method.
Morett33 has described a l3C NMR method for the determination of chlorine
in polystyrene. Qi and Pickup37 used x-ray emission analysis to determine the ratio of
chlorine to sulphur present in copolymers based on poly (3-methyl thiophene).
Johnson and Leonard26 have described a method (Method 79) for the determination of
fluorine based on decomposition of the sample by oxygen flask combustion followed
by spectrophotometric determination of the fluoride produced by a spectrophotometric
procedure involving the reaction with the cerium III complex of alizarin complexan
(1,2-dihydroxy-anthraquinone 3-ylmethylamine N,N-diacetic acid).
3.4.2 Sulphur
An oxygen flask combustion procedure is described in Method 80 for the

determination of sulphur in amounts from 50 ppm upwards in polyolefins and other
polymers.
Sodium peroxide fusion in a metal bomb has also been used27 to decompose
polymers prior to the determination of down to 50 ppm sulphur. In the procedure
described in Method 81 sodium is removed from the fusion product by means of a
cation exchange resin and the sulphate is determined by titration with standardised
0.005M barium perchlorate. Chlorine, fluorine and nitrogen in amounts up to 2 mg.
in the sample are without serious effect on the determination of sulphur. The effect
oflarger amounts of fluorine can be suppressed by the addition of boric acid.
The method described in Method 82 for the determination of macro amounts
of sulphur in polymers is based on combustion of the sample in an oxygen filled flask
over a solution of hydrogen peroxide. The amount of sulphuric acid produced is
determined by titration with 0.005 M or 0.0005 M barium perchlorate the equivalence
point being obtained photoelectrically. The use of a photoelectric method of end-
point detection overcomes the difficulties associated with visual end-point detection
described in Methods 80 and 81 as it makes the assessment of end-point independent
of invididual operators observation of colours.
Inductively coupled plasma atomic emission spectrometryl3,34 has been used
to determine sulphur in polymers.
96
3.4.3 Nitrogen
Various methods are available for the determination of nitrogen in polymers.

The first method (Method 83) based on kjeldahl digestion - boric acid titration, is
designed to determine very low concentration (50 - 100 ppm) of nitrogen in polymers
and as such is suitable for the determination of low concentrations of nitrogen
containing additives in polymers (eg. 0.25% Nonox CI antioxidant in polyolefins).
Method 84 also based on kjeldahl digestion - boric acid titration, is suitable for the
determination of much higher concentrations of nitrogen (1 - 90%) in nitrogen
containing copolymers. Method 85 has a wide range of application (0.002 - 75%
nitrogen) and is based on kjeldahl digestion with a spectrophotometric indophenol
blue finish for the determination of the ammonia produced on digestion of the poly-
mer. The final method (Method 86) is based on micro dumas combustion and is
capable of determining nitrogen in the range 1 - 50% in copolymers. This method is
available in a commercially produced automated version (eg. the Perkin Elmer CHN
Analyser).
Hernadei 9 has described an alternative procedure based on pyro-
chemiluminescence which he applied to the determination of 250 to 1500 ppm
nitrogen in polyethylene. In this technique the nitrogen is the sample is subjected to
oxidative pyrolysis to produce nitric oxide. This when contacted with ozone produces
a metastable nitrogen dioxide molecule which, as it relaxes to a stable state, emits a
photon of light. This emission is measured quantitatively at 700 - 900 nm.
3.4.4 Phosphorus
Two oxygen flask methods are described in Method 87 and 88 for the
determination of phosphorus in polymers. The first is applicable in the range 0.01 to
2% phosphorus and the second in the range 2 to 13% phosphorus.
A further method for the determination of organic phosphorus is based on
digestion of the sample with concentrated sulphuric - perchloric acids, followed by a
spectrophotometric finish (Method 89).
Phosphorus has been determined28 in thermally stable polymers by
mineralizing with a nitric-perchloric acid mixture and subsequent titration with
lanthanum nitrate or by photometric determination of the phosphomolybdenum blue
complex.
97
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25. Tanaka, Y. and Morikawa, T., Kagaku to Kogyo (Osaka), 48 (10) 387 (1974);
Chern. Abstr., 82 98702w (1974)
26. Johnson, C.A. and Leonard, M.A., Analyst (London), 111lOl (1961)
27. Colson, A.S., Analyst (London), 113 791 (1963)
28. Kalinina, L.S., Nikitina, N.I., Motorina, M.A. and Sedova, I.V., Plast. Massy.,
566 (1976)
29. Hernandez, H.A., International Laboratory 84 September (1981)
30. Fassy, H., Lalet, P., Chern. Analyst, 521281 (1970)
31. Havranek, E., Bumbalova, A., Kapisinka, V., Chemicky Prum., 20 536 (1970)
32. Hsu, A.T., Marshall, AG., Analytical Chemistry, 60 817 (1988)
33. Morrett, S., Horowicz, Analytical Chemistry, 521529 (1980)
98
34. Di Pasquale, G., Caselta, B., Atomic Spectroscopy, 5 209 (1984)
35. Haukka, S., Analyst (London), 116 1055 (1991)
36. Deacon, M, Smyth, M.R., Leonard, R.G., Analyst (London), 116 897 (1991)
37. Qi, Z., Pickup, P.G., Analytical Chemistry, 65 696 (1993)
99
CHAPTER 4
COMPOSITIONAL ANALYSIS
Functional group analysis and the determination of monomer unit concentrations
can be used to determine the monomer composition and hence the empirical formula of a
copolymer qr terpolymer. Thus, if a styrene-butadiene copolymer contains 6% (6/56
moles) bound butadiene and 94% (94/104 moles) bound styrene, then the empirical
formula is:
Sty ,&Bu 94 StYS.44 Bu

6 104
ie. there are 8.44 moles of styrene per mole of butadiene in the copolymer.
4.1 STYRENE BUTADIENE COPOLYMERS
The compositional analysis of styrene butadiene copolymers is discussed in

Section 2.1.1.
Some other examples are discussed below of the application of these principles to
copolymer and terpolymer analysis.
4.2 ACRYLONITRILE-BUTADIENE - STYRENE TERPOLYMERS
Acrylonitrile can be determined via a determination of organic nitrogen by the

Kjeldahl procedure (Section 3.4.3). Styrene units can be determined by infrared
spectroscopy. Butadiene units can be determined by the iodine monochloride procedure
(Section 2.1.1). Some typical results obtained on an ABS terpolymer are presented
below:
Analysis of Analysis of Analysis of

original polymer chlorobenzene isolated-
soluble fraction chlorobenzene
(56%) of original insoluble gel
polymer (44%) content
of original
polymer
Butadiene (B) 20.5 30.8 10.3

Acrylonitrile (A) 23.8 22.1 27.6
Styrene (S) 54.0 48.0 62.0
100
Total 98.3 100.9 99.9
Empirical formula ABo.813 Suss AB1.320 SU03 ABO.3S3 SU46
Oxidation with osmium tetroxide has been used as the basis for a method of
determining bound butadiene in acrylonitrile - butadiene - styrene terpolymers. 1
4.3 NATURAL RUBBER, STYRENE-BUTADIENE RUBBER AND ETHYLENE-

PROPYLENE-DIENE TERPOLYMER IN CURED STOCKS
Krishen2 has described a procedure for the determination of these monomer units
(Method 90). He quantitatively analysed the gaseous pyrolysis products from natural
rubber, styrene-butadiene rubber and ethylene-propylene diene terpolymer rubber by gas
chromatography. He showed that the 2-methyl-2-butene peak was linear with the natural
rubber content of the sample. Styrene-butadiene rubber was determined from the peak
area of the 1,3-butadiene peak. The ethylene-propylene-terpolymer content was
deducted from the I-pentane peak area of the pyrolysis products.
Miller et al61 used transmission spectroscopy in the near infrared region (1100 -
2500 nm) to determine cis-l,4 butadiene, trans-l.4 butadiene and 1.2 butadiene units in
butadiene rubber and styrene-butadiene rubber in bulk and in carbon tetrachloride
solution.
4.4 STYRENE ISOPRENE COPOLYMERS
Prime62 coupled a thermogravimetic analyser and an atmospheric pressure

chemical ionization tandem triple quadruple mass spectrometer system to carry out
evolved gas analysis on isoprene-styrene copolymers thereby obtaining information on
comonomer ratios.
Thermogravimetric analysis has also been coupled63 with gas chromatography
!mass spectrometry and with gas chromatography to obtain information on styrene-
isoprene block copolymers.
4.5 ALKENE COPOLYMERS
4.5.1 Ethylene-Propylene Copolymen
An infrared spectroscopic method for the determination of bound ethylene in

ethylene propylene copolymers is described in Method 91. This method utilizes the
absorbance of the 732 cm· 1 infrared absorption band attributed to (gamma)r (CHv3
groups characteristic of an ethylene unit isolated between two head to tail propylene
units;
4.1
101
Dekmesian and Morioka64 applied Fourier Transform infrared spectroscopy to the
fractions obtained by gel permeation chromatography of ethylene-propylene rubbers.
Varlous other workers have studied the application of infrared spectroscopy to the
determination of propylene groups in ethylene-propylene copolymers. This work is
summarized in Table 4.1.
13C NMR spectroscopy has also been applied to the determination of the ethylene
propylene ratio in these copolymers. so
. Carbon 13 NMR has proved to be an excellent technique for analysis of sequence
distributions and comonomer contents in ethylene-propylene copolymer. 18 . 26 These
analyses are particularly straightforward if one of the monomer units is present at a level
of 94% or greater because the other monomer will then occur primarily as an isolated
unit.
Paxton and Randalf7 used carbon-13 NMR (Method 92) and infrared
spectroscopy (see Method 91) to measure the concentration of ethylene is ethylene-
propylene copolymers. These polymers contained greater than 95% propylene, with the
ethylene units present as isolated entities between two head-to-tail propylene units.
These workers point out that most infrared bands used for determining copolymer
compositions are sensitive to sequences of both monomers. This infrared method for
compositional analysis can be calibrated if: (a) known standards of similar consitiution to
the copolymers being analysed are available and (b) assignments and behaviour of the
calibration bands are well established; preferably the absorptivities of these bands should
be relatively independent of the position of monomer units in the chain. Thus,
quantitative infrared analysis of copolymers depends primarily on the standards
employed whose composition can be determined directly and reliably. Paxton and
Randalt2' used 13 C-NMR (Method 92) to provide such reference standards for the less
time-consuming infrared measurements by Method 91. Because it is reletively
inexpensive and easy to operate for copolymer analysis they showed that an excellent
correlation is obtained between 13 C-NMR and infrared results on a series of ethylene-
propylene copolymers containing greater than 95% wt% propylene.28
4.5.2 Ethylene-Butene Copolymers
A method29 is discussed below for the determination of the composition of an

ethylene-butene-l copolymer containing up to about 10% butene. This technique has
been applied to the pyrolysis gas chromatography of ethylene-butene copolymers.
Pyrolysis were carried out at 410°C in an evacuated gas vial and the products swept into
the gas chromatograph. Under these pyrolysis conditions, it is possible to analyse the
pyrolysis gas components and obtain data within a range of about 10% relative. The
peaks observed on the chromatogram were methane, ethylene, ethane, combined
propylene and propane, isobutane, I-butene, trans-2-butene, cis-2-butene, 2-methyl-
butane and n-pentane.
A straight line relationship exists between the amount of ethylene produced on
pyrolysis and the amount of i-butene in the ethylene - butene copolymer. The y intercept
of 16.3% ethylene should represent that amount of ethane which would result from a
purely linear polyethylene. An essentially unbranched Phillips-type polyethylene poly-
mer yielded 14.5% ethylene, which is fairly close to the predicted 16.3%.
102
Table 4.1 - Application ofInfrared Spectroscopy to the Determination of Propylene in
Ethylene-Propylene Copolymers
Wavelength Related to Comments Ref
7.25 (CCl. solution) 7.25 methyl groups High scatter in results 3-5
Ratio 13.95/8.7 Propylene content in Results adversly affected by 6-8
(solid film) range 30 - 50"10 polymer crystallinity
propylene
Ratio 7.25 band (solid Propylene content Calibrated versus CI4labelled 9
diecast film) and ethylene or propylene copolymers
product of absGrb- by plotting ratio 7.25/6.55 versus
ance by the halfwidth % propylene weight fraction
of the 6.85 hand
7.25 and ratio 7.25, methyl groups Copolymers containing 30% 10
8.612.32 (CCI. propylene
solution)
Ratio 1.69211.764 1.692 CH3 groups Applicable to copolymers containing 11
(CCl. solution) 1.764 CH2 groups 15 - 52% propylene
13.7 and solid film 13.70-13.89 crystal- Calibrated versus known compos- 40
scanned at 180°C line phase ition copolymers prepared with 15-17
13 .89 amorphous C14 labelled ethylene
phase
Ratio 11.00/11.25 11.00 vinyl groups Ratio 11.00/11.25 varies with 14
pyrolysis of film 11.25 vinylidine propylene content of copolymer
at 450°C groups copolymers ctg >8% propylene 12,13
In this method, accurately prepared standard copolymers are required for

calibration purposes. Physical blends of the two homopolymers, polyethylene and
polybutene-I will not suffice as these behave differently in the methods to the true
copolymers. An excellent method for preparing such standards is to copolymerize blends
of ethylene and 14C labelled butene -I of known activity. From the activity of the
copolymer determined by scintillation counting its butene -1 content can be calculated.
Numerous methods have been applied to the anal~sis of I-butene-olefin
copolymers, including pyrolysis gas chromatography,29,30,2 differential thennal
analysis32 x-ray crystallography34 and meltin~-point fractionation. 3S The most widely
adopted technique is infrared spectrom~4. 3 either using a heated cell to eliminate the
effects of crystallinity, or more simply by scanning a film of known thickness and
comparing the absorbance to those of standards. Infrared is the easiest method to run and
the least demanding in equipment. It requires, however, a set of standards for calibration
of the instrument used. These standards have in the past been ~uently obtained by
copolymerization of 14-C tagged monomer and radioassay.14,3 This technique
introduces additional manipulations and the possibility of isotope effects and is time-
consuming.
Fisch and Dannenberg41 have reported that for the analysis of propylene butene-I
copolymers containing up to 11 % bound propylene, satisfactory calibration standards can
be obtained using l3-C NMR analysis.
Other NMR methods for the determination of the composition of olefms copoly-
mers are tabulated in Table 4.2.
103
4.5.3 Ethylene -Alpha Olefin Copolymers
Hatfield et al 69 applied melt state MAS 13C NMR to the determination of

comonomer types and composition in ethylene-alpha olefin copolymers. Melt state I3 C
NMR with magic angle spinning and dipolar coupling was used for this analysis and
gave the advantages of reduced analysis time and the ability to analyse samples which
were not amenable to solution state NMR. Hatfield et al 69 examined five different
ethylene -alpha olefin copolymers; one cross linked ie. insoluble. Good agreement was
obtained between melt and solution NMR methods.
4.6 OTHER ETHYLENE COPOLYMERS
4.6.1 Ethylene-Vinyl Acetate Copolymers
Jones and McCIelland65 have demonstrated the application of transient infrared emission
spectroscopy (TIRES) to quantitative compositional analysis of ethylene-vinyl acetate
copolymers. Standard errors are less than 1%.
4.6.2 Ethylene - Tetrafluoroethylene Copolymers
Morelli et al66 used evolved gas mass spectrometry to carry out compositional
analysis of ethylene-tetrafluoroethylene copolymers. The technique responded to the
HF+ signal observed in the evolved gas analysis mass spectrum.
4.7 ACRYLIC COPOLYMERS
4.7.1 Styrene-Acrylate Copolymers
Anderson et al 51 determined acrylate units and styrene units in copolymers of

acrylic acid or methacrylic acid with styrene, vinyl chloride and acrylamide by a
combination of techniques. Acrylate groups were determined by carrying out a Ziesel
reaction with hydrogen iodide to convert acrylate groups to alkyl iodides which were
determined by gas chromatography. This method is discussed in further detail in the
earlier section on the determination of ac~late groups (Section 2.7.1., Method 62).
Styrene units were determined, I as described in Method 93, by infrared
spectroscopy at 700 cm·' (l4.28u) which is the phenyl ring out of plane mode. This
frequency provides specificity, freedom from interferences and an absorption that is
directly proportional to the styrene content.
Cheng-Yu Wang et aI'° applied pyrolysis gas chromatography to the deter-
mination of the structure of styrene-n-butyl acrylate copolymers. The number average
sequence length which reflects monomer arrangement was calculated using formulae that
incorporate pure trimer peak intensities and hybrid trimer peak intensities.
The degree of structure ie. number average sequence lengths also composition
were determined for styrene-n-butyl acrylate copolymers and compared to those obtained
for homogenous ie. non-structured (random) copolymers.
104
Table 4.2 - NMR Methods for Determining Copolymer Composition
Polymer Detennined Reference
Ethylene-propylene Propylene 42
Ethylene-propylene alpha- olefms 43
4-methyl-isopentene-l-pentene 4-methyl-l-pentene 44
Butene-propylene Butene 45
4-methy lpentene-I-pentene 4-methyl pentene 46
Propylene-butene Propylene 45,47,48
Propylene-vinyl chloride Propylene 49
4.7.2 Styrene-Methacrylate Copolymers
Evans et a1 S2 have described techniques employing pyrolysis - gas chrom-

atography, (Method 95) proton NMR (Method 94) and carbon analysis for the
determination of styrene and methacrylate units in styrene - methylmethacrylate and
styrene-n-butyl methacrylate copolymers. Agreement between the three independent
methods is excellent. The comparison stresses the complementary nature of all three
methods. The pyrolysis gas chromatography method possesses advantages such as
simplicity and rapidity.
Various other workers S3 -S8 have used NMR to determine methyl-methyl-
methacrylate in styrene - methmethacrylate copolymers.
Cheng Yu Wang and Smith71 used pyrolysis gas chromatography to carry out
quantitative analysis and microstructure determination of styrene-methyl methacrylate
copolymer. Compositional analysis was achieved by measurement of monomer peak
intensities. Due to the poor stability of methyl methacrylate oligomers, neither methyl
methacrylate dimers or trimers were detected under normal pyrolysis conditions. The
number average sequence length for styrene units was determined from pure and hybrid
trimer peak intensities. The number average sequence length for methyl methacrylate
was determined using formulae that incorporate composition and the number average
sequence length of styrene units.
4.7.3 Methylmethyacrylate - Metbacrylic Acid Copolymers
In titrating copolymers of methyl methacrylate and methacrylic acid with

standard base to determine composition, a number of deficiences have been encountered.
For example, there were two common sources of "contamination" that gave rise to
underdermination of the acid content: I), the copolymers tended to be hygroscopic and
hence, could on occasion contain up to 5% absorbed moisture and 2), they could, on
occasion, retain solvents and/or monomers. Additionally, the method has been found to
be inapplicable to copolymers of high molecular weight (MW > 106) and/or high acid
content (> 60% acid) because of the tendency of such systems to reprecwitate during the
titration procedure. Because of these limitations, Johnson et al s examined the
applicability of Fourier Transform \3 C NMR to the compositional analysis of
methylmethacrylate acid copolymers, (Method 96). In pyridine solutions of these
105
copolymers, the resonances arising from acid carboxyl and ester carbonyl carbons are
sufficiently resolved to allow the determination of relative integrals.
4.7.4 Butyl Methacrylate-Methyl Methacrylate Copolymers
Transient infrared emission spectroscopy (TIRES)6S and transient infrared

transmission spectroscopy (TIRTS)6 have both been applied to quantitative
compositional analysis of butyl methacrylate methyl-methacrylate copolymers. Standard
errors are less than 1%.
4.7.5 Acrylic Acid-Methacrylic Acid Copolymers
Sharp and Patterson68have described a pyrolysis - gas chromatographic procedure

(Method 61) for the determination of up to 10% of copolymerized acrylic acid and
methacrylic acid in acrylic copolymers.
4.7.6 Functional Group Analysis of Acrylic Copolymers
The determination of carboxyl, ester and epoxy groups in various acrylic

copolymers is discussed in Section 2.7.1. In many cases such analyses enable copolymer
analysis to be carried out.
4.7.7 Vinyl Chloride-Vinylidene Chloride Copolymers
Chang Yu Wang and Smith72 used pyrolysis - gas chromatography to elucidate

the composition of and carry out structural studies on vinyl chloride-vinylidene chloride
copolymers. The number average sequence length, which reflects monomer arrangement
in the copolymer, were calculated using formulae that incorporate pure trimer and hybrid
trimer peak intensities.
Due to the difference in reactivity between vinyl chloride and vinylidene chloride
monomers the structure of the polymer was further investigated on the basis on the
percentage of grouped monomers (ie. the number average sequence length for vinyl
chloride and vinylidene chloride repeat units). The results obtained for compositional
analysis achieved by this method and by H NMR were in excellent agreement. In the
method 2.5 mg of sample was pyrolysed in a quartz tube, equilibriated for 5 minutes at
180°C, then pyrolysed at 700°C for 20 seconds using a pyroprobe CD5190 with platinum
coil. Gas chromatography was carried out using a flame ionization or mass spectrometric
detector.
4.8 HEXAFLUOROPROPYLENE - VINYLIDENE FLUORIDE COPOLYMERS
Two methods have been described for determining the compositional analysis of
these copolymers, one based on high resolution continuous and Fourier Transform 19 F
NMR and the other on pyrolysis - gas chromatography,33 (Method 97).
4.8.1 19 F NMR.
When it is desired to measure the composition of a single component in a

mixture, it is necessary to relate the component resonance to that of another compound,
106
an internal standard, which is of known chemical composition and has been added in
known weight to a known weight of unknown. Brame and Yeager31 used dichloro-
benzotrifluoride as an internal standard in the continuous wave method for determining
the compositional analysis of both repeat units in hexafluoro-propylene-vinylidene
fluoride copolymers. This work demonstrated the utility of the Fourier transform NMR
method in quantitative analysis of the copolymer in relation to results obtained by
continuous wave 19 F NMR and proton NMR.
The lines observed are attributed to the following:
CF3 group (delta = -70 to -75), CF2 groups (delta = ~90 to -120) and CF group
(delta = -180 to -185).
The results of the determination on a copolymer sample are given in Table 4.3.
The value obtained is in excellent agreement with those obtained by mass balance.
4.8.2 Pyrolysis - Gas Chromatography.
Blackwe1l33 used a Curie point pyrolyser to carry out quantitative analysis of

monomer units in polyhexafluoropropylene - vinylidene fluoride (Method 97). The
polymer composition is calculated from the relative amounts of monomer regenerated
and the trifluoromethane (CHF3) produced during pyrolysis. The exact mechanism by
which trifluoromethane is produced during pyrolysis is not known but it is presumed that
the free trifluoromethyl group is cleaved from the polymer backbone. The
trifluoromethyl group then extracts a proton from the polymer chain to form
trifluoromethane.
i I rill
4.2
3
AH
-c-c-c-c-c-c- -+ CF3H +
IIIIII
F H F F H F
F F H F
I
- c - c· +
III
·c - c - c - c-
II
F H
III
F F H
I
F
107
Table 4.3 - HFPNF 2 Copolymer Compositions
Sample Mass balance, wt % VF 2 FT-NMR
wt"10 HFP
A 48±2 46.6 ± 1.1&
• Precision at 95% confidence level. From Brame and Jaeger)l. American Chemical Society
108
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CHAPTER 5
ADDITIVE MIXTURES
Generally speaking, the methods described in Chapters I and 2 for the

detennination of additives in polymers refer to particular known additives or, at least, to a
particular class of additives such as phenolic antioxidants. Frequently, however, the
analyst is faced with the problem of dealing with unknown additives in polymers, either
single additives or, more commonly, mixtures of additives. He has first to identify the
additive then detennine it, usually in a mixture with other additives, which may interfere
in the detennination of the additive in which he is interested.
A variety of procedures have been evolved for handling this situation. Naturally,
since mixtures may be involved, chromatographic techniques feature strongly in the
repertoire of analytical methodology available. These include gas chromatography, high
perfonnance liquid chromatography, liquid column chromatography, supercritical fluid
chromatography and thin layer chromatography. Any of these separation techniques
might be coupled with an identification technique such as mass spectrometry and infrared
spectroscopy or, indeed, in some instances, these latter techniques may be applicable
without a prior chromatographic separation. Generally, however, chromatography will be
required.
A further technique is based on pyrolysis or photolysis of the polymer additives
followed by gas chromatography and/or mass spectrometry of the products produced in
order to facilitate their identification and, consequently, the identity of the original
additive. First, however, and certainly in the case of chromatographic techniques, it is
necessary to quantitatively separate the additives from the polymer and to determine the
elements present in the polymer and in extracts. These aspects are discussed below.
It is advisable when commencing the analysis of a polymer for unknown additives
to detennine first its content of various non-metallic and metallic elements as discussed in
Chapter 3. Any element found to be present must be accounted for in the subsequent
examination for, and identification of, additives. Hence, elemental analysis reduces the
possibility of overlooking any additive which contains elements other than carbon,
hydrogen and oxygen. The analytical methods used to detennine elements should be
sufficiently sensitive to detennine about 10 ppm of an element in the polymer, ie. should
be able to detect in a polymer a substance present at 0.01% and containing down to 10%
of the element in question.
This requirement is met for almost all the important elements by use of optical
emission spectroscopy and x-ray fluorescence spectrometry and other classical methods
discussed in Chapter 3. X-ray fluorescence spectrometry is applicable to all elements
with an atomic number greater than 12. Using these two techniques, all metals and non-
metals down to an atomic number of 15 (phosphorus) can be determined in polymers at
the required concentration (Cook et al,· Hous and Silverman,2 Mitchell and O'Hear3 and
Bergmann et al4). Nitrogen is determinable at these levels by micro Kjeldahl digestion
techniques.
111
5.1 SEPARATION METHOD FOR ADDITIVE MIXTURES
Squirrel' has described general analysis schemes for the examination for the
presence of additives and process residues in PVC, polyolefins and acrylics.
Foreknowledge of the types of additives present is not required in these schemes, which
are therefore very useful when examining polymers of unknown composition. In the
schematics shown in Figures 5.1 to 5.3, the major points to note are as follows. Where
identification, particularly of minor organic components is required, then some separation
from the plastic compound is often necessary. Special care and specialised techniques are
required when dealing with laminates and surface-coated films. For major components
the separation is made quantitatively and the analysis is completed by various techniques.
For volatile components, separation, identification and quantification can often be carried
out in one analytical process.
5.1.1 Solvent Extraction Methods
The main extraction procedures used are summarised in Table 5.1 and although
most of them can be carried out on material cut to a particle size of less than 2 mm
diameter, it is often advantageous to produce material of a smaller size and with a larger
surface area to mass ratio. This is conveniently done by grinding at the temperature of
liquid nitrogen using an efficient and easily cleaned cutter mill.
The extraction of additives strongly adsorbed or chemisorbed on the polymer
filler matrix must be carefully watched by the analyst, as a change of the method of
manufacture of, for example, the filler or in the method of compounding the plastic
formulation, can also markedly alter the degree of adsorption being produced and hence
invalidate an established quantitative extraction procedure. The use of "stronger"
extraction reagents can cause complications at the measurement stage and hence each
system must be carefully screened and frequently checked. Polymer extraction
procedures using organic solvents do not extract all types of organic additives from
polymers, also many inorganic compounds and metal inorganic compounds (eg. calcium
stearate) are insoluble. The presence of metals will have been indicated in the
preliminary examination of the polymer. Most types of organic polymer additives,
however, can be readily extracted from polymers with organic solvents of various types.
The first stage is to solvent-extract the total additives from the polymer in high yield and
with minimum contamination by low molecular polymer. Extracts should be used for
analysis without delay as they may contain light or oxygen sensitive compounds. When
delay is unavoidable, storage in actinic glassware under nitrogen in a refrigerator
minimises the risk of decomposition.
Total internal plus external additives can be extracted from low and high density
polyethylene and polystyrene by procedures involving solution or dispersion of the
polymer powder or granules (3 g) in cold redistilled sulphur-free toluene (50 - 100 ml),
followed in the case of polyethylene by refluxing for several hours. Rubber-modified
polystyrene does not completely dissolve in toluene if it contains gel. Methyl ethyl
ketone or propylene oxide are alternative suitable solvents for polystyrene. Dissolved
polymer is then reprecipitated by the addition of methyl alcohol or absolute ethanol (up to
300 ml) and polymer removed by filtration or centrifuging. The additive-containing
extract can then be gently concentrated to dryness as described previously. Alternative
procedures for the extraction of polyethylene and polypropylene involve refluxing with
chloroform for 6 hours or contacting with cold diethyl ether for 24 hours or soxhlet
extraction with diethyl ether, methylene dichloride, chloroform or carbon tetrachloride for
112
I
PVC COMPOSITION
Extract with dlethyl ether
I I
SOLUBLE INSOLUBLE
I
Plasticisers.
I
PVC polvmer. filler.
most lubricants. pigment. stabillser.
most stabilisers. modifier. processing ald.
UV absorbers residual tJlastlclser.
emulsilier. lome lubricants
Extract with methanol I
I
SOLUBLE INSOLUBLE
Some stabifisers. PVC polymer. filler.
emulsifiers. pigment. stabiliser,
residual blowing agent modifier. processing ald.
residual plasticiser.
some lubricants
Extract with tetrahvdrofuran and

cenlriluge 3 000 rev min - ,
SOLUBLE INSOlUSlE
PVC polvmer, processing aid. Filler. pigment, stabiliser.
residual pla5ticiser. some modifiers
modifier lin suspension),
some lubricnnts
Centrifuge at
17000 rev min-'
SOLUBLE INSOLUBLE
PVC polvmer, processing aid, Modifier.
residual plasticlser, some filler
some lubricants
Add methanol
:
SOLUBLE
I
INSOLUBLE
Residual plasticiser. PVC polymer,
some lubricants processing aid
Figure 5.1. Analysis of PVC compositions. From Squirrel5 with pennission. Royal Society of Chemistry,
London
113
Analysis of acrylic samples
Dissolve
I
Powder Sheet in
I aceto, ne
I
Dissolve
"'---C-~~13 ~R IR, CentrifUge
T,'trat,'on
I
I T,'trat,'on Add
" A d d light petroleum
Opacifying
agents
Peroxides UV
I
Monomer, methanol I
water I Separate
Decant ~
Plasticisers, L Precipitate Modifiers
UVabsorbers I I
So~V" po,!m.. ' ' 'ito

Catalyst Plasticisers,
residues lubricants
Figure 5.2. Analysis of acrylic samples. From Squirrels with permission. Royal Society of Chemistry,
London
Analysis of polyolefine.
Direct
examination of ,
Identification
Separation
Granules
and
sheet
Fir GLC --HPLC--TLC
I
I
I II
I R, Values
Determination
I I Fluorescence
XRF IR IR
GLC UV GLC
XRF Colorimetric
GLC UV·
HPLC
MS
UV IR MS NMR Spray
Ethanol solution reagents
Ethanol- KOH
Ethanol- NiO,
Ethanol· NiO, • KOH
Figure 5.3. Analysis of polyolefines. From SquirrelS with permission. Royal Society of Chemistry,
London
114
6 - 24 hours followed by concentration of the extract. Methylene dischloride is a partic-
ularly good solvent for polypropylene extraction because of its high volatility. In add-
ition to additives, most solvents also extract some low molecular weight polymer with
subsequent contamination of the extract. To overcome this, Slonaker and Sievers l6 have
described a procedure for obtaining polymer-free additive extracts from polyethylene
based on low temperature extraction with n-hexane at OoC. This procedure is also
applicable to polypropylene and polystyrene.
5.1.2 Solution Precipitation Methods
This method of extraction involves dissolution of the organic phase of the plastic
composition in a suitable (sometimes hot) solvent, followed by precipitation of the
polymeric constituents, often in a finely divided form in suspension with the inorganic
fillers, by cooling or by means of another solvent in which the analyte compound is also
soluble. This method is labour intensive but very effective and if it does not completely
release any chemisorbed constituents from the polymer, for example filler matrix, it will
often leave them in a form very vulnerable to attack by the analytical reagent(s) finally
used in the determination. .
5.1.3 Vacuum Thermal Displacement Extraction Method
These procedures are used extensively for the direct isolation or release of volatile
components from a polymeric matrix and may involve the combined use of vacuum and
heat, as for example in the mass spectrometer direct insertion probe or during dry vacuum
distillation. Alternatively, the volatiles may be swept from the heated sample by a flow
of inert gas for concentration by freeze trapping and/or collection on to a solid adsorbent
prior to thermal or solvent desorption for gas-chromatographic or mass spectrometric
examination
5.2 CHROMATOGRAPHIC METHODS OF SEPARATION
When the above procedures for preliminary isolation of the analyte materials from
the polymer matrix are completed, further separation is often required for identification
and determination.. Four forms of chromatography are generally used; gas chrom-
atography (section 5.2.1), thin layer chromatography (section 5.2.2), high performance
liquid chromatography (section 5.2.3) and more recently supercritical fluid
chromatography (section 5.2.4).
5.2.1 Gas Chromatography
Gas chromatography in all its forms with appropriate detectors and, when
necessary, temperature programming, heart cutting and back-flushing techniques, is used
extensively for volatile components.
Headspace methods are used extensively for the determination of residual
monomers and other residues in polymer compositions after dissolution or dispersion in a
suitable solvent and equilibration in a sealed vial at constant temperature prior to
chromatography of the headspace gas. For samples in the form of fine powders or thin
films, the technique can be applied directly to the solid and liquid samples. (Tables 5.2
and 5.3).
115
Table 5.1 - Examples of Extraction Methods
Extraction Method Polymer or Solvent(s) Additives or Contaminant

Compound Extracted
Single solvent (Soxhlet) PVC Diethyl ether Plasticisers

Single solvent (reflux) Polyethylene Chloroform-I,I,I- Antioxidants
trichloroethane
Solvent + reagent (reflux) Polypropylene Ethylene dichloride- Chemisorbed
trichloroacetic acid amideslamines
Polyester Methanol-Karl Fischer Water
reagent
Solution/precipitation Polyoletines Toluene-methanol, UV absorbers, antioxidants,
xylene-methanol slip agents
Acrylics Acetone-light petroleum Plasticiser, lubricants
Steam/solvent distillation Packaging films Water - diethyl ether Odour and taint-forming
additives
Vacuumlthennal Nylon Water
extraction Fluorocarbon Process fumes
polymers
The attraction of gas chromatography lies in its ability to simultaneously separate,

identify and estimate· sub milligram quantities of complex mixtures. There are certain
drawbacks to the technique. Retention times are no more specific for gas chrom-
atography than are Rr values for thin-layer and paper chromatography. Day-to-day
reproducibility of retention times is not good for some types of instruments, especially
when operating at high column temperatures. Since many polymer additives are not very
volatile, low stationary-phase loadings have to be used in order to reduce retention times
to a sensible value, which means that large areas of uncoated solid support appear which
in tum lead to bonding with compounds such as phenolic and amine antioxidants. This
results in distortion of peaks and in lengthening of retention times. There are measures
which can be taken to meet these difficulties. Thus, relative retention times are often
more reproducible than unadjusted retention times. Non-volatile sample components can
be converted into more volatile derivatives such as tri-methyl-silyl ethers. The solid
support can also be treated with hexamethyldisilazane, for example, to reduce the number
of active sites on the column material available for bonding. The formation of derivatives
before chromatography does, however, in some applications lead to sample loss and can
often lead to the appearance of spurious peaks on the chromatogram. Nevertheless,
despite these limitations gas chromatography has found numerous applications in the
identification, characterization and estimation of additives in polymers.
Gas chromatography is particularly useful for the characterisation of more volatile
substances such as mixtures of fatty acids or of alcohols, esters or hydrocarbons which
are used in polymer formulations. It has the advantage that it provides more information
regarding the carbon number distribution of each of these types of compounds than can
be obtained by infrared spectroscopy alone. Similarly, if the polymer is known or
suspected to contain dicarboxylic acids, polyol esters, polyhydric alcohols or alcohol
esters of phthalic, sebacic, adipic or azelaic acids, then frequently, information on the
type of compound present can be obtained by comparing under the same conditions the
retention time of the unknown with those of known authentic substances.
116
Table 5.2 - Some Examples of Gas Chromatographic Procedures Applied to Liquids
Solids Packaging films and printing solvent

(direct examination) residues, residual monomers
Polyethylene Catalyst carrier,
Granular polymers Polypropylene process residues,
Ethylene-vinyl acetate co- ethylene, vinyl
polymers acetate, acetic acid
PVC and co-polymers Monomers, moisture
Polymer powders Poly(ethylene terephthalate acetaldehyde
Foodstuffs Biscuits, cakes and crisps Migratory trace
monomers
Solids Polymer solutions PVC compositions, Residual monomers
(indirect (normally 10%) ABS
examination)
Table 5.3 - Some Examples of Gas Chromatographic Procedures applied to Liquids
Liquids Cooking oils, fruit squashes, Migatory trace monomers

Foodstuffs water, wine, spirits
Liquids Solution extracts of absorption Vinyl chloride in dichloromethane,
tubes (atmospheric acrylonitrile in benzyl alcohol,
monitoring) benzene in ethylene carbonate
Liquids Latices Butadiene, styrene, acrylate
monomers, methacrylate monomers
dimers and co-dimers
Liquids Whole blood Vinyl chloride from PVC trans-
Biological fusion sachets, trichloroethylene,
. samples trichloroethanol
Urine Trichloroethanol, trichloroacetic
acid
Some typical applications of gas chromatography to the determination of

antioxidants in polymers are tabulated in Table 5.4
5.2.2 Thin Layer Chromatography
For additives extracted from polyolefins, usually with diethyl ether, the extract is
refluxed with ethanol and the solution is decanted from the insoluble residual polymer.
On cooling, additives such as dilauryl and distearyl thiodipropionate separate out and are
identified by infrared examination. A 30 l.d volume of the ethanolic solution is then
spotted on to a thin Kieselgel 60 TLC plate and eluted with a suitable solvent, usually
98.5 + 1.5 toluene-ethyl acetate. The eluted plate is dried and sprayed with colour-
developing reagents and the spots are examined. If the spots are to be submitted to mass
spectrometric examination, methanolic iodine is used as the colour-developing reagent as
this does not over-complicate the mass spectrometry.
The normal spray procedure uses a 0.5% solution of 2,6-dibromo-ll-benzo-
quinone-4-chlorimine in ethanol followed, after drying, by a 0.5% borax solution. After
this spray the plate is dried at 120°C for 5 minutes to develop the colours.
117
Table 5.4 - Separation of Phenolic Antioxidants - Gas Liquid Chromatographic
Techniques
Substances separated Stationary phase Column Other details Ref

DC
2,5-Di-t-butyl-p-cresol, 25% LAC-2R1446 \35 H2 carrier gas, F.LD. 6

(2-hydroxy-5-methyl- (adipate ester) + 2% error± 1%
phenyl) benzotriazole Hl P04 on Chromosorb
2,6-Di-t-butyl-p-cresol, 10% Apiezon N on 164 H2 carrier, F.LD. 10- 7
2, 6-di-t-butyl-phenyl Celite 545 3 M in presence of
others can be detected
2,4,6-Tri-t-butyl phenol, Apiezon F.I.D. 8
Diphenylamine
2,6-Di-t-butyl-p-cresol
Halogenated bis-phenols 10% DC-710 Silicone 225- 12 in glass column Yo 9
oil on Chromoport 80- 250 in o.d. Carrier: \30 ml
100 mesh He/min
Low b.p. phenols Capi\lery column coated 125 F.I.D. 10
with 10% xylenol
phosphate
Phenols and 5-t-butyl Silicone oil 550-Carbo- 200 Mean deviation II
derivatives wax 400 (3:2) 0.4%
Phenols and cresols 5% WIW ofvarious 110 120 cm x 4.5 mm 12
phosphate esters of column Pye-Argon
phenols Chromatography
lonox 330 a) 20% DC-710 Silicone 200- a) 12 x 3/16in column \3
oil on Chromosorb 300 in.
b) 2% SE30 Silicone gum 10 minb) 12 x 1116in stainless
on Chromosorb mesh steel column
Low molecular weight Silicone-coated capillary Converted to trime- 14
phenol column thyl silyl esters before
chromatography
2,6-Di-4-methylphenol 20% SE30 on HMDS- 200 E.C. detector 15
treated 60 mesh
Chromosorb W
Some typical applications of thin-layer chromatography to the determination of

one type of additive, namely antioxidants, in polymers are tabulated in Table 5.5 (Rf
values) and Table 5.6.
5.2.2.1 Thin-layer Chromatography followed by Infrared, Ultraviolet and Mass

Spectrometry.
This technique, described in Method 98 is applied when it is required to identify

mixtures of additives in polymers. Firstly, it is necessary to separate total additives from
the polymer by a suitable solvent extraction procedure as discussed in Section 5.1. The
total extract is the subject to thin-layer chromatography to separate it into individual
additives which are then separately removed from the plate by scraping off bands of the
plate coating. The individual portions of plate coating are then each separately extracted
with a suitable low boiling solvent Jrior to examination by one or more of the afore-
mentioned spectroscopic techniques.
118
Table 5.5 - Thin-layer Chromatography ofPolYfuer Additives
Revalue·
Additive Solvent I Solvent 2 Solvent 3 Solvent 4 Colour of spot
TopanolOC 1.00 1.00 1.00 1.00 Pale yellow

centre with
pink outer
DLTDP 0.40 1.00 0.05 0.30 Yellow-brown
DSTDP 0.45 1.00 0.10 0.35 Yellow-brown
Distearyl disulphide 1.10 1.05 1.20 1.20 Bright yellow
DTB glycol ester 0.00 0.75 0.00 0.00 Brown centre
& mauve outer
lonox 330 1.05 1.05 0.80 0.80 Pinkish brown
Irganox259 0.30 1.05 0.00 0.65 Brown
Irganox 288 0.25 1.05 0.00 0.60 Brown
Irganox 1010 0.30 1.10 0.00 0.60 Brown
Irganox 1076 0.85 1.05 0.60 0.95 Brown
NonoxWSP 0.85 0.95 0.45 0.35 Bright yellow
centre with pink outer
Polygard 0.30,0.15 0.80,0.70 0.10 0.05 Blue and red
Santonox R 0.35 0.80 0.10 0.00 Purple
Tinuvin 326 1.05 1.05 0.95 1.05 Yellow
Tinuvin 327 1.05 1.05 1.05 1.10 Yellow
Tinuvin 328 1.00 1.00 1.00 1.05 Yellow
Topanol CA 0.10 0.60 0.00 0.00 Brown
UV531 0.75 1.00 0.35 0.80 Blue
BoechstD55 0.85,0.75 0.90,0.85 0.55,0.45 1.10,0.45 Blue and red
0.55,0.35 0.25,0.15 0.25,0.15
0.30,0.20 0.10,0.00
Oleamide 0.00 0.00 0.00 0.00 These additives
Erucamide 0.00 0.00 0.00 0.00 give only a very
Ethomeen T12 0.00 0.00 0.00 0.00 faint brown
Stearic acid 0.00 0.00 0.00 0.00 coloration
• Rr values quoted to the nearest 0.05. Solvent 1 = toluene - ethyl acetate (98.5 + 1.5); solvent 2 = toluene
- isopropanol (88 + 12); solvent 3 = toluene -light petroleum (b.p. 60-80 0c) (I + I); and solvent 4 =
cyclohexane - toluene - methanol (88 + 10 + 2).
Dohrman 68 discusses preparative-layer chromatography which, can separate considerably

larger Quantities of compounds on plate layers up to 2 mm thick and 100 cm x 20 cm in
area. 29-'2
5.2.3 High Performance Liquid Chromatography
This has now become a very valuable tool for plastics analysis,73-77 particularly in
the additive field. This technique can be used with both reverse-phase and adsorption
columns and isocratic and gradient elution.
One of the difficulties of column chromatography is the problem of identifying the
fractions in which the separated compounds are concentrated. This can be achieved by
the laborious process of examining all the fractions, for example, by infrared or
ultraviolet spectroscopy or by evaporating to dryness and weighing the residues; or by the
less laborious process of monitoring the effluent as it leaves the chromatographic column
so that solute-containing fractions from the fraction collector can be picked out from the
fractions which do not contain any substances. Several types of effluent monitors are
available, based on the measurement of the ultraviolet absorption, conductivity, etc.
119
Table 5.6 - Separation of Antioxidants - Thin-layer Chromatographic Methods
Substances Stationary Mobile phase Detection Ref

separated phase
Phenolic Silica Gel G Methanol-cyclohexane 30% Molybdoph- 16

antioxidants (1:24) osphoric acid +
amonia vapour
Organo-tin Not stated Acetic acid-isopropyl 20".4 Molybdoph- 17
stabilizers ether (1.5:98.5) osphoric acid +
amonia vapour
Antioxidants Not stated Light petroleum-ethyl a) Ethanolic 2,6- 18
acetate (9:1) dichloro-p-benzo
quinone-4 chlor-
imine + 2% aq.
Nal B.07
b) Diatzotized
p-nitroaniline
Organic KieselgelG Ethanol-free 19
stabilizers chlorofonn
Phenolic Polyamide Methanol-water (3:2) Diazotized sulph- 20
antioxidants powder or methanol-carbon anillic acid
tetrachloride (1 :9)
Phenyl salicylate, Kieselgel G Dichloromethane Ultraviolet 21
Resorcinol or isoproyl ether-light
benzoate petroleum (40-60".4)
(7:3)
BHA,2,6-di-t- Silica gel Chlorofonn 20".4 Molybdophos 22
butyl-p-cresol -phoric acid +
amonia vapour
Antioxidants Polyamide Methanol-acetone Diazotized sulpan- 23
powder -water (6:1:3) ilic acid or moly-
bdophosphoric acid
Antioxidants KieselgelG alpha, alpha'- 24
Diphenyl-beta-
picryl hydrazyl
(free radical)
Antioxidants Alumina + 5% Petrol-dioxan (10:1) 5% Ethanol, phos- 25
plaster of paris phomolybdic acid
on microscope
slide
Antioxidants Silica gel Acetone, chlorofonn, 26
benzene, carbon tetra-
chloride or binary
mixtures
Antioxidants a) 10% starch Methanol-acetone- 27
in polyamide water (3: 1: I) light petro-
powder leum-benzene-acetic acid
b) 10".4 PVC in DMF (40:40:20:1)
polyamide
Antioxidants Silica Gel G Benzene 0.5% FCJ(SO.h 28
in sulphuric acid
+ 0.2% K.Fe(CN)6
1:1
120
These have the disadvantage of beihg too specific for dealing with mixtures of
compounds of unknown type. For example, compounds which do not either absorb in the
ultraviolet or ionize would be missed using these detectors. The most useful general
purpose monitors are those based on the measurement of refractive index and on thermal
effects. The latter operates on the principle that as each separated compound moves
down the column it is accompanied by heat of absorption and desorption due to
interaction between solute molecules and the stationary phases. These heat pockets (ie.
separated compounds) are detected by a thermistor at the column outlet and recorded on a
strip chart which can be operated in conjunction with a fraction collector. Thus,
separated fractions can be readily located and bulked if necessary for further examination.
The most recent development in liquid chromatography, namely high pressure liquid
chromatography, combines the advantages of built-in detectors with improved resolution
in the separation of mixtures due to improved column packings and operation at an
elevated pressure. A number of high-efficiency liquid chromatographic supports are now
available. These include Zipax (DuPont's CSP SUpport)46,48,49 Corasil I and n47-49 and
Durapak (Waters Associates).49 With the exception of Durapak, these materials in the
micron particle range, consist of particles with a solid core and thin porous coating. This
unique combination gives very high coefficients of mass transfer. Durapaks consist of
conventional liquid phases, such as J3,J3'oxy-dipropionitrile, chemically bonded to a rigid
porous bead. Textured glass beads for liquid-liquid chromatograEhy similar to those
reported for gas chromatography44 have been developed by Coming. 5
Fig. 5.4 shows a chromatogram of a mixture of antioxidants and ultra-violet
absorbers. A reversed-phase system is again preferred because it can be washed clean
with methanol but this time an isocratic solvent system is used. With the variable
wavelength detector, the optimum wavelength can be set for the type of compounds being
examined.
Majors 51 has described a high performance liquid chromatographic system for the
determination of antioxidants in polyethylene and plasticizers in PVC, (Method 99).30-
41,52
5.2.4 Supercritical Flow Chromatography78-79
Raynor et al 7l separated additives in complex mixtures by capillery supercritical

flow chromatography and deposited the separated products in potassium bromide discs
prior to measurement of their infrared spectra by FTIR spectroscopy. Supercritical flow
chromatography coupled with F.T. infrared spectroscopy (SFC-FTIR) has been used to
provide quantitative information on and characterization of a range of polymeric
surfactants. 80 Bartle et alSO and Chester70 also investigated this technique.
5.3 MASS SPECTROMETRY
Like other forms of molecular spectroscopy, mass spectrometry84,85 may be used

as a "fingerprint" technique to identify the components of additive systems extracted
from polymers. The strengths of mass spectrometry are high sensitivity and the ability to
distinguish between closely related compounds of differing relative molecular mass, ego
the various alkyl thiodipropionates used as synergistic stabilisers in polyolefins and the
ultraviolet absorbing benzotriazole derivatives. Often it is not necessary to separate the
components before examination as some separation may be achieved by careful variation
of the sample probe temperature to produce in effect, a fractional distillation of the
components. The presence, however, of large amounts of low relative molecular weight
121
E
Figure 5.4. Determination of additives from polypropylene by HPLC. Chromatographic

conditions: column Spherisorb ODS (5pm), 100 x 5 mm; solvent, 90% VN methanol: flow-rate 40 cm3h'l;
detection, absorbance at 280 mm and 0.2 a.u.f.s. A, injection (lOpl); B, solvent front; C, Topanol CA,
10.12 mg per 50 em3 ; 0, Tinuvin 326, 4.96 mg per 50 em 3; and F, Irganox 1010, 10.10 mg per 50 em3•
polymers such as polyethylene and polypropylene can cause interference by producing a

high hydrocarbon background extending to several hundred relative atomic mass units.
In such instances thin-layer chromatographic separation can be used as a clean-up
procedure.
B1estos72 produced time of flight secondary ion mass spectra of thick films of
poly(dimethylsiloxane) and fluorocarbon polymers containing additives in the range mlz
up to 4500. The spectra obtained were characteristic of the polymer and its additives or
any surface contamination.
5.3.1 Static Secondary Ion Mass Spectrometry (SSIMS)86
Rudewicz and Manson 53 have reported a method for the determination of

additives in polypropylene without prior separation by solvent extraction or precipitation
techniques, (Method 100)54. The additives are vaporized from polypropylene samples in
a heatable glass probe under chemical ionization conditions using a 1.1 % ammonia in
methane reagent gas mixture. The dominant ion in this mixture, NH4 + is a low energy
reagent ion that reacts with the additives to give very simple spectra of (M + H)+ or (M +
122
NHtt ions and little fragmentation. The detection of additives in a hydrocarbon matrix is
very selective.
5.3.2 Liquid Chromatography - Mass Spectrometry
The infonnation obtained by absorbance detection when coupled with liquid

chromatography is usually not specific enough to allow the qualitative identification of
compounds present in complex polymer samples with any degree of certainty. With the
use of mass spectrometric detection Vargo and Olsonss showed that characteristic mass
spectral data can be obtained which greatly aid in elucidating the identity of unknown
compounds. They used mass spectrometric detection in series with absorbance detection
to identify or characterise antioxidants and ultra-violet light stabilizing additives in plastic
materials, which were separated by liquid chromatography, (Method 101).
5.3.3 Gas Chromatography - Mass Spectrometry
Polymers contain trace amounts of residues of the organic catalyst used in their
preparation and the identification of these is often necessary. The use of gas
chromatography is conjunction with mass spectrometry is required in order to separate
the complex mixture of components that are extracted. For example, tetra-
methylsuccinodinitrile has been detected in extracts of polymers prepared using
azobisiso-butyronitrile catalyst. Substantial losses of tetramethylsuccinodinitrile occur in
the evaporation of methanolic solutions which explained earlier difficulties in detecting
residues of this catalyst. Even without concentration of the polymer extract it was
possible to achieve a lower limit of detection of 20 ppm in the polymer.
A further family of catalysts often used are peroxides (eg. benzoyl or lauroyl
peroxide), these produce acids as residues which may be detected by mass spectrometry
or by methylation of the evaporated extract prior to gas chromatography - mass
spectrometry examination.
.The analyst in the plastics industry may be required to trace the cause of odour
and taint produced in foodstuffs packaged in plastic materials. This provides good
examples of the use of high sensitivity gas chromatography - mass spectrometry in the
identificatic;lO of such compounds. Two methods have proved useful for the concentration
of these components.
(A) Where the sample is a sealed plastic bag the headspace gas from the bag (or
many bags) is withdrawn through an adsorption tube normally packed with Porapak Q.
The trapped organic species are then thermally desorbed for gas chromatography - mass
spectrometry examination. This has enabled residual printing and coating solvents in the
bag headspace to be identified as causes of odour and taint.
(B) For containers and foods, the Likens and Nickerson combined solvent
extraction - steam distillation procedureS6 has proved useful. The advantage of this form
of extraction is that large amounts of sample may be extracted with a small volume of
organic solvent prior to further concentration by evaporation. In this procedure the
evaporation of the organic solvent can concentrate trace amounts of solvent impurities to
a significant proportion of the final extract and redistilled solvent. Therefore, distilled
rather than deionised water is used as deionized water can contain trace organics from the
resin bed. A blank extraction is always carried out. Extracts can be examined by gas
chromatography - mass spectrometry.
123
5.4 ADDITIVE DEGRADATION TECHNIQUES
5.4.1 Photolytic Degradation - Gas Chromatography
Juvet et al" showed that characteristic reaction products occur during photolytic
degradation and polymer additives may on this basis be identified without separation
from the polymer samples. The excellent reproducibility reported for photolytic
degradation of liquid samples indicated the possibility of quantitative determination of
polymer additives (Method 102). They developed equations to predict the shape of
calibration curves expected for both trace level additives and those present at higher
concentration. Photolytic degradation has been shown to yield simple and more
reproducible decomposition patterns due to greater control of input energy and the more
predictable manner in which compounds decompose photolytically.
Since photolytic analysis does not require separative steps and can be performed
with samples weighing less than a milligram, it provides a rapid, practical approach for
the determination of additives in polymeric materials.
5.4.2 Pyrolysis - Gas Chromatography - Mass Spectrometry
Pyrolysis - gas chromatography has been used for many years for the character-
isation of plastics materials, particularly when they are of an intractable nature owing to
cross-linking or are very heavily filled. The technique has now been extended to include
mass spectrometry and is of particular value when minor components need to be
identified. An example has been described by Sharp and PatersonS8 for the identification
of small amounts (1- 10%) of copolymerised unsaturated acids in acrylic polymers. The
method can be summarised as follows:
CH 3 R CH 3 R
5.1
-
I
C - CH 2 - -
I
C - CH 2 - ...
propylation I
C - CH 2 -
I C - CH 2 -
I
c=o
I
c=o
I
c=o
. I c=o
I
OCH 3 n
I
OH m
I
OCH 3 n
I OC 3 H7 m
CH 3 R
I I
pyrolyais
.. C=CH 2 C =CH 2 + alcohols, alkenes, CO 2 , etc.
I
c=o C=O
I
I
OCH 3
I
OC 3 H7
The copolymerised acid is propylated by treatment of the sample with Propyl 8
reagent, the resultant polymer is pyrolysed and the propyl ester of the acid, if present, is
identified by gas chromatography - mass spectrometry. By this procedure copolymerised
acrylic or methacrylic acid has been identified in terpolymers with (a) butyl acrylate and
styrene, (b) methyl methacrylate and ethyl acrylate and (c) ethylene and propylene. A
methyl methacrylate - alpha-methylstryene - maleic acid terpolymer, when examined by
124
this proylation - pyrolysis procedure, yielded dipropyl fumarate and a smaller amount of
dipropylmaleate.
- CH 2CCOOH Me - CH Ph - CH Me - CHCOOH - CHCOOH - ...
pyrolysis
5.2
- CH 2 - CCOOH Me - CH Ph - CH Me - CHCOOC3H7 - CHCOOC 3H7 -
pyrolysis
.... -CH2 - CCOOH Me - CH Ph - CH Me - +
COOC3H7 COOC 3H7 COOC 3H7
+
~ /
CH = CH +
I
CH=CH
I
COOC 3H7
5.5 INFRARED SPECTROSCOPY
5.5.1 Infrared Laser Raman Spectroscopy81-83
Although both of these spectroscopic methods have a wide use in their own right,
the example given below demonstrated well the complementary value of the two
methods, taking advantage of the fact that elements of high atomic number, ego antimony
and bromine, have relatively more intense Raman spectra but the lighter elements show
up clearly in the infrared spectra.
An example of the application of these techniques is the identification of additives
in PVC. When a sample of PVC was examined by infrared spectroscopy the strongest
bands (9.8 and 14.9 um) were due to a talc-type material and bands of medium intensity
were assigned to polypropylene and possibly antimony trioxide (13.4 um). Additional
weak bands in the 7.3 - 7.7 um region were possibly due to decabromodiphenyl ether. In
the Raman spectrum, however, the strongest bands (250 and 185 cm-' shift) confirmed
the presence of antimony trioxide and some bands of medium intensity confirmed the
presence of decabromodiphenyl ether (doublet at 140, triplet at 220 cm-l -l shift) and
polypropylene (800, 835, 1150, 1325, 1450 and 2900 cm- -1 shift). The silicate bands
that obscured the regions of the infrared spectrum were not observed in the Raman
spectrum.
Examples of other spectroscopic techniques that have been applied to the
identification of additives in polymers are given in Table 5.7.
5.5.2 Laser Desorption - Fourier Transform Techniques
These relatively new techniques viz laser desorption/ionization Fourier transform

mass spectrometry and fast atom bombardment87 and laser desorption Fourier transform
ion cyclotron resonance mass spectrometry88 have been applied to the determination of
non volatile polymer additives (thioester, phosphite, phosphonate and hindered amine
antioxidant types) and antioxidants, ultraviolet absorbers and amide waxes.
5.5.3 Gas Chromatography - Infrared Spectroscopy
The direct application of gas chromatography to the identification and

determination of unknown additives in polymers has its limitations. Amongst these are
125
the fact that retention times are purely relative and not always exactly reproducible; even
when the chemical class of the sample constituents is known, identification by
comparison of the retention times of the unknown with those of standards requires exact
reproduction of column operating conditions. Difficulty can also arise when non-
symmetrical peaks are produced; the peak-maximum retention time of a component then
depends on concentrations. Peaks can also overlap and certain combinations of
substances are often difficult to separate.
Chromatographically a single peak is no criterion of purity, since more than one
substance may be present, the components present could often be resolved if their
presence was suspected and alternative column operating conditions were selected.
Confirmation of homogeneity of fractions is therefore required together with
unequivocal identification and accurate quantitative determination of the product. The
analytical method used should involve some property of the molecule other than boiling
point. Often, only fractional milligram amounts of material can be recovered from a
column. Of the few techniques that are applicable to these small quantities of material,
mass and infrared spectroscopy are particularly suited.
The use of fraction collecting techniques in conjunction with gas chromatography
is now well establisheds9-6s and is an attractive proposition in additive identification
problems, despite the fact that little published work has yet appeared on the application of
this technique to polymer additives. In this technique the separated compound as it
emerges from the gas chromatographic column is swept by the carrier gas through a cold
trap where it condenses. The material in the trap is then either transferred to an infrared
gas cell for examination in the vapour phase, or is transferred as a liquid to a suitable
micro cell or may be condensed on a cold surface as a solid for examination by
conventional spectroscopic techniques.
Anderson66 has described in detail a technique for collecting individual products
separated from mixtures by gas chromatography followed by their identification by
vapour phase infrared spectroscopy using a double beam spectrometer. He claimed that
the technique would identify and determine to within ± 2% amounts as Iowa S umole of
all substances having a boiling point up to about 17SoC. Heated gas cells enable liquids
of higher boiling point to be examined. Naturally, as the infrared spectrum of a
compound in the liquid and vapour form are different, it is necessary to compare spectra
obtained by the above technique with spectra of standard vapours. Generally speaking,
the additive constituents of polymers have boiling points which are appreciably higher
than 200°C and hence cannot be handled in infrared gas cells. For such substances,
infrared examination as a liquid or a solid, as is discussed in Method 103 is more
relevant.
Volatile constituents are, however, sometimes encountered, viz expanding agents,
plasticizers, lubricants, adhesives, solvents, monomers and degradation products of
additives or of the polymer itself and infrared gas cell techniques can be of value in the
examination of gas chromatographic fractions containing these types of substances.
Haslam et al67 have studied in detail the collection of volatile and liquid fractions
emerging from a gas chromatographic column and their subsequent identification by
infrared spectroscopy. They applied these techniques to various polymeric materials
encountered in the plastics industry (Method 103).
126
Table 5.7 - Other Techniques Applied in Plastics Analysis
Technique Principal use
X-ray diffraction Identification of crystalline additives in situ (eg hydrates),

Identification of polymer phases
NMR Identification of additives after extraction. Calibration of
infrared methods (structure). Identification of "bound" additives
Wide-line NMR for liquid - solid phase blends
ESCA Surface composition studies, eg presence of slip additive and
antistatic agents at polymer surfaces
MOLE Particulate contamination at or near film surfaces
SIMS Ultra-surface analysis: catalyst studies
Spectrofluorescence Degradation studies: surface oxidation; study of scintillation
additives
127
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130
CHAPTER 6
PRELIMINARY QUALITATIVE IDENTIFICATION OF

POLYMERS
The polymer analyst working in industry is frequently asked to identify a polymer
or at least to give an opinion as to the type of a polymer. This might arise as a result of
an interest in the materials being used by competitors or manufacturers of components or
packaging materials. Obviously, if a detailed examination of a polymer or copolymer and
its additive system is required then other chapters of this book should be referred to.
However, if a quick opinion is all that is required then some simple physical and
chemical tests and the preliminary qualitative identification or fingerprinting approach
discussed in this chapter might suffice.
Simple Pbysical and Chemical Tests
Physical and chemical tests considered here are elemental analysis, saponification
number, solvent solubility, ignition tests, colour reactions and burning/heating tests.
6.1 PRELIMINARY REMOVAL OF ADDITIVES FROM POLYMERS
Chemically pure high polymers are rarely used in practive. They are usually
mixed with additives. As these additives influence the reactions of the plastic it may be
necessary to remove them by one of the methods listed below before attempting to
identify the polymer by the methods listed above under Physical and Chemical Tests.
A. Fractional precipitation (Table 6.1.1)
(a) The polymer is first completely diluted in a good solvent. The resulting
plastic solution is stirred into at least 10 times its amount of a solvent which acts as a
precipitant for the dissolved plastic but which combines completely with the first solvent.
The precipitated plastic is separated from the solvent mixture by centrifuging or filtration
and is pulverzed and repeatedly extracted with the precipitant/solvent or redissolved in a
good solvent and precipitated. This treatment provides additive-free polymer. (See Table
6. 1.1 a)
(b) The plastic is dissolved in a solvent which dissolves the plastic at higher
temperatures; the plastic separates out on cooling while the additives remain in solution.
(See Table 6. 1.1 b)
(c) Plastic dispersions can often be separated by nUllifying the action of the
emulsifier and/or dispersing agent. The following methods can be used according to the
type of emulsifier. (See Table 6.1.2)
1. Alteration of the· solvent phase, ie. addition of a further solvent to coagulate the
polymer. (Table 6.1.2a)
131
2. Precipitation of the emulsifier by the addition of acids or a counter interfacially
active ion. (Table 6.1.2b)
3. Freezing the dispersion out with dry ice. (Table 6.1.2c)
4. Subjection of the dispersion to dialysis, whereby the water-soluble inorganic
salts and relatively low-molecular emulsifiers are diffused through cellophane
membranes so that the protective colloid and the polymerizate can now be
easily separated quantitatively by centrifuging. (Table 6.1.2d)
B. Separation by Fractional Extraction. (Table 6.1.3)
Fractional extraction can be used in three ways, depending on the substance under
examination:
(a) Finely shredded solid polymers are extracted in a Soxhlet apparatus with a set
of solvents of increasing solvent power. Some of the extracts will contain polymer and
some will contain the additives. (See Table 6.l.3a)
(b) To ensure that the polymer particles are fine enough to allow the components
to be extracted to diffuse sufficiently quickly, a solution or dispersion of the polymer is
poured over an inert carrier, such as silica gel or sterchamol, the solvent is allowed to
evaporate from the solid phase and the carrier is then extracted in a heatable column with
solvents of increasing solvent power to isolate a solution of the polymer. (Table 6.1 jb)
(c) The components of a polymer are distributed between two non-miscible
liquids in separating funnels or distribution apparatus with the correct selection of
solvents, one phase will contain the additives and the other will contain the polymer.
(Table 6.1.3c)
C. Separation by Diffusion. (Table 6.1.4)
The polymer is precipitated from a solution or dispersion in a glass vessel as a

thin film on the inner wall. Then a solvent which is a non-solvent towards the polymer is
added in several stages. This solvent will dissolve certain additives, ego plasticizers
leaving an additive free film of polymer on the inner wall of the vessel. (Table 6.1.4)
D. Separation by Dialysis or Electro-Dialysis. (Table 6.1.5)
This method has only been used for separating low-molecular salts and
interfacialy active substances from protective colloids and high polymer polymers and for
fractionating pure polymers according to their molecular weight.
Some examples of these procedures are given in Table 6.1.
6.2 CLASSIFICATION OF POLYMERS
6.2.1 Classification By Elements
An undoubtedly incomplete classificatiori of polymers based on elemental

classification and saponification number is provided in Table 6.2. Note that copolymers
are not included in this list.
A cautionary note is that, in addition to the polymer itself, the polymer additive
system may contain elements other than carbon, hydrogen and oxygen. The detection of
an element such as nitrogen, sulphur, halogens, phosphorus, silicon or boron in a polymer
132
Table 6.1 - Examples of Separating Procedures
Plastic Operation Aim or separating

procedure
6.1.1 Fractional precipitation procedures (precipitation by addition of non-solvent for polymer to solvent
solution of polymer)
Polyvinyl chloride Stirring of a concentrated Plasticizers, emulsifiers

solution of tetrahydrofuran remain in solution, PVC and
into methanol its co-polymers are
precipitated
Polyacrylate Stirring the solution in Emulsifiers, watersoluble
acetone into 20 times the resins and salts remain in
amount of water solution, polymerizate is
precipitated
Polyacrylate Water is added to the Emulsifiers, watersoluble
solution in acetone until resins and salts remain in
faint turbidity occurs, solution, polymerizate is
acetone then distilled off precipitated
under vacuum
6.l.1a Fractional precipitation (thermal precipitation of polymer from solution at low temperature)
Polyethylene Dissolve in enough benzene Polymerizate is precipitated

to make a clear solution additives soluble in cold
appear when warmed then benzene, paraffin, waxes,
cool resins remain in solution
6.1.2 Emulsion breaking methods
6.1.2a Addition of solvent
Polymethacrylate- Dispersion is stirred into 20 Polymerizate is precipitated

dispersions times its amount of emulsifier and any protect-
methanol or isopropanol ive colloid remain in
solution
6.1.2b Emulsifier precipitation by acid addition
Rubber or butadiene Dispersion is broken by After acidifying, fatty or

acidifying as long as soap resin acid is extractable with
is used as the emulsifier ether; latex is precipitated
6.1.2c Freezing out dispersion by cardice addition
Polyvinyl acetate or Action of emulsifier Polymerizate is precipitated,

silicone oil dispersions destroyed by cold can now be filtered off or
centrifuged off
6.1.2d Application of dialysis
Polyvinyl acetate ester Salts and low molecular In the dialyzate, salts and
or polyacrylate emulsifiers are dialyzed emulsifiers, in the dialyzate
dispersions residue, protective colloid
polymerizate
6.1.3 Fractional extraction procedures
133
Table 6.1 continued
6.1.3a Solvent extraction of shredded plastic
Polyvinyl chloride Consecutive extractions with Isolation of stabilizers and

CC~, ether, bel)mne, CH2 plasticizers, recognition of
CCI2, tetrahydrqftjran copolymers or poly blends
6.l.3b Solution or dispersion of plastic passed over inert carrier on which plastic absorbs. solvent
evaporation from carrier. then desorbtion from camer with strong solvents
Polyethylene Consecutive extraction of In the gasoline: waxes; in

silica with gasoline, CH]OH: emulsifiers; in
methanol, CHCI], water, CHCI]; montan waxes in
methanol or acetone, then water: cellulose derivatives
benzene or toluene (perhaps and polyvinyl alcohol; in
warm) benzene!toluene: polyethylene
6.1.3c Plastics components distributed between two non-miscible liquids
Polyvinyl acetate Extracted from aqueous Isolation of plasticizers

methanol solutions or
dispersions with pentane!
ether mixtures
6.1.4 Separation by diffusion
Polyvinyl acetate Polymer precipitated with Isolation of the plasticizers,

Iigroin or Iigroin/ether can also be used for traces
mixtures
6.1.5 Separation by dialysis or electrodialysis
Polyacrylate see 6.1.2d
is indicative that the elements originate in the polymer and not the additive system if the
element is present at relatively high concentrations such as several per cent. This is
highlighted by the example of a high density polyethylene which might contain 0.2 - 1%
chlorine originating from polymerization residues and PVC homopolymer which contains
more than 50% chlorine.
Useful rapid tests for elements which can be used qualitatively or quantitatively
are tabulated in Table 6.3.
Haslam et at1 have adopted the oxygen flask combustion technique to the
qualitative detection in polymers ~f nitrogen, chlorine, bromine, iodine, fluorine, phos-
phorus and sulphur in amounts down to 0.25%, (see Method 104).
6.2.2 Classification By Solubility
This technique is of limited value, especially when applied to copolymers.

Solubility does not only depend on the type of the monomer base products but also to a
large extent on the degree of polymerization (ie. on the molecular weight) on the
branching and cross-linking of the molecules and on the sterlc configuration of the
polymerizate. Very efficient solvents can however be distinguished from the less
efficient ones for different plastics.
134
Table 6.2 - Elemental Analysis and Saponification Number
Principal elements C,H
Aliphatic Aromatic
Polyethylene Polystyrene
Polypropylene Polyindene
Polyisobutylene Polyxyleneyls
Polybutadiene Polymer petroleum fractions
Polyisoprene
Natural rubber
Butyl rubber
II Principal elements C,H,O
Saponification Saponification Saponification

number=O number = < 200 number = > 200
Regenerated cellulose Natural resin Cellulose acetate

Polyvinyl alcohol Modified phenoplasts Cellulose butyrate
Phenoplasts Cellulose acetate butyrate
Phenol-furfural resins Polyvinyl acetate and its
co-polymers
Xylene-formaldehyde resins Polyvinyl propionate
Cellulose ether Polyacrylate
Polymethacrylate
Polyvinyl ether Alkyd resins
Coumarone resins Polyester
Polyglycols Polycarboxylic acid anhydride
Polyvinyl acetals Polycarbonic ester
Polymer aldehydes
Polyketones
Epoxy resins
III Principal element, halogen
Polymer halogen olefins Rubber derivatives Others
Polyvinyl chloride (PVC) Chlorinated rubber Colophen resins

PVC co-polymers Rubber hydrochloride Chloronaphthalenes
Polyvinylidene chloride Chlorinated synthetic rubber Chlorinated paraffins
Poly-2-chlorobutadiene
Polychlorostyrene
Polytetrafluoroethylene
Polytrifluorochloroethylene
Polyvinyl fluoride
IV Principal elements N or Nand 0
Polyacrylic and polyvinyl Basic components of Others

compounds formaldehyde aminoplasts
Polyacrylonitrile Urea Nitrocellulose

Polyacrylamide Ethy lene urea Polyamides
Polymethacrylamide Propylene urea Polyurethanes
135
Table 6.2 continued
Polyvinylidene cyanide Dicyandiamide Polyureas

Polyvinyl pyridine Melamine Phenoplasts and epoxy
resins cured with amines
Polyvinyl pyrrolidone Acetylene diurea
Glyoxylureides
AniJines
V Principal elements, S in addition to 0
Products of synthesis Modified natural products
Polyethylene polysulphide Vulcanized rubber

Polydiethylether-polysulphides Sulphurized stand oils
Polythioether
VI Principal element, silicon
Silicon oils and rubbers

Silica acid esters
VII Principal elements, nitrogen and sulphur
Thiourea formaldehyde resins

Sulphonamide resins
Polyacrylamides, polyacrylimides
VIII Principal elements, halogen and sulphur
Sulphochlorinated polyethylene and its vulcanizates

Polychlorobutadiene, vulcanized with compounds containing sulphur
IX Principal elements, nitrogen, sulphur and phosphorus
Casein condensates
X Principal elements, phosphorus, nitrogen and halogen
Polyphosphoric nitrile chloride
Co-polymers usually dissolve in a greater number of solvents than homo-

polymers, ego poly(vinyl chloride) is only very slightly soluble in acetone or methylene
chloride, in which co-polymers with vinyl acetate or acrylates easily dissolve. Attempts
have failed to separate plastics according to their solubility in the same way in which
cations are separated in inorganic qualitative analysis. Table 6.4 summarizes the
solubility of plastics.
6.2.3 Classification By Colour Reactions
Colour reactions for particular homopolymers are listed in Table 6.5. These tests
are rather laborious and are perhaps best regarded as confirmatory tests for polymer
identifications achieved by other means.
136
Table 6.3 - Methods of Determination of Traces of Various Elements in Polymers
Element Procedure Ref Interferences
Sulphur up Combusted in oxygen-filled flask over 1,2 Chloride, fluoride, phosphate,

to 30mg dilute hydrogen peroxide solution nitrogen, boron and metals all
Potentiometric titration of sulphuric acid interfere
with N/IOO sodium hydroxide or Up to 2 mg chlorine, fluorine,
photometric titration of sulphate with nitrogen, boron and metals do
Nil 00 barium perchlorate not interfere in the
determination of I mg sulphur.
Phosphorus (up to 2 mg)
interferes in the determination of
sulphur (I mg) but this
interference can be overcome
using the procedure of Colson
(1,2)
Chlorine or Combustion as above
bromine
Chloride titrated potentiometricalIy with
N/IOO silver nitrate in presence of nitric
acid in acetone
Chlorine or Combustion as above 3 Up to 8 mg phosphorus,
bromine or fluorine, sulphur, do not
iodine Halide titrated with mercuric nitrate interfere in determination of 2
mgchlorine
Phosphorus, Digested with sulphuric acid/perchloric 4 No interference by sulphur,
0.1 g acid chlorine, fluorine, nitrogen
polymer Digest diluted with ammonium
vanadate/molybdate added. YelIow
phosphovandmolybdate complex evaluated
at430nm
Nitrogen Digestion carried out on O.S-I.Og polymer 6 No interference by chlorine and
a) Kjeldahl digest made alkaline and nitrogen
distilled into 4% boric acid. Ammonia
estimated by acid titration
b) Spectrophotometric estimation at 630
nm of phenol indophenol derivative
Fluorine 30 mg polymer combusted in an oxygen S No interference by large
filled flask over distilled water excesses of sulphur, chlorine.
Reacted with buffered alizarin phosphorus and nitrogen
complexlcerous nitrate, blue colour
produced evaluated at 610 nm
Silicon 30 mg polymer in gelatin capsule and No interference by sulphur,
combusted with sodium peroxide, sucrose halogens, phosphorus, nitrogen
and benzoic acid in 22 ml capacity Parr and boron
Bomb
Boron O.lg polymer digested with concentrated 6 No interference by chlorine and

nitric acid in a sealed ampoule to convert nitrogen
organoboron compounds to boric acid
Digest dissolved in methyl alcohol and
boron estimated flame-photometricalIy at
S.9.5nm
137
Table 6.4 - Summary of the Solubility of Plastics
Plastics Typical solvents Typical non-solvents
Polyethylene Benzene, xylene Gasoline, alcohols, esters

tetrahydronaphthalene hydrocarbon halides
Polypropylene Xylene, trichloroethylene Alcohols, gasoline, esters
chlorofonn
Polyisobutylene Gasoline, ether Alcohols, esters
Polybutadiene Benzene Gasoline, alcohols, esters
ketones
Polyisoprene Benzene Gasoline, alcohols, esters
ketones
Natural rubber Hydrocarbons and Gasoline, alcohols, esters
hydrocarbon halides ketones
Polystyrene Dioxane, benzene, Gasoline, alcohols
chlorohydrocarbons
Regenerated cellulose No solvent
Polyvinyl alcohol Water, fonnamide Gasoline, aromatic hydrocarbons
alcohols
Phenolic plastics uncured Alcohol, ketones Gasoline, hydrocarbon
halides
Phenolic plastics cured Insoluble and often infusible
Cellulose methyl ether Ethylene chlorohydrin, water Aliphatic and aromatic
dilute solution of caustic hydrocarbons
soda
Cellulose ethyl ether Methylene chloride/methanol Water, aliphatic and
aromatic hydrocarbons
Cellulose benzyl ether Acetone, butanol Water, aliphatic and
aromatic hydrocarbons
Polyvinyl methyl ether Water, methanol Gasoline
Polyvinyl ethyl ether Gasoline, aromatic hydro- Water
carbons, hydrocarbon halides
alcohols, esters, ketones
Polyvinyl butyl ether Aromatic and hydro- Methanol, ethanol
carbon halides, ketones
Polyglycols Water, hydrocarbon halides, Gasoline
alcohols
Polyvinyl fonnal Tetrahydrofuran, ketones Methanol, aliphatic
esters hydrocarbons
Polyvinyl acetal Tetrahydrofuran, ketones Methanol, aliphatic
esters hydrocarbons
Polyvinyl butyral Tetrahydrofuran, ketones, Methanol, aliphatic
esters, chlorofonn-methanol
(9+1)
Polymer aldehydes Ketones, esters Gasoline, alcohols
Polymer ketones Ketones, esters Gasoline, alcohols
Epoxy resins, uncured Alcohol, esters, Water, hydrocarbons
ketones, dioxane
Natural resins Alcohol, benzene, hydro- Gasoline
carbon halides, esters,
ether
Modified phenoplasts, Ethanol Aliphatic and hydrocarbon
accord. to cure halides
Polymethacrylates Esters, aromatic and chlor- Aliphatic hydrocrbons,
inated hydrocarbons, alcohols, ether
ketones, dioxane
Polyacrylates Aromatic hydrocarbons, Gasoline
hydrocarbon halides, esters
ketones, tetrahydrofuran
138
Table 6.4 continued
Polyvinyl acetate Aromatic and chlorinated Gasoline

hydrocarbons, methanol,
ketones
Polyesters Phenols, halogen phenols, Hydrocarbons, alcohols
nitrohydrocarbons, benzyl
alcohol
Alkyd resins Aromatic hydrocarbons, Hydrocarbons
hydrocarbon halides, hydro-
carbons, lower alcohols,
ketones, esters
Cellulose esters Ketones, esters Aliphatic hydrocarbons
Polyvinyl chloride Tetrahydrofuran Hydrocarbons, butyl acetate
alcohols
Polyvinylidene chloride Tetrahydrofuran, dioxane Alcohols, hydrocarbons
ketones, butyl acetate
Polyvinyl chloride co- Tetrahydrofuran, methylene Hydrocarbons, alcohols
polymer with vinyl acetate chloride
Acrylic esters Tetrahydrofuran, methylene Hydrocarbons, alcohols
chloride
Maleic esters Tetrahydrofuran, methylene Hydrocarbons, alcohols
chloride
Chlorinated rubber Carbon tetrachloride, ketones Aliphatic hydrocarbons
esters, tetrahydrofuran
Rubber hydrochloride Ketones Aliphatic hydrocarbons,
carbon tetrachloride
Neoprene Toluene, hydrocarbon Alcohols, esters
halides
Tritluorochloroethylene none
Tetrafluoroethylene none
Polyamides Formic acid, phenols Alcohols, esters, aliphatic
trifluoroethanol and aromatic hydrocarbons
Cellulose nitrate Lower alcohols, acetic Ether, benzene, hydro-
esters, ketones, etherl carbon halides
alcohol (3: I)
PolyacryJonitrile Dimethyl formamide, Alcohols, esters, ketones
nitrophenol, ethylene hydrocarbons
carbonate
Polyacrylamide Water Alcohols, esters, hydrocarbons
6.2.4 Classification By BuminglHeating Tests
These tests are of limited value although Biri3 has described a simple thermal
test for the identification of plastic films, (Method 105). The above tests are of limited
value nowadays becaused of the wide range of polymers now being manufactured and
certainly are probably of no value in the case of copolymers. Conventional low impact
polystyrene is soluble in hot toluene, whereas high density polyethylene or propylene
have little or no solubility in this solvent. However, if the polystyrene contains some
copolymeriZed butadiene, as occurs in the case of high impact polystyrenes, then due to
the presence of crosslinked gel, the polymer would not completely dissolve in hot
toluene. So even in the case of simple polymers solubility tests are of limited value and
for them to provide any useful information required detailed knowledge. Polystyrene on
the other hand, unlike the polyolefins when it is held in a flame, due to its aromatic nature
139
Table 6.S - Colour Reactions to Show Structures and Functional Groups
Plastics Reagent Reaction Functional group Ref

Responsible for
Colour Reaction
Polyvinyl Boric acid/iodine Greenish blue Hydroxy 8,9

alcohol
Cellulose Alpha-naphthollH2S04 Reddish violet Hydroxy 10
derivatives Aniline acetate Turns filter Acetyl 11
paper red
Anthrone Violet Acetyl 12
Polyvinyl ether Solution in acetic Blue-violet Ether 13-15
anhydride + cone,
H2SO4
Dichloroacetic acid Blue Ether 9
Coumarone Bromo-glacial acetic Tumsperm- Phenolic 16-17
resins acid with solution anently red
ofCHC~
Phenolic resins Diazotized 2-nitro-4- Red Phenolic 18
chloroaniline
2,6 dibromoquinone Blue Phenolic 19
FeCI] Green Phenolic 20
Millon's reagent Violet Aldehyde 11
Furfural Aniline acetate Turns filter 21,22
resins paper red
Epoxy resins Nitration reactions Epoxy 21,22
Mercuric sulphate Precipitate Epoxy 23
Paraformaldehydel Bright blue Epoxy 24,25
cone. H2S04
Reaction with pyridine Blue 13,14
or quinoline bases
Natural resins Acetic anhydrideIH2S04 Reddish violet 5
Polymethacry- Reaction of depolymeriz- Blue colouring 29
lates ates with cone. HNO, which can be
Znpower removed with
CHCI]
HCHOamino CarbazoleIH2S04 Dark blue
plastics
Hydrocarbon Solution in pyridine Red-brown Halogen 11,30,32
halides + methanolic KOH
will burn with a smoky flame. However, ifit is a non-flame grade it will not burn. PVC
will, when burnt, produce an acrid odour of hydrogen chloride, so will poly(vinylidene
chloride) and many copolymers containing vinyl chloride or vinylidene chloride. If the
polymer contained fluorine, smelling the odours produced on combustion might be a
hazardous operation as it would be in the case of acrylonitrile and polyurethane polymers
which, in these circumstances, are likely to produce hydrogen cyanide. Density
measurement, ie. whether the polymer sinks or floats in water is another simple parameter
that can be observed. It will distinguish polyethylene with a density of less than one from
a highly chlorinated polymer with a density of greater than one. However, if the
polyethylene contains lead stearate or iron oxide filler, its density may well exceed unity.
Enough has been said to indicate that with the exception of elemental analysis, in
many instances simpl,e physical tests just do not provide definitive information.
140
Qualitative or quantitative examination for the presence of elements and the pyrolysis gas
chromatograph or infrared fingerprinting approach, as discussed below, do however
provide more useful information and indeed in many cases will lead to a successful
resolution of the problem.
6.3 QUALITATIVE IDENTIFICATION BY PYROLYSIS-GAS

CHROMATOGRAPHY
Pyrolysis is an analytical technique whereby complex involatile materials are

broken down into smaller volatile constituent molecules by the use of very high
temperatures. Polymeric materials lend themselves very readily to analysis by this
technique. Providing that the pyrolysis conditions are kept constant, a sample should
always degrade into the same constituent molecules. Therefore, if the degradation
products are introduced into a gas chromatograph, the resulting chromatogram should
always be the same and a chromatogram uniquely characteristic of the original sample
should be obtained.
In one technique a pyrolyser probe is inserted into a purpose designed adaptor
which is installed in the injector unit of the gas chromatograph. Different types of
adaptor are available for packed or capillary column work. Correct selection of the
appropriate adaptor is a pre-requisite for optimum system performance. The choice of
packed or capillary pyrolysis gas chromatography is generally a matter of personal
requirements. The type and range of samples to be analysed, the complexity of pyrogram
required and the length of the analysis - all will playa significant role in decision making.
For the general examination of a wide range of rubbers or plastics, packed column
pyrolysis is more than adequate. However, for comparison of one batch of rubber with
another batch of the same rubber, the detail obtained from capillery pyrolysis gas
chromatography will probably give the best results because minor details can be
compared. Applications for pyrolysis are vast and include all types of synthetic
polymers, rubbers and plastics, as well as latexes, paints and varnishes; in fact, almost
any sample that contains involatile organic material that can be contained in a tube or
coated onto a platinum ribbon so that it may be pyrolysed.
Pyrolysis-gas chromatographic procedures have generally followed one of two
basic patterns. In the flash technique, a sample is deposited on an electrically heatable
filament, or placed in a boat in a furnace, and the gas chromatographic carrier stream used
to transport the pyrolyzate directly to the column. The alternative procedure involves
heating of the polymer in a separate enclosure, trapping the off-gases and admitting the
pyrolyzate to the chromatograph after a given collection interval. Each approach has
certain advantages and the type of information desired from pyrolysis - gas
chromatograms should therefore, dictate the sampling method to be employed.
6.3.1 Filament Pyrolysis
For qualitative identification a thin film of sample is usually coated onto

Nichrome or platinum spiral or is placed in a small boat so that the weight of the residue
remaining after heating can be determined. Although the filament may catalyze the
degradation, Jones and Moyles34 showed that with 30 - 30 ug 'samples the pyrograms
obtained with Nichrome, platinum or gold-plated platinum filaments are identical. The
power supply to the filament is generally controlled by a variable transformer and timed
by a stopwatch, but exact measurement of the filament temperature is difficult. More
elaborate automatic time and voltage controls have been suggested.3S,36 If desired, the
141
pyrolyzer temperature can also be manually programmed to obtain more rapid
equilibrium and the remove the pyrolysis products from the heated zone immediately
after they are formed. 37 For quantitative studies of the mechanism and the kinetics of
polymer degradation where accurate analysis of the volatile and non-volatile reaction
products obtained at a certain temperature and under closely controlled conditions is
required, it is preferable to employ preheated tube furnaces than to refine the design of
the filament-type pyrolyser. Despite the fact that the filament-type pyrolyzer does not
allow optinum control of degradation conditions the pyrograms are entirely satisfactory
for identification purposes when polymers of known composition are available for
comparison.
Giacobbo and Simon38 have described a very useful pyrolysis unit for microgram
samples. The material coated on a small ferromagnetic wire is pushed by means of a
magnet into the pyrolysis capillary which is surrounded by an induction coil. Using a
frequency of 450 Khz the high frequency induction oven will heat an iron wire of 0.6 mm
diameter to the Curie temperature in 2 x 10·3s. During the heating time, which can be
controlled from 0.06 s to several seconds, the temperature of the wire remains at an
approximate constant maximum (of a fixed frequency). The pyrolysis temperature can be
varied by choosing a ferromagnetic conductor with a suitable Curie point temperature.
With a reactor capillary of 0.6 mm and a wire of 0.5 mm diameter and 1 cm length the
carrier gas will pass through the reactor in 5 x 10·3s, assuming a flow rate of 10 cm3/min.
May et al39 have used this Curie point filament pyrolyser to produce pyrolysis -
gas chromatograms for various polymers (Method 106).
Voigt40-42 employed the platinum filament pyrolyser. This unit is attached directly
to the gas inlet of the gas chromatograph for the examination of ethylene - propylene
copolymers.
Pyrograms will differentiate between random copolymers and block polymers or
polymer mixtures. 3'.40.4M 6 Presence of foreign monomer may interrupt chain transfer
processes involved in the degradation. Similar products result but their quantities as
determined from peak heights are different.
Systematic identification of plastics was attempted by Nelson et al47 by pyrolyzing
0.2 - 0.5 mg samples for 10 sat 650 - 750°C in an argon gas chromatograph using a 4 ft
column of 5% silicone oil on Chromosorb W. Similar plastics were distinguished from
pyrograms obtained at two different temperatures.
Groten48 used a platinum filament type pyrolyser and six-way gas sampling valve
pyrolyser in conjunction with an isothermal gas chromatograph by heating of a platinum
coil at 9500 C for 26 s. For the 150 different polymers investigated, the individual
members of a group generally gave pyrograms that allowed unambiguous identification
of the original material. The attainment of mazimum temperature is quite rapid under all
conditions and is fairly insensitive for variations in carrier gas flow rate.
6.3.2 Combustion Furnace Pyrolysers
Earlier pyrolysis equipment tended to be somewhat complex in design and

operation. Thus, Cox and Ellis49described a micro-reactor pyrolyser which they applied
to large numbers of polymers. Temperatures increases of 700 - l0000C were used in
order to completely pyrolyse O.1g samples of the polymers. The pyrolysis products were
collected for 15 min then swept onto a gas chromatographic column equipped with a
flame ionization detector.. This type of equipment has now been displaced by the more
recently described equipment as discussed later.
142
so .
Kolb and Kaiser pyrolyzed 4 mg oi'PQlyethylene in an oven furnace at l000DC
for lOs. The first peak of the repeated groups of triplet peaks of the pyrogram was
identified as the normal paraffm.
Cieplinski et al s have investigated extensively the thermal degradation products
of polyoleflns in an oven furnace using a chromatograph equipped with a differential
flame ionization detector. Samples (50 - 70 mg) were pyrolyzed in a reaction chamber as
described by Ettre and Veradi s and the volatile reaction products were passed through a
linearly programmed temperature, open tubular (Golay) column. On pyrolysis at 690DC a
large number of triplet peaks up to C22 were obtained. The last peak in each triplet group
was identified as the normal paraffin.
Comparison of pyrograms of high and low density polyethylenes indicates
significant differences for peaks above C21, with the relative amounts of the two major
peaks being reversed. Thus, for the low density polyethylene the last peak corresponding
to the a-paraffin is always larger, whereas for high density type polyethylene the first
peak predominates. The pyrograms of polymethylene obtained by Ciepielsky et al SI are
greatly dependent on the pyrolysis temperature.
Two procedures have been described, (I) flash fllament pyrolysis (Section 6.3.1)
and (ii) heating the polymer in a micro-reactor and collecting the total volatiles produced,
(Section 6.3.2). In yet another more recent approach, the pyrolyser probe method
discussed below, the polymer is placed in a quartz tube which is then inserted into a
platinum coil heater element. The coil heater is switched on to release the pyrolysis
products which are then directly swept into the gas chromatograph.
Chemical Data Systems UK supply a range of pyrolyser probes which are
discussed in Method 107. These probes can be used in conjunction with any suitable gas
chromatograph.
A large number of materials can be analysed by packed column pyrolysis gas
chromatography. The chromatograms obtained are relatively simple and the analysis
time comparatively short. These chromatograms are therefore especially suitable for
qualitative polymer identifications. Relatively large amounts of sample can be
introduced onto the column and therefore minor differences between batches of similar
sample may be observed. Figs 6.l(a) and (b) are examples of two types of acrylic
material, both analyzed using the same conditions. Note the similarity of the peak pattern
produced from the identical thermal degradation of the two samples, but also note the
relative difference in the size of the peak at 12.8 min and also the presence of the peak at
5.04 min in the modacrylic chromatogram. The results obtained from this type of
analysis are qualitative. Quantitative analysis is difficult as the identities of the separated
degradation products are' usually unknown. Packed column analysis of pyrolysis
products generally allows observation of the more volatile constituents produced by the
thermal degradation.
The chromatograms obtained from using capillary columns to separate the
pyrolysis products are generally complex. Separation of all the more volatile fragments is
not possible without cryogenic cooling of the oven. Under standard chromatographic
conditions it is the high boiling degradation products that are readily separated as can be
seen from fig. 6.2(a) and (b). Therefore, it is the latter part of the chromatogram that is
used for identification. Because it is the higher boiling degradation products that are
being observed, a number of polymers give very similar pyrograms. Thus the pyrograms
obtained for polyethyl acrylate and polyvinylacetate are almost identical. The only
observable differences are the presence of the two additional peaks in the polyvinyl-
acetate pyrogram at 8.74 minutes and 12.79 minutes. Therefore, capillary column
pyrolysis gas chromatography is slightly less useful than packed column pyrolysis as a
143
.. a b
"a.
0
..
III
.
L.
L.
"0
.
L.
0
(J
u::
Time (min)
Figure 6.1. Pyrolysis - gas chromatography of (a) modacrylic resin; (b) acrylic resin.
Instrument: P-E8310 series
Column: 1m Porapak QS
Conditions: 50 C (2.0 mins) IS deg C min I 230 C (IS mins)
Pyrolysis: 9S0 C for 10 sec
strict identification technique. However, the complexity of the pyrograms produced

allows minute details to be observed. Analysis times used in capillary column pyrolysis
are two to three times longer than those for packed column pyrolysis gas chrom-
atography; runs are generally in the order of 60 minutes in length. The high split ratio
and very small amounts of sample required to obtain good results with capillary column
pyrolysis gas chromatography mean that there is an obvious advantage in using this
technique when only very minute amounts of sample are available for analysis.
In the chemical data systems - filament coil type pyrolyser, Pyro-probe 122.the
polymer samples are held in a quartz tube that is inserted into the platinum coil. If
pyrolyses are to be conducted at slow rates the pyrolyser is interfaced to a sample
concentration (Model 320, Chemical Data Systems) which collected the pyrolysates on a
Tenax filled trap. In this way polymer samples can be processed for minutes or hours at
slow heating rates and the pyrolysates collected for a single gas chromatographic
analysis. When the pyrolysis is complete, the trap is pulse heated and backflushed with
the carrier gas. The desorbed pyrolysates are transferred to a gas chromatograph (Model
3700 Varian or equivalent) equipped with a 50 m x 0.25 mm i.d. SE-54 capillary column
(Quadrex).
A 6-:1 split was established at the injection port of the gas chromatograph and the
column was programmed from 50 to 280° at a rate of 40°C min'l. A flame ionization
detector is used and the area data obtained from a recording integrator.
Wampler and Levy') used this apparatus to study the effects of slow heating rates
on the products formed during the pyrolysis of polyethylene. They showed that both the
pyrolysis temperature and the rate at which that temperature is achieved have significant
effects on the formation of pyrolysates from a solid polymer.
144
A
Figure 6.2. Pyrolysis - gas chromatography of (a) polyethylene; (b) polypropylene - polyethylene
copolymer.
Instrument: P-E 8310 Series with split/split less injector.
Column 25, SE30 Capillary (0.25 mm Ld.)
Conditions: 50 C (2.0 mins) 5 deg C min 1 230 C (after last peak)
Pyrolysis: 850 C for 10 sec.
Pyrolysis coupled with simultaneous multidetector gas chromatograwhy has been

applied to studies of the structure of end-groups in polymethylmethacrylate. 8
6.4 LASER PYROLYSIS - GAS CHROMATOGRAPHY
The advantages claimed for this technique54,55 include rapid heating and cooling
of the sample and relatively simple fragmentation patterns, (Method 108).
6.5 PHOTOLYSIS - GAS CHROMATOGRAPHY
Juvet et al 56 have used this technique for the preparation of pyrograms of

polymers. They claim that this technique yields considerably more simple and
reproducible decomposition patterns than filament, furnace and Curie point pyrolysers
and claim that this is due to greater control of energy input and a more predictable
manner in which the polymers decompose photolytically. Photolysis is carried out on a
pure thin film of the polymer by irradiation using a medium pressure mercury source.
The photolysis products are swept onto a gas chromatogram to produce a pattern
characteristic of the polymer.
145
A tabulation of the photolysis products of some common polymers is given in
Table 6.6.
Polyethylene yields on photolysis primarily a series of products eluting at integral
multiples of 1 = 100; these are undoubetedly n-alkanes and the corresponding alkenes.
Products at intermediate 1 values are probably due to branched chain hydrocarbon
fragments.
Polystyrene yields benzene (I = 660) as the major photolysis product, smaller
amounts of toluene, ethylbenzene and styrene are produced. Quantitation of the last three
materials is complicated by variable amounts of residual monomer in the samples
available and a small amount of thermal decomposition occurring in the injection port.
The ultraviolet absorbance of the polymer influences the response to photolytic
degradation. Polyolefins, which are relatively transparent in the ultraviolet, receive
essentially constant radiation throughout the sample and thus yield photolysis products as
a function of total sample weight. Highly ultraviolet absorbing polymers, such as
polystyrene, strongly attenuate the incident radiation. Measurements of the photolysis
yield of benzene from polystyrene films over a ten-fold range of sample weight and film
thickness show that in the case of polystyrene, photolysis is surface area controlled and
products are formed primarily within a thin surface layer. If the injection port
temperature of the gas chromatograph is maintained below the glass transition point of
polystyrene, less than ten per cent of the photolysis products formed are volatilized.
Raising the temperature above the glass transition temperature lowers the viscosity of the
polymer and allows photolysis products to diffuse out of the polymer and be swept into
the column.
Photolysis of poly (methyl methacrylate) proceeds primarily by formation of the
monomer, corresponding to the product observed at 1 = 720. As in the case of
polystyrene, small amounts of residual monomer and monomer formed from thermal
decomposition were observed in non-irradiated sampled. Methanol and methyl formate,
which have also been reported as photolysis products are not separated on SE-30 but
analysis on Carbowax 20 M give two peaks corresponding to these substances.
6.6 PYROLYSIS - MASS SPECTROMETRY
Hughes et alS7 and Meuzelaars8 have shown that pyrolysis - mass spectrometry
has considerable potential for the characterisation and discrimination of natural and
synthetic polymers. A Curie-point pyrolyser, combined with a dual flame detector gas
chromatograph and V.G. Micromass 12 F mass spectrometer were used by these workers.
The pyrolyser was mounted on the front of the gas chromatograph and was purged with
helium at a flow rate of 5 cms min"l. Samples were pyrolysed at 610°C (heating time 15
s) and the pyrolysate was swept into an empty 45 cm x 6.35 mm o.d. x 2 mm Ld. glass
column maintained at 200°C in the gas chromatograph. A make-up flow of helium (10
cm3 min"l) was introduced at the end of the column by using a Swagelok stainless-steel
114 - 1116 in reducing union with a length of 1116 in o.d. stainless steel tubing brazed into
it. The mixed outlet flow was passed through a length of glass-lined stainless-steel
microbore tubing to the jet separator of the mass spectrometer. The mass spectrometer
was operated under standard electron impact conditions; electron energy 70 eV, emission
current 100 uA, accelerating voltage 4 kV and a source temperature of 240°C. The mass
range (25 - 200) was scanned at 3 s per decade with a magnet re-set time of 3 s. About 40
- 50 scans of the pyrolysate were made with acquision, storage and processing of spectra
carried out with a V.G. 2040 data system, supplemented with an X - Yplotter.
146
Table 6.6 - Photolysis Products of Common P01ymers
Polymer Retention Index ReI. peak area'
Ion SE-30
<500 1.0
604± 12 0.1
680±8 0.Q2
702±6 0.1
765±5 0.02
800±5 O.lS
876±S 0.01
900±5 0.07
Polystyrene < 500 0.02
660± 10 1.0
784 ±8)
830 ± 8)
886 ±6)
Poly(methylmethacrylate) < SOO 1.0
720±8 O.S
152S±5 0.2
ISS0 ±S 0.2
Poly(tetrafluoroethylene) < SOO
• Irradiation time, 30 minutes. b Total of three incompletely resolved peaks. From Juvet56 American
Chemical Society
The system was used to study a wide range of polymeric materials. The
sensitivity is sufficiently high to allow samples of 5 ug or less to give adequate electron-
impact spectra, but in the chemical ionisation mode larger samples are necessary. Mass
pyrograms are usually characteristic of the sample type and frequently allow
discrimination between samples of similar composition.
The advantages of pyrolysis - mass spectrometry over pyrolysis - gas chrom-
atography for generating information about polymeric materials are its speed, sensitivity,
ease of producing data that can be computer processed and the elimination of the
variables associated with gas chromatography. A major disadvantage of pyrolysis - mass
spectrometry is that a complex mixture is produced by a combination of pyrolysis and
electron - impact fragmentation, which makes a mass pyrogram more difficult to interpret
than the chromatograms produced in pyrolysis - gas chromatography, in which only a
pyrolytic breakdown stage is involved.
Jackson and WaikerS9 studied the applicability of pyrolysis combined with
capillary column gas chromatography m~s spectrometry to the examination of phenyl
polymers (eg. styrene-isoprene copolymer) and polymer like phenyl ethers (eg. bis(m-(m-
phenoxy phenoxy)phenyl)ether). They examined the effect of varying parameters
affecting the nature of products formed and relative product distribution in routine
pyrolysis. These parameters include the effects of pyrolysis temperature rise times,
pyrolysis temperatures up to 985°C and pyrolysis duration. Temperature rise time (0.1 to
1.5 s) is not a critical factor in the Curie point pyrolysis of a styrene-isoprene copolymer,
either with regard to the nature of the products formed or their relative distributions.
Additionally, the variation of pyrolysis duration or hold time (2.0 to 12.5 s) at a fixed
Curie temperature reflected no change in the nature of components formed; however
changes in product distributions were observed. Variations in Curie temperature at a
fixed pyrolysis duration produced drastic changes in product distributions such as a three-
147
fold change in isoprene dimer formation in styrene-isoprene copolymers; however,
temperature variance did not change the nature of the products formed. Bis(m-(m-
phenoxy Phenoxy)phenyl)ether) produced two primary pyrolysis products, diphenylether
and dibenzofuran. In the procedure a 10010 w/v solution of the polymer in a volatile
solvent (benzene) is prepared. The pyrolysis Curie point temperature wire is dipped 0.25
in into the polymer solution and the wire placed in a vacuum oven at 75 to 80°C for 30
min to remove the solvent.
A pyrogram of the copolymer (isoprene-styrene) resulting from a lOs pyrolysis at
601°C yields product distributions similar to the sum of the two constituent product
distributions. For example, when the polymer polyisoprene is pyrolyzed, C2, C3, C4,
isoprene and C IO HI6 dimers are produced. When polystyrene is pyrolyzed, styrene and
aromatic hydrocarbons are the products. The copolymer product distribution and relative
area basis resemble the two individual polymer product distributions.
Mattern et al44 carried out laser mass spectrometry on polytetrafiuoroethylenes.
They found a fragmentation mechanism common to each fluoropolymer yields struc-
turally relevant ions indicative of the orientation of monomer units within the polymer
chain. A unique set of structural fragments distinguished the positive ion spectra of each
homopolymer, allowing identification.
Chin_An_Hu63 has described a pyrolysis mass spectrometric method for polymer
characterisation.
Qian et al91 carried out a rapid identification of polymers using a technique based
on ion source direct pyrolysis mass spectrometry and library searching. Polymers were
pyrolysed using a coiled filament designed for desorption chemical ionization/desorption
electron ionization applications. Pyrolysis products were ionized at 70 ev electron
impact. This yielded highly reproducible spectra characteristic of the polymer. Using
these techniques and library searching a comprehensive library of 150 polymers was
developed.
6.7 TYPICAL POLYMER PYROGRAMS
6.7.1 Filament and Furnace Pyrolysis
Samples can be pyrolyzed at a series of temperatures between 400 and 10000 C

and the change in degradation behaviour as evidenced by the (1) "appearance
temperatures" of various peaks and (2) relative abundance of products as a function of
temperature noted. 60•61 Changes of the most characteristic breakdown products versus
temperature can also be plotted. For homopotymers the temperatures at which
degradation products are first obtained may be more distinctive than the retention times
of the products. The utility of the pyrolysis technique is that the chemist can assemble a
collection of pyrograms of polymers which are of particular interest and use them to
identify unknown polymers. For example, Figure 6.3 shows pyrograms obtained by
furnace and filament methods of pyrolysis via a range of synthetic elasomers. An
example of a sofhisticated recent application of pyrolysis gas chromatography is the
work of Denig6 Figure 6.4(a) and (b) who compares the pyrograms of PVC and
poly(vinylidene chloride). The high quality of these pyrograms is self-evident and makes
it possible to distinguish between the two polymers. The technique also distinguished
between a physical mixture of poly(ethylene acrylate) and poly(isobutyl acrylate) and a
poly(ethylacrylate)-poly(isobutyl acrylate) copolymer.
148
6.7.1 Curie Point Pyrolysis
In Figure 6.5 are shown some pyrograms obtained using a Curie Point pyrolyser
in conjunction with a Pye 104 Model 64 gas chromatograph.39 The polymers were not
pre-treated in any way and they were pyrolysed in the solid phase as received. The
pyrograms are those for a linseed pentaerythritol-o-phthalate alkyd (Figure 6.5(b), an
acrylic emulsion (Figure 6.5 (c» and a vinylchloride (95 per cent)-vinyl acetate (5 per
cent copolymer (Figure 6.5(a». A solid phase Poropak Q column was used.
May et alM have published a full reference collection of Curie point pyrograms.
6.7.3 Laser Pyrolysis
Some typical laser pyrograms are reproduced in Figure 6.6. 54,55
6.8 POLYMER IDENTIFICATION BY INFRARED SPECTROSCOPY
Infrared spectra of thin films of polymer in the region up to 4000 cm" are
characteristic of the polymer. The spectra Can be run either as potassium bromide discs
(1.5 - 2 ug polymer per 400 mg potassium bromide) or as polymer film of varying
thickness ~ to 12 micron using a sodium chloride prism under the following
conditions:6
Adjustment 0 to 100 cent Tat 2.00 u

Gain: 3.9 - 4.0 (on the brink. of aperiodicity)
Time constant of the amplifier: 2
Speed of the optical attenuator: 1100
Resolution (split programme): 927
Scanning speed: I x to + scan program (about 11 min from 1.25 to 15.25 u)
Speed supression: 8
Nemst current: 0.30 to 0.35 A
Wavelength region scanned: 1.25 to 15.25 u
Table 6.7 tabulates data on the infrared absorptions occuring in polymers. It

should be emphasised that any conclusions reached following examination of infrared
spectra should be confirmed by other techniques such as elemental analysis and pyrolysis
- gas chromatograrhy.
Denchant6 has discussed in detail the infrared spectra of 35 polymers and Hippe
and Kerste69 developed an algorithm for the infrared identification of vinyl polymers.
Pyrolysis followed by infrared spectroscopy is a particularly useful technique for
application to polymers which are rendered opaque or completely non-transparent by the
presence of pigments or fillers.
Leukoth70 used this technique to determine the chemical composition of polymers
and rubbers containing high proportions of pigments or fillers.
Alexander71 has described a method for obtaining spectra of thin films of polymer
which are free of interference fringes. The method is based on measuring a
transmission/reflection spectrum of the polymer using a specular reflectance accessory on
the infrared instrument. The film is placed on a reflectance accessory with a mirror above
it. The radiation transmitted through the film is returned by the mirror and so is measured
together with the radiation reflected by the film.
149
A
Isobutylene " -
Dipentene
I
AI Jl4
B
Isoprene's
( Dipentene
c
Vinylbenzene -..
D Isobutylene -+
Butadlene_
~
0
i
.!
~
J E
G
Isoprene ....
Dipentene
oj
40 30 20 10 o
TIME (min.)
150
Figure 6.3 Pyrolysis - gas chromatograms for
(a) natural rubber

(b) isobutylene - isoprene elastomers
(c) mixture of natural rubber and isobutylene - isoprene elastomer
(d) cis-butadiene elastomer
(e) 1: 1 mixture of cis-butadiene and isobutylene - isoprene elastomer
(f) 1:9 mixture of cis-butadiene and isobutylene - isoprene elastomer
(g) Chloroprene elastomer
Osland26 has described a heated press for the preparation of plastic films for
analysis by infrared spectroscopy. The press can produce films as thick as 500 urn and of
reproducible thickness. Earlier workers have used the hot press film method, where the
sample is heated until molten, pressed to a thin film and allowed to solidifY. Sampling
handling accessories are now available with which films of constant thickness can be
prepared. Alternatively, the sample material can be dissolved in a suitable organic
solvent and a film cast onto glass or a cell window.
These techniques are adequate for identifYing the bulk polymer but polymer
blends can contain many other components which must be identified or quantified and for
this purpose they are generally unsuitable, the reason being that they cannot produce thick
films or reproducible film thicknesses.
Other approaches to obtaining the infrared spectrum of polymers are surface
reflectance technique21 •28 and infrared microscopy.66
Gardalla and Grobe28 compared attenuated total reflectance and photoacoustic
sampling for surface analysis of polymer mixtures by Fourier transform infrared
spectroscopy. They show that analysis by attenuated total reflectance is more suitable for
smooth surfaces and is faster. Photoacoustic methods have shallower sampling depths
than attenuated total reflectance but the latter technique is applicable over a range that is
more controllable.
Fox6s employed Fourier Transform infrared spectroscopy for the identification of
traces ofpoly(dimethylsiloxane).
Brako and Wexle~1 have described a useful technique for differentiating the
presence or absence of functional groups such as hydroxyl, carboxylic acid or ester in
polymers containing small percentage components of such groups. Films of latices or
polymers are subjected to chemical treatment which results in marked changes in the
infrared spectrum which can be associated with the disappearance of a functional group
or its replacement by another functional group. Infrared data may be readily interpreted
negatively so that one may definitely preclude the presence of hydroxyl, carbonyl, amine,
amide, nitrile, ester, carboxylic, aromatic, methylene, tertiary butyl and terminal vinyl
groups, if the corresponding group vibmtions are absent in the infrared spectrogram.
More difficult is the assignment of functional groups where multiple or several alternate
possibilities exist as in the mixture of a carboxylic and keto group or in the assignment of
a band to an olefinic group.
When applying infrared spectroscopy to the preliminary qualitative identification
of polymers it is desirable to assemble a libmry of standard spectra. Razinger et al4] have
described a minicomputer procedure for digitization, maintenance and retrieval of an
infared spectral collection.
151
A
V=4
I--Stm---i
V=2
Retention time (mins)
Figure 6.4
(A) Pyrolysis - gas chromatogram of PVC (a) biphenyl, (b) methyl naphthalene, (e) naphthalene,
(d) methylindene, (e) tetralin, (f) methyl indene, (g) indene, (h) indane, (I) styrene, (j) o-xylene, (k)
ethylbenzene, (I) toluene, (m) benzene.
(8) Pyrolysis - gas chromatography of polyvinylidene chloride, (a) tetra-chlorostyrene, (b)
trichlorostyrene, (c) 1,3,5 trichlorobenzene, (d) m-dichlorobenzene, (e) trichlorobutadiene, (t)
chlorobenzene, (g) vinyldene-chloride. From Denig with permission. 6l Carol Hauser Verlag Munich
6.9 POLYMER IDENTIFICATION BY LASER DESORPTION -ION MOBILITY

SPECTROMETRY
In this technique the pulse from a NdlYAG laser ablates the surface of the
polymer generating molecular fragments in the vapour phase that are representative of the
target material. These vapour phase components are drawn into the ion mobility
spectrometer source where they are ionized. Both positive and negative ions are formed
152
9
A
8
4
5
25 20
9
B 11
c 2
..
20 15 10 o
Time I Minutes
Figure 6.5
(A) Pyrogram for vinyl chloride (95 per cent) - vinyl acetate (5 per cent) copolymer. Peak I,
methane; 2, ethylene; 3, ethane; 4, propylene; 5, propane; 6, n-butene; 7, n-butane; 8, acetic acid; 9,
benzene and 10, toluene. Amount pyrolysed 41 ug.
(8) pyrogram for a linseed pentaerythritol o-phthalate alkyd. Peak I, methane; 2, ethylene; 3,
ethane; 4, propylene; 5, propane; 6, acetaldehyde; 7, n-butene; 8, n-butane; 9, acrolein; 10, allyl alcohol
and II, methacrolein. Amount pigmented paint pyrolysed 14 ug.
(C) pyrogram for an acrylic emulsion. Peak I, methane; 2, ethylene; 3, ethane; 4, methanol; 5,
acetaldehyde; 6, ethanol and 7, methyl acrylate. Amount pyrolysed 7 ug.
From May et al with permission. J9 Royal Society of Chemistry, London
and the spectrometer can operate in either mode. The ions are formed and the
spectrometer can operate in either mode. The ions are resolved into a pattern or signature
characteristic of the polymer. Simpson et aI'2 examined PVC, Nylon 66, acrylonitrile-
butadiene-styrene terpolymer, polyethylene terephthalate and polyethylenes by this tech-
153
~ A B
lij!
oj
a!
oj
2!:
!i!'J
iii
d
i~~~~~l~A~~A~A~A~A~~
lij!
d
8
°0.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00 18.00 18.00 20.00 0.00 2.00 4.110 8.00 8.00 10.00 12.00 14-00 16.00 1100 20.00
C
~ ! 0
~
~
I!!
~~
>-
~
::Iii!
iii
d
!
lij! R
d d
~~~~~~~~~,~~ 8~~~~-===~~~~~
1800 18.00 20.00 c O.OO 1.00 2.00 3.00 • .00 5.00 8.00 7.00 800 9.00 10.00
. TIME IN MINUTES
Figure 6.6
Lazer pyrogram of (a) green polyethylene. (b) black polyethylene, (c) saran, (d) teflon.
From Folmer et al with permission. 14.11 American Chemical Society
nique. Similar materials such as high and low density polyethylenes could be differ-
entiated.
6.10 OTHER MASS SPECTROMETRIC TECHNIQUES
Perfluoroethylenes have been characterized by desorption chemical ionization and

tandem mass spectrometry83 Fourier transform ion cyclotron resonance mass
spectroscopy has also been applied to the identification of polymers, ego polyethylene
glycols. 84 Comparative complimentary plasma desorption mass spectrometry/secondary
ion mass spectrometry has been applied to the identification of oligomers of various
polymers including polyethylene glycol, polytetrafluoroethylene, polycarbonate,
polyacrylates, polyethylene terephthalate and siloxanes. 8l
Shick et al 92used radio frequency powered glow discharge atomization/ionization
mass spectrometry (Rf GDMS) for the characterisation of bulk polymers. Fingerprint
mass spectra were obtained for a series of polytetrafluoroethylene based polymers by
looking at the differing base peaks and relative peak intensities. The technique exhibited
excellent discharge stabilization and internal stability characteristics with a relative
154
Table 6.7 - Some Infrared Spectral Lines of Polymers
1. Polyacrylonitrile C=N,4.47
Aliphatic C - H, 3.41, 3.49
C = 0 stretching, 5.78
Others 6.01, 6.90, 3.34, 3.41
2. Polyfonnaldehyde C - H stretching, 4.90, 6.80, 7.0, 7.23, 8.08, 9.15
Others, 3.34, 3.41, IUS (strong)
3. Polyisobutylene Aliphatic CH ) 3.35 - 3.50
)6.70 - 6.90
Others, 7.20, 7.32, 8.15
Doublet at 10.56, 10.87
4. Polyester resin Aliphatic CH, 3.30, 3.40
C = 0 stretching, 5.80 (strong)
C = 0 stretching ester, 7.65 - 8.03
Others, 6.09, 6.15, 6.S0, 6.61, 6.70, 7.6S and 12.90 and 14.3S
(characteristics)
5. Buna Rubber Afiphatic CH, 3.40
Double bond, S.90
Others, 6.10, 6.2S, 6.69, 6.90 - 6.96
Strong, 10.36, 11.0, 13.22, 14.33
6. Vinylite polymers (Union Vinylite VMCH aliphatic CH, 3.40
Carbide) copolymerized vinyl C = 0 stretching, 3.6S, S.76
chloride - vinyl acetate H 0 H binding absorbed water, 6.16
C - 0 stretching, 7.00, 7.32, 7.56, 8.1
Others, 9.17, 9.28
7.. Vinylite VAGH Aliphatic CH, 3.4S, 3.S6
C = 0 stretching, S.79
Adsorbed water, 6.16
C - 0 stretching, 7.02, 7.5S, 8.0S
Others, 9.16, 10.42
On comparing with above spectra for Vinylite VMCH it is seen
that there are sufficient differences to make positive identification
possible in the region 7.0-7.5 and 9.S-10
8. Vinylite XYHL The difference between this and the spectra ofVinylite VMCH and
Vinylite VAGH is the strong absorption at 8.73
9. Silicone oil Methyl in Si-CH3, 7.9S, 9-10,12.6
Si-O-Si, 12.6
Aliphatic CH, 3.36, 3.43 - vibrations
10. Methyl cellulose OH stretching, 2.90
Aliphatic CH stretching, 3.42, 3.S1
Adsorbed water, 6.1S
(similar spectrum to cellulose)
11. Ethyl cellulose Splitting of aliphatic CH stretching vibration at 3.37-3/50
Others, 6.94, 7.27 (strong), 10.90, 11.37 (weak)
12. Carboxyl methylcellulose Resembles spectrum of cellulose
sodium salt
13. Carboxy methyl cellulose C = 0 stretching, S.S7 (strong)
(free) Carboxy, 3-4
14. Nitrocullulose R-O - N02, 6.0S, 7.80 (characteristic)
15. Phenol fonnaldehyde C-H groups, 3.3 (weak)
(asbestos filled) Double bond plus C-H absorption, 6.2S double peak
-Si 0 (from asbestos), 9.5-10.0
16. Melamine fonnaldehyde N-H groups 2.7S
(asbestos filled) Si 0 (from asbestos), 9.S-10.0
17. Polycarbonate OH, 2.90, 6.12 (adsorbed water) CH adjacent to double bond, 3.28
(aromatic CH)
Aliphatic C-H, 3.37, 3.48
C = 0 stretching, 5.88 (strong)
CH, 6.9, 7.10-7.37
ISS
Table 6.7 continued
Carbonyl ester, 8.0
1.4 disubstitution, 12.1, 13.8
18. Polyethylene glycol OH, 2.90 weak
Aliphatic C - H, 3.45 (strong), 6.75-7.50
- CH2 - O-CH2 band, 9
19. Polypropylene glycol CH adsorption, 2.90
Triple C-H, 3.35 - 3.50
CH,6.9
CH3, 7.3 (strong)
C-O-C, 9 (strong)
Others, 10.8, 11.6, 12.0
20. Polyvinylidene chloride Aliphatic C-H, 3.4-3.5
C = 0 absorption, 5.75 (impurity)
CH, 7.10, 7.31
C-CI, 13.35 (usually 13.3-14.3)
21. Chlorinated polypropylene Absorbed water, 2.93, 6.16
Aliphatic C-H, 3.40, 6.96, 7.25
Methyl C-CI13.15, 13.65, 12.75 (probably)
22. Polyvinylacetal OH,2.91
Aliphatic CH, 3.4
C = 0 ester, 5.76
Methyl groups, 7.28
- CHz - 0 - CR, 8.8
23. Polyacrylamide C=O,6.00
C = N (probably), 4.5
OH (moisture), 2.95
24. Cellulose propionate Moisture, 2.9, 6.13
Triple C - H adsorption, 3.4
Ester carbonyl, 5.7, 8.6
Others (characteristic), 7.25-8.5, 11.4, 12.45, 13.45
25. Cellulose acetate butyrate Characteristic absorptions, 10.5, 11.1, 12.0, 12.6, 13.4, 14.5
26. Butyl rubber Aliphatic Ch, 3.4 (strong), 6.8
Two methyls attached to carbon, 7.19,7.31
CH adjacent to aliphatic double band, 10.55, 10.85
27. Nitrile rubber CH adjacent to double band, 10.3 (strong), 3.25, 6.00, 6.10, 6.25
(strong)
Aliphatic C - H, 3.40, 3.49, 6.9
C=N,4.46
28. Styrene-butadiene rubber Polystyrene bands, 3.25, 3.30, 3.35
(C - H adjacent to double band)
Monosubstituted benzene ring, 5.6, 13.2, 14.33
C - H adsorption, 10.35
29. Styrene-butadiene Mositure, 2.92, 6.12
acrylonitrile Aromatic C - H, 3.28, 3.31, 6.28 and C - H adjacent to double
bond'
Aliphatic C - H, 3.41, 3.50, 6.88, C =N, 4.47
Monosustituted benzene ring, weak 13.2, 14.35
30. Ethylene-propylene Closely resembles polyethylene spectrum plus double bonds, 10.3
copolymer Aliphatic C - H, 3.4
CH adjacent to double bond, 3.3
Methyl groups, 7.25
31. Ethylene-propylene-diene Closely resembles spectrum of ethylene propylene copolymer.
terpolymer Addition spectral lines
Aliphatic double bands, 3.3 (weak) 10.65
32. Epoxy resin (araJdite) Hydroxy, 2.9, 9.04
C - H, 3.27,3.34,6.20, 6.30
Split methyl group, 7.20, 7.32
1,4-di-substituted benzene ring, 5.6 (weak) 12.3
Aliphatic C - H, 3.39, 3.43, 3.45,6.84
156
Table 6.7 continued
33. Coumarone-indene resin Adsorbed water, 2.92

Aromatic C- H, 3.31, 6.49
Substituted benzene ring, 13.4, 14.3
Aliphatic C - H, 3.42, 3.50, 6.90
34. Polyvinylacetate C=O,5.75
Ester, 8.0, 9.8
35. Polyvinyl butyral Characteristic absorptions, 7.25, 8.05, 8.9, 10.0
36. Polytetratluorethylene CF2,8.4
Others, 8.4, 4-5
37. Polyethylene terephthate OH stretching, 2.82
(Terylene) C = 0, 2.90, 5.80
H stretching, 3.25
CH2 stretching, 3.35, 3.43
CH2 deformation, 7.08, 7.20
CH deformation, 7.90
C-O-C stretching, 8.51, 9.59
C-C, 6.80
Others, 5.80, 6.19,11.45,13.77,6.65,7.30,7.45,8.86,9.10,9.80,
10.3, 11.15, 11.45, 11.80, 12.62, 13.75
38. Polymethlmethacrylate Ester carbonyl,S. 75
C-O-C stretching, 6.70-6.95, 8.30-8.80
Other, 10.00, 10.40
39. Cellulose (cellophane) Water Absorption, 2.8 - 3,4
OH stretching, 3.4
CH stretching, 3.4
C = 0 stretching, 5.8
COO - ion stretching, 6.28
CH2 deformation, 7.0
CH deformation, 7.3, 7.6, 11.1
OH deformation, 7.5, 8.9, 15.4
C - 0 stretching, 8.6
OH bending, 9.4
C - OH stretching, 9.8
C-OH,8.9
C - 0, C - C stretching, 10.0
Other absorption, 9.0, 6.1
40. Cellulose acetate Adsorbed water, 2.9
Ester carbonyl, 5.75
Other absorption, 3.5-5.35, S.O, 7.5-\0.0
41. Melamine Characteristic absorptions, 3.0, 6.0-6.5, 9.7, 12.3
42. Urea formaldehyde Characteristic absorptions, 6.0-6.2, 6.9, 8.0, 10.0
43. Natural rubber C=C,6.0S
CH2 and CH3 deformation, 7.0, 7.25,12.00
Other absorption, 7.5 - II
standard deviation of less than 5%. In-depth profiles of polymers were obtained for
copper layers deposited on a PTFE substrate. The following polymers were examined;
PTFE
PTFE - perfluoromethylvinyl ether copolymer
PTFE - hexafluoropropylene - polyvinylidene fluoride terpolymer.
It was observed that side chain structure had a dramatic effect in the fingerprint
mass spectra.
157
6.11 EXAMINATION OF POLYMER SURFACES
Polymer films for certain specific applications such as food wrapping film consist
of laminates of very thin layers of two or more different polymers. Various techniques
have been adopted for the identification of the different layers in such laminates by
examining each side of the film separately.
Techniques that have been applied include time of flight static secondary ion mass
spectrome"1; (SSIMS),73.76 low energy ion scattering spectrometry, x-ray photoelectron
microscopy 7 scanning electrochemical microscopy (SECM),78 laser ionization mass
spectrometry/9 surface enhanced infrared reflection spectroscopy,80 Fourier Transform
. firared spectroscopy
10 . 81 and nucI ' resonance spectroscopy.82
ear magnetic
Time of flight static secondary ion mass spectroscopy (SSIMS) has been applied
to perfluorinated polymers,88 polystyrene,89 polyacylacrylates (including poly cyclo-
hexylmethacrylate, polybenzyl methacrylate, polyphenyl methacrylate, poly n-hexyl
methacrylate, poly n-butyl methacrylate, polymethylmethacrylate, poly n-propyl meth-
acrylate, polyisopropyl methacrylate and poly secbutyl methac~late). Blends of
polystyrene and polyvinyl chloride,87 bisphenol A and polys~rene/ polycarbonate and
polystyrene73 and tetramethyl bisphenol A and polycarbonate7 have also been studied by
this technique.
Scanning electrochemical microscopy (SECM) has been applied to polymethyl-
methacrylate, polystyrene and polyethylene glycol. 78 Surface enhanced infrared
reflection microscopy was applied to polyacrylonitrile, polybutadiene and styrene resins 80
whilst Fourier transform infrared spectroscopy was applied to polyimides.81 Finally,
nuclear magnetic resonance spectroscopy has been applied to the examination of the
surfaces of films of polyethylene, Suryln and ethylene-vinyl acetate copolymer. 82
Schreimer and Li93 carried out a surface analysis of bulk polymers using laser
induced photoelectron ionization with laser desorption in a time of flight mass
spectrometer. In this technique the carbon dioxide laser beam is focussed on the polymer
surface to induce fast thermal dissociation and/or photo dissociation of the polymeric
materials. The resulting neutral species are then ionized using photoelectron ionization
(PEl). The PEl process involves a laser metal interaction in which a low power pulsed
ultraviolet laser beam is directed to an appropriate metal surface exterior to the source
region of a Wiley-McLaren time of flight mass spectrometer. The photoelectrons
generated are accelerated as a narrowly distributed beam by the fringing fields of the
source region. The electron beam, travelling in a direction almost parallel to the
extraction grid is used to ionize the desorbed neutral molecules that are entrained into the
ionization region. The technique was applied to the following polymers;
polystyrene
poly (2-vinyl pyridine)
polystyrene-2-vinyl pyridine
polethylene glycol
poly (methylmethacrylate)
Plots of signal intensity versus mlz all gave readily interpretable mass spectra
suitable for structural analysis and chemical identification. The technique was also used
for end-group analysis. Results compared well with those obtained by other mass
spectrometric methods. The detection sensitivity was high, ego a limit of detection of less
than 100 a mole per laser shot for polyethylene glycol.
158
Lin et al94 carried out an analysis of photoablation products resulting from
polymer materials following supersonic beam/multi-photon ionization/time of flight mass
spectrometry. They examined the photo-ablation products obtained in this technique and
compared them with those obtained by thermal decomposition.
The high sensitivity provided by supersonic beam spectrometry permitted the
detection of minor species, thus styrene monomer is produced from poly alpha methyl-
styrene by cleavage of a methyl group and by proton rearrangement. Because the
ablation is carried out at high temperatures it is possible to obtain results on thermally
stable polymers such as poly-p-methyl styrene. The technique was applied to polystyrene
foam, styrene-butadiene copolymers and acrylonitrile-butadiene-styrene terpolymers.
159
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162
PART 2
ANALYTICAL METHODS
Various detailed methods of analysis, many previously unpublished, are described

in Chapter 7
CHAPTER 7.1
POLYMER ANALYSIS
Methods 1 - 52
METHOD 1 - DETERMINATION OF WATER AND VOLATILES IN

POLYALKENES. GAS CHROMATOGRAPHIC METHOD.
1.1 SUMMARY
A method for the determination of down to 0.01% of water and organic volatiles
in polyethylene and polypropylene.
1.2 APPARATUS
The instrument is shown diagrammatically in Figure 7.1 and consists essentially

of a sample tube, forming an extemalloop connected to a gas chromatograph.
1.3 METHOD
The solid polymer is placed in a gas chromatograph sample loop which is then
heated under controlled conditions and the volatiles swept by helium carrier gas on to a
gas chromatographic column prior to determination of water and volatiles.
1.4 EXPERIMENTAL PROCEDURE
The sample loop (Figure 7.1) can be isolated and the sample heated to the
required temperature. After an initial heating period the volatile constituents liberated
from the sample are "flushed" on to the chromatographic column by a flow of carrier gas
through, or over the sample and the required components separated and determined
quantitatively. A pneumatic switch valve located in the chromatograph oven to prevent
the condensation of volatile constituents within the valve and a split heater mounted on a
horizontal travel in a plane at right angles to the sample tube, are essential parts of the
apparatus. The instrument is semi-automatic.
The carrier gas flows through the copper sulphate in tube D, which imparts a
constant amount of water (about 3 p.p.m. w/v) to the helium. The "wet" carrier gas pre-
164
C,
A, C,
~==D!......,II.
Hydrolen _ _C t - ( n -
Air
o
Heliuln_ -oCl:--(:
At. A. and A. == Edwards VPC I pressure controller

8,. B. and B.... Pressure cauees 0 to 30 p.s.l. *
K, and K. = Straight redueln, couplln,s. captive
seal type. for I to Inch o.d. tubln, (Drallim.
Cat. No. L/SO/D/B)
C" C. and C. - Rotameter-type flow ,au,es L == Chromatocraphlc column
o - Clear plastlclsed PVC tubin, (5 foot lon, X M .. Flame-Ionls.tlon detector
! Inch bore). packed with copper sulphate =
N, and N. Electrically actuated 3-port pilot valves
crystals. CuSO•. 5HaO. > 44 mesh (Marti nair. Type 557C/IZ)
E - Katharometer P - Nickel - chromium/nickel - aluminium
F - Pneumatlcsamplevalve (PyeCat. No. 12900): thermocouple embedded In the spilt heater
fitted with P 9904 chan,e-over block Q '" Electronic temperature controller. pro-
G "" Internal loop portional type
H - External loor made In part of 18-caule R ... Sample-valve time-delay unit. contain In,
stalnless-atee capillary tubln, three synchrollOus time .. and I seml-c:on-
ductor. proportional ener,y controller for
_ Sample split heater the sample heater
Figure 7.1. Details of general purpose instrument for gas chromatographic determination of water and
volatiles in polymers.
vents the gas-flow lines from "drying out". Dry pipework tends to adsorb moisture,
which can then be desorbed, thus leading to spurious results. The determination of water
in a sample in unaffected as the "wet" carrier gas flows continuously through both the
reference and analysis cells of the katharometer. The copper SUlphate crystals are sieved
and any fine powder rejected. The copper sulphate tube is changed when two thirds of its
length has visibly changed colour.
The pneumatic sample value F, operates merely as a switch valve, directing the
carrier gas flow either around the internal loop G, or the extemalloop H. The pilot valve,
N I operates samples valve F. The sample split heater J shown in more detail in Figure
7.1 consists of a cylindrical aluminium block, 6 inches long with a 2 mm hole through the
centre. The block is split axially and the two halves hinged. Each half of the block
contains two cartridge - heater elements, each 5.5 inches long, 3/s inch o.d. and one half
contains a thermocouple pocket to accommodate the thermocouple P. The cartridge
heaters are supplied by a semi-conductor energy controller contained in R, which is
controlled by a galvanometer, two-position, temperature controller Q. The heater is
mounted on a horizontal travel in a plane at right angles to the sample tube. A jig for
mounting the sample tubes is also part of the heater assembly. The 3/S inch coupling, KI
is brazed to its mounting bracket, which is rigidly attached to the heater base. This
coupling accurately centres with the central hole through the aluminium block. The
165
coupling, K2 is brazed to the flexible carrier gas inlet tube and rests loosely in the second
mounting bracket. The 318 inch couplings are supplied with neoprene, or butyl rubber
captive seals. Neither of these materials is suitable for continuous use at elevated
temperatures, especially as the seals are made and broken many times a day. Alternative
seals have been cut from silicone rubber tubing, 9 mm bore and 2 mm wall and fitted
inside with 318 inch coupling nuts. Such seals give trouble free operation for 2 or 3 days
at heater temperatures up to 350°C before replacement is necessary.
The sample heater assembly is placed on top of the gas chromatograph oven so
that the L-bend of tis inch o.d. SIS tubing disappears almost immediately into an opening
on the top of the oven. In practice, both the inlet tube (6 inches long, 1/4 inch o.d. and t/8
inch Ld. copper) and the exist tube (1/8 inch o.d.) are wrapped with heating tape and
lagging to maintain the temperature of the whole assembly at about 100°C. The inlet tube
is wrapped to a length of 4 to 5 inches and the L-bend of the exit tube is wrapped to a
point 3 inches inside the oven. Both tubes are wrapped up to, and including, the 1/4 inch
thread of the Drallim coupling, leaving only the centre nut and the 3/8 inch coupling nut
exposed so that the sample tubes can be readily changed. These two tap heaters are
connected in series and supplied by a Type V-5HMPS Variac transformer, output 0 to
270 V (2A). Without these heaters, volatile constituents condense at the cold ends of the
sample tube and are swept away comparatively slowly on switching the carrier gas
through the sample. This leads to diffuse and unsymmetrical peaks in the chromatogram.
The apparatus shown in Figure 7.1 is fitted with katharometer and flame
ionisation detectors.
Disposable sample tubes are made by cutting 9 mm o.d. heat-resistant glass tubing
into 6 \ inch (± 1116) lengths. The cut ends of the tubing are fire-polished in a flame.
Such tubes will contain from 1.5 to 5 g of sample, depending on the polymer and its
physical form.
N2 acts as a pressure release valve to the external loop H. The sample valve time-
delay unit R, contains three synchronous timers: (I) a variable 3 to 60 synchronous
process timer (Chronoset Type CF.D. Robinson & Co.): (ii) a miniature, fixed cycle
synchronous timer and (iii) a variable 30 s to 12 min synchronous process timer. Timers
(i) and (ii) are linked, and are initiated by a push button. Timer (iii) operated
independently and again is started by a second push button. The unit also incorporates a
re-set button that re-sets timers (i) and (iii).
The oven contains the column, the katharometer and the pneumatic switch valve
so that no condensation can take place in the switch valve. Other items of the gas
chromatographic equipment not shown in Figure 7.1 include the katharometer bridge
unit, the flame ionisation amplifier and the respective potentiometric recorders for the
two detectors (I mY, f.s.d.)
The chromatographic columns for the determination of water in different
polymers consist of 10 per cent wlw stationary phase on polytetrafluoroethylene powder
(I.C.1. "Fluon" CD4).
To examine a polymer for water and organic volatiles, the small glass sample
tube is fitted with a small quartz-wool plug at about I inch from one end, and these are
stored in an oven until just before use. Transfer several tubes from the oven to a
desiccator containing phosphorus pentoxide and allow to cool. (The desiccant should be
examined at weekly intervals and renewed when necessary). Use the tubes from the
desiccator as required. Weigh a sample tube and pour the sample (powder or granule)
into the tube. Re-weigh and insert a second quartz-wool plug with tweezers. These plugs
are pre-prepared, oven-dried and stored in the desiccator. Place the sample tube in the
heater jig between the couplings and tighten the couplings.
166
Set the heater to the appropriate temperature for the sample under examination.
Operate the first push button on unit R (Figure 7.1). This starts timer (i) set for 15 sand
at the same time activates pilot valve N I> which operates the pneumatic switch valve,
allowing helium carrier gas to flow around loop H, through the sample tube (still at room
temperature) for 15 s and sweep the sample free from air. At the end of this 15 spurge
period the pneumatic switch valve closes, thus isolating the sample. After a further 2 s
delay (fixed timer (ii)) the second pilot valve, N2, is activated for 2 s allowing the excess
of helium pressure in the closed sample loop to escape to atmosphere via the tee-piece
and capillary tubing attached to N2 • This valve sequence follows automatically on
operating the first push button, and its completion is denoted by an indicator light. Open
the split heater, move it over the sample and close. Operate the second push button for
timer (iii). The sequence described below then follows.
Set timer (iii) (Figure 7.1) for 5 min. Open the split heater, move it forward on its
travel and close it over the sample tube. Operate the push button for timer (iii). After the
set time of 5 min the pilot valve, MI> is triggered which operated the pneumatic switch
valve, F, thus allowing helium carrier gas to flow around the external loop, H, through the
sample tube and flushing the liberated volatile constituents on to the gas chromatographic
column. The carrier gas remains routed around the external loop, H, until the re-set
button is pressed. It is then diverted through the internal loop, G.
Two chromatograms are obtained. The first, resulting from the 15 s purge of
helium through the cold tube, shows a peak for air followed by a small peak for water.
This is developed while the sample is being heated for 5 min.
The second chromatogram, after the heating period, shows the liberated water
followed by a peak for any organic volatiles present. Carry out a blank determination in
the same manner on an "empty" tube containing two quartz-wool plugs only. Add the
values for the two water peaks resulting from each determination and correct the sample
figure for the blank value.
To calibrate for polyalkenes the polymer is heated above its "melting point" to
obtain the total moisture; a horizontal sample tube is, therefore, used. The powder,
provided it is not packed too tightly, contracts on melting and sinks to the bottom of the
tube, thus allowing a free passage for the carrier gas above the sample. In this case
calibration is best carried out with barium chloride dihydrate crystals, weighed into empty
sample tubes. Barium chloride loses its water of crystallisation, 15.75 per cent w/wat
115°C. Chromatograms obtained in this manner are similar to those obtained on samples,
ie. a small water peak after the heating period when the water is released from the
crystals.
If calibration is carried out by direct injection of water on to a quartz-wool plug in
an "empty" tube with a Hamilton syringe, 75 to 90 per cent of this water is purged on to
the column during the 15 s period. Chromatograms are, therefore, obtained that are quite
unlike those obtained for a sample, although the total amount of water should be
unchanged.
Weigh about 12 mg of barium chloride crystals into an empty sample tube and
obtain chromatograms as indicated under Procedure. Repeat with 9. 6. 3 and 1 mg
amounts of barium chloride crystals. Add the values for the two peaks obtained for water
in each determination and correct for the blank. Construct a calibration graph relating
milligrams of water to the corrected total peak height (or peak area) measured from the
recorder chart.
The peak on the plot, obtained by heating polypropylene powders in the presence
of air, corresponds to the visible melting point of the polymer, the temperature at which
the polymer begins to flow. Above this temperature the amount of water falls off before
167
rising again at still higher temperatures. This falloff is presumably due to the sudden
contraction of the surface area exposed to the oxidising atmosphere as the polymer flows.
No corresponding peak is obtained with granular samples (powder that has been
compounded, extruded and cut into small pellets). The continuous-line plots obtained by
the second method indicate that all the moisture is not released from the polymer until the
"melting point" is approached in the case of powder samples, and is exceeded in the case
of granular samples. The heater temperature used for the determination of moisture in
polypropylene samples was, therefore, chosen as 240°C as this temperature is applicable
to both powder and granular samples.
The gas chromatographic conditions recommended for the determination of
moisture in polypropylene are: column, 5 foot (1/4 inch o.d.), stainless-steel tubing,
packed with lO per cent w/w "Ucon" 50 HB 2000 fluid on "Flucon" CD4 powder; oven
temperature, lOOoC; and helium inlet pressure, 6 p.s.i.
1.S DISCUSSION OF RESULTS
Low density polyethylene contains only very low concentrations of water (0.01 -
0.05% w/w) whilst polypropylene contains 0.02 to 0.5% water w/w.
At this high sensitivity and with lower amounts of water, blank determinations
can be somewhat erratic with a reproducibility of 150% unless great care is taken with the
storage of the dried tubes. For example, a tube that has been stored overnight in a
desiccator over phosphorus pentoxide will give a much lower blank than a tube taken
from the desiccator when the desiccator has been opened and closed several times. Plots
relating the temperature of the sample to the amount of moisture liberated per gram of
sample shows that 150°C is the minimum temperature that should be used and that, in the
presence of air, oxidation, giving rapid formation of water, starts at 170°C. A heater
temperature of 200°C was used for polyethylene.
Within the above concentration ranges, the reproducibility given by the gas
chromatographic method is 15 ± 5 per cent relative.
METHOD 1- DETERMINATION OF WATER IN POLYALKENES. SEMI-

AUTOMATED KARL FISCHER TITRATION METHOD.
1.1 SUMMARY
This method is specific for water in polyalkenes. Other volatile constituents in

the polymer do not interfere.
1.1 APPARATUS
Apparatus is sho'\\'O in Figures 7.2 and 7.3 and component parts are listed in Table
7.1.
The instrument operates by means of a standard Karl Fischer dead-stop indicator
circuit, with a moving coil relay replacing the microammeter. The moving coil relay
operates as a switch, in conjunction with a second relay, to deactivate (at the end-point)
168
and to activate (when water is present) an automatic titrant dispenser, which dispenses a
given volume of titrant into the titrand each time it is activated.
METHOD 3 - DETERMINATION OF SANTONOX R PHENOLIC

ANTIOXIDANT IN POLYETHYLENE. 2,2'-DIPYRIDYL SPECTROPHOTO-
METRIC METHOD.1
3.1 SUMMARY
A method for the d~rmination of various types of antioxidants in polyethylene

as exemplified by the determination of Santonox R phenolic antioxidant, (Note 1).
3.2 APPARATUS
Miscellaneous glassware. Round-bottomed flasks 100 cm3, vertical condensers,

volumetric flasks 100 cm3 and 10 cm3 (black painted), pipettes 25 cm3 and 1 cm3, filter
funnel 3 in. diameter.
Spectrophotometer. Unicam SP 600 or equivalent instrument. Water bath
thermostatted at 25 ±O.5°C.
3.3 REAGENTS
Toluene, "Analar" redistilled

Ethanol, Absolute,
2,2'-dipyridyl, 0.5%; dissolve O.5g 2,2'dipyridyl in 100 ml absolute alcohol.
Ferric chloride 0.2%: dissolve 0.2g ferric chloride hexahydrate "Analar" in 100
ml absolute ethanol, (Note 3)..
To avoid photochemical reduction of this reagent by sunlight, store in an amber
glass bottle which is covered with black paper. Renew the reagent daily.
3.4 METHOD
The method involves oxidation of the antioxidant under controlled conditions

with an absolute ethanol solution of ferric chliride:
A reduced + Fe3+ = A oxidized + Fe2+
This reaction is followed by reaction of ferrous iron produced with 2,2'-dipyridyl

to form a coloured complex the intensity of which is proportional to the concentration of
antioxidant present in the polymer.
169
End·point
detector End' po int timer and
circuit d .c. power unit Burette unit alarm unit
I r~
N V2 L
I
~ I
52 ·· ···N, .. ..
Clutch
6<50e
UWI
TRI-
O
, 2 3 • 8,
RECI PLI
d.c. d.c.
B +
240 V
neutral
T, T2
o Reaction cell
Figure 7.2 Semi automatic Karl Fischer water apparatus, Burette valve construction.
~
I in
PTfE bloc~
t. /""jU'li"g 'crow
~ I". ___
J \ "
PTH noulo
PTFE
tubing 1mm bot.
2",,., o.d .
Figure 7.3 Semi automatic Karl Fischer water apparatus, Burette valve construction.
170
Table 7.1 - Components List (Instrument assembly by ICAM Ltd. Northop, Mold,
Flintshire)
Item Description Manufacturer
SI SwitchSPDT )
S2 Switch SPOT )
TI andT2 Insulated terminals ) Radiospares Limited
NI Panel neon clear 240V ) P.O. Box 2BH
TRI Transformer Hygrade 240V ) 4 - 8 Maple Street
50 cycles 2 x 6.3V ) London, W.1.
RECI Rectifier Rec 20 )
RLY2 Relay Type I. 12V d.c. 120 ohms )
01 Diode 10 DE Type REC50A )
PI Potentiometer Model A 10 tum Beckman, Glenrothes
500 ohms and Duo-Dial Model RB Scotland
RLYI S170 d.c. relay make at 90 micro- Sangamo Weston
amps resistance 3300 ohms Enfield, Middlesex
Spec SI70/1/457
PLI and 6-pin plug and socket Part No. A.F. Bulgin, Barking
SOC I PI94 Essex
MSI and Microswitch Type HA I Crouzet Ltd,
MS2 Brentford, Middlesex
VI 1.5V d.c. battery
V2 240V a.c. supply
A Audible alarm Bleeptone A.P. Beeson Ltd,
12V d.c. Hove, Sussex
Burette Unit Fisons automatic dispenser Fisons Ltd
includes Rl 4700 ohm tesistance Loughborough
and CI 0.4 uF condenser
PTFEvalve ICAM Ltd, Northop,
block Mold, Flintshire
Counter Reset vending counter Part No. Veeder-Root, Croyden
KKI441
Timer Chronoset CF 0-36 minutes Technical Representations
direct clutch model Ltd, Stockport, Cheshire
Case Type DA 40168 Bedco Ltd, Harpenden, Herts.
Accurately weigh 1 g of sample into a 100 ml round-bottomed flask. Into the

flask pipette 25 ml toluene (Note 2) and connect the flask to a vertical condenser. Heat
for 90 min on a boiling water bath with occasional swirling. Low density (ie. high
pressure) polyethylenes usually completely dissolve during the reflux. High density
polyethylenes (ie. Zeigler low pressure) either completely dissolve or disperse
sufficiently to allow full extraction of Santonox into the solvent phase.
Whilst the toluene solution is still hot pour 25 - 30 mI absolute ethanol down the
condenser to precipitate dissolved polyethylene. Leave the flask to cool, stopper and
shake well (refilter if the solution in the volumetric flask is cloudy). Wash the filter paper
and polymer with absolute ethanol into the 100 ml volumetric flask until the liquid level
reaches the 100 mI mark. Shake the flask contents well.
In a thermostatted (25 ± 0.s°C) water bath clamp two dry 10 ml volumetric flasks
painted with several layers of black paint (Note 3). Ensure that the flasks are almost
171
completely immersed in water. In one flask pipette 10 cm3 of the polyethylene extraction
solution (sample flask). Into the other flask pipette 10 ml 25:75 (v/v) toluene: absolute
ethanol.
Into each flask pipette 0.5 cm3 of 2,2' -dipyridyl reagent and then 1.0 cm3 of iron
(III) chloride reagent. Start a stopwatch, stopper both flasks and mix well. After 57 min
remove both flasks from the water bath and pour into two 1 cm glass spectrophotometer
cells (avoiding exposure to direct light as much as possible) and transfer the two cells to
the spectrophotometer. Measure the optical density of the sample solution against the
blank solution (in the comparison cell) at 60 ± 1 min after starting the stopwatch.
Evaluate the solutions under the following spectrophotometric conditions.
Instrument: visible spectrophotometer.
Cells: 1 cm glass.
Blank solution: fill comparison cell with reagent blank as referred to in text.
Wavelength: 520 nm.
Temperature: 25 ± 0.5°C.
3.5.1 Calibration of Method.
Weigh out accurately 0.03g Santonox R into a 100 cm3 volumetric flask. Make
up to the 100 cm3 mark with 25:75 v/v toluene: absolute ethanol and shake thoroughly to
completely dissolve the solid (using a warm water bath to assist solution if necessary).
Pipette 5 cm3 of this solution into a further 100 cm3 volumetric flask and make up to 100
cm3 with 25:75 v/v toluene: ethanol. Prepare the dilutions indicated below and proceed
with the colour development and measurement of optical density as described above.
To prepare a calibration graph plot optical density against the corresponding
weights of Santonox R present in the 10 cm3 volumetric flask.
Volume of 0.015 mg/cm3 Volume of2s:75 v/v Mass of Santonox

Santonox solution/cm3 toluene:ethanol/cm3 mg
1. o (blank) 10 0.00
2. 2 8 0.Q3
3. 4 6 0.06
4. 6 4 0.09
5. 8 2 0.12
6. 10 o 0.15
3.6 TYPICAL RESULTS
Convert the optical density obtained from the polyethylene extract to milligram
Santonox R by means of the calibration graph. Calculate the Santonox R content of the
polyethylene as follows:
Santonox R (% w/w) = 1000

W
N = Weight (g) of Santonox R in 10 cm3 polyethylene extract obtained by

referring determined optical density to the calibration graph.
W = Weight (g) of polyethylene sample taken for analysis.
172
A typical application of the procedure is given below, viz. the determination of
down to 0.01% of Santonox R (4,4'-thiobis-3-methyl-6-tert-butyl phenol) in polyeth-
ylene. As this procedure determines Santonox R only in its reduced form it does not
include any Santonox R which may be present in the oxidized form in the original
polymer, for example produced by atmospheric oxidation of the additive during polymer
processing at elevated temperatures. Total reduced plus oxidized Santonox R can be
determined by ultraviolet spectroscopic procedures, for example, the differential
procedure described later (Method 6) and oxidized Santonox can then be obtained by
difference from the two methods. Alternatively, total unoxidized plus oxidized Santonox
R can be determined by the direct ultraviolet spectroscopy.
3.7 DISCUSSION OF RESULTS
Down to O.oI % Santonox in polymer can be determined by this procedure with an

accuracy of ± 5%.
3.7.1 Note 1. Compounds which Interfere in the 2,2'DipyridyllFerric Chloride

Method.
The following compounds are known to interfere in the procedure for determining
Santonox R. The described method may indeed, be used to determine these substances in
polyethylene.
Succonox IS N-stearoyl-p-amino phenol

B.H.T. Butylated hydroxy toluene
D.C.P. Di-cresylol propane
lonol 2,6-di-tert-butyl-p-cresol
NonoxCI N ,N' -di-S-naphthyl-p-phenylene diamine
Compounds used as light stabilizers in polyalkenes do not usually interfere in the

described procedure as they are not capable of reducing iron to the ferrous state.
3.7.2 Note 2. Composition of Solvent in which Colour Development is Carried Out.
In the procedure recommended by Metcalf and Tomlinson2 the polyethylene

sample is heated with 10 cm3 toluene and then made up to 100 cm3 with ethanol (ie. final
solution contains 10% ethanol). This procedure was applied to some pOlyethylene
samples and gave lower Santonox R contentS than expected.
The Metcalf procedure was modified by refluxing the polyethylene with 25 cm3
toluene and making up to 100 cm3 with ethanol (ie. 25% toluene in final extract instead of
10% toluene as in the Metcalf method).
3.7.3 Note 3. Photochemical Reduction ofIron (III) Chloride Reagent.
Alcoholic solutions of iron (III) chloride are reduced photochemically at an

appreciable rate upon exposure to daylight. Reaction of the polyethylene extract with
ferric chloride and 2,2' -dipyridyl reagents is carried out, therefore, in black painted
173
volumetric flasks. The iron (III) chloride reagent bottle must also be protected from
daylight.
METHOD 4· DETERMINATION OF PHENOLIC ANTIOXIDANTS IN

POLYETHYLENE. P·NITROANILINE COUPLING· SPECTRO·
PHOTOMETRIC PROCEDURE.
4.1 SUMMARY
A method for the determination of phenolic antioxidants in amounts down to

0.01 % in polyethylene.
4.2 APPARATUS
Underwriters extraction cup

Volumetric flasks 100 ml
Visible spectrometer
Pipettes, 10 ml
4.3 REAGENTS
Ethyl alcohol, 95% sodium hydroxide, reagent grade, 4M; 160 g of sodium
hydroxide per litre (distilled water).
o-Nitroaniline, melting point 146 - 147°C.
Sodium nitrite, analytical Reagent grade.
Coupling agent, 2,800 g of p-nitroaniline dissolved in 10 cm3 of hot concentrated
hydrochloric acid and diluted with water to 250 cm3• After cooling to room temperature,
the volume of liquid is adjusted to exactly 250 cm3• A second solution is made
containing 1.44 g sodium nitrite in exactly 250 cm3 of distilled water. Both of the above
solutions are reputed to be stable indefinitely.
25 cm3 of each of these solutions are pipetted into separate 100 cm3 beakers and
are chilled in ice to below 10°C. The contents are mixed by combining the solutions and
pouring them back and forth from one beaker to the other. Pure nitrogen is bubbled
through the mixture and it is allowed to warm to room temperature. Finally, add 10 mg
urea to destroy excess nitrous acid.
4.4 METHOD
The method is applicable to the determination of a wide range of antioxidants, see

Table 7.2.
2.000 ± 0.020 g of film or powdered sample is accurately weighed and wrapped

with extraction cloth which has been· previously extracted to remove sizing, etc. The
sample is placed in an Underwriter's extraction cup and extracted for 16 hr with 95%
174
Table 7.2 - Composition and Absorptivity Date for Phenolic Antioxidants
Antioxidant Composition Absorptivity Wavelength

A max-A max.mu
700
AgeRite Alba Hydroquinone monobenzyl 31.48 565

ether
AgeRite Spar Styrenated phenol 44.06 548
AgeRite Superlite A polyalkyl polyphenol 23.40 560
Antioxidant 5 Not disclosed 18.81 585
Antioxidant 425 2,2'-Methylene-bis (6-tert-butyl
4-methylphenol) 22.30 585
Antioxidant 2246 2,2'-Methylene-bis (6-tert-butyl
4-methylphenol) 20.60 578
Deenax 2,6,Di-tert-butyl-p-cresol Does not couple
lonol 2,6,Di-tert-butyl-p-cresol Does not couple
I-Naphthol I-Naphthol 120.1 598
2-Naphthol 2-Naphthol 115.1 540
Naugawhite Alkylated phenol 8.20 580
Nevastain A Not disclosed 12.44 550
Nevastain B Not disclosed 6.62 550
Nonyl phenol Nonyl phenol 36.25 538
p-Phenyl phenol p-Phenyl phenol 80.80 548
Polygard Tris (nonylated phenyl) Must be hydrolysed before
phosphite it will couple
Santovar A 2,5-Di-tert-amyl-hydroquinone Colour too weak
SantovarO 2,5-Di-tert-amyl-hydroquinone Colour too weak
Santowhite crystals 4,4'-Thio-bis (6-tert-butyl-2-
methyl phenol) 78.84 565
Santowhite MK Reaction product of 6-tert-butyl
m-cresol and SCI2 66.94 560
Santowhite powder 4,4'-Butylidene-bis (3-methyl-6-
tert-butyl phenol) Colour too weak
Solux N-p-Hydroxyphenyl-morpholine Colour too weak
Stabilite white powder Not disclosed Colour too weak
Styphen 1 Styrenated phenol 22.61 558
Wingstay S Styrenated phenol 50.82 545
WingstayT A hindered phenol 10.27 590
From Hilton'. American Chemical Society
ethanol or methanol. The alcohol extract is transferred to a 100 cm3 volumetric flask,
cooled to room temperature and brought to the mark with the extraction solvent. A 10
cm3 aliquot is transferred to a 100 ml volumetric flask. Two millilitres of coupling
reagent are added. The solution is thoroughly mixed and 3 cm3 of 4M sodium hydroxide
solution are added. The solution is then brought to the mark with 95% ethanol or
methanol.
The absorption spectrum is determined from 400 - 700 nm using a suitable
spectrophotometer with quartz cells. The colour formation is complete by the time the
solution is brought to the mark and is stable for at least 2 h. Ethyl alcohol is used in the
reference cell unless the alcohol extract is strongly coloured. In this case, the reference
solvent is taken to be a 10 cm3 aliquot of the ethyl alcohol extract diluted to 100 cm3 with
ethyl alcohol. The absorbance readings are plotted on semilogarithmic graph paper. The
175
per cent antioxidant is calculated using the equation developed for the antioxidant
concerned.
The method is capable of determining down to 0.01 % antioxidant in polyethylene

with an accuracy of ± 5%.
METHOD 5 - DETERMINATION OF IONOL PHENOLIC ANTIOXIDANT IN

POLYETHYLENE. ULTRAVIOLET SPECTROSCOPY.
5.1 SUMMARY
A method for the determination of lonol antioxidant in amounts down to 0.01 % in

polye~ylene.
5.2 APPARATUS
Ultraviolet spectrophotometer, recording type.

Sample cells, quartz - I cm path length.
Miscellaneous glassware.
Heating mantle, electrical, 250 cm3 capacity, with variable contol.
5.3 REAGENTS
Chloroform - AR
lonol CP - dried by vacuum desiccation for 4 h before use.
5.4 METHOD
The absorption maximum occuring at 278 nm of a chloroform extract of the

polyethylene is measured and the lonol content of the sample then deduced from an
appropriate calibration curve prepared with pure lonol.
5.5.1 Extraction.
Weigh 20.0g of polymer sample into a 250 cm3 round-bottomed flask and add 50
cm3 of chloroform. Connect the water-cooled condenser, place on the electric heating
mantle and bring gently to boiling point. Reflux for 30 min at a moderate rate. Allow to
cool and then carefully decant the chloroform solution into a 100 cm3 volumetric flask
(filter if necessary) and stopper, add a further 40 cm3 of chloroform to the round-
bottomed flask and carry out a second extraction of the polymer. When cool, filter the
176
contents into the volumetric flask containing the first extract. Wash the residue with
sufficient chloroform to make up to the mark. Shake the flask to ensure homogeneity.
Record the ultraviolet spectrum of the chloroform extract against a chloroform
blank from 250 to 310 nm using 1 cm cells.
Measure the absorbance of the lonol absorption peak at 278 nm. Determine the
concentration of lonol present in the extract by reference to the prepared calibration
curve.
5.5.2 Calibration.
Make up accurately a 0.05% w/v solution of lonol CP in 250 cm3 chloroform.

Dilute this stock solution to obtain lonol CP solutions of 0.02, 0.01, 0.025, 0.0003% w/v.
Record the ultraviolet spectrum of each of the above solution against a chloroform
blank from 250 to 310 nm using I cm cells. Measure the absorbance of the absorption
peak at 278 nm by drawing a base-line from approximately 260 to 300 nm.
Plot a calibration curve of absorbance against concentration of lonol CP in
chloroform.
5.5.3 Calculation.
Calculate the concentration of lonol present in the polymer by means of the

following expressions:
% w/w lonol CP in polymer = 5 x (% w.v lonol in chloroform extract)
The method is capable of determining down to 0.01% lonol in polyethylene with

an accuracy of ± 5%. Any other substance in the polymer which absorbs between 250
and 310 nm will interfere.

ANTIOXIDANT IN POLYETHYLENE. ULTRAVIOLET SPECTROSCOPY.
6.1 SUMMARY
A method for the determination of Santonox R phenolic antioxidant in amounts

down to 0,01 % in polyethylene.
6.2 APPARATUS
Apex Mill
Spectrophotometer
Water bath
I em silica cells
Volumetric flasks, 50, 100, 1000 ml
Condensers with ground glass neck
Filter funnels
177
Pipettes,S, 10,20 ml
Graduated cylinders, 25 ml
Filter paper, Green's No. 802 or similar
6.3 REAGENTS
Santonox R, 4,4'-thio-bis-(6-tert-butyl-3-methylphenol). Standard Santonox R

solution: dissolve 0.1000 g Santonox R in cyclohexane in a 1000 cm3 standard flask and
dilute to the graduation mark.
Cyclohexane - spectroscopic grade.
Sodium hydroxide pellets - Analar, 42 gr l
6.4 METHOD
Santonox R is extracted from a finely ground sample with boiling cyclohexane.

The extract is then shaken with aqueous sodium hydroxide. Santonox R fonns a sodium
salt in the alkali layer. This layer is then examined on an ultraviolet spectrophotometer.
The base line absorbance is calculated and referred to a previously prepared calibrated
graph relating weight of Santonox R to base line absorbance. lonol does not interfere in
the determination
6.5.1 Analysis of sample.

Grind a representative sample in the Apex Mill. Weigh about 1 g of the sample
into a 100 cm] round-bottomed flask and add 20 cm] cyclohexane. Fit a condenser to the
flask and allow the cyclohexane to reflux on a water bath for 1 h. Wash down the
condenser with 20 cm] cyclohexane, remove the flask from the bath, cool to room
tempera,ture and shake well. Filter through a No. 802 filter paper into a 100 cm]
separating funnel. Wash the filter paper with a further 10 em3 eyclohexane. Add 25 em3
freshly prepared sodium hydroxide solution, shake for 3 min then allow to settle. Run off
the aqueous layer into a 100 em] standard flask. Repeat the extraction with another 2 x
25 em3 portions of alkali, make the extract up to 100 ml with alkali and mix well. Read
the optical density in 1 cm silica cells at the following wavelengths, 335, 266 and 236 om
and use sodium hydroxide solution as a blank. Calculate the baseline absorbance from
the following equation.
Where ABL = base line absorbance.
Am, A266• A236 = absorbance at 335, 266 and 236 om respectively.
Read the concentration of Santonox from the calibration graph.
178
6.5.2 Calibration.
Put accurately measured portions of 5, 10, 15 and 20 cm3 standard Santonox R

solution into 50 em3 standard flasks and dilute to the graduation mark. Transfer each into
a 100 cm3 separating funnel and dilute to graduation mark. Transfer each into a 100 cm3
separating funnel and add 25 cm3 freshly prepared sodium hydroxide solution. Shake for
3 min, allow to settle, then run the lower layer into a 100 cm3 standard flask. Repeat the
extraction with another 2 x 25 cm3 portions of alkali. Make up the volume to 100 cm3
and mix thoroughly. Read against sodium hydroxide in 1 cm silica cells at the following
wavelengths - 335, 266, 236 nm. Calculate the base line absorbance as above. Plot the
base line absorbance against the concentration of Santonox R in mg/l 00 cm3•
6.5.3 Calculation of Results.
Calculate the Santonox R content as follows:
Weight % Santonox R = I!
W
where B = Santonox R content of extract in mg/l 00 ml

W = weight of sample (g)
Note 1. The optical density of the cyclohexane should not exceed 0.15 at 247 nm.
Note 2. The sodium hydroxide must be Analar - and carbonate free. Carbonate
adhering to the pellets may be removed by washing the pellets with distilled water.
The method is capable of determining down to 0.01 % Santonox R in polyethylene

with an accuracy of ± 5%. Any other substance in the polymer which absorbs between
236 and 335 nm in sodium hydroxide extract will interfere. lonol does not interfere.
METHOD 7 - DETERMINATION OF 2,6-DITERT-BUTYL-4-METHYLPHENOL

AND 4 SUBSTITUTED 2,6-XYLENOL PHENOLIC ANTIOXIDANTS IN
POLYPROPYLENE. DERIVATIVE ULTRAVIOLET SPECTROSCOPy.4
7.1 SUMMARY
Derivative ultraviolet spectroscopy is used to determine down to 0.01% 2,6 ditert-

butyl-4-methylphenol and 4 substituted 2,6 xylenol phenolic antioxidants in poly-
propylene.
7.2 APPARATUS
A spectrophotometer with a microcomputer differentiation module and a digital

output or equivalent can be used for measurements ofUV absorption spectra. The second
derivative - difference spectra were measured under the following conditions: response, 2
179
s; slit width, 2 run; and scan speed, 10 on min:! The samples were placed in quartz cells
of 10 nun path length.
7.3 REAGENTS
Heptane - UV grade, free from aromatics, purified by treatment with concentrated

sulphuric acid and distilled. Check purity by UV spectroscopy.
Propan-2-01. Analytical reagent grade, distilled and absence of interference
checked by UV spectroscopy.
Solution of potassium hydroxide in propan-2-01. This was prepared by saturating
propan-2-01 with potassium hydroxide at elevated temperature. After cooling, the
solution was filtered and standardised by titration with 0.1 M hydrochloric acid using
phenolphthalein as indicator. The solution was stored in the cold and dark. The solution
was prepared freshly every month.
2,6-xylenol (substituted in the 4 position by a ca. C4S hydrocarbon chain) and 2,6-
Di-tert-butyl-4-methylphenol. Heptane solutions of both these phenolic antioxidants
were stable for 2 months under laboratory conditions.
7.4 METHOD
In non-alkaline medium the two antioxidants have virtually identical ultraviolet

spectra. In alkaline medium the spectra are sufficiently different to permit the two
substances to be determined without mutual interence.
The principle of the 4-substituted 2,6-xylenol method is as follows. First, the
phenolic component without steric hindrance is determined by means of second
derivative - difference spectroscopy of the bathochromically shifted, basified extract
using the non-basified extract as a reference. The second derivative spectral amplitudes
of a non-basified extract are Bdditive for both antioxidants. The contribution of 4-
substituted 2,6-xylenol to the total second derivative amplitude is then subtracted and the
residual corrected amplitude corresponds to the 2,6-di tert-butyl-4-methyl phenol content.
7.5.1 Extraction of Phenols from Polypropylene Sheet.
Samples of 0.5 nun thick 50 x 50 nun polypropylene sheets were weighed and
refluxed for 3 h in 50 ml of boiling heptane.
7.5.2 Preparation of Solutions for Spectroscopic Measurements.
The heptane extract was transferred quantitatively into a 50 cm3 calibrated flask
and made up to the mark with heptane (solution A). The following solutions were then
prepared.
Solution of phenolics (solution B). Two millilitres of propan-2-o1 plus 8 cm3 of

solution A.
Solution of phenolates (solution C). Two millilitres of a solution of potassium
hydroxide in propan-2-o1 (0.005 mol cm3) plus 8 cm3 of solution A.
Blank. (solution D). Two millilitres ofpropan-2-01 plus 8 cm3 of heptane.
180
7.5.3 Calibrations and Calculations.
Solutions containing 2,6-tert-butyl-4-methyl phenol in the concentration range c\

= 30 - 150 mg elm3 in a heptane-propan-2-o1 mixture (4 + 1 v/v) are measured using the
second derivative of the absorption spectra. The peak amplitude, Db at wavelengths of
285 and 292 nm is read off (Figure' 7.4) as a function of phenol concentration. The
calibration constant, K\ = D/C\ was found to be constant (10 x 10-4 mg-\) (standard
deviation (SD) = 0.13 x 10-4 mg-\
The maxima of the second derivatives of the absorption spectra of the two
components do not exhibit identical positions. Therefore, calibration was carried out
using the method of standard additions in order to eliminate the absorbance due to the 2,6
xylenol component. A mixture of both components with concentrations Col (2,di-tert-
butyl-4-methylphenolic) and C2 (2,6-xylenol) in the range 30 - 120 mg dm3 was prepared.
The peak amplitude, Dt , at wavelengths of 285 - 292 nm was measured in the form of the
second derivative of the absorption spectrum of the mixture (Figure 7.4). The calibration
constant, K3 = (Dt - C\K\)/C2, was found to be 5.2 x 10-4 mg-\ dm3 (SD = 0.17 x 10-4 mg
eIm-3 from nine measurements at two constant levels of 2,6-di-tert-butyl-4-methylphenol
concentrations (32 and 48 mg dm-\ using known additions of 2,6 ditertbutyl-4-
methylphenol. Table 7.3 shows the results for C\ = 32 mg dm-3• The derivative
amplitude, D3 for 2,6 xylenol is a linear function of its concentration and passes through
the origin.
The 2,6-xylenol content is determined using the second derivative - difference
absorption spectrum of its phenolate as the peak amplitude, D2, at wavelengths of 302.0 -
312.5 nm. The calibration constant, K.2 = D2/C 2, was found to be 5.71 X 10-4 mg-\ dm3
(SD = 0.07 x 10-4 mg-\ elm3) calculated from six measurements). The positions of the
maxima on the second derivative curves are influenced by the mode of derivation
(electronic, microcomputer) and by the setting of the spectrophotometer controls.
7.5.4 Calculation ofthe Antioxidant Concentrations in Extract.
The 4-substituted 2,6-xylenol concentration is calculated from the phenolate

spectrum of the extract:
The 2,6-di-tert-butyl-4-methylphenol concentration is calculated from the phenol

spectrum of the extract:
To calculate the concentrations of the antioxidants in the polymer, the mass of the
polypropylene sample, the volume ofthe extract and its dilution must be known.
The relative standard deviation of this procedure at the 0.1 - 0.2% w/w additive in
polymer level is between 7 and 8%.
181
+0.1
-0.1
J 0.2
0.1
Figure 7.4 - Nonnal and derivative spectra of antioxidants. Concentration of each oxidant, 30 mg
I'·. 1. Nonnal spectrum of Chemantox AO-49 (4 substituted 2.6 xylenol). 2. Nonnal spectrum A0-4K
'2.6 ditert butyl-4-methyl phenol. 3. Second-derivative spectrum of Chemantox A0-49. 4. Second-
derivative spectrum of a mixture of Chemantox AO-49. S. Nonnal spectrum of a mixture of Chemantox
A0-49 and A0-4K. 6. Second derivative spectrum of a mixture of Chemantox A0-49 and AO-4K.
Conditions for measurement of nonnal spectra, slit width 2 nm, scan speed, 40 nm min'·. Conditions for
measurement of second-derivative spectra: d (wavelength), 4 nm, slit width 2 nm, scan speed 10 nm min'·.
Concentrations correspond to extraction of antioxidants from I g of a stabilised sheet in 50 ml of heptane.
From Soncek and Jelinkova with permission.4 Royal Society of Chemistry, London.
Table 7.3 - Data for calculation ofK3 and for checking the linearity of the product K3C2
Dt D3=Dt-D.
AO-4K: AO-49: absorbance absorbance
c./mg I'· cz/mg I'· units units K#mg'·1
32 0.332
32 16 0.341 0.009 5.6 x 10-4
32 32 0.349 0.017 5.3x 10-4
32 48 0.357 0.025 5.2x 10-4
32 64 0.365 0.033 5.2 x 10-4
32 128 0.399 0.067 5.2 x 10-4
From Soncek and Jelinkova4• Royal Society of Chemistry, London
182
METHOD 8 - DETERMINATION OF TOPANOL OC, BINOX M AND IONOX
330 PHENOLIC ANTIOXIDANTS IN POLYETHYLENE. ULTRAVIOLET
SHIFT MEmOD.5
8.1 SUMMARY
This is a low interference method for the determination of down to 0.01%

Topanol OC, Binox M and Ionox 330 phenolic antioxidants in polyethylene
8.2 APPARATUS
A recording ultraviolet spectrophotometer capable of measurements over the

range 200 to 700 nm.
8.3 REAGENTS
Ethanol - spectroscopic grade absolute ethanol.

Ethanolic potassium hydroxide solution. Dissolve 109 of analytical reagent
grade potassium hydroxide in 10 cm3 of distilled water and dilute the solution to 100 cm3
with absolute ethanol.
Nickel peroxide - B.D.H.laboratory reagent grade.
8.4 METHOD
Ultraviolet measurements (250 - 450 nm) are carried out on the following four
solutions:
1. ethanol extract of polymer
ii. alkaline ethanol extract of polymer
iii. ethanol extract of polymer after treatment with nickel peroxide
iv. alkaline ethanol extract of polymer after treatement with nickel peroxide
These four spectra are compared with spectra obtained with synthetic standard
solutions of the antioxidants, similarly treated, and the antioxidant contents of the
polymer deduced.
Prepare the polymer compound containing the unknown stabiliser by cutting or

grinding to small pieces and extract about 5 g by heating under reflux for 24 h with 50 ml
of ethanol. Cool the extract to room temperature and filter off the polymer. Treat a
solvent blank of 50 ml of ethanol identically.
Measure the ultraviolet absorption spectrum of the extract over the range 250 to
450 nm with the solvent blank in the comparison beam. Dilute the extract if necessary,
so that the absorbance of the main band is about 0.6.
To 10 cm3 of this solution add 1 cm3 of distilled water and 2 cm3 of ethanolic
potassium hydroxide solution. Mix well and measure the ultraviolet absorption spectrum
of this alkaline solution over the same range against a solvent blank similarly treated.
183
Transfer 20 cm 3 of the extract to a 50 cm3 flask, add about 0.5 g of nickel
peroxide, stopper the flask and shake, with a mechanical shaker for 5 m. Filter the
solution and measure the absorption spectrum as before, over the range 250 to 450 nm
with a solvent blank in the comparison beam. If necessary, because of the high
absorption, dilute the filtered reaction products before measurement and note the dilution
used. If the solutions are coloured, also measure the absorption spectrum over the range
450 to 700 nm.
Add 2 drops of ethanolic potassium hydroxide solution to the above cell solution,
mix well and re-measure the absorption spectrum over the same range as before.
The above procedures give four spectra for each extract, which are then compared
with the spectra obtained by carrying out the procedures with known stabiliser solutions.
The three antioxidants can be individually determined in amounts down to 0.02%

with an accuracy of ± 10%. There are no mutual interference effects.

ANTIOXIDANT IN POLYOLEFINS. THIN LAYER CHROMATOGRAPHY.
9.1 SUMMARY
A thin layer chromatographic method for the determination of down to 0.002% of

Santonox R in polyolefins.
9.2 APPARATUS
Thin layer chromatography tank.

Thin layer plate 20 cm x 20 cm, pre-coated with a 250 u layer of Merck.
CF254 silica gel, U.K. Distributors - Anderman & Co Ltd., Battlebridge House,
Tooley Street, London SEt.
Hypodermic syringe - 25 ul capacity.
Ultraviolet lamp - wavelength 254 nm.
9.3 REAGENTS
Chloroform, analar, British Drug Houses.

Petroleum ether, 40/60 Analar, British Drug Houses.
Santonox R - (4,4'-thiobis-3-methyI6-6-butylphenol).
Ethyl acetate, Analar, British Drug Houses.
2,5-dibromo-p-benzoquinone-4-chlorimine, British Drug Houses.
Sodium tetraborate (borax), Analar, British Drug Houses.
184
9.4 METHOD
A toluene extract of the polymer is spotted on to a thin layer plate which is then
developed with a petroleum ether:ethyl acetate mixture (5:1). The developed plate is
sprayed with 2,6-dibromo-p-benzoquinone-4-chlorimine solution to reveal coloured spots
which are proportional in intensity to the Santonox R content of the original polymer.
9.S EXPERIMENTAL PROCEDURE
9.S.1 Polyethylene Extraction Procedure.
Accurately weigh 5 g of polymer into a 500 ml round-bottomed flask. Add 65 ml

of toluene and heat on a boiling water bath for 90 min using a reflux condenser.
Remove the flask from the water bath and immediately pour 85 ml of absolute
ethanol down the condenser to precipitate the dissolved polyethylene from the hot toluene
solution. Allow the flask to cool to room tempemture, remove the condenser, stopper the
flask and shake well. Filter the solution through a No. 42 Whatman filter paper into a
250 ml beaker. Wash the flask and residue with a further 100 ml of ethanol.
Evapomte the toluene/ethanol solution almost to dryness on a boiling water bath
with the aid of a stream of nitrogen and finally to dryness using only the nitrogen stream.
If more polymer is precipitated during the evaporation, refilter the solution into a smaller
beaker. Wash the residue into a 2 ml volumetric flask with chloroform and make up to
the mark. .
Santonox R is extracted from polyethylene by precipitation of the polymer with
ethanol from hot toluene solution as described above. The extract is evapomted to
dryness, dissolved in chloroform and an aliquot applied to a thin-layer plate and the
chromatogmm developed. The concentration of Santonox R in the polyethyolene is
estimated by visually comparing the intensity of the spot obtained with corresponding
spots from known quantities of Santonox R.
Place 20 ul of the chloroform extract of the polyethylene sample as a spot on a
thin layer plate. Also apply 20 ul aliquots of standard solutions of Santonox R in
chloroform, 0.05%, 0.04%, 0.03%, w/v. Develop the chromatogmm to a distance of 10
cm in a chromatogmphy tank containing petroleum ether (40:60)/ethyl acetate (5:1 v/v
mixture) as the eluent.
Inspect the plate under ultraviolet light (254 nm) and compare the intensity of the
Santonox R spot from the polyethylene extract with the intensities of the standard spots.
If the spot is of lower intensity than that of the 0.03% w/v standard than a new
chromatogram should be developed using standards, 0.025%, 0.015% and 0.005% w/v of
Santonox R in chloroform.
Visually compare under an ultraviolet lamp the intensity of the spot from the
polyethylene extract with the standard spots and thus estimate the percentage level of
Santonox R in the chloroform solution. Spray the thin-layer plate with a 2% w/v ethanol
solution of 2,6-dibromo-p-benzoquinone-4-chlorimine. Allow the thin-layer plate to dry
and re-spray using a 2% w/v aqueous solution of borax. Re-estimate the amount of
Santonox R present in the chloroform solution by visually comparing the purple spots
produced.
185
9.S.2 Calculation of Results
Santonox R from 5 g of polyethylene is concentrated into a 2 ml chlorofonn

solution.
Thus the weight % of Santonox R in high density polyethylene = 2/5 x the level of
Santonox R present in the 2 ml chlorofonn solution (as determined by thin-layer
chromatography in % w/v).
Santonox R can be detennined in polyolefms in amounts down to 0.002% with an

accuracy of ± 20% of the detennined amount.
METHOD 10 - DETERMINATION OF PHENOLIC ANTIOXIDANTS IN

POLYALKENES. THIN LAYER CHROMATOGRAPHY.'
10.1 SUMMARY
A general thin-layer chromatographic method for the detennination of 0.02% of a

range of phenolic antioxidants in polyalkenes.
10.2 APPARATUS
Soxhlet extraction apparatus, 250 ml.

Extraction thimble, F & S no. 603 size 33 x 94 mm.
Thin layer plates. Silica Gel G tiniplates (8 in x 8 in) and Silica Gel G Uniplates,
reverse phase 5% Dow Silicone (8 in x 8 in) or equivalent. The plates are given a short
equilibration time in the development solvent vapours.
Capillary pipet, 20 ml.
Chromatographic chamber. Inner diameter, 103/ 8 in x 2\ in X 101/4 in with glass
cover. The chamber contains a 8 in x 8 in sheet of Whatman no. E-17 filter paper to
maintain a saturated solvent atmosphere during development.
Chromatography sprayer.
Densitometer. 0.0 - 1.0 optical density wedge with 620 om filter.
10.3 REAGENTS
Extraction solvent. n-heptane:-n-octane 4:1 v/v.

Detection system. Phosphomolybdic acid (3.0g) was dissolved in a 100 cm3
volumetric flask with ethanol and diluted to volume with water. Filter if necessary to
remove any solids prior to use. The solution must be prepared fresh every two days.
Development solvent. System A (for identification of antioxidants). 240 volumes
of ethanol were added to 80 volumes of distilled water. System B (for quantitative
analysis). 300 volumes of practical grade cyclohexane were added to 6.volumes of
reagent grade methanol.
186
10.4 MEmOD
A n:hepane-n-octane (4:1 v.v) extract of the polymer is applied to a thin-layer

plate which is then developed with ethanol, water or cyclobexane-methanol development
solvents. Spraying the plate with phosphomolybdate revealed spots due to separated
antioxidants. The method was calibrated against standard solutions of antioxidants.
10.5.1 Extraction Procedure.
The polyethylene or polypropylene film, (5.0 g precut into strips approximately I

in x 1 in) is weighed into the extraction thimble, 130 ml of the extraction solvent and a
few glass beads are added to the 250 cm3 flat bottomed flask, the extraction apparatus is
connected and heated to boiling. After 3 h the system is allowed to cool to room
temperature and the solvent drained into the 250 cm3 flat bottom flask. The extraction
thimble and extraction apparatus are rinsed down with 25 - 30 cm3 of the extraction
solvent and drained into a 250 cm3 flask. The contents of the 250 cm3 flask are
quantitatively transferred to a 250 cm3 Pyrex glass beaker and concentrated to a 25 - 30
cm3 volume by evaporation on a hot plate then quantitatively transferred to a 50 cm3
beaker, concentrated to 6 - 7 ml, and transferred to a 10 cm3 volumetric flask and diluted
to volume with the extraction solvent.
10.5.2 Chromatographic Procedure.
Two 20 ul aliquots of both the sample and the synthetic standard are applied to the
thin-layer plate, the spots are dried with a heat gun and the chromatograms eluted for 30 -
40 min in the development solvent. The resulting chromatogram is dried with a heat gun,
sprayed with the detection reagent, redried, exposed to ammonium hydroxide vapors and
scanned on the photodensitometer.
10.6 TYPICAL RESULTS
The areas of each zone were calculated by triangulation (area calculated by

multiplying the height times the width at half height). The quantitative results are
calculated from the following ratio:
% antioxidant in the polyolefin = A' x P

A
where A = the average numerical area recorded for the synthetic standard;
A' = the average numerical area recorded for the sample;
P = actual percentage of the antioxidant present in the synthetic standard based
upon the weight of the sample.
The method was applied to the following six antioxidants:
4,4'-butylidene (2~tert-butyl-5-methyl) phenol; 4,4-thiobis (6-tert-butyl-m-cresol);

pentaerythritol tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate); 2,2' -methaylenebis
187
(4-methyl-6-tert-butylphenol); octadecyl (3,5-di-tert-butyl-4-hydroxyphenol) acetate; 2,6-
di-tert-butyl-o-cresol.
In Table 7.4 are reproduced Revalues obtained by Dobies6 when 20 ul of standard

solutions (100 mg/200 rnI) of the above mentioned antioxidants were applied to thin-layer
plates and eluted with the development solvent.
In Table 7.5 are shown the results obtained by Dobies6 in applying his method
over a three day period to samples of polyethylene and polypropylene containing
approximately 0.1 %. 2.2' -methylenebis (4-methyl-6-tert-butylphenol), compound with
results obtained by an ultraviolet spectrophotometric method. Although there are minor
differences in the results of the methods, the thin-layer procedure shows the presence of
an additional zone, attributed to the presence of 2,6-di-tert-butyl-p-cresol. The presence
of this antioxidant, although not determined by the thin-layer chromatographic procedure,
could interfere with the ultraviolet procedure thus giving higher results.
The method has been used to determine down to 0.02% of six antioxidants in
polyalkenes with an accuracy of ± 10%. As mentioned above, there exists a risk of
interference effects by other antioxidants. Consequently, the method must be applied
with caution.
METHOD 11 - DETERMINATION OF PHENOLIC AND AMINE

ANTIOXIDANTS, ULTRAVIOLET ABSORBERS AND ORGANOTIN
STABILIZERS IN POLYALKENES AND OTHER POLYMERS. THIN LAYER
CHROMATOGRAPHY.'
11.1 SUMMARY
This thin-layer method is capable of determining a wide range of polymer

additives, viz amine antioxidants, uv absorbers and organotin stabilizers in amounts down
to 0.02% in polyalkenes.
11.2 APPARATUS
Thin layer plates, Merck.

Kieselgel GF254 (silica gel containing a fluorescent additive, thickness C.25
mm).
11.3 REAGENTS
Benzene-ethyl acetate - acetone (100 + 5 + 2) used for antioxidants.

Chloroform - hexane (2 + 1) - used for ultraviolet absorbers.
Butanol - glacial acetic acid (97 + 3) - used for organotin compounds.
2,6-Dichloro-p-benzoquinone-4-chlorimine, 0.2 per cent, w/v solution in absolute
ethanol.
188
Table 7.4 - Rr Values of Antioxidants
System A: Silica Gel G, reverse phase 5% Dow Silicone; developing solvent, ethanol-water.
System B: Silica Gel G Uniplates; developing solvent, cyclohexane-methanol
Rr Values
Antioxidant System A SystemB
4,4'-Butylidenebis (2-tert-butyl-5-methyl) phenol 0.80 0.0

4,4'-Thiobis (6-tert-butyl-m-cresol) 0.84 0.0
Pentaerythritol tetrakis (3,5-di-tert-butyl-
4-hydroxyhydrocinnamate) 0.60 0.29
2,2' -Methylenebis (4-methyl-6-tert-butyl-phenol) 0.76 0.34
Octadecyl (3,5-di-tert-butyl-4-hydroxy-phenyl) acetate 0.33 0.70
2,6-Di-tert-butyl-p-cresol 0.71 0.72
From Dobiel Elsevier Science Publishers, Netherlands
Table 7.5 - Replicate Determination of Approximately 0,1% 2,2'-methylenebis (4-

methyl-6-tert-butylphenol) in Polyethylene and Polypropylene
% Antioxidant
Sample
1st day 2nd day 3rdday Average ByU.V.
analysis analysis
Polyethylene 0.095, 0.094 0.1 03, 0.1 00 0.087,0.089 0.094 0.102,0.105

0.096, 0.092 0.087
Polypropylene 0.080, 0.084 0.079, 0.078 0.078, 0,078 0.079 0.083, 0.083
0.073, 0.086 0.079
From Dobies6 Elsevier Science Publishers, Netherlands
Borax, 2 per cent, w/v solution, dissolve 2 g of sodium tetraborate decahydrate in

100 cm3 of 5 per cent, v/v ethanol.
Catechol violet, 0.1 per cent, w/v solution in 95 per cent ethanol.
Diethyl ether (Analar).
Chloroform (Analar).
Ethanol (Analar).
11.4 METHOD
A diethyl ether extract of the polymer is applied to a thin-layer plate which is then
developed with various solvent mixtures. The plate is then sprayed with a range of
reagents specific for the compounds to be determined and the coloured spots compared
visually with standards to determine the concentration of polymer additives.
189
Weigh two 2 - 5 g amounts of plastics material and extract each with diethyl ether
for 8 h in a Soxhlet continuous extraction apparatus.
Remove the diethyl ether by distillation on a water-bath and add 5 cm3 of ethanol
to each flask. Allow the flasks to stand for 10 minutes. Evaporate the contents of one
flask to dryness (sample A) and those of the other to very small bulk (sample B).
Dissolve sample A in a small amount of chloroform and make up to volume in a 5
cm3 calibrated flask. Transfer sample B quantitatively to a 5 cm3 calibrated flask and
dilute to volume with ethanol. Use sample A solution for the determination of
antioxidant and ultraviolet absorber, and sample B solution for the determination of
organotin compounds.
Spot 2 ul of solution A on to each of two Merck Kieselgel GF254 plates and 2 ul
of solution B on to a third plate. Place each plate into a chromatogram sandwich chamber
and, by using the appropriate mobile phase, allow the solvent to travel a suitable distance.
Locate the spots as described below:
11.5.1 Determination of Antioxidant.
Mobile phase - Benzene - ethyl acetate - acetone (l00 + 5 + 2), Chromogenisis -

View the plate under ultraviolet light and mark any spots located. Then spray the plate
with 2,6-dichloro-p-benzoquinone-4-chlorimine solution, heat it with a drier for a few
minutes and mark any spots coloured by the reagent. Finally, allow the plate to stand in a
tank in contact with iodine vapour for 5 min.
11.5.2 Determination of Ultraviolet Absorben.
Mobile phase - Chloroform - hexane (2 + 1), Chromogenesis - View the plate

under ultraviolet light and mark any spots located. Spray the plate with borax solution
followed by 2,6-dichloro-p-benzoquinone-4-chlorimine solution, heat it with a drier for a
few minutes and mark any spots coloured by the reagents.
It was possible to detect down almost to 1 ug per spot applied in certain cases and
at least 10 ug per spot applied.
In Table 7.6 are tabulated some R, values obtained by this method for various
types of polymer additives.
The method is capable of determining down to 0.05% of a wide range of additives

in polyaIkenes with an accuracy of ± 10%.
190
Table 7.6 - Results Obtained for Each Additive in Each Mobile Phase
Substance Rr value in Benzene-ethyl Rrvalue in

acetate-acetone-hexane chlorofonn-hexane
Antioxidants:
NonoxSP 0.61,0.93 0.50
NonoxTBC 0.98 0.62
NonoxWSP 0.85 0.52
NonoxEX 0.56 0.38
NonoxWSL 0.82 0.54
BUT 0.98 0.91
2246 0.75 0.56
NonoxCI 0.65,0.84 0.49
NonoxDPPD 0.66 0.48
NonoxOD 0.56 0.40
NonoxZA 0.43,0.38 0.38
Santoflex 0.15,0.61,0.74 0.47,0.54
Santoflex AW 0.80, 0.51, 0.55 0.54,0.45
SantoflexR 0.26,0.53 0.39
DLTP 0.61 0.41
NonoxNS 0.52 0.4
Superlite 0.64,0.93 0.58
Polygard 0.52,0.61 0.53
NonoxUO 0.46, 0.64, 0.60, 0.99 0.52
NonoxWSO 0.58 0.39
Irganox 1076 0.57,0.75 0.56
Ultraviolet absorbers:
Eastman DOBP 0.76 0.39
Uvinul400 0.22 0.08
PennylBIOO 0.24 0.08
Salol 0.73 0.45
TinuvinHE 0.71
Tinuvin P 0.76 0.59
EastmanOPS 0.79 0.65
UV318 0.26 0.14
Cyasorb 1988 0.26 0.12
Cyasorb 1084 0.24 0.08
UvinulN35 0.28 0.16
From Simpson and Currell'. Royal society of Chemistry, London
METHOD 12 - DETERMINATION OF IRGANOX 1076, IRGANOX 1010 AND

BUTYLATED HYDROXYTOLUENE PHENOLIC ANTIOXIDANTS IN
POLYETHYLENE_ HIGH PERFORMANCE LIQUID CHROMATOGRAPHY.8
12.1 SUMMARY
This high performance liquid chromatographic method is capable of determining

down to 0.001% of Irganox 1076, Irganox 1010 and butylated hydroxy toluene
antioxidants in polyethylene.
191
12.2 APPARATUS
Waters Model 204 liquid chromatograph equipped with two Model 6000 A
pumps, a Model 660 solvent programmer and a U6K injector. Elution was monitored
with a Waters Model 450 variable wavelength detector set at 280 nm and a 10 mv strip
chart recorder.
Column - 3.9 mm x 30 cm u-Porasil column packed with 10 urn porous silica
obtained from Waters Associates, Milford, Mass.
Thermolyne type 1000 stir plates (Sargent Welch).
Stir bars 318 inch o.d. x 1'12 inch Teflon coated magnetic stir bars.
Sample filtering apparatus - a Waters 20 - 30 nm' stainless steel solvent reservoir
filter was connected to about a 2" length of 3 mm i.d. Teflon tubing. The other end of
the Teflon tubing was connected to a 1'/2 inch long blunt 16 gauge Luer lock needle with
a 1/16 inch stainless steel nut and ferrule at the end of the needle. The needle was
connected to a Hamilton No. 1010 W gastight 10 ml S)q'inge with Teflon plunger.
12.3 REAGENTS
Heptane, spectrograde.
Chloroform, Mallinckrodt AR grade, Scientific Products.
Methylene chloride, distilled in glass.
The above mobile phase solvents were all filtered through MiIIipore Type F-H 0.5
urn filters prior to use.
12.4 METHOD
A decalin extract of the polymer was chromatographed on a program set to

gradient elute with mixtures of heptane and methylene dichloride. Detection of eluted
compounds was achieved by a uv detector. The method was calibrated against approp-
riate standard solutions.
12.5 PROCEDURE
Heated standard solution: A 50 ml portion of a standard solution containing about

0.02 mg/ml each of BHT, Irganox 1076 and Irganox 1010 is pipetted into a 100 ml
beaker. A stirring bar is added and the solution is heated to 110°C with a gentle stirring
for 30 min. The solution is transferred to a cool stirrer and cooled to room temperature.
This heated and cooled standard solution is used to obtain quantitative data on the sample
extract solutions.
About 2 g of polyethylene pellets are weighed into a 100 ml beaker. A stirring
bar is added and 50 ml of decal in is pipetted into the beaker. The mixture is heated at
110°C on a hot plate with gentle stirring for about 30 minutes or until dissolution is
complete. The beaker is then transferred to a cool stirrer and cooled to room temperature
with stirring to precipitate the polyethylene.
The precipitated polyethylene from the above extraction is pushed aside with a
microspatula. The porous metal filter portion of the filter apparatus is inserted into the
solution and about 5-10 ml of solution is drawn into the syringe. The Teflon tube is
removed from the ferrule on the needle and the filtered solution is dispensed into a small
192
vial. The filter apparatus is rinsed with acetone and dried between samples. After
extensive use, the metal filter became partially clogged and is regenerated by placing it in
hot decalin and stirring.
The Model 660 solvent programmer is set at Program 6 (linear) going from 100%
heptane to 100% methylene chloride in 5 min. The total flow rate is 3 mVmin. The
Model 450 UV detector is set at 0.2 or 0.4 absorbance unit sensitivity and the recorder
chart speed is 1 cm/min. Duplicate injections of 100 ul of each of the standard and
sample solutions are made. The mobile phase gradient is started at the point of injection.
The retention volumes (VR) for BHT, Irganox 1076 and Irganox 1010 are 10.3,
14.8 and 22.2 ml respectively. The amount of each additive is determined from each
sample injection by comparing peak heights for samples and standards. A blank decalin
injection is made to determine from what points on the base line, peak heights should be
measured. Gradient reset is instantaneous, from 100% methylene chloride to 100%
heptane. Sample injection could be made any time after the appearance of a refractive
index peak from the UV detector, signifying the emergence of heptane from the column.
Excellent antioxidant recoveries are obtained by this procedure, Table 7.7.
12.7 DISCUSSION
The method is very sensitive, being capable of determining down to 0.001% of

the three antioxidants with an accuracy of ± 10%. As always with chromatographic
methods the possible effects of interfering substances must be considered.
METHOD 13 - DETERMINATION OF NONOX CI AMINE ANTIOXIDANT IN

POLYALKENES. ACID HYDROGEN PEROXIDE SPECTROPHOTOMETRIC
METHOD.'
13.1 SUMMARY
This spectrophotometric method is capable of determining down to 0.01% of

Nonox CI amine antioxidant in polyalkenes.
13.2 APPARATUS
(a) Miscellaneous
Conical flasks B24, 250 ml, T-piece with B 19 cone and side arc.
Reflux condenser, Liebig type 16 in with B25 cone and BI9 socket.
Volumetric flasks, 25 cm3, 100 cm3•
Pipettes, 2 ml, 20, 50 cm3 .
Rubber suction bulb.
Filter funnels, 3 in.
Glass rod 1/8 in diameter.
Wash bottle (all glass).
Porous pot broken into approximately 1/16 in pieces.
193
Hotplates.
(b) Spectrophotometer
Visible and or visible/uv instrument
13.3 REAGENTS
Toluene - redistilled B.D.H. Laboratory reagent grade (sulphur free).

Ethanol - redistilled industrial methylated spirit.
Hydrogen peroxide reagent. Dilute 25 cm3 of 20% v sulphuric acid solution and 4
milOO vol. hydrogen peroxide (Aoalar) to 100 cm3 with distilled water and shake. Allow
to stand for 2 hours before use. Prepare this reagent fresh daily.
Natural polyethylene (powder or nibs), antioxidant free.
Pure Nonox CI for calibration purposes - add 50 cm3 redistilled industrial methyl
alcohol to approximately 5 g of commercial ''Nonox'' and warm to 60°C with constant
stirring. Filter the mixture through a Whatman No.4 filter paper. Thoroughly wash the
solid remaining on the paper with 6 x 40 cm3 portions of hot alcohol as quickly as
possible. Reject the highly coloured filtrate. Allow the paper to drain for 2 to 3 min and
transfer to a vacuum desiccator. Apply vacuum until paper and solid are absolutely dry.
Store the pure ''Nonox'' under nitrogen in a brown glass bottle.
13.4 METHOD
A toluene extract of the polymer is reacted with ethanolic hydrogen peroxide to

produce·a coloured compound with an absorption maximum of 830 mm proportional to
the Nonox CI content of the polymer. The method is calibrated against solutions of
purified Nonox CI.
13.5.1 Extraction of Antioxidant from Polymer.
Weigh a suitable amount (eg 0.5 - I g if 0.1% Nonox present) of polyethylene

powder, shavings or nibs, usually not exceeding 0.6 g into a 250 ml conical flask.
Pipette 50 cm3 toluene into the flask and add 2 g of broken porous pot. Purge the
interior of the flask with nitrogen and connect immediately to a condenser which has been
previously purged with nitrogen. Connect aT-piece to the open end of the condenser and
pass a gentle purge of nitrogen through the T-piece during the reflux period. Reflux
gently for one hour. Allow the contents of the flask to cool to approximately 40°C and
add 20 cm3 of ethanol to reprecipitate any dissolved polymer. Filter the contents of the
conical flask through a Whatman No. 54 filter paper into a 100 ml volumetric flask and
make up to 100 ml with ethanol.
13.5.2 Determination of Antioxidant.
Pipette 20 cm3 of the f?lyethylene extract into a 25 cm3 volumetric flask. Pipette in 2
cm3 ethanol and 2 cm hydrogen peroxide reagent and adjust the solution temperature to
25 ± 3°C and make up to the 25 cm3 mark with ethanol and mix well.
194
Table 7.7 - Recoveries ofBHT, Irganox 1076 and Irganox 1010 from three Polyethylene
Samples
Amount Adde!!. mg AmQl!!!l Fo!!!!!!. mg Percent Recovered

Sample' amount BHT Irganox Irganox BHT Irganox lrganox BHT Irganox Irganox
g 1076 1010 1076 1010 1076 1010
A 1.96 1.02 1.00 1.01 1.04 1.08 1.03 130 108 102
A 2.01 1.02 1.00 1.01 1.06 1.10 1.13 104 110 112
B 2.02 1.01 1.00 1.01 1.02 1.07 0.99 100 107 98
B 1.97 1.02 1.00 1.01 0.99 1.09 0.94 98 109 93
C 1.97 1.02 1.00 1.01 1.04 1.05 0.98 102 105 97
C 2.04 1.02 1.00 1.01 1.07 1.06 1.05 105 106 104
From Scltabon and FetISh'. American Chemical Society
After 25 to 30 min fill a spectrophotometer cell with the test solution. Record the
optical density at 5 min intervals until the maximum reading is obtained. The maximum
optical density is usually obtained between 40 min and 120 min after addition of the
hydrogen peroxide reagent depending on the concentration of Nonox in the test solution.
Spectrophotometer conditions.
Cells: 4 cm glass.
Blank solution: 1: 1 (v/v) toluene:ethanol.
Wavelength: 830 nm.
13.5.3 Preparation of Calibration Graph.
The procedure is calibrated against Nonox which has been purified by elution
with ethanol. Weigh out 0.0250 ± 0.00002 g purified Nonox into a dry 100 cm3
volumetric flask. Add 50 cm3 toluene and swirl in a water bath until the solid is
dissolved. Cool to room temperature, make up to 100 cm3 with toluene and mix well.
Use this stock solution of the day of preparation. Transfer 0.2, 0.5, 1.0,2.0,3.0,4.0 and
5.0 cm3 aliquots, (ie. containing 50 to 1250 micrograms Nonox) of this solution to dry
250 cm3 conical flasks and add sufficient toluene to make the volume up to 50 cm3• To
the contents of each flask add approximately 0.3 g of natural antioxidant free
polyethylene powder or nibs and make up to 100 ml with ethanol. Continue the colour
development on 20 ml of this solution as described in Section 13.5. Plot a calibration
graph relating optical density readings obtained and the number of micrograms of Nonox
present in the 20 cm3 aliquots of test solution used for colour development.
13.5.4 Calculation.
From the calibration graph read off the number of micrograms of Nonox
corresponding to the maximum optical density reading obtained. The concentration of
Nonox in the polyethylene is given by:
Nonox % (w/w) = 102 X lQ2 x 10-6,X£

20xW
where P = weight of Nonox read off from the calibration graph (microgram)
195
W = weight of polyethylene taken for analysis (g).
13.6 DISCUSSION
This method is capable of detennining down to 0.01% Nonox CI in both low and
high density polyethylene with an accuracy of ± 10% of the detennined Nonox CI
content.
METHOD 14 - DETERMINATION OF AMINE ANTIOXIDANTS IN

POLYALKENES AND OTHER POLYMERS. P-NITROANILINE COUPLING -
SPECTROPHOTOMETRIC PROCEDURE. to
14.1 SUMMARY
This spectrophotometric method is capable of detennining down to 0.01% of a

wide range of amine antioxidants in polyalkenes.
14.2 APPARATUS
All of the absorption measurements were made on a visible spectrophotometer

using quartz cells having a light path of 1 cm.
14.3 REAGENTS
Methanol- pure synthetic methanol (99.85%).

Hydrochloroic acid - Analar, concentrated.
p-Nitroaniline - micro analytical reagent.
Sodium nitrite - reagent grade.
Coupling agent - 2.800 g of p-nitroaniline is dissolved in 32 cm3 of hot
concentrated hydrochloric acid and the solution is diluted with distilled water to 250 cm3•
After cooling to room temperature the volume of liquid is adjusted to 250 cml . A second
solution is made containing 1.44 g of sodium nitrite in 250 cml of distilled water.
Twenty-five cm3 of each of these solutions are pipetted into separate 100 cml beakers,
mixed and chilled in ice to below 10DC. Pure nitrogen is bubbled through the mixture as
it warms to room temperature. Finally, 10 mg of urea (or 1 cml of 0.1 gllOcml solution)
is added to destroy any excess nitrous acid. Fresh reagent should be made every day.
Methanol -hydrochloric acid solvent. Three volumes of methanol plus one
volume of concentrated hydrochloric acid.
14.4 METHOD
An ethanol or methanol extract of the polymer is reacted with diazotized p-

nitroaniline to produce a colour in the 350 - 700 nm range proportional to the amine
antioxidant content of the polymer. The colour is evaluated spectrophotometrically at its
absorption maximum and compared with calibration standards.
196
The sample to be analysed must be very thinly sheeted or powdered. Weigh a

1.000 ± 0.0005 g sample. Wrap with extraction cloth which has been previously
extracted to remove sizing, etc. Place in an Underwriter's extraction cup and extract for
16 hr with 95% ethanol or methanol. Transfer the alcohol extract to a 100 cm3
volumetric flask. Cool to room temperature and bring to the mark with the extraction
solvent. Transfer a 10 cm3 aliquot to a 100 cm3 volumetric flask. Add 15 cm3 methanol-
hydrochloric acid solution and 1 cm3 of coupling agent. Place in dark for 1.5 h and then
bring to the mark with methanol-hydrochloric acid. Determine the absorption spectrum
from 350 - 700 nm. Measure the optical chemistry at the absorption maximum. Calibrate
the methanol against amine antioxidant standards prepared in ethanol or methanol, treated
as above and evaluated at the same wavelength.
Amine antioxidants which can be determined:
Agerite Excel Flectol H

Agerite Gel Flexamine
Agerite Resin NeozoneA
Agerite Resin D NeozoneC
Agerite Stalite Octamine
Akroflex C Polylite
Albasan Stabilite
Aminox Stabilite ALBA
Antox Stabilite L
Aranox Thermoflex
Amine antioxidants which cannot be determined include:
Agerite White Santoflex 35

Antioxidant 4010 Santoflex 75
BXA Tenamine2
Eastozone 32 Tenamine 30
JZF (DPPD) Tonox
OZ088 TonoxD
Santoflex AW D.O.P.88
Santoflex BX D.O.P.288
Santoflex DD
14.7 DISCUSSION
The method is capable of determining down to 0.02 to 0.05% of amine

antioxidants in polyalkenes with an accuracy of ± 5%. The colour obtained with phenyl-
B-naphthylamine antioxidant fades too rapidly to enable it to be determined.
197
METHOD 15 - DETERMINATION OF DIORGANOSULPHIDE AND TERTIARY
PHOSPHITE ANTIOXIDANT IN POLYETHYLENE. M-
CHLOROPEROXYBENZOIC ACID OXIDATION METHOD!'
15.1 SUMMARY
This titration method is capable of determining down to 0.05% of

diorganosulphide and tert phosphite type of antioxidants in polyethylene.
15.2 APPARATUS
Titration burette, 10 ml.
15.3 REAGENTS
Heptane, chloroform, sodium iodide, glacial acetic acid and isopropanol.

m-chloroperoxybenzoic acid, technical grade (85%) (available from Aldrich
Chemical Co., main impurity being m-chlorobenzoic acid).
Oxidizing solution, dissolve 1.6 g of m-chloroperoxybenzoic acid in chloroform
and dilute to 200 cm3with chloroform.
Sodium iodide solution, prepared by saturating iso-propanol with the solid salt at
refluxing tempemture.
Sodium thiosulphate 0.05N.
15.4 METHOD
The antioxidant is reacted with an excess of m chlorophenoxybenzoic acid.
(RO)3P + CIC~4COOOH = (RO)3PO + CIC6 H4COOH 7.1

(ROOCCH2CHJ2S + 2 CIC6H4COOOH = (ROOCCH2CH20)2S
+ 2 CIC6 H4COOH
Unused m-chloroperoxybenzoic acid is then reacted with potassium iodide in

acidic medium to produce iodine which is estimated by sodium thiosulphate titration.
The amount of m-chloroperoxybenzoic acid consumed by a known weight of the

sample can be used to calculate the concentration of antioxidant present.
The polyolefin sample was ground in a Wiley Mill to pass through a 60 mesh
screen. Extract a 10 - 20 g portion of sample in a Soxhlet apparatus with heptane for a
minimum of 6 h. Transfer the extraci to a 300 cm3beaker, evapomte to approximately 20
cm3 and then dilute to 40 cm3 with chloroform. Pipette ten milliliters of the m-
chloroperoxybenzoic acid solution into the beaker and allow to react for 45 min at room
198
temperature. Pipette 2 cml glacial acetic acid into the beaker followed by 100 cml of dry
isopropanol and 10 cml of the sodium iodide-saturated isopropanol. Allow 60 min for
complete decomposition of the excess peroxide. Add 25 cm] of water and titrate with
0.05 M sodium thiosulfate to the disappearance of iodine colour. A blank consisting of
the oxidant and all reagents used was run along with the samples.
Calculations. For sulfide antioxidants, the calculations to obtain percentage pres-

ent in the original polymer sample was:
% sulfur-containing antioxidant = (cml) (N) (MW) CO. 1)

(sample wt) (4)
Weight per cent phosphite compound present in the original polymer sample was
calculated as:
% phosphite antioxidant = (eml) (N) (MW) (0.1)

(sample wt) (2)
where cml is the milliliters of thiosulfate used for the sample subtracted from the
milliliters used for the blank, M is the molarity of the sodium thiosulfate, and MW is the
molecular weight of the antioxidant being determined which divided by 4 for sulfides and
by 2 for phosphites places the equation of a molar basis and allows the calculation of
percentage. Recoveries of the following antioxidants were usually in excess of 99%:
Distearyl thiodipropionate
Dilauryl thiodipropionate
4,4' -Thiobis (6-tert-butyl-m cresol)
1,1'-Thiobis (2-naphthol)
Triphenyl phosphite
Triethyl phosphite
Tri-p-tolyl phosphite
Tris(dinonyl phenyl)-phosphite
2,2' -Thiobis (6-tert-butyl-p-cresol)
Tri isopropyl phosphite
15.7 DISCUSSION
The method is capable of determining down to 0.05% of diorganosulphide and

tertiary phosphite type antioxidants in polyalkenes with an accuracy of ± 5%. Table 7.8
shows the results obtained by applying the oxidation method to blends of antioxidants in
unstabilized polyethylene. The results are in excellent agreement with the theoretical
antioxidant content of these polymers.
199
METHOD 16 - DETERMINATION OF DIORGANOSULPHIDE
ANTIOXIDANTS IN POLYALKENES. GAS CHROMATOGRAPHY
16.1 SUMMARY
This gas chromatographic method is capable of determining diorganosulphide

secondary antioxidants in polyalkenes in amounts down to 0.02%.
16.1 APPARATUS
Dual column chromatograph equipped with flame ionisation detectors and an

isothermal column oven. The oven was operated isothermally at 165°C and the injection
port at 300°C.
Column - 6 foot x 1 inch glass column, packed with 1.5 per cent of fluorisilicone
oil FS-1265 on 80 to 100 mesh Chromosorb W AW-DMCS.
Argon carrier gas, flow rate of 30 ml min'l.
16.3 REAGENTS
Dilauryl 68' -thiodipropionate.

Dilauryl sulphenyl- 88-dipropionate - prepared by oxidation of dilauryl 88'-
thlodipropionate with chromic acid in an acetic acid medium to 60 to 80°C (melting point
74oC).
Dilauryl sulphonyl- 88'dipropionate - prepared from dilauryl- 8B'-thiodi-
propionate by oxidation with hydrogen peroxide.
n-Octadecane - analytical reagent grade quality.
Chloroform - analytical reagent grade quality.
Methanol- analytical reagent grade quality.
Potassium hydroxide - analytical reagent grade quality.
Standard lauryl alcohol solution 0.07% in chloroform.
n-Octadecane solution - 0.2% in chloroform.
Standard potassium hydroxide, 5 M solution in methanol.
Diorganosulphide calibration solution. Place 5 cm3 of solution containing 0.1 to 3
mg of dilauryl 86' -thiodipropionate, dilauryl sulphenyl- 88' -dipropionate or dilauryl
sulphonyl- 86' -dipropionate in a test tube provided with a B29 ground glass joint and
evaporate off the solvent under a stream of nitrogen. Add I cm3 of freshly prepared
methanolic potassium hydroxide solution, fit a reflux condenser and immerse the tube in
a heating bath at SO°C. After heating for 30 min, transfer the contents of the tube into a
25 cm3 separating funnel with 10 cm3 of water. Finally, rinse the tube with 2 ml of
chloroform and add the rinsings to the water in the funnel. Shake the funnel well and
when the layers have separated collect the bottom layer in a 10 cm3 calibrated flask.
Repeat the extraction a further three times, using 1.5 cm3 of chloroform for each run.
Add 1 cm3 of n-octadecane solution to the combined extracts in the flask and make the
solution up to 10 cm3 with chloroform.
200
Table 7.S - Analysis of typical Polypropylene Samples with Various Stabilizers Present
Additive Per Cent Added Per Cent Found
Distearyl thiodipropionate 0.20 0.19

Distearyl thiodipropionate 0.20 0.39 total
4,4'-Thiobis (6-tert-butyl-m-cresol) 0.20 0.30 total
Distearyl thiodipropionate 0.20 0.30 total
From Kellum ll . American Chemical Society
16.4 METHOD
A chloroform extract of the polymer is treated with methanolic potassium

hydroxide to hydrolyse the diorganosulphide antioxidant to lauryl alcohol. n-octadecene
internal standard is added and the resulting solution gas chromatographed to determine
lauryl alcohol which is proportional in amount to the diorganosulphide content of the
original polymer. The procedure is calibrated against standard lauryl alcohol solutions
that have been put through the whole test regime.
Pipette 50 cm3 of chloroform into a 250 cm3 conical flask and add 0.6 g of
polyolefin sample. Reflux gently for 1 h. Allow the contents to cool to 40·C and add 20
cm] of ethanol to precipitate dissolved polymer. Carefully transfer the flask contents via
Whatman No. 54 filter paper into a 100 cm3 volumetric flask and make up to 100 cm3
with ethanol.
To 5 cm3 of this solution add I cm3 of 5M methanolic potassium hydroxide and
heat to SO·C for 30 min. Transfer this solution to a 25 cm3 separating funnel using 10 cm3
of distilled water. Run off the lower chloroform layer into a 10 cm3 volumetric flask
together with three 1.5 cm3 chloroform washings of the aqueous phase. Add 1 cm3 of n-
octadecene in chloroform internal standard and make up to 10 cm3 with chloroform.
Calibrate against the appropriate hydrolysed diorganosulphide calibration solution
referred to under Reagents.
This method is capable of determining down to 0.02% diorganosulphide

antioxidants in polyalkenes with an accuracy of ± 5%. Because of the specificity of the
gas chromatographic method there is little liklihood of interferences.
201
METHOD 17 - DETERMINATION OF CYASORB UV 531 ULTRAVIOLET
ABSORBER IN POLYETHYLENE. INFRARED SPECTROSCOPY.
17.1 SUMMARY
Cyasorb UV 531 ultraviolet absorber (2-hydroxy-4-n octoxybenzophenone) is

determined in polyethylene by infrared spectroscopy of a polymer extract in amounts
down to 0.02%.
17.2 APPARATUS
Double beam spectrometer covering the 15 - 17 micron region (eg. Grubb Parsons
GS2A).
Hydraulic press with heated and water-cooled platens.
Stainless steel moulding plates (6" x 6" x lIlt).
Shims 0.06 cm thick (circular I" diameter or rectangular 1" long).
Aluminium foil.
Clear plastic rule calibrated in millimetres.
Dial gauge calibrated in 0.01 rom divisions.
17.3.1 Preparation of Sample Film.
Cover two stainless steel moulding plates with aluminium foil and place up to six
0.06 cm thick shims on one of these. Place approximately 0.2 g of polymer sample in the
centre of each shim and carefully place the second moulding plates on top. Position the
two plates in the press and apply contact pressure. Switch on the heating supply and set
the thermostat to I20·C. When the temperature reaches 120·C increase the pressure to
3000lb/in2, switch off the heating supply and water cool to room temperature. Carefully
strip off the aluminium foil from the polymer films and push out the films from the
shims. Carefully strip off the aluminium foil from the polymer films and push out the
films from the shims. Check the thickness of each film by means of the dial gauge. Six
readings on each film should not vary by more than 0.03 rom. Reject any which has air
bubbles, is uneven or is wedge-shaped. Shape the film to fit the spectroscopic sample
holder and gently scrape one of the surfaces with a fine emery board to produce a series
of fine parallel lines. This reduces the incidence of interference fringes.
17.3.2 Recording the Infrared Spectmm.
Place the film in the sample holder and position in the infrared instrument so that
the beam passes through the film at right angles to the scratch marks.
Record the infrared spectrum from 15.5 to 16.5 micron using a scanning speed of
1/2 micron per minute.
Before removing the film from the instrument, mark the position of the infrared
beam. Remove the sample from the holder and measure the thickness to the nearest O.ot
202
mm by means of the dial gauge at six points within the marked area. Calculate the mean
of these six measurements.
17.3.3 Measurement of Absorbance.
Remove the chart from the spectrometer and with a sharp pencil rule a base-line
from approximately 15..8 micron to approximately 16.2 micron. With a ruler measure I
and 10 to the nearest 0.1 mm at the wavelength of the peak maximum. Calculate the
absorbance at 15.94 micron and hence the absorbance per unit thickness by means of the
following expression:
Absorbance per unit thickness = l.Qglo!o

film ofthlckness (in cm)
Prepare duplicate rums from the standard sheets containing 0.1, 0.3, 0.5 and 1.0
wt'lo. UV 531 as above. Record the infrared spectrum as described above and calculate
the absorbance per unit thickness as described under measurement of absorbance.
Construct a calibration curve by plotting absorbance per unit thickness against percentage
weight UV 531 for each standard film. Use this calibration curve to obtain the UV 531
content of the polyethylene sample.
This method is capable of determining down to 0.02% Cyasorb UV 531

ultraviolet absorber in polyethylene with an accuracy of ± 5%.
METHOD 18 - DETERMINATION OF CYASORB UV S31 ULTRAVIOLET

ABSORBER IN POLYOLEFINS. THIN LAYER CHROMATOGRAPHY.
18.1 SUMMARY
This thin-layer chromatographic method is capable of determining Cyasorb UV

531 ultra-violet stabilizer in polyolefins in amounts down to 0.02%.
18.2 APPARATUS
Thin layer chromatography tank.

Thin layer plate 20 cm x 20 cm pre-coated with a 250 u layer of OF245 silica gel.
Hamilton syringe (25 ul)
Ultraviolet lamp (wavelength 254 nm).
Sintered glass ruter sticks, 1/2" diameter.
10 ml standard flasks.
Ultraviolet spectrophotometer
Silica spectrophotometer cells, 3 cm.
203
18.3 REAGENTS
Methylene chloride.
Chloroform A.R.
Cyasorb UV 531 ex Cyanamid Ltd.
Standard UV 531 solution, 0.2% w/v in chloroform, for use as a "marker" to
locate correct position of UV 531 on plate.
Standard UV 531 polymer blends - prepare by miUing a series of blends of 0.05,
0.1, 0.2, 0.3, 0.4 and 0.5% w/w UV 531 in additive-free polyethylene powder.
UV 531 is extracted from the polymer by precipitation of the polymer with

ethanol from a hot toluene solution. An aliquot of the extract is applied to a thin layer
plate and chromatographed. The zone corresponding to UV 531 is removed from the
plate and extracted with ethanol. The concentration of UV 531 is determined by
measuring the ultraviolet absorption peak near 295 nm in ethanol solution and referring to
a calibration graph.
To calibrate the procedure, weigh out 0.5 g of each of the standard polymer - UV
531 blends and 0.5 to 1.0 g of the unknown polyethylene sample and put each through the
polyethylene solvent extraction procedure (toluene-ethanol) as described in Method 3.
Apply 25 ul portions of each of the standard polymer extracts and the sample
extract to the base line of a thin layer plate in the form of a spot. Develop the
chromatogram to a distance of 10 cm by using methylene chloride as eluant. Remove the
plate from the tank and allow the solvent to evaporate.
Inspect the plate under ultraviolet light (254 nm) and locate UV 531 as a dark blue
spot. Mark with a pointed marker the zones corresponding to the UV 531 in the
standards and the sample and also an equivalent blank area of silica gel. Carefully scrape
the silica gel zones from the plate and transfer to separate sintered glass filter columns.
Extract the UV 531 from each with absolute ethanol into a 10 ml standard flask and
finally make to volume.
Measure the optical density at 295 nm of the standard and sample extracts against
the TLC plate blank extract in the reference cell in 3 cm silica cells.
Plot a calibration curve for net optical density at 295 nm against microgramsUV
531 in final solution (10 ml). Hence, deduce the concentration of UV 531 in the
unknown polyethylene sample.
18.S DISCUSSION OF RESULTS
This method is capable of determining Cyasorb UV 531 in polyethylene in

amounts down to 0.02% with an accuracy of± 10%.
204
METHOD 19· DETERMINATION OF TINUVIN 326 ULTRAVIOLET
ABSORBER IN POLYPROPYLENE. ULTRAVIOLET SPECTROSCOPy. 12
19.1 SUMMARY
This ultraviolet spectroscopic procedure determines Tinuvin 326 ultraviolet

absorber in polypropylene in amounts down to 0.02%.
19.2 APPARATUS
Ultraviolet spectrophotometer, recording type. Sample cells, quartz - 1 cm path

length.
Water bath
Miscellaneous glassware.
19.3 REAGENTS
Chloroform AR
Tinuvin 326
19.3 METHOD
The Tinuvin 326 is extracted from the polymer with chloroform under reflux
conditions. The concentration of Tinuvin 326 in the chloroform extract is determined by
measuring the ultraviolet absorption peak at 355 nm and by reference to a prepared
calibration curve.
19.5.1 Procedure
Weigh accurately into a 250 cm3 round-bottomed flask a portion of the

polypropylene sample, containing about 5 mg Tinuvin 325. Add 50 cm of chloroform,
place the flask under a reflux condenser and boil for 30 min. Decant the cooled solution
into a 100 cm3 volumetric flask after filtering through a No. 42 Whatman filter paper.
Transfer any polymer collected in the filter paper to the round-bottomed flask and add 40
cm3 of chloroform. Repeat the extraction procedure and combine with the first extract.
Make up to the 100 ml mark with chloroform. Shake the solution well and then pipette 5
cm3 into a 50 ml volumetric flask and make up to the mark with chloroform.
Record the ultraviolet spectrum of the diluted chloroform extract from 300 to 370
nm against a chloroform blank using 1 cm cells.
205
19.5.1 Calibration.
Dilute the 0.20% w/v chloroform solution of Tinuvin 326 to obtain solutions of
0.001,0.0008,0.0004,0.0002% w/v.
Record the ultraviolet spectrum of each of these solutions against a chloroform
blank from 300 mu to 380 Dm using 1 cm cells.
Measure the absorbance of the Tinuvin 326 absorption peak at 355 Dm.
Determine the amount of Tinuvin 326 present in the diluted extract by reference to a
prepared calibration curve.
% W.w Tinuvin 326 in polymer = (% w/w Tinuvin 326 in diluted extract x 1000
weight of original polymer
This method is capable of determining Tinuvin 326 ultraviolet absorber in

amounts down to 0.02% with an accuracy of ± 5%.
METHOD 10· DETERMINATION OF AROMATIC VOLATILES IN

POLYSTYRENE. GAS CHROMATOGRAPHY PROCEDURE.
10.1 SUMMARY
This gas chromatographic method is capable of determining down to 0.001% of a

wide range of saturated and unsaturated aromatic volatiles in polystyrene.
20.2 APPARATUS
Gas chromatograph with a hydrogen flame ionization detector and an injection

port fitted with a glass liner, very loosely packed with glass fibre (Figure 7.5).
Column, copper tube (15 ft x 1/4 in o.d. x 3/16 in Ld.) packed with 10 per cent w/w
Carbowax 15 - 20 m supported on 60 -72 B.S. mesh Celite.
Gas pressures and flows:
Helium 30 Ibflin2 gauge, 100 ml/min
Air 7 Ibf/in2 ,auge, 650 ml/min
Hydrogen 12lbf/in gauge, 75 mt/min
Temperatures:
Injection 150°C
Detector 150°C
Column 80°C
Flame 200°C
Recorder, 0.2 to + 1.0 mV range, 1 sec response, 15 in (381 mm)1hr chart speed.
206
20.3 REAGENTS
Carbowax 15 - 20 M and 60 - 72 B.S. mesh Celite

Styrene and propylene oxide, Ortho-, meta- and para-xylenes, cumene,n-propyl
benzene, iso-butyl benzene, alpha-methyl styrene and mixed meta-/para-diethyl benzenes,
tert-, sec- and n-butyl benzenes, ortho-methyl styrene, mixed meta-/para-methyl styrenes
and n-undecane, meta- and para-ethyl toluenes, ortho-ethyl toluene.
20.4.1 Calibration.
Weigh in turn into a 1- cm3 volumetric flask 1.0 cm3 n-undecane, internal
standard plus 1.0 cm3 of any of the above aromatic hydrocarbons it is required to
determine. Dilute to 10 cm3 with propylene oxide and then further dilute 0.25 cm3 of the
solution to 25 m1 with propylene oxide. Chromatograph 5 ul of the calibration blend.
This calibration procedure should be carried out daily.
To analyse samples, weigh I g polymer into a 25 cm3 stoppered measuring
cylinder, add exactly 10 cm3 of the propylene oxide containing 0.1 % v/v n-undecane
internal standard, seal with a serum cap and shake until the polymer has dissolved. Gel,
pigment and filler may remain as an undissolved suspension without detriment to the
analysis. Chromatograph 5 ul of the solution at a range setting of x 10 and suitable
attenuation settings.
20.4.2 Relative Retention Distances.
Retention distances (injection point to peak centres) are corrected for the gas hold-
up of the column and are expressed relative to styrene.
Calculation. In the calibration and analysis chromatograms, measure the peak

heights of the n-undecane and the aromatic hydrocarbons allowing for any attenuation
factors.
From the calibration chromatogram, determine the response factor for each
component as follows:
A = weight of component in calibration blend
B = weight of n-undecane in calibration blend
C = peak height of component on calibration chromatogram
D = peak height of n-undecane on calibration chromatogram
Component response factor f = A x D

B x C
From the analysis chromatogram, determine the concentration of each component

as follows:
F = component response factor
G = peak height of component on analysis chromatogram
H = peak height of n-undecane on analysis chromatogram
207
Gloss liner
- T o column ---
---- Sample injection
septum
Carrier Injection port chamber

005
Figure 7.S • Injection port glass liner fitted to F & M Model 1609 gas chromatograph. The glass
liner measures 60 mm x 40 mm o.d. x 2 mm i.d. and is very loosely packed with glass fibre.
J = per cent w/v n-undecane in polymer solvent

K = weight of polymer taken
Component (per cent w/w) = 10 x G x F x J

HxK
Report results to two significant figures.

The above method of calculation applies only to those components for which
calibration factors have been determined. The remaining components are either
determined coincidentally with styrene (sec-butyl benzene) or are likely to be present in
such small amounts (o-ethyl toluene, iso-tert-butyl benzenes, m-diethyl benzene, n-butyl
benzene/para-diethyl benzene and o/mlp methyl styrenes that they may be determined by
comparing directly their peak areas with that of styrene or n-undecane.
Table 7.9 shows some results obtained for various types of polystyrene.
Using this method several polystyrenes from five different manufacturers were
heated at 200°C for 15 min under helium, and the liberated volatiles were examined by
gas chromatography. All the samples liberated the same range of aromatic hydrocarbons,
these differing only in their relative concentrations. However, the non-aromatic
hydrocarbon material, eluted from the gas chromatographic column prior to ethyl
benzene, showed marked differences from sample to sample.
20.6 DISCUSSION
The method is capable of determining down to 0.001% of various aromatic

volatiles in polystyrene with an accuracy of ± 5%. The quantitative aspects of this
technique itself were investigated by analysing the volatiles liberated by heating
polystyrene at 200°C and then re- analysing the polymer as a solution in propylene oxide.
Several samples of polystyrene were examined in this way and in each case component
peak areas were normalized and compared. The results (Table 7.10) show that the values
obtained by head-space analysis technique differ by up to 20% from those obtained by the
solution procedure which are known to be correct.
208
Table 7.9 - Analysis of some Different Grades of Polystyrene
Weight Per Cent
Self High Foodstuff

Component Crystal Expandable extinguishing impact packaging
grade grade grade grade grade
Benzene <0.001 < 0.001 < 0.001 <0.001 <0.001

Toluene 0.001 0.003 <0.001 <0.001 <0.001
Ethyl benzene 0.066 0.081 0.047 0.086 0.060
m-Ip-Xylene 0.002 0.002 0.063 < 0.001 <0.001
Cumene 0.046 0.049 0.039 0.011 0.030
o-Xylene 0.007 0.008 0.006 0.002 < 0.001
n-Propyl benzene 0.017 0.016 0.014 0.004 0.016
m/p-Etbyl toluenes 0.016 0.011 0.013 0.002 <0.001
Styrene 0.033 0.32 0.080 0.18 0.04
Table 7.10 - Comparison of Normalized peak areas calculated from chromatograms of

polystyrene solutions and polystyrene volatiles liberated by heating at 200°C
Nonnalized Peak Area
Analysis of Polymer as a Analysis of Volatiles

Component Solution in Propylene Liberated by Heating
Oxide Polymer at 200·C
A B C D A B C D
Ethyl benzene 16.4 17.4 27.2 27.5 20.2 23.4 35.4 34.4
n-Propyl benzene 5.5 5.3 3.5 3.2 3.2 2.5 1.9 2.3
Cumene 17.7 18.1 10.4 10.8 15.4 12.7 10.2 10.7
m/p-Xylenes 4.1 2.5 2.7 2.0 l.l 1.3 0.6 0.7
m/p-Etbyl toluenes 1.7 1.7 2.0 1.5 0.8 0.7 0.5 0.6
Styrene 54.6 55.0 54.2 55.0 59.3 59.4 51.4 51.3
METHOD 21-. DETERMINATION OF AROMATIC VOLATILES IN

POLYSTYRENE. HEAD SPACE ANALYSIS.u
21.1 SUMMARY
This head space method is capable of determining down to 0.001% of a wide

range of aromatic volatiles in polystyrene.
21.1 APPARATUS
The apparatus is illustrated in Figure 7.6. A glass ignition tube is supported as

shown in a Wade 1/4 inch diameter brass coupling nut, covered with a silicone rubber
septum and sealed with a Wade 1/4 inch brass stop-end body. The stop-end body has two
1 mm diameter holes drilled through the cap. The whole unit is placed in a slot in a
cylindrical copper block ( 3 in long x 2 in diam) which is heated by two Bray (240 V, 85
209
W) cartridge heaters and controlled at temperatures up to 300°C, from a variable
transformer. The temperature is measured with a thermocouple capable of accurately
measuring temperatures in the 100° - 3000 C temperature range with a maximum error of
± 5 per cent. The thermocouple is inserted in the slot adjacent to the ignition tube, it has
been shown that under these conditions the thermocouple records the true temperature of
the contents of the tube. The provision of a slot in the copper block enables more than
one ignition tube to be heated simultaneously if required.
Gas chromatography, see Method 20.
Pure standard aromatic compounds, see Method 20.
21.3 METHOD
In this method the polymer is heated to 300°C in a sealed tube in the absence of
solvents. The head space gas in the tube is then swept into a gas chromatograph where
the individual aromatics are determined. The method is calibrated against standard
injections of pure aromatics into the gas chromatograph.
A sample of the polymer (0.25 - 0.50 g) is placed in an ignition tube and sealed
with Wade fittings and a septum (Figure 7.6). If necessary, the tube is then purged with a
suitable gas by inserting two hypodermic needles through the septum via the holes in the
cap of the stop-end body and passil,1g the gas into the tube through one hole and allowing
it to vent through the other. After purging, the two needles are removed simultaneously
and the tube is then heated in the copper block under the required conditions of time and
temperature. A sample (1 - 2 ml) of the head space gas is withdrawn from the ignition
tube into a Hamilton gas-tight hypodermic syringe via the septum and injected into a gas
chromatograph. It is advisable to fill the syringe with the gas used initially in the ignition
tube and to inject this into the tube before withdrawing the sample. This facilitates
sampling by preventing the creation of a partial vacuum in the ignition tube or the
syringe, or both. It also minimizes any undesirable entry of air into the ignition tube.
Calibrate the gas chromatograph as described in Method 20.
With the apparatus, a polymer may be heated under any desired gas and, while
this may frequently be the carrier gas used with the gas chromatograph, it is also possible
to carry out studies in oxidising or reducing atmospheres. A polymer may also be heated
to any known temperature and samples of the head space gas may be withdrawn at
intermediate temperatures and times to determine under what conditions any particular
volatile is liberated. By using gas chromatographic detectors of suitable sensitivities and
selectivities, it is possible to examine polymer for the presence or formation of volatiles
at both the percentage and parts-per-million levels. For example, traces of organic
volatiles may be examined with an ionization detector and traces or organic halogen
compounds lend themselves to analysis with an electron capture detector. Thermal
conductivity cells of the hot-wire or thermistor type are suitable for the detection or
inorganic volatiles and a helium ionization detector could be used for analysing trace
amounts of permanent gases.
210
I ...... HOLES
~ I'.", SfOP-ENO BODY
~
GLASS IGNITION .
_ . - SILICONE RUBIER SEPTUM
1"""
TIIH
l+-I'41~CX:IUP\..ING NUT
CARTltIDGE HEATER
(240VII5W)
.EA'" ('''''''sYi)
2;~
1"/'"
The method is capable of determining down to 0.001% aromatic volatiles in

polystyrene with an accuracy of ± 5%.
211
METHOD 22· DETERMINATION OF VOLATILES IN POLYSTYRENE.
HEAD-SPACE ANALYSIS TECHNIQUE. 14
22.1 SUMMARY
This head space technique is capable of determining a range of different types of

volatiles in polystyrene in amounts down to 0.002%.
22.2 APPARATUS
Kilner jars (l Ib) - these jars have metal lids. A brass 1/4 inch pipe union is sealed
with Araldite into a hole drilled through each lid, this ftrmly holds a rubber septum.
Gas chromatograph with a flame-ionisation detector. This can be fitted with any
column that will satisfactorily separate the various solvents from each other and from the
internal standard. A suitable liquid phase is 9 parts silicone oil modified by the addition
of2 parts ofUCON HB2000 (polyalkylene glycol) and 100 parts of Chromosorb w.
22.3 REAGENTS
Internal standard. This can be any solvent that is known to be absent from the
sample material.
22.4 METHOD
The sample together with internal standard is heated to 100°C until equiJibrum
then a measured volume of headspace gas is withdrawn with a gas tight syringe and
injected into a gas chromatograph. The method is calibrated against known blends of the
substances to be determined and internal standard.
About 250 cm3 of sample is placed in a Kilner jar and the jar is closed. Internal
standard (3.00 ul) is injected into the jar through the rubber septum. The jar is then
placed in an oven at lOOoC for the minimum specified period (see under discussion) at the
end of which it is removed from the oven and about 2 ml of the atmosphere within are
immediately extracted with an all-glass unlubricated syringe and injected into the gas
chromatograph. The ratios of the peak heights of the solvents, (a, b, c, etc) to that of the
internal standard are calculated. The same amount of internal standard as used with the
samples, plus 2.00 ul of each of the solvents a, b, c, etc is introduced, for calibration
purposes, into each of the Kilner jars. These jars are heated together with those
containing samples.
The content of retained solvent, eg, a, is given in milligrams per square metre by
the expression:
212
AxB x 20,000 x D x E
CxFxG
where
A = Peak height of solvent "a" in sam~le jar
B = Specific quantity of solvent, g cm
C = Peak height of internal standard in sample jar
D = Peak height of solvent "a" in calibration jar
E = "a" content of retained solvent mg square metre
F = Peak height of internal standard in calibration jar
G = Area of sample in square cm.
The method has been used to determine many solvents in polystyrene,

polyethylene, polypropylene and cellophane including ethanol, ethyl acetate, methyl ethyl
ketone, 2-ethoxy ethanol, propanol-l and toluene.
METHOD 23 - DETERMINATION OF RESIDUAL ISO-BUTANE IN

EXPANDABLE AND EXPANDED POLYSTYRENE. GAS
CHROMATOGRAPHY.
23.1 SUMMARY
This gas chromatographic method determines iso-butane in amounts down to 10

ppm in expanded polystyrene.
23.2 APPARATUS
Gas chromatograph run under the following conditions:
Column - Copper tube (10 ft x 1/4 in o.d. x 3/ 16 in Ld.) packed with 25% w/w di-n-
butyl phthalate on 44 - 60 Celite.
Gases -
Air 7 psig
Helium 30 psig
Hydrogen 22 psig
Temperatures -
Injection 150°C
Column 40°C
Detector 150°C
Flame 200°C
Recorder - 1 mV full scale deflection, 6- inlhr chart speed.
23.3 REAGENTS
Solvent - Weigh a stoppered 100 cm3 volumetric flask containing about 98 ml

propylene oxide. Add 1 cm3 2,2-dimethyl butane, internal standard, reweigh and then
dilute to 100 cm3 with propylene oxide. Shake thoroughly.
213
23.4 METHOD
A solution of the polystyrene sample and 2,2-dimethylbutane internal standard in

propylene oxide is injected into the gas chromatograph. Calibration is achieved with
known blends of internal standard and iso-butane in propylene oxide.
Weigh accurately about I g sample into a stoppered type 2S cm3 measuring

cylinder. Add exactly 10 cm3 of the prepared solvent, seal the cylinder with a serum cap
and shake to dissolve. Chromatograph 1 micro-litre at a range ofx 1000 and attenuations
suitable for the sample (usually x 4 for the iso-butane and x 2 for the 2,2-dimethyl
butane). For each peak, draw in the escribed triangle and calculate the product of peak
height and peak width at the base, allowing for any attenuation factors.
Calculation.
B = product of peak height and peak width at the base of the isobutane peak.
D = product of peak height and peak width at the base of the 2,2-dimethyl butane
peak.
S = weight of2,2-dimethyl butane in 10 cm3 solvent.
W = weight of sample taken for analysis.
Iso-butane (% w/w) = 100 x B x S

DxW
The following are the uncorrected retention distances (to peak centres) and the
corresponding relative values (2,2-dimethyl butane = 1.00).
Component DR
mm ReI
Impurity ex propylene oxide 24.5 0.25
Iso-butane 32 0.35
2,2-dimethyl butane 98 1.00
Propylene oxide 150 1.53
The analysis is complete with the elution of propylene oxide. This takes 10 min.
This method is capable of determining down to 10 ppm of iso-butane in poly-

styrene with an accuracy of ± 5%.
It is necessary to ensure that the injection port on the gas chromatograph is fitted
with a glass liner (very loosly packed with glass fibre) and check that this is not blocked
with polymer. Daily replacement is advisable.
214
METHOD 24 - DETERMINATION OF RESIDUAL ISOHEXANE IN
EXPANDABLE AND EXPANDED POLYSTYRENE. GAS
CHROMATOGRAPHY.
24.1 SUMMARY
This gas chromatographic method determines isohexane in amounts down to 10

24.2 APPARATUS
Column - see Method 23.

Gases -
Helium 30 psig
Air 2.5 psig
Hydrogen 7.S psig
Temperatures -
Injection ISO°C
Column SO°C
Detector ISO°C
Flame 140°C
Recorder/chart speed 10 in/hr.
24.3 REAGENTS
Prepared solvent. Weigh I cm3 2,4-dimethyl pentane into a 100 cm3 volumetric
flask and dilute to 100 ml with methylene dichloride.
24.4 METHOD
A solution of the polystyrene sample and 2,4 dimethyl-pentane internal standard

in methylene dichloride is injected into the gas chromatograph. Calibration is achieved
with known blends of internal standard and 2,4 dimethylbutane in methylene dichliride.
Weigh 1 g sample into a 2S cm3 measuring cylinder, add 10 cm3 prepared solvent,
seal with a serum cap and shake to dissolve. Chromatograph 5 micro-Htres at a range of x
100 and suitable attenuations.
24.S.1 Calculation.
Measure the retention distances (injection point to peak apex) and peak heights of
all the components. For each, calculate the product of retention distance and peak height,
215
allowing for any attenuation factor. Determine the concentration of each component as
follows:
W = % w/v 2:4-dimethyl pentane in solvent

S = weight of sample taken
C = product of retention distance and peak height of component
D = product of retention distance and peak height of 2:4-dimethyl pentane
Component (% w/w) = ~ x 10xW

D S
Report results to the nearest 0.1% w/w.
24.5.2 Retention Data.
The following are uncorrected retention distances (injection point to peak apex)
and the corresponding relative values (2:4,dimethyl pentane = 1.00).
Component DR
iso-Pentane 12 0.24
n-Pentane 18 0.35
2,2-dimethyl butane 23.5 0.46
2-methyl pentane + 2,3-dimethyl butane 31 0.61
3-methyl pentane + cyclo-pentane 36 0.71
n-Hexane 41 0.80
2:4-dimethyl pentane 51 1.00
This method is capable of determining down to 10 ppm of isohexane in expanded

polystyrene with an accuracy of ± 5%. It is necessary to ensure that the injection port on
the gas chromatograph is fitted with a glass liner (very loosely packed with glass fibre)
and check that this is not blocked with polymer. Daily replacement is advisable.
METHOD 25 - DETERMINATION OF RESIDUAL NAND ISOPENT ANE IN

EXPANDED AND EXPANDABLE POLYSTYRENE. GAS
CHROMATOGRAPHY.
25.1 SUMMARY
This gas chromatographic method determines n- and iso-pentane in amounts

down to 10 ppm in expanded polystyrene.
216
25.2 APPARATUS

Column see Method 23
Carrier gas Helium at 0.6 kglcm2
Temperature Injection 45°C, column 45°C, detector 45°C.
Bridge 250 rnA
Chart speed 30 cmlhr
25.3 REAGENTS
Prepared solvent. Into a 100 cm3 volumetric flask weigh 1.0 cm3 2:2 dimethyl
butane, sealing the flask with a serum cap during the weighing. Dilute to 100 cm3 with
propylene oxide and re-seal with the serum cap.
25.4 METHOD
A solution of the polystyrene sample and 2,2 dimethylbutane internal standard in

propylene oxide is injected into the gas chromatograph. Calibration is achieved with
known blends of internal standard and n- and iso-butane in propylene oxide.
Into a 25 cm3 measuring cylinder (stoppered type) weigh 2 g sample and add
exactly 25 cm3 of the prepared solvent. Seal with a serum cap and shake to dissolve.
Chromatograph 10 ul (from a 50 ul syringe) at an attenuation of XI. Immediately wash
out the syringe with propylene oxide. Measure the peak heights or the integrated areas of
the iso-pentane, n-pentane and 2:2-dimethyl butane.
25.5.1 Calibration.
Into a 100 em3 volumetric flask, weigh in turn 0.40 em3 iso-pentane, 0.50 em3 n-
pentane and 0.80 cm3 2:2-dimethyl butane. Seal the flask with a serum cap during each
weighing. Dilute the mixture to 100 cm3 with propylene oxide, seal with the serum cap
and mix thoroughly. Chromatograph 10 ul (from a 50 ul syringe) at an attenuation of XI.
Measure either the peak heights or the integrated areas of the iso-pentane, n-pentane and
2:2-dimethyl butane.
Calculation.
WI = wt of iso-pentane in calibration blend.
W2 = wt of n-pentane in calibration blend
W3 = wt of 2:2 dimethyl butane in calibration blend.
W4 = wt of2:2 dimethyl butane in 100 cm3 solvent.
W5 = wt of sample
PI = peak height or integrated area of iso-pentane in calibration blend.
217
P2 = peak height or integrated area of n-pentane in calibration blend
P3 = peak height or integrated area of2:2 dimethyl butane in calibration blend.
P4 = peak height or integrated area of iso-pentane in analysis solution.
P5 = peak height or integrated area of n-pentane in analysis solution.
P6 = peak height or integrated area of2:2 dimethyl butane in analysis solution.
% w/w iso-pentane = 25 x WI x W4 x P3 x P4
W3 x W5 x PI x P6
% w/w n-pentane = 25 x W2 x W4 x P3 x P5
W3x W5xP2xP6
Relative retention values (corrected and to peak centre)
DR
Air =0.00
Propylene oxide impurity =0.19
iso-pentane =0.77
n-pentane = 1.00
2:2 dimethyl butane = 1.41
Propylene oxide Clear within 30 min.
This method is capable of determining down to 10 ppm of n-and iso pentane in

polystyrene with an accuracy of ± 5%.
It is necessary to ensure that the injection port on the gas chromatograph is fitted
with a glass liner (very loosly packed with glass fibre) and check that this is not blocked
with polymer. Daily replacement is advisable.
METHOD 26 - DETERMINATION OF RESIDUAL NEO-HEXANE IN

EXPANDED POLYSTYRENE AND EXPANDABLE POLYSTYRENE. GAS
CHROMATOGRAPHY.
26.1 SUMMARY
This gas chromatographic method determines neo-hexane in amounts down to 10

26.2 APPARATUS

Column see Meth:od 23
Gases:
helium see Method 23
air see Method 23
hydrogen see Method 23
218
Temperatures:
injection see Method 24
column see Method 24
detector see Method 24
flame see Method 24
Recorder/chart speed ImV, 10 inlhr.
26.3 REAGENTS
Prepared solvent. Weigh 1 cm3 n-pentane internal standard into a 100 cm3
volumetric flask and dilute to 100 cm3 with propylene oxide.
26.4 METHOD
A solution of the polystyrene sample and n-pentane internal standard in propylene

oxide is injected into the gas chromatograph. Calibmtion is achieved with known blends
of internal standard and neo-hexane in propylene oxide.
Weigh 1 g sample into a 25 cm3 measuring cylinder, add 10 ml solvent, seal with
a serum cap and shake to dissolve. Chromatograph 5 micro litres at a range of x 100 and
suitable attenuations. Measure the retention distances (injection point to peak apex) and
peak heights of the n-pentane and neo-hexane. For each, calculate the product of
retention distance and peak height, allowing for any attenuation factor.
Determine the concentmtion of neo-hexane as follows:

W - % w/v n-pentane in solvent
S = weight of sample taken.
C = product of retention distance and peak height of neo-hexane.
D - product of retention distance and peak height of n-pentane.
neo-Hexane (% w/w = C x 10 x W
DxS
Report results to the nearest 0.1 % w/w.
The method is capable of determining down to 10 ppm neo-hexane in polystyrene

with an accumcy of ± 10%. It is necessary to ensure that the injection port on the gas
chromatograph is fitted with a glass liner (very loosly packed with glass fibre) and check
that this is not blocked. Daily replacement is advisable.
219
METHOD 27 - SOLVENTLESS PROCEDURE FOR THE DETERMINATION OF
RESIDUAL N- AND ISO-PENTANE IN EXPANDABLE AND EXPANDED
POLYSTYRENE. GAS CHROMATOGRAPHY.
27.1 SUMMARY
This head space method is capable of determining down to 0.001% ofn- and iso
pentane in polystyrene.
27.2 APPARATUS
Head space analysis equipment is discussed in Method 21 and illustrated in Figure

7.6. Gas chromatograph operated under the following conditions:
Column. Copper tube (15 ft x 3f16 in i.d.) packed with 10% wtlwt Carbowax 15 -
20 M on 60 - 62 BS mesh acid washed Celite.
Gas flows. Helium - 30 psig, rotameter = 10.0 (100 cm3 fmin)
Hydrogen - 13 psig rotameter = 10.0 (75 cm3 fmin)
Air - 7 psig, rotameter = 10.0 (650 cm3 fmin)
Temperatures. Injection 155°C
Column 80°C
Detector 125°C
Flame 200°C
Recorder. 1 mV full scale deflection, 1 second response, 10 inlhr chart speed.
27.3 METHOD
In this method the polymer is heated to 240°C for 5 min in a sealed tube in the
absence of solvents. The head space gas in the tube is then swept into a gas
chromatograph where the n- and iso-pentane are determined. The gas chromatograph is
calibrated against known blends of n- and iso-pentane and n-undecane internal standard
dissolved in propylene oxide.
See Method 21.
METHOD 28 - DETERMINATION OF HYDROCARBON IMPURITIES IN

STYRENE MONOMER. GAS CHROMATOGRAPHY.
28.1 SUMMARY
This method is capable of determining a wide range of alkyl benzene impurities in

styrene monomer in amounts down to 5 ppm.
220
28.2 APPARATUS
Gas chromatograph opemting conditions are listed in Table 7.11.
28.3 REAGENTS
Internal standard, n-butyl benzene.

Pure aromatic hydrocarbons for calibmtion.
28.4 METHOD
A weighed amount of internal standard, usually n-butyl benzene, is added to the styrene
monomer sample which is then gas chromatogmphed on two columns (Squalane and
Carbowax). The method is calibmted against known blends of internal standard and the
aromatics to be determined.
28.5.1 Analysis on Squalane Column.
Under the conditions given in Table 7.11 chromatograph 5 ul of the sample and
from the chromatogmm decide on a suitable internal standard, eg n-butyl benzene.
Prepare an accurate w/w solution of the chosen internal standard in the sample and
chromatogmph 5 ul of the solution under the conditions given in Table 7.11. Determine
the peak areas of the standard and of the relevent impurity peaks and, knowing the
concentration of the standard and assuming that all components have the same response
factor, calculate the results:
% w/w component = Ac x lOOW

As (lOO-W)
where Ac = peak area of impurity being determined

As = peak area of internal standard
W = concentration (%w/w) ofintemal standard in the sample
28.5.2 Analysis on Carbowax Column.
Under the conditions given in Table 7.11 chromatogmph 1 ul of the sample. As

soon as the styrene has been eluted, it is convenient to raise the column tempemture to
180°C to hasten the elution of those high boiling components which it is not necessary to
determine at this stage. Determine the peak areas of the relative impurity peaks, choosing
one of them already determined (eg. n-propyl benzene) on the squalane column as a
reference standard.
Assuming that all the components have the same response factor, calculate the
results:
% w/w component = Ac x Cp
Ap
221
Table 7.11 - Gas Chromatograph Operating Conditions
Squaline Column Carbowax Column
Instrument used Perkin-Elmer Model FIll fitted F. and M. ModelBlO, fitted

with a flame ionisation detector with a flame ionisation detector
and a sample injection splitter
Column Stainless steel tube (sOm x 1116 Copper tube (15 ft x 14 in 0.0. x
in 0.0. 14 mm 1.0.) coated with 3116 in 1.0.) packed with 10%
squalane w/w Carbowax IS·20M on 60 -
72 Celite
Gases
Air 30 Ibf/in2 gauge 20 Ibftlin2 gauge
Nitrogen 20 Ibf/in2 gauge
Helium SO Ibftlin2 gauge contolled at
lOOmVmin
Hydrogen 20 Ibflin2 gauge 30 Ibf/in2 gauge
Temperatures
Injection I 85·C 200·e
Column BO·C BO·e
Detector BO·C 200·e
Recorder Honeywell-Brown, ImV full Honeywell-Brown, ImV full
scale deflection, 30 inlh chart scale deflection, IS inlh chart
speed speed
Sample split ratio 160:1
Each chromatograph was operated in conjunction with an electronic integrator
where Ac = peak area of impurity being determined

Ap = peak area of n-propyl benzene
Cp = concentration (%w/w) ofn-propyl benzene as determined on
the squalane column.
For the purpose of calculating results it can be assumed that each trace impurity in
the mixture has the same response factor.
Retention data for some of the impurities found in styrene monomer are given in
Table 7.12.
Table 7.13 gives the results for the analysis of some typical crude and
polymerisation grade styrene monomer samples. It is seen that in the crude material
approximately 40 impurities were detected, their concentration being 2.6% w/w
(unsaturated) 3.3% w/w (saturated and unsaturated). In comparison, the purified
monomer contained far fewer impurities at a total concentration ofless than 0.5% w/w.
The method is capable of determining up to 40 aromatic impurities in styrene

monomer in amounts down to 5 ppm with an accuracy of ± 5%.
222
Table 7.12 - Relative Corrected Retention Time of Likely Styrene Impurities on Squalane
and Carbowax Columns
Pure reference compounds were not available for components marked with asterisks. Tentative identities
have been ascribed from boiling points
Relative corrected
retention times
B.Pt(°C) Squalane Carbowax
Benzene 80.1 0.042 0.238

Toluene 110.6 0.102 0.394
Ethyl benzene 136.2 0.212 0.628
n-propyl benzene 159.3 0.439 1.000
n-butyl benzene 183.3 1.000
Cumene 152.5 0.346 0.818
iso-butyl benzene 172.5 0.683
sec-butyl benzene 173.5 0.683
ter/-butyl benzene 169.0 0.597
o-xylene 144.4 0.286 0.874
m-xylene 139.1 0.243 0.654
p-xylene 138.4 0.238 0.680
o-ethyl toluene· 165.2 0.553
m-ethyl toluene 161.0 0.490 1.104
p-ethyl toluene 162.0 0.499 1.104
o-diethyl benzene· 183.4 1.000
m-diethyl benzene 181.1 0.952
p-diethyl benzene 183.8 1.037
Styrene 145.2 0.264 1.268

-methyl styrene 165.4 0.541
B-methyl styrene· 176.0 0.777
o-methyl styrene 171.6 0.623
m-methy1 styrene 170.9 0.631
p-methyl styrene 170.6 0.641
o-ethyl styrene· 1.131
m-ethyl styrene 1.253
p-ethyl styrene 1.345
o-divinyl benzene· 1.414
m-divinyl benzene 1.558
p-divinyJ benzene 1.705
METHOD 29 - DETERMINATION OF HYDROCARBON IMPURITIES IN

STYRENE MONOMER, TEMPERATURE-PROGRAMMED GAS
CHROMATOGRAPHY.
29.1 SUMMARY
This method is capable of determining a wide range of alkyl benzene impurities in

styrene monomer in one hour and in amounts down to 5 ppm.
223
Table 7.13 - Analysis of Crude and Pure Styrene Monomer Samples
Crude Styrene Monomer Pure Styrene Monomer
Components %w/w %w/w
Sample 1 Sample 2 Sample 1 Sample 2
Benzene 0.0004 0.004 < 0.0005 0.0003

Toluene 0.0018 0.0019 0.0005 0.0007
Ethyl benzene 0.0097 0.0175 0.025 0.051
m-xylenelp-xylene 0.0013 0.0023 0.0003 0.0017
Cumene 0.094 0.093 0.021 0.021
o-xylene 0.0054 0.0069 0.0032 0.0041
n-propyl benzene 0.066 0.067 0.0067 0.016
m-ethyl toluene 0.039 0.046 0.0022 0.013
p-ethyl toluene 0.023 0.023 0.00\3 0.0071
-methyl styrene 2.0 2.1 0.083 0.14
o-ethyl toluene 0.092 0.10 0.0013 0.0027
tert-butyl benzene < 0.0005 < 0.0005 < 0.0005 < 0.0005
o-methyl styrene < 0.0005 < 0.0005 < 0.0005 < 0.0005
m-methyl styrene 0.064 0.067 < 0.0005 0.0049
p-methyl styrene 0.029 0.039 < 0.0005 0.0022
iso-butyl benzene )
sec-butyl benzene ) 0.093 0.096 0.0009 0.0066
B-methyl styrene 0.24 0.25 < 0.0005 0.0007
m-diethyl benzene 0.19 0.15 < 0.0005 0.0005
n-butyl benzene )
o-diethyl benzene ) 0.0043 0.0031 < 0.0005 < 0.0005
p-diethyl benzene 0.059 0.040 < 0.0005 < 0.0005
o-ethyl styrene 0.0006 0.0010 < 0.0005 < 0.0005
m-ethyl styrene 0.098 0.10 < 0.0005 < 0.0005
p-ethyl styrene 0.020 0.019 < 0.0005 < 0.0005
o-divinyl benzene < 0.0005 < 0.0005 < 0.0005 < 0.0005
m-divinyl benzene 0.041 0.039 < 0.0005 < 0.0005
p-divinyl benzene 0.0097 0.0075 < 0.0005 < 0.0005
Unidentified A 0.033 0.016 < 0.0020 0.0063
Unidentified B 0.057 0.057 0.0005 0.0057
Total number of 36 - 41 36 -41 20 24-29

impurities exceeding
0.0005% concentration
Tentative identities ascribed from boiling point data.
'Unidentified A' includes JO components of unknown identities eluted from the Carbowax column.
'Unidentified B' includes 5 components of unknown identities eluted from the squalane column.
29.2 APPARATUS
Gas chromatograph, see Table 7.14.

Gas chromatograph operating conditions are listed in Table 7.14.
29.3 REAGENTS
Internal standard, n-undecane.

Pure aromatic hydrocarbons for calibration.
224
29.4 METHOD
A weighed amount of n-undecane internal standard is added to the styrene

monomer sample which is then gas chromatographed. The method is calibrated against
known blends of internal standard and the aromatics to be determined.
Using the conditions given in Table 7.14 chromatograph 5 micro litres of the
styrene sample at a range of x 10 and an attenuation appropriate to the concentration of
impurities present. Prepare an accurate 1% wlw solution of n-undecane internal standard
in the styrene sample. Chromatograph 5 microlitres ofthis solution attenuating the peaks
as necessary. Measure the peak areas of the internal standard and of the components to
be determined.
From the known concentration of the internal standard obtain weight per cent
values, assuming that styrene impurity peak area is directly proportional to concen-
trations. The concentrations of impurities in the styrene monomer sample are obtained as
follows:
% wlw impurity in styrene monomer = Ac x lOOW

A~ (lOO-W)
where W = concentration (% w/s) of internal standard in styrene sample
As = peak area of internal standard
Ac = peak area of impurity
In Table 7.15 are tabulated relative corrected retention distance data obtained
using isothermal and temperature programmed Carbowax columns for a range of
impurities in styrene monomer. It is seen that different separations are obtained by the
two methods of analysis. The selection of method is dependent on the separations it is
required to achieve.
This method is capable of determining up to 40 aromatic impurities in styrene

monomer with an accuracy of ± 5%.
225
Table 7.14 - Instrumental Conditions
Temperature Programmed Method
Instrument used Carbowax column
F & M Model 810 with flame ionization detector
Column Copper tube (IS ft x 0.25" in 0 d X 3/16" i d) packed with 10"..1. w/w
Carbowax 15-20 M on 60-72 mesh Celite.
Gases
Air 20 Ib f/in2 gauge
Nitrogen SO Ib f/in2 gauge (controlled at 100 mllmin)
Helium 30 Ib flin2 gauge
Temperature, ·C
Injection 200
Column Isothermally at 100·C for 12 minutes, then programmed at 4· per minute
to 140·C then held at 140·C for 20 minutes.
Detector 200
Recorder Honeywell Brown IMV F.S.D. IS inlhr chart speed
Internal standard 1% w/w n-undecane in sample
226
Table 7.15 - Impurities in Styrene Monomer, Relative Corrected Retention Distances
Earlier Method Isothermal Column Temperature Programmed

Column
Column: Squalane Carbowox Carbowax

(Relative to n-butyl benzene) (Relative to n-propyl benzene) Relative to n-undecane for
compounds
appearing below styrene (b) and
relative to alpha methyl styrene for
compounds
appearing above styrene (c)
n-undecane 1.000 (b) used as internal

standard
Benzene a 0.283 0.580 (b)
Toluene a 0.394 0.850 (b)
Ethyl benzene a 0.628 1.230 (b)
o-xylene a 0.874 1.600 (b)
m-xylene a 0.654 1.310 (b)
p-xylene a 0.680 1.310 (b)
Cumene a 0.818 1.510 (b)
n-propyl benzene 0.439 1.000 1.780 (b)
m-ethyl toluene 0.490 1.104 1.920 (b)
p-ethyl toluene 0.499 1.104 1.920 (b)
-methyl styrene 0.541 1.000 (c)
o-ethyl toluene 0.553 a
tert-butyl benzene 0.597 a a
o-methyl styrene 0.623 1.090 (c)
m-methyl styrene 0.631 1.090 (c)
p-methyl styrene 0.641 1.090 (c)
iso-butyl benzene 0.683 a a
sec-butyl benzene 0.683 a a
B-methyl styrene 0.777 not examined
~ m-diethyl benzene 0.952 0.910 (c)
~ Table 7.15 continued
00
n-butyl benzene 1.000 (used as internal standard) 0.950 (c)

o-diethyl benzene 1.000 not examined
p-diethyl benzene 1.037 0.950 (c)
o-ethyl styrene 1.131 not examined
m-ethyl styrene 1.253 1.350 (c)
p-etbyl styrene 1.345 1.380 (c)
o-divinyl benzene 1.414 not examined
m-divinyl benzene 1.558 1.730 (c)
p-divinyl benzene 1.705 1.800 (c)
benzaldehyde not examined 1.600 (c)
Number of unidentified peaks: 5 13 14

1 prior to 0.439 1 - 6 prior to 0.283 1. 0.230, 8. 0.650
2 between 0.641 & 0.683 7 - 12 between 0.283 & 2. 0.260, 9. 0.720
3 between 0.683 & 0.677 0.394 3. 0.290, 10. 0.790
4 between 0.777 & 0.952 13 between 0.934 & 4. 0.310, 11. 0.860
5 between 1.414 & 1.558 0.628 5. 0.360, 12. 1.80
6. 0.490, 13. 1.24
7. 0.560, 14. 1.93
a Masked by styrene (major constituent)

METHOD 30 - DETERMINATION OF BENZALDEHYDE IN STYRENE
MONOMER. GAS CHROMATOGRAPHY.
30.1 SUMMARY
This gas chromatographic method is capable of determining benzaldehyde in

amounts down to 5 ppm in styrene monomer.
30.2 APPARATUS
Gas chromatograph, see Table 7.14

Gas chromatograph operating conditions, see Table 7.14
30.3 REAGENTS
Internal standard, n-hexadecane

Benzaldehyde
Propylene oxide
30.4 METHOD
This gas chromatographic method determines benzaldehyde in amounts down to 5

ppm in styrene monomer.
I~to' a 100 cm3 stoppered volumetric flask, weigh 10 ml of styrene sample and
exactly 1 ml of a 0.5% v/v solution of n-hexadecane internal standard in propylene oxide.
Chromatograph 2 ul of this solution on a Carbowax Celite column at a range of x 10 and
suitable attenuations using the conditions indicated in Table 7.14 with the exception that
the injection and column temperatures are set at 150°C and 140°C respectively.
Calibrate the procedure as follows. Weigh into a 100 cm3 .volumetric flask
exactly 0.5 cm3 of pure benzaldehyde and 1.0 cm3 n-hexadecane and dilute to 100 cm 3
with propylene oxide. Chromatograph 2 ul of this solution at a range of x 10 and suitable
attenuations. Run the chromatogram to the peak following that of benzaldehyde.
Retention distances uncorrected injection point to peak apex
mm relative
n hexadecane 145 1.00
Benzaldehyde 173.5 1.20
229
On the calibration chromatogram determine the response factor for benzaldehyde
as follows:
where A = weight of benzaldehyde in calibration blend

B = weight of n-hexadecane in calibration blend
C = peak height of benzaldehyde on calibration chromatogram
D = peak height of n-hexadecane on calibration chromatogram
Benzaldehyde factor, F = A x D
B x C
From the analysis chromatogram, determine the concentration of benzaldehyde as

follows:
where A = weight of benzaldehyde in calibration blend

B = weight of n-hexadecane in calibration blend
C = peak height of benzaldehyde on calibration chromatogram
D = peak height of n-hexadecane on calibration chromatogram
Benzaldehyde factor F = A x D
B x C
From the analysis chromatogram, determine the concentration of benzaldehyde as

follows:
where G = peak height of benzaldehyde on analysis chromatogram

H = peak height of n-hexadecane on analysis chromatogram
J = % w/v n-hexadecane in solvent
K = weight of sample taken
F = benzaldehyde response factor
Benzaldehyde (% w/w) = lOx G x F x J
H x K
It is seen in Table 7.15 that in the temperature programmed gas chromatographic

method benzaldehyde with a retention distance relative to methyl styrene of 1.60 is well
resolved from all other impurities in styrene monomer.
This method is capable of determining benzaldehyde in amounts down to 5 ppm

in styrene monomer with an accuracy of ± 5%.
230
METHOD 31- DETERMINATION OF PHENOLIC ANTIOXIDANTS IN
POLYSTYRENE. P-NITROANILINE COUPLING - SPECTROPHOTOMETRIC
METHOD.3
31.1 SUMMARY
This spectrophotometric procedure determines phenolic antioxidants in amounts

down to 0.02% in polystyrene.
31.2 APPARATUS
Visible spectrophotometer, 1 cm quartz cells.
31.3 REAGENTS
Ethyl alcohol 95%

Sodium hydroxide, 4M, Analar.
p-Nitroaniline.
Sodium nitrite, analytical reagent grade.
Coupling agent, 2.800 grams of p-nitroaniline dissolved in 32 cm3 of hot
concentrated hydrochloric acid and diluted with water to 250 cm3• After cooling to room
temperature, the volume of liquid is adjusted to exactly 250 cm3• A second solution is
made containing 1.44 (0.0209 mole) of sodium nitrite in 250 cm3 of distilled water. Both
the above solutions are stable indefinitely. Pipette 25 cm3 of each of these solutions into
separate 100 cm3 beakers and chill to below lOoC. Bubble pure nitrogen through the
mixture as it is allowed to warm to room temperature. Finally, add 10 mg of urea to
destroy any excess nitrous acid. Fresh reagent should be made every day.
31.4 METHOD
A 95% alcohol extract of the polymer is reacted with diazotisation reagent to

produce a colour which is evaluated spectrophotometrically. The method is calibrated
against ethanol solutions of the phenolic antioxidant being determined.
The sample to be analysed must be very thinly sheeted (or powdered by passing
through a Wiley Mill). Weigh a 2.000 ± 0.020 gram sample and wrap with extraction
cloth which has been previously extracted to remove sizing. Place the sample in an
Underwriter's extraction cup and extract for 16 hours with 95% ethanol or methanol.
Transfer the extract to a 100 cm3 volumetric flask, cool and adjust to 100 ml with the
extraction solvent. Transfer 10 ml of this solution to a 100 m1 volumetric flask and add 2
cm3 of coupling reagent and 3 cm3 of 4 M sodium hydroxide solution then adjust to 100
ml with 95% ethanol or methanol.
231
Detennine the absorption spectrum from 700 to 400 nm. The colour is stable for
at least 2 hours. Ethyl alcohol is used in the reference cell unless the alcohol extract is
strongly coloured. In this case, use a 10 cm3 aliquot of the ethyl alcohol extract diluted to
100 cm3 with ethyl alcohol as reference. Plot absorbance against concentration on
semilogarithmic graph paper. The per cent antioxidant is calculated using the equation
developed for the antioxidant concerned.
This method is capable of detennining down to 0.02% of phenolic antioxidants in

polymers with an accuracy of ± 5%. To calibrate the method it is necessary to know the
particular antioxidant being detennined, ie. the method is only applicable to known
antioxidants.
MEmOD 32 - DETERMINATION OF UVITEX OB ULTRAVIOLET

ABSORBER IN POLYSTYRENE. FLUOROMETRIC PROCEDURE.
32.1 SUMMARY
This fluorometric method determines Uvitex OB ultraviolet absorber in poly-

styrene in amounts down to 0.02%.
32.2 APPARATUS
Spectrometer with fluorimetric attachment.

1 cm silica fluorimetric cells.
25 cm3 and 100 cm3 graduated flasks.
Ultraviolet lam~ (wavelength 350 mu).
5 cm3 and 1 cm graduated pipettes.
Mechanical shaker.
32.3 REAGENTS
Chlorofonn, spectroscopic or analar grade.

Polystyrene, free ofUvitex OB.
Uvitex OB standard, 0.01% in chlorofonn.
32.4 METHOD
A chlorofonn extract of the polystyrene is subject to excitation by ultraviolet

radiation of wavelength 370 nm from a mercury vapour lamp and the fluorescence
spectrum of the sample recorded over the range 400 - 440 nm. The reading from the
fluorimeter is noted and the Uvitex OB concentration in the polystyrene detennined by
reference to a prepared calibration graph.
232
32.5.1 Procedure
Run 0.8% w/v solutions of polystyrene in chloroform as below and record peak
height at 435 nm. Obtain the Uvitex OB content of the polymer by reference to the
calibration curve.
32.5.2 Calibration.
Into each of seven 100 cm3 volumetric flasks weigh 0.800 g of additive free
polystyrene then make up to 100 ml with additions of 0.1 to 5 cm3 of 0.01% w/v Uvitex
standard. Record the fluorescence spectrum of each solution, prepared as above from 400
to 440 nm at a suitable slit width. If the 435 nm peak is less than 15 divisions, or greater
than 80 divisions in height, re-run the trace on a higher or lower slit width, respectively.
Measure the height of the peaks at 435 nm for the set of calibration solutions at each slit
width setting used. Plot a calibration curve of peak height versus the corresponding
concentrations ofUvitex OB in the standard solutions.
Antioxidants such a lonol CP (2,6,di-tert-butyl p-cresol), Ionox 330 (1,3,5-tri-

methyl-2,4-6-tri(3 ,5-di-tert-butyl-4-hydroxybenzyl)benzene), Polygard (tris (nonylated
phenyl) phosphite), Wingstay T (described as a butylated cresol), and Wingstay W and
many others, do not interfere in this procedure.
This method is capable of determining down to 0.02% Uvitex OB in polystyrene
METHOD 33 - DETERMINATION OF P-TERT-BUTYL PERBENZOATE IN

POLYSTYRENE. CATHODE-RAY POLAROGRAPHY.
33.1 SUMMARY
This polarographic method determines down to 0.02% p-tert-butyl perbenzoate in

polystyrene.
33.2 APPARATUS
Cathode-ray polarograph with dropping mercury electrode, 10 cm) polarograph

cells and thermostatted (25°C) water bath.
Micrometer syringe capable of delivery 0.01 cm3 with an accuracy of 0.0002 cm).
Volumetric glassware, pipettes, 50 cm3, 25 cm3, 5 cm3, volumetric flasks 100
3
cm.
Centrifuge to take 250 cm3 centrifuge bottles.
233
33.3 REAGENTS
Toluene, redistilled pure grade, rendered peroxide-free by shaking 1 L of the

solvent with 10 cm] of iron sulphate solution, prepared by mixing 60 g iron II sulphate, 6
cm] concentrated sulphuric acid and 110 cm] distilled water, followed by redistillation.
Store in a stoppered brown glass bottle.
Base electrolyte (0.6 M) remove peroxides from 1 L of methyl alcohol as
described above. Weigh out 2.544 g lithium chloride (Analar) and make up to 100 ml
with methyl alcohol.
p-tert-butyl perbenzoate.
Standard addition solution. Prepared by diluting a suitable weight of p-tert-butyl
perbenzoate with toluene.
Nitrogen, oxygen content less than 25 ppm Mercury, pure for polarographic
analysis, use trebly distilled mercury, the manufacturers should be requested to supply
this mercury in stone containers as over a period of time mercury picks up an impurity
from polyethylene storage bottles which interferes in polarography.
33.4 METHOD
To a toluene extract of the polymer is added methanolic lithium chloride base

electrolyte. Precipitated polymer is removed and the resulting clear layer polarographed.
Calibration is achieved by polarography of known toluene-methanol solutions of p-tert
butyl perbenzoate.
33.5.1 Procedure
Transfer 5.0 ± 0.01 g of sample to a 250 cm] Pyrex glass centrifuge bottle and add
50 cm] of toluene. Drop a polythene coated magnetic stirrer rotor into the bottle and
stopper with a cork (avoid rubber bungs). Stand the bottle on a magnetic stirrer and leave
for several hours until the sample has completely dissolved or dispersed in the solvent.
Accurately pipette in 50 cm3 of 0.6 M lithium chloride reagent.
Centrifuge the bottle at 700 - 900 g until insolubles have completely settled to the
bottom of the bottle leaving an absolutely clear upper phase containing the peroxide.
Dilute 50 cm] toluene with 50 cm] of lithium chloride solution to serve as a blank.
Pipette 5 cm] of the sample solution and 5 cm] of the blank solution into two polaro-
graphic cells and immerse these in the constant temperature tank of the cathode-ray
polarograph (thermostatted at 25°C). Carry out the degassing operations with oxygen free
nitrogen on the sample and on the blank solutions immediately before carrying out
polarographic measurements.
The analytical condition with the cathode-ray polarograph (with single cell
operation) are as follows:
Cathode dropping mercury
Reference anode mercury pool
Circuit forward sweep (with derivatives units control
switch off)
Sensitivity contol select a suitable current scale factor and keep this
constant throughout the analysis, adjust the
234
instrument sensitivity by means of the shunt scale
factor control.
Start potential -0.1V
By means of the "Y" shift contol, adjust the light spot to the origin of axes on the
left-hand side of the graticule on the cathode-ray tube. Repeat this operation at different
shunt scale-factor settings, until the polarographic wave is visible on the graticule.
Take the readings on the freshly degassed solutions as follows. Adjust the
polarograph to the p-tert-butyl perbenzoate start potential (-0.7 V) and obtain the wave as
described above for the polystyrene sample solution. Read otT from the graticule the
maximum height of the peak (at above -0.9 V). Raise the dropping mercury electrode
from the cell and deliver into the sample solution a suitable "standard addition" of a
toluene solution ofpara-tert-butyl perbenzoate.
Limit the volume of "standard addition" solution to less than 0.05 cm! in order to
avoid dilution errors. Lower the electrode into the sample cell and again pass oxygen free
nitrogen for 2 min. Immediately read the new peak height at - 0.9 V. Similarly,
determine the peak height at - 0.9 V on the degassed polystyrene-free reagent blank
solution.
33.5.2 Calculations
p-tert-butyl perbenzoate (ppm w/w)
= 100xMx 106 x {h1S.1~

5W (h;S; - h~S~)
where
W = weight (g) of polystyrene sample taken for analysis (assuming 5 cm3portion

taken for polarography)
hI = peak height (graticule divisions) of sample solution before standard addition
h2 = peak height (graticule divisions) of sample solution after standard addition
h3 = peak height (graticule divisions) of polymer-free reagent blank solution.
Sl' S2 and S3 are the corresponding instrument sensitivity settings (the product of
h and S are known as peak currents in microamps)
M = weight (g) of p-tert-butyl perbenzoate in volume of "standard addition"
solution added to cell solution.
This method is capable of determining down to 0.02% of p-tert-butyl perbenzoate

in polystyrene with an accuracy of ± 5%. Other organic peroxides which reduce at or
near - 0.9 V will interfere.
235
METHOD 34· DETECTION AND DETERMINATION OF P·TERTBUTYL
PERBENZOATE AND BENZOYL PEROXIDE RESIDUES IN EXPANDABLE
POLYSTYRENE. THIN LAYER CHORMATOGRAPHY.
34.1 SUMMARY
This thin layer chromatographic method determines p-tert-butyl perbenzoate

and/or benzoyl peroxide residues in expandable polystyrene in amounts down to 0.002%.
34.2 APPARATUS
Thin layer chromatography tank to take 8 in x 8 in plates.

Thin layer chromatography plates (8 in x 8 in) precoated with a 1 micron layer
Merck OF 254 silica gel.
Hypodermic syringes - 25 ul capacity.
Filter paper - Whaman No. 42
Spray for chromogenic reagents.
Volumetric flasks, 2 ml capacity.
Beakers 50 ml.
Ultraviolet lamp, 254 mu
34.3 REAGENTS
Potassium iodide starch, mix 1 g potassium iodide Analar and 0.1 g zinc dust with
100 m14:1 (v/v) glacial acetic acid water.
Starch,I%.
Ferric rhodamide reagent, dissolve 0.2 g ammonium rhodamide in 15 cm3
acetone. Shortly before use, dilute this solution with 10 cm3 4% aqueous ferrous
sulphate, use the solution immediately.
Diethyl ether, redistilled pure grade. Render peroxide free by shaking with 1 litre
of solvent with 10 - 20 cm3 of iron II sulphate solution, prepare by mixing 60 g iron II
sulphate, 6 cm3 concentrated sulphuric acid and 110 cm3 distilled water followed by
redistillation. Store in a well stoppered brown glass bottle.
Benzene, redistilled pure grade, peroxide free (see above).
Benzoyl peroxide.
Standard benzoyl peroxide stock, 0.5% w/v in peroxide free benzene, prepare
0.005% to 0.15% dilutions of this by diluting with benzene.
p-tert butyl perbenzoate.
Standard p-tert-butyl perbenzoate, 0.5% w/v in peroxide free benzene, prepare
0.005% to 0.15% dilutions of this by diluting with benzene.
34.4 METHOD
An ether extract of the polystyrene is applied to a thin-layer chromatographic

plate and developed with benzene. Expose to ultraviolet light and the application of
specific spray reagents reveals spots due to the peroxides which are compared visually
with standard solutions of pure peroxides to quantify the procedure.
236
34.5.1 Extraction
Weigh out 5 ± 0.1 g of sample and add 25 cm3 diethyl ether. Cover with a watch
glass and leave overnight. Decant the ether and wash the beads with two further 10 cm3
portions of ether, decanting each washing into the main extract. By means of an air line
and warm water bath carefully evaporate off the ether until about 1 ml of solution
remains. Transfer this to a 2 cm3 volumetric flask. Rinse round the walls of the beaker
with 5 - 10 cm3 of ether and concentrate to about 0.5 cm3• Transfer this solution to the 2
cm3 volumetric flask and make the flask contents up to 2 cm3 with diethyl ether.
34.5.2 Chromatography.
Activate the silica gel coated plates by heating in a ventilated oven for 30 min at
110°C. Store the plates in a dessicator until use, they should be used on the same day that
they are activated.
Fill a chromatograph tank to a depth of about 0.5 in with benzene and place sheets
of filter paper against the internal walls of the tank and dipping in the benzene. Replace
the lid and leave the tank for 30 min to equilibriate in a constant temperature area free
from draughts.
Transfer by microsyringe two 20 ul portions of the diethyl ether extract of the
sample as separate spots on the starting line on the plate. Also apply 20 ul portions of the
standard solutions of the peroxides in benzene (ie. 0.005 to 0.15% equivalent to 1 to 30
ug peroxide) to the plate. Develop the chromatogram to a distance of 15 cm from the
starting line. Remove the plate from the tank and allow to air dry.
Inspect the plate under a 254 nm ultraviolet lamp and compare the intensities of
the sample and standard spots which show as dark areas on a blue fluorescent
background. Spray the plate with either of the spray reagent systems (ie. potassium
iodide/starch or ferric rhodamide). Estimate the concentration of peroxides in the sample
spots by comparison with the standards.
34.5.3 Calculation.
Peroxide from 6 g polyethylene is concentrated into a 2 ml ether solution and 0.02

ml (20 ul) taken for thin-layer chromatography.
Thus % peroxide in polymer = 2x5x P

0.02
Where
P = weight (g) of peroxide present in standard spot which compares in intensity

with the intensity of the sample spot.
This method is capable of determining down to 0.002% p-tert-butyl peroxide or

benzoyl peroxide in polystyrene with an accuracy of ± 10%.
237
METHOD 35 - TESTS FOR INHIBITORS IN STYRENE MONOMER. IRON m
CHLORIDEIPOTASSIUM FERRICYANIDE PROCEDURE.
35.1 SUMMARY
This spectrophotometric method determines inhibitors such as hydroquinone, p-

tert butyl catechol or p-methoxy phenol in amounts down to 10 ppm in styrene monomer.
35.2 APPARATUS
Ultraviolet-visible spectrophotometer
35.3 REAGENTS
Iron III chloride, 0.05% w/vaqueous

Potassium ferricyanide, 0,01% w/v aqueous.
35.4 METHOD
Toluene solutions of the styrene monomer sample are extracted with the reagents
to provide aqueous extracts which are evaluated spectrophotometrically. The procedure
is calibrated against standard solutions of the inhibitors.
35.5.1 Procedure
If the monomer sample contains up to 0.005% of inhibitor then pipette 0.1 to 2

cm3 of the sample directly into a 100 cm3 separatory funnel, make the volume up to 2 ml
with toluene. Into a second (reagent blank) separatory funnel pipette 2 cm3 of pure
toluene. To each funnel add 1 em3 of freshly prepared iron III chloride solution (0.5%)
and shake for one min. Add 10 em3 water and allow the phases to separate. Run the
aqueous phases into two 100 em3 volumetric flasks. Into each volumetric flask pipette 1
cm3 of potassium ferrieyanide solution and dilute to 100 cm3 •
Evaluate the sample and blank solutions on a spectrophotometer under the
following conditions:
Cells 1 cm glass
Blank solution Fill comparison cell with the inhibitor free reagent
blank solution referred to above.
Wavelength Determine the wavelength at which maximum
absorption occurs.
Temperature 25 ±2°C
Colour development time IS to 20 min from addition of first reagent
238
35.5.2 Calibration.
Accurately weigh out on a watch glass 0.006g of the stabilizer that is being
determined in the monomer sample. Transfer this solid to a 100 cm3 volumetric flask
with toluene and make up to the mark. Into each of seven 100 cm3 separatory funnels
pipette the volumes of 0.006% monomer solution and pure toluene shown below.
Continue as described under procedure. Construct a calibration graph by plotting the
determined optical densities of the solution against the corresponding number of grams of
inhibitor in each 100 ml separatory funnel.
Volumes of 0.006% inhibitor solution - required for preparation of calibration

graph.
Volumes added to 100 cm3 Weight of inhibitor added g

separatory funnel
0.006% w/v inhibitor in Pure toluene

toluene cm3 •
0.0 (blank) 3.0 0.00000

0.5 (sample) 2.5 0.00003
1.0 (sample) 2.0 0.00006
1.5 (sample) 1.5 0.00009
2.0 (sample) 1.0 0.00012
2.5 (sample) 0.5 0.00015
3.0 (sample) 0.0 0.00018
35.5.3 Calculation
Convert the optical density obtained for the sample solution to grams of inhibitor
by means of the appropriate calibration graph obtained for a pure specimen of the
inhibitor. Calculate the inhibitor content of the monomer as follows:
Inhibitor content of monomer

Inhibitor (% 2/v) = Nx 100
V
where
N = weight (g) of inhibitor obtained by refering the sample optical density to the
calibration graph.
V = volume (cm3) of monomer sample taken for analysis (allow for any
preliminary dilution of the monomer that has been made before analysis)
This method is capable of determining styrene monomer inhibitors in styrene in

amounts down to 10 ppm with an accuracy of ± 5%. To obtain quantitative results it is
necessary to know the identity of the particular inhibitor present in the styrene monomer
sample.
239
METHOD 36 - TESTS FOR INHIBITORS IN STYRENE MONOMERS.
SODIUM PHOSPHOTUNGSTATE PROCEDURE NESSLERIZATION
METHOD.
36.1 SUMMARY
This visual colour comparison method determines inhibitors such as hydro-

quinone, p-tertiary butyl catechol and o-methoxy phenol in amounts down to 1 ppm in
styrene monomer.
36.2 APPARATUS
Nesslerizer tubes, 50 ml.

Separatory funnels, 50 ml
36.3 REAGENTS
Toluene
Sodium phosphotungstate, 2% aqueous.
Sodium carbonate, 10% aqueous.
36.4 METHOD
Toluene solutions of the styrene monomer are extracted with distilled water and to
the extract are added sodium phosphotungstate and sodium carbonate solutions. The
intensity of the blue colour produced is compared visually with that of standards
comprising solutions of the inhibitor in toluene which have been similarly treated.
Into a 50 cm3 separatory funnel pipette 1 cm3 (or for greater sensitivity use 10 cm3
) of the monomer sample.
Into seven further 5 em3 separatory funnels pipette 0.1, 0.5, 1.0,2.0, 5.0, 7.5 and
10.0 cm3 of a 10 ppm toluene solution of the inhibitor which is being determined in the
monomer sample (ie. additions of between 5 and 100 u g of inhibitor. Extract the sample
funnel and the seven standard funnels with 20 cm3 distilled water then two 10 cm3
portions of distilled water and collect the 40 cm3 aqueous extracts in 50 cm3 Nessler
cylinders (filtering if necessary). Dilute to 50 cm3 with water. To the sample and
standard solutions add 2 cm3 sodium phosphotungstate reagent and 4 cm3 of sodium
carbonate (10%) in this order and mix well after the addition of each reagent. Leave the
solutions for 15 min and compare the depth of the blue colour obtained for the sample
with that obtained from the various standard solutions. If necessary, repeat the run this
time more closely bracketing the sample solution with the standards to obtain a better
colour match between sample and standards.
240
This method is capable of determining styrene monomer inhibitors in styrene in

amounts down to 1 ppm with an accuracy of ± 10%. To obtain quantitative results it is
necessary to know the identity of the particular inhibitor present in the styrene monomer
sample.
METHOD 37 - DETERMINATION OF HYDROQUINONE INHmITOR IN

MONOMERS. CATHODE-RAY POLAROGRAPHY.
37.1 SUMMARY
A cathode-ray polarographic procedure is described which determines hydro-

quinone, substituted benzoquinone and anthraquinone inhibitors in styrene monomer in
amounts down to 5 ppm.
37.2 APPARATUS
Cathode ray polarograph complete with dropping mercury electrode polarographic

cells (10 cm3) and thermostated (at 75°C) water bath. The sensitivity of the procedure for
determining hydroquinone depends on the cleanness of the capillary used in the dropping
mercury electrode. A new capillary should be used when any decrease in sensitivity in
the polarographic procedure is noted.
Agla micrometer syringe capable of delivery 0.01 cm3 with an accuracy of 0.002
cm •
3
Volumetric glassware. Pipettes 25 cm3, 5 cm3, volumetric flasks, 10 cm3•
37.3 REAGENTS
For polarography of aqueous samples.

Aqueous lithium phosphate base electrolyte PH 7.0. Dissolve 3.60 ± 0.03 g of
lithium hydroxide ANALAR in distilled water and make up to 100 cm3 • Dilute 11.5 ±
0.1 g of 85% phosphoric acid to 100 cm3. with distilled water. Pipette 10 ml of the
lithium hydroxide solution, 500 cm3 distilled water and 10 cm3 of the phosphoric acid
solution into a 1 litre flask and dilute to the one litre mark with distilled water.
Hydroquinone, for calibration.
Aqueous solution ofhydroquinone, 0.1%. Prepare freshly each day.
For polarography of alcohol soluble samples.
Alcoholic acetate base electrolyte PH 7.4. Dissolve 8.2 ± 0.1 g of anhydrous
sodium acetate ANALAR in distilled water and dilute to 100 cm3• Dilute 6.05 ± 0.05 g
glacial acetic acid ANALAR to 100 cm3 with distilled water. Pipette 5 cm3 of each of
these solutions and 2.5 cm3 distilled water into a 500 cm3 volumetric flask. Dilute to the
500 cm3 mark with absolute ethanol and mix.
Standard hydroquinone for calibration, alcoholic solution in absolute ethanol
0.1%, prepare freshly each day.
241
Mercury, pure for polarographic analysis, use trebly distilled mercury supplied in
stone containers. Over a period of time mercury picks up an impurity from polyethylene
storage bottles which might interfere in polarography (see note 1).
Nitrogen, oxygen content, 25 ppm.
37.4 METHOD
The monomer sample is diluted with a suitable aqueous or alcoholic

polarographic base electrolyte solution.
The deoxygenated base electrolyte solution of monomer is then polarographed in
the range - 0.2 volts to + 0.3 V. The wave occuring at 0.0 V due to hydroquinone is then
evaluated. The concentration of hydroquinone in the cell solution is then determined by
making "standard additions" of a solution of hydroquinone.
37.5.1 Procedure
Depending on the expected hydroquinone content of the sample, weigh out a

suitable amount of monomer ( up to 1 g) into a clean 10 cm3 volumetric flask. Make the
sample up to the 10 cm3 mark with the alcoholic or the aqueous base electrolytes.
Pipette 5 cm3 of the sample solution and 5 cm3 sample-free blank base electrolyte
solution into two polarographic cells and immerse these in the constant temperature tank
ofthe cathode ray polarograph (thermostated at 25°C)
The degrassing operations described in this section must be performed on the
sample and on the blank solutions immediately before carrying out all polarographic
measurements. Connect a supply of oxygen-free nitrogen to the polarographic cell.
Lower the dropping mercury electrode system over this cell, so that the outer glass sleeve
of the electrode dips 1 to 2 mm into the water tank (providing a water seal to prevent the
ingress of atmospheric oxygen - note 2). Immerse the anode connection in the side arm
of the polarographic cell. Pass nitrogen for 3 min to completely displace oxygen from the
cell solution, then switch off the nitrogen. Leave the glass sleeve in position to prevent
re-entry of atmospheric oxygen into the cell solution and carry out the polarographic
measurements described below within 1 to 3 min of stopping the nitrogen purge.
The analysis is carried out using a dropping mercury electrode and a mercury pool
reference electrode (note 3). Operate the polarograph using the anodic direct circuit.
First adjust the instrument to -0.25 V start potential. Move the X-shift control until the
light spot on the cathode ray tube graticule commences its horizontal sweep exactly at the
left hand vertical axis of the graticule. Now move the Y shift control until the light spot
commences its sweep at the origin of axes of the graticule (left hand side).
If the polarographic wave is not now visible on the graticule then the instrument is
being operated at too Iowa sensitivity setting. Switch to higher sensitivity settings and
repeat the operations described in the previous paragraph until the 0.0 V polarographic
wave for hydroquinone is visible. Read off from the graticule the maximum height of the
hydroquinone peak.
Similarly, in the case of the reagent blank solution obtain the height of the wave
occuring at 0.0 V (use the same instrument sensitivity setting that is employed when
evaluating the sample solution).
242
Raise the electrode from the cell and deliver into the sample solution a suitable
"standard addition" (note 4) of a 0.1 % solution of hydroquinone in ethanol (or in water)
using a micrometer syringe for delivery (see note 5). In order to avoid sample dilution
errors "standard additions" should be kept below 0.05 cm3 at this stage of the analysis.
Lower the electrode into sample cell and pass nitrogen for 3 min before continuing the
detennination. If necessary, reset the polarograph at a suitable sensitivity setting and note
the new height of the hydroquinone wave at 0.0 V (equivalent to reagent blank plus
hydroquinone in sample plus hydroquinone in "standard addition" solution.
37.5.2 Calculations
Hydroquinone (ppm/w/v) in monomer = 106lLM.ili&1~

W (H3S; --HIS;) -
where
W = weight (g) of monomer sample taken for analysis.

M = weight (g) of hydroquinone present in "standard addition" of hydroquinone
solution made to polarographic cell.
HI = peak height (cms) at 0.0 V of sample solution before standard addition.
H2 = peak height (cms) at 0.0 V of reagent blank solution.
H3 = peak height (cms) at 0.0 V of sample solution after "standard addition".
SI' S2 and S3 are the corresponding instrument sensitivity settings (the product of
Hand S is known as peak current in u amps)
37.5.3 Note 1. Cleanness of Mercury
Blocking or contamination of the dropping mercury electrode capillary is

prevented only by using mercury of the highest degree of purity. Mercury should be
transferred to the electrode reservoir through a pin hole in the cone of a No. 40 Whatman
filter paper. The filter paper should be cleaned and unmarked at the end of the mercury
filtration.
37.5.4 Note 2. Removal of Dissolved Oxygen from Cell Solution.
Prior to polarography oxygen must be completely removed from the cell solution
in order to prevent it interfering in the detennination of hydroquinone.
37.5.5 Note 3. Operation of Polarograph.
After the solution has been placed in the cell and de-oxygenated by bubbling with
nitrogen, the start potential control is set to a voltage about 0.1 V more positive than the
half-wave potential of the ion under examination. The X and Y shift controls are then
employed to set the spot to the zero point on the graticule. The sensitivity control is set
to give a convenient step height and the instrument is allowed to sweep several times in
order to come into synchronism with the mercury drops. This usually takes place in
about two sweeps, but may be hastened by detaching the mercury drop from the capillary
by a sharp tap on the stand base as the spot is passing between 0.4 and 0.5 V on the
horizontal scale. As soon as synchronism has been achieved, the height of the peak may
be read of the graticule. Further peaks, if present, may then be examined by simply re-
setting the start potential control and bringing the spot back to the zero point.
243
37.5.6 Note 4. Calibration of Polarograph.
The "standard addition" calibration technique is used. The peak current (C))
(corrected for reagent blank) due to hydroquinone in the sample solution is noted.
"Standard addition" of a known weight of hydroquinone (Mgrarns) is then made to the
cell solution and the peak current increase (C 2) corresponding to this addition is noted.
Then: weight of monomer in sample = M x C)

C2 -
Note 5. Use of Microsyringe.
More accurate deliveries result when the barrel of the microsyringe are held in a
horizontal position when delivering a "standard addition" into the cell solution.
37.6 DISCUSSION
A cathode-ray polarographic method is described for the determination of

hydroquinone in amounts down to five parts per million in the following organic
monomers with an accuracy of ± 5%.
Methyl methacrylate.
Methyl alphachloroacrylate.
Alpha methyl styrene.
Styrene.
Vinylidene chloride.
Methacrylanitrile.
Acrylonitrile.
Dimethyl itaconate.
The procedure is applicable to samples which are soluble in alcohol or in water.

Benzoquinone is also included in the determination of hydroquinone. (Benzoquinone is
the oxidation product of hydroquinone and might also be present in monomer samples).
Copper, iron and other materials which reduce near 0.0 V will interfere in the
polarographic determination of hydroquinone.
Substituted benzoquinones and anthraquinones can also be determined by the
described procedure. They are reduced in the range 0.0 to 1.0 V and some of these will
interfere in the determination of hydroquinone.
Hindered phenolic types of monomer stabilizers (eg. p-methoxy phenol and p-tert
butyl catechol) do not interfere in the described procedure.
METHOD 38 - DETERMINATION OF P-TERTBUTYL CATECHOL

INHIBITOR IN STYRENE MONOMER. SPECTROPHOTOMETRIC METHOD.
38.1 SUMMARY
This spectrophotometric method determines p-tert butyl catachol inhibitor in

styrene monomer in amounts down to 0.1 ppm.
244
38.2 APPARATUS
Ultraviolet visible spectrometer.

Cells, 1 cm path length, fused glass with lids.
Miscellaneous glassware - pipettes, separator funnels, Idm3 capacity, filter
funnels.
38.3 REAGENTS
Sodium hydroxide, 1 M, aqueous, carbonate free.

p-tert-butyl catechol - solid styrene monomer - purified. Wash severallitres of
styrene monomer with separate portions of aqueous 1 normal sodium hydroxide solution
until the aqueous layer shows no red colouration due to p-tert butyl catechol.
38.4 METHOD
The sample of styrene monomer is shaken with sodium hydroxide solution in the
presence of air. The inhibitor is oxidised to form a red coloured quinoid compound
which extracts into the sodium hydroxide phase. The colour intensity of the complex is
measured using a spectrophotometer at a wavelength of 480 nm and hence the amount of
p-tert butyl catechol present in the styrene monomer may be read off directly from a
prepared calibration graph.
Pipette 10 cm3 of 1 M sodium hydroxide solution into a 1 cm3 separatory funnel

and add 500 cm3 of the styrene monomer sample. Shake the mixture for exactly three
min and allow to settle for 8 ± 1 min (see note 1). Run off the aqueous layer into a 1 cm
cell (see note 2) and measure the optical density of the solution versus I M sodium
hydroxide solution in the reference cell at a wavelength of 480 nm and at 12 min after the
initial addition of monomer sample to the sodium hydroxide reagent.
38.5.1 Calibration.
Pipette I, 2, 3,4, 5 and 10 cm3 of a 100 ppm solution of p-tert butyl catechol
dissolved in purified styrene monomer, into a separate 500 cm3 volumetric flasks and
dilute to the mark with purified monomer. Mix the solutions thoroughly and proceed as
described under Method. Plot the optical density values obtained against the concent-
ration of p-tert butyl catechol (ppm) present in the 500 cm3 dilutions.
38.5.2 Calculation.
From the optical density obtained read off the p-tert butyl catechol concentration
present in the 500 cm3 styrene monomer sample, directly from the calibration graph.
245
38.5.3 Note 1.
The colour of the oxidised p-tert butyl catachol fades grad~ly with time and the
optical density of the solution must be read a stipulated time after shaking.
38.5.4 Note 2.
If the aqueous layer shows any turbidity it must be filtered through glass wool
into the 1 cm3 cell, to remove turbidity.
This method is capable of determining down to 0.1 ppm p-tert butyl catechol
inhibitor in styrene monomer with an accuracy of ±5%.
METHOD 39 - IDENTIFICATION OF TIN CONTAINING DIALKYLTIN

STABILIZERS IN PVC.
39.1 SUMMARY
This procedure involving the use of infrared and NMR spectroscopy is used for
the identification of sulphur containing organotin stabilizers in PVC. Compounds
belonging to this group include:
dialkyl tindialkylthioglycollates,
R2S. (SCH2COOR') (S CH2COOR")
dialkytin dilauryl mercaptides,
Rz8. (8 CHiCH2)lo CH3)2
and stabilizers in which the dialkyl tin group is combined with both thiol and
carboxyl groups. R, R' and R" denote alkyl groups - they can be the same or different.
39.2 APPARATUS
Infrared spectrometer.
NMR spectrometer.
X-Ray fluorescence spectrometer (for checking for the presence of sulphur).
Gas liquid chromatograph (for identification of alcohols).
Filter paper, Whatman No. 541.
Thin-layer chromatography apparatus.
39.3 REAGENTS
Acetone, Analar.
Silver nitrate, aqueous 50010.
Diethyl ether, Analar.
Hydrochloric acid, concentrated.
246
Sodium hydroxide, 5M.
39.4 METHOD
A variety of techniques as reviewed below are used to identify different sulphur

containing stabilizers in PVC.
esters and metal carboxylates infrared spectroscopy
alcohols infrared spectroscopy and gas chromatography
thio acids and thiols infrared spectroscopy and NMR spectroscopy
alkyl groups attached to tin infrared spectroscopy and thin-layer
chromatography
The scheme of analysis in Figure 7.7 illustrates the chemical procedures involved
in the characterisation of the structural groups present.
39.5.1 Infrared Spectroscopy in Presence of Ester and Carboxylate.
The infrared spectrum of the sample will show the presence of ester groups, metal
carboxylates, etc., and will indicate whether or not the sample is a mixture and in need of
separation (eg. the detection of impurities and of stabiliser in the presence of excess of
plasticiser).
Place about Ig of the sample into a 150 em3 flat-bottomed stoppered flask and add
100 cm of acetone. Swirl to dissolve, then add dropwise, with swirling 1 cm3 of a 50 per
3
cent solution of silver nitrate, in distilled water. Shake the flask well and allow it to stand
until the precipitate has settled out. Filter the precipitate through a Whatman No. 541
filter paper, wash it with a small amount of distilled water, then with acetone and finally
with a small amount of diethyl ether. Retain the filtrate and washings (filtrate A, Figure
7.7). Dry the precipitate (precipitate B) in a desiccator and determine its infrared
spectrum of using the nujol emulsion technique.
39.5.2 Infrared Spectroscopy and Gas Chromatography. Identification of Alcohols.
If the infrared spectrum of precipitate B (Figure 7.7) shows the presence of ester
bands transfer the precipitate to a 150 cm3 flat bottomed flask and shake it with 50 cm3 of
diethyl ether. Add 1 cm3 of concentrated hydrochloric acid and shake the flask
vigorously for 1 min to precipitate the silver as silver chloride. Allow it to stand for 30
min then decant into a 150 cm3 flat bottomed extraction flask through a Whatman No.
541 filter paper, washing the flask and the precipitate with 20 cm3 of diethyl ether.
Reject the precipitate but evaporate the ether extract to dryness on a water-bath. This
yields the residue C (see Figure 7.7). Determine the infrared spectrum of the residue.
This spectrum should show the presence of ester bands and may already suggest the
nature of the alcohol involved.
Next, add 20 cm3 of 10 per cent aqueous sodium hydroxide solution and saponify
the ester by refluxing on a hot-plate. Normally a refluxing time of 1.5 h is sufficient.
Wash the condenser with a small amount of distilled water and allow to cool, then
transfer the reaction mixture to a distillation apparatus. Distil, separate and identify the
alcohols by gas -liquid choonatographic methods. If the gas -liquid chromatography
247
Sample
Examine i.r. spectrophotometrically
Dissolve in acetone.
Add silver nitrate solution.
Filter
Filtrate A P '3cipitate B (ester present)
Add hydrochloric acid. Treat with ether and

Filter hydrochloric acid.
Filter
Filtrate preciritate Precipitate Filtrate

I
Add sodium hydroxide Silver chloride.
I
Silver chloride.
I
Evaporate to dryness, C.
solution. Reject Reject Saponify with sodium hydroxide.
Filter Distil off alcohols (or extract
with ether if only higher alcohols
known to be presentl
I I
Preci pitate Filtrate I
I I I (~her extract
"I·'....
Distillate
(r:~l
Dialkyltin oxide; retain Reject
for identification
li.r.1 Al.....
Extract with ether (if alcohols retain for
I
recovered by distillatlonl ldentiflcetion (g.l.c.,
n.m.r., l.r.l. (u.v. abtorblng
stabilisers may also
be present)
~I--------~--------,I
Aqueous phase D Ether extract evaporated
Acidify ~ith
hydrochloric acid.
I
Traces of alcohols, Ithlol')
Extract with ether unsaponlfled ester and, possibly,
I u.v. absorbing stabilisers. Examina
, by I.r.
I
Ether extract Aqueous phase
I
Evaporate an aliquot to
I
Reject
dryness and retain for
identification (I.r., n.m.r.).
To the rest add sliver
nitrate solution.
Filter
Precipitate Filtrata
I
Silver·thioacid or thiol complex.
I
Reject
Examine by Lr. Treat with chloroform-
hydrochloric acid and examine by n.m.r. for
identification of the thioacld·thiol.
If necessary, recover the acid (thiol)
by ether.hydrochloric acid treatment and
re-examine
Figure 7.7. Scheme for analysis of dialkytin thiocompounds. From Udris with permission. IS Royal
retention times alone are considered unsatisfactory for complete identification, use the
separated fractions for infrared and for nuclear magnetic resonance spectroscopic
examination. Sometimes the gas - liquid chromatographic examination can provide
information as to the approximate ratio of the alcohols present.
248
Extract the aqueous phase by shaking it with diethyl ether. Evaporate the ether
extract to dryness and examine by infrared spectrophotometry. Retain the aqueous phase
(Figure 7.7) for examination for thioacids.
If the infrared spectrum of precipitate B suggests the presence of only a
mercaptide or carboxylate or mecapto-carboxylate with no ester bands proceed as
outlined under the identification of thioacids and thiols as described below, ie. omitting
the saponification step.
In the case of the less volatile alcohols, such as 2-ethylhexanol and higher
alcohols, the alcohol can be recovered by extraction of the alkaline saponification mixture
with diethyl ether, followed by careful evaporation of the solvent. Subsequent infrared
(or nuclear magnetic resonance) examination of the residue usually suffices for the
identification of the alcohol. Of course, if more than one alcohol is present, the gas -
liquid chromatographic examination is called for.
39.5.3 Infrared Speetroscopy and NMR Speetroscopy. Identification of Thioacids

and Thiols.
Acidify the aqueous phase D, remaining after the removal of alcohols (see above)
with concentrated hydrochloric acid and extract the liberated thioacid with diethyl ether.
Liquid - liquid extraction for 4 hours produces more material, but shaking with 50 cm3 of
diethyl ether for about 1 min normally gives enough extract for identification. Because of
partial decomposition of the thioacid during the foregoing saponification, sulphides are
produced and the above acidification and extraction should be carried out in a fume
cupboard. The ether extract can be evaporated to dryness on a water bath and examined
by infrared or nuclear magnetic resonance spectroscopy or by both techniques, but,
because of partial decomposition a better way of identification at least for the thioacid, is
as follows:
Evaporate to dryness and examine only an aliquot' of the ether extract. To the rest,
prior to evaporation, add a few drops of 50 per cent silver nitrate solution, dropwise, with
shaking. Shake well and allow the precipitate to settle, then filter through a Whatman
No. 541 filter paper washing well with ether. Dry in a desiccator and examine by infrared
spectrophotometry and the nujol emulsion technique. Also, suspend an aliquot of the
precipitate in chloroform, acidify with a little hydrochloric acid, shake and carry out
nuclear magnetic resonance spectroscopic examination of the chloroform extract. This
should suffice for the identification of the thioacid. The dark colour of the silver complex
is probably due to the presence of silver sulphide.
If precipitate B contains no ester groups (see Figure 7.7) the hydrolysis with
sodium hydroxide should be omitted. In this event, examine the precipitate by the above
infrared and nuclear magnetic resonance technique for identification of the thioacid or the
thiol.. Although this particular nuclear magnetic resonance technique was not used for
the identification ofthiols, it could prove equally effective. .
If required, the free acid, usually thioglycollic, or thiol can be obtained in a purer
state by acidifying the silver complex with hydrochloric acid and extracting the liberated
acid and thiol with diethyl ether. The infrared and nuclear magnetic resonance
examinations can then be repeated on the thioacid or thiol itself.
Mass spectrometric examination is also a useful test for the identification of
thioacids, for example, thioglycollic acid gives the characteristic ion at mle = 91.
249
39.5.4 Infrared Spectroscopy and Thin-Layer Chromatography. Identification of
the Alkyl Groups Attached Directly to Tin. Precipitation with Sodium Hydroxide
and Infrared Examination.
To filtrate A add a slight excess of concentrated hydrochloric acid (about 1 cm3)

to precipitate the excess of silver ions as silver chloride. Shake the mixture well, allow to
settle and filter through a Whatman No. 541 filter paper. Make the filtrate alkaline by the
addition of 25 cm3 of 10 per cent sodium hydroxide solution and again shake and filter
through a Whatman No. 541 filter paper, this time washing well with acetone. Dry at
105°C for 30 mins. This gives a crude sample of the dialkyltin oxide but this is
sufficiently pure for identification by infrared spectrophotometric examination
(potassium bromide).
Good samples of dibutyl and dioctyltin oxides have also been obtained by
dispersing about 0.8 g of the stabiliser in 25 cm3 of methanol and refluxing for 3 h with
20 ml of M sodium hydroxide solution. The white pOWder, isolated after filtering
through a G3 sintered glass crucible, washing with distilled water followed by methanol
and drying at 105°C, usually gives a characteristic infrared spectrum of the dialkyltin
oxide, believed to be in polymeric form.
In addition to the infrared spectroscopy techniques described above thin-layer
chromatography with hexane: glacial acetic acid (12 + 1) as eluting agent is satisfactory
for the identification of thioacids and thiols. A small amount of the original tin stabiliser
is dissolved in the elution solvent, applied to a thin-layer chromatographic plate coated
with 0.25 mm thick layer of Kieselger G as the stationary phase, and eluted with the
hexane: glacial acetic acid mixture. After drying, the stationary phase is sprayed with 0.1
per cent solution of catechol violet in 95 per cent ethanol, blue spots appearing where tin
compounds are present.
If mixed tin stabilisers are believed to be present, for example, a thiocompound
and a dialkyltin dialkylcarboxylate, it is advantageous to acidify the acetone filtrate after
removal of the dialkyltin oxides with hydrochloric acid, evaporate most of the acetone on
a water-bath under an air-jet, cool and extract by shaking with diethyl ether. The ether
extract then contains hemiesters, acids, etc., liberated from the other type oftin stabilisers
originally present and can be examined further. Although reaction products produced by
the action of sodium hydroxide or acetone are often present, esters of maleic and benzoic
acids have been identified in this way.
These methods are basically qualitative although in some instances the methods
can be put on a quantitative basis, ego the gas chromatographic determination of alcohols
produced by the hydrolysis of ester groups. Figure 7.8 shows an infrared spectrum of
dibutyl tin dichloride showing that this compound can be easily identified by this
technique. Good samples of dialkyltin dichlorides have been isolated by the above
method from mixtures of tin stabilisers with diisooctyl phthalate and tritolyl phosphate;
the dialkyltin groups have been identified in dibutyltin dinonylmaleate, dioctyltin
dilaurate, dibutyltin dinonylthioglycollate and dioctyltin thioglycollate.
250
METHOD 40 - IDENTIFICATION OF DIALKYLTIN CARBOXATED AND
HEMIESTERS STABILIZERS IN PVc. IS
40.1 SUMMARY
This procedure involving the use of infrared spectroscopy, gas chromatography

and thin-layer chromatography is used for the identification of sulphur-free type
organotin stabilizers in PVC.
To this group belong stabilisers like dialkltin maleates, (R2Sn(OOCCH =
CHCOORi )2' dialkyl tin dilaurates (R2Sn(OOC(CH2)IOCH3)2' where R and R' may be the
same or different.
40.2 APPARATUS
Gas chromatograph.
Thin-layer chromatography apparatus.
Separating funnel: 150 ml.
Filter paper Whatman No. 541.
Water bath.
40.3 REAGENTS
Sodium hydroxide, aqueous, 10%.

Diethyl ether, Analar.
Hydrochloric acid, concentrated
40.4 METHOD
A variety of techniques, as discussed below, are used to identifY different types of

non-sulphur containing stabilizers in PVC.
ester and carboxylate infrared spectroscopy

alcohols gas chromatography
alkyl groups attached to tin infrared spectroscopy and
thin-layer chromatography
The scheme in Figure 7.9 illustrates the analytical procedures involved in the
characterisation of the structural groups present.
40.S.1 Infrared Spectroscopy. Ester and Carboxy Groups.
Examine the infrared spectrum of the sample and deduce its general nature from
the absence or presence of ester groups, free carboxyl groups, plasticizers or significant
251
~ 100
QI
...
U
80
8.
QI"
u
c
! 40
'E
c'" 20
l!
t- O
3 4 5 6 7 8 9 10 11 12 13 14 15
Wavelengthlpm
Figure 7.S. Infrared spectrum ofdibutyltin-dichloride. From Udris with permission. 15 Royal Society of
Chemistry, London.
amounts of other constituents. More detailed methods of examination for the presence of
impurities and additivies, or both, and techniques of separation are described below.
40.5.2 Gas Cbromatography. Identification of Alcobols.
Place about 1 g of the sample containing ester groups into a 150 cm3 extraction
flask and saponify by refluxing with 50 cm3 of 10 per cent aqueous sodium hydroxide
solution for 4 hours. Wash the condenser with distilled water, cool the flask, transfer it to
a distillation apparatus and distill off the alcohols. Identify the alcohols and, if possible,
determine their approximate ratios by gas - liquid chromatographic methods. Retain the
alkaline solution (see aqueous phase A, Figure 7.9).
40.5.3 Infrared Spectroscopy and Thin-Layer Chromatography. Identification of

the Alkyl Groups Attached to Tin.
Transfer the alkaline solution, aqueous phase A, to a 150 cm3 separating funnel,
adding more water if necessary and extract by carefully shaking with 50 cm3 of diethyl
ether.
Filter the aqueous phase, diluting with distilled water or warming if necessary,
through a Whatrnan No. 541 filter paper and wash the precipitate with hot distilled water,
especially if a long-chain acid salt is present. Dry the precipitate at 105°C and examine
by infrared spectrophotometry to identify the dialkyltin group. Retain the filtrate, filtrate
B (Figure 7.9) but evaporate the ether to dryness and examine the residue by infrared
spectrophotometry. This may contain traces of alcohols, unsaponified esters, etc.
If the only concern is the identification of the dialkyl groups attached directly to
tin, then a method using methanolic sodium hydroxide solution is recommended (Figure
7.9). The thin-layer chromatographic method described is also suitable. For pure
samples of dialkyltin carboxylates with no ester present, the time of reflux with alkali can
usually be much reduced, the recovery and identification of the dialkyltin oxide, believed
to be in polymeric form, still being quite satisfactory. In addition, maleic acid can be
recovered from a sample of dibutyltin maleate after decomposition by this simplified
method.
252
40.5.4 Infrared Spectroscopy. Identification of Acids.
Reduce the volume of filtrate B (Figure 7.9) to about 150 cm\ by boiling, acidify
it with hydrochloric acid and extract by shaking it with 50 cm3 of diethyl ether.
Evaporate the solvent on a water-bath, dry the residue at 105°C for 20 minutes and
determine its infrared spectrum to identify the acid readily soluble in ether.
Extract the aqueous phase with diethyl ether for 4 h by liquid - liquid extraction,
evaporate the solvent, dry the residue at 105°C and again examine it by infrared
spectrophotometry, this time to identify the acid less soluble in ether, usually maleic acid.
If the infrared spectrum of the first ether extract, ie. the one obtained by shaking,
indicates a mixture of a long-chain and another acid, triturate the residue several times
with small amounts of distilled water. Recover the fraction soluble in water by
evaporation and dry both fractions at 105°C. Examine both the water-soluble and the
water-insoluble fractions by infrared spectrophotometry. If necessary, prepare and
examine the barium salt of the long-chain acids. Udris l5 separated and identified a
mixture of phthalic and lauric acids by this method.
The long-chain acids obtained by this method are usually contaminated by metal
salts and a dialkyltin dichloride, the latter originating from the presence of residual
dialkyltin groups. F or positive identification of the acid by infrared spectroscopic
examination, the preparation of the barium salt has been found helpful. Alternatively, the
acid can be identified by mass spectrometric examination.
These methods are basically qualitative although in some instances the methods
can be put on a quantitative basis, ego the determination of ester groups and alcohols by
gas chromatography.
METHOD 41 - IDENTIFICATION OF ACCELERATORS AND ANTIOXIDANTS

IN NON-VULCANIZED RUBBER COMPOUNDS. THIN LAYER
CHROMATOGRAPHY. 16
41.1 SUMMARY
This thin-layer chromatographic method determines a range of accelerators and

antioxidants in non-vulcanized rubber compounds in amounts down to 5 ppm.
41.2 APPARATUS
Sil G UV254 pre-coated plastic sheets of silica gel.

Laboratory mill with freeze drying attachment.
Equipment for thin-layer chromatography.
41.3 REAGENTS
Liquid nitrogen.
Developing solvents:
253
Sample
Examine i.r. spectrophotometrlcally
Add sodium hydroxide solution.
Saponify.
Distil off alcohols.
If ester groups are absent, the saponification-
distillation step may be omitted
r
AqUeOUj phase A. Distillate
I
Alcohols. Retain for identification
e"""
(g.l.c.,n.m.r.,i.r.). May also contain
~"" u.v. absorbing stabilisers (lopanol 0)
I
Ether extract evaporated I
I
Aqueous phase
Traces of alcohols, unsaponified

ester. May contain u.v.-absorbing
I
Rewarm and filter
I
stabilisers. Examine by i.r.
I
Filtrate B
I
Precipitate, well washed
I
Acidify with hydrochloric acid.
I
Dialkyltin oxide
Shake with ethi' Retain for identification (I.r.)
I I
Aqueous phase Ether extract evaporated
I
Liquid-liquid extract
I
Acids very soluble In ether.
Retain for Identification lI.r.l.
with ethel May need separation (e.g., extraction with water etc.)
or purification via the barium salt
I
Aqueou s phase
I
Ether extract evaporated
I
Reject
I
Acids not very soluble In
ether (maleic acid).
Retain for identification (I.r.)
Figure 7.9. Scheme of analysis of dialkytin carboxylates and hemiesters. From Udris with permission. IS
Royal Society of Chemistry, London
(a) Petroleum ether (30° - 40°C) diethyl ether 110:20 (pre-developing solvent),
(b) Benzene: ethyl acetate, acetone, 100:7:2 v/v (primary solvent mixture)
(c) Cyclohexane
(d) Toluene:ethyl acetate:ammonium hydroxide 100:5:0.1
(e) Cyclohexane:diethylamine, 75:25 v/v
(t) Chloroform: Benzene, 100:90 v/v
(g) Acetone: ammonium hydroxide, 100:1 v/v (confirmation guanidines)
(h) Isopropanol, A.R
Visualizing reagents:
254
(a) Iodoplatinate solution, 3 cm3 of 10% platinum chloride solution mixed with
97 cm3 of water to which are added 100 cm3 of a 6% aqueous solution of potassium
iodide.
(b) Dibromo benzoquinone chlorimide, 1% solution in methanol
Sodium hypochlorite, 4% aqueous
Sodium bicarbonate, 1%.
41.4 METHOD
The unwlcanized rubber sample is extracted with isopropanol to remove

accelerators and antioxidants. Isopropanol is removed and the residue dissolved in
chloroform and applied to a thin-layer plate. Development with a range of solvent
mixtures separates the components which are then detected with a range of spray
reagents. Calibration is achieved by applying the procedure to prepared pure standard
solutions.
Immerse 3.0 grams of non-vulcanized sample, cut into small pieces, in liquid
nitrogen until hard and grind to a fine state using a laboratory mill with freeze dryinj
attachment. Transfer the ground sample to a glass stoppered 30 cm3 test tube, add S cm
of isopropanol and extract by infusion for I hour at room temperature.
Decant off extract and leave overnight in a deep freezer, filter and evaporate off
solvent from the filtrate at room temperature. Redissolve the extract in I cm3 of
chloroform and apply amounts of I - 10 ul to a thin-layer chromatography plate
evaporating off solvent with cold air between applications. After development examine
plate under short and long UV and recotd observations.
Spray the sheet with the iodoplatinate solution and dry in an air oven at 100°C.
The iodoplatinate reagent visualizes accelerators as white, yellow, orange and brown
spots ona brick-red background.
When using the combination of sprays, spray with the chlorlmide and dry at 6SoC.
Examine and then lIpray with iodoplatinate and dry at 100°C. A second plate is sprayed
with chlorimide reagent. Both accelerators and antioxidants produce coloured spots with
this reagent. On overspraying with the iodoplatinate, the antioxidant spots retain their
color, while the accelerator spots fade or become a darkened centre with an intense white
halo.
Calibrate the procedure against chloroform solutions of pure specimens of the
compounds being determined.
Accelerators studied were representative of a wide range of chemical types
including guanidines, thiazoles, thiurams, sulfenamides, diethiocarbamides and
morpholine disUlfides. All the accelerators tested gave a positive response to the
iodoplatinate reagent and a list of colour reactions is shown in Table 7.16. In Table 7.16
are shown the colour reactions of a wide range of antioxidants tested involving both
phenolic and amine types. Only those antioxidants based on phenylene diamine gave a
colour reaction with the iodoplatinate reagent. Colours produced are distinctively
different - cyclamens, purples and greens.
An overspray of sodium bicarbonate immediately following the chlorimide spray
and then overspraying with iodoplatinate can be·useful for confirming the presence of the
following accelerators: tetramethyl thiuram monosulfide (TMTM), tetramethyl thiuram
255
disulfide (1MTD), zinc diethyl dithiocarbamate (ZDC), 2-(morpholinothio)
benzothiazole (Santocure MOR) and mercaptobenzothiazole (MBT).
Chromatograms should be observed at intervals through a period of 48 hours.
Colours tend to become more definite or fade, leaving a pale spot with a discoloured
centre. This would appear to be characteristic of accelerators treated with the
iodoplatinate reagent, and could serve as a distinguishing feature when analyzing
accelerators in the presence of antioxidants, (Table 7.16).
This method is capable of determining accelerators and antioxidants in un-

vulcanized rubber compounds with an accuracy of ± 10%.
For quantitative determinations it is of course necessary to know the identity of
the compound being determined and to calibrate the procedure accordingly.
METHOD 42- IDENTIFICATION AND DETERMINATION OF

ANTIOZONANTS AND ANTIOXIDANTS IN RUBBER VULCANIZATES-
MASS SPECTROMETRy.17
42.1 SUMMARY
This mass spectrometric method determines down to 0.01% antiozonants and

antioxidants in rubber vulcanizates.
42.2 APPARATUS
Mass spectrometer/data system Finnigan MAT 311/A

Incos 2400 or equivalent with combined EIICI (electron inpaceJchemical ioniz-
ation ion source)
EI, FD, FAB analysis
Computer mass range up to mlz 1450. Ion source temperature, 250°C,
accelerating voltage 3 kV, resolution MldM 1000 (10% valley). The electron energy for
EI was 70 eV; the CI (chemical ionization) reagent gas was generally isobutane, but
methane was also used.
Spectra were acquired as the direct probe was heated over the range 50 - 300°C.
Accurate mass measurements made by peak matching in either EI or CI mode (resolution
MldM about 10000).
FD and FAB (fast atom bombardment) spectra acquired with the same instrument
using a combined EIIFDIFAB ion source. For FD analysis, the residues were taken up in
the extraction solvent (either acetone, acetonitrile or dichloromethane) and deposited
using the standard dipping technique onto the emitter wire. Standard high temperature
activated carbon emitters were used. For FD the ion source temperature was 90°C, the
accelerating voltage 3 kV, the extraction plate voltage 6kV and the resolution MldM
about 600. Spectra were acquired as the emitter was heated manually with 0 - 30 rnA
heating current. For FAB the viscous extraction residues were deposited directly on a
stainless steel FAB probe, either neat or else mixed with a little thioglycerol solvent. For
256
Table 7.16 - Reactionsa of Antioxidants and Accelerators
Chemical Trade name Spray I Spray 2 Spray 2 Primary

or iodoplatinate chlorimide plus solvent
abbreviation Spray 1 system
Rr
(a) Reactions of Antioxidants
Acetone diphenylamine NonoxBL Pale green Green 0.53
condensation product blue
Butraldehyde aniline Antox Brown yellow Grey 0.40
condensation product edge purple
4,4'-Butylidene-bis(6-tert- Santowhite Purple Grey 0.37
butyl-3-metbylphenol) powder
4-Phenyl-N"cyclohexyl-p- Antioxidant Grey blue Purple Purple
phenylene diamine 4010
2;2' -Metbylene-bis(4-ethyl-6- Antioxidant Green white Rust 0.58
tert-butylphenol) 425 centre yellow
Diphenylamine acetone Ble Green blue Yellow Rust 0.48
reaction product (weak)
N-Phenyl-N'-I,3-dimethyl Santoflex Blue brown Brown yellow Purple 0.48
butyl p-phenylenediamine 13 edge
6-Dodecyl-1 ;2-dihydro-2;2,4- Santoflex Yellow Rust 0.38
trimethylquinoline DO yellow
centre
Diphenyl-p-phenylene- DPPD Green Purple Purple 0.47
diamine
Mixture of diaryl p- Wingstay Brown green Brown yellow Purple 0.50
phenylenediamines 100 edge
6-Ethoxy-I,2-dihydro-2-2,4- Santoflex Cyclamen Purple 0.40
trimetbylquinoline AW
N,N'-Bis(l-ethyl-3-methyl- UOP88 Cyclamen Cyclamen Cyclamen
pentyl)-p-phenylenediamine
N,N'-Bis(l-metbylheptyl)-p- Santoflex Purple Pink grey edge Purple 0.25
phenylenediamine 217
N,N'-Bis(I,4-dimethyl Santoflex 77 Purple Brown Purple 0.23
pentyl)-p-phenylenediamine
2;2'-Metbylene-bis(6 alpha- NonoxWSP Yellow Yellow
methylcyclohexyl-4-methyl- orange
phenol) edge
4-Isopropyl- NonoxZA Grey green Brown yellow Purple 0.33
aminodiphenylamine edge
A substituted phenol NonoxWSL Rust Yellow 0.55
purple
edge
beta-Naphylamine Brown Purple 0.22
Tri-(nonylated phenyl)- Polygard White Purple, orange White 0.57,
phosphite purple 0.33
edge
Substituted styrenated phenol Wingstay S Purple, blue Purple 0.60,
0.37
2,6-di-tert-butyl-4- lonol Rust Yellow 0.90
methylphenol brown
edge
2,2'-Metbylene-bis(4-methyl Antox2246 Yellow Orange 0.57
6-tert-butylphenol) brown
edge
Modified phenyl beta- NonoxDN Pink Purple 0.53
naphthylamine
257
A phenol condensation NonoxEX Yellow Yellow 0.38

product purple
streak
A blend ofarylamines NonoxHFN Pink Purple 0.53
Sym. di-beta-naphthyl-p- Nonox CI Brown streak Lavender 0.00
phenylenediamine streak
Phenyl-beta-naphthylamine + NonoxHP Weak pale Yellow, purple Purple 0.47,
diphenyl-p-phenylenediamine green 0.53
A phenol condensation Nonox WSP Yellow Rust 0.37
product
Octylated diphenylamines Octamine Pale Pink Brown 0.99
green
2,2,4-Trimethyl-I ,2- Flectol (Weak Turquoise Green 0.45,
dihydroquinoline Flakes response) 0.35,
0.20,
0.13,
0.05
A phenol condensation A.F.D. Grey 0.60
product
N,N' -Bis( I-methyl heptyl)-p- UOP288 Cyclamen Pink, blue Purple 0.50,
phenylenediamine 0.08
(b) Reactions of Accelerators (Included are a few Pel!tizers)

Diphenylguanidine DPG Brown, Blue Green, 0.00
white edge white
edge
Di-o-tolyguanidine DOTG Brown, Blue Green, 0.00
white edge white
edge
2-Mercaptobenzothiazole MBT Yellow Orange Rust, 0.30
white
edge
Benzothiazyl disulfide MBTS Cream Pale Yellow Orange 0.50
streak streak,
white
edge
Tetramethylthiuram disulfide TMTD Yellow, Dark red pink Red, 0.45
brown white edge white
edge edge
Tetramethylthiuram TMIM Yellow, Dark red pink Yellow, 0.45
monosulfide brown white edge red edge
edge
N,N- VucazitDZ Yellow, Yellow orange Orange, 0.70
Dicylcylohexylbenzothiazole white edge white
-2-sulfenamide edge
Phosphorus-containing Vulcadone 3 White, grey Yellow Rust, 0.85
polysulfide SN edge white
edge
N-Cyclohexyl-2- Santocure Yellow, pale Yellow orange Orange, 0.63
benzothiazole sulfenamide edge white
edge
N-tert-butyl-2-2benzothiazole Santocure Yellow, pale Yellow orange Orange, 0.55
sulfenamide NS edge white
edge
Zinc diethyl-dithiocarbamate ZDC Yellow Brown, red Rust, 0.73
edge white
edge
258
Zinc salt of 2 mercaptobenzo- 2MBT Yellow Red Rust 0.25

thiazole white
2-Benzothiazyl-N,N- Ethylene Yellow, Yellow orange Rust, 0.39
diethylthio-carbamyl sulfide white edge white
edge
4-Morpholine disulfide Morfax White Yellow Brown, 0.35
white
edge
Copper dimethyl- Cumate Pale brown Red streak Brown 0.20-
dithiocarbamate streak streak 0.70
Diphenylmethylene thiuram TetroneA Brown Orange yellow Red streak 0.30-
tetrasulfide streak cream 0.80
centre
2-(Morpholinthio)- Sanocure Yellow, Yellow Orange, 0.30,
benzothiazole MOR cream white 0.63
edge
Hexamethylene tetramine Vulcacit Red, white Yellow Red, 0.00

H30 edge white
edge
Morpholine disulfide SulfasanR Grey, white Yellow Rust, 0.38,
edge white 0.20
edge
2-Mercapto imidazoline Na22 White Brown Brown 0.00
orange
2,2'-Dibenzamido-diphenyl Pepton 22 Cream, Pale orange Red, 0.35

disulfide brown edge white
edge
• Colour reactions given in the tables refer to pure compounds. At the dilution level in a rubber stock,
many of the positive responses given by antioxidants to the iodoplatinate reagent are weak and in many
instances, could be regarded as negative. From Milligen l6 American Chemical Society
FAB the ion soW"Ce temperature was 70·C and the resolution MldM about 1000. The fast
atom gun (IonTech Model FAB-tt-GG) provided xenon atoms at an energy of 8.0 keY.
FI analysis. For FI analysis a Varian MAT 731188200 mass spectrometer/data
system (Wiesbaden) was used. Standard high temperature activated carbon emitters were
used with a combined EIIFIIFD ion source. The ion soW"Ce temperature was 50·C, the
accelerating voltage 8 kV, the extraction plate voltage 3 kV, and the resolution MldM
about 2000. A heated direct probe was used for sample introduction.
42.3 METHOD
The technique can be applied either to solvent extracts of rubbers or directly to the
rubber sample. Electron impact or chemical ionization mass spectra are prepared and the
individual additives identified and, if pure calibration standards are available, determined.
259
42.4 EXPERIMENAL PROCEDURE
42.4.1 Rubber Extract Analysis.
The cured rubbers are cut into small pieces (about 2 mm square) and extracted for
24 h with either acetone, acetonitrile or dichloromethane in a Soxhlet apparatus. The
extraction solvents are evaporated under a stream of nitrogen at room temperature. The
extmct residues are placed in aluminium crucibles for EI or CI mass spectral analysis.
42.4.2 Direct Rubber Analysis.
Small pieces of rubber are cut from the ASTM sheets using a razor blade and
placed in aluminium crucibles for direct mass spectral analysis. EI and CI spectra were
acquired by using the same MAT 311 A instrument with the conditions as described
above. Spectra were acquired as the probe was heated from 50 to 300°C. For direct FAB
analysis, the vulcanizates were cut into strips (8 x 3 x 2 mm) which were attached to the
stainless steel FAB probe with scotch 924 transfer tape. The experimental conditions for
FAB were the same as described above (no FAB solvent was used with the samples).
The various classes of additives are discussed individually below in terms of their
ability to be detected in the vulcanizates by mass spectrometry.
Antioxidants and antiozonants examined include aromatic arnines (HPPD,
DOPPD, DODPA and poly-TMDQ) and a hindered bisphenol (AO 425). These
compounds could be identified quite readily by either extraction or direct analysis and by
use of any vaporization/ionization method.
Stearic acid could be identified only by direct analysis of the rubber, using any
vaporization/ionization method. Stearic acid was not observed in any of the extracts; this
indicates that it remains in the rubber bulk during the extraction process.
METHOD 43 - DETERMINATION OF ACID AND GLYCOL UNITS IN

TERYLENE AND OTHER POLYESTERS. HYDROLYSIS - GAS
CHROMATOGRAPHY.
43.1 SUMMARY
This gas chromatographic method determines acid and glycol units in polyesters
in amounts down to 0.05%.
43.2 APPARATUS
Hewlett-Packard model 5711A gas chromatograph equipped with a flame

ionization detector and a Hewlett-Packard model 3352B laboratory data systems were
used.
260
43.3 REAGENTS
Redistilled Eastman Kodak 2-ethoxyethanol (practical grade). Internal standard

solutions:
Dodecane, 1 g diluted to 100 ml with 2-ethoxyethanol.
Nonyl alcohol, 5 g diluted to 100 ml with 2-ethoxyethanol.
Propyl alcohol, 0.4 g diluted to 100 ml with 2-ethoxyethanol.
Heptadecane, 1 g diluted to 100 ml with 2-ethoxyethanol.
N,O-bis (trimethylsilyl) trifluoroactamide.
Potassium hydroxide (1 M) in 2-ethoxyethanol.
Hydrochloric acid, concentrated.
Pyridine, Analar.
43.4 METHOD
The polyester is refluxed with a 2-ethoxyethanol solution of potassium hydroxide

to break down ester linkages to alcohols and carboxylic acids, ego
7.2
[CH 2 - CH 2 OOC - (0) - coo] n ..

KOH
HOCH 2 CH 2 - OH + nKOOC - (0) -COOK
After acidification and the addition of an internal standard the extract is reacted
with N,O-bis (trimethylsilyl) trifluoroacetamide to produce the sHyl ethers of glycols and
the sHyl esters of carboxylic acids. Gas chromatography of this reaction mixture enables
the numbers of acid and glycol units in the polymer to be estimated.
The amount of sample used for the alkaline hydrolysis is controlled by the type of
detennination. For example, a 1 g sample is sufficient for the determination of the
glycols and acids comprising the major portion of the repeat units. A 4 g sample is used
when determining trace components such as the methyl ester end-groups.
The sample is weighed into a 100 m1 flask and 50 m1 of 1 N potassium hydroxide
in 2-ethoxyethanol is added to the flask. A condenser cooled by chilled water is attached
to the flask and the reaction mixture is protected from carbon dioxide by means of a tube
packed with Ascarite absorbent and Drierite desicant. The contents of the flask are
heated and maintained at reflux temperature for 10 min with constant stirring. The flask
is allowed to cool to room temperature and the hydrolysate is adjusted to a pH of 1 using
concentrated hydrochloric acid (5 m1). An internal standard is added to the flask.
Pyridine (25 ml) is added to dissolve the acids present and an aliquot sample is
centrifuged to remove the potassium chloride. Approximately 50 ul of hydrolysed
sample is allowed to react at room temperature for 5 to 10 min with 500 ul of N,O-
bis(trimethylsilyl)trifluoracetamide to form sUyl ethers and esters of the glycols and
acids, respectively. The sUyated hydrolysate is chromatographed by injecting 0.1 ul of
sample into the gas chromatograph.
261
The silyl derivative of diethylene glycol is separated from the silyl derivative of
ethylene glycol using a lOft x 118 inch stainless steel column packed with 100-200 mesh
Chromosorb G-HP solid support containing 3% by weight of Versilube F-SO liquid
phase, Versilube F-SO is the trademark for a mixture of trichlorophenyl silicone (10%)
and methyl silicone manufactured by General Electric.
Figure 7.10 is a chromatogram obtained for the silyl derivatives of the hydrolysate
of an experimental polyethylene terephthalate. Dodecane is used as an internal standard
and the column is operated isothermally at 127°C with a nitrogen carrier gas flow rate of
10 mllmin.
High boiling acids, such a terephthalic and isophthalic acids are separated using a
6 ft x 118 in stainless steel column packed with 100-200 mesh Chromosorb W-HP solid
support containing 10% by weight Versilube F-SO liquid phase.
Another important use of the alkaline hydrolysis/gas chromatographic procedure
is the determination of methyl ester end groups. If the polyester is terminated with
methyl ester end groups, then methyl alcohol is produced when the polyester is
hydrolysed. By determining the concentration of methyl alcohol, one can calculate the
number of methyl ester end groups in polyethylene terephthalate. The hydrolysis
procedure for determining methyl ester end-groups is the same as discussed for the
glycols and acids. The gas chromatographic procedure is different in that no silylation
reagent is used. The hydrolysed sample is separated using a 6 ft x 114 inch glass column
containing 60-80 mesh Chromosorb 102 column packing.
Propyl alcohol is used as the internal standard, and the column is operated
isothermally at 14SoC with a nitrogen carrier gas flow rate of 10 mllmin.
The data given in Table 7.17 shows that the precision of the overall method is
good. This method is relatively simple and fast. The method has been used to analyse
experimental polyester for the amount of monomers present in the repeat units and for
detennining. the composition of copolymers and polymer blends. The relative standard
deviation varies from 0.8% for the determination of 1,4-butanediol to approximately 2%
for 1,4-cyclohexanedimethanol. For the determination of different concentrations of
isophthalic acid, the standard deviation varies from 0.7 to 2.4%.
METHOD 44 - DETERMINATION OF WATER IN POLYESTERS.

DERIVATIVIZATION - GAS CHROMATOGRAPHY. 19
44.1 SUMMARY
This gas chromatographic procedure determines water in polyesters in amounts

down to SO ppm.
44.2 APPARATUS
Auto injection vial, 1.9 ml (Wheaton Glass) with cape lined with Teflon resin are
sealed with a crimpmg tool
262
::=========-- DIETHYLENE GLYCOL. TMS ETHER
INTERNAL STANDARD
LIQUID PHASE: "YERSllUSE" "-50

COLUMN TEMP: 127'C
NI FLOW RATE: IOML/MIN
ETHYLENE GLYCOL. TMS ETHER
Figure 7.10. Chromatogram ofTMS derivatives of the glycols from the hydrolysis
ofpoly{ethylene terephthalate). From Allen et al with permission. IS American
Chemical Society.
Table 7.17 - Precision of Hydrolysis - Gas Chromatographic Method
Component Concn. SD No.

%
Diethylene glycol, TMS ether 1.781 0.019 40

1,4-Butanediol, TMS ether 6.59 0.050 20
1,4-Cyclohexanedimethanol TMS ether 20.45 0.40 20
Isophthalic acid, TMS ether 5.00 0.12 20
lsophthalic acid, TMS ether 60.00 0.44 20
Methyl alcohol 0.088 0.002 20
From Allen'·. American Chemical Society
Serum vials, 10 cm3 Neutraglass with Teflon-lined caps are sealed with a larger
crimping tool. The latter vials contain a maximum of 14 cm3 •
Hamilton syringes, 1 and 10 ul.
A dry box flushed with dry nitrogen from a liquid air supply.
Gas chromatograph used with a computer for peak integration.
263
Gas chromatograph conditions:
A 4 m 6.4 mm o.d. 2 mm Ld. glass column packed with 1% OV-l on high
performance Chromosorb W. The column temperature set to ambient, (actual
temperature is close to SO°C because of heat from the manifold and injection block).
Hydrogen flame detector, lSO°C, injection port 100°C and manifold 100°C.
Helium flow, 33 cm3/min.
Attenuation 103 X 2, and the chart speed S min/inch.
44.3 REAGENTS
Tri-Sil silyation reagent mixture of hexamethyldisilazane and trimethyl-

chlorosilane (Pierce Chemical Co., P.O. Box 117, Rockford, III. 6110S).
Pyridine dried with Linde SA molecular sieve.
Carbon tetrachloride, dried with Linde SA molecular sieve.
Molecular sieves.
44.4 METHOD
The water in the sample is reacted with a mixture of hexamethyldisilazane and

trimethylchlorosilane to form hexamethyldisiloxane
7.3
The hexamethyldisiloxane equivalent to the water content of the sample is

separated from other silanized active hydrogen constituents and determined by gas
chromatography.
Weigh O.S - 1.0 g of polymer in ground or pellet form into a dry 2 cm 3 vial and
add 1 cm3 silylation reagent, 1 cm 3 dry carbon tetrachloride internal standard and 10 cm 3
dry pyridine by syringe then crimp the cap. Pick up of water may be avoided by filling
the vial in a dry box. Place the samples in the oven at lOSoC for 40 min. After cooling to
ambient temperature, inject 1 ul samples into the gas chromatograph. The peak area
ratios between sample and standard are converted to micrograms of water by means of
the calibration curve.
44.5.1 Calibration.
Fill a large dry serum vial with 4 ml Tri-SiJ, 1 cm 3 carbon tetrachloride, as

internal standard and 10 cm 3 dried pyridine. Seal immediately with a Teflon lined cap
using a crimping tool. Transfer 1 cm 3 of this reagent to a 2 cm 3 auto-injector vial by
means of a syringe. From this smaller vial, inject 1 ul amounts into the gas
chromatograph. Having established a stable blank value, inject 200 ul increments of
water into the vial and after each increment has reacted for a few minutes, inject into the
gas chromatograph. The ratio of the areas of the hexamethyldisiloxane peaks to the
carbon tetrachloride peaks is plotted vs. the ug water/ cm 3. A calibration curve is thus
constructed which is linear and intersects the ordinate at the reagent blank ratio value. It
264
is recommended that the analyses is carried out after standardization without delay, in
order to avoid a blank value due to adsorbed water on the column.
This procedure is capable of determining down to 50 ppm of water in polyesters

with a relative standard deviation of 13% at the 200 ppm water level.
METHOD 45 - DETERMINATION OF ACRYLIC ACID MONOMER IN

POLYACRYLATES. HIGH PERFORMANCE LIQUID
CHROMATOGRAPHy.2o
45.1 SUMMARY
This high performance liquid chromatographic procedure determines acrylic acid

monomer in polyacrylate resins in amounts down to 0.005%.
45.2 APPARATUS·
Liquid chromatograph fitted with a Whatman PXS 10/25 urn PAC column (250 x
4 mm i.d.) a variable wavelength spectrophotometer and a recorder.
A Rheodyne, model 7105 (Perkins Elmer) injection valve with a 175 ul sample
loop is used to inject the sample on to the analytical column.
Syringe, 100 ul.
Ultrasonic bath, to deairate the solvents used as the eluents.
Orbital shaker.
45.3 REAGENTS
All standards and solvents are of Analar or Nanograde quality unless otherwise
stated.
Solvents. - Isopropanol, hexane and methanol (HPLC grade).
Concentrated orthophosphoric acid, sp. gr. 1.75.
Eluent, 0.01% vlv orthophosphoric acid in distilled water.
Acrylic acid, 99% pure. 0.25% aqueous.
Anhydrous sodium sulphate heated at 600°C for 24 h, dried and stored in a grease-
free desiccator.
Distilled water. Clean up by passing through a Whatman SAX (strong anion
exchange) column stored in glass under nitrogen.
Glassware. - All glassware is soaked in a chromic acid bath, washed in distilled
water and oven dried at 110°C.
265
45.4 METHOD
A methanol extract of the polymer is injected into a high performance liquid

chromatograph and the acrylic acid peak evaluated. The method is calibrated against
standard methanolic solutions of acrylic acid.
Add a known mass of polymer (500 mg) to a methanol distilled water mixture (1
+ 1, 50 cm 3) and allow to stand overnight.
Inject an aliquot (12 ul) of the sample into the liquid chromatographs Rheodyne
valve and chromatograph under the following conditions: column Whatman PXS 10/25
um PAC (250 x 4 mm i.d.); mobile phase, 0.01% v/v orthophosphoric acid in distilled
water; flow rate, 4 cm 3 min"; pressure, 2000 lb in,2; detector wavelength 195 nm; chart
speed, 0.5 cm min"; and absorbance scale 0.02.
45.5.1 Calibration.
Treat standard solutions of acrylic acid (0, 0.05, 0.117, 0.5, 1.17, 3.5, 4.0, 5.0, 7.0,
8.0, 10.0, 11.7 and 14.0 mg I") in the same manner as the samples described above. The
slope of the calibration graph of absorbance (peak height) versus concentration does not
chan~e by what was considered an appreciable amount for an eluent flow rate of 4 cm 3
min' over the period studied.
Calculations. The concentration of acrylic acid in a sample calculated from the

absorbance ofa 100 uI injection on an absorbance scale of 0.01 a.u.f.s., ie:
mean absorbance of concentrate x 100 x absorbance scale

Total absorbance = volume of concentrate injected 0.01
The concentration of acrylic acid is found by comparison with a previously

prepared calibration graph of total absorbance versus original acrylic acid concentration.
The method is capable of determining down to 50 ppm acrylic acid monomer in

polyacrylates with an accuracy of ± 5%.
METHOD 46· DETERMINATION OF HYDROXYL GROUPS IN

POLY(ETHYLENE GLYCOL). SILATION - SPECTROPHOTOMETRY.Zl
46.1 SUMMARY
This silation spectrophotometric method is capable of determining down to 0.1 %

of hydroxy groups in a molecular weight 3000 poly(ethylene glycol).
266
46.2 APPARATUS
Gas chromatograph equipped with flame ionization detectors?1 The carrier gas
was helium.
Spectrographs: IR spectrometer, UV .spectrophotometer.
46.3 REAGENTS
Pentane, spectroscopic grade.

Petroleum ether, 40:60.
Ethanol, spectroscopic grade.
l-napthyl dimethyl (dimethylamino) silane (preparation). A 10010 solution of 1
equiv monochlorosilane (napthyl dimethyl chlorosilane) in hexane (in benzene if
necessary for solubility reasons) is stirred in a flask equipped with a reflux condenser
cooled at - 20°C. From a communicating flask 2.2 equiv of dimethylamine vapor is
slowly introduced over the solution and the mixture kept at room temperature overnight.
After filtration and evaporation of the solvent, the residue is distilled.
7.4
Purification of the poly(ethylene glycols) (Hydroxyl terminated) H-PEG.

A solution of 100 g of commercial practical grade polymer in 400 ml of 0.01 M
sodium hydroxide is digested at 40°C for 24 h, then passed through two ion-exchange
columns, the first containing 50 cm 3 of Amberlite IR 120 (H+ form) and the second 50
cm 3 of Lewatite MP 7080 (base form). After evaporation of the water, the residue is
dissolved in 1 cm 3 of toluene and filtered on an aluminium oxide column (50 g). The
agitated solution is then thermostated at the temperature indicated below and 5.0 cm 3 of
of petroleum ether added dropwise. The slurry is cooled to oOe, allowed to stand for 15
min and the precipitate filtered. The temperature of precipitation is critical; it was oOe
for H-PEG of molecular weight 600 (H-PEG-600), 100 e for H-PEG-IOOO), 200 e for H-
PEG-2000 and 300 e for polymers of higher molecular weight. The purified product is
dried at room temperature and 0.1 Torr pressure.
46.4 METHOD
A 1,2 dimethoxyethane solution of the polyglycol is silylated with napthyl

dimethyl dimethylamino-silane. After some working up the extract is dissolved in
ethanol and the chromophore concentration evaluated spectrophotometrically. The
method is calibrated against polyglycols of known equivalent weight.
267
Determination of the hydroxyl content of poly(ethylene glycols). For polymers

with expected equivalent weights higher than 1000 a sample of I g (0.5 g for lower
equivalent weights) is dissolved in 5 cm 3 of dry 1,2-dimethyoxyethane. The dissolution
is omitted if the melting point of the polymer is less than 60"C. The flask is purged with
dry argon (or nitrogen) and three equivalents for each expected equivalent hydroxyl (but
not less than 200 mg) of l-napthyl dimethylaminosilane is added. The homogenized
mixture is kept at 60·C for 30 min. The sample is then diluted at room temperature to 10
cm 3 with 1,2-dimethyloxyethane. After cooling it to an appropriate temperature, the
silyated polymer is precipitated by adding dropwise 50 cm 3 of low boiling petroleum
ether to the stirred solution (the temperature of the precipitation is critical: see under
section" Purification ofH-PEG''). After precipitation, the mixture is stirred at O·C for 15
min, then filtered on a sintered glass filter (03) and washed with 5 em3 portions of
petroleum ether. The precipitate is redissolved on the filter in 5 cm3 of warm 1,2-
dimethyloxyethane and precipitated a second time as above. If the expected hydroxyl
content of the polymer is lower than 10'· mol kg'·, the precipitation should be repeated a
third time. After the last precipitation the polymer is washed on the filter with 20 cm3 of
spectroscopic grade pentane, dried for 5 h at room temperature/OJ Torr or in a stream of
dry nitrogen. A portion of the dry sample is dissolved in spectroscopic grade ethanol so
as to yield an absorbance of 0.2 - 0.8. The absorbance of the solution is measured vs.
ethanol as reference at 282.5 nm. If the sample concentration is higher than 10 g dm·· (=
c) an ethanolic solution of the pure poly(ethylene glycol) of about the same concentration
must be used as a reference.
The molarity of the silyl groups in the solution M... is given by:
Mso.=Na = clEWPSii mol L· I
where A is the absorbance of the solution, c is the concentration of the silylated

polymer in dm3 ', a is the molar absorptivity of the silylating agent and EWPSilis the
equivalent weight of the silylated polymer which can be calculated by:
EWPSiI = Ca g morl
A
In order to obtain the equivalent weight of the hydroxy terminated polymer,
EWPOH the molecular weight of the silyl group MWSil and that of the substituted proton
must be taken into account
EWPOH=Ca -(MWsiI-l) gmol·1

A
The molarity of the hydroxyl groups in I kg of original polymer, 1lloH is then

given by:
1lloH = 1000lEWPOH = 1000 AI.(Ca- A (MWsiI - 1» mol kg·1
268
For the I-naphthyldimethylsilyl substituent, MWSil = 185
The values of the molar absorptivities are given in Table 7.18. 1-

naphthyldimethyl(dimethylamino) silane quantitatively silated primary and secondary
groups at 60°C but little of tertiary hydroxyl groups.
The above procedure with l-naphthyldimethyl(dimethylamino)silane was applied
to four polymers, two of them hydroxyl terminated, the other two with methoxy end
groups of unknown, but very low, hydroxyl content. Two nominal molecular weights
were chosen for both types of polymers, 600 and 20,000 representing extreme types
regarding the difficulties involved in the purification of the silylated polymers by
precipitation and filtration. For this operation, the best pair of solvents proved to be 1,2-
dimethyloxyethane and low boiling petroleum ether. The samples were redissolved and
precipitated repeatedly and each time a portion of the precipitate was subjected to
photometric analysis. Apparent hydroxyl contents expressed as a function of the number
of precipitations showed that in the case of the hydroxyl terminated polymers a constant
silyl concentration is attained after the first precipitation. Three precipitations were
necessary however, for the methylated polymers in order to obtain consistent results.
This method is capable of determining down to 0.01% of hydroxy groups in a

3000 molecular weight poly(ethylene glycol), (or I % of hydroxy groups in a 30,000
molecular weight poly(ethylene glycol» with a precision of ± 45%.
METHOD 47 - DETERMINATION OF AMINE ANTIOXIDANTS AND

ANTIDEGRADANTS IN RUBBER. GEL PERMEATION,
CHROMATOGRAPHY.12
47.1 SUMMARY
This gel permeation chromatographic method determines a range of amine

antioxidants and antidegredants in rubbers in amounts down to 0.02%.
47.2 APPARATUS
Chromatographic system comprising a series of six stainless steel columns (1200

x 8 mm) connected to a flow refractometer (R 40z Waters Ass., Framingham, Mass.,
U.S.A.) or equivalent and to a 254 flow ultraviolet analyzer. The data provided by both
detectors and the photocell which was used for checking the volume of the elution agent
were recorded. The measurements were carried out at 30°C, the flow rates of the elution
agent through the columns were 35 - 40 cm3/h and the pressure in the columns was about
5 atm. The columns were packed with Copolymer ST-DVS, No. IX polystyrene gel
(United Chemical and Metallurgical Works, Usti., Czechoslovakia), 0.040 - 0.056 mesh.
47.3 REAGENTS
Tetrahydrofuran, distilled prior to use, was used as the elution agent.
269
Table 7.18· Physical Data ofR', R" and R'" (2' methoxyethoxy) Silanes
- bp("C)fforr mp("C) d20gcm·3 20., Molar Absorbtivity

R',R",R'"
mol·l(nrn)
I-napthyl-
dimethyl 111°'0.03 1.051 1.5582 7.33 x JOl
at 282.5 nrn
The samples were injected as 2 - 5% solutions in tetrahydrofuran in amounts of

about 0.5 ± 0.1 cm3 into the columns. The elution volumes, V, characteristic of each
compound in the given system and corresponding to the size of the molecules of the
given compound in solution, were determined.
Since the gel permeation method does not allow a direct determination of the
molecular weights or molar volumes of the samples under investigation, calibrations are
made by using standard compounds in the form of a graphic dependence of their molar
volume on the elution volume.23•26 Normal hydrocarbons (pentane, hexane, heptane,
dodecane, hexadecane, octadecane) and aliphatic esters (octyl adipate and octyl sebacate)
are used as standards. The' molar volumes (mVmole) were plotted against elution
volumes, V (ml) in the calibration curves, as shown in Table 7.19. The molar volumes
were calculated from the atomic volumes and structural coefficients.24
47.S TYPICAL RESULTS
The results of the gel permeation chromatography measurements by Protivova and

Pospisil22 of the elution volumes of aromatic amines, their molecular weights, calculated
molar volumes and the effective molar volumes observed and read from the calibration
curves are given in Table 7.20. A comparison of the calculated and effective molar
volumes revealed deviations in the behaviour of all the amines they investigated,
compared to similar aliphatic hydrocarbons.
This method is capable of determining down to 0.02% of amine antioxidants and

antidegradants in rubbers with an accuracy of ± 5%.
METHOD 48 • DETERMINATION OF WATER IN CELLULOSE· KARL

FISCHER TITRATION.
48.1 SUMMARY
This titration method is capable of determining down to 0.2% water in cellulose.
270
Table 7.19 - The Behaviour of Standard Compounds in Gel Permeation Chromatography
Molar Volumes Calculated
Compound Molecular Molar Volume V.

weight (ml/mole) (ml)
n-Pentane 72.15 118.4 246

n-Hexane 86.18 140.6 239
n-Heptane 100.20 162.8 233
n-Dodecane 170.33 273.8 220
n-Hexadecane 226.43 362.6 212
n-Octadecane 254.48 414.4 206
Octyl adipate 270.14 495.4 20
Octyl sebacate 326.24 613.8 192
From Protovova and Posposae2. Elsevier Science Publishers, Netherlands
Table 7.20 - The Behaviour of Amine Antioxidants, Antiozonants and Model

Compounds in Gel Permeation Chromatography
Chemical Structure Molecular V. Molar Effective Deviation
Weight (ml) Volume
(ml/mole)
Calculated
Aniline 93.12 238 110.2 150.3 + 40.1

4-methylaniline 107.15 238 132.4 130.3 + 17.9
2,3-Dimethylaniline 121.18 247 154.6 115.6 39.0
2,4,6-Trimethylaniline 135.2 232 168.8 183.2 + 14.4
2,3,5,6-Tetramethylaniline 149.24 247 199.0 115.6 83.4
N.Methylaniline 107.15 253 133.9 95.9 38.0
N,N-Dimethylaniline 121.18 278 156.1 44.2 - 111.9
I-Naphthylamine 143.18 242 161.8 134.9 26.9
2-Naphthylamine 143.18 241 161.8 139.0 22.8
Diphenylamine 169.22 229 200.3 201.0 + 0.7
Phenyl-2-naphthylminea 219.27 235 251.9 166.7 85.2
o-Phenylenediamine 108.14 238 124.4 150.3 + 25.9
m-Phenylenediamine 108.14 220 124.4 266.1 + 141.7
p-Phenylenediamine 108.14 248 121.4 111.4 10.0
4-Aminodiphenylamine 184.23 221 214.5 257'.6 + 43.1
4,4' -Bis-(dimethylamino)
diphenylamine 255.41 228 320.5 212.3 - 108.2
Benzidine 184.23 217 213.0 291.7 + 78.7
o-Tolidine 212.28 224 257.4 234.4 23.0
N,N' -Dimethy1-p-phenylene-
diamine 136.22 247 171.8 115.6 56.2
N,N' -Diethyl-p-phenylene-
diamine 164.14 222 216.2 249.5 + 33.3
N.N'-Di-sec-butyl-p-
phenylenediamineb 220.38 236 305.0 162.2 - 142.8
N,N'-Di-iso-hepyl-p-
phenylenediamine" 305.4 202 438.2 462.4 + 24.2
N,N'-Di-iso-octyl-p-
penylenediamined 332.58 200 482.6 495.5 + 12.9
N,N,N'-Trimethyl-p-
phenylenediamine 150.28 252 186.0 98.9 87.1
N,N'-Dimethyl-2-methyl-p
phenylenediamine 150.28 250 186.0 105.2 80.8
271
N,N'-Diphenyl-p
phenylenediamine· 260.36 208 304.6 384.5 + 79.9
N,N'-DinaphthyljP
phenylendiamine 360.46 205 415.2 421.7 + 6.5
N-iso-Propyl-N'-phenyl-
p-phenylenediamineB 226.34 222 282.6 249.5 33.1
N-iso-Butyl-N'-phenyl-p-
phenylenediamineh 240.36 214 304.8 319.9 + 15.1
N-Cyclohexyl-N'-phenyl-p-
phenylenediamine' 266.41 206 326.8 410.2 + 83.4
N-octyl-N' -phenyl-p-
phenylenediaminek 296.47 206 393.6 410.2 + 16.6
N,N'-Bis-4-(beta,N-dimethyl-
amino)-phenyl-p-phenylene-
diamine 346.55 218 424.8 283.1 - 141.7
• Agent Rite Powder (Anchor Chemical Company Ltd., Manchester, Great Britain)
b Topanol M (ICI, Macclesfield, Great Britain)
o Santoflex 77 (Monsanto, SI. Louis, Mo., USA)
d UOP 88, UOP 288 (UOP Chemical Company, East Rutherford, N.J., USA)
• DPPD (Monsanto), Altofane DIP (Etablissements Kuhlmann, Paris, France) JZF
f Santowhite CI (Monsanto), Antioxidant 123 (Anchor), DNPD (Chemical works of J. Dimitrov,
Bratislava, Czechoslovakia), ASM DNP (Bayer, Leverkusen, Germany)
8 ASM 4010 NA (Bayer), Nonox ZA (Arnold, Hoffman & Co., Providence, R.I., USA)
h Santoflex 13 (Monsanto)
I Flexone 6-H (U.S. Rubber Co., Naugatuck Division)
k UOP 688 (UOP)
From Protivova and Posposil 22 • Elsevier Science Publishers, Netherlands
48.2 APPARATUS
Burette assembly. An all glass enclosed buret system. The connection glass
tubes fitted with spherical joints afford flexibility and ease of assembly. Teflon
stopcocks are used in the buret and connecting lines.
Protect all vents against atmospheric moisture by adequate drying tubes, the use if
"Indicating Drierite" is recommended. Lubricate all joints with "High Vacuum Silicone
Grease" (Dow-Coming Corp., Midland, Michigan).
Glass stoppered flasks, 250 cm3•
48.3 REAGENTS
Fischer reagent. Dissolve 133 g cp iodine in 425 cm3 of cp pyridine in a dry,

glass stoppered bottle, add 425 cm3 of anhydrous methyl cellosolve (see note 2) and cool
in an ice water bath, add with constant swirling, 70 cm3 of anhydrous liquid sulfur
dioxide. The water equivalent to this reagent is approximately 6 mg of water per ml of
reagent. Standardize the reagent as follows: introduce 10 cm3 of anhydrous methanol
into a volumetric flask and titrate with Fischer reagent until the straw-yellow colour
changes to an orange-red which remains after vigorous swirling of the stoppered flask,
view the colour by transmitted light.
To calibrate, weigh from a Lunge weighing bottle between 0.15 and 0.18 g of
water. Mix and titrate with Fischer reagent to the original orange-red end point colour.
272
Calculate the equivalency factor. F. as milligrams of water equivalent to 1 cm3 of the
Fischer reagent.
~.4 EXPE~NTALPROCEDURE
Introduce 25 cm3 anhydrous methanol into each of two 250 cm3 glass-stoppered
volumetric flasks and titrate with Fischer reagent to the end-point colour. Retain one
flask and. to the other flask, add a weighed quantity of sample containing between 0.1
and 0.2 g of water. Small particle size is necessary when the sample is insoluble in
methanol. Allow the reaction mixture to stand 1 hour and titrate to the end-point colour
of the standard. An end-point stable for fifteen minutes usually indicates complete
extraction. (notes I and 2).
48.5 METHOD
In this Karl Fischer titration procedure a methanol extract of the sample is titrated
with standardized Karl Fischer reagent to a visual end-point.
Calculation. From the standardization. calculate the equivalency factor. F. in
milligrams of water equivalent to 1 ml of Fischer reagent, by means of the following
equation:
F= <WJ (1000)
- V.
where
W. = weight of water grams. used for the standardization if Fischer reagent.
V. = volume of Fischer reagent, millilitres. consumed in the standardization.
Calculate the water content of the sample as follows:
Water. %0 = (S - B)(Fl
(W)(10)
where
S = volume of Fischer reagent, millilitres, required by samples.
B = volume of Fischer reagent, millilitres. required by blank determination (if
necessary)
F = equivalency factor for Fischer reagent.
W = weight of sample. grams.
Note 1. View the colour by transmitted daylight or by transmitted light.

Note 2. If the water content of methyl Cellosolve or ethylene glycol is
appreciably greater than 0.1 % they may be dried by distilling off about 5% and using the
remaining 95%. .
Note 3. The analysis should be completed within four hours. since longer
standing encourages side reactions. Other inert suspending media besides methanol are
sometimes useful. Ethylene glycol. for example. exerts a greater solvent action upon
some salts.
273
48.6 DISCUSSION OFRESULTS
This method is intended for the determination of water in substances that are inert
to Fischer reagent and from which all the water can be released. It may be applied, by
proper choice of technique, to a wide variety of polymers. The method is not applicable
in the presence of hydrogen sulfide, mercaptans or appreciable amounts of
hydroperoxides and it is not applicable to any compound or mixture which partially reacts
under the conditions of the test, to produce water.
METHOD 49 - DETERMINATION OF AMINO GROUPS IN AROMATIC

POLYAMIDES, POLYIMIDES AND POLY(AMIDES-IMIDES). POTASSIUM
HYDROXIDE FUSION-GAS CHROMATOGRAPHy.27
49.1 SUMMARY
This aIkali fusion gas chromatographic method determines down to 0.02% of

amino groups in aromatic polyamides, polyimides and poly(amides-imides).
49.2 APPARATUS
The total analysis (reaction, trapping, separation and quantitation) is performed in

a single piece of apparatus, Figure 7.11. The reaction portion consists of a pyrolysis tube,
combustion furnace assembly and a mounting frame taken from a commercial unit
(Perkin Elmer Pyrolysis Accessory 154-0825, Norwalk, Conn. 06856). Samples,
standards and reagent are contained in miniature platinum boats (10 mm x 4 mm x 4 mm,
Fisher Scientific Co., Pittsburgh, Pa. 15219) and are magnetically manipulated within the
confines of the glass tubing with metal cylinders and a hoe-shaped retriever. The
combusion furnace assembly monitors and controls the temperature within the reaction
zone.
A loop-shaped piece of 316 grade stainless steel tubing (0.125 inch o.d. 0.093
inch i.d.) connected between the outlet of the reaction furnace and a special low dead
volume GC injector assembly (H) (Perkin Elmer Part No. 009-1276) serves as a trap for
efficiently concentrating most volatile reaction products. All of the transfer tubing from
the reaction zone to the injection port, except the lower section of the loop, is heated to
300°C by a clam-shell type combustion furnace clamped around the tubing. The exposed
piece of tubing, which is loosely packed with quartz wool, is cooled in a liquid nitrogen-
filled Dewar flask when concentrating the evolved products and heated with a 400°C
nichrome wire heater when "injecting" the products into the gas chromatograph. Helium
carrier gas flows (60,Vmin) through the reaction unit and cold trap before entering the
chromatographic column.
49.3 REAGENTS
Fusion reagent. The alkali fusion is a prefused mixture of potassium hydroxide

(J.T. Baker, Analytical reagent grade) and 0.5% sodium acetate.
Typically. the mixture melts around 110°C and contains 13-14% water. When
preparing this reagent, it is important to avoid excessive heating. If too much water is
274
lost, the molten reaction mass may solidify before the hydrolysis reaction is complete.
On the other hand, too much water will make the reagent sticky and difficult to handle.
Additionally, it is possible to plug the cold trap iflarge amounts of water are released. To
prevent adsorption of moisture from the atmosphere, the powdered reagent is stored in a
small desiccator within a nitrogen-filled glove bag.
49.4 METHOD
Samples are hydrolyzed with a molten potassium hydroxide reagent at elevated

temperatures in a flowing inert atmosphere. Volatile reaction products are concentrated
in a cold trap before separation by gas chromatography. The identity of amine and/or
diamine products aids in the characterization of the monomer or polymer; the amount of
each compound generated is used as the basis for quantitative analysis. The average per
cent relative standard deviation of the method is ± 1.0%.
One to five milligrams (± I ug) of powdered sample or standard is weighed into

the tared platinum micro-boats. The boats are then filled with the powdered caustic
reagent in the nitrogen-purged glove bag and quickly loaded into the storage arm of the
reaction tube with a metal cylinder behind each. When making quantitative analysis, the
first sample reacted in a series of runs is used to condition the apparatus. Boats are
usually loaded at the end of a work day, thus permitting entrapped air to be purged from
the system overnight. When samples are loaded in the morning, the tube is purged for 1
hour before turning on the thermal conductivity detector current.
Once a stable baseline is obtained, the liquid nitrogen-filled Dewar flask (-196°C)
is positioned around the unheated section of the trap. The first metal cylinder is
magnetically move forward, pushing the boat in front of it into the heated reaction zone.
The cylinder is removed to storage area. The optimum reaction temperature profile for a
fusion reaction will depend on the reactivity of the samples. The furnace temperature
was programmed from 100 to 300°C over a period of 10 min. As the reaction occurs, the
volatile reaction products and water, liberated from the molten mixture, are carried by the
flowing helium carrier gas and concentrated in the trap. At the end of the reaction period,
ie. 10 minutes, the boat is withdrawn from the furnace with the magnetic retriever and
deposited with its cylinder. After adjusting the furnace control to its initial temperature
setting, the trapped compounds are revolatilized and directed into the gas chromatograph
by replacing the Dewar flask with the heater (400°C). When the separtion and integration
are completed and the initial conditions re-established, the procedure is repeated for each
sample and standard. Matched 6 foot by 114 inch o.d. stainless steel columns packed with
60/80 mesh Chromosorb 103 (Johns-Manville) were used to separate the amine reaction
products. Diamines were chromatographed on 4 foot by 118 inch o.d. stainless steel
columns packed with 10% FF AP on 60/70 mesh Anakrom AB.
Calibration curves were prepared daily for each compound determined.
Anhydrous ammonia was injected with a calibrated 1000 ul gas tight syringe through the
septum inlet of the reaction tube. Ambient temperature and pressure corrections were
made to determine the actual amount of gas injected. Benzylamine was generated from
reaction of the hydrochloride salt with potassium hydroxide. The diamine standards were
weighed into boats, covered with caustic reagent and volatilized by moving the boat into
the heated furnace. In each case, the standard compounds were trapped and
275
oII o
II 7.5
C COK
©X >- RK;©(
C ~ C - OK
+ RNH2
u
o I'
o
B G
Figure 7.11. Diagram of the reaction and trapping unit used for alkali fusion reaction GC. The mounting
rack and electrical control units are shown. A, storage area for unreacted samples: B, storage area of
reacted samples: C, quartz reaction zone: D, carrier gas inlet: E, side with rubber septum: F, variable
temperature furnace: G, trap loop: H, injector assembly into gas chromatograph: I, combustion furnace
surround transfer tubing: J, metal cylinder behind platinum sample boat: K, magnetic retriever.
From Frankoski and Siggia with permission.27 American Chemical Society.
chromatographed in the same manner as the volatile reaction products. The best straight
line calibration curves were determined by a least-square regression curve fitting
computer programme.
Table 7.21 lists the results obtained from the analysis of mixtures of polymers.
The amount of m-phenylenediamine produced was, in all cases within 1.2% relative of
the theoretical value. .
276
Table 7.21 - Analysis of Polymer Mixtures by Alkali Fusion Reaction Gas
Chromatography
Polymer Micromoles of Recovery

Mixture m·phenylenediamine %
Taken" Found
PI·2 2.24 )
PAI·2 9.26 ) 11.50 11.36 98.8
PA·I 7.23 )
PA·2 7.43) 14.66 14.71 100.3
PAl· I 4.99)
PI·2 7.67) 12.66 12.58 99.4
PAl· I 5.28 )
PAI·2 7.09) 12.37 12.48 100.9
PA·I 5.51 )
PAI·2 5.81 ) 14.21 14.33 100.8
PI·2 2.89 )
PA·2 8.79 )
PAl· I 3.25 ) 14.80 14.98 101.2
PA·I 2.76)
" These values were calculated from the weight of polymer taken and were corrected for the weight of
adsorbed water (Table 7.22) and the average experimental recovery (Table 7.23).
From Frankoski and Siggia27• American Chemical Society
Table 7.22 summarizes the chemical structures and sample designations of the
polymers studied by Fronkoski and Siggia.27 The weight percent of adsorbed water and
the decomposition temperature, both determined by thermogravimetric analysis, are also
included. The water content was needed to calculate the dry weight of polymer in each
sample. It was not possible to simply dry and weigh the polymers because they tended to
readsorb moisture from the atmosphere too rapidly. Table 7.23 summarizes the diamine
recoveries obtained with isothermal (5 min at 380"C) or programmed (100 to 390·C over
30 min) reaction temperatures. These numbers represent the mole per cent of theoretical
diamine based on the dry weight of sample and the idealized linear polymer repeat units
depicted in Table 7.22. Recoveries were, in all cases, between 90 and 101% of theory.
The amount of diamine recovered from a polymer reacted isothermally, was within ± 3%
of the amount produced by the programmed temperature approach. Average percent
relative standard deviations were similar in both cases (± 0.9%, vs. 1.1%).
The reaction gas chromatograph obtained from poly(amide-imide) PAI-2 showed
only one diamine was produced whilst that from the fusion reaction of the polyimide
terpolymer PI-3, contains peaks for each diamine. The quantitative analysis of both
products revealed that the weight ratio of 2,4 toluenediamine to 4,4' .methylenedianiline
in the polymer was 2 to 1.
In an attempt to correlate the aIkali fusion recovepes (expressed as weight percent
nitrogen) with the elemental nitrogen analyses of the polymers, it was noted that the
elemental nitrogen analyses of the polymers were higher. Analysis of the fusion residue
indicated that no detectable amounts of nitrogen were present This led to the discovery
that ammonia was also produced from the samples. When the nitrogen contribution from
277
Table 7.22 - Structure, Water Content and Decomposition Temperatre of the Polymers
Studied
Designation Structure of Repeat Unit Wt"10 Decomposition

Water Temp., ·C
tr1JN-@-<-roJ-
PI-I 6.5 385
L~(Q). a J. .~-~
{~--©r:l
PI-2 2.2 410
-f~©:}-'t. 410
PI-3 3.4
... "©tCN, ... -@-CMr-@-

PI-4 0.6 310
U~C:'-@-~
4,4' ·Methylenedi"n1liDe
315
f-L©ri-NN-©i
PA-I 5.8
PA-2
t R N
_C~c- ... ~J
I ~ 9.7 330
1
rl§r{-©Jt
0
PAl-I 6.2 340
PA[-2
t-'-©}-©t 12.6 395
PAI-3 f-i-©:}-©r"~ o '

8.9 340
From Frankoski and Siggia27. American Chemical Society
ammonia was added to that of the diamine, the total was in good agreement with the
elemental value.
278
Table 7.23 - Analysis ofPolyimides, Polyamides and Poly(amide-imides) by Alkali
Fusion Reaction Gas Chromatography
Sample Diamine Produced Mol % of theoretical" ± RSD6
5 min at 380·C 30 min at lOO-390·C
PI-l 4,4' -Metbylenedianiline 98.3±0.8 97.5±0.9

PI-2 m-Phenylenediamine 89.1 ± 0.7
91.2 ± 0.9 91.0±0.8
91.6 ± 1.3 91.0 ± 0.7
PI-3 2,4-Toluenediamine 73.1 ±0.2 73.2± 1.0
97.8 ±0.5 99.1±1.2
4,4-Methylenedianiline 24.8±0.3 25.9±0.2
PA-I m-Phenylenediamine lOO.7±0.6 97.0 ± 1.7
97.7 ± 1.7
97.9 ± 1.0
99.6±2.6
PA-2 m-Phenylenediamine 95.9±0.6 92.9 ± 1.0
96.4 ± 1.5 93.3 ±0.6
PAI-l m-Phenylenediamine 93.5 ±0.9 93.1 ± 0.7
95.3 ±0.5
PAI-2 m-Phenylenediamine 93.5 ± l.l 97.4±0.9
94.1 ±0.6
95.1 ± 1.2
PAI-3 4,4'Methylenedianiline 98.0 ± l.l 98.8 ± l.l
From Frankoski and Siggia21 • American Chemical Society

" These recovery values are based on the structures shown in Table 7.22, which assume that one mole of
diamine is produced for each mole of repeat unit. b The relative standard deviation is based on five or more
determinations.
METHOD 50 - DETERMINATION OF ACRYLAMIDE MONOMER IN

POLYACRYLAMIDE. DIFFERENTIAL PULSE POLAROGRAPHY.28
50.1 SUMMARY
This differential pulse polarographic method enables down to 0.02% acrylamide

monomer to be determined in polyacrylamide.
50.2 APPARATUS
Differential pulse polarographic analyzer equipped with a PARC Droptimer.

X - Y recorder.
The polarographic cell assembly comprising cell base and cover with a dropping
mercury electrode as the cathode, a platinum wire auxiliary electrode as the anode and a
saturated calomel reference electrode making solution contact via a liquid junction
bridge. The mercury column is kept at a constant height, to have a natural drop time of
about 4 s. The instrumental conditions for the differential pulse technique were: 0.5 s
drop time, -10mV/S scan rate, 50 mV modulation amplitude.
279
50.3 REAGENTS
All reagents were reagent grade and were used without further purification unless
specified.
Tetra-n-butylammonium hydroxide and chloride solutions polarographic grade.
Resin: Analytical grade mixed bed resin, AG 501-X8, 20 - 50 mesh fully
regenerated (Bio-Rad Laboratories, Richmond, Calif.). Prepared by washing with
copious quantities of pure methanol for several hours, washing with the 80 - 20
methanoVwater solvent and then air-drying.
Methanol, distilled-in-glass.
Acrylamide.
50.4 METHOD
The polyacrylamide sample is extracted with aqueous methanol and tetra n-butyl
ammonium hydroxide added as base electrolyte. This solution is polarographed and the
peak height at -2V of the polyacrylamide peak evaluated using a platinum wire anode
electrode and a saturated calomel reference electrode. The method is calibrated against
standard aqueous methanolic solutions of acrylamide.
Add 1 to 109 of the polymer to 50 cm3 of an 80/20 volume: volume methanol

Iwater solution in a glass bottle. A magnetic stirring bar coated with Teflon resin is
added, the solution stirred and the acrylamide monomer allowed to extract for at least 3 h,
preferably overnight.
After an appropriate length of time, 25 em3 of the methanolic extraction solution
are removed and added to a bottle containing 5 g of mixed resin and a magnetic stirring
bar coated with Teflon resin and stirred for 20 min. This mixed resin treatment removes
interfering cationic and anionic species. However, impurities extracted from the resin do
increase the polarographic residual current and, therefore, it is necessary that a blank be
run using the same resin treatment time (viz about 20 min).
After 20 min, 10 cm3 of the resin treated analyte are added to the polarographic
cell, 0.5 cm3 of 1 M tetra-n-butylammonium hydroxide in water is also added as a
supporting electrolyte.
The dropping mercury electrode, a platinum wire auxiliary electrode and a
saturated calomel reference electrode assembly are inserted into the cell. Solution
contact, from the methanolic solution to the saturated calomel reference electrode, is
made via a salt bridge containing 0.1 M tetra-n-butylammonium chloride in water. The
cell solution is deaerated for 5 min by purging with pre-purified nitrogen which has been
passed through a scrubbing tower containing an 80;20 methanoVwater (v/v) solution.
After deaeration, a differential pulse polarogram is obtained on the solution, the solution
is spiked with an appropriate amount of an acrylamide standard (such that the total
solution concentration does not exceed ca, 100 ppm acrylamide), deaerated and a second
differential pulse polarogram obtained.
280
SO.6 TYPICAL RESULTS
The differential pulse polarogram of a 10 ug/ml methanolic solution of acrylamide

showed a well-defined and well-resolved peak. The differential pulse polarographic
acrylamide reduction current is directly proportional to concentration as shown in Table
7.24. The polarographic detection limit for acrylamide is less than 1 pg acrylamidelcm3•
The reduction of the acrylamide monomer occurs at ca - 2.0 V vs SCE. In this
region of the polarogram, reduction of alkali cations occurs. The mixed resin treatment is
used to remove polarographically interfering ionic species, such as sodium and potassium
cations, which are major interferences.
Acrylo-type compounds, such as acrylic acid, acrylonitrile and acrolein can be

present in polyacrylamides. Their unsaturated characteristics could cause them to
interfere with the acrylamide analysis. Acrylic acid is electroreducible, but its anionic
form, acrylate is not. A polarogram of acrylic acid and acrylamide in an 80:20 (v/v)
methanoVwater solution with tetra-n-butylammonium chloride as the supporting
electrolyte showed that the reduction of the associated acid occurs at ca. - 1.7 V vs SCE,
0.3 V more positive than the acrylamide reduction. The reduction peak of acrylic acid is
easily resolved from acrylamide. Esters of acrylic acid are electroreducible and some,
such as the alkyl esters (eg. ethyl acrylate) reduce in the same potential region as
acrylamide and do constitute an interference. Acrylonitrile is also electroreducible at the
same potential as acrylamide. However, the high volatility of acrylonitrile allows it to be
readily purged from the analyte solution. The detection limit of acrylamide monomer by
this technique is less than I ppm.
MEmOD 51- DETERMINATION OF ACRYLONITRILE AND

MEmACRYLONITRILE MONOMERS IN POLYACRYLAMIDE. HIGH
PERFORMANCE LIQUID CHROMATOGRAPHY.19
51.1 SUMMARY
This high performance liquid chromatographic method enables acrylonitrile and

methacrylonitrile to be determined in polyacrylamide in amounts down to 0.1 ppm.
51.2 APPARATUS
Liquid chromatograph with a variable wavelength detector, operated at 208 nm;

(Perkin Elmer LC-55 or equivalent instrument).
A mini pump (model 396-31 Milton Roy instrument or equivalent)
Injection valve with 20 ulloop (Rheodyne model 70-10 or equivalent),
Recorder, having I - 100 mV output.
Whatman Inc. Partisil-IO ODS-2 4.6 x 250 mm reverse phase column. The
analytical column was protected with a guard column 2.1 x 60 mm in size containing
pellicular reverse phase packing.
8 ul 6 mm path length flow through cell.
281
a 3000 psig pressure gauge was located between the pump and the injection valve.
51.3 REAGENTS
Water eluent. Laboratory deionized water was circulated through a Milliport

Corp. Milli-Q water system. It was then degassed by laboratory vacuum.
Acrylamide (Eastman Kodak electrophoresis grade).
Methanol (distilled in glass grade).
51.4 METHOD
Water soluble compounds such as acrylamide and methacrylamide have sufficient

lipophilic character such that they can be retained and separated on HPLC reverse-phase
columns using water as the eluent. By employing a low-wavelength ultraviolet detector,
these compounds can be measured with high sensitivity.
An aqueous methanol extract of the polyacrylamide sample was injected into the
high performance liquid chromatograph equipped with an ultraviolet detector and eluted
with methanol-methylene chloride 15:85 v/v. The acrylonitrile and methacrylonitrile
peaks were evaluated. The method was calibrated against standard aqueous methanol
solutions of the two monomers.
Five g of polyacrylamide are placed into a 4 ox bottle. Fifty cm3 of 80:20

methanoUwater (v/v) are added and the mixture placed on a mechanical shaker for 3 - 4 h.
Twenty ul of the clear phase are injected under the following chromatographic conditions
and the peak height recorded.
Liquid chromatographic conditions. The water eluent is pumped at 2 cm3/min
which gave a pressure of about 1600 psig. The variable wavelength ultraviolet detector is
set at 208 nm. Recorder response is generally at 0.04 aufs for acrylamide monomer in
polymer. Chart speed is 0.2 in/min and injection volume 20 ul.
The above extracts can also be examined by ion exclusion liquid chromatography
under the following conditions. 3o
Column Partial lOP AC (250 x 4.6 mm) (% octadecylloading = 5

acrylonitrile retention for 5 min.
Mobile phase 15% methanol, 85% v/v methylene chloride.
Flow rate I cm3/min
Pressure 500 psi
Detector 240mm
The acrylamide response is linear from 1 - 500 ppm monomer in solution using a
20 ul injection. This equates to 0.02 - 10 ug acrylamide injected. Area response obtained
from a computing integrator is also found to be linear.
282
Table 7.24 - Differential Pulse Polarographic Response to Acrylamide Monomer
Acrylamide Peak currentb Peak potential, V ipeak/concn,

concna, ppm A vs. SCE uA/ppm
o 0.00
1 0.35 -2.01 0.35
2 0.68 -2.01 0.34
3 1.07 -2.01 0.36
4 1.37 -2.02 0.34
5 1.67 -2.02 0.33
11 3.61 -2.02 0.33
15 5.51 -2.02 0.37
21 7.44 -2.02 0.35
31 11.3 -2.03 0.36
41 15.0 -2.03 0.37
51 19.2 -2.03 0.38
96 37.3 -2.04 0.39
• 9.5mlSO/20 methanoVwater + 0.5mll N tetra-n-butylammonium hydroxide. b Peak current is calculated

as current above baseline
From Betso and McLean28 . American Chemical Society
51.5.1 Calibration.
A 10 ppm acrylamide standard is prepared in 80:20 v/v methanol/water. 20 ul are

injected and the peak height recorded.
The retention times for acrylamide and related compounds are given in Table
7.25.
The sensitivity of acrylamide detection is about 0.1 ppm in solution based on a 20

ul injection. Relative precision of the 95% confidence level for acrylamide is ± 7.5%.
METHOD 52 - DETERMINATION OF TRACES OF 2,4- AND 2,6-

DIAMINOTOLUENES IN FLEXIBLE POLYURETHANE FOAMS. TmN-
LAYER CHROMATOGRAPHY-FLUORIMETRIC METHOD.31
52.1 SUMMARY
This fluorimetric method determines 2,4 and 2,6 diaminotoluene in amounts down
to 1 ppm in flexible polyurethane foams.
283
52.2 APPARATUS
Spectrophoto fluorimeter with a thin film chromatographic scanner and photo-

multiplier microphotometer (Amino Bouman or equivalent).
Strip chart recorder, 10 V output fsd.
52.3 REAGENTS
Methanol and acetone (reagent grade)

2,4 and 2,6 diaminotoluenes (Eastman and Aldrich).
Fluram reagent (American Instrument Company, 8030 Georgia Avenue, Silver
Spring, Md.) 20910.
2,4 and 2,6 diaminotoluene standards, 2-20 mg cm3 in methanol.
52.4 METHOD
A methanol extract of the polyurethane is applied to a thin-layer chromatography

plate and developed with a mixture of chloroform, ethylacetate, ethanol, glacial acetic
acid (120:33:20:7 v.v). Fluran spray reagent reveals the two diaminotoluene isomers.
The intensity of the spots are evaluated (500 nm excitation 340 nm emission) using a
spectrofluorimeter coupled to a thin film scanner and photomultiplier microphotometer.
The method is calibrated against standard solutions of the two diaminotoluene isomers.
Weigh I - 2 g of foam and cover with 75 cm3 of methanol and soak for 5 min with
occasional compression. Decant the methanol and squeeze the foam to express the
methanol. Repeat twice with fresh methanol, concentrate the combined extracts and
make up to 25 cm3 with methanol. On the TLC plate spot the standard solutions (20 uL)
at six positions 3 cm from the bottom of the plate, spot the foam extract at the seventh
position.
After the spots have dried, place the plate in a developing tank which contains 120
cm3 of chloroform, 33 cm3 of ethyl acetate, 20 ml of ethanol and 7 cm3 of glacial acetic
acid. Development takes I h and is complete when the developing solution reaches a line
15 cm above the bottom of the plate.
Dry the plate in a horizontal position for 5 - 10 min, then spray uniformly with a
0.015% solution of Fluram in acetone. The spots, which appear approximately 6 cm (2,4-
isomer) and 8 cm (2,6-isomer) above the bottom of the plate, can be located with an
ultraviolet light. The sides of the plate are marked to indicate the line through which the
plate is to be scanned.
Place the plate in the scanner and set the excitation wave-length at 500 nm to
produce a visible light spot. Adjust the plate position so that the visible spot is in
position to scan across the line of diaminotoluene spots. Close the cover of the scanner
and set the excitation and emission wavelengths at 390 and 500 nm respectively. Scan
the plate starting with the strongest standard spot to generate a calibration. The plate
must be read within 1 h after development because the Fluram adducts are unstable.
Peak heights are measured from the baseline and are plotted against concentration
in ug ml· l • The concentration of diaminotoluene in the extract is then calculated from the
284
Table 7.25 - HPLC Retention Times· for Acrylamide and Related Compounds
Compound Min.
Acrylic acid 1.4

B-hydroxypropanamide 2.1
Acetamide 3.0
Acrylamide 5.4
Propanamide 7.3
Acrylonitrile 11.8
Methacrylamide 18.0
Butanamide 20.8
Methacrylonitrile 46.0
• Partisil-I 0 ODS-2, water, 2.0mUmin, 208 nm, 0.04 aufs
From Skelly and Husse? American Chemical Society
known concentrations of the standard solutions. To express this value as parts per mil-
lion in the original foam, the following equation is used:
Diaminotoluene, ppm in foam =

(Diaminotoluene in extract. ug/mL) (mL extract)
foam weight, g
This method is capable of determining down to I ppm of 2,4 and 2,6

diaminotoluenes in polyurethanes with a precision of ± 30% at the 20 ppm level.
28S
CHAPTER 7.2
COPOLYMERS AND CONDENSATION PRODUCTS

Methods 53 - 64
METHOD 53 - DETERMINATION OF STYRENE MONOMER AND OTHER

VOLATILES IN CONVENTIONAL POLYSTYRENE AND STYRENE -
BUTADIENE COPOLYMERS. GAS CHROMATOGRAPHY.32
53.1 SUMMARY
This gas chromatographic method is capable of determining styrene monomer and

a wide range of aromatic volatiles in polystyrene and styrene-butadiene copolymers in
amounts down to 50 ppm.
53.2 APPARATUS
Gas chromatograph with a hydrogen flame ionization detector and an injection

port fitted with a glass liner, very loosely packed with glass fibre (Figure 7.5).
Column, copper tube (15 ft x 1.4 o.d. x 3.16 in i.d.) packed with 10 per cent w/v
Carbowax 15 - 20 M supported on 60 - 72 B.S. mesh Celite.
Gas pressures and flows.

Helium 30 Ibflin2 gauge, 100 cm3/min
Air 7 Ibf/in2 ¥auge, 650 cm3/min.
Hydrogen 121bflin gauge, 75 cm3/min.
Temperatures
Injection 1500
Detector 1500
Column 800
Flame 2000
Recorder, -0.2 to + 1.0 mV range, I sec response, 15 in (381 mm).hr chart speed.
53.3 REAGENTS
Celite, 60 - 72 BS mesh.
Carbowax 15 - 20 M.
Styrene.
Propylene oxide.
0, m- and p- xylenes.
286
Cumene.
n-propyl benzene.
iso-butyl benzene.
alpha-methyl styrene.
m and p diethylbenzenes
tert, sec- and n- butyl benzenes
o,m and p methyl styrene.
0, m and ethyl toluenes
n-undecane (internal standard).
53.4 MEmOD
The polymer sample and a known weight of n-undecane internal standard are
dissolved in propylene oxide and injected into the gas chromatograph. Calibration is
achieved against propylene oxide standard solutions of internal standard and the
substances to be determined.
53.5.1 Solution of Polymer.
Prepare the polymer solvent by weighing 0.1 cm3 n-undecane into a 100 cm3
volumetric flask and then diluting to 100 cm3 with propylene oxide. Weigh accurately
about 1 g polymer into a 25 cm3 stoppered measuring cylinder, add exactly 10 eml of the
prepared polymer solvent from a pipette, seal with a serum cap and shake until the
polymer has dissolved. Gel, pigment and filler may remain as an undissolved suspension
without detriment to the analysis. Chromatograph 5 ul of the solution at a range setting
of x 10 and suitable attenuation settings.
53.5.2 Calibration.
Weigh in tum into a 10 cm3 volumetric flask 1.0 cm3 n-undecane, 1.0 cm3 alpha-
methyl styrene, 1.0 cm3 styrene, 0.5 em3 ethyl benzene, 0.5 em3 eumene, 0.5 em3 of n-
propyl benzene, 0.25 cm3 m or p xylene, 0.25 cm3 o-xylene, 0.25 cm3 m or p-ethyl
toluene, 0.25 cml toluene and 0.1 cm3 benzene. Dilute to 10 cm3 with propylene oxide
and then further dilute 0.25 cm3 of the solution to 25 cml with propylene oxide.
Chromatograph 5 ul of the calibration blend at a range setting of x 10 and suitable
attenuation settings. This calibration procedure should be carried out daily.
53.5.3 Caleulation.
On the calibration and analysis chromatograms, measure the peak heights of the
n-undecane and the aromatic hydrocarbons allowing for any attenuation factors.
From the calibration chromatogram, determine the response factor for each
component as follows:
A = weight of component in calibration blend.

B = weight of n-undecane in calibration blend.
C = peak height of component on calibration chromatogram.
287
D = peak height of n-undecane on calibration chromatogram.
Component response factor, f= A. x Q

B C
From the analysis chromatogram, determine the concentration of each component
as follows:
F - component response factor.

G = peak height of component on analysis chromatogram.
H = peak height of n-undecane on analysis chromatogram.
J = per cent w/v n-undecane in polymer solvent.
K = weight (g) of polymer taken.
Component (per cent w/w) = 10 x G x F x J

H x K
Relative retention distances. Retention distances (injection point to peak centres)

are corrected for the gas hold-up of the columns and are expressed relative to styrene:
Benzene 0.17
Toluene 0.29
m-undecane 0.40
Ethyl benzene 0.47
m-xylene 0.50
p-xylene 0.50
Cumene 0.62
o-xylene 0.66
n-propyl benzene 0.77
p-ethyl toluene 0.84
m-ethyl toluene 0.84
iso-butyl benzene 0.92
tert-butyl benzene 0.92
sec-butyl benzene 1.00
Styrene 1.00
o-ethyl toluene 1.05
m-diethyl benzene 1.35
p-diethyl benzene 1.44
n-butyl benzene 1.44
alpha-methyl styrene 1.60
o-methyl styrene 1.86
m-methyl styrene 1.86
p-methyl styrene 1.86
288
Some results obtained by this method for different types of polystyrene and
copolymers are shown in Table 7.26
In this procedure down to 50 ppm of styrene monomer and other aromatic

volatiles can be determined in polystyrene and styrene-butadiene latices with an accuracy
of±5%.
METHOD 54 - DETERMINATION OF STEARIC ACID AND SODIUM

STEARATE IN STYRENE-BUTADIENE RUBBER SOLUTIONS.
TITRIMETRIC PROCEDURE.
54.1 SUMMARY
This titrimetric procedure is capable of determining down to 0.01 % of stearic acid

and sodium stearate in styrene-butadiene rubber solutions.
54.2 APPARATUS
Burettes, 2 cml, 5 mI., 10 ml.

Conical flasks, 500 cml .
Graduated cylinders, 100 cm3.
Pipettes, 25 cml .
54.3 REAGENTS
Toluene/absolute ethanol mixed solvent 5:1, five volumes of redistilled toluene

and one volume absolute ethanol mixed.
Ethanolic sodium hydroxide 0.1 M, standardize against potassium hydrogen
phthalate to the m-cresol purple end-point.
0.05 M hydrochloric acid/alcohol, standardized, dissolve 4.2 ml concentrated
hydrochloric acid in 1 cm3 absolute ethanol.
m-cresol purple, dissolve 0.3 g m-cresol purple in 95% ethanol and add 7.9 cml
0.1 M sodium hydroxide. Make up to 100 cm3• with 95% ethanol.
54.4 METHOD
A suitable amount (50 to 100 g) of sample is weighed into a flask and diluted with
toluene/absolute ethanol mixed solvent. The stearic acid is determined by titration with
0.1 M ethanolic sodium hydroxide solution to the m-cresol purple end-point. To
determine sodium stearate a separate 100 g quantity of diluted sample is titrated with 0.05
M ethanolic hydrochloric acid solution to the m-cresol purple end-point.
289
Table 7.26 - Analysis of Some Different Grades of Polystyrene
Weight Per Cent
Component
Self High Foodstuff
Crystal Expandable Extinguishing Impact Packaging
Grade Grade Grade Grade Grade
Benzene <0.001 <0.001 <0.001 <0.001 <0.001

Toluene 0.001 0.003 <0.001 <0.001 <0.001
Ethyl benzene 0.066 0.081 0.047 0.086 0.060
m/p-Xylene 0.002 0.002 0.063 <0.001 <0.001
Cumene 0.046 0.049 0.039 0.011 0.030
a-Xylene 0.007 0.008 0.006 0.002 <0.001
n-Propylbenzene 0.017 0.016 0.014 0.004 0.016
m/p-Ethyl toluenes 0.016 0.011 0.013 0.002 <0.001
Styrene 0.033 0.32 0.080 0.18 0.G4
From Crompton and Myers32
54.5.1 Determination of Stearic Acid.
Weigh out a suitable quantity of sample (50 g if 0.3%) to within ± 0.5 g into a 500
cm3 conical flask and add 35 cm3 toluene/absolute ethanol dilution solvent and 7 drops
m-cresol purple indicator. Titrate with 0.1 M ethanolic sodium hydroxide contained in a
10 cm3 burette from the yellow colour to the first permanent blue colour.
54.5.2 Determination of Sodium Stearate.
Weigh out a suitable quantity of sample (100 g if 0.02%) to within ± 0.5 g into a
500 cm3 conical flask and add 70 ml of 5.1 toluene: absolute ethanol dilution solvent and
15 drops of m-cresol purple indicator. Titrate with 0.05 M ethanolic hydrochloric acid
from the yellow colour to the first permanent pink colour.
54.5.3 Calculations.
Stearic acid in rubber solution,
= (TI- ToWl x 284

. 10 x WI
where
TI = Titration of 0.1 M alcoholic sodium hydroxide solution (sample) cm3•

TB = Titration of 0.1 M alcoholic sodium hydroxide solution (styrene monomer
blank) cm3•
fl = Molarity of alcoholic sodium hydroxide solution.
WI = Weight of sample taken, g.
290
Sodium stearate in rubber solution, %w,
T, X f, x 306
10 x W2
where
T2 = titration of 0.05 M alcoholic hydrochloric acid, cm3•

f2 = molarity of alcoholic hydrochloric acid, cm3•
W2 = weight of sample taken, g.
This method is capable of determining down to 0.01 % of stearic acid and sodium
stearate in styrene-butadiene latices with an. accuracy of ± 5%.
MEmOD 55· DETERMINATION OF STYRENE AND ACRYLONITRILE

MONOMERS IN STYRENE· ACRYLONITRILE COPOLYMERS. CATHODE·
RAY POLAROGRAPHY.»
55.1 SUMMARY
This polarographic method is capable of determining down to 20 ppm styrene and

2 ppm acrylonitrile monomers in styrene-acrylonitrile copolymers.
55.2 APPARATUS
Cathode ray polarograph. Complete with stand for dropping mercury electrode,
polarographic cells (10 m1) and thermostatted ~at 25°q waterbath.
Micrometer syringe delivering 0.01 cm with an accuracy of 0.0002 cm3•
Calibrated glassware· pipettes, 25 and 5 em3 capacities; 50 cm3 calibrated flasks.
55.3 REAGENTS
NN'dimethylformamide, if necessary, purify as follows, dry 1 litre N.N'dimethyl-

formamide by standing over 50 g of anhydrous potassium carbonate for 3 d. Distill the
product through an 80 cm Fenske column. Discard the first 200 cml of distillate and
collect in a dry flask the fraction boiling between 151.5° and 153°C.
Tetrabutylammonium iodide base-electrolyte, 0.2 M in dimethylformamide:water.
Purge with nitrogen and use within 1 d.
Acrylonitrile and styrene monomers. Store in a refrigerator. Re-distill the
monomers immediately before use.
Mercury - for polarographic analysis. Use trebly distilled mercury, supplied in
stone containers. Mercury picks up an impurity that might interfere in polarography from
polyethylene bottles.
Hydrogen or nitrogen - extremely low oxygen content.
291
55.4 METHOD
A dimethyl fonnamide solution of the sample containing 0.2 M tetrabutyl

ammonium iodide base electrolyte is polarographed at start potentials of -2.0 V (styrene)
and -1.7 V (acrylonitrile). The styrene and acrylonitrile waves are evaluated. The
method is calibrated by standard additions of the two monomers.
55.5.1 Sample Preparation
Purge the stock bottle of dimethylfonnamide with oxygen-free nitrogen or

hydrogen for 30 to 40 min to sweep out dissolved oxygen. Keep the bottle well
stoppered and re-purge each time it is opened. Use freshly purged dimethylfonnamide
solvent throughout the analysis.
Weigh 1.25 ± 0.01 g of the styrene-acrylonitrile sample into a 50 cm3 calibrated
flask. Transfer 25 cm3 of anhydrous dimethylfonnamide to dissolve the polymer. Dilute
the solution to the mark with the 0.2 M tetrabutylammonium iodide reagent. For the
blank solution, transfer 25 cm3 of dimethylfonnamide and 25 cm3 of the 0.2 M
tetrabutylarnmonium iodide reagent to a 50 cm3 calibrated flask. Transfer 5 cm3 of the
sample solution and 5 cm3 of the blank solution into two polarographic cells and immerse
these in the constant temperature bath of the polarograph.
Purging the cell with hydrogen or nitrogen must be perfonned immediately before
any polarographic measurements are made. Lower the dropping mercury electrode
system over this cell, so that the outer sleeve of the electrode dips I to 2 mm into the
water tank (providing a water seal to prevent the ingress of atmospheric oxygen) and
immerse the anode connection in the side arm of the polarographic cell. Pass hydrogen
or nitrogen for 15 min, then switch off the gas supply. Carry out the polarographic
measurements described below within I to 3 min of stopping the purge with gas.
The analytical conditions are as follows:
Cathode dropping mercury

Reference anode mercury pool
Circuit cathodic direct
Start potential styrene - 2.0 V
acrylonitrile - 1.7 V.
Adjust the poalrograph to its minimum sensitivity setting (ie. x 25). Adjust the X-
shift and the Y-shift contois until the light spot commences its sweep at the origin of axes
at the left-hand side of the graticule on the cathode-ray tube. Repeat this operation at
decreasing sensitivity settings until the polarographic wave is visible on the graticule.
55.5.2 Determination of Styrene.
Take the readings of the freshly de-gassed sample solutions as indicated below.
Adjust the polarograph to the styrene start potential (-2.0 V) and obtain the
styrene wave as described above. Read off from the graticule the maximum height ofthe
styrene peak and note the voltage. VSTY, at which this maximum polarographic reading
occurs. Raise the electrode from the cell and deliver into the sample solution by means of
292
a horizontally held Agla syringe a suitable "standard addition" of a solution of styrene in
dimethylformamide: water (95:5 v/v) mixture. Limit the volume of standard addition
solution to less than 0.05 cmJ in order to avoid dilution errors. Lower the electrode into
the sample cell and again pass hydrogen or nitrogen for 5 min. Note the new height of
the styrene wave corresponding to VSTY volts.
55.5.3 Determination of Acrylonitrile.
Take the readings indicated below on the same sample solution as used to
determine styrene.
Adjust the polarograph to the acrylonitrile start potential (-1.7 V). To determine
acrylonitrile, repeat the operations described above for styrene by using a solution of
acrylonitrile in dimethylformamide - water (95:5, v/v) mixture to make the "standard
addition" of acrylonitrile. Note the voltage VACN, at which the maximum polarographic
reading occurs.
Measurement of reagent blank solution. Take the readings indicated above on the
freshly de-gassed reagent blank solution. Set the instrument at the styrene start potential.
Adjust the instrument to obtain the reagent blank wave on the graticule. Measure the
blank peak height corresponding to VSTY volts. Similarly adjust the instrument to the
acrylonitrile start potential and measure the blank peak height corresponding to V ACN
volts.
55.5.4 Calculations
Acrylonitrile monomer content of copolymer, ppm =
Styrene monomer content of copolymer, ppm =
where:
W = weight in g. of original styrene - acrylonitrile copolymer sample made up to
50 cm3 in base electrolyte solution (5 cmJ portion used for polarography)
For acrylonitrile determinations:
h) = peak height in cm at V ACN V, of sample solution before the standard addition.

h2 = peak height in cm at V ACN V, of sample solution after the standard addition.
hJ = peak height in cm at VACN V, of the polymer-free reagent blank solution.
S), S2' S3 are the corresponding instrument sensitivity settings (the products of h
and S are known as peak currents in uA) and
AACN = weight in g of acrylonitrile present in volume of "standard addition"
solution added to the cell solution.
For styrene determination:
293
h.t = peak height in cm at VSTY V, of sample solution before the standard addition.
hs = peak height in cm at VSTY V, of sample solution after the standard addition.
h _= peak height in cm, at VSTY V, of the polymer free reagent blank solution.
S4' Ss, S6 are the corresponding instrument sensitivity settings and
AsTY = weight in g of styrene present in volume of "standard addition" solution
added to the cell solution.
Table 7.27 shows the results obtained in determinations of acrylonitrile monomer

in some copolymers by the polarographic procedure. Comparison of these results with
. those obtained by the dodecyl mercaptan procedure34 show that acrylonitrile contents
some 30 per cent higher are obtained by the latter method.
The acrylonitrile and styrene monomer contents of several copolymers were
determined by the polarographic procedure. The styrene monomer content of these
samples was also determined by a procedure involving evaluation by ultraviolet
spectroscopy at 292 run of solutions of the samples in carbon tetrachloride. The results
obtained (see Table 7.28) show that styrene contents determined by the two procedures
are in good agreement with each other.
The above method is capable of determining down to 2 ppm of acrylonitrile and

20 ppm of styrene monomer in styrene-acrylonitrile copolymers with an accuracy of ±
5% when a 2.5% solution of polymer in base electrolyte is used.
METHOD 56· DETERMINATION OF STYRENE AND ACRYLONITRILE

MONOMERS IN STYRENE·ACRYLONITRILE COPOLYMER. TITRATION
PROCEDURES.
56.1 SUMMARY
These titration procedures are capable of determining, respectively, down to 50

ppm and 100 ppm of styrene and acrylonitrile monomers in styrene-acrylonitrile
copolymers.
56.2 APPARATUS
pH meter.
Read stop titrimeter.
56.3 REAGENTS
Styrene determination.
Benzene, Analar.
294
Table 7.27 - Determination of Acrylonitrile: Comparison of Polarographic and Chemical
Methods
Acrylonitrile content, percent w/w, detennined by:
Polarograph Titration with
Dodecyl Mercaptan
0.06 0.07 0.090.09

0.08 0.12
O.II 0.15
O.II 0.19
0.12 0.15
0.12 0.17
0.14 0.18
0.21 0.31 0.29
From Crompton and Buckley". Royal Society of Chemistry, London
Table 7.28 - Determination of Acrylonitrile and Styrene Monomers in Copolymers

Acrylonitrile Detennined by Styrene, Per Cent wlw Determined by:
Polarography, Per Cent, w/w
Polarography Spectroscopy
0.015 0.014 0.20 0.21

0.015 0.015 0.15 0.13 0.15
0.035 0.036 1.60 1.53
From Crompton and Buckleyll. Royal Society of Chemistry, London
Potassium bromide-bromate solution 0.083M (0.5N). Dissolve 13.92 g of

potassium bromate and 51 g of potassium bromide in 1 cm3 0fwater.
Potassium bromide - bromate solution, 0.003M (0.02N). Dissolve 0.557 g of
potassium bromate and 2.04 g of potassium bromide in 1 L of water.
Titration solvent. Prepare 1 L of titration solvent by mixing the following: 714
cm3 of glacial acetic acid, 134 cm3 of carbon tetrachloride, 116 cm3 of methanol, 18 cm3
of sulphuric acid (1 + 5) and 18 cm3 of a methanolic solution of mercury (II) chloride
(lOOg -I).
Acrylonitrile determination.
Propan-2-01.
Ethanolic potassium hydroxide solution. Dissolve 25 g of potassium hydroxide in
1 L of ethanol.
~tandard silver nitrate solution, 0.05 and 0.01 M.
Nitric acid. Mix 3 volumes of concentrated nitric acid (sp. gr. 1.42) with 5
volumes of water.
Standard ammonium thiocyanate solution, 0.05M. Standardise the solution by
titration against standard silver nitrate solution.
Indicator solution. Dissolve 40 g of ammonium iron(III) sulphate dodecahydrate
(ferric alum) in a mixture of 20 cm3 of nitric acid:water (3:5 v.v) and 80 cm3 of water.
Heat to boiling and dilute with 3 volumes of water.
Dodecanethiol solutions. Solution A: dissolve 16 cm3 of dodecanethiol in 1 L of
propan-2-o1. Solution B: dissolve 4 em3 of dodecanethiol in 1 L of propan-2-01.
295
56.4 METHOD
Styrene monomer. A benzene solution of the sample is acidified and titrated with
standard potassium bromide bromate solution. The styrene consumes a stoichioimetric
amount of the liberated free bromine. The end-point of the titration is detected using a
dead-stop titrimeter equipped with glass and calomel electrodes. The styrene content is
calculated from the amount of bromine consumed.
, Acrylonitrile monomer. An isopropanol solution of the polymer is treated with an
excess of standard dodecanethiol solution and standard ethanolic potassium hydroxide.
Excess dodecanethiol is determined by titration with standard silver nitrate. The
acrylonitrile content of the sample is calculated from the amount of dodecanethiol
consumed.
56.5.1 Determination of Residual Styrene Monomer in Styrene Acrylonitrile

Copolymers.
A 2.5 g sample of polymer (accurately weighed to the nearest milligram) is taken

in a 150 cm3 wide-mouthed stoppered bottle and 25 cm3 of benzene added. The bottle
and contents are kept for 50 h with occasional stirring and the resulting extract is added to
100 cm3 of titration solvent. Styrene is then determined by titration with 0.083M or
O.003M bromide-bromate solution in a dead stop titrimeter using glass and calomel
electrodes.
56.5.2 Determination of Residual Acrylonitrile.
The amount of acrylonitrile is determined by using the following procedure. A

known amount of the synthetic mixture is dissolved in 100 cm3 ofpropan-2-01 and to this
solution 10 cm3 of dodecanethiol solution A is added with continuous stirring by means
of a magnetic stirrer. A 2 cm3 volume of ethanolic potassium hydroxide solution is added
and after 2 min the excess of alkali is neutralised by adding 2 cm3 of nitric acid:water (3:5
v/v). Then 25 cm3 of 0.05M silver nitrate solution and 25 ml of water are added. The
excess of silver nitrate is titrated with 0.05M ammonium thiocyanate solution, using
ammonium iron III sulphate as indicator.
Styrene, % = (A - Bl x M x 5.2
Wx6
where A ml is the volume of bromide-bromate solution required for the sample.

B ml is the volumes of bromide-bromate solution required for the blank. M is the
molarity of the bromide-bromate solution and W is the mass of sample solution.
Acrylonitrile, % = (A - Bl x M x 5.3
W
296
where A ml is the volume of ammonium thiocyanate solution required for the
sample, B ml is the volume of ammonium thiocyanate solution required for the blank, M
is the molarity of the ammonium thiocyanate solution and W g is the mass of sample
solution.
These procedures are capable of determining styrene and acrylonitrile monomers,

respectively, in amounts down to 50 and 100 ppm in styrene-acrylonitrile copolymers
METHOD 57 - DETERMINATION OF VINYL CHLORIDE, BUTADIENE,

ACRYLONITRILE, STYRENE AND 2-ETHYLHEXYL ACRYLATE
MONOMERS IN POLYMERS. HEAD SPACE ANALYSIS.u
57.1 SUMMARY
This head space method is capable of determining vinyl chloride, butadiene,

acrylonitrile styrene and 2-ethylhexyl acrylate monomers in a range of polymers in
amounts down to 0.05 - 0.5ppm.
57.2 APPARATUS
Gas chromatograph.
Automated head space analyzer equipped with a flame ionization detector.
Operating conditions are listed in Table 7.29.
Glass vials (24 cm3 of capacity) equipped with septa and aluminium sealing rings.
Manual crimper for sealing vials.
6 ft x 118 in 0.4% Carbowax 1500 on Carbopak A, GC column.
57.3 REAGENTS
N,N' -dimethylacetamide.
o-dichlorobenzene
Vinyl chloride monomer and 1,3-butadiene in pressurized cylinders.
The polymerization inhibitors in styrene, acrylonitrile and 2-ethyl hexyl acrylate
were removed by passing the monomer over Amberlyst resins (Rohm and Haas) - A-27
resin for styrene and A-21 resin for acrylonitrile and 2-ethylhexylacrylate.
Preparation of standard monomer solutions, (see Table 7.30). Vinyl chloride and
butadiene. Pour about 1 cm3 of monomer into a tared vial containing 20.0 cm3 of N,N-
dimethylacetamide. Seal the vial immediately with a septum and weigh. This standard is
diluted to obtain an appropriate concentration of monomer.
Preparation of standard monomer solutions, acrylonitrile, styrene and 2-ethyl
acrylate. Weigh 0.2 g portion of monomer into a tared 25 cm3 volumetric flask and dilute
with solvent. Dilute 1 cm3 of this solution to 25 cm3 and store in a septum sealed vial.
The above standard solutions are prepared fresh each week and refrigerated when
not in use.
297
Preparation of monomer free calibration standards (see Table 7.30). Vinyl
chloride, butadiene and acrylonitrile. Dissolve four 0.500 g portions of monomer free
polymer (ie. < 8 ppm monomer) at 90°C in septum sealed vials containing 5.0 em3 of
N,N' dimethylacetamide. Cool the vials to room temperature. Inject aliquots of the
standard monomer solution (5, 10, 20 and 40 ul) into the polymer solutions using a 50 ul
syringe. These solutions are equilibrated at 90°C for a minimum of 30 min prior to head-
space sampling.
Preparation of calibration standards, styrene and 2-ethylhexyl acrylate. Dissolve
four 0.5 g portions of monomer free polymer (ie. < 8 ppm monomer) in septum sealed
vials containing measured aliquots ofN,N'-dimethylacetamide. Heat vials to 90°C to aid
dissolution of the polymer then cool to room temperature. Inject aliquots of the standard
monomer solution (5, 10,20 and 40 ul) into the polymer solutions using a 50 ul syringe.
Swirl the solutions to mix and inject an aliquot of distilled water into each polymer
solution. Shake the vials briefly to assure complete mixing of the water with the organic
phase and to prevent the precipitated polymer from forming a film on top of the solution.
Equilibriate the vials at 90° C for 60 min prior to head space sampling.
57.4 METHOD
A N,N' dimethyl acetamide solution of the polymer is subject to head space

analysis. Measurement of the concentrations of monomers in the head space by gas
chromatography enables their concentrations in the original polymers to be calculated
using appropriate calibration data.
The more volatile monomers (vinyl chloride, butadiene, and acrylonitrile) are
determined by dissolution of the polymer. The injections of water into polymer solutions
containing styrene and 2-ethyl hexyl acrylate monomers prior to head-space analysis
greatly enhanced the detection capability for these monomers.
Dissolve a weighed portion of polymer sample with the appropriate solvent in a

septum sealed vial. (Table 7.30). Dissolution of the polymer is assisted by heating at
90°C. After the entire sample has dissolved, one of the procedures listed below is
followed.
Polymers containing vinyl chloride, butadiene or acrylonitrile. Equilibrate the
vials containing polymer solution for a minimum of 30 min at 90°C prior to head space
sampling.
Polymers containing styrene and ethylhexylacrylate. Inject a measured volume of
water into each vial and shake the vial vigorously. The vials and their contents are
equilibrated for 60 min at 90°C prior to head space sampling.
57.6 TVPICALRESULTS
Peak heights are used for quantitation. A response factor for each monomer is
determined by dividing the weight (ug) of monomer added to each standard solution by
the adjusted peak height. The adjusted peak height is the product of the measured peak
height, the attenuation and the range settings.
298
Table 7.29 - Operating Conditions for the GC Multifract F-40
GCcolumns VCMa, BD and AN 6 ft x in S.S. tubing packed with 0.4% Carbowax

1500 on Carbopak Ab
Styrene and 2-EHA 8 ft x in S.S. tubing packed with 10"10
poly(phenyl ether) (6R) on Chromosorb W (60/80
mesh)
Column temperatures VCM, BD, AN and 100°C
Styrene, and EHA 130°
Injection times VCM, BD and AN 1=2,
Styrene 1= 10,
2-EHA 1=20,
Thermostated sample 90°C
tray
Injector/detector 180°C
Dosing Line 180°C
Carrier Gas Helium, 30 cm 3/min
• The GC conditions used for VCM were suggested by N. A. Sebestyen of Perkin-Elmer Corporation. b
Supe\co, Inc. recently announced (Chromatography Lipids, IX, July (\ 975» that this column packing is
being replaced by an equivalent packing, 0.2% Carbowax 1500 on Carbopak C.
From Steichen36 • American Chemical Society
Table 7.30 - Details for Preparation of Calibration Standards8 and Sample Solutions
Monomer Polymer Volume and H20 injection

Weight, g Solventb ml
VCM 0.500 5 em3 DMA None

Butadiene 0.500 5 cm3 DMA None
Acrylonitrile 0.500 5 cm3 DCB None
Styrene 0.200 4 cm3 DMA 3
2-EHA 0.100 2cm3 DMA 5
• Calibration standards also contain added known amounts of monomer. b N,N' Dimethylactamide (DMA)
and orthodichlorobenzene
From Steichen36 • American Chemical Society
The monomer concentration in the polymer is calculated from the response factor
(Rf) the adjusted peak height of the sample (H), and the weight of the sample in grams
(W).
Ppm=RfH
W
The presence of polymers in solution affected the equilibrium head-space

concentration of monomer. To compensate for this effect, polymer containing a low level
of residual monomer are included in the calibration standards to simulate the polymer
matrix of the sample solution. At the polymer concentrations recommended, failure to
incorporate polymer into the calibration standards resulted in a -8% error in the
determination ofvinylchloride and a -30% error for 2-ethylhexyl acrylate.
299
The sensitivity achieved by the head space method can be improved by decreasing
the solubility of the 2-ethylhexylacrylate monomer in the solution of polymer in N,N'-
dimethyl acetamide through the introduction of a second solvent. Water is the most
effective solvent for this purpose (see Table 7.31). A greater than 200 fold increase in the
2-ethylhexylacrylate equilibrium head space concentration resulted when water is
injected into its polymer solutions. A significant increase in the styrene head space
concentration is also obtained when polystyrene solutions are treated with water. In the
region where styrene and 2-ethylhexylacrylate monomers elute, no increase in baseline
noise results from the injections of water.
The response for styrene and 2-ethylhexylacrylate was affected by the relative
amount of water injected into the polymer solution. Increasing the relative amounts of
water caused a continuing increase in monomer peak height with no plateau.
It is possible to determine vinyl chloride and butadiene at the 0.05 ppm level and
acrylonitrile down to 0.5 ppm. The injection of water in the case of styrene and 2-
ethylhexyl acrylate makes it possible to determine styrene down to I ppm and 2-ethyl
hexyl acrylate at 5 ppm. The relative precision and error in the determination of these
monomers near the quantitation limit is less than 7%.
METHOD 58 - DETERMINATION OF HYDROXYL NUMBER OF GLYCEROL-

ALKYLENE OXIDE POLYETHERS AND BUTANE, 1,4-DIOL ADIPIC ACID
POLYESTERS. DIRECT INJECTION ENTHALPIMETRy.37
58.1 SUMMARY
This direct injection enthalpimetric method is capable of determining hydroxy

values of polyesters and polyethers in less than to minutes.
58.2 APPARATUS
The basic electrical circuies is a simple d.c. Wheatstone bridge incorporating in

one arm a thermistor of nominal resistance 10k ohm at 25°C. The off-balance voltage is
recorded on a recording potentiometer (to mV full-scale deflection) with a chart speed of
4cmmin·1•
A glass bottle (of capacity about 25 ml) is used for titrations, it was thermally
insulted in a block of polystyrene. The titrand is stirred at a constant rate by a PTFE
covered magnet.
58.3 REAGENTS
Titrant for polyethers. Polyethers 2 % v/v sulphuric acid (98 % v/v); 23% v/v
acetic anhydride, 25% v/v carbon tetrachloride and 50% v/v glacial acetic acid.
Titrant for polyesters. 2% v/v sulphuric acid (98% v/v); 23% v/v acetic
anhydride, 25% v/v glacial acetic acid and 50% v/v methylene chloride.
Carbon tetrachloride.
Methylene chloride.
300
Table 7.31 - Investigation of Solvents for Displacing 2-EHA Monomer from DMA-
Polymer Solutions into Headspace8
Displacing Solvent GC Headspace Response b Effect of Displacing Solvent

for2-EHA upon Polymer Solution
None added o Clear solution

Water 652% Polymer precipitates
Heptane o Turbid solution
Ethyl-Cellosolve o Clear solution
Ethylene glycol 54% Polymer precipitates
From Steichen36• American Chemical Society

• A 0.10 g portion of resin was dissolved in a septum-sealed vial with 2 ml ofDMA. An aliquot ofa
standard solution containing 76 ug of2-EHA was added. To this, 5.0 ml of the displacing solvent was
injected. b Percent of full scale response at lowest instrument attenuation.
The titrant consists of 100 to 200 ul of a solution of a sample dissolved in either

carbon tetrachloride (for polyethers) or methylene chloride (for polyesters) delivered
from a micro litre syringe. These organic solvents are dried over molecular sieve (grade
5A). When the hydroxyl value is less than 100 mg g.1 of potassium hydroxide, the titrant
is used at a 33.3 per cent mN solution; for hydroxy values exceeding 100 mg g.1 it is
made up to 20 per cent mN.
Six portions, each 200 ul in volume of a titrant added separately to one sample of
titrand yields the same recorder deflection after each addition. The deflections produced
by two samples and one standard can thus be determined in duplicate without renewing
the titrand. All samples are examined in duplicate or triplicate and deflections on the
recorder are usually reproducible to ± 0.025 per cent of full-scale deflection.
Plots of dT (defined as the height of the recorder deflection) against hydroxyl

value (detennined by the conventional phthalic anhydride method) for five gylcerol-
propylene oxide condensates ranging in molecular weight between 300 and 4000 pass
very near to the origin.
This method is capable of detennining hydroxy values of polyethers and

polyesters down to 10 mg kg' I with an accuracy of ± 2%.
301
METHOD 59 - DETERMINATION OF PRIMARY AND SECONDARY
HYDROXYL GROUPS IN ETHYLENE OXIDE TIPPED GLYCEROL-
PROPYLENE OXIDE CONDENSATES. PHENYL ISOCYANATE KINETIC
MEmOD.
59.1 SUMMARY
In many situations it is necessary to be able to determine both primary and

secondary hydroxy groups in polymers. This kinetic method, based on the difference in
reaction rate of primary and secondary hydroxy groups with phenyl isocyanate enables
both groups to be determined.
The reaction is carried out under standard conditions in which a calculated weight
of the polyol (depending on its hydroxyl number) is reacted under standard conditions
with an excess of a standard toluene solution of phenyl isocyanate in the presence of a
basic catalyst.
7.6
Unconsumed phenyl isocyanate is then reacted with excess standard potassium

hydroxide.
7.7
Excess potassium hydroxide is estimated by titration with standard acetic acid to

the phenol phthalein end-point. A blank run is performed in which the sample is omitted.
From the difference between the sample and the blank titrations it is possible to calculate
the hydroxyl content of the original polymer:
1 mole hydroxyl groups :: 1 mole phenyl isocyanate :: 2000 ml N KOH
Reactivity is calculated by a kinetic procedure in which the percentage of the

original phenyl isocyanate addition, which reacts with the sample in a given time, it taken
as an index of its reactivity. A calibration graph can be prepared in which the determined
phenyl isocyanate reactivity is plotted against the ethylene oxide content, and this enables
a determination to be made of the ethylene oxide content of unknown samples from the
calibration graph by interpolation.
302
59.2 APPARATUS
(a) apparatus for preparation, storage and dispensing of dry toluene (containing
less than 15 ppm water) A description of the apparatus required is given with the method
of drying toluene described later. Figure 7.12 shows the apparatus required for storing
and dispensing the dried toluene.
(b) apparatus for reducing water content of polyol sample to 100 - 150 ppm
(Figure 7.13). The water content of the neat polyol is reduced to 100 - 150 ppm by
subjecting it to vacuum treatment for 2 hours at 70 - 80·C. Connect a vacuum pump of
approximately 50 cu ftlmin capacity (capable of attaining a vacuum of 0.005 mm
mercury) to a 700 ml Quickfit flange type flask assembly and a Manostat gauge, (via a
cardice/isopropanol filled cold trap, see Figure 7.13). Provision is made for feeding dry
nitrogen into the flask when the vacuum treatment is completed. During vacuum
treatment the temperature of the reaction flask is maintained at 70· to 80· by immersion in
a Simmerstat controlled water bath.
(c) apparatus for reaction of polyol with phenyl isocyanate (Figure 7.14). The
reaction of the polyol with phenyl isocyanate is carried out in a 700 cm3 Quickfit flange
type vessel (as described above). This apparatus is mounted in a rectangular aluminium
tank dimensions 24 in x 7 in high, thermostatted at 40 ± 0.1 ·C. The tank is fitted with a
Perspex top having holes cut to accommodate two reaction flasks and the thermostatted
heater/stirrer.
(d) miscellaneous apparatus. Precision torsion balance, capacity 4000 g, scale
divisions 1 g.
Stopwatches.
Long stemmed sampling pipette, capacity 10 - 12 cm3 from tip to graduation on
top of bulk.
Miscellaneous volumetric glassware.
59.3 REAGENTS
(a) preparation and storage of dry toluene (containing less than 15 ppm water).
Reflux 4 cm3 of toluene with 30 g calcium hydride for 6 to 8 h in a 5 cm3 B24 neck flask
with 24 in vertical condenser attached. Connect a horizontal condenser to the 5 cm3 flask.
(excluding moist air). To the end of this condenser connect a dry three-neck B25 5 dm3
flask containing 100 g freshly ignited molecular sieves, (6 in x 1 in molecular sieve trap
also connected to 5 dml flask - molecular sieves dried 3 to 4 h at 120·C). Now distil 3 to
3.5 dml of the toluene from the calcium hydride into the dry receiver containing
molecular sieves. Deactivate the calcium hydride remaining in the distillation flask by
slowly adding a 10:1 hexane:ethanol solution and dispose of this solution in an open
drain.
Connect the toluene receiver to a dry dispensing system as shown in Figure 7.12.
In this apparatus the solvent is kept dry (ie. less than 15 ppm water) by standing over
molecular sieves under an atmosphere of dry nitrogen. To the outlet end of this
dispensing apparatus connect a dry 500 cml graduated cylinder. By suitable adjustment
of stopcocks keep this cylinder dry by continuously purging with dry nitrogen when the
apparatus is not in use.
Immediately before dry toluene is required for an analysis syphon a suitable
volume into the dry 500 cml graduated cylinder by adjustment of the stopcocks. The
303
M&\CURY
IIU88L£R
CONICAL
",. JOINT
500 lolL GRADlJATED TOUJENE STORAGE

CYLINDER VESSEL 5 UTRE
Figure 7.12 Apparatus for preparation, storage and dispensing of dry toluene.
water content of the toluene stock should be checked periodically by a Karl Fischer
procedure to ensure that it is below the required limit of 15 ppm.
(b) Toluene solution of phenyl isocyanate, 1.00 ± 0.005 M. Weigh 120 ± .2 g
phenyl isocyanate into an oven dried, stoppered, I dm3 volumetric flask. Run dry toluene
(less than 15 ppm water) into this flask from the dispenser (see section a and Figure 7.12)
until approximately 950 cm3 of liquid is present in the volumetric flask. Immerse the
stoppered volumetric flask in a water bath, thermostatted at 25 ± 1°C and leave for 15
min with occasional mixing. Finally make the volume of liquid in the flask up to I dm3
at 25°C with dry toluene. Stopper and mix well. This solution is to be maintained in a
water bath thermostatted at 25 ± 1°C when portions of it are withdrawn for
standardization or for use in the determination of the reactivity of polyols. A measured
volume of the solution then contains a constant weight of phenyl isocyanate.
Standardisation of phenyl isocyanate solution.
Hydrochloric acid, 0.1 M aqueous.
Bromophenol blue indicator, 0.1 %.
Dissolve 0.1 g bromophenol blue in 100 cm3 distilled water, add 1.5 ml of 0.1 M
sodium hydroxide solution.
Methanol redistilled.
Di-n-butylamine 0.2 M (approx) in dry toluene, (less than 15 ppm water).
Transfer 9.3 ml di-n-butylamine ANALAR to a dry 250 cm3 volumetric flask. Make up
304
LINOE SIEVE
DRYER
DEWAR FLA$I(
AND COLD "mAP
FlANGE AEACTa! IN
HOT WATER BATH
Figure 7.13 Apparatus for reducing water content of polyol sample.
to the mark with dry toluene and thoroughly mix the solution. Keep this reagent well
stoppered when not in use and renew weekl S'
Adjust the temperature of the 1 cm flask of 1 M phenyl isocyanate solution by
immersing it in a water bath at 25 ± 1°C with dry toluene (less than 15 ppm water) and
thoroughly mix the contents of the 250 ml flask.
Pipette 25 ml 0.2 M di-n-butylamine solution into two dry stoppered 250 em3
conical flasks (ie. asample and a blank flask). Allow a 15 s pipette draining time during
these operations. Into one of the flasks pipette 25 cm3 of the ten-fold diluted phenyl
isocyanate solution (samfled at 25°C using a 15 s pipette draining time) and into the
blank flask pipette 25 cm of toluene. Leave both solutions for 15 min to react, then add
to each 100 cm3 methanol and 5 drops bromophenol blue indicator. Using 0.1 M
hydrochloric acid titrate the sample (Ts ml of f normal hydrochloric acid) and the blank
solutions (TB ml of f normal hydrochloric acid) to the yellow-green end point.
The normality (F) of the 1 cm3 undiluted stock phenyl isocyanate solution of25 ±
1°C is then given by:
F = lOx fx (TB..:...Isl
25
The molarity of the phenyl isocyanate solution at 25 ± 1°C, prepared as described

above, should be slightly greater than 1.000M. Finally, adjust the strength of the 1 cm3 of
305
Figure 7.14. Apparatus for reaction of polyoI with phenyl isocyanate.
stock phenol isocyanate solution to within the range 1.000 ± 0.005 M by addition of a
calculated volume of dry toluene. Mix the I cm3 stock solution well in the thermostatted
25 ± lOe water bath and recheck the normality of a ten-fold dilution as described above.
Due to the high coefficient of cubical expansion of toluene, the normality of a
toluene solution of phenyl isocyanate varies as its temperature is changed. It is for this
reason that the solution is prepared at 25 ± l°e and subsequently standardized at the same
temperature.
For the purpose of calculating results, it is necessary to know the weight of 50
cm3 of the phenyl isocyanate at 25 ± l°C. This may be obtained by weighing 50 cm 3 of
the reagent from the thermostatted stock flask in a dry 50 cm3 stoppered volumetric flask.
The normal phenyl isocyanate stock solution should be well stoppered when not
in use and should be left open for a minimum period when sampling (to exclude
atmospheric moisture). Recheck the normality of the solution at 25 ± lOe at frequent
intervals.
306
(c) Dabco catalyst solution (0.56% w/v)
Dabco is the trade name for triethylerie diamine (Jacobson and Van den Burg and
Co. (U.K.) Ltd, 3 - 5 Crutched Friars, London, E.C.3). Weigh out 6 ± 0.1 g Dabco and
transfer to an over-dried I litre volumetric flask. Add dry toluene (less than 15 ppm
water) from the dispenser (see Figure 7.12) to make the volume up to approximately 950
cml . Dissolve the Dabco by shaking and stand the flask in a water bath thermostatted at
25 ± 1°C. When the solution has reached 25°C make up to the 1 dml mark with dry
toluene and mix thoroughly. Stand the solution in a water bath, thermostatted at 25 ±
1°C. A measured volume of this solution then contains a constant weight of Dabco
catalyst.
Standardisation of the Dabco solution.
Immerse the 1 dml flask of stock solution of Dabco in a water bath thermostatted
at 25 ± 1°C and leave until the solution reaches this temperature. Pipette 25 eml of this
solution (15 s draining time) into a 250 cml conical flask containing 100 cml methanol
and 5 drops 1% aqueous bromophenol blue indicator. Using 0.1 M hydrochloric acid,
titrate the sample solution (T cml offM hydrochloric acid) to the yellow-green end point.
The reaction which has occured at the bromophenol blue indicator end point is:
N (C2H4)lN + HC1 = N (C2H4)l N.HC1 7.8

The strength (% w/v) of the 1 dml ofDabco solution at 25 ± 1°C is given by:
Dabco (% w/v) = 4 x 112 x T x f
1000
The strength of the Dabco solution at 25 ± 1°C must be in the range 0.56 ± 0.01 %
w/v.
For the purpose of calculating results it is necessary to know the weight of 50 cm3
of the Dabco catalyst solution at 25 ± 1°C. This may be obtained simply by weighing 50
ml of the reagent from the thermostatted stock flask into a dry 250 ml stoppered conical
flask.
This solution should be well stoppered when not in use and should be left open
for a minimum time when sampling (to exclude atmospheric moisture).
59.4 MEmOD
The described kinetic procedure, based on the difference in the reaction rates with
phenyl isocyanate of the terminal primary and secondary hydroxyl groups present in
ethylene oxide tipped glycerol/propylene oxide condensates must be carried out under
rigidly standardized conditions. Primary hydroxyl groups react with phenyl isocyanate to
form a urethane faster than do secondary hydroxyl groups. The greater the amount of
terminal ethylene oxide units in a glycerol/propylene oxide condensate, therefore, the
greater its reactivity (ie. rate of reaction) with phenyl isocyanate. The method may be
used, therefore, for evaluating the reactivity of ethylene oxide tipped polyols.
(a) Calculation of the weight of polyoI required for analysis.

It is explained in note 1 that the analysis is carried out using a toluene solution of
the polyol which is exactly decimolar with respect to total primary and secondary
hydroxyl groups in the sample. First determine the hydroxyl value (H, mg KOWg) of the
307
polyol sample by a modified catalyzed acetylation procedure (see Method 60). Calculate
the weight W (g) of polyol required to produce 500 cm3 of a decinormal toluene solution
(at 25°C ±1°C) from the following equation:
W (g) = 56.1 x 50
H
Transfer approximately 95 g of polyol sample to a clean 100 cm3 conical flask

and weigh to the nearest 0.01 g. Transfer from this flask exactly the calculated weight
(W) of polyoI into a 700 cm3 Quickfit flanged reaction vessel (see Figure 7.14). Reweigh
the conical flask to check that the weight of polyol added to the reaction vessel is correct
to within 0.01 g.
(b) Removal of water from polyol.
Assemble the reaction apparatus with multineck adaptor, stirrer and gland,
thermometer pocket and vacuum assembly as shown in Figure 7.13.
Mount the flask in a suitable water bath and connect the stirrer motor and vacuum
line. Maintain the cardice-isopropanol cold trap at -60°C and operate the stirrer at
approximately 200 rpm.
Close stopcock A (Figure 7.13) and connect (a) to (c) with stopcock B. Heat the
water bath up to 70 to 80°C and allow the stirred reactor contents to reach this
temperature. Switch on the vacuum pump. Reduce the pressure in the reaction flask to 2
mm over a period of 5 min by momentarily turning tap B to connect (a) to (b) several
times (if the pressure is reduced too rapidly to 2 mm then violent de-gassing of the polyol
may take place due to the presence of dissolved propylene oxide in the sample). When
de-gassing is complete turn tap B to connect (a) to (b) and continue the vacuum treatment
for 2 hours. After half an hour the pressure in the flask should be less than 0.1 mm.
When the vacuum treatment is completed switch off the bath heater and the stirrer
motor. Isolate the flask from the vacuum line by turning tap B to connect (c) to (b). Now
apply a rapid purge of dry nitrogen at the nitrogen inlet and cautiously open stopcock A
to allow nitrogen to fill the reaction vessel. Replace the thermometer pocket by a stopper,
remove the flask from the water bath and dry the outside of the flask. The moisture
content of the polyol should now be in the range 80 - 150 ppm.
(c) Toluene dilution of polyo1.
Stand the stoppered reaction flask on a cork ring placed on a balance. Fill the 500
cm3 graduated cylinder of the dry toluene dispensing unit (Figure 7.12) with toluene and
attach a molecular sieve filled guard tube to the top of this cylinder. Run a suitable
weight (Wg) of toluene (to the nearest I g) from the graduated cylinder into the reaction
flask and immediately stopper the flask to exclude atmospheric moisture. The weight
(Wg) of toluene required is given by the following expression.
Weight of toluene required to make the volume of test solution up to 400 cm3 at
W(g) = 0.861 x (400 - WI)

S
where:
WI = weight (g) of polyol used in experiment.
S = specific gravity of neat polyol at 25°C (usually assumed to be 1.00).
0.861 = specific gravity of pure toluene at 25°C.
308
(d) Commencement of the reaction.
Immerse the reaction flask with multineck adaptor in an aluminium water tank of
the type shown in Figure 7.14. This tank is thermostatted at 40 ± 1°C. Insert the cold
trap and sampling fitting with Gaco seal into the multineck adaptor. Maintain the cold
trap at -60°C with cardice/isopropanol during the whole run.
Connect to the top of the cold trap a supply of dry nitrogen and maintain a slight
pressure of nitrogen in the reaction flask. The nitrogen stream should be very gentle,
otherwise some loss of toluene vapour, with consequential analytical errors may occur
when the reaction flask is opened for sampling. Adjust the stirrer speed to 200 rpm and
leave the contents of the flask for 30 min to reach thermal equilibrium with the bath at
40°C. .
Whilst the reaction flask is reaching thermal equilibrium carry out the following
two operations:
(1) Place the two 1 litre reagent flasks containing the stocks of 1.000 ± 0.005 M
phenyl isocyanate solution and of 0.56% w/v Dabco catalyst solution in a separate water
bath thermostatted at 25 ± 1°C, and allow these flasks to reach this temperature ovc:r a
period of30 min.
(2) Pipette 10 ml 0.2 N di-n-butylamine solution into each of twelve dry 100 cm3
conical flasks and quickly replace the stoppers (15 s pipette draining time). Ensure that
the same amount of di-n-butylamine is introduced into each flask by keeping the
temperature of the stock di-n-butylamine solution constant during the pipetting. These
flasks will be used later for the determination of the phenylisocyanate content of samples
withdrawn from the polyol/phenyl isocyanate reaction at various times.
When the reaction flask containing the toluene solution of polyol has reached
40°C, pipette into this flask 50 cm3 of normal phenyl isocyanate stock solution (at 25°C),
allowing a 15 s pipette draining time. No reaction occurs between polyol and phenyl
isocyanate in the absence of Dabco catalyst. Leave the mixture 15 min to reach thermal
equilibrium. Transfer, by pipette, 50 cm3 of stock 0.56% w/v Dabco solution from the
storage vessel (thermostatted at 25°C) into a dry 50 cm3 volumetric flask. Remove the
B341B24 sampling adaptor from the reaction flask assembly and insert the neck of the 50
cm3 volumetric flask into the B34 socket to introduce the Dabco catalyst into the reaction
mixture. Allow a 15 s draining time for the Dabco flask and replace the B341B24
sampling adaptor. Start the stopwatch at the same moment that the Dabco solution is first
tipped into the reaction flask, (ie. at the exact moment that the DabcO catalyzed reaction
between polyol and phenyl isocyanate commences).
(e) Sampling the polyol/phenyl isocyanate reactor.
Samples are now withdrawn periodically from the reactor for determination of
residual phenyl isocyanate. Immediately before starting the reaction between polyol and
phenyl isocyanate by the addition of Dabco catalyst, (ie. time zero) weigh to the nearest 1
mg, one of the twelve 100 cm3 conical flasks containing 10 cm3 0.2 M di-n-butylamine
(referred to in section (2». Withdraw approximately 10 cm3 of the polyol/phenyl
isocyanate reaction mixture by means of a long stemmed 10 cm3 pipette via the Gaco seal
on the sampling point and exactly one minute after starting the reaction (ie. addition of
Dabco) run this solution into the di-n-butylamine solution contained in the weighed flask.
Stopper and reweigh the conical flask to obtain the weight of polyol/phenyl isocyanate
reaction mixture withdrawn for analysis (this weight is needed in the calculation of
results). Leave the mixture for 15 min, or longer, to react. Transfer the contents of this
flask quantitatively to a 250 cm3 conical flask with 100 cm3 redistilled methanol and add
5 drops 0.1% bromo-phenol blue indicator. Using 0.1 M hydrochloric acid, titrate the
sample to the yellow-green end-point and record this titration.
309
To one of the blank flasks referred to in section (2) add 10 cm3 toluene and
transfer the contents of a 250 cm3 conical flask with 100 cm3 methanol. Add 5 drops
bromophenol blue indicator and titrate with 0.1 normal hydrochloric acid to the yellow-
green end-point.
Similarly, withdraw samples from the polyol/phenyl isocyanate reaction solution
at various other times intervals (see table below) after commencement of the reaction and
immediately introduce the sample into 10 ml di-n-butylamine in order to analyze for
phenyl isocyanate content as just described. Tabulate the titrations obtained. Titrations
of the 10 cm3 0.2 M di-n-butylamine blank solution carried out at the beginning and at
the end of the experiment usually agree within 0.05 ml.
di-n-butylamine Test Time interval between adding Dabco

flask no. catalyst (ie. start of reaction) and
sampling for phenyl isocyanate
determination (min).
1 Blank run
2 Sample run 1
3 Sample run 15
4 Sample run 30
5 Sample run 55
6 Sample run 60
7 Sample run 65
8 Sample run 95
9 Sample run 100
10 Sample run 105
11 Sample run 120
12 Blank run
The small amount of Dabco catalyst present in samples taken from the reaction
flask interferes slightly in these determinations of residual phenyl isocyanate. This
interference is allowed for in the method of calculation.
(f) Graphical plotting of experimental data.
The method of calculating % of the original phenyl isocyanate addition consumed
under standard conditions (denoted by P%) is given below. On graph paper plot P%
versus the corresponding time (in minutes) from the commencement of reaction of each
of the ten samples withdrawn from the reaction flask. Draw a smooth line through the 10
points. From this graph read (P%) corresponding to 60 min and P% corresponding to 100
min., ie. (P%)60mln and (P%) 100 min.
(g) Correlation of reactivities with ethylene oxide content of sample.

As (P%)60 min and (P%)100 min are determined under rigidly standardized test
conditions these quantities are dependent upon the reactivity of the polyol sample
analyzed and therefore, constitute a parameter by which it is possible to compare one
batch of polyol with another. In ethylene oxide tipped condensates prepared under
specified conditions, the reactivity of the polyol increases with its ethylene oxide content.
A series of molecular weight 5000 glycerol/propylene oxide condensates
containing between nil and 9 moles ethylene oxide per mole of glycerol can be used to
prepare a calibration graph. The procedure under calculations was then used to determine
(P%)60 min and (P%) 100 minfor the standard samples.
310
Prepare plots of (P%)60 min and (P%) 100 min respectively versus the weight addition
ethylene oxide content (expressed in moles ethylene oxide per mole glycerol). The
ethylene oxide contents of ethylene oxide tipped glycerol/propylene oxide condensates of
unknown ethylene oxide content may be determined by referring their determined (P%)60
min and (P%),oo min reactivity figures to this calibration graph. The two determinations
usually agree within ± 0.1 ethylene oxide units.
It is necessary to ensure that the samples used to prepare the calibration curve
were manufactured in the same way as the unknown samples being analyzed, thus the
standard samples should be manufactured using the same polymerization catalyst that is
used to manufacture the unknown samples.
Calculations.
(a) To calculate total weight of initial reaction flask charge let;
W,(g) = weight of neat polyol taken for analysis
Wig) = weight of toluene required to make the volume of polyol/toluene test
solution up to 400 ml at 25 ± IOC
W3(g) = weight of 50 cm3 1.000 ± 0.005 normal phenyl isocyanate (in toluene)
reagent at 25 ± IOC.
W4(g) = weight of 50 cm3 0.56% Dabco (in toluene) reagent at 25 ± IOC
WA(g) = total weight of initial reaction flask charge.
= W, + W2 + W3 + W4
(b) to calculate weight of phenyl isocyanate in total initial weight of reaction flask
charge before the polyol/phenyl isocyanate reaction is started
Let F = normality of phenyl isocyanate stock solution at 25 ± I°C.
Then the original weight of phenyl isocyanate present WB(g) in the total reaction
flask charge WA(g) (ie. before reaction with polyol commences) is given by:
WB(g) = 50 x F x 119.13 gphenylisocyanatepresentinWA(g)ofreaction

1000 flask charge.
(c) To calculate initial weight of phenyl isocyanate (ie. before reaction with
polyol is started) in the portion of reaction solution withdrawn for phenyl isocyanate
determination.
Let We = weight (g) of an approximately 10 cm3 sample taken from the reactor
during the run for determination of phenyl isocyanate.
Then calculated weight of phenyl isocyanate WD(g) present in the Wc(g) portion
of reaction solution withdrawn for phenyl isocyanate determination (ie. before reaction
between polyol and phenyl isocyanate is started by addition of Dabco) is given by
(d) To calculate the titration correction (TD cm3) required to allow for the
presence of Dabco catalyst in the portion of reaction solution Wdg) withdrawn for
phenyl isocyanate determination
311
1l2g Dabco = 1000 cm3 1.0000 M hydrochloric acid (Dabco titrated to the
bromophenol blue end-point)
In the reactivity determination there is present 50 cm3 0.56% w/v Dabco solution
(ie. 0.28g pure Dabco) in WA{g) of initial reaction flask charge.
Now 0.28g pure Dabco consumes 0.56 x 50 x 1000 cm3

100 x 112
= 2.5 cm3 1.0000 M hydrochloric acid.ie. the Dabco present in WA{g) of initial
reaction flask charge consumes 2.5 cm3 1.000 M hydrochloric acid.
The hydrochloric acid titration correction (To cm3) required to allow for the
presence of Dabco catalyst in the portion of reaction solutions Wc(g) withdrawn for
phenyl isocyanate determination is given by:
To (cm3) = 2.5 x We cm3 1.000 M hydrochloric acid

WA
To obtain the actual weight of phenyl isocyanate, WE{g) (corrected for Dabco
present) remaining in Wc(g) portion of reaction solution withdrawn for phenyl isocyanate
determination after time T min (ie. T min after the Dabco catalyzed reaction of polyol and
phenyl isocyanate has been started).
If, in the phenyl isocyanate determination by the di-n-butylamine method:
TB = volume of hydrochloric acid (cm3) required in blank titration of 10 cm3 of
0.2 M di-n-butylamine solution
TA = volume of hydrochloric acid (cm3) required to titrate a mixture of 10 cm3 0.2
M di-n-butylamine and the Wdg) of reactor sample which was withdrawn for phenyl
isocyanate determination after time T min.
f = normality of hydrochloric acid used in phenyl isocyanate determination
To = Dabco titration correction, see Section 59.6.
119.13 = molecular weight of phenyl isocyanate
Then the actual weight WE(g) of phenyl isocyanate (corrected for Dabco present)
in a Wc(g) portion of reaction solution withdrawn for phenyl isocyanate determination
after time T min is given by:
WE{g) = {TB x f - (TA X f - To» 119.13

1000
g phenyl isocyanate
or
WE{g) = {TBxf - (TAxf -2.5xWe » 119.13
WA 1000
g phenyl isocyanate
To calculate the percentage (P) of the original addition of phenyl isocyanate

consumed in the reaction solution after time T min denoted by (PT min)
=Wo- WEllQQ
Wo
This method has been applied to a range of glycerol/propylene oxide adducts

containing various accurately known amounts of ethylene oxide tipping, up to 5.3 moles
312
(Table 7.32). Increasing the ethylene oxide tip content of a polyol leads to a distinct
increase in the reactivity of the polyol with phenyl isocyanate. As expected, "untipped"
polyols which are relatively free from primary hydroxyl groups react comparatively
slowly with phenyl isocyanate. Decinormal solutions of "untipped" glycerol/propylene
oxide condensates of molecular weight 3000 and 5000 has an identical rate of reaction
with phenyl isocyanate. Thus, the rate of reaction with phenyl isocyanate of the terminal
isopropanol end-groups in polyols is independent of molecular weight in the molecular
weight range 3000 to 5000 and depends only on proportions of primary and secondary
end groups present.
A calibration curve is prepared by plotting moles ethylene oxide per mole of
glycerol for the range of standard tipped polyols of known ethylene oxide content against
% of original phenyl isocyanate addition consumed after 60 and lOO min, ie. P60% and
P 100%. This curve can be used to obtain from P60% and P 100% data obtained for tipped
glycerol propylene oxide polyols of unknown composition their tipped ethylene oxide
contents (in moles ethylene oxide per mole glycerpl).
For polyols which contain less than 4 moles ethylene oxide per mole of glycerol
the reactivity method has an accuracy of better than ± 5% of the determined value. For
polyols which contain between 5 and 15 moles ethylene oxide per mole of glycerol, the
accuracy is in the range ± 10%.
METHOD 60 - DETERMINATION OF OXYALKYLENE GROUPS IN

POLYETHERBASES AND POLYURETHANE POLYMERS. MIXED
ANHYDRIDE CLEAVAGE - GAS CHROMATOGRAPHY.3'
60.1 SUMMARY
This acetic anhydride - toluene-p-sulphonic acid cleavage - gas chromatography

procedure is capable of determining down to 0.05% of oxyalkylene and oxypropylene
groups in polyethers and polyurethanes.
60.2 APPARATUS
Gas chromatograph, equipped with a thermal conductivity detector or equivalent.

The column consists of aim length of 1 mm Ld. stainless steel tubing packed with 15%
mlm FFAP (free fatty acid phase) or 10% mlm SE-30 silicone) coated on 60-80 mesh
Uniport B. Helium is used as a carrier gas.
60.3 REAGENTS
Cleavage reagent. Acetic anhydride (80g) is added dropwise to 120 g of toluene-

p-sulphonic acid contained in a 300 ml round-bottomed flask at room temperature and the
mixture is refluxed at 120°C for 30 minutes. The product obtained is used as the reagent
without removal of the acetic acid produced and the excess of acetic anhydride.
Sodium carbonate, 50% aqueous.
313
Table 7.32 - Application of Reactivity Method to Standard Ethylene Oxide Tipped
Polyols
Sample Approximate Hydroxyl Ethylene Reactivity, ie. percentage of

Identific- Molecular Number Oxide Tipp- Original Phenyl Isocyanate
ation Weight mgKOWg ing,Moles Addition Consumed in:-
Polyol Ethylene
OxideIMole
Glycerol (by
Weight
Addition)
60 min. 100 min

Reaction Reaction
A 3000 59.0 0.0 25.2 35.2

B 5000 34.9 0.0 27.1 36.8
C 5000 34.3 3.0 41.5 46.6
D 5000 35.9 3.5 44.4 51.0
E 5000 36.0 4.3 47.5 54.1
F 5000 33.3 5.3 51.9 57.4
Diethyl ether.
60.4 MEmOD
The sample, for example, polyethylene glycol, is reacted with acetic anhydride in
the presence of toluene-p-sulphonic acid catalyst to produce a glycol diacetate:
7.9
The diacetate content, proportional to the oxyethylene content of the original

polymer is determined by gas chromatography. The procedure is calibrated against
polyols of known molecular weight and oxyalkylene content.
A 100 mg amount of sample and 2 ml of reagent are mixed in a 20 ml round-

bottomed flask and the mixture refluxed on an oil-bath at 120°C for 2 hours. The
contents of the flask are cooled to room temperature and then neutralised with 50%
aqueous sodium carbonate solution, followed by extraction with about 20 ml of diethyl
ether. The ether layer is washed with de-ionised water and concentrated to a small
volume on a steam bath: the concentrate is then injected into the gas chromatograph.
The FFAP column is operated isothermally at the appropriate temperature for the purpose
of both identifying the base compounds and determining their oxyethylene groups
contents. For the analysis of the polyether based on 1,2-diaminoethane or 2,2'-
diaminodiethylamine the SE-30 column is used.
314
60.5.1 Identification of Polyol Base Compounds.
The acetate peaks are satisfactorily separated from each other and the peak of
propylene glycol diacetate produced by the cleavage of the polyoxypropylene groups did
not overlap those of the derivatives from polyol base compounds except that for the
polyether based on propylene glycol. These base compounds could therefore be easily
distinguished and identified. By decreasing the temperature of the gas chromatographic
column, the peak for propylene glycol diacetate can be accurately identified.
Polyethers based on sorbitol yielded complex products that consist of the acetates
of sorbitans and sorbides produced by dehydration. However, the gas chromatograms
always showed similar patterns, so that the base compound (sorbitol) can be identified
from the chromatogram.
In order to obtain the peaks of the reaction products of polyethers based on 1,2-
diaminomethane and 2,2'-diaminodiethylamine, the SE-30 column is operated
isothermally at 230°C and the flow-rate of the carrier gas was maintained at 60ml/min-l.
These base compounds can also be distinguished and identified.
60.5.2 Determination of Oxyethylene and Oxypropylene Groups.
The ethylene oxide propylene oxide copolymers and polyols that were
oxypropylated and then oxyethylated were decomposed as described above for the
determination of the polyol base compounds. The FFAP column is operated isothermally
at 65°C and the flow-rate of the carrier gas is regulated at 60 ml/min-l.
A typical chromatogram for the reaction of the 1,2-diaminoethane ethylene oxide-
propylene oxide adduct showed ethylene glycol diacetate and propylene glycol diacetate
peaks, produced from polyoxyethylene and polyoxypropylene groups respectively. The
proportions of ethylene and propylene oxide can be determined by measuring the two
peak areas (ie. of the ethylene glycol and propylene glycol diacetates) and applying the
appropriate calculations. The derivative from the base compound itself (1,2-diamino-
ethane) do not appear in the chromatogram and so do not interfere in the determination of
the ratio of oxyethylene to oxypropylene groups.
This procedure is capable of determining down to 0.005% of oxyalkylene and

oxypropylene groups in polyethers and polyurethanes with an accuracy of ± 3%. The
method is also capable of identifying . and determining the base compounds in
polyurethanes with similar accuracy.
METHOD 61- IDENTIFICATION OF ACRYLIC ACID AND METHACRYLIC

ACID IN ACRYLIC COPOLYMERS. PROPYLATION - PYROLYSIS GAS
CHROMATOGRAPHY.40
61.1 SUMMARY
This pyrolysis - gas chromatographic method enables bound acrylic acid and
methacrylic acid units to be determined in acrylic copolymers in amounts down to 0.1 %.
315
61.2 APPARATUS
Glass vials of capacity 15-30 ml with Teflon-lines septa (Pierce Hypo-vials) are
suitable.
A thermostatically controlled oven at 60°C capable of being evacuated in less than
2kPA, was used.
Pyrolysis - gas chromatographic - mass spectrometric equipment, Perkin Elmer
filament pyrolysis unit fitted in a Perkin Elmer FII gas chromatograph (pyrolysis
temperature control 250-550°C) or equivalent. The gas chromatographic column used is
a 1.7 m x 3 mm o.d. stainless steel column packed with 30% mlm silicone oil
(Embaphase) on acid washed Celite, operated at 80°C with a helium flow rate of 30
ml/min-I. The column effluent is split in the ratio 2: I between a flame ionization detector
and an AFI MS12 mass spectrometer equipped with a glass fit type of molecular
separator at 150°C. Mass spectra are scanned from mle 200 to 20 at 8 seconds per decade
under standard electron bombardment conditions, electron energy 70 eV, emission
current 500 uA, accelerating voltage 8 kV and source temperature 200°C.
61.3 REAGENTS
Dimethylformamide dipropyl acetal (2 mequiv mrl in pyridine) (Propyl-8, Pierce

Chemical Co.).
61.4 METHOD
In this procedure the acrylic acid and methacrylic acid groups in acrylic
copolymers are first propylated using dimethyl formamide dipropyl acetal then this
product pyrolysed according to the following scheme:
CH 3 R CH 3 R
I
C - CH 2 - -
I
C - CH 2 -
propylation
-+
I
C - CH 2 - -
I
C - CH 2 -
7.10
I
c=o
I
c=o
I
c=o
Ic=o
LH3 n L m LH3 n
I
OC 3 H7 m
CH 3
I
pyrolysis
C =CH 2 + alcohols. alkenes. CO 2 , etc.
I
,=0
OCH 3
The resulting pyrolysis products (propyl acrylate and methacrylate) are separated
on a gas chromatograph and analysed by mass spectrometry.
316
61.5.1 Direct Pyrolysis.
Transfer 1 mg of polymer or an amount of latex or solution containing this mass

of polymer on to the pyrolysis filament. Remove any water or solvent by blowing with
hot air from a hairdryer. Insert the filament into the pyrolysis chamber and connect the
carrier gas and gas chromatographic apparatus. Heat the filament at 250°C for 15
seconds to ensure the removal of water, solvent or volatile additives. Pyrolyse the
polymer by heating the filament at 550°C for 15 seconds.
61.5.2 Propylation and Pyrolysis.
Transfer about 0.25 g of polymer or an amount of the acrylic latex or solution

containing this mass of polymer into a glass vial and dry by evacuation at 60°C for 15
hours. Seal the vial and inject by means of a hypodermic syringe 1 ml of the Propyl.8
reagent on the dried polymer film. Heat at 60°C for 16 hours then let the vial and
contents cool to ambient temperature. Transfer a smear of the gel or viscous solution
produced on to the pyrolysis filament and remove the bulk of the propylation reagent by
blowing with warm air from a hairdryer. Heat the filament for 15 second periods at
250°C in the stream of carrier gas until the chromatogram indicates the complete removal
of reagent residues and fmally pyrolyse at 550°C. Identify by mass spectrometry any
eluted compounds that were not observed in the original direct pyrogram or that occur to
a significantly greater extent in the pyrogram of the propylated polymer.
The presence of propyl acrylate or propyl methacrylate in the pyrogram of the
propylated polymer indicates that the original polymer contained acrylic or methacrylic
acid respectively.
The mass to charge (mle) ratio and relative abundance of the molecular and
fragment ions observed are listed below:
Propyl acrylate (C 6HIO0 2),Mn = 114

mle 55 73 29 42 41 43 27 85 31 39 59
relative abundance 100 46 15 11 9 7 6 55 5 4
mle 15 99 114
ralative abundance 1 1 0.2
Propyl methacrylate (C 7H120 2), Mn = 128

mle 41 69 43 87 39 42 27 59 29 86 70
relative abundance 100 91 66 66 38 34 25 9 6 6 5
mle 31 38 88 26 99 13 128
relative abundance 4 3 3 2 2 2 2
By this procedure, copolymerised acrylic or methacrylic acid has been identified

in terpolymers with (a) butyl acrylate and styrene (b) methyl methacrylate and ethyl
acrylate and (c) ethylene and propylene. A methyl methacrylate· methylstyrene· maleic
acid terpolymer, when examined by this propylation • pyrolysis procedure, yielded
dipropyl fumerate and a smaller amount of dipropyl maleate.
317
This method enables acrylic acid and methacrylic acid units to be determined in
acrylic copolymers in amounts down to 0.1 % with an accuracy of ±5%.
METHOD 62· DETERMINATION OF ACRYLIC ESTER GROUPS IN

COPOLYMERS. HYDRIODIC ACID REDUCTION· GAS
CHROMATOGRAPHY.41
62.1 SUMMARY
This hydriodic acid reduction - gas chromatography procedure enables acrylic

ester groups in copolymers to be determined in amounts down to 0.2%.
62.2 APPARATUS
Hewlett Packard 5756 gas chromatograph equipped with flame ionization detector
or equivalent. A stainless steel column, 10 ft D0-401 on 60-80 mesh Gas Pak WAB.
helium flow rate 10 mllmin with an inlet pressure of 65 psi. Injection port and detector
temperatures: 210 and 250·C respectively.
Column temperature I50oC.
62.3 REAGENTS
Spectrograde acetone, methyl ethyl ketone, hexane, I,I,2-trichloroethane and

isopropylbenzene (Eastmen Organic Chemicals).
Tetrahydrofuran (E.I. du Pont de Nemours) is distilled over triphenyl phosphite
and nitrogen to remove any water and butylated hydroxy toluene inhibitor. After
distillation, tetrahydrofuran is stored in amber bottles over thin strips of copper metal to
prevent the formation of peroxides.
Hydriodic acid (Fisher Scientific Company) is freshly distilled over hypopho-
sphorus acid and nitrogen. Only the 57% hydriodic acid azeotrope boiling at 127·C is
retained. The distillate is stabilised with hypophosphorus acid.
62.4 METHOD
A weighed portion of the polymer is dissolved or swollen in a mixture of glacial

acetic acid, molten phenol and acetic anhydride.
7.11
H H H R' H H H R'
I I I I I I I I
- C- C- - C- C- - + HI-- C - C - - C- C
I I I I I I I I
H Ph H C =0 H Ph H C =0
I I
OR OH
318
The mixture in then digested with hydriodic acid to produce alkyl iodides
corresponding to the acrylic ester groups present in the polymer.
The alkyl iodides up to butyl iodide is analysed by gas chromatography. The
method is calibrated against standard solutions of alkyl iodides and internal standard.
62.5.1 Zeisel Cleavage Reaction.
Approximately 200 mg of the dried polymer is placed in the reaction flask.

Figure 7.15. To that is added 10 ml of molten phenol, 5 ml of glacial acetic acid and 5 ml
of acetic anhydride to swell and dissolve the polymer and scavenge any water that might
be present. The reaction flask is then placed in a heating mantle held at 125°C until the
polymer is completely dissolved or sufficiently swollen to allow attack by the hydriodic
acid. While the sample mixture is heating, 5 ml ofa 1% w/v solution of 1, I ,2-trichloro-
ethane in isopropylbenzene is pipetted into the receiver which is then placed in a dry ice-
acetone bath. After the solution is obtained, the contents of the reaction flask are cooled
and 25 ml of hydriodic acid is added. The nitrogen flow rate is set at 10 mlImin and the
reaction flask placed in an oil bath at 132 ± 1°C. The position of the reaction flask placed
in the oil bath is extremely important. The reaction mixture in the flask was level with
the oil in the bath. Care is taken to prevent the refluxing mixture from reaching the
desiccant.
62.5.2 Analysis of Alkyl Iodides.
Periodically, 2 ul samples of the reaction products are removed from the receiver
and analysed by gas chromatography. Prior to taking a sample, the receiver is loosened
and the trapping solution shaken around the glass spiral to form a homogenous solution
of the alkyl iodides and the internal standard. Care is taken not to raise the delivery tube
above the liquid level in the receiver. The reaction is allowed to proceed until the ratio of
the longest chain alkyl iodide to the internal standard became constant. Details of the
determination of relative response factors and calculation of copolymer composition are
given below.
62.5.3 Determination of Response Factors.
An accurately known blend of the alkyl iodides and the internal standard (1,1,2-
trichloroethane) is prepared and analysed using gas chromatography. The areas of the
peaks in the chromatograms are determined and the response factors of the alkyl iodides
calculated using the equation:
where
K\ = response factor of the respective alkyl iodide
K,. = response factor of 1,1 ,2-trichloroethane (arbitarily set equal to 1.00)
319
"""
63",",
..I
t'I
I
'"
6"""
E
E
I I
00
t'I CoCI2
'"
J
t'I
DUSICANT
TI~20
I SEPTUM
~
E
E
3
E
0-
E
E
E 00
E 9",",
t'I
~
2",",
! I - - - - T 1~20
Figure 7.15. Apparatus for Zeisel cleavage of acrylic esters. From Anderson with permission. 41 American
Chemical Society.
WI = weight of the respective alkyl iodide in the calibration blend

Wx = weight of l,l,2-trichloroethane in the calibration blend
AI = area of the respective alkyl iodide peak
Ax = area of 1,1 ,2-trichloroethane peak
320
Response factors determined at two-week intervals were found to deviate. Best
results are obtained when response factors were determined just prior to each analysis.
62.5.4 Determination of Copolymer Composition.
Samples from the receiver are periodically removed through the rubber septum
and analysed using gas chromatography. The areas of the alkyl iodide and internal
standard peaks are determined and the copolymer composition calculated using the
following equation:
(K I) (AI) (Wx) (MWA (100))

% acrylate =
(Ax) (Wrs) (MW I )
where
KI = response factor of the respective alkyl iodide
AI = area of the respective alkyl iodide peak in the chromatogram
Ax = area of 1,1,2-trichloroethane peak in the chromatogram
Wx = weight of 1,1 ,2-trichloroethane added to the receiver
Wrs = weight of the sample used
MWa = weight of acrylate or methylacrylate being analysed for
MWI - molecular weight of the respective alkyl iodide
Duplicate determinations should agree within ± 3% relative.
In Table 7.33 is shown some results obtained by applying this method to a range
of acrylic polymers. The calculated recoveries are greater than 95%, for polymers
containing between 10% and 100% acrylic monomer. The method has 99% confidence
interval of 0.8. The presence of comonomers such as styrene, acrylonitrile, vinyl acetate,
acrylamide or acrylic acid does not change the recovery of acrylate or methacrylate
esters. Non-quantitative results are obtained, however, for polymers containing hydroxy-
propyl methacrylate.
This method enables methyl to butyl acrylate ester groups to be determined in

acrylate copolymers in amounts down to 0.2% with an accuracy of ± 3%.
METHOD 63 - DETERMINATION OF COMBINED VINYL ACETATE IN

VINYL-ACETATE-VINYLCHLORIDE COPOLYMERS. ISOTOPE DILUTION -
DERIVATIVE METHOD.42
63.1 SUMMARY
This isotope dilution method enables vinylacetate units to be determined in vinyl

acetate-vinyl chloride copolymers in amounts down to 0.2%.
321
Table 7.33 - Recovery of Alkyl Iodides from the Zeisel Cleavage of Acrylic Polymers'
Polymer Methyl Methyl Ethyl Ethyl Butyl Butyl

Acrylate % Methacry- Acrylate % Methacry- Acrylate % Methacry-
late % late % late %
33.7 33.0 32.7

(33.3) (33.3) (33.3)
2 33.6 33.4 31.9
(33.3) (33.3) (33.3)
3 19.5
(20.0)
4 50.1 30.5
(50.0) (30.0)
5 59.9 39.8
(60.0) (40.0)
6 29.7 29.8
(30.0) (30.0)
7 59.8 9.8
(60.0) (10.0)
8 19.9 19.8 19.8
(20.0) (20.0) (20.0)
9 30.1 30.0 29.8
(30.0) (30.0) (30.0)
10 29.9 29.6 39.7
(30.0) (30.0) (40.0)
11 60.1 30.1 9.5
(60.0) (30.0) (10.0)
From Anderson43 • American Chemical Society

• All values are the average of at least three determinations and are reported as % monomer found (%
monomer in polymer).
63.2 APPARATUS
A Packard Model 3303 liquid scintillation spectrometer for radioassays.

Erlenmeyer flasks, 125 ml.
63.3 REAGENTS
An aqueous solution of acetic 2 14C acid containing 0.1-1.0 millimole per gram is
prepared from acetic anhydride. Its specific activity of acetic anhydride was determined
by treating a portion with an excess of aniline to form acetanilide 14C which was
crystallized from water and assayed in dioxane-naphthalene scintillator solution.
Methyl ethyl ketone reagent grade, is stirred with calcium hydride and distilled.
Sodium hydroxide, 1 molar, is prepared in 9: 1 methanol: water.
o-Phenylene diamine is crystallized twice from water with the aid of activated
charcoal.
The scintillator solution is prepared by dissolving naphthalene (200 grams) PPO
(2,5-diphenyloxazole) (14.0 grams) and POPOD (1,4 bis-2-(5-phenyloxazolyl)benzene)
(0.06 gram) in scintillation grade dioxane, diluting to 2 litres and adding 200 ml of
methanol.
322
63.4 METHOD
In this method a known amount of methyl labelled acetic 2}4C acid is added to a
solution or suspension of the resin in methyl ethyl ketone and the ester is hydrolyzed with
sodium hydroxide. The major portion of the sodium acetate 14C is isolated and converted
to 20methylbenzimidazole-methyl 14C by means of the Phillips reaction78 with 0-
phenylene diamine.
7.12
The product is radio assayed following addition of a scintillator and the vinyl
acetate content calculated from the determined specific activities.
A specimen containing approximately one millimole of vinyl acetate, but not

exceeding 4 grams, is weighed into a 125 ml Erlenmeyer flask and 40-50 ml of distilled
methyl ethyl ketone is added. The solvent is added carefully so as to prevent agglo-
meration of the resin. A weighed aliquot of the solution of labelled acetic acid in water,
containing 0.10-1.15 millimole of the acid is then added, after which 5 ml of the sodium
hydroxide solution is introduced. The stoppered flasks are swirled with periodic
immersion in an oil bath at 60°C to redisperse any precipitated resin and then placed in
the bath for 16 hours.
The contents of the cooled flasks are transferred to a 125 ml separatory funnel and
the flasks are rinsed with two 15 ml portions of water. The funnel is shaken vigorously
and the lower phase is removed to a 250 ml beaker. After evaporation of the contents of
the beaker to dryness, the sodium acetate 14C is extracted from the residue with 10-12 ml
of hot methanol and the solution is decanted into a 50 ml beaker. The methanol is then
carefully evaporated on a water bath.
The derivative is prepared in a thick-walled glass (polymerization) tube to which
an excess of approximately 10% (130 mg) of purified o-phenylene diamine is added
initially. The residue in the 50 ml beaker is dissolved in 3-5 ml of water and the solution
is transferred to the tube, to which 1.5 ml of ION hydrochloric acid is added. The tube is
then sealed, enclosed in a protective sleeve of glass cloth and heated one hour in an oven
at 180°C. After cooling, the contents of the tube are transferred to a 30 ml beaker and a
slight excess of 1: 1 ammonium hydroxide is added with vigorous stirring to precipitate
the 2-methylbenzimidazole. The beaker is then placed in an ice bath for 30-60 minutes.
The crude derivative is collected on qualitative filter paper cut to fit a micro (1
cm) Buchner funnel and washed with 2-3 ml of ice water. The compound is then
transferred to a 30 ml beaker, dissolved in 10-12 ml of water by heating to incipient
boiling, and the solution is decolorized with 30-35 mg of activated charcoal. The
suspension is stirred briefly then filtered as before to remove the charcoal. The filtrate is
transferred to a 30 ml beaker, which is placed in an ice bath and the solution is stirred
323
vigorously with a glass rod to initiate crystallization. After 30-60 minutes, the purified
derivative is collected by filtration, washed with 2-3 ml of ice water and dried in vacuum
over phosphorus pentoxide. The product is assayed by weighing 4-6 mg into a counting
vial and adding 15 ml of scintillator solution, or by weighing a larger amount into a 50 ml
volumetric flask and removing aliquots.
Vinyl acetate, % by weight = (WI @o - 1) 8.609

SI Ws
where
WI = millimoles ofacetic-2.l 4C acid added
So = specific activity of the acetic-2- 14C acid, uCilmmole
SI = specific activity of the 2-methylbenzimidazole, uCilmmol
Ws = weight of sample, grams
This method is capable of determining down to 0.2% vinyl acetate units in vinyl
acetate-vinyl chloride copolymers with an accuracy of ± 5%. A relative standard
deviation of approximately 0.48% was obtained for a copolymer containing 11.1 % of
vinyl acetate.
METHOD 64 - DETERMINATION OF ETHERIFICATION LEVELS IN

ACRYLAMIDEINTERPOLYMERS.ALCOHOLEXCHANGE-GAS
CHROMATOGRAPHY.43
64.1 SUMMARY
This alcohol exchange gas chromatographic method is applicable to the

identification and determination of etherifying alcohols present in thermosecting
acrylamide interpolymers of the type:
R 7.13
- CH 2 - ~H - ] - fcH2 - ~ 1-
l
[
C =° C = ~
I x I Y
NHR" O,R'
where
R=HorCH3
RI = H, CH3, C2HS C4H9 or CsH17
Rll = H,CH20C4H9 or CH20H
324
64.2 APPARATUS
Gas chromatographic separations are performed using a Hewlett-Packard 5760

gas chromatograph or equivalent equipped with flame ionization detectors. A 12 ft x
0.125 in o.d. stainless steel column is packed with 20% Carbowax 20 M on 60-80 mesh
Gas Pak WAB. Helium flow rate: 20 mVmin with an inlet pressure of 65 psi. Injection
port and detector temperatures: 220 and 240°C respectively. The column temperature:
held at 105°C until the elution of the pentanol peak, then programmed from 105 to 205°C
at 10°C/min and held until the 2-ethylhexanol eluted.
The glass assembly used to carry out the alcohol exchange reaction consists of a
50 ml erlenmeyer flask equipped with a 14/20 joint topped with a Liebig condenser with
a 14/20 joint. .
64.3 REAGENTS
Reagent grade 2-ethylhexanol, n-butanol, n-pentanol, butyl cellosolve and acetone

(Eastman Organic Chemicals).
Paraformaldehyde, p-toluenesulfonic acid and propionamide (Eastman Organic
Chemicals) used without further purification.
64.4 METHOD
Cast films of the acrylamide interpolymer are reacted with an alcohol, ego octyl
alcohol, to exchange with etherifying alcohols present in the polymer backbone as
follows:
7.14
- CH 2 - CH
-
I
C
I
= ° + C4H90H
NHCH 20OC eH17
The etherifying alcohol content of the digest, in this case butanol, is determined
by gas chromatography. The method is calibrated against standard solutions of the
etherifying alcohol and an internal standard.
64.S.1 Drying of Polymer.
All acrylamide interpolymer samples are initially diluted to 10% nonvolatile resin
with acetone. Thin films of the resin solutions are uniformly cast on clean glass plates
using a smooth glass r9d and immediately dried at 50°C under 5 cm Hg for 2.5 hours to
remove all solvents. The film thickness of the dried polymers is kept below 0.5 ml to
ensure complete solvent removal. The films are removed from the glass plates using oil
free razor blades and stored in vials.
325
64.5.2 Alcohol Exchange Reaction.
The etherifying alcohols present in the polymer backbone are exchanged

according to the above reaction. Approximately 200 mg of dried polymer is placed in a
reaction flask along with 20 ml of 2-ethylhexanol. To this solution 5 ml of a 0.4% w/v
solution of p-toluenesulfonic acid in 2-ethylhexanol and 5 ml of a 1% w/v solution of n-
pentanol in 2-ethylhexanol are added. A magnetic stirring bar is placed in the flask, the
condenser is fitted to the flask and placed on a magnetic stirrer hot plate. Heating and
stirring are employed until a vigorous reflux begins. The reaction is allowed to continue
for four hours with the reaction flask being checked periodically to ensure constant
refluxing. After the reaction period is complete, the reaction mixture is allowed to cool to
room temperature. The condenser is thoroughly washed with fresh 2-ethylhexanol to
wash all products into the reaction flask. After allowing total diainage from the
condenser, the reaction flask is stoppered until gas chromatographic analysis.
64.5.3 Analysis of Exchanged Alcohols.
Determination of response factors - an accurately known blend of the etherifying

alcohols and internal standard (n-pentanol) is prepared and analysed by gas
chromatography. The areas of the peaks in the chromatograms are determined by
triangulation and the response factors of the etherifying alcohols calculated using the
following equation:
ilY,)(AJ (KJ
K, = (Wx) (AI)
where
KI = response factor of etherifying alcohol,
Kx = response factor of n-pentanol (arbitrarily set equal to 1.00)
WI = weight of respective etherifying alcohol in the calibration blend
Wx= weight of n-pentanol in the calibration blend
AI = area of respective etherifying alcohol peak
Ax = area of n-pentanol peak
Response factors determined at two-week intervals were found to deviate. Best

results were obtained when response factors were determined just prior to analysis.
A 2 ul sample of exchanged alcohols is removed from the reaction flask and is

analysed by gas chromatography. Prior to sampling, the reaction mixture is thoroughly
shaken to ensure uniform composition. The areas of the etherifying alcohols and internal
standard peaks are determined by triangulation and the moles of etherifying alcohol
calculated using the following equation:
326
where
MA = moles of etherifying alcohol per gram of dried polymer
AA = area ofn-pentanol peak
Wx = weight ofn-pentanol added to flask
WA= weight of dried polymer added to flask
MWA = molecular weight of etherifying alcohol
Each reaction mixture is analysed in duplicate and the average value used for
further calculations. Duplicate determinations do not vary by more than ± 2% relative.
99.7% recovery was obtained with this procedure.
The moles of acrylamide present in the polymer are determined from the nitrogen
content of the dried polymer. The acrylamide content is calculated using the following
equation:
(%N)
Ma = (14.01) (100)
where
M. = moles of acrylamide per gram of dried polymer
14.01 = molecular weight of nitrogen
%N = percent nitrogen in dried polymer.
The percent etherification of the acrylamide in the polymer may be calculated as

follows:
% etherification =
where
MA = moles of etherifying alcohol per gram of dried polymer
Ma = moles of acrylamide per gram of dried polymer
The total etherification is calculated by adding the % etherification due to all

etherifying alcohols.
The level of alcohol obtained during the exchange reaction of acrylamide is
correlated with data obtained using Zeisel cleavage of the alkoxy groups. These data are
summarised in Table 7.34. Comparable results are obtained using both procedures,
however, the Zeisel cleavage reaction will also cleave ester linkages as well as ether
functionalities. This presents no problem with polymers which do not contain ester
groups. In systems employing both butyl esters and butyl ethers the Zeisel cleavage
reaction gives a total O-C4H9 content in the sample. Alcohol exchange, on the other
hand, will cleave only the butyl ether groups in the sample. By subtracting the alcohol
exchange data from that obtained from Zeisel cleavage, one can assess the relative
amounts of alkyl ester and alkyl ether in the sample.
327
Table 7.34 - Correlation of Alcohol Exchange and Zeisel Cleavage
Sample Percent Butylated Acrylamide"
Alcohol Exchange Zeisel Cleavage
14% Acrylamide 100 101

23% Acrylamide 101 100
From Anderson43 • American Chemical Society

I Based on experimentally determined butoxy and nitrogen content
328
CHAPTER 7.3
DETERMINATION OF ELEMENTS
Methods 65 - 89
METHOD 65 - DETERMINATION OF IRON, TITANIUM AND ALUMINIUM

CATALYST RESIDUES INPOLYALKENESAND POLYALKENE
COPOLYMERS. ASHING - SPECTROPHOTOMETRIC PROCEDURE.
65.1 SUMMARY
Most of the published work on the detennination of functional groups, not

unexpectedly, has been carried out on copolymers. This is because the determination of a
functional group that is specific to one of the copolymer constituents is the key to the
determination of the monomer ratios in the copolymer.
The method describes procedures for the determination of trace amounts of titan-
ium, aluminium and iron in polyolefins. Analysis of a 5 g sample enables aluminium,
iron and titanium to be determined in amounts down to I ppm with an accuracy of ± I
ppm.
65.2 APPARATUS
Muflle furnace - maximum operating temperature 900°C.

Silica crucibles - 50 cm3 capacity
Visible spectrophotometer
Standard volumetric glassware.
65.3 REAGENTS
Potassium hydrogen sulphate, AR grade.

Sulphuric acid, 0.5% and 50010 v/v.
Tiron solution - 4 g of 1.2 dihydroxybenzene, 3:5 sulphonic acid sodium salt in
100 m1 distilled water.
Buffer solution - pH 4.7 acetic acid/sodium acetate. Dissolve 136 g of
CH3COONa3H20 in 1 cm3 of water. Dilute 57 cm3 of glacial acetic acid to 1 cm3 with
water. The pH 4.7 buffer solution is prepared by mixing equal volumes of these two
solutions.
Sodium hydro sulphite - solid AR grade.
Ammonia solution - mix equal volumes of 0.880 ammonia and water.
Potassium titanyl oxalate - pure grade.
329
Aluminon solution - dissolve each of the following reagents in a minimum
volume of distilled water; 7 g ammonium acetate AR grade, 2.5 cm3 concentrated
hydrochloric acid, AR grade, 0.2 g aluminon reagent, 0.5 g gum acacia. Transfer the
solutions in the above order to a 500 cm3 standard volumetric flask and dilute to the mark
with distilled water.
Aluminium powder - AR grade
Thioglycollic acid - 98% AR grade.
Ammonia - specific gravity 0.830, AR grade.
Iron wire - AR grade.
65.4 METHOD
Polymer samples are ashed to remove organic material. The ash residues are
fused with potassium hydrogen sulphate to effect solution of the metals. The resulting
ash in dissolved in hot water containing sulphuric acid and diluted to a standard volume.
Suitable aliquots of the aqeuous solutions are reacted with organic reagents under
controlled conditions, ie. titanium is determined spectrophotometrically with "Tiron",
aluminium is determined spectrophotometrically by the "Aluminon" procedure and iron
is determined spectrophotometrically by a procedure using thioglycollic acid.
Weigh accurately about 5 g of polymer into a silica crucible and ignite the sample
in a muffle furnace. Allow the temperature to increase gradually to 800·C over a period
of 4 hours, maintain this tempemture for 1 h.
Remove the crucibles from the muffle furnace when cold and add 5 g of fused
potassium hydrogen sulphate. Heat the mixture over a bunsen burner until a clear melt is
obtained, cool and dissolve in 25 cm3 of hot water containing 1 cm3 of 50% w/v sulphuric
acid. Make the solution up to 100 cm3• Carry out a blank under identical conditions
omitting the sample.
65.5.1 Titanium.
Pipette an aliquot of the test and blank solutions (maximum 35 cm3) into two
sepamte 50 cm3 standard volumetric flasks. If the volume added is less than 35 cm3 then
adjust the volume to 35 cm3 • Add 5 cm3 of Tiron to each flask and neutralize to Congo
red paper with 50% ammonia solution. Add 5 cm3 of sodium acetate-acetic acid buffer
solution (PH 4.7) and dilute to 50 cm3 with distilled water.
Transfer the coloured solutions to 1 cm cells and add 5 mg of sodium
hydrosuiphite, mix with a glass rod. Immediately measure the optical density of the
sample solution against the blank solution in the comparison cell at a wavelength of 41 0
nm. Read off the titanium content of the solution from the calibmtion graph and calculate
the titanium content of the original sample.
65.5.2 Aluminium.
Pipette an aliquot of the test and blank solutions (maximum 20 cm3 ) into two
sepamte 50 cm3 standard volumetric flasks. If the volume taken is less than 20 cm3 adjust
the volume to 20 cm3 with distilled water. Add 20 cm3 of Aluminon reagent and immerse
330
the flasks in a boiling water bath for 10 min to allow the colour to develop. Cool the
flasks and dilute to 50 cm3 with distilled water.
Measure the optical density of the sample solution against the blank solution in
the comparison cell, using the spectrophotometer at a wavelength of 535 mu in 1 cm
cells. Read off the concentration of aluminium from the appropriate calibration graph.
Calculate the aluminium content of the original sample. The Aluminon reagent solution
must be ,discarded when the optical density of the blank solution exceeds 0.09 compared
with distilled water.
65.5.3 Iron.
Transfer an aliquot of the sample and blank solutions (maximum 40 ml) into two
separate 50 cm3 standard volumetric flasks and add 0.2 cm3 ofthioglycollic acid.
Adjust the volume of the solutions to 40 cm3 with distilled water and add 5 cm3 of
0.880 ammonia. Check that the solution is alkaline to litmus and dilute to 50 cm3 with
distilled water. Mix thoroughly and measure the optical density of the sample solution
versus the blank solution in the comparison cell at a wavelength of 535 mu using 4 cm
glass cells.
Read off the iron content of the sample solution from the calibration graph and
calculate the iron content of the original sample.
Ti or Al or Fe ppm = Mx 100
WxV
where
M = weight (microgram) of titanium or aluminium or iron found from calibration
graph.
W = weight (g) of sample taken for analysis
V = volume (cm3) of 100 cm3 of ash solution taken from colour development.
65.5.5 Calibration Procedure for Determination of Titanium.
Into six 50 em3 standard volumetric flasks pipette the following volumes of
standard 5 ug/ cm3 titanium solution.
Oml lO cm3 20 cm3 25 cm3

o 50 100 125 ug Ti
Add the required volume of distilled water to take the volume of each solution up
to 35 cm3• Add 5 cm3 of Tiron reagent and neutralize to Congo red paper with 50%
ammonia solution, add 5 cm3 of pH 4.7 acetic acid/sodium acetate buffer solution and
dilute to the mark with distilled water.
Transfer the solutions to 1 cm cells and read off the optical density at a
wavelength of 41 0 om using the solution containing no titanium as the reference solution.
Plot a graph of optical density against ug of titanium contained in the 50 em3 standard
volumetric flasks.
331
65.5.5 Calibration Procedure for Determination of Aluminium.
Into seven sets of 50 cm3 volumetric flasks pipette the volumes of 7.5 ug/ cm3
aluminium solution shown below and also 2 cm3 of 5 ug 1 cm3 titanium solution (ie. 10
mg Ti). Take the seven flasks comprising set 1. Add to each flask sufficient distilled
water to make the volume up to 20 cm3• Add 20 cm3 Aluminon reagent and immerse the
seven flasks in a boiling water bath for 10 min to allow the colour to develop. Cool the
flasks under running water and dilute to 50 cm3 with distilled water and mix well.
o 1 2 5 10 15 20 30cm3
o 7.5 15 22.5 30 67.5 90 135 ug ml
Measure the optical density at 535 nm of the solution in 1 cm cells against the
aluminium and titanium free reagent blank solution in the comparison cell. Plot a graph
of ug aluminium present in the 50 cm3 solution versus determined optical density.
Repeat these operations six times using the same volumes of aluminium standards but
using 0.5, 10, 20 and 25 cm3 of the 5 ug/ cm3 titanium standard. Plot the seven
aluminium calibration graphs and indicate on each graph the constant amount of titanium
(micrograms) in each calibration solution (ie. between 0 and 125 ug of titanium).
Recalibrate the procedure each time a new batch of Aluminon reagent is used in the
analysis.
65.5.6 Calibration Procedure for Determination of Iron.
Pipette 10 cm3 of the 100 ug/ cm3 iron solution into a 100 cm3 standard
volumetric flask and dilute to the mark with 0.2 nitric acid solution, mix thoroUghly.
This solution contains 10 ug/Fe/ cm3•
Into six 50 cm3 standard volumetric flasks pipette the following volumes of 10
ug/ml iron solution.
o I 2 5 10 15 cm3
o 10 20 50 100 150ugFe
Add the required volume of 0.2 M nitric acid solution to make the volume of each
solution 40 cm3• Add 5 cm3 of 0.880 ammonia solution and check that the solution is
alkaline to litmus paper. Dilute to 50 cm3 with distilled water and mix thoroughly.
Measure the optical density of the solutions. Transfer the solutions to 4 cm glass cells
and read off the optical density at a wavelength of 535 nm using the solution containing 0
ug iron as the reference solution. Plot a graph of optical density against ug of iron present
in the 50 cm3 standard volumetric flask.
This method is capable of determining down to I ppm of aluminium, iron and

titanium in polyolefins with an accuracy of ± 1 ppm.
332
METHOD 66 - DETERMINATION OF ALUMINIUM AND VANADIUM
CATALYST RESIDUES IN POLYALKENES AND POLYALKENE
COPOLYMERS. ASHING - SPECTROPHOTOMETRIC PROCEDURE. 44
66.1 SUMMARY
This spectrophotometric procedure determines aluminium and vanadium catalyst

residues in polyolefins and their copolymers in amounts down to 20 ppm (aluminium)
and 1 ppm (vanadium).
66.2 APPARATUS
Glass chromatographic column - lOin x 1 in.

Muffle furnace - capable of maintaining a temperature of 600°C.
Platinum dish, 75 mm in diameter.
66.3 REAGENTS
Toluene, AR.
Dowex 50 W x 8 cation exchange resin, 50 - 100 mesh.
Digest 5 g Dewex in 100 cm3 of 5M sulphuric acid transfer the slurry to the
column to give a resin-bed depth of 50 mm. Run off the sulfuric acid until the level of
the liquid falls to 1 to 2 mm from the top of the resin bed. Wash the resin bed with 2.5 M
sulfuric acid until the effluent from the bottom of the column is colourless leaving 1 to 2
mm depth of liquid on top of the resin bed. Add 20 cm) of a 0.25 M sulfuric acid - 1%
hydrogen peroxide solution as described above. When the last of the sulfuric acid-
hydrogen peroxide solutions has been added, turn off the column tap.
Hydrochloric acid, AR, 38% sp. gr 1.19.
Hydrofluoric acid, AR, 40% sp. gr. 1.13.
Hydrogen peroxide, AR, 30%, 100 vol.
Nitric acid, AR, 65% sp. gr. 1.4.
Sulfur, cp crystals.
Sulfuric acid, AR, 98% sp. gr. 1.84.
Sulfuric acid,S M and 2.5 M.
Sulfuric acid, 0.25 M hydrogen peroxide 1% solution. Add 3.3 cm3 of hydrogen
peroxide (30%) to 25 cm3 of 1M sulphuric acid and dilute to 100 ml.
66.4 METHOD
The sample is ignited and the ash dissolved in acids. Hydrogen peroxide is added
and the solution passed down a cation exchange column. Vanadium, present as a
pentavalent peroxide complex, passes unadsorbed down the column and is determined
photo-absorptiometrically. Aluminium is removed from the column by elution with a
more concentrated acid and determined by a complexometric titration.
333
66.5.1 Determination of Vanadium.
Weigh 10 g of sample into a platinum dish. Dissolve 1 g of sulfur in 20 cm3 of

toluene and add to the contents of the dish. Evaporate off the toluene.
Ignite the sample over a bunsen flame until fumes are no longer evolved, transfer
the dish to a muffle furnace at 600°C until all the carbonaceous material has been
removed.
Treat the ash with 5 cm3 of water, 5 cm3 hydrofluoric acid, 5 drops of nitric acid
and 12 drops of sulfuric acid (98%) taking care to moisten the inner wall of the dish
completely. Evaporate first on a water bath and then on a hot plate to dryness.
Redissolve the sample in 1 cm3 of hydrochloric acid, 5 cm3 of water and 2.4 cm3 of2.5 M
sulfuric acid, taking care to moisten the inner wall of the dish completely. Warm on the
water bath until all the hydrochloric acid has been removed. Transfer the sample to a 25
cm3volumetric flask containing 1 cm3 of30% hydrogen peroxide and make up to 25cm3•
Transfer 10 cm3 of this solution to the ion exchange column. Allow the sample to pass
down the column at a flow rate of not more than 1 cm3/min. Collect the effluent when
the 10 cm3 aliquot has fallen to 1 to 2 mm from the top of the resin bed elute with 15 cm3
of sulfuric acid-hydrogen peroxide solution added at a flow rate of not more than I
cm3/min maintaining 1 to 2 mm depth of liquid on top of the resin bed. When the 15 cm3
of sulfuric acid-hydrogen peroxide solution have been added transfer the effluent, which
contains the vanadium, to the water bath and complete the vanadium determination as
described below.
Evaporate the contents of the vanadium extract first on a water bath and then on a
hot plate to dryness. Dissolve the vanadium in 1 cm3 of hydrochloric acid, 5 cm3 of water
and 1 cm3 of 1 M sulfuric acid. Heat the dish on the water bath until all the hydrochloric
acid is removed. Transfer the vanadium solution to a conical flask using 70 cm3 of water.
Complete the vanadium determination as described in the spectrophotometric
procedure described in Method 67.
66.5.2 Determination of Aluminium.
Elute the resin column with 25 cm3 of 2.5 M sulfuric acid at a flow rate of not
more than 1 cm3/min again always maintaining a 1 to 2 mm depth of liquid on top of the
resin bed. Collect the effluent, which contains the aluminium in a 250 cm3 beaker.
Evaporate first on a water bath and subsequently on a hot plate to dryness.
Dissolve the aluminium in about 50 cm3 of water and 3 drops of nitric acid by
boiling. Complete the determination of aluminium by the spectrophotometric procedure
as described in Method 65. Run a blank, taking care to use the same quantities of all
reagents as used in the determination.
This method describes a procedure for the determination of 20 to 250 ppm of

aluminium and more than 1 ppm of vanadium in polymer samples. Tin and zinc and
large amount of cobalt, nickel and lead interfere with the aluminium determination.
These interfering metals can be removed by a suitable modification of the basic
procedure.
334
METHOD 67 - DETERMINATION OF VANADIUM CATALYST RESIDUES IN
ETHYLENE - PROPYLENE RUBBER. ASmNG - SPECTROPHOTOMETRIC
PROCEDURE.""
67.1 SUMMARY
This spectrophotometric procedure determines vanadium catalyst residues in

amounts down to 2 ppm in ethylene-propylene rubbers.
67.2 APPARATUS
Visible spectrophotometer with 1 and 5 cm cells.
67.3 REAGENTS
Standard vanadium solution. Prepare 5 ug per cm3 or 50 ug per cm3 from

ammonium metavanadate.
3,3'-diaminobenzidine tetrachloride solution. 0.5% w/v store at 4°C under
nitrogen.
Phosphoric acid, 85%.
Nitric acid concentrated.
Potassium, pyrosulphate, AR solid.
67.4 METHOD
The polymer is ashed then dissolved in nitric acid - phosphoric acid. 3,3'diamino-
benzidine tetrachloride is added and the colour produced evaluated spectrophoto-
metrically at 470 nm. Calibration is achieved against similarly prepared solutions of pure
vanadium.
Ash a 10 gram sample of elastomer solution in a platinum crucible by c~ on

a hot plate followed by heating over a meker burner. Add 10 cm3 of water and 2 cm of
nitric acid then transfer to a 100 cm3 beaker. To ensure complete removal of vanadium,
melt a gram of potassium pyrosulfate in the crucible, cool, then wash the salt into the
beaker with hot water. Evaporate to about 10 cm3 and transfer the contents to a 25 cm3
volumetric flask. Before diluting to the mark, add 1 cm3 of 85% phosphoric acid and 1
cm3 of3,3'diaminobenzidine tetrachloride solution. Measure the absorbance at 470 nm in
a suitable cell, using a reagent blank, after standing 15 min in the dark.
67.5.1 Calibration.
Add suitable aliquots of standard vanadium solution to 100 cm3 beakers which
contain 50 cm3 0f water, 2 cm3 of nitric acid and I gram of potassium pyrosulfate.
Reduce the volume to about 10 cm3 by boiling and transfer the contents to a 25 cm3
volumetric flask. React with phosphoric acid and 3,3'-diaminobenzidine tetrachloride
335
solution as described for sample analysis. For vanadium contents from 5 to 50 ug
measure the absorbance in a 4 cm cell using a reagent blank.
Data in Table 7.35 shows good agreement between data obtained by this method
and neutron activation analysis for a range of ethylene-propylene copolymer samples.
67.7 DISCUSSIONOFRESULTS
This method is capable of determining down to 2 ppm vanadium in ethylene

propylene elastomers with an accuracy of ± 5%.
METHOD 68 - DETERMINATION OF SILICA CATALYST SUPPORT IN HIGH

DENSITY POLYETHYLENE. INFRARED SPECTROSCOPY AND NEUTRON
ACTIVATION ANALYSIS.45
68.1 SUMMARY
Three methods are described for the determination of down to 50 ppm of silica
catalyst supports in high density polyethylene. These methods involve direct ashing and
weighing, infrared spectroscopy and neutron activation analysis.
68.2 APPARATUS
Quartz bowl.
Meker burner.
Buehler mold assembly.
68.3 METHODS
Ashing. The polymer is ignited at 650°C and the residual silica weighed.
Infrared spectroscopy. Films of the polymer are examined at 1118 and 470 cm'!.
The method is calibrated against known blends of silica in high density polyethylene.
Neutron activation analysis. Polymer powder is irradiated with neutrons. Silicon

is activated by the reaction 28Si(N,p)28AI. The concentration of silicon is measured by
counting the 1.78 MeV gamma - ray emission from the decay of 28Al. A silicon standard
is used for calibration.
336
Table 7.35 - Vanadium (ppm)
Sample Dry Ashing Neutron Activation
A 10.2 9.9 ± 0.2

B 14.0 14.1 ± 0.1
C 14.6 15.6 ± 0.3
D 0.5 0.14 ± 0.01
E 13.0 14.S ± 0.2
F 0.9 0.27 ± O,ol
G 15.2 IS.8 + 0.3
H IS.2 17.9 ± 0.3
68.4 EXPERIMENTAL PROCEDURES
68.4.1 Ashing Technique.
Productivity by the ashing technique is determined by weighing approximately

100 g of polymer into a dry quartz bowl, which is then placed on a small burner, and the
sample gently ignited. After most of the polymer is burned away, the bowl is set in a
mufile furnace at 650°C to oxidize residual carbon. Finally, the bowl is allowed to cool
in a desiccator and then weighed.
68.4.2 Infrared Method.
Polymer fllms are prepared on a Buehler mold assembly by placing 0.52 g of the
sample between aluminium foil disks in a I mm spacer. The mold is heated to 160°C, the
pressure set to 6000 psig and the sample then cooled to 35°C by means of an air stream.
The film is mounted on a holder and the thickness is measured to the nearest 0.01 mm
with a micrometer.
All spectra obtained on the infrared spectrometer were taken under the following
conditions: 100 scans, 4 em'· resolution, boxcar apodization TGS detector.
The absorbance bands at 1118 and 470 cm'· are used to determine the quantity of
silica in polyethylene.
68.4.3 Neutron Activation Analysis.
Approximately I - 2 g of polyethylene powder is irradiated with neutrons

obtained with a 500 ke V neutron activator accordin~ to the following reaction:
3H(D,n)"He. Silicon is activated by the reaction 28 Si(N,p) 8AI, and the concentration of
silicon is then measured by counting the 1. 78 MeV gamma-ray emission from the decay
of 28AI. A Conostan 5000 ppm Si standard is used for instrument calibration. Two 3 in
sodium iodide detectors are used to measure the 1.78 MeV gamma-rays.
68.S TYPICAL RESULTS
Infrared method Thicker fllms (500 - 1000 um) of high density polyethylene
yield spectra in which the presence of down to 0.01 % silica can be detected. The bands at
about 1118, 800, and 470 em'· indicate silica. The absorbance bands at approximately
1118 and 470 em'· may both be used to determine the quantity of silica in polyethylene.
337
The standard base line technique of determining absorbance was used in both cases. A
further infrared method involves the direct measurement of the absorbance of 470 cm"\
band of silica. The 470 cm"\ absorbance band of silica is in the region of the infrared
spectrum which is relatively free of polyethylene absorbance bands. The absorbance
value of the 470 cm"\ band is calculated for each standard by use of the peak heifht
determined by means ofthe base line technique between minima near 350 and 580 cm" .
Results obtained for polyethylene samples containing residual silica support of
three different catalysts by infrared (470 cm"\ method), neutron activation analysis,
ashing and weight are shown in Table 7.36. Infrared results differ from neutron
activation analysis results by 0 - 5% while ashing and weighing techniques differ from
neutron activation analysis results by 5 - 21 % and 5 - 28% respectively.
These methods are capable of determining down to 50 ppm of silica in high

density polyethylene with an accuracy of ±2 to 6%.
METHOD 69 - DETERMINATION OF SODIUM NEUTRALIZING AID IN mGH

DENSITY POLYETHYLENE AND POLYPROPYLENE. EMISSION AND
FLAME PHOTOMETRIC PROCEDURES.
69.1 SUMMARY
This emission and flame photometric procedure determines sodium in amounts

down to 0.2 ppm.
69.2 APPARATUS
Flame photometry.
Flame photometer.
Platinum dish, 100 ml.
Muffle furnace.
Emission spectrography.
Emission spectrograph.
Platinum dish.
Muffle furnace.
69.3 REAGENTS
Flame photometry.
Standard sodium solution, 10 ug/cmJ sodium in deionized water.
Sulphur, (Specpure).
Magnesium AC dope (magnesium in salt of long chain fatty acids) in Xylene (36
Nitric acid, Nil Analytical reagent grade.

Filter paper, Whatman No. 42 or equivalent.
338
Table 7.36 - Catalyst Productivity for Some Test Samples
Sample IR at 21.27 Micron NNA Ashing at 6SO"C Weight
I" 1893 (J.3t 1923 (4.9) 1923 (4.9)

2" 4165 (0) 4165 4545 (9.1) 3571 (14.3)
3b 1759 (2.9) 1709 2222 (30.0) 2007 (17.4)
4' 1727 (5.4) 1825 2000 (9.6) 2000(9.6)
5' 2207 (3.5) 1288 2778 (21.4) 2941 (28.5)
From Battiste et al45 • American Chemical Society

I Catalyst A. b Catalyst B. ' Cabosil 517. d Values in parentheses are percent deviation from NAA.
69.4 METHOD
Flame photometry. The polymer is ashed in platinum with sulphur and a xylene
solution of magnesium AC dope. A nitric acid solution of the residual ash is analysed by
flame photometry. Calibration is achieved against standard solutions of sodium in nitric
acid.
Emission spectrography. The polymer is ashed as above and the ash blended with
carbon containing 0.1 % palladium prior to emission spectrographic analysis for sodium.
Calibration is achieved against known blends of sodium carbonate in magnesium
sulphate.
69.5.1 Sample Ashing.
Ten grams of sample are weighed into a clean, dry 100 ml platinum basin, and 1 g
sulphur (Specpure and 5 ml of a solution in xylene of magnesium AC dope magnesium
salt oflong chain fatty acids) (35 gIlitre) added.
The dishes are heated gently over a bunsen until the xylene has evaporated and the
temperature then raised until the polymer starts to decompose. Careful heating is
maintained such that the vapours never ignite and heating is continued until all light
volatile matter has been removed. The dishes are transferred to a cold electric muffle and
ashed overnight at 500°C then weighed.
69.5.2 Flame Photometric Procedure.
Nitric acid solution (25 cm3 of 1 M) is added to the ash in the platinum crucible
which is then heated to 70 - 80°C and filtered through a Whatman No. 42 filter paper into
a 100 cm3volumetric flask. The residue on the filter paper is washed three times with 15
cm3 of hot 1 M nitric acid. The flask is cooled and made to 100 cm3• A blank solution is
prepared by passing the same volume of hot nitric acid through a Whatman No. 42 filter
paper and making up to 100 cm.3
The procedure is calibrated against a 5 ppm standard sodium solution. The
sodium concentration of the sample is obtained as:
Sodium (ppm) = Percentage deflection x 5 x 100 x F

100xW
339
where the percentage deflection is the difference between % sample and % blank.
deflections, W is weight of sample taken, and F is a calibration factor.
69.5.3 Emission Spectrography.
The ash is mixed with twice its weight of carbon powder containing 0.1%
palladium. Two electrodes were filled with the ash/carbon mixture and each is burned as
the cathode of an electric are under the conditions described below:
Electrodes: sample - RingsdorfRW v, 4.6 mm diameter with cup size

0.125 in o.d., 0.0625 in Ld. and depth 8 mm.
counter RingsdorfRW v, 4.6 rom diameter, plane ends.
Analytical gap 6mm
Excitation unit Hilger FF 402 rectifier unit, output 230 volts D.C., 15 amps
maximum.
Arc current 8 amp
Preburn None
Burn and exposure 3 min.
Spectrograph Hilger large quartz, E 742, prism marked to admit light
from cathode tip and 5 mm of arc column.
Wavelength range om 245 to 350.
Slit width, u 10.
Condensing lens Hilger F 1025,2 cm from slit.
Sector None.
Filter Hilger F 1534, nominal densitive, 0, 0.6 and 12, with step
height 1.2 rom each.
Photographic emulsion Kodak B 10 or equivalent.
Developer Kodak D 19 b, or equivalent diluted to 113 strength, 20°C, 3
min.
Plate calibration Step filter.
Line pair Na 3303.0, Pd 2763.1.
Spectrograms are recorded on photographic plates and the log spectral line
intensity ratio Na 3303.01Pd 2763.1 evaluated. Emulsion calibrations of the two
wavelengths are established using the microphotometer transmittance data from adjacent
steps of the spectrograms.
Concentration calibration is carried out by compounding standard mixtures
containing 10%, 3.16%, 1%,0.32% and 0.1% sodium carbonate in magnesium sulphate.
Spectral line intensity ratios corresponding to these sodium concentrations are obtained
using the same spectrographic procedure as for the samples. An analytical curve is
established relating log intensity ratio and log concentration for the standard and by
interpolation of the sample log intensity ratios in this curve the sodium concentration in
the ash is obtained.
The concentration of sodium in the polymer is obtained by multiplying the
sodium concentration in the ash by the ratio of ash weight to sample weight.
340
The results in Table 7.37 show clearly that flame photometry following dope
ashing at 500°C gives a quantitative recovery of sodium relative to results obtained by a
non-destructive method of analysis vis neutron activation analysis. Direct ashing without
an ashing aid at 500°C causes losses of 10% or more of the sodium whilst direct ashing at
800DC causes even greater losses.
These methods are capable of determining down to 0.2 ppm of sodium in

polyethylene and polypropylene with an accuracy of ± 5%.
METHOD 70 - DETERMINATION OF LITHIUM IN POLYALKENES AND

COPOLYMERS. ASHING-FLAME PHOTOMETRIC METHOD.
70.1 SUMMARY
This flame photometric method determines lithium neutralizing aid in polyalkenes

in amounts down to 0.2 ppm.
70.2 APPARATUS
Flame photometer.
Platinum dish, 100 mi.
Volumetric glassware.
70.3 REAGENTS
Lithium stock solution, 100 micrograms per cm3•

Dissolve 0.9219g lithium sulphate monohydrate in 1 M nitric acid and make up to
1 cm3 with 1 M nitric acid.
Nitric acid, 1 M solution.
Water, distilled or deionised.
Calibration solutions (a) 0 to 10 ppm Li, (b) 0 - 1 ppm Li.
Prepare standard solutions by diluting to 100 ml aliquots of the stock solution
using 1 M nitric acid.
70.4 METHOD
The polymer is ashed in platinum and a dilute nitric acid solution of the ash
analysed by flame photometry at 670.9 um.
341
Table 7.37 - The Effects of Modification of Ashing Procedure on the Flame Photometric
Determination of Sodium (sodium ppm)
By Flame Photometry
By Neutron By Emission Original (Ashed Dope Ash Direct Ash

Activaton Spectrography between 650·C at500·C at500·C
and 800·C)
99,96,99 95 60,75,55 100 75

256,247,259 258,259 160,178,271 225 208
343,321,339 339,287 250,312 282 265
213,210,212 218,212 140, 196 210 191
194, 189, 192 209, 198 80,158,229 196 169
186,191, 198 191,191 95,95,173 193 173
70.5.1 Sample Preparation.
Weigh 10 g of the polymer sample into a platinum dish. Place the dish in the cold
electric muffle which is then programmed as follows:
Time from start: 0 to 1 h Heat to 200°C

1 to 3 h Heat to 200°C
3 to 5 h Heat to 450°C
5 to 8 h Hold at 450°C
Remove the dish from the muffle, when cool add 5 cm3 1 M nitric acid and warm
the dish on a hot plate to ensure complete dissolution of soluble salts. Transfer the
solution to a 10 cm volumetric flask. Rinse the dish with further 1 cm3 portions of nitric
acid and add each to the volumetric flask. When the flask and the contents are cool, make
up the volume to 10 cm3 and mix thoroughly.
Set the flame photometer wavelength to 670.9 nm and adjust the slit, zero and
gain controls of the flame photometer until 0% and 100% scale readings are obtained for
1 N nitric acid solution and the I or 10 ppm Li standard solution. Obtain the scale
readings for each standard solution in turn, followed by the sample at 670.9, 685.9 and
655.9nm.
70.5.2 Calibration.
Subtract the mean of the 685.9 and 655.9 scale readings from the value obtained
at 670.9 nm to give a background corrected scale reading for each solution. Plot a
calibration graph of the background corrected scale readings for the standard solutions
against lithium concentrations under the conditions given above, the standard solutions
given above are equivalent to 0.3 and 10 ppm lithium in polymer. Interpolate the sample
background corrected scale reading into the calibration to obtain the concentration of
lithium in the polymer.
342
This method is capable of determining down to 0.2 ppm of lithium in polyalkenes

with an accuracy of ± 5%. Sodium in amounts up to I ppm does not interfere.
METHOD 71 - DETERMINATION OF TRACES OF NICKEL, COPPER, ZINC,

IRON, MANGANESE, LEAD, CADMIUM AND CHROMIUM IN POLYMERS.
ASHING - ATOMIC ABSORPTION SPECTROMETRY.
71.1 SUMMARY
This atomic absorption specroscopic procedure determines eight heavy metals in

polymers in amounts down to 0.03 to 0.13 ppm.
71.2 APPARATUS
Platinum dishes, 100 cm3•

Volumetric flasks, 10,25 cm3,
Atomic absorption spectrometer.
71.3 REAGENTS
Nitric acid, 1 molar prepared using Aristar nitric acid.
71.4 METHOD
The polymer is ashed in platinum. A nitric acid extract of the ash is examined by
atomic absorption spectroscopy for concentrations of nickel, copper, zinc, iron,
manganese, lead, cadmium and chromium at specific wavelengths. The method is
calibrated against standard solutions of the heavy metals in nitric acid.
Accurately weigh 10 g of dry polymer into a platinum dish. Place the dish in a
cold contamination-free muffle furnace and temperature programme as follows:
Time from start: O-Ih Heat to 200°C

I -3h Hold at 200°C
3-5h Heat to 450°C
5-8h Hold at 450°C
Remove the dish from the furnace and allow to cool in a dessicator. When cool,
add 5 cm3 1 M nitric acid and warm the dish gently on a hot plate to ensure complete
dissolution of the metallic salts. Transfer the solution quantitatively with pure water to a
25 cm3 volumetric flask and make up to the mark (final solution 0.2 M with respect to
nitric acid). Blanks and standard solutions should also be prepared in 0.2 M nitric acid.
343
Atomic absorption instrument operating conditions,
Instrument:
Single beam
Background correction using deuterium arc
Grating monochrometer.
Burner:
Single slot 10 cm long
Burner aligned along optical axis for each metal
Fuel gas - Acetylene 12 lb/sq in
Support gas - compressed air, oil-less. Compressor model SY 006.
Aspiration rate: 9.5 cm3/min
Spoiler left in position for all elements.
Recorder single pen.
Renew the calibration standards every two weeks from 10 uglcm3 stock solutions,
by dilution with 0.2 M nitric acid (Aristar). Renew the 10 uglcm3 stock solutions
monthly.
71.6 TYPICAL RESULTS AND DISCUSSION
The detection limits for metals in polymers achievable by this procedure are given
in Table 7.38.
METHOD 72 - DETERMINATION OF TRACES OF COPPER IN

POLYALKENES. MATRIXASHING. SPECTROPHOTOMETRIC
PROCEDURE.
72.1 SUMMARY
This spectrophotometric procedure determines down to 0.1 ppm copper in

polyalkenes.
72.2 APPARATUS
Silica crucibles, Vitrosil, cleaned periodically by soaking in concentrated nitric

acid.
Miscellaneous volumetric glassware. Pipettes miscellaneous, graduated pipette 5
cm3, volumetric flasks 50 cm3, 25 cm3• Graduated cylinder 10 mi. Separatory funnels 50
cm3 (ungreased stopcock), cleaned by soaking in concentrated nitric acid followed by
rinsing with distilled water before use.
Electric hotplate with Simmerstat control.
Absorption spectrophotometer.
344
Table 7.38 - Analytical Conditions. Metals in Polymers
Element Wavelength Band Operating Detection Concentration of

nm Pass Range (in Limit (in Standard Solu-
Polymer)ppm Polymer) ppm tion ug L· 1
Iron 284.3 OJ 5 0.57 500

Manganese 279.5 0.5 1.25 0.03 250
Chromium 357.9 0.5 2.5 0.03 500
Cadmium 228.8 1.0 0.5 O.oI5 50
Copper 324.7 1.0 1.25 0.045 250
Lead 217.0 1.0 5 0.15 1250
Nickel 232.0 0.15 2.5 0.07 500
Zinc 213.9 1.0 0.5 0.015 125
72.3 REAGENTS
Sodium diethyldithiocarbamate solution 1% aqueous.

EDTA - citrate solution. Dissolve 18.2 g of citric in distilled water and add the
theoretical quantity of 0.880 S.O. ammonia (both B.D.H. lead-free reagent; for foodstuff
analysis grade) to produce the triammonium salt. The final solution should be slightly
alkaline to litmus, add 5 g of disodium EDTA "Analar" and dilute to 100 ml with
distilled water.
Ammonium hydroxide (1 :3). Mix one volume of S.O. 0.880 ammonia (B.D.H.
lead-free reagents foodstuff analysis grade) with 3 volumes of distilled water.
Cresol red indicator, 0.04% ethanolic.
Carbon tetrachloride, redistilled, passed dithizone test.
Standard stock copper solution, dissolve 0.1 g copper in 15 ml I + 4 nitric acid,
(use B.D.H. lead-free reagent for foodstuff analysis grade nitric acid), boil gently to expel
nitrous fumes, cool and dilute to 100 cm3 with distilled water.
Dilute copper solution for calibration (10 ug cm\ dilute 5 cm3 stock copper to
500 cm3 as required. Use only on day of analysis.
Magnesium nitrate solution 7%. Dissolve 70 g of hydrated magnesium nitrate,
(Mg(N03)26H20) Analar in 1 litre 30:70 v/v absolute ethanol: distilled water.
Sulphuric: nitric acid mixture 1:3. Mix one volume of concentrated sulphuric
acid with three volumes of concentration nitric acid (both B.D.H. lead-free reagents for
foodstuff analysis grade).
72.4 METHOD
A known weight of the polymer is mixed with an aqueous alcoholic solution of

magnesium nitrate. The mix is then ashed and carbon removal is completed by wet
digestion with a mixture of nitric and sulphuric acids.
The acid digest is taken up in water and suitable complexing agents, which
prevent interference by other metals are added. Copper is then extracted from this
solution with carbon tetrachloride, as the coloured copper diethyl dithiocarbamate
complex, and the colour is evaluated spectrophotometrically at 432 nm.
345
72.5.1 Ashing Procedure.
Weigh out 10 g sample into a silica crucible. Pipette in 10 ml magnesium nitrate

solution. Stir the mixture with a thin glass rod to ensure thorough contact between the
polymer and the liquid. The addition of a further 5 cm3 of distilled water may be
necessary at this stage. Heat strongly on a bunsen until most of the carbon is removed.
Allow the crucible to cool. Run 2 cm3 of 1:3 sulphuric-nitric acid mixture down the wall
of the crucible using a thin glass rod to transfer any remaining carbon to the bottom of the
crucible. Heat again until sulphuric acid fumes are produced, do not heat to dryness.
Allow to cool and repeat the treatment with a further 2 ml of sulphuric - nitric acid
mixture. Dilute the contents of the crucible with 10 cm3 of cold distilled water and boil
gently. Quantitatively transfer this solution, together with hot distilled water crucible
washings, to a 50 em3 volumetric flask and make up to the 50 cm3 mark with distilled
water. Filter this solution if necessary.
Perform a reagent blank determination in exactly the same manner as described
above, omitting only the addition of polymer. Make the blank solution also up to 50 cm3•
72.5.2 Determination of Copper.
Transfer a suitable volume of the sample extract containing not more than 30 ug
of copper and the same volume of the reagent blanks solution to two 50 cm3 separatory
funnels. Pipette 10 cm3 of EDTA citrate solution and add 2 drops of cresol-red indicator
into the sample and blank solutions and then add 1:3 ammonia until the solution becomes
purple red in colour. Allow to cool and add 1 cm3 of sodium diethyldithiocarbamate
solution. Pipette in 10 cm3 carbon tetrachloride and shake for 2 min. Allow the layers to
separate, then filter the lower layer through dry filter paper into a 25 cm3 volumetric
flask. Extract the aqueous layer with further 5 cm3 portions of carbon tetrachloride until
no further colour is extracted. Make the combined filtrates up to the 25 cm3 mark with
carbon tetrachloride. Filter this solution through dry filter paper if cloudy.
Determine the optical density of the sample solution approximately 30 min after
the addition of sodium diethyldithiocarbamate reagent under the following conditions.
Spectrophotometer conditions:
Wavelength 432 om
Cells 4 cm glass
Blank solution This is the reagent blank which has been through the
whole test procedure from the ashing stage.
Pipette 40 cm3 distilled water into several clean 50 cm3 separatory funnels and
pipette in 0.5, 1.0,2.0,2.5, 3.0 and 3.5 cm3 of freshly prepared dilute (10 ug per cm3)
standard copper solution. Include a further separatory funnel containing 40 ml distilled
water only as a blank. Continue as described above from the addition of EDTA citrate
reagent. Employ the extract obtained in the reagent blank determination in the
comparison cell. Construct a graph relating these optical densities to the number of
micrograms (ug) of copper present in the calibration solutions.
346
Calculations. Refer the optical density given by the carbon tetrachloride extract
obtained from the sample to the copper calibration graph and read off the number of
micrograms of copper present in 25 cm3 of carbon tetrachloride solution. Calculate the
copper content of the polymer sample from the following equation:
Copper, ppm = n x 105 X 50 5N

106 x V V
assuming of 109 of polymer is ashed, where:
N = number of micrograms ug of copper present in 25 em3 of carbon tetrachloride

solution.
V = volume (cm3) of aqueous solution taken for extraction with carbon
tetrachloride from the 50 cm3 dissolved polymer ash solution.
The results in Table 7.39 show that distinctly higher copper determinations are
obtained on polyolefins by the procedure involving the use of an ashing aid than are
obtained without an ashing aid or by the use of a molten potassium bisulphate fusion
technique to take up the polymer ash.
This method is capable of determining down to 0.1 copper in polyalkenes with an

accuracy of ± 5%. Bismuth is the only metal known to interfere in the determination of
copper by the described procedure.
347
...,
~
Table 7.39 - Determination of Copper in Polyolefins
Type of Original Copper Known Synthetic Total Total Determined COI1~r Content of PolYmer I1l1m
Polymer Content of Polymer Addition of Copper Expected Copper Obtained by Obtained by Obtained by
Obtained by Proposed to Polymer Content of Polymer Proposed Method Direct Ashing Potassium
Method (lOg sample) (calculated) Described under without Ashing Bisulphate
Described under Procedure (lOg Aid aFusion b
Procedure sample)
ppm ppm ppm ppm % Rec. ppm % Rec. ppm % Rec.
Polyethylene 1.1 0.0 1.1 0.9, 1.0, 1.1 90 0.4 36 0.5 45

Polyethylene 1.1 1.5 2.6 2.5 96 0.6 22 1.0,0.7,0.5 28
Polypropylene 2.7 0.0 2.7 2.7,2.6,2.5 96 104,0.9, 1.1 42 004 14
Polypropylene 2.7 1.5 4.2 4.2 100 104 33 2.3, 2.8, 2.0 56
Ethylene-
propylene 4.8 0.0 4.8 4.8, 4.6, 4.5 96 2.0, lA, 1.6 35 0.6 \3
copolymer 4.8 1.5 6.3 62 98 3.5 55 2.7 43
(a) 109 polymer ashed in silica at 600"C. Ash dissolved in 2 ml concentrated nitric-sulphuric acid mixture (3: I) and evaporated gently to dryness prior to dissolving in water.
(b) 109 polymer ashed at 600·C. Ash fused with 2.5g potassium bisulphate and residue dissolved in water.
METHOD 73 - DETERMINATION OF TRACES OF ARSENIC IN ACRYLIC
FIBRES CONTAINING ANTIMONY TRIOXIDE FIRE RETARDENT AGENT.
ACID DIGESTION ATOMIC ABSORPTION SPECTROMETRY."
73.1 SUMMARY
This atomic absorption spectrometric method detennines down to 0.02% arsenic

trioxide ftre retardent in acrylic ftbres.
73.2 APPARATUS
Atomic absorption and flame-emission spectrophotometer, 10 cm slit burner,

equipped with a arsenic measurement unit or equivalent and an arsenic hollow-cathode
lamp. A schematic diagram of the apparatus used for the arsenic measurement is shown in
Figure 7.16.
73.3 REAGENTS
All reagents used were of analytical reagent grade.

Arsenic III standard solution.
1000 ug }"I. Dissolve 132.0 mg of arsenic (III) oxide (purity 99.91'10) in 2 cm' of 4%
mlv sodium hydroxide solution. Add dilute sulphuric acid until the solution becomes
slightly acidic and then dilute to 100 cm' with distilled water.
Arsenic (V) standard solution, 1000 ug 1-1. Oxidize the above arsenic (III) standard
solution with a sufficient amount of hydrogen peroxide and evaporate the excess by boiling.
Cool the resulting solution and dilute it to the required volume with distilled water.
Nitric acid, concentrated, Analar.
Perchloric acid, concentrated, Analar.
Sulphuric acid, concentrated, Analar.
Benzene, Analar.
Zinc tablet.
Tablet comprising 1 g of zinc powder containing a binder.
Potassium iodide, 20% u.v aqueous made from Analar solid, prepared weekly.
Titanium (III) solution 10% mIV.
Dissolve 50.0 g of titanium (III) chloride in concentrated hydrochloric acid· and
dilute to 500 cm3 with concentrated hydrochloric acid. Store this solution in a refrigerator.
• Hydrochloric acid to have an arsenic content less than 0.5 ugl- I .
73.4 METHOD
A concentrated nitric acid - perchloric acid - sulphuric acid digest of the polymer is
analysed at 193.7 nm by atomic absorption spectrometry. The procedure is calibrated
against standards of arsenic free acrylic ftbre and pure arsenic trioxide.
349
r'--~A
r--.----.----.---.-,
J7t1.c-+-J1 ASD·1A .
Figure 7.16. Schematic diagram of apparatus used for the arsenic measurement. A, slit burner; B,
trap; C, change·over cock; D, buffer tank; E, arsine generator (glass reaction bottle); F, magnetic stirrer; G,
pressure gauge; H, gas flow meter; I, back·sweep cock; J, stock·cock; and K, pressure controller. a. sweep;
and b. by·pass. From Korenaga with permission. 46 Royal Society of Chemistry, London
73.5.1 Preparation of Sample Solution.
Weigh 1 g of sample (to contain less than 2 ug of arsenic) into a Kjeldahl

decomposition flask. Add 3 cm3 of concentrated nitric acid, 3 cm 3 of concentrated
perchloric acid and 3 cm3 of concentrated sulphuric acid. Heat the flask on an electric hot
plate (about 1200 W) until the acrylic fibre sample is completely decomposed. If the
sample cannot be decomposed completely, add a further 3 cm3 of concentrated nitric acid
and 3 cm3 of concentrated perchloric acid to the flask and repeat the heating until the
solution becomes clear, cool the resulting solution. After the digestion of the sample the
amount of sulphuric acid remaining is about 3 cm3•
Transfer the solution into a 50 cm3 separating funnel and rinse the Kjeldahl
decomposition flask with 7 cm3 of concentrated hydrochloric acid. Add 5 cm3 of 10% mJV
titanium (III) chloride in concentrated hydrochloric acid solution then leave to stand for 30
min at 60°C in a waterbath (the funnel must occasionally be shaken and frequently de-
gassed in order to avoid an explosion). Cool the solution to room temperature, add 10 cm3
of benzene and shake the funnel for a few minutes. Discard the aqueous phase, add 10 cm3
of distilled water and shake the funnel for a few min. In this way, arsenic (V) in the
digested sample is reduced to arsenic (III), and only the arsenic (III) is extracted into
benzene and then back-extracted quantitatively into the aqueous phase.
73.5.2 Atomic Absorption Spectrophotometry.
Transfer by pipette the aqueous solution containing arsenic III (not more than 2 ug
of arsenic) obtained by the above procedure into a glass reaction bottle (E in Figure 7.16).
Add 5 cm 3 of concentrated hydrochloric acid, 1 cm3 of 20% mJV potassium iodide solution
and 0.5 cm3 of 20% mJV tin (II) chloride solution. Dilute the solution with distilled water
to give a final volume of25 cm3 (final concentration of hydrochloric acid 2.4 M). Mix well
and allow to stand for 20 min. Drop a zinc tablet containing about 1 g of zinc powder into
350
the reaction bottle (E) and immediately connect the bottle to the collection tank (D). Store
the generated arsine gas obtained by mixing the sample solutions with a magnetic stirrer (F)
to ensure complete arsine generation in the 100 cm3 collection tank (D) for about 1 min
(until the pressure of arsine generation gas reaches 0.5 kg cm-2). As soon as the pressure of
arsine generation gas (H) reaches 0.5 kg cm-2 switch the stopcock (C) from the by-pass (b)
and introduce the collected arsine into the flame with a stream of nitrogen carrier gas. Use
the peak height on the recordings to determine the concentration of arsenic.
According to the analytical conditions given above, arsenic (III) obtained in the
aqueous solution was determined at the 193.7 nm absorption line by using arsine generation
and atomic absorption spectrophotometry (Figure 7.16). A calibration graph was prepared
by using 0.25 - 2.0 ug of standard arsenic (III) solution throughout the procedure for the
preparation of the sample solution and was then used for subsequent determinations of
arsenic concentrations.
Arsenic (III) separated into the aqueous phase from the matrix antimony after the
benzene extraction and back-extraction with distilled water was determined by using arsine
generation atomic-absorption spectrophotometry as described under Atomic Absorption
Spectrophotometry. A calibration graph was prepared by analysing a standard arsenic (V)
solution and an acylic fibre containing no antimony oxide by the recommended procedure.
Although the calibration graph obtained was not a straight line, amounts of arsenic in the
range 0.25 - 2.0 ug could be determined with good reproducibility under the conditions
given above.
The results for arsenic obtained with various acrylic fibre samples containing
antimony oxide are given in Table 7.40. The relative standard deviations in these
determinations were less than 7%.
This method is capable of determining down to 0.02% arsenic in acrylic fibres with
an accuracy of ± 5%. Antimony present in the sample does not interfere.
METHOD 74 - IDENTIFICATION OF PIGMENTS IN POLYMERS. THERMAL

ULTRAVIOLET ABSORPTION SPECTROSCOPy.47
74.1 SUMMARY
This thermal UV absorption procedure is capable of identifying various coloured

pigments in polymers.
74.2 APPARATUS
Graphite furnace atomic absorption spectrophotometer equipped with a flameless

atomizer and deuterium lamp.
Argon purge gas.
351
Table 7.40 - Results for the Determination of Arsenic in Acrylic Fibres Containing
Antimony Oxide
Sample Supplier Content of No of Arsenic Content

no. Sb2O,*% Determinations ppm
I A 5.1 4 50:!: I
2 A 5.1 3 84:!:4
3 A 4.5 2 94:!:7
4 A 4.6 5 10.3 :!:0.5
5 A 5.0 5 4.1 :!:0.2
6 B 3.0 (Sb203) 3 45:!:0
7 C 2 180:!: 11
8 C 4 103:!:6
9 D 2.4 (Sb203) 2 8.5:!:0.5
10 E 1.0 (Sb203) 4 3.2:!: 0.1
11 SbzO,50mg+
acrylic fibre
(no Sb) Ig 2 0.47:!:0.03
12 Sb2O,IOmg+
acrylic fibre
(no Sb) Ig 0.08
From Korenaga46 • Royal Society of Chemistry, London.

• Even when antimony (III) oxide was present in acrylic fibres (samples 6, 9 and to), antimony (UI) was
easily and completely oxidised to antimony (V) by the wet digestion with a mixture of nitric, perchloric and
sulphuric acids. Hence, arsenic in acrylic fibres containing antimony (III) oxide could be determined as well
as that in acrylic fibre samples containing antimony (V) oxide by this method.
74.3 METHOD
Pellets of the polymer sample are introduced into the graphite furnace of an atomic
absorption spectrometer and heated to temperatures between 300 and 900°C. The UV
absorption bands occuring are examined in the atomic absorption spectrometer and the
thermal ultraviolet profiles characteristic of the pigment obtained. Each pigment has a
characteristic thermal UV profile at a partiCUlar temperature.
Pigments and organic compounds are investigated directly without dissolution.

Powdered samples of the pigments are pressed in pellets about 0.5 mm thick at 107 Pa.
Small pieces of 0.5 mm x 0.5 mm wide are introduced into the graphite tube through the
central sampling hole. The pellet position must be checked carefully as its shift along the
tube axis causes remarkable changes in the temperature (about 50 - 700 q and absorbance
(30%) of the thermal ultraviolet profiles. The tube is then inserted into the furnace and the
thermal cycle for vapor phase measurements is performed.
The instrumental conditions of the atomic absorption spectrometer are as follows:
200 nm wavelength, 0.7 nm bandwidth, background mode and time constant depending on
the selected thermal cycle. Three different thermal cycles are carried out (Table 7.41), the
choice of the cycle is based on the type of pigment examined.
Thermal cycle 1 is used for rapid screening, ie. to investigate whether the pigments
contain organic or inorganic compounds or both, therml;\l cycles 2 and 3 are employed
352
respectively for identification or organic and inorganic pigments. Owing the heating from
step 1 to step 2 (thermal cycles 1 and 2) or from step 2 to step 3 (thermal cycle 3)
ultraviolet absorption is recorded at the temperature of the furnace to obtain TUV profiles
of the vapours.
Purge gas (argon) flow is maintained at 300 cm3/min during the whole thermal
cycle, as its reduction gives rise to condensation of vapours and decomposition products in
the cooler parts of the furnace with subsequent memory effeOt. This effect is noteworthy
especially in the case of inorganic pigment identification. On these grOUnds the heating
rate plays the main role in the resolution ofTUV profiles.
A practical example of. the identification of pigments is given in Figure 7.17. AI: 1
mixture of organic pigment yellow/(2-nitro-p-toluidine coupled with acetoacetanilide) and
inorganic P.Y 34 (lead chromate) was vaporized following thermal cycle 1. The thermal
ultraviolet profile shows clearly two absorption bands at about 500°C and 1250oC. The
first band is attributable to the vapours which originate from the decomposition and
pyrolysis of the organic pigment, the second band corresponds to the decomposition and
vaporization of lead chromate at high temperature (mp 844°C). It is possible therefore to
determine by a rapid run whether the pigment is a mixture or belongs to ,the organic or
inorganic group.
This procedure is useful for obtaining qualitative information regarding the types of
organic and inorganic pigments in polymers.
METHOD 75 - DETERMINATION OF TRACES OF CHLORINE IN

POLYALKENES AND POLYALKENE COPOLYMERS. SODIUM CARBONATE
FUSION - TITRATION PROCEDURE.
75.1 SUMMARY
This sodium carbonate fusion - titration procedure is capable of determining chlo-

rine residues in amounts down to 50 ppm in polyalkenes and polyalkene copolymers.
75.2 APPARATUS
Titration burette, 10 mI.

Platinum crucible.
75.3 REAGENTS
Silver nitrate, MIlO.

Silver nitrate, MllOO.
353
Table 7.41 - Experimental Conditions for TUV Profile Recording
Thennal Cycle I Thennal Cycle 2 Thennal Cycle 3
2 3 2 3 4 2 3 4
Temperature ·C 200 2000 2650 ISO 1000 1500 2650 150 700 2300 2650
Ramp Time,s 10 80 2 \0 110 2 2 10 10 40 I
Hold Time,s 25 \0 5 25 20 5 5 20 5 I 5
Recorder • •
Time Constant,s 0.5 0.5 0.4
From Tittareli et a147• American Chemical Society
0.2
~
i
~0.1
m
C
~~~~=OOO~~==I~~===aoco=
TEMPERATURE, 'e
Figure 7.17. TUV profile of (a) 1.1 mixture of organic pigment yellow (2-nitro p-toluidine coupled with
acetoacetanilide) and inorganic pigment PY 34 (lead chromate). Thennal cycle temp, ·C 200 ramp times, S
10 hold temp, ·C 25. From Tittareli et al with pennission!' American Chemical Society.
Nitric acid, 30% aqueous, dilute 30 cm3 concentrated nitric acid (M.A.R.) with 100
cm3 distilled water.
Sodium carbonate, solid microanalytical reagent grade.
Xylene cyanol/methyl orange mixed indicator, alcoholic solution.
Acetone, A.R. grade.
Acid buffer solution: to approximately 200 cm3 of distilled water, in a 500 cm3
volumetric flask add 100 cm3 glacial acetic acid and 6.5 ml concentrated nitric acid (sp gr.
1.42), dilute to the mark with distilled water.
Gelatine solution: add to 250 cm3 of deionized water, 2.5 g gelatine and 5 g thymol
blue. Heat slowly to the boil and stir until solution is complete. Add 0.5 g thymol as
preservative and dilute to 500 cm3 with distilled water. The solution is stable for up to 3
months at room temperature.
354
75.4 METHOD
In the method polyethylene is mixed with pure sodium carbonate and ashed in
muftle furnace at 500°C. The residual ash is dissolved in aqueous nitric acid and then
diluted with acetone. This solution is titrated potentiometrically with standard silver
nitrate.
Accurately weigh 5 g of polymer into a platinum crucible and cover the polymer
with a layer of 2 g sodium carbonate. Place in a cold muftle furnace and increase the
temperature gradually to 500°C, maintaining this temperature for four h. Allow the
crucibles to cool then dissolve the residue in 15 - 20 m1 distilled water. Transfer this
solution with crucible washings to a 100 cm3 beaker. Adjust the final volume of water to
30 cm3• Add 5 drops of screened methyl orange indicator solution and neutralise the
mixture by dropwise addition of 30% nitric acid to the purple red coloured endr.int. Add
a further 10 drops of 30% nitric acid solution to the beaker and then add 30 cm of acetone.
Titrate the resultant solution potentiometrically with silver nitrate solution (MIIOO) using
an automatic titrator equipped with a silver measuring electrode and glass reference
electrode. Carry out a blank determination exactly as described above, omitting only the
sample addition.
Calculation:
ppm (w/w) chlorine in polymer
3
= ITs - TB) x M x 35.46 x 10
W
where
TB = titration of silver nitrate (mls) in blank determination
Ts = titration of silver nitrate (mls) in sample determiantion
M = molarity of silver nitrate solution
W = weight (g) of polymer sample.
Note: If a polyolefin sample does not contain any free residual alkali left in the
manufacturing process then there exists a danger that some chlorine will be lost during the
ignition process and low chlorine analyses will result. If this is suspected to be the case the
polymer sample (50 g) should first be contacted with twice its volume of2% WN alcoholic
potassium hydroxide solution and left in an oven at 70°C until the polymer is dry. The
above method is then applied.
In Table 7.42 are compared chlorine contents obtained by x-ray fluorescence
spectroscopy with those obtained by the above method involving fusion at 500°C with
sodium carbonate. Analyses were carried out on samples which had been previously
treated with alcoholic potassium hydroxide and samples which had not been so treated. It
is seen in Table 7.42 that, when carried out on the same sample, this chemical method gives
considerably more reproducible duplicate results than those obtained by the x-ray method
(compare columns A and C). In the case of alcoholic potassium hydroxide treated samples
3SS
the average of duplicate analyses carried out by the x-ray and the chemical method agree
satisfactorily within ± 15% of each other. In the case of untreated samples the chemical
method tends to give lower chlorine contents than the x-ray method.
This method is capable of determining down to 50 ppm chlorine in polyalkenes and

polyalkene copolymers with an accuracy of ± 5%.
356
Table 7.42 - Comparison of Chlorine Contents by X-Ray Fluorescence and Chemical Method
Polymer not Treated with Alcoholic Potassium Hydroxide Before Analysis, Polymer Treated with Alcoholic Potassium Hydroxide Before
ppm Chlorine ppm Chlorine
Sample X-Rayon Chemical Chemical Diff. (%) between X-Rayon Chemical Chemical
Discs (avg in Method on Method on Av. X-Ray & Chern. Discs (av. in Method on Same Method on
brackets) Same Disc as Powder (av. in Anal. "D"= brackets) Disc as used for Powder (av. in
"A" used for brackets) ("A" - "C") x 100 "E" X-Ray anal. brackets)
X-Ray anal. "e" '~" "F" "G"
"B"
480,540 456 502,499 +2 865,815 700 786,761

(510) (500) (840) (773)
2 365,480 334 380,355 +15 535,570 606 636,651
(422) (367) (552) (643)
3 435,445 338 349,353 +25 785,675 598 650,654
(440) (351) (730) (652)
4 425,570 392 395,404 +24 625,675 600 637,684
(497) (400) (650) (660)
5 390,530 371 416,399 +13 895,870 733 828,816
(460) (408) (882) (822)
...,
~
METHOD 76 - DETERMINATION OF CHLORINE IN CHLOROBUTYL AND
OTHER CHLORINE CONTAINING POLYMERS. OXYGEN FLASK
COMBUSTION - TURBIDIMETRy.48
76.1 SUMMARY
This oxygen flask combustion turbidimetric method is capable of determining

total chlorine in amounts down to 5 ppm in chlorobutyl and other chlorine containing
polymers.
76.2 APPARATUS
Conventional 1 and 2 litre Schoniger type oxygen combustion apparatus.

The absorbance measurements were obtained using a spectrophotometer with a I
cm cell and a tungsten lamp as the energy source, or equivalent.
76.3 REAGENTS
Standard aqueous potassium chloride solution in demineralized water to contain

1000 ppm chloride. Dilutions made from this standard stock solution to those containing
very low chloride levels.
Silver nitrate, 0.01 M aqueous.
Nitric acid, 0.01 M potassium nitrate 0.01 M aqueous.
76.4 METHOD
A weighed sample is combusted in an oxygen filled flask over dilute nitric acid.
Silver nitrate solution is then added and the resulting silver chloride, ie. chlorine,
estimated turbidimetrically at 420 nm using a grating spectrophotometer.
The preparation of the calibration curve involves the preparation of six standard
chloride solutions to contain 0 to 4 ppm chloride. Acidified om M silver nitrate is added
to each solution to form a silver chloride suspension. All the solutions are swirled briefly
and allowed to stand at least 35 minutes with occasional shaking. The absorbance of each
of these solutions is then measured at 420 nm in a 1 cm cell. A straight line curve
passing through the origin is obtained covering chloride concentrations from 0 to 4 ppm.
The ideal absorbance is approximately in the range of 0.03 to 0.2 absorbance units.
During the preparation of standards swirling each solution for a few seconds is
sufficient. Prolonged agitation tends to agglomerate the silver chloride particles.
Generally, about 100 mg of a weighed sample are combusted in a 2 litre
Schoniger flask containing 10 ml of 0.01 M nitric acid. After the combustion, the flask is
allowed to stand at least 15 minutes with occasional shaking before 5 ml of 0.01 M silver
nitrate solution are added.
358
If the polymeric sample is difficult to combust, the nonnal platinum sample
basket may be wrapped with 52 mesh platinum gauze to prevent hot and partially burned
sample from dripping out of the sample basket. For subsequent combustions of this
sample, a smaller sample size and the use of twice the nonnal volume of nitric acid
absorbent are recommended.
The measurement of the absorbance of the silver chloride suspensions should be
done within 35 - 60 minutes of turbidity development of both the sample and standard
chloride solutions. The absorbances of the standard solutions are measured fIrst,
followed by the sample solutions, then the standard solutions are measured again.
The calculation of results is made in two different ways. For samples of low
halogen level and if the combustion results in a clear solution, no removal of a solution
aliquot is necessary and the calculation is as follows:
ppm chloride x 15 x 100

%CI = sample weight (mg) x 1000
The value for ppm chloride is obtained from the calibration curve.
If combustion of the sample is such that a clear solution is not obtained and an
organic mm results in the combustion flask, an S ml aliquot is usually removed and only
4 ml silver nitrate is added to the clear aliquot. Here again, the ratio of sample solution
aliquot volume to that of silver nitrate is still 1: 1 and the calculation for chloride is the
same as above.
This method is capable of detennining down to 5 ppm total chlorine in chlorine

containing polymers with an accuracy of ± 5%.
METHOD 77 - DETERMINATION OF UP TO 80% CHLORINE, BROMINE

AND IODINE IN POLYMERS. OXYGEN FLASK COMBUSTION - TITRATION
PROCEDURE.
77.1 SUMMARY
This oxygen flask combustion - titration procedure is capable of detennining

between 2 and SO% of total chlorine, bromine or iodine in polymers.
77.2 APPARATUS
Combustion flask - Pyrex, 500 ml capacity conical flask with B24 conical ground
stopper. .
Stopper B24 - with a fixed in platinum wire (30 mm long, O.S mm diameter)
carrying a 15 x 20 mm piece of 40 mesh platinum gauze or carrying a 5/S" long x 114"
diameter bucket fabricated in 40 mesh platinum gauze.
Safety jacket - for co~bustion flask to serve as a protection during the
combu~tion. Conical shaped, detachable metal wire gauze fitting around the conical
flask. (Figure 7.1S).
359
Automatic titrimeter - with silver/glass electrode system. Wick lighter, small
burner fed with sulphur and halogen free fuel.
Cellulose capsules - halogen free.
77.3 REAGENTS
Silver nitrate solution standard, 0.1 N.

Sodium hydroxide solution, 0.01 N approximately, dissolve 0.4 g of sodium
hydroxide in distilled water and dilute to 1 litre.
Sodium metabisulphite solution, 0.05% w/v, (Micranalytical Reagent Grade,
available from British Drug Houses Ltd., Poole, Dorset) dissolve 0.05 g of sodium
metabisulphite in distilled water and dilute to 100 ml.
Barium nitrate, Analar, solid.
Oxygen, cylinder.
Nitric acid, Analar, concentrated.
Methyl alcohol, Analar.
Acetone, pure grade, redistilled.
Water, deionized halogen content less than 0.05 ppm.
Filter paper, any grade with a halogen content less than 50 ppm.
77.4 METHOD
The sample is burnt in oxygen in a sealed Schoniger flask and the resultant
volatiles are absorbed in a suitable absorption solution. This solution is acidified and
titrated potentiometrically with standard silver nitrate solution.
77.5.1 Combustion Technique
The method requires different absorption solutions for the various halogens as
follows:
Chlorine 10 ml of 0.01 N sodium hydroxide solution.

Bromine and/or iodine 10 ml 0.05% w/v solution metabisulphite solution.
Chlorine and bromine 5 mlO.ot N sodium hydroxide solution and 5 ml
and/or iodine 0.05% w/v sodium metabisulphite solution.
Pipette the required absorption solution into the flask and fill with oxygen,
stopper securely. Accurately weigh out 10 - 30 mg of sample into a cellulose capsule and .
place the capsule in the Schoniger basket with a strip of filter paper, to act as a fuse.
Light the fuse and quickly insert the basket into the oxygen filled flask. During the
combustion hold the basket in the flask firmly and at the same time lift the flask off the
bench. Allow the mist formed in the flask to subside with periodic shaking over 15 to 30
minutes. Transfer the solution to a 250 ml beaker using 50 ml of distilled water and 120
mg of methanol. (If the halogen content of the sample is less than 5% then 120 ml
acetone should be used instead of methanol).
360
FILTER STRIP
as a 24 --It-- (ACTUAL SIZE)
~----- __ Pt GAUZE
40 MESH
- - - \ - - 5OO-ml FLASK
Figure 7.18. Stopper conical flask: with platinum wire gauze to suspend the sample.
If any carbonaceous matter is evident in the solution then the determination

should be abandoned and a further combustion carried out using a smaller sample weight.
Carry out a reagent blank combustion including the paper and all reagents, but
Add 1 drop of concentrated nitric acid and, if a mixture of halogens is present, a
few crystals of barium nitrate. Titrate the solution potentiometrically using 0.1 N silver
nitrate solution.
361
77.S.2 Calculations.
The halogens are titrated in the following order: chlorine, bromine, iodine.
Calculate the halogen content as follows:
(Ts - Tbl x N x 35.46 x 100

Chlorine % w/w = Wx 1000
as - Tbl x N x 79.92 x 100

Bromine % w/w = Wx lOOO
(Ts - Tblx N x 126.91 x lOO

Iodine % w/w = WxlOOO
where:
Ts = sodium nitrate titration (mls) obtained in sample combustion.
Tb = silver nitrate titrations (mls) obtained in blank combustion.
N = normality of silver nitrate.
W = weight (g) of sample taken for analysis.
This method is capable of determining micro (2 - 80%) amounts of chlorine,

bromine or iodine in halogenated polymers with an accuracy of ± 3%.
METHOD 78 - DETERMINATION OF CHLORINE IN POLYMERS

CONTAINING CHLORIDE AND SULPHUR AND/OR PHOSPHORUS AND/OR
FLUORINE. OXYGEN FLASK COMBUSTION - MERCURIMETRIC
TITRATION.
78.1 SUMMARY
This oxygen flask combustion - titration method is capable of determining down

to 5 ppm chlorine in polymers without interference from 'any sulphur, phosphorus or
fluorine present in the polymer sample.
78.2 APPARATUS
Oxygen flask - 500 ml capacity, see Figure 7.18.

A conical flask provided with B24 ground glass stopper, sealed at the lower end to
a glass tube 5 rom in external diameter. The lower end of this tube is sealed and flattened
to form a slight flange. The length from the lower edge of the ground portion of the
stopper to the flanged end of the tube is 70 rom. The sample holder is constructed from
80 mesh platinum gauze in the form of a cylinder 6 rom in diameter and about 10 mm
long. It is closed at one end and fastened to the flanged tube by a length of 0.5 mm
diameter wire, one end of which is bent over the edge of the open end of the cylinder and
pinched so that the gauze is firmly gripped. The arrangement has significant advantages
362
over the usual type of sample holder. The platinum gauze and wire can be renewed with
ease and the thermal capacity of the assembly is relatively small.
Magnetic stirrer.
Content pipette, 2.0 ml capacity - conforming to B.S. 1428.
Microburette, 10 ml capacity - conforming to B.S. 1428.
78.3 REAGENTS
Sodium hydroxide, 0.1 N.

Nitric acid, 0.1 N.
Bromophenol blue indicator solution, dissolve 50 mg of bromophenol blue in 500
ml of ethanol.
Diphenylcarbazone indicator solution, dissolve 20 mg of diphenylcarbazone in 20
ml of ethanol. Keep the solution in the dark and renew it after 2 weeks.
Sulphur dioxide solution, saturate 50 ml of water with sulphur dioxide. Renew it
after 2 to 3 days.
Hydrogen peroxide, 100 volume, micro-analytical reagent grade.
Barium nitrate solution, a saturated aqueous solution of analytical reagent grade
barium nitrate.
Thorium nitrate solution, dissolve 15.0 g of analytical reagent grade thorium
nitrate tetrahydrate in water and dilute the solution to 1000 mi.
Ethanol, absolute.
Mercuric nitrate, approximately 0.005 M, dissolve 3.5 g of mercuric nitrate in 570
ml of O.oI N nitric acid and set the solution aside for at least 2 days. Filter off any
precipitate and dilute the filtrate to 2 litres.
Sodium chloride, 0.025 M.
Standardisation of the mercuric nitrate solution Measure out 2.0 ml of 0.025 M

sodium chloride solution by means of a content pipette. Dilute to 15.0 ml with water and
add 0.05 ml of bromophenol blue indicator solution. Add 0.1 N nitric acid until the
yellow colour of the indicator appears and then add a further 0.5 ml of acid. After the
addition of 100 ml of ethanol and 0.5 ml of diphenylcarbazone indicator solution, titrate
the solution with the mercuric nitrate solution to the first appearance of a permanent
voilet colour. The solution should be stirred magnetically throughout the titration period.
The use of a content pipette for measuring the sodium chloride solution is recommended,
since it has been found that the reproducibility of repeated titrations is better than that
obtained with, for example, a 5.0 ml delivery pipette, in conjunction with O.oI M sodium
chloride solution. The titration carried out as described must be corrected for the
indicator blank value, obtained by the titration of 15.0 mI of water. This blank value is
usually less than 0.05 ml of mercuric nitrate solution but much higher values have been
obtained occasionally and these have been found to be due to the presence of chloride in
the ethanol. In such instances, a suitable stock of ethanol may be mixed with a
predetermined volume of the mercuric nitrate solution, sufficient to reduce the blank
value to less than 0.05 ml.
78.4 METHOD
The polymer sample is combusted in an oxygen filled flask over water, after
neutralization to the bromophenol blue end-point and the addition of thorium nitrate,
363
diphenyl carbazide and ethanol the solution is titrated to the violet end-point with
standard mercuric intrate solution:
7.15
The chlorine content of the polymer can then be calculated from the consumption
of standard mercuric nitrate solution. Modifications to the method are described for
overcoming interferences by any sulphur, phosphorus or fluorine present in the polymer.
The procedures described below are restricted to the determination of chlorine in

organic compounds containing phosphorus or fluorine, or both, in the presence or absence
of sulphur. For compounds containing little if any hydrogen, a preferred alternative
procedure is given. The determination of iodine or bromine in the presence of
phosphorus or fluorine is not included since the determination of these halogens is in this
instance best completed by other well known volumetric methods, such as Leipert's
method for iodine and oxidation to bromate for bromine.
78.S.1 Compounds Containing Phosphorus or Fluorine, or Both.
Weigh out an amount of sample corresponding to 1.0 to 2.0 mg of chlorine and

decompose it in an oxygen flask containing 5.0 ml of water. Wash the stopper and
sample holder with 10.0 ml of water, add 0.1 ml of bromophenol blue indicator solution
and neutralise the solution with 0.1 N sodium hydroxide to the blue colour of the
indicator. Add 0.75 ml of thorium nitrate solution, 0.5 ml of diphenylcarbazone indicator
solution and 100 ml of ethanol and titrate the stirred solution with standard mercuric
nitrate solution to the appearance of a permanent violet colour.
78.5.2 Compounds Containing Sulphur and Either Phosphorus or Fluorine or all

Three Together:
Proceed as before up to the washing of the stopper, etc. Boil the solution for 60
seconds, holding the flask directly over a small bunsen burner flame and swirling the
solution continuously. Add 0.5 ml of barium nitrate solution, 0.1 ml of bromophenol
blue indicator solution and sufficient 0.1 N sodium hydroxide to produce the blue colour
of the indicator. After the addition of thorium nitrate, complete the determination as
before.
78.5.3 Compounds Containing Phosphorus or Fluorine or Both, and Little

Hydrogen:
Decompose the weighed sample in an oxygen flask containing 5.0 ml of water and
0.25 ml of saturated solution of sulphur dioxide. Wash the stopper etc. with 10.0 ml of
water and complete the determination as described for the analysis of compounds
containing sulphur. In this procedure the volume of barium nitrate should be increased if
0.5 ml is found to be insufficient for complete precipitation of the sulphate.
364
Blank determinations on the reagents, etc. should be carried out in conjunction
with each of the procedures described above. These blank values should not exceed
about 0.2 ml of 0.005 M mercuric nitrate.
The method has a precision of approximately 0.1 ppm at the 22% chlorine level.
METHOD 79 - DETERMINATION OF FLUORINE IN FLUORINATED

POLYMERS. OXYGEN FLASK COMBUSTION - SPECTROPHOTOMETRIC
PROCEDURE.49
79.1 SUMMARY
This oxygen flask combustion spectrophotometric procedure is capable of

determining fluorine in fluorinated polymers such as PTFE in amounts down to 0.5%.
79.2 APPARATUS
The combustions apparatus consists of silica or boronfree glass 500 ml

Erlenmeyer flask constructed of suitable glass, (see Method 76). Into the stopper is fused
one end of a length of platinum wire, 1 rom in diameter, to the free end of which is
attached a piece of 36 mesh platinum gauze, 1.5 cm x 2 cm to act as a sample holder.
The flask shall be essentially free from boron and aluminium. Low results are obtained
using borosilicate glass flasks.
Optical densities were measured in 4 cm cells with a Unicam SP600 visual range
spectrophotometer.
79.3 REAGENTS
Alizarin complexan, 0.0005 M, transfer 0.385 g of alizarin complexan to a 2 litre

calibrated flask by means of 20 ml of recently prepared 0.5 N sodium hydroxide and set
aside for 5 minutes with occasional swirling, to ensure complete solution. Dilute to about
1500 ml with water, add 0.2 g of hydrated sodium acetate and adjust the pH to about 5 by
careful addition of 1 N hydrochloric acid. Dilute to the mark and filter into a brown glass
bottle. This solution is stable for at least 4 months.
Cerous nitrate, 0.0005 M, standardise approximately 0.02 M cerous nitrate by
titration against standard ethylenediaminetetra-acetic acid solution at pH 6 with xylenol
orange as indicator. To a suitable volume of this solution (about 50 ml) add 0.2 ml of
concentrated nitric acid, 0.1 g of hydroxylamine hydrochloride and sufficient water to
produce 2litres and filter.
Acetate buffer solution, pH 4.6, dissolve 150 g of hydrated sodium acetate in
about 600 ml of water, add 75 ml of glacial acetic acid, dilute to 1 litre with water and
filter.
Standard fluoride solution, 5 ug per ml, dissolve about 22 mg (accurately
weighed) of dried analytical reagent grade sodium fluoride in water and adjust the
volume to 2 litres. Store in a polythene container.
365
79.4 METHOD
The method for the determination of fluorine is based on decomposition of the

sample by oxygen flask combustion followed by spectrophotometric determination of the
fluoride produced by a spectrophotometric procedure involving the reaction with the
cerium III complex of alizarin complexan (l,2-dihydroxy-anthraquinone 2-ylmethyl-
amine N, N-diacetic acid). The blue colour of the fluoride containing complex (absorp-
tion maximum, 565 nm) is completely distinguishable from either the yellow of the free
dye (maximum absorption, 423 nm) or the red of its cerium III chelate (maximum
absorption, 495 nm).
In each of a series of 100 ml calibrated flasks place 50 ml of distilled water, an

accurately measured volume between 2 and 8 ml of standard fluoride solution, 10 ml of
alizarin complexan solution and 3 ml of acetate buffer solution. Mix each solution
thoroughly, add 10 ml of 0.0005 M cerous nitrate, dilute to the mark with distilled water
and set aside, protected from direct light for 1 hour. At the same time, prepare a blank
solution in a similar fashion by omitting the standard fluoride solution. Measure the
optical densities of the test solutions against the blank in 4 cm cells at 610 nm and plot a
graph of optical density against amount of fluoride present.
79.S.2 Procedure.
Accurately weigh an appropriate amount of the sample (5 to 25 mg) on a strip of

filter paper approximately 3 cm x 4 cm (Whatman No.1 grade is suitable) that has been
folded into three along its length. Enclose the sample in the paper, insert a narrow strip
of filter paper to act as a fuse and fix it in the platinum gauze sample holder. Place 20 ml
of water in the combustion flask, fill the flask with oxygen, ignite the fuse and
immediately insert the stopper. Carefully tilt the flask and when combustion is complete,
set it aside the 10 minutes, with intermittent shaking. Quantitatively transfer the liquid to
a 250 ml calibrated flask, dilute to the mark and treat an aliquot expected to contain about
25 mg of fluoride by the procedure described for colour development under Preparation
of Calibration Graph. At the same time prepare a standard colour from 5 ml of standard
fluoride solution to serve as a check on the calibration graph.
Liquid samples can be satisfactorily decomposed by burning in a small gelatin or
preferably, methylcellulose capsule containing approximately 30 mg of powdered
cellulose.
For solutions derived from the combustion of sulphur containing compounds, boil
gently for about 10 seconds with 1 ml of 100 volume hydrogen peroxide, neutralise to
phenolphthalein with 1 N sodium hydroxide and then add 1 ml in excess; boil to destroy
excess of peroxide, cool and adjust the pH to about 4 with 1 N hydrochloric acid.
Using this method Johnson and Leonard49 obtained from polytetrafluoroethylene a

content of 75.8% fluorine using a silica or boron-free glass combustion flask against a
366
theoretical value of 76%. Using a boroscilicate glass combustion flask they obtained a
low fluorine recovery of 72.1 %.
This procedure is capable of determining down to 0.5% total fluorine in

fluorinated polymers with an accuracy of ± 5%.
METHOD 80 - DETERMINATION OF SULPHUR IN POLYMERS. OXYGEN

FLASK COMBUSTION - DIRECT TITRATION PROCEDURE.
80.1 SUMMARY
This oxygen flask combustion - titration method is capable of determining total

sulphur in amounts down to 50 ppm in sulphur containing polymers.
80.2 APPARATUS
Conical flask - Pyrex or Jala glass, 500 ml capacity, provided with conical ground
joint BS-B 24, (see Method 76).
Stopper, BS-B 24, with fused in platinum wire (30 mm long, 0.8 mm diameter)
carrying a 15 x 20 mm piece of 40 mesh platinum gauze.
Safety jacket, to serve as a protection during the combustion. Detachable metal
wire gauze jacket fitting around the conical flask.
Syringe - 0.05 ml capacity, with 0.001 ml divisions.
Lighter - any suitable small flame fed with sulphur-free fuel, ego alcohol.
Micro burette assembly, with 10 ml burette and Pyrex supply bottle, two required.
Ultramicro burette, with 0.001 ml divisions and provided with a glass capillary
delivery tube.
Photoelectric colorimeter equipped with two 100 ml optical cells and two 520 om
interference filters in rim, or equivalent.
Electric stirrer, of suitable dimensions to fit on and close the colorimeter
compartment, provided with small glass propeller-shaped stirrer.
Filter paper for sample wrapping. Any grade with sulphur content less than 100
ppm ego Whatman No. 41 or 42. Cut out paper, sized and shaped according to Figure
7.18. Fold them along the dotted line to the U shape and store in a closed bottle to protect
from any sulphur present in the atmosphere. As the paper contains a small amount of
sulphur it is necessary to ensure that the same weight (30 to 40 mg) is used in the sample
and the blank combustions.
80.3 REAGENTS
Barium perchlorate standard solution 0.0005 M, dissolve 0.17 g barium

perchlorate in 200 cm3 of deionized water and make up to 1 litre with redistilled
isopropanol. Adjust to pH 3.5 by additions of 10% perchloric acid solution. Standardize
in an optical cell against sulphuric acid using 1 cm3 of isopropanol. Add 1 drop (approx.
361
0.05 cm3) of perchloric acid solution 3% and 200 ± 1 ul of 0.07% w/v Thorin indicator
solution and proceed as described under Procedure. Run a blank titration in the same way
using exactly the same amounts of reagents but omitting the sulfuric acid and applying 20
± 0.5 cm3 of deionized water instead of 10 cm3• Obtain the net normality of the barium
perchlorate solution.
Barium perchlorate solution standard 0.005 M.
Dissolve 1.7 g barium perchlorate in 200 cm3 of deionized water and make up to 1
litre with redistilled isopropanol. Adjust to pH 3.5 by additions of 10% perchloric acid.
Standardize in an optical cell against sulfuric acid using 10 cm3 of standard 0.005 M
sulphuric acid solution. Dilute with 10 ±0.5 cm3 of deionised water and add 80 ±2 cm3
of isopropanol. Add 1 drop (approx O.OS cm3) ofperchloric acid solution 3% and 200 ± 1
ul (1 ul = 0.001 cm3) of 0.02% w/v Thorin indicator solution and proceed as described
under Procedure. Run a blank titration in the same way using exactly the same amounts
of reagents but omitting the sulfuric acid and applying 20 ± O.S ml of deionized water
instead of 10 cm3• Obtain the net normality of the barium perchlorate solution.
Hydrogen peroxide: 100 volume Microanalytical reagent grade.
Isopropyl alcohol, redistilled.
Oxygen, free from sulphur compounds.
Perchloric acid, 0.01 M microanalytical reagent grade in glacial acetic acid.
Sulphuric acid, O.OOS M prepared by accurate dilution ofO.OS M acid.
Sulphuric acid, 0.0002S M, prepared by accurate dilution of 0.005 M acid.
Prepare the O.OOOS N reagent at least once daily as required.
Thiorin indicator solution: 0.02% aqueous Thorin (sodium salt of 2(2-hydro-3,6-
disulpho-l-napthylazo) benzene arsonic acid).
Water, deionised, sulphate content less than O.OS ppm.
80.4 METHOD
The sample is wrapped in a piece of filter paper and burnt in a closed conical flask
filled with oxygen at atmospheric pressure. The sulphur dioxide produced in the reaction
reacts with dilute hydrogen peroxide solution contained in the reaction flask to produce
an equivalent amount of sulphuric acid which is estimated by visual titration with 0.005
M or 0.0005 M barium perchlorate using Thorin indicator.
80.5.1 Sample Combustion.
The weight of sample taken should be sufficient to produce a titration of about 4

cm3 of 0.005 or O.OOOS M barium perchlorate. The maximum permissible sample weight
for complete combustion is 30 mg. Weigh a blank piece of filter paper of similar size and
check that its weight is within ± S% of the weight of the paper used in the sample
analysis. Wrap the sample up in the following way. First cover the sample with the
raised edges of the paper strip and then roll up the body of the strip towards the narrow
strip at the end, which will serve as a fuse. Now clamp the packet in the platinum gauze
or bucket on the flask stopper, keeping the fuse free from and in line with the platinum
suspension wire. Repeat this operation with the blank piece of filter paper. Pipette 4.0 ±
0.5 ml deionised water and O.IS cm3 hydrogen peroxide solution into a clean combustion
flask. Place the flask in the safety jacket. Replace the air in the conical flask with a rapid
368
stream of oxygen. Ignite the end of the fuse of the sample packet and immediately insert
the sample into the combustion flask. Keep the flask firmly closed and keep it upside
down for a minute. Shake the flask for one min and allow it to stand for 15 min. When
all the mist has disappeared, wet the rim of the flask with isopropyl alcohol, carefully
open the flask and transfer the flask contents quantitatively to a 100 cm3 beaker by means
of 65 cm3 isopropyl alcohol and 12 cm3 water. To the beaker add 2 cm3 0.02% Thorin
indicator, 3 drops of 0.05 M perchloric acid and 1 cm3 of 0.00025 M sulphuric acid (by
pipette). Carry out a blank combustion including the paper and all the reagents but
Titrate the sample and blank solutions with 0.005 M or 0.0005 M barium
perchlorate solution using a 5 cm3 syringe.
Calculate the sulphur content of the sample as follows:
Sulphur (ppm) (V - B) x M x 16 x W
W
where:
V = volume (cm3) of barium perchlorate solution consumed in actual
determination
B = volume (cm3) of barium perchlorate solution consumed in blank
determination
W = weight of sample in g
M = molarity of barium perchlorate.
The procedure is capable of determining sulphur in amounts from 500 ppm

upwards in polyolefms and in other polymers. The repeatability of the method is ± 40%
of the determined sulphur content at the 500 ppm sulphur level, improving to ± 2% at the
1% level. Chlorine and nitrogen concentrations in the sample may exceed the sulphur
concentration several times over without causing interferences. Fluorine does not
interfere unless present in concentrations exceeding 30% of the sulphur content.
Phosphorus interferes even when present in moderate amounts. Metallic constituents also
interfere when present in moderate amounts.
METHOD 81 - DETERMINATION OF MACRO-AMOUNTS OF SULPHUR IN

POLYMERS. SODIUM PEROXIDE FUSION - TITRATION PROCEDURE.50
81.1 SUMMARY
This sodium peroxide fusion - titration procedure is capable of determining total

sulphur in polymers in amounts down to 500 ppm.
369
81.2 APPARATUS
Nickel "fluorine bomb" capacity 2 ml - obtainable from Charles W. Cook and

Sons Ltd., 97 Walshall Road, Perry Barr, Birmingham.
Conical flask with ground glass stopper, capacity 150 or 200 ml.
Magnetic stirrer.
Microburette, capacity 10 ml- conforming to BS. 1428.
81.3 REAGENTS
Sodium peroxide, MAR grade.

Ethanol, absolute.
Barium perchlorate, 0.01 N aqueous, adjust to about pH 3.0 by adding perchloric
acid.
Thorin indicator solution, dissolve 25 mg of thorin in 5 ml of distilled water.
Methylene blue indicator solution, dissolve 15 mg of methylene blue in 50 ml of
water.
Cation exchange resin, Amberlite IR-120 (H).
Pre-treatment of the resin. By the column method wash about 400 g of the
analytical grade resin with about 700 ml of 3.0 N hydrochloric acid and then with 4 or 5
litres of water. Transfer the resin to a 1 litre flask, remove most of the water by
decantation and shake the resin thoroughly for several minutes with three succesive 100
ml portions of ethanol. Remove the residual ethanol by repeated washing with water and
shake the resin vigorously with 400 ml of 0.5 N sodium hydroxide for about 10 minutes.
Decant the slightly turbid solution, wash the resin with water until all suspended fine
particles have been removed, and filter on a Buchner funnel. Press the resin between
filter papers and store it in a glass stoppered bottle sealed with adhesive tape.
81.4 METHOD
The polymer sample is fuzed with sodium peroxide in a sealed bomb. The fusion
product is dissolved in water and sodium ions removed on a cation exchange column.
The sodium-free eluate is titrated with standard barium perchlorate solution to the thorin -
methylene blue end-point to estimate the amount of sulphate present.
81.5.1 Fusion ofthe Sample with Sodium Peroxide:
Place in the dry bomb 0.5 g of powdered sodium peroxide, a suitable weighed
amount of the sample (5 to 15 mg) and a further 0.5 g of sodium peroxide. Close the
bomb and mix the contents by rotation. Heat the bomb in a muflle furnace for 3 minutes
at 650·C. Cool the bomb, remove the lid and extract the fusion product by placing the
bomb in a small beaker containing 10 to 15 ml of water and warming until effervescence
ceases. Remove the bomb, rinse it with water and then rinse the lid. Transfer the
combined solutions quantitatively to a 50 ml calibrated flask and dilute to the mark.
370
81.5.2 Removal of Sodium from Fusion Product and Titration
Place about 30 g of the cation exchange resin in a conical flask. Add about 25 ml
of ethanol, shake the stoppered flask for about 1 minute, remove the ethanol by
decantation and repeat the operation with a further 20 mJ of ethanol. Transfer 25 mJ of
the fusion product extract to the resin, shake for about 5 minutes and decant the solution
into a suitable conical titration flask containing a magnetic stirrer bar. Rinse the resin
with four successive 25 ml portions of ethanol, add all washings to the contents of the
titration flask. Add 0.1 ml each of thorin and methylene blue indicator solutions and
titrate with 0.01 N barium perchlorate to a pink end-point colour persisting for about 20
seconds. Carry out a blank determination in the same manner, omitting only the sample.
The blank value should lie between 0.1 and 0.2 ml.
Precautions:
When the sodium peroxide fusion is carried out as described, only a small amount
of insoluble matter should be found in the aqueous extract of the fusion product, but this
material can interfere with the detection of the end-point of the titration. For the best
results the extract should be set aside overnight, so that a clear portion can be withdrawn
for titration.
End-points in the barium perchlorate titration may be unsatisfactory if the ethanol
washed resin is set aside for more than about 2 hours before use. If such a delay is
unavoidable, the resin should be washed once more with about 20 ml of ethanol
immediately before use.
With some batches of resin it has been observed that after pre-treatment in the
prescribed manner, unsatisfactory end-points are obtained in the titration of the resin
treated sample sOlution. If this defect is found with any portion of a given batch of resin,
it is recommended that all subsequent portions should be vigorously shaken with about
25 ml of 0.5 N sodium hydroxide for about 10 minutes and then washed with water and
ethanol in succession before use.
This procedure is capable of determining down to 500 ppm of total sulphur in

sulphur containing polymers with an accuracy of ± 5%.
Chlorine, fluorine and nitrogen in amounts up to 2 mg in the sample are without
serious effect on the determination of sulphur. The effect of larger amounts of fluorine
can be suppressed by the addition of boric acid.
METHOD 82 - DETERMINATION OF SULPHUR IN POLYMERS. OXYGEN

FLASK COMBUSTION - PHOTOMETRIC TITRATION PROCEDURE.
82.1 SUMMARY
This oxygen flask combustion photometric titration procedure is capable of

determining total sulphur in polymers in amounts down to 50 ppm.
371
82.2 APPARATUS
A general view of the titration arrangement is given in Figure 7.19.

Conical flask - pyrex or Jena glass, 500 cm3 capacity, provided with conical
ground joint B 24, (see Method 76)
Stopper, B 24 with fused in platinum wire (30 mm long, 0.8 mm diameter)
carrying a 15 x 20 mm piece of 40 mesh platinum gauze (see Figure 7.18 and Method
76).
Safety jacket, to serve as a protection during the combustion. Detachable metal
wire gauze jacket fitting around the conical flask.
Syringe - 0.05 cm3 capacity, with 0.001 cm3 divisions.
Lighter - any suitable small flame fed with sulfur-free fuel, ego alcohol.
Microburette assembly, with 10 cm3 burette and Pyrex supply bottle, two
required.
Ultramicro burette, with 0.001 cm3 divisions and provided with a glass capillary
delivery tube.
Photoelectric colorimeter equipped with two 100 cm3 optical cells and two 520
nm interference filters in rim.
Electric stirrer of suitable dimensions to fit on and close the colorimeter
compartment, provided with small glass propeller-shaped stirrer (Figure 7.19).
82.3 REAGENTS
Barium perchlorate solution, standard 0.005 M, prepare as described in Method

80.
Barium perchlorate solution standard 0.0005 M, prepare as described in Method
80.
Filter paper, ash-free. Schlekher and Schull No. 5892 is recommended. Store in
a closed bottle.
Hydrogen peroxide, 30% AR.
Isopropanol, cp, denatured.
Oxygen, compressed, free of sulphur compounds.
Perchloric acid, 10% AR.
Perchloric acid, 3%, AR.
Sulphuric acid solution, standard, 0.01 N prepare by accurate dilution of
standardized 0.1 N sulphuric acid solution.
Sulphuric acid solution, 0.0005 N, prepare by accurate dilution of 0.01 N
sulphuric acid solution.
Thorin indicator solution, 0.2% aqueous solution of thorin (sodium salt of 2(2-
hydroxy-3, 6-disulfo-I-napthylazo) benzene-arsonic acid). The thorin quality marketed
by Merck, Darmstadt, West Germany, is recommended.
Water, deionized.
82.4 METHOD
The sample, contained in a piece of filter paper and suitably suspended, is rapidly
and completely burnt in a closed conical flask filled with oxygen at atmospheric pressure.
The products of combustion are allowed to enter a hydrogen peroxide solution. The
amount of sulfuric acid formed is determined by titration with barium perchlorate, using
372
Thorin as the indicator. The equivalence point is obtained photoelectrically by
comparing the optical density of the solution with that of a standard reference solution.
82.5.1 Sample Combustion
Weigh a filter strip to the nearest 0.1 mg. Place approximately 30 mg of sample
onto the middle of the filter strip and weigh again. Wrap the sample up in the following
way: first cover the sample with the raised edges of the strip and then roll up the body of
the strip towards the end, which will serve as a fuse. Now clamp the packet in the
platinum gauze of the stopper, keeping the fuse free and in line with the platinum
suspension wire.
Introduce 4 ± 0.4 ml of deionized water and 3 drops of hydrogen peroxide
solution 30% into the conical flask. Install the safety jacket.
Replace the air in the conical flask by oxygen by introducing a rapid stream of
oxygen at a point near the bottom for 30 seconds. (Place a G 3 porosity glass filter in the
outlet end of the oxygen line to prevent contamination of the absorption liquid).
Place the flame of the lighter close to the top of the conical flask, ignite the end of
the fuse of the sample packet and immediately insert the stopper.
Keep the flask firmly closed and keep it upside down to prevent the flame from
touching the walls or bottom of the flasK. When the combustion slows down bring the
flask in an inclined position to promote complete combustion also of any dropping
particles. Remove the safety jacket, shake the bottle for one minute and allow it to stand
for 15 minutes.
82.5.2 Spectrophotometric Evaluation
In an optical cell prepare a colour reference solution by mixing 100 ml of

deionized water and 200 ± 1 ul of thorin indicator solution (measured from the ultramicro
burette). Measure the optical density using the deflection method. This value should be
0.17 ± 0.01, adjust if necessary by adding a known amount of either 0.0005 N sodium
hydrogen carbonate solution or 0.0025 N sulphuric acid solution.
Prepare a double amount of the colour reference solution described in the previous
paragraph in a beaker. Introduce half of it into each optical cell and check the optical
density of the solution. With both cells in the compartments and the photometer adjusted
for highest sensitivity bring the pointer at position 50 of the linear scale marked "abs".
Check whether the cells are matched by interchanging them. During the actual
determination keep the right-hand cell in its place and titrate in the left-hand cell.
Prepare and measure a fresh colour reference solution at least once a day and
whenever a new batch of deionized water or thorin indication solution is used. Switch on
the photometer at least two hours before use.
Introduce 1 ml of 0.00025 N sulphuric acid solution by means ofa pipette and 15
± 0.5 ml of deionized water into the optical cell. Wet the rim between flask and stopper
with some isopropanol and open the flask to draw the liquid in. Use 80 ± 2 ml of
isopropanol to wash the stopper and the platinum gauze and to transfer the solution under
test quantitatively to the cell. Add I drop (approx 0.05 ml) of 3% perchloric acid solution
and 200 ± 1 ul of thorin indicator solution.
373
Figure 7.19. Titration assembly for the photometric sulfate titration.
Place the optical cell in the photometer and install the electric stirrer. Immerse the
burette tip into the cell solution and stir. Titrate at a slow rate with barium perchlorate
solution, until the pointer reaches 50 again. Use the 0.005 M barium perchlorate solution
for sulphur contents exceeding 0.15% and the 0.0005 M barium perchlorate solution for
the lower sulphur concentrations.
Especially in the lower sulphur range, aminimum titration time of two minutes is
recommended. Run a blank determination including all reagents used (also filter paper)
but omitting the sample.
82.5.3 Calculation.
Calculate the sulphur content by means of the following equation:
Sulphur % w = (V - 8) x N x 16 x I ~
W
where:
V = volume of barium perchlorate solution consumed in the actual determination,
millilitres.
B = volume of barium perchlorate solution consumed in the blank determination,
millilitres.
N = normality of the barium perchlorate solution.
W = weight of sample milligrams.
374
The following data should be used for judging the acceptability of results (95%
probability). Duplicate results by the Same operator should not differ by more than the
following amounts;
Sulphur content Repeatability
Above 0.5% 0.05

Below 0.5% 2% of amount present but not better than 0.005
Chlorine and nitrogen concentrations in the sample may exceed the sulfur
concentrations several times over without causing interference. Fluorine does not
interfere unless present in concentrations exceeding 30 per cent of the sulfur content.
Phosphorus and metallic constituents interfere even when present in moderate amounts.
METHOD 83 - DETERMINATION OF DOWN TO 50 PPM ORGANIC

NITROGEN IN POLYOLEFINS. KJELDAHL DIGESTION - BORIC ACID
TITRATION METHOD.
83.1 SUMMARY
This kjeldahl digestion - titration procedure determines organic nitrogen in

amounts down to 50 ppm in polyalkenes.
83.2 APPARATUS
Kjeldahl digestion flasks: 500 cm3 • Kjeldahl flask heater, 120 watts. Mount
flasks in heater at an angle of 30 degrees to the horizontal.
Distillation apparatus.
Microburette, capacity 10 cm3•
83.3 REAGENTS
Boric acid, 4% w/v.

Mercuric oxide/cupric sulphate catalyst: grind together 109 mercuric oxide and 5
g cupric sulphate (anhydrous).
Selenium powder.
Iron III chloride: 40% w/v aqueous, to 100 cm3 of this solution add 5 drops of
concentrated sulphuric acid.
Sulphuric acid, 98% use nitrogen-free grade. Keep well stoppered to ensure
minimum contamination of this reagent by nitrogen containing impurities in the
laboratory atmosphere.
Potassium sulphate - AR.
Sodium hydroxide, 40% w/v aqueous, made from AR reagent.
Hydrochloric acid, 0.02 M.
375
Tashiro indicator, 0.125% w/v methyl red and 0.0083% w/v methylene blue in
ethyl alcohol.
83.4 METHOD
A sample of polymer (up to 5 g) is digested with a mixture of sulphuric acid,

mercuric oxide, copper sulphate and selenium catalysts to convert nitrogen containing
organic compounds to ammonium sulphate. Digestion is completed by adding sufficient
potassium sulphate to the digestion mixture to raise its boiling point to 380°C followed by
heating to completely remove any carbonaceous matter present.
The solution is then transferred to a distillation apparatus and excess sodium
hydroxide added to convert ammonium sulphate to free ammonia. The ammonia is
distilled off and collected in boric acid solution and the ammonia content of the steam
distillate is determined by titration with standard hydrochloric acid solution.
83.5.1 Sample Digestion.
Weigh out a known amount of the polymer (maximum 5 g) and carefully transfer
into a 500 cm3 Kjeldahl digestion flask. Into a second (blank) flask transfer the same
weight of nitrogen-free polymer. To each flask add 0.2 g mercuric oxide/cupric sulphate
mixture, 10 mg selenium, some glass beads and 15 cm3 concentrated sulphuric acid. In
addition to each flask add a further 10 cm3 concentrated sulphuric acid per g of polymer
present in the sample flask. Place the digestion flasks on the electric heaters and raise to
the boiling point as rapidly as possible with occasional swirling. Continue heating until
the sample solution becomes yellow/brown in colour (this usually takes 2 to 4 h). If
necessary add further similar quantities of concentrated sulphuric acid to the sample and
blank flasks to maintain a minimum volume of 20 cm3 of acid. Leave the flasks to cool
and note the weight of the flask contents. To the sample and blank flask add 0.72 g
potassium sulphate per g of flask contents. Again place the flasks in the heating mantle
and boil for a further 90 min to complete the digestion process. Allow the flasks to cool
and to each add approximately five volumes of deionized water per volume of acid
present (care). Add 2 drops iron III chloride reagent.
Fill the steam generator with water and add to it a few pellets of sodium hydr-
oxide. Connect the generator to the steam distillation apparatus and steam out the appar-
atus for 20 min (run steam distillate to waste). Transfer the sulphuric acid digestion
mixture into the IL- sample flask and pass steam through the sample of a further twenty
min (removes any volatile acids present in the sulphuric acid digest). Into a 250 cm3
conical flask (B 24 socket) pipette 25 cm3 4% boric acid solution and add 100 ml
deionized water and 5 drops of Tashiro indicator. If necessary add a few drops of MIlO
sodium hydroxide solution to produce a green colour and then back titrate each flask with
Ml50 hydrochloric acid to a turquoise blue colour. Transfer 30 cm] of this solution into
each of the two 250 cm3 clean stoppered conical flasks. Retain one of the flasks (flask A)
as a comparison standard for the final ammonia titration. At the end of the steam
purging, connect the second 250 cm3 titration flask (flask B) to the freshly purged steam
distillation apparatus. Continue passing steam through the apparatus and fill the
separatory funnel on the steam distillation apparatus with 40% sodium hydroxide. Run
this solution into the hot acid mixture until a slight excess of alkali is present (indicated
376
by formation of brown precipitate of cupric hydroxide). Run in a further 5 to 10 cm3
excess of sodium hydroxide. Continue the steam distillation until about 130 cm3 of
liquid is present in conical flask B. Remove this flask from the distillation apparatus and
leave until about 130 cm3 ofliquid is present in the flask.
83.5.2 Sample Titration.
Titrate the contents of the sample conical flask B with 0.02 M hydrochloric acid
until it has the same shade (turquoise or bluish grey) as the contents of the comparison
flask A. Note the volume of hydrochloric acid used in the titration.
83.5.3 Calculation.
Calculate the nitrogen content of the polymer as follows:
Nitrogen (ppm) = <VI - V2) x M x 14 X 106

l000xW
where:
VI = titration (cm3 ) of standard hydrochloric acid in sample determination.
M = molarity of hydrochloric acid.
V2 = titration (cm3 ) of standard hydrochloric acid in reagent blank determ-
ination.
This procedure is capable of determining down to 50 ppm of organic nitrogen in

polymers with an accuracy of ± 10%.
METHOD 84 - DETERMINATION OF 1 TO 90% ORGANIC NITROGEN IN

POLYMERS. KJELDAHL DIGESTION - BORIC ACID TITRATION METHOD.
84.1 SUMMARY
This Kjeldahl digestion - titration procedure is capable of determining between 1

and 90% of organic nitrogen in polymers.
84.2 APPARATUS
a) Kjeldahl digestion apparatus consisting:

Kjeldahl digestion flasks - 100 ml Pyrex glass.
Electric heating "Bun ray" electric bunsens suitable (minimum loading 375 watts)
or Kjeldahl digestion flask heaters with flask supports (l00 ml flask size).
b) Ammonia recovery apparatus consisting of (see Figure 7.20). Condenser
(B24 cone and socket), Leibig 12". Round bottomed steam generation flask, 1000 ml
central B24 and 2 x B19 side. Three way stopcock, vertical arm connected to B24 cone.
Separatory funnel 250 ml with B19 cone.
377
Recovery apparatus proper:
Consisting of steam stripping vessel (interior vessel large enough to hold 150 ml
solution). Separatory funnel 50 ml with B14 cone and short delivery stem. Steam trap
leading to vertical condenser and guard tube containing activated silica gel which is
connected by a suitable adaptor (note 2). Activated silica gel. Self indicating, mesh 6-20,
available from British Drug Houses Ltd., Poole. To regenerate gel, heat for 6 hours at
1500 C in a vacuum oven.
c) Apparatus for determination of ammonia in distillate, miscellaneous glassware:
Burette, 50 ml pipettes.
84.3 REAGENTS
Sulphuric acid, preferably nitrogen-free quality supplied by British Drug Houses

Ltd., Poole.
Glucose, micro analytical reagent (MAR) grade, British Drug Houses Ltd., Poole.
Kjeldahl digestion catalysts, the following supplied by British Drug Houses Ltd.,
Poole.
Tablets each consisting of 1 g sodium sulphate and the equivalent of 0.05 g
selenium (as selenium dioxide).
Tablets each consisting of 1 g sodium sulphate and equivalent of 0.05 g of
mercury (as mercuric oxide).
Cupric sulphate, 25% w, dissolve 25 g CuS044H20 Analar in water and make up
to 100 ml (0.2 ml of this solution contains 0.05 g CuS045H20.
Mercuric oxide, pure grade.
Potassium sulphate, Analar.
Sodium hydroxide, (use when mercury - free catalysts are used for Kjeldahl
digestion). Pour 1600 ml distilled water into a 4 litre beaker and add 1500 g of sodium
hydroxide Analar. When dissolved allow to cool and transfer to a winchester.
Sodium hydroxide - sodium thiosulphate (use when mercury containing catalysts
are used for Kjeldahl digestion). Pour 1400 ml distilled water into a 4 litre beaker and
add 1500 g sodium hydroxide Analar. When dissolved allow to cool. In a further beaker
dissolve 150 g sodium thisulphate 5H20 Analar in 200 ml distilled water. Mixt the two
solutions and transfer to a winchester. Remove nitrogenous impurities from either
reagent as follows: Add 5 g zinc powder and pass a slow stream of nitrogen for 48 hours
to sweep our ammonia. Filter the cold solution through a 40 cm Whatrnan No. 1 filter
paper to remove sodium carbonate. Store the reagent in polyethylene bottles. Carry out
these operations in a fume cupboard to avoid contamination of the solutions by any
ammonia impurity present in the laboratory atmosphere.
Boric acid, 4% w, dissolve 40 g boric acid (H3B03) Analar in 1000 ml distilled
water contained in a 2 litre round bottomed flask. Boil for 20 minutes to expel carbon
dioxide. Connect a carbon dioxide absorbing guard tube and cool. Transfer to a I litre
volumetric flask. Make up to I litre with cold boiled out distilled water and mix.
Methyl red, bromo-cresol green indicator: Mix 5 volumes of 0.2% bromo-cresol
green with 1 volume of 0.2% methyl red, both in 95% ethanol.
Hydrochloric acid, 0.05 N.
Hydrochloric acid, 0.02 N prepared daily by dilution of the 0.05 N hydrochloric
acid stock.
378
l-WAY
STOPCOCK a40 CONNECTION
TI
SAMPLE VESSEL
CAPACITY 150.1
ELECTRICALLY
WASTE HEATED LlTIIE
FLASK STEAM GENERATOR
Figure 7.20. Ammonia recovery steam stripper assembly.
84.4 METHOD
The procedure involves Kjeldahl digestion followed by collection of generated

ammonia in boric acid.
A suitable weight of sample is digested with concentrated sulphuric acid, sodium
or potassium sulphate and digestion catalysts using an electrical heater (note 1). A
reagent blank determination is also carried out. The digested sample, after dilution, is
transferred to a steam distillation apparatus. The addition of sodium hydroxide liberates
ammonia equivalent to the nitrogen content of the sample. Liberated ammonia is
coIlected in boric acid solution and determined by titration with standard hydrochloric
acid.
84.5.1 Sample Digestion
The weights of sample required for the determination of nitrogen in compounds

containing between 1% and 90% of nitrogen are shown below. Also shown is the
normality of the hydrochloric acid required for the titration of ammonia at the end of the
determination.
379
Recommended sample size and normality of hydrochloric acid used in final
ammonia titration.
Weighing with 4·place balance
Nitrogen content of Weight ofsample for Strength (N) of hydrochloric acid

sample % digestion (g) to be used in titration of
ammonia, normality
)·3 0.2 0.Q2

5 0.2·0.1 0.02
10 0.1 0.02
20 0.1 ·0.05 0.02
40 0.03 or 0.05 0.02 or 0.05
60 0.05 0.05
80·90 0.03 0.05
Methods of sample transfer into Kjeldahl digestion - Solids: These may be

transferred directly to the Kjeldahl flask or wrapped in a cigarette paper, (use potassium
nitrate free brand of paper) which is dropped into the flask.
Aqueous solutions of polymers: Pipette a suitable aliquot of test solution into the
flask and add 6 drops of 0.5 N sulphuric acid (include in blank). Heat at 50°C under
vacuum to reduce the volume to approximately I ml. The sample is now ready for
analysis.
In the Kjeldahl flask containing the sample introduce a small piece of clean
porous pot. Depending on the weight of sample to be digested, add the recommended
quantities of a suitable catalyst mixture and of concentrated sulphuric acid as indicated in
Table 7.43 also 0.05 g glucose (note 3).
To the flask used for the reagent blank determination introduce the same amount
of catalyst mixture, sulphuric acid and glucose. Suitable catalysts and length of sulphuric
acid digestion time for the digestion of various types of nitrogen compounds and
polymers are shown in Table 7.44.
Mount the digestion flask containing sample, sulphuric acid, catalysts and glucose
on an electrical heater (note 2) and insert a small funnel in the neck of the flasks. Digest
gently at fIrSt and then increase the digestion temperature steadily, at five or ten minute
intervals over the recommended digestion period (Table 7.44). After the first 45 minutes
digestion the heating rate should be such that the acid is condensing about half way up
the neck of the digestion flask (maximum digestion temperature 380°C). Ensure that the
carbon char becomes completely oxidized during digestion. Continue the digestion 20
minutes at least, at maximum temperature after the solution has clarified. When digestion
is complete, switch off the heaters. Leave to cool at room temperature. At least half of
the original sulphuric acid addition should remain in the digestion flasks at this stage
(note 5). Add distilled water to the contents of each digestion flask.
84.5.2 Ammonia Recovery by Steam Distillation.
Set up the distillation apparatus shown in Figure 7.20. To the I litre steam
generation flask add several pellets of sodium hydroxide and some boiling chips and
three quarters fill with distilled water. Tum stopcock II to connect A to C. Boil the
contents of the generator for 5 minutes (note I) to sweep out dissolved ammonia into the
waste flask. Then turn stopcock TI to connect B to C thereby passing steam through the
380
steam stripper (stopcock D and clip at E closed). Again divert the steam supply to the
waste flask.
Transfer the contents of a digestion flask with two or three 5 ml distilled water
washings together with 0.2 ml 25% cupric sulphate solution via the funnel on the steam
stripper to the interior sample vessel and close the stopcock D. Open the outlet E to
waste and turn stopcock Tl to reconnect B and C. Pass steam until it exits at E.
Meantime pour an excess of 40% sodium hydroxide into the (closed) funnel at D. Use 10
mI, 20 ml or 40 ml sodium hydroxide respectively, depending on whether 2 ml, 5 ml or
10 ml of concentrated sulphuric acid was used for acid digestion. If the digestion catalyst
used contains mercury or mercuric oxide use instead, the same volumes of sodium
hydroxide - sodium thiosulphate solution (note 6). Use the same amount of alkali in both
sample and blank determinations.
Connect to the vertical condenser of the steam stripper a 250 ml flask. Connect a
guard tube containing freshly activated silica gel in position above this receiving flask
(note 2). When steam is emitting from the steam stripper outlet E close the clip thereby
allowing steam to pass through the sample solution. Steam distil until about 50 ml
distillate has been collected (note 7) and disconnect the flask from the apparatus.lnto a
clean 250 ml ammonia receiving flask pipette 25 ml 4% boric acid solution and add 4
drops of bromo-cresol green - methyl red mixed indicator. If this solution is blue-green
in colour (due to the presence of a trace of dissolved ammonia), then add single drops of
0.01 N hydrochloric acid from a burette until the solution becomes neutral grey in colour.
Connect this flask to the vertical condenser of the steam stripper, (silica gel guard tube
still in position).
When steam is emitting from the steam stripper outlet E, close the clip thereby
allowing steam to pass through the sample solution. Open stopcock D and slowly admit
the alkaline reagent in several portions. Leave 1 ml of alkali in the funnel to act as a seal.
It is necessary to ensure that an excess of alkali is added at this stage. Alkalinity is
indicated by the formation of, first, a soluble deep blue cupramine salt then a precipitate
of brown copper oxide.
Steam distil until the volume of liquid in the receiver is approximately 100 ml, ie.
for about 20 minutes. Remove the receiver flask from the apparatus. Clean the steam
stripper ready for the next analysis (note 8).
Titrate the contents of the receiver flask with either 0.05 N or 0.02 N hydrochloric
depending on the amount of sample digested and its nitrogen content.
The colour change at the end-point is from green to neutral grey. The addition of
a further drop of hydrochloric acid beyond this end-point should produce a pale pink
colour.
84.5.3 Calculation.
The nitrogen content of the sample is given by:
%N(%) = fTa-Tb) x f x 14
W x 10
where:
Ta = titration (ml) of hydrochloric acid, sample.
Tb = titration (ml) of hydrochloric acid, blank.
f = normality of hydrochloric acid.
381
Table 7.43 - Catalyst and Sulphuric Acid Additions
Weight of Sample Catalyst and Alkali Sulphate Volume of
Digested (g) Mixture Concentrated
Sulphuric Acid
Used for
Digestion, ml
0.1 - 0.3* AU 0.4g Sodium Sulphate 2

0.02 g Selenium (as Dioxide)
0.02 g CuSo45HzO
or
B 0.4 g Sodium Sulphate 2
0.02 g Mercury (as Oxide)
or
C 1.3 g Potassium Sulphate 2
0.04 g Mercuric Oxide
0.03 - O.OS* AU I g Sodium Sulphate 5

0.05 g CuS045H20
or
B I g Sodium Sulphate 5
or
C 3 g Potassium Sulphate 5
0.1 g Mercuric Oxide
O.OS - 0.2 AU 2 g Sodium Sulphate 10

0.1 g CuS045HzO
or
B 2 g Sodium Sulphate 10
• Use a micro or semi-micro balance when weighing out 0.01 - 0.03 g samples
•• Recommended as a good general digestion catalyst. The sodium sulphate-selenium catalyst is available
in tablet form from B.D.H. Ltd.
Note 1. Electrical heating during the Kjeldahl digestion and ammonia recovery is
preferable to gas heating. The chance of contamination of the sample by nitrogenous
impurities in coal gas is thereby avoided.
Note 2. Pick up of ammonia impurity from laboratory atmosphere. The apparatus

used for steam distillation from alkali to recover ammonia from the acid digest is fitted
with an activated silica gel guard tube. This prevents contamination of the distillate with
any ammonia impurity that is present in the laboratory atmosphere.
Note 3. Addition of glucose in Kjeldahl digestion. Normally no organic matter

would be present in the blank digestion flask. If the nitrogen impurity in the reagents is
in both oxidized and reduced forms, therefore, it is necessary to add some organic
material to the contents of the blank flask in order to ensure that nitrogen impurity is
382
Table 7.44 - Selection of Suitable Catalysts and'Digestion Times
Type of Compound Digested Catalyst and Alkali Total Digestion

Metal Sulphate Mixture Time with Sulph-
Recommended· uric Acid (hrs)
(see Table 7.43)
Amines, amino compounds amino acids, amides and A,BorC 1.5·2

their simple derivatives
Nitriles and their simple derivatives also: styrene· A 3
acrylonitrile copolymers and polyacrylonitrile
Refractory nitrogen compounds C 4
Nitro, nitroso and azo compounds hydrozones, See Note 4 4
oximes and some heterocyclic nitrogen compounds
Many azo compounds, volatile nitro compounds, No successful Kjeldahl
diazo ketones and certain semicarbazones digestion procedure
known
completely reduced. The addition of 0.05 g pure glucose to the blank (and sample) is
sufficient for this purpose.
Note 4. Reduction of nitrogen compounds prior to Kjeldahl digestion. Nitro,

nitroso and azo compounds also, hydrazones, oximes and some heterocyclic compounds
are not quantitatively digested by the catalysts A, B or C shown in Table 7.43. If
compounds of these types are being analysed either add 0.5 g pure sucrose (or glucose) to
the mixture of catalyst A or B, sulphuric acid and a suitable weight of sample or carry out
a preliminary reduction of the sample with hydriodic acid and red phosphorus as
described below.
Transfer a suitable weight of sample (catalysts and sulphuric acid absent) and 5
ml of pure hydriodic acid (Analar about 55%) to a clean Kjeldahl flask with B19 quickfit
socket. Warm gently and introduce 50 mg pure red phosphorus and some porous pot.
Reflux for 45 minutes and then dilute with 5 ml water. Add 5 ml concentrated sulphuric
acid and mix. Boil the mixture rapidly (without condenser) to remove hydriodic acid and
iodine vapour. If iodine is not completely removed add a further 5 ml of water and boil
again until the mixture fumes. Carry out an identical reagent blank omitting only the
sample additions. Add a suitable quantity of Kjeldahl digestion catalysts A or B (Table
7.43), concentrated sulphuric acid and 0.05 g glucose (note 3) to the reduced sample and
blank solutions.
Suitable quantities of catalyst and acid for the digestion of various sample weights
are shown in Table 7.43. Continue by the normal Kjeldahl digestion as described in
section b) under procedure.
Various other methods have been proposed for the reduction of nitro groups prior
to digestion. These include the use of thiosalicylic acid, salicylic acid - sodium
thiosulphate, sodium hydrosulphite-ethanolic hydrochloric acid and zinc dust - pyrogallic
acid.
To obtain satisfactory results in the digestion of pyridine it is necessary to leave
the sample in contact with catalysts and sulphuric acid for 8 hours at room temperature.
Then digest at a low temperature for 1 hour and at a higher temperature for 4 hours.
Alternatively add a crystal of iodine to the sample, sulphuric acid and catalysts and digest
in the normal manner.
383
No satisfactory general method for the digestion of nitrogen compounds with an
N-N linkage is known.
Note 5. Loss of nitrogen during digestion. Some sulphuric acid is usually lost
during digestion. The boiling temperature of the digestion mixture then increases due to
the increase in the alkali metal sulphate concentration in the digestion mixture. If the
temperature of the mixture becomes too high, due to loss of acid, then a partial loss of
nitrogen also occurs. No loss of nitrogen occurs, however, provided the volume of
sulphuric acid left at the end of the digestion is at least half of the amount originally
added.
Note 6. Modification of ammonia recovery stage when mercury containing

catalysts are used for digestion Low ammonia recoveries result during steam distillation
from sodium hydroxide when mercury containing catalysts are used in the Kjeldahl
digestion. This is due to the partial formation of a mercuric-amine which is not
completely decomposed by sodium hydroxide. The addition of a mixture of sodium
hydroxide and sodium thiosulphate completely degrades this complex and quantitative
ammonia recoveries result.
Note 7. Volatile acids in digestion mixture. It has been found that traces of steam
volatile acids remain in the acid digestion mixture after digestion of certain organic
materials. These are removed by passing steam through the diluted digestion mixture
prior to sodium hydroxide addition. This acidic distillate is rejected.
Note 8. Cleaning of steam distillation apparatus. Clean the steam stripper ready
for the next determination as follows. With clip E closed, turn stopcock II to divert the
steam supply to the waste flask (ie. connect A to C). The sample solution now syphons
from the sample vessel into the outer vessel and is disposed of by opening clip E. Now
fill the sample vessel with water via the funnel (clip E again closed) and pass steam
through this water until it boils. Syphon the water from the sample vessel as before.
Repeat this cleaning operation until the interior of the vessel is perfectly clean.
The method is capable of determining nitrogen in polymers which contain

between 1% and 90% of this element. The accuracy of results obtained is of the order of
± 1.0% of the true nitrogen content.
The Kjeldahl digestion procedures described quantitatively decomposes amines,
amino compounds, amino acids, amides, nitriles and their simple derivatives and also
many refractory nitrogen compounds. Quantitative decomposition of nitrogen containing
polymers, ego styrene-acrylonitrile copolymers and polyacrylonitrile, is achieved.
Reduction of nitrogen compounds prior to Kjeldahl digestion-Nitro, nitroso and
azo compound also, hydrazones, oximes and some heterocyclic compounds are not
quantitatively digested by the catalysts A, B or C shown in Table 7.43. If compounds of
these types are being analyzed either add 0.5 g pure sucrose (or glucose) to the mixtue of
catalyst A or B, sulphuric acid and a suitable weight of sample or carry out a preliminary
reduction of the sample with hydriodic acid and red phosphorus.
Various other methods have been proposed for the reduction of nitro groups prior
to digestion. These include the use of thiosalicylic acid, salicylic acid - sodium
384
thiosulphate, sodiwn hydrosulphite, ethanolic hydrochloric acid and zinc dust and
pyrogallic acid.
To obtain satisfactory results in the digestion of pyridine it is necessary to leave
the sample in contact with catalysts and sulphuric acid for 8 h at room temperature. Then
digest at a low temperature for I h and at a higher temperature for 4 h. Alternatively add
a crystal of iodine to the sample, sulphuric acid and catalysts and digest in the normal
manner.
No satisfactory general method for the digestion of nitrogen compounds with an
N-N linkage is known.
Normally no organic matter would be present in the blank digestion flask. If the
nitrogen impurity in the reagents is in both oxidized and reduced forms, therefore, it is
necessary to add some organic material to the contents of the blank flask in order to
ensure that nitrogen impurity is completely reduced. The addition of 0.05 g pure glucose
to the blank (and sample) is sufficient for this purpose.
METHOD 85 - DETERMINATION OF BETWEEN 0.002% AND 75% ORGANIC

NITROGEN IN POLYMERS. KJELDAHL DIGESTION - SPECTROMETRIC
INDOPHENOL BLUE METHOD.
85.1 SUMMARY
This Kjeldahl digestion - spectrophotometric method is capable of determining

organic nitrogen in polymers in amounts between 0.002 and 75%.
85.1 APPARATUS
Kjeldahl digestion apparatus consisting of (see Figure 7.21).

Kjeldahl digestioJ} flasks 100 cm3 Pyrex glass, B19 sockets.
Kjeldahl flask glass bulbs, with inlet and outlet and B19 cone.
Kjeldahl digestion flask heaters, with flask supports (100 ml flask size).
Nitrogen purifying train (see Figure 7.21), fot purifying nitrogen supply to
digestion flasks.
Two glass tubes, (approximately 18 in x 2 in) of approximately 1 cm3 capacity
with No.1 sintered glass discs and gas inlet at base and gas.oUtlet at top. Third tube (with
gas inlet and outlet) packed with glass wool to remove spray. Glass connections by ball
and socket joints.
Ammonia recovery apparatus consisting of:
(Figure 7.20) miscellaneous items.
Condenser, Liebig 12 in (B24 cone and socket) round bottomed steam generator
flask B24, central and 2 x B19 side, 1 dm3• Three-way stopcock, with vertical arm
connected to B24 cone. Separatory funnel with B19 cone, 250 cm3, Conical flasks B24,
250cm3•
Recovery apparatus proper:
Consisting of steam strippin~ vessel (interior vessel large enough to hold 150 cm3
solution). Separatory funnel 50 cm with B14 cone and short delivery stem, steam trap
leading to vertical condenser. Guard tube containing activated silica gel connected by
suitable adaptors to lower end of condenser. (Silica gel to be regenerated daily, note 3).
Activated silica gel:
385
Self indicating, mesh 6 - 20, regenerate gel: heat for 6 h at 150°C in a vacuum
oven.
Apparatus for concentration of ammonia steam distillate consisting of:
Concentration apparatus B24 to B24 (70 degree bend) distillation flask head
connected to slightly (horizontally) inclined 12 inch Liebig condenser with B24 cone and
socket. Connected to outlet end of Liebig condenser (ie. to B24 cone) an 8 in vertical
delivery tube (B24 socket) with I in diameter bulb 4 in from the open end. Open end of
delivery tube dipping in dilute sulphuric acid solution.
Silica gel guard tubes, 8 in x 1 in with B24 cone at base, packed with freshly
activated silica gel.
Apparatus for preparation of ammonia free distilled water.
Round bottomed flask (2 dm3) in electric mantle: connected via adaptor and steam
trap to slightly (horizontally) inclined 14 in Liebig condenser (B24 cone and socket).
Delivery end of condenser (B24 cone) connected by suitable B24 socket to B24
cone) adaptor to 2 dm3 separatory funnel receiver (with activated silica gel guard tube
connected by PVC tubing on side arm of the adaptor). The apparatus is totally enclosed-
the only exit to atmosphere being via the silica gel guard tube (silica gel tube regenerated
daily).
Colorimetric determination of ammonia.
Stoppered cylinders graduated, 50 cm3• Pipette 5cm3 bulb, 1 cm3 graduated.
Spectrophotometer - 4 cm glass cells.
85.3 REAGENTS
Ammonia free water. Use water which has been redistilled from 100 cm3 5%
sulphuric acid and fresh boiling chips in an apparatus which is sealed from atmosphere by
a guard tube containing freshly regenerated silica gel.
Sulphuric acid, (93%). Nitrogen free quality.
Dextrose, Analar.
Kjeldahl digestion catalysts, the following supplied by British Drug Houses Ltd.,
Poole.
selenium as selenium dioxide.
mercury as mercuric oxide.
Tablets each consisting of 1 g sodium sulphate and 0.05 g hydrated cupric
sulphate.
Tablets each consisting of 1 g sodium sulphate.
The following reagents may also be required for Kjeldahl digestion:
Copper II sulphate (25% w/v), prepared from Cu S04 5H20, aqueous.
Potassium sulphate (nitrogen free) Purify Analar potassium sulphate by
recrystallization in the following way:
Introduce into a 4 cm3 beaker 3 cm3 of distilled water, 2 g sodium hydroxide and
fresh boiling chips, heat to incipient boiling and add 675 g of Analar potassium sulphate.
Adjust to pH 10 or higher by sodium hydroxide addition. Boil for 20 mins to expel
ammonia. Filter the boiling solution on a buchner funnel through (previously hot water
washed) Whatman No. 42 filter paper. Cool the filtrate to 5°C and vacuum filter off the
small uniform crystals. Dry the crystals in an air oven (yield 450 g). Allow to cool in a
desiccator and store in well stoppered glass bottle.
386
- - - P.V_C_ TUI!>ING CONNECTIONS
------------------,
----- ------ ---1 1
-- -------1 , 1 KJELOAHL FL.t.SK I!>ULI!>S
! : (I!>. 19.)
,,
,,1 ,
1-
1... _ -
1
'--
INCLINED
DIGESTION
GlASS WOOL FL.t.SKS
SPRAY mAP
NITROGEN --
SUPPLY
El£CTIlICAL KJBJlAHL
so'o No OH 5"10 H2SO4 flASK HEATER
SCRU8aER SCRUBBeR
Figure 7.21. Kjeldahl digestion apparatus.
Sodium hydroxide (use when mercury free catalysts are used for Kjeldahl
digestion). Pour 1600 cm3 distilled water into a 4 cm3 beaker and add 1500 g sodium
hydroxide Analar. When dissolved allow to cool and transfer to a winchester_
Sodium hydroxide - sodium thiosulphate (use when mercury containing catalyst
are used for Kjeldahl digestion), (see Method 84).
Sulphuric acid 0.25 M. Prepare by dilution of nitrogen free concentrated
sulphuric acid.
Phenol, 8% in ammonia-free water. Store in a brown glass bottle.
Sodium hypochlorite (6 w/v available chlorine). Made by diluting sodium
hypochlorite solutions: (10 - 14% available chlorine) to 6.0 ± 0.1 % w/v available chlorine
content with ammonia free water.
Standard nitrogen solution (for calibration of the indophenol blue method).
Stock solution, dry ammonia sulphate Analar at 100 to 11 oDe for 1 h and weigh
out exactly 0.118 g. Transfer to a 250 cm3 volumetric flask and make up to volume with
ammonia free water. This solution contains 100 microgram nitrogen per cm3 •
Working solution: for calibration purposes take 25 cm3 of the solution and dilute
to 250 cm3 with ammonia free water. The solution contains 10 microgram nitrogen per
ml. Prepare this solution daily by dilution of the stock solution.
387
85.4 METHOD
A known weight of sample is digested with "nitrogervfree" sulphuric acid,

dextrose, potassium or sodium sulphate and digestion catalysts for 1.5 to 2 h using an
electrical heater. A suitable blank digestion is also carried out. The cooled digestion
mixture, after dilution, is transferred to a semimicro steam distillation apparatus. Steam
is passed through the sample and excess sodium hydroxide added. The liberated
ammonia is collected in slightly acidulated water.
To a standard volume of this solution is added phenol and sodium hypochlorite
reagents. An indophenol blue colour, proportional in intensity to the concentration of
ammonia present, is produced. This colour is evaluated spectrophotometrically at 625
nm using a spectrophotometer which has been calibrated against a standard ammonia
solution.
85.5.1 Analytical Conditions.
Choose an appropriate weight of sample as indicated below:

Approximate nitrogen Amount of sample Volume of Dilution to be
content of sample required for analysis H2S04 needed applied to 50 ml
in Kjeldahl of steam
distilate
%w/w ppm g mg digestion cm;!.
0.0025 25 0.6 600 10 nil
0.005 - 0.05 50 - 500 0.3 300 5 nil
0.075 750 0.l5 150 5 nil
0,1 1000 0.1 100 5 nil
0.15 1500 0.075 75 5 nil
0.2 2000 0.05 50 5 nil
0.2-2 0.05 50 5 nil orx 10
1.0 - 2.5 0.01-0.005 10 5 xlO
75 0.005 5 x50
85.5.2 Setting up Nitrogen Purifying Train (Figure 7.21).
Charge the first bubbler with 250 to 300 cm3 5% sodium hydroxide solution and
the second bubbler with 250 to 300 cm3 5% sulphuric acid solution (replace these
solutions daily). Connect four digestion flask bulbs (see Figure 7.21) in parallel, at the
outlet end of the nitrogen purifying train by means of PVC tubing. Purge the system by
passing nitrogen for I hour before commencing sample digestion.
Into two 100 cm3 digestion flasks containing a suitable weight of sample and two
blank flasks containing no sample, (ie. perform sample and blank determinations in
duplicate), introduce 0.05 g dextrose and one small piece of clean porous pot. Keep the
flasks stoppered between reagent additions to prevent contamination with any ammonia
in the laboratory atmosphere. From this point treat the blank and sample determinations
388
in an identical manner throughout the whole determination. Now add alkali metal
sulphate, digestion catalysts and acid to sample and blank digestion flasks, as indicated
below:
Amounts of reagents for the digestion of up to OJ g sample.
Digestion reagents, g Concentrated sulphuric acid, cm3
Sodium sulphate, 1 g (selenium, 0.05 g

copper II sulphate 5H20), 0.05 g 5±0.2
Sodium sulphate, 1 g mercury added as
metal or mercury II oxide, 0.05 - 0.1 g 5±0.2
Sodium sulphate, 1 g: copper II sulphate
5H20, 0.05, - 0.1 g 5±0.2
Sodium sulphate, 1 g: mercury 0.05 g
copper II sulphate 5H20, 0.05 g 5±0.2
Digest the samples gently and at an even rate for 20 min. Now increase the
digestion temperature steadily at five min intervals over a period of one h so that
eventually the acid is condensing about half way up the neck of the digestion flask.
Ensure that the carbon char is completely oxidized (maximum digestion temperature
380"C), Continue digestion for 15 to 20 min at maximum temperature after the solution
has clarified.
Maintain a gentle purge of pure nitrogen through the bulbs during the acid
digestion and also, during the cooling period which follows digestion. If the nitrogen
compound is known to be refractory then extend the total acid digestion period to 4 h.
Switch off the heaters and allow the flasks to cool to room temperature with the pure
nitrogen stream still flowing. At least half of the original sulphuric acid additions should
remain in the digestion flasks at this stage. Carefully add 5 cm3 of ammonia free distilled
water to each flask, remove the flasks from the digestion rack and stopper tightly.
85.5.4 Ammonia Recovery by Steam Distillation.
To the I litre steam generator (Figure 7.20) add some pellets of sodium hydroxide
and boiling chips. Three quarters fill the flask,with distilled water. Turn stopcock Tl to
connect A to C. Boil the contents of the generator for 5 to 10 min on an electric hotplate,
to sweep dissolved ammonia impurity into the waste flask. Then tum stopcock Tl to
connect B to C thereby passing steam through the steam stripper for 5 min to clean the
stripper (stopcock at D and clip at E closed). Again divert the steam supply to the waste
flask.
Quickly transfer the contents of a digestion flask with two or three 5 cm3
ammonia free water washings together with 0.2 ml 25% copper II sulphate solution via
the funnel on the steam stripper to the interior of the sample vessel. Close stopcock D
immediately. Open outlet E to waste and turn stopcock Tl to reconnect Band C. Pass
steam until it exists at E. Meantime pour an excess of 40% sodium hydroxide into the
(closed) funnel at D. Use 20 cm3 or 40 cm3 respectively, depending on whether 5 cm3 or
10 cm3 of concentrated sulphuric acid was used for acid digestion. If, however, the
digestion catalyst used contains mercury or mercury II oxide use the same volumes of
sodium hydroxide - sodium thiosulphate instead. Use the same amount of alkali in both
sample and blank determinations.
389
Connect to the vertical condenser of the steam stripper a clean 250 cm 3 flask.
Connect a guard tube containing freshly activated silica gel in position above this
receiving flask.
When steam is emitting from the steam stripper outlet E close the clip thereby
allowing steam to pass through the sample solution. Steam distill until about 50 cm3
distillate has been collected. Disconnect the flask from the apparatus and replace
immediately by a clean 250 cm3 ammonia receiving flask containing 50 cm3 ammonia-
free water and 6 drops 0.25 M nitrogen free sulphuric acid (silica gel guard tube still in
position). Open stopcock D and slowly admit the alkaline reagent in several portions.
Leave 1 cm3 of alkali in the funnel to act as a seal.
It is necessary to ensure that an excess of alkali is added at this stage. Alkalinity
is indicated by the formation of first, a soluble deep blue cupramine salt then a precipitate
of brown copper oxide (formed by reaction between free ammonia and sodium hydroxide,
respectively, with the previously added copper II sulphate).
Steam distil for about 20 min ie. until about 100 cm3 to 120 cm3 of liquid is in the
receiver. Remove the B24 neck ammonia receiving flask from the apparatus and tightly
connect an 8 in vertical guard tube (24 cone) containing activated silica gel to prevent
contamination of the distillate by any ammonia impurity in the laboratory atmosphere.
Remove the silica gel guard tube from the ammonia receiver flask and stand on an
electric hotplate. Connect the flask immediately to a horizontally inclined Liebig
condenser fitted with a delivery tube immersed in dilute sulphuric acid solution.
Boil until the contents of the distillation flask reduce to 20 to 25 cm3 Immediately
disconnect the flask and connect a B24 silica gel guard tube and leave to cool. If up to
150 microgram of nitrogen is present in the concentrated sample solution transfer this
solution and the blank solution (with 2 x 5 cm3 ammonia free water washings) to two
clean 50 cm3 graduated cylinders and make up to 40 cm3 with ammonia free water. If
more than 100 to 150 micrograms of nitrogen is present in the sample solution transfer
this solution and the blank solution to two 50 cm3 volumetric flasks and make up to the
mark with ammonia free water. Then transfer to a 50 cm3 graduated cylinder a volume of
the sample solution containing 100 to 150 micrograms nitrogen. Transfer the same
volume of blank solution from the 50 cm] volumetric flask to a further 50 cm] graduated
cylinder. Make the volume of the sample and blank solutions in the graduated cylinders
up to 40 cm3 with ammonia free water.
85.5.5 Spectrophotometric Evaluation.
Pipette into the 50 cm3 graduated cylinders containing the blank and the sample
solutions 5 em3 8% phenol solution and mix. Then pipette 5 cm3 sodium hypochlorite
solution into each cylinder and again mix. Immerse the two cylinders up to the neck
(stoppers loosened) into a 2 dm3 beaker of water which has been brought previously to
the boil. Remove the cylinders from the water bath after exactly 7 min and cool to 20 ±
1°C by standing in a beaker of water.
Determine the optical density of the indophenol blue colour produced between 15
and 30 min after addition of the phenol and sodium hypochlorite reagents.
Spectrophotometer conditions:
Instrument: Visible spectrophoto,meter.
Wavelength: 625 nm
390
Cells: 4 cm glass
Blank solution: Use the reagent blank referred to in the text, ie. a test solution
prepared identically to the sample test solution omitting only the addition of sample at the
Kjeldahl digestion stage in the determination. To determine the magnitude of the blank
optical density, (as a check the reproducibility obtained in duplicate determinations)
measure the optical density of the blank solution at 625 nm relative to distilled water in
the comparison cell.
Accurately pipette 2, 5, 10, 15 and 20 cm3 of a freshly prepared standard nitrogen

solution (containing 10 microgram nitrogen per cm3) into five clean 50 cm3 graduated
cylinders, ie. between 20 to 200 micrograms nitrogen. Include a further 50 cm3 graduated
(blank) cylinder containing no standard nitrogen solution addition.
Make the contents of the cylinders up to 40 cm3 with ammonia free distilled
water. Continue as described under spectrophotometric evaluation.
Measure the optical densities at 625 nm of the standard nitrogen solutions in 4 cm
glass employing the reagent blank solution (ie. containing no addition of standard
nitrogen solution), in the comparison cell. Construct a weekly calibration graph relating
these optical densities to the number of micrograms of nitrogen present in the nitrogen
calibration solutions.
Refer the optical density (reagent blank solution in comparison cell), given by the
sample solution to the nitrogen calibration graph and read off the number of micrograms
of nitrogen present. Calculate the nitrogen content of the sample from the following
equations:
Nitrogen, % = N x 10-6 X 100

W
Nitrogen, ppm = N
w
where:
N = number of micrograms of nitrogen present in 50 cm3 final test solutions used
for colour development.
W = weight of sample (g) which contains N microgram nitrogen.
N.B. any dilution of the test solution prior to the development of colour with
phenol and sodium hypochlorite must be allowed for when calculating W.
The overall reproducibility of this nitrogen determination method is ± 5% in the

nitrogen content range 0.002 to 75%. The sodium sulphate - selenium - copper sulphate
mixture is particularly suitable for the quantitative digestion of all compounds in which
the nitrogen is present in an easily decomposed form (eg. as amine, amino compounds,
amino acids, amide or nitrile and their simple derivatives). Forms of nitrogen for which
391
accurate results are not usually obtained include those with -N-N (eg. diazo) and N-O (eg.
nitro) linkages and some resistant heterocyclic structures.
METHOD 86 - DETERMINATION OF 1 - 50% ORGANIC NITROGEN IN

POLYMERS. MICRO DUMAS COMBUSTION PROCEDURE.
86.1 SUMMARY
This Micro Dumas combustion procedure is capable of determining organic nitro-

gen in amounts down to 1% in a wide range of polymers.
86.2 APPARATUS
Dumas nitrogen apparatus: as shown diagrammatically in Figure 7.22.

Combustion tube, quartz, 11 to 12 mm o.d., 610 mm long, equipped with an 18/9
socket joint at one end. The tube is shown in Figure 7.23.
Auxiliary combustion tube, quartz, 10 mm o.d. and 230 mm long, equipped with a
12/5 socket joint at each end, as shown in Figure 7.24.
Carbon dioxide absorption tower: an ungraduated glass tube, approximately 15
mm o.d. and 310 mm long with a 7 mm section of I mm capillary tubing at the upper end
(Figure 7.22). A 100 cm3 levelling bulb is attached to a side arm near the bottom of the
tower by means of a length of rubber tubing. A stopcock is provided at the upper end of
the tower and a ring is etched at about the centre of the capillary section.
Weight azotometer, as shown in Figure 7.25.
Electrolytic oxygen generator. Direct current (0.08 amps and 817 volts) is
supplied to the electrodes by a suitable rectifier, the positive lead being attached to the
arm having the oxygen reservoir.
Combustion boats, platinum, micro.
Capillary sample bulbs. Draw 6 mm Pyrex tubing to form a capillary. Heat the
tubing with a small oxygen gas flame, 2 to 6 mm from the base of the capillary and draw
out to form another capillary, thus forming a bulb with capillaries at each end. The size
of the bulb is determined by the amount of sample to be taken. The bore of the capillary
depends upon the volatility of the sample: use sample bulbs with fine capillaries for
volatile liquids.
Filling device for capillary sampling bulbs. To one end of a glass T-tube, attach a
short piece of rubber tubing and close the open end of the rubber tubing with a small cork
with 0.5 mm hole through its centre. Attach the opposite end of the T-tube to the vacuum
line. The other arm of the T allows finger control of the vacuum.
Weighing bottle, glass, micro.
Quartz plug, approximately 7 mm in diameter and 50 mm long. Make a lip at one
end ofthe plug loop to facilitate removal from the combustion tube.
Hook, stainless steel rod, approximately 2 mm in diameter and 270 mm long, with
a small hook formed at one end.
Platinum tray, approximately 5 mm wide, 4 mm deep and 60 mm long.
392
Auxiliary Furnace
A
700·C
:I
... Stalnless Steel
Leveling Hypodermic
Bulb Tubing
High Temp. Hopcalite

Furnace lOOO·C Furnace
llO·C
Figure 7.22 Gas flow system for micro-dumas apparatus.
Dimensions A Nickel Gauze - 60 mesh

in mm.
B Oxidized Nickel Powder - 150 mesh
C Nickel Powder - 150 mesh
D Quartz Wool
E Copper Gauze - 40 mesh
F Hopcalite
G Glass Wool
Figure 7.23. High temperature combustion tube and details of tube packing.
86.3 REAGENTS
Nickel gauze, 60 mesh.

Nickel powder, 150 mesh.
Quartz wool.
Hopcalite. Obtainable from Mine Safety Appliances Co., Pittsburgh, Penny-
slvania.
Glass wool, pyrex.
Copper oxide, precipitated, containing 1% iron oxide.
Copper gauze, 40 mesh.
Potassium hydroxide solution, 30% w/v.
Mercury.
Potassium hydroxide solution, 2.5% w/v.
393
10mm. O.D. Quartz Tublrig
Iz/s
Z30
Dimensions A Copper Gauze 40 mesh

inmm. B Precipitated Copper Oxide plus
Iron Oxide
Figure 7.24. Auxiliary combustion tube and details of tube packing.
Carbon dioxide gas, containing less than 0.02% by volume of nitrogen or inert
gases.
Hydrogen, commercial.
Oxygen, commercial.
86.4 METHOD
The sample is vaporized and carried by a stream of carbon dioxide over nickel
oxide at 10000 C to oxidize the sample to carbon dioxide, water and nitrogen. Nitrogen
oxides are reduced by metallic nickel in the heated combustion tube. Carbon monoxide,
formed by reduction of carbon dioxide by nickel, is oxidised by passage through
hopcalite at 110°C. Traces of unoxidized methane are completely oxidized by passage
through specially prepared copper oxide at 700°C. Any carbonaceous sample residue,
which might retain nitrogen, is completely oxidized by passing oxygen over the heated
residue. The mixture of carbon dioxide and nitrogen is collected over 30% potassium
hydroxide which absorbs the carbon dioxide and the residual gas, nitrogen, is measured
by displacing and weighing an equal volume of mercury.
86.5.1 Apparatus Preparation.
Electrolytic oxygen generator. Place 500 cm3 of 2.5% potassium hydroxide

solution in a liter flask and boil for 5 min. Pour the 2.5% potassium hydroxide into the
generator. By means of a glass tube inserted above the liquid level in the oxygen
reservoir, flush the air from the reservoir with oxygen to expedite the necessary flushing
with generated oxygen from the electrodes. Seal all connections with sealing wax. Add
sufficient mercury to the mer~ury by-pass line to give a 5-10 cm head above the sintered
disk. Connect the electrodes to the rectifier.
Combustion tubes. Pack the 610 mm tube with nickel powder and nickel gauze as
shown in Figure 7.22. Hold the tube in a horizontal position
394
Figure 7.25. Weight azotometer (approximately 1/2 scale).
and tap to form a channel along the top of the nickel powder. Insert the tube into the
furnaces as shown in Figure 7.22 and attach the inlet assembly. Adjust the tempemture of
the main furnace to 800°C and that of the hopcalite to 110°C. Pass carbon dioxide
through stopcocks G, F, E and D to remove air from the gas manifold, then turn stopcock
G so that carbon dioxide flows through the tube. By means of tubber tubing, attach
stopcock F to a source of commercial hydrogen. Pass a small amount of hydrogen
through F, E and D to remove air from the connecting tubing. Tum off the carbon
dioxide flow and pass hydrogen, at a rate of 10 cm3 per minute, into the tube through
stopcocks F and G until manifold with carbon dioxide. Without removing the tube from
the furnace, pack the exit end of the tube with hopcalite as shown in Figure 7.23. Pack
the auxiliary tube with special copper oxide as described by Figure 7.24. Insert the
auxilliary tube into its furnace and connect one end to the tube containing the nickel,
using a section of glass tubing equipped with ball joints at each end. Connect the other
end to stopcock E by means of hypodermic tubing fitted with metal ball joints. Seal the
joints with sealing wax. Set the temperature of the auxiliary tube at approximately
300°C. Disconnect stopcock F from the hydrogen source and sweep hydrogen from the
rubber tubing by introducing carbon dioxide through stopcocks G and F. Sweep
hydrogen from the absorption tower by passing carbon dioxide through stopcocks G, F
and E. Attach the rubber tubing to a source of commercial oxygen. Remove the cap
from the front end of the tube and turn stopcocks F and E so that oxygen can be
introduced into the combustion tube through the auxiliary furnace. Adjust the flow of
oxygen to 10 cm3 per min and oxidize the nickel for a distance of 90 mm. Recap the
front end of the tube and tum stopcocks F, G and E so that oxygen flows through the
combustion tube and into the carbon dioxide absorption tower: leave stopcock D open to
the atmosphere. Oxidize about a 70 mm section of the nickel, then, slowly (to prevent
surface oxidation of the nickel) sweep oxygen from the tube with carbon dioxide. Adjust
the temperature of the main furnace to 1000°C and that of the auxiliary furnace to 700°C.
When not in use, keep the system filled with carbon dioxide and at operating
temperatures. Disconnect the tubing from F.
395
Weight azotometer. Lubricate the stopcocks of the weight azotometer and fill the
unit with mercury to within 10 mm of the side arm.
Carbon dioxide absorption tower. Add sufficient 30010 potassium hydroxide to the
levelling bulb to completely fill the absorption tower. Cover the bottom of, the absorber
with mercury to a height of 10 mm.
86.5.2 Conditioning of Apparatus.
To obtain accurate results, it is necessary to condition the high temperature

combustion tube. Assemble the apparatus and perform carbon dioxide and operation
blanks as described below under Procedure. Determine the nitrogen content of
acetanilide as described below under Analysis of Samples. Repeat the test until a value is
obtained which shows a deviation from the true result of 0.1 % nitrogen or less. Usually 4
- 5 determinations must be made before a satisfactory value is obtained.
86.5.3 Procedure. Blanks.
Before beginning the first analysis of the day, purge the carbon dioxide and
oxygen lines by venting the gasses to the atmosphere through stopcock F and then
perform carbon dioxide and operational blanks as described below.
Carbon dioxide blank. Open stopcock D to the atmosphere and raise the levelling
bulb until the potassium hydroxide solution rises to the mark etched on the capillary
portion of the absorption tower: mark the position of the levelling bulb so that it can be
returned to this position. Close stopcock D and lower the levelling bulb. Pass 60 cm3 of
carbon dioxide, at a rate of 10 cm3 per min, through stopcock G, the combustion tubes,
stopcock E and into the absorption tower. Open stopcock D and return the level of
potassium hydroxide solution to the mark. Close stopcock D and lower the levelling
bulb. Again, pass 60 cm3 of carbon dioxide into the absorption tower at a rate of 10 cm3
per min. Close stopcocks A, B and E and raise the levelling bulb to the previously fixed
upper position. Turn stopcock D to connect the absorption tower to the weight
azotometer and, by means of stopcock C, drain mercury into a weighed container, until
the level of the potassium hydroxide solution returns to the mark. Weigh the mercury.
The amount of mercury displaced should be less than 0.1 gram.
Operational blank. Open stopcock D to the atmosphere, bring the level of the
potassium hydroxide solution to the mark. Close stopcock D and open E to the
absorption tower: lower the levelling bulb. Pass carbon dioxide through the apparatus
and into the absorption tower for 17 m at a rate of 3 ml per m. Change the gas flow to
oxygen and pass oxygen through the tube for 6 m at a rate of 5 cm3 per m. Follow with
carbon dioxide at a rate of 5 cm3 per m for 4 m. Increase the rate of flow of carbon
dioxide to 10 ml per m and maintain this flow for 5 m. Open stopcocks A and B to the
atmosphere for a few s and determine the amount of residual gas by displacing mercury
as directed under carbon dioxide blank. Weigh the mercury; less than 0.2 g of mercury
should be obtained.
396
86.5.4 Analysis of Samples.
Bring the level of potassium hydroxide solution to the mark, close stopcock D and
lower the levelling bulb. Accurately weigh sufficient sample to yield 0.5 to 2.0 mg of
nitrogen, but do not take more than 25 mg. Weigh solids and nonvolatile liquids in
platinum boats. W~igh hygroscopic samples in boats enclosed in a glass piggy. Weigh
volatile samples in a previously weighed glass capillary with a bulb in the middle. To
fIll, insert one end of the sample bulb into the hole in the cork stopper of the special
flliing device and completely fIll the sample tube with sample by applying vacuum. Seal
one end of the sample tube. Weigh the capillary plus sample and quickly dip the open
end into melted paraffm. Place the capillary on a platinum tray before putting it in the
combustion tube.
Place a quantity of solid carbon dioxide over that section of the combustion tube
which contains the sample. Open the front end of the combustion tube and reverse purge
by passing carbon dioxide through stopcocks G, F and E and into the exit end of the
auxiliary tube. Adjust the rate of flow to 40 cm] per m. Insert the sample and, with the
hook, push the sample to within 4 - 6 cm of the high temperature furnace.
Insert the quartz plug so that it touches the boat, replace the cap on the front end
of the combustion tube: screw the cap on fumly. Quickly turn stopcocks G and E so that
carbon dioxide flows through the combustion tubes and into the absorption tower.
Reduce the flow of carbon dioxide to 10 m1 per m and maintain this flow for 6 m. Open
stopcock D to the atmosphere and allow the potassium hydroxide solution to flow into the
levelling bulb. Bring the level of potassium hydroxide to the mark on the capillary as
before: close stopcock D and perform a carbon dioxide blank as described under Analysis
of Sample, above. Repeat if not normal. Continued high blanks indicate that the sample
is vaporizing or the system is leaking. Open stopcock D and return the level of potassium
hydroxide solution to the mark. Close stopcock D, lower the levelling bulb, turn on the
carbon dioxide and adjust the flow to 3 cm3 per m. Remove the solid carbon dioxide
from around the combustion tube and turn on the heater of the travelling furnace. Move
the furnace to within 1 - 2 cm of the sample and allow it to warm up for about 2 m. Start
the furnace travelling by increasing the drive motor voltage with the variable
autotransformer located on the front panel of the unit. Adjust the rate of travel so that the
sample is burned slowly and at a uniform rate, as indicated by the rate of formation and
size of the gas bubbles in the absorption tower. Conduct the combustion at such a rate
that the travelling furnace reaches the high temperature furnace in less than 17 m. When
a total of 17 m has elapsed from the time the travel of the furnace was started, return the
travelling furnace to a position directly over the sample. Turn off the carbon dioxide,
turn on the oxygen and adjust its flow to 5 cm3 per m. After two m has elapsed, start the
furnace travelling at such a rate that it will reach the high temperature furnace in 4 m.
Turn off the oxygen and pass carbon dioxide through the tube for 4 m at a rate of 5 cm3
per m; thenJor 5 m at a rate of 10 cm3per m. Turn off the carbon dioxide, the heater of
the travelling furnace, and close stopcock E. Momentarily open stopcocks A and B to the
atmosphere, place the levelling bulb in its upper position and open stopcock D to the
weight azotometer. Drain mercury into a weighed container through stopcock C until the
level of potassium hydroxide solution returns to the mark on the capillary. Weigh the
mercury to the nearest 0.005 g.
397
86.S.S Calculations.
Calculate the nitrogen content of the sample by means of the following equation:
Nitrogen % w = co - g) CO 100
S
where:
G = grams of mercury from sample.
g = grams of mercury from operational blank.
f = factor for converting grams of mercury to milligrams of nitrogen, the factor is
obtained from the nomograph (Figure 7.26).
S = weight of sample in milligrams.
This method gives results which do not differ from the true nitrogen content of the
sample by more than 0.2%. Replicate analysis agree within 0.1 %.
METHOD 87 - DETERMINATION OF 0.01 - 2% PHOSPHORUS IN

POLYMERS. OXYGEN FLASK COMBUSTION - SPECTROPHOTOMETRIC
METHOD.
87.1 SUMMARY
This oxygen flask combustion - spectrophotometric method determines 0.01 to

2% total phosphorus in phosphorus containing polymers.
87.2 APPARATUS
500 ml conical combustion flask fitted with a reducing adaptor and joint carrying
approximately I" square platinum gauze, (see Method 76).
Unicam SP 500 spectrophotometric with 1 and 4 em glass cells and tungsten
lamp.
Methyl cellulose capsules - No. 4 small, Arthur H Thomas Co. Catalogue No.
6471-0.
Sodium carbonate scoop - fabricated from glass tubing - 4 mm in outside diameter
and marked to contain 50 ± 10 mg of anhydrous sodium carbonate powder.
Filter paper fuses approximately 1.5 x 1/S" in size made from ashless filter paper.
100 m1 volumetric flasks: 150 ml conical flasks: pipettes, etc.
87.3 REAGENTS
Demineralised water used throughout.

Ammonium molybdate solution, dissolve 40 g reagent grade ammonium
molybdate (NH4)6Mo,024' 4H20) in a cooled mixture of 450 m1 concentrated sulphuric
acid and I litre water. Dilute to 2litres with water.
398
750
0.086
18 0.085
755
iii 20
til
0.084
B
....... U
22
II
~ "
II
II
24
III t, 0.083
..
III
760 ...
II
P.
II
S
fI4I
i
26
g
0
t4l III.
.082
. t
G 28
,z ... 30
.081
765
32
,,, .080
170
0.078
Figure 7.26. Nomograph for micro-dumas calculation using a weight azotometer.
Hydrazine sulphate solution, 1.5 gllitre.

Molybdate-hydrazine reagent, dilute 50 ml of ammonium molybdate solution with
130 ml of water, add 20 ml of hydrazine sulphate solution and mix well. Use 50 ml for
each determination and prepare no earlier than 1 hour before use as this mixture is
unstable.
Stock standard phosphorus solution, dissolve 4.393 g of dried Analar potassium
dihydrogen phosphate (KH2P04) in 150 ml of 1:10 sulphuric acid and dilute to 1 litre
with water (1.0 mg/ml phosphorus). From this prepare solutions containing 0.01 mg P/ml
and 0.001 mg P/ml.
399
Oxygen.
Sodium carbonate, anhydrous, Analar.
87.4 METHOD
The ground polymers mixed with sodium carbonate is decomposed by igniting in

an oxygen filled flask containing dilute sulphuric acid. The solution is treated with
molybdate-hydrazine reagent and the phosphate measured colorimetrically as its
heteropoly-blue equivalent.
87.S.1 Sample Digestion.
Place I scoop of anhydrous sodium carbonate in the bottom half of a methyl

cellulose capsule. Weigh a sample of not more than 32 mg estimated to contain between
0.001 and 0.06 mg phosphorus, directly onto the sodium carbonate bed. Cover the
sample with another scoop of sodium carbonate. Insert a filter paper fuse between the top
and bottom halves of the capsule after making a small slit in the top half to give the
clearance required. Secure the capsule in the platinum gauze with the wick towards the
stopper.
Pass oxygen into the flask containing 10 ml of 1: 10 sulphuric acid for 30 seconds.
Holding the flask horizontally remove the oxygen lead, light the sample fuse and quickly
insert the stopper in the flask. See Note l. Tilt the flask immediatley at an angle of 135°
from the vertical so that the absorbing solution forms a liquid seal at the neck of the flask.
During the period of maximum flame height completely invert the flask to prevent
impingement of the flame on the flask walls. Hold the stopper firmly in place during the
combustion (Note 1). After combustion allow the flask to stand for 10 to 15 minutes.
Open the flask and wash the platinum gauze and surfaces of the reducing adaptor
with a maximum of 35 ml of water. Remove the adaptor and lower the gauze into the
solution.
Add 50 ml molybdate hydrazine reagent, (Note 2). Heat the solution rapidly to
boiling and boil for 2 - 3 minutes. Cool to room temperature in an ice-water bath,
transfer to 1000 ml volumetric flask and dilute to volume.
Measure the absorbance against water in appropriate cells at 830 nm.
Carry out a blank determination.
87.S.3 Calibration Curve.
Prepare separate calibrations from standard phosphorus solutions for 1 cm and 4

cm cells containing 0-0.06 mg PIlOO ml and 0-0.Ql5 mg P/I00 ml respectively as
follows:
Measure appropriate amounts of the phosphorus standards into 150 ml conical
flasks and dilute to approximately 30 ml with water. Add 10 ml of 1:10 sulphuric acid
and 50 ml of molybdatelhydrazine reagent and develop the colour as before.
Measure the absorbance against water in appropriate cells at 830 mu.
400
Prepare graphs of corrected absorbance against weight of phosphorus (mg per 100
ml). Linear calibrations are obtained.
Note I. Gloves and goggles should be worn and the ignition carried out behind a
protective glass screen.
Note 2. It is essential that the solution is diluted before the molybdate hydrazine
reagent is added.
This method is capable of determining total phosphorus in polymers in amounts

down to 0.01 % and up to 2% with an accuracy of ± 5%.
METHOD 88 - DETERMINATION OF 2 - 13% PHOSPHORUS IN POLYMERS.

OXYGEN FLASK COMBUSTION - SPECTROPHOTOMETRIC METHOD.
88.1 SUMMARY
This oxygen flask combustion - spectrophotometric procedure determines total

phosphorus in polymers in the concentration range 2 to 13% phosphorus.
88.2 APPARATUS
500 ml conical flask fitted with a reducing adaptor and joint carrying
approximately I" square of platinum gauze, (see Method 76).
Methyl cellulose capsules - No. 4 small, Arthur H Thomas Co. Catalogue No.
6471-0.
Sodium carbonate scoop, fabricated from glass tubing 4 mm in outside diameter
and marked to contain 50 ± 10 mg of anhydrous sodium carbonate powder.
Filter paper fuses, approximately 1.5" x liS" in size made from ashless filter
paper.
Unicam SP 500 spectrophotometer with I and 4 cm cells and tungsten lamp.
100 volumetric flasks, 150 ml conical flasks, pipettes, etc.
88.3 REAGENTS
Oxygen.
Sodium hydroxide, 0.5 N.
Saturated bromine water.
Percolated water, prepared by percolating distilled water through a mixed resin
bed containing Amberlite IR 120 (H) and Amberlite IRA 400 (OH).
Ammonium molybdate, 5%v. Dissolve 50 g ammonium molybdate in a litre of
warm distilled water.
Ammonium vanadate, 0.25% w. Dissolve 2.5 g of ammonium vandate in 500 ml
hot water. Cool and add 20 ml of concentrated nitric acid. Cool and dilute to 1 litre.
Aqueous sulphuric acid, 25% w.
401
88.4 METHOD
The ground polymer, mixed with sodium carbonate, is decomposed by igniting in

an oxygen-filled flask containing saturated bromine water and sodium hydroxide. The
solution is acidified, boiled and made up to 100 ml. The phosphorus is determined
colorimetrically as molydovanadophosphoric acid.
Pass oxygen into a flask containing 5 ml of 0.5 N sodium hydroxide and 4 ml

saturated bromine water for 30 seconds.
Place I scoop of anhydrous sodium carbonate in the bottom half of a methyl
cellulose capsule supported in a bored cork. Weigh a sample of not more than 32 mg,
estimated to contain between 0.05 and 2.5 mg phosphorus, directly onto the sodium
carbonate bed. Cover the sample with another scoop of sodium carbonate. Insert a filter
paper fuse between the top and bottom halves of the capsule after making a small slit in
the top half to give the clearance required. Secure the capsule in the platinum gauze with
the wick towards the stopper.
Holding the flask horizontally remove the oxygen lead, light the sample fuse and
quickly insert the stopper in the flask. Tilt the flask immediately at an angle of 135· from
the vertical, so that the absorbing solution forms a liquid seal at the neck of the flask.
During the period of maximum flame height, completely invert the flask to prevent
impingement of the flame on the flask walls. Set aside until the mist has cleared (l0 to
15 minutes is usually sufficient).
Open the flask and wash down the platinum gauze and surfaces of the reducing
adaptor with demineralised water. Remove the adaptor and lower the gauze into the
solution.
Add to the solution 6 ml of 25% v. sulphuric acid and boil the solution for 15
minutes. Cool and transfer the solution to a 100 ml graduated flask. Add 10 ml of
ammonium vanadate, followed by 10 ml of ammonium molybdate and make up to 100
ml. Allow 30 minutes for colour development.
Using either I or 4 cells, read off the optical density at 460 Dm.
88.5.3 Preparation of Calibration Curve.
Prepare separate calibration curves from standard phosphorus solutions for I cm

and 4 cm cells containing 0 - 0.25 mg P/IOO cm·3 and 0 - 0.06 mg P/lOO cm3 respectively,
as follows:
Measure appropriate amounts of phosphorus standards into 100 cm3 graduated
flasks. Add 10 cm] of ammonium molybdate and 10 cm3 of ammonium vanadate and
make up to 100 cm3• Allow 30 minutes for colour development.
Using either 1 cm or 4 cm cells read off the optical density at 460 Dm. Carry out a
reagent blank.
402
Prepare graphs of corrected absorbance against weight of phosphorus (mg per 100
cm3).
This method is capable of determining phosphorus in polymers in amounts down

to 2% and up to 13% with an accuracy of ± 5%.
METHOD 89 - MICRO DETERMINATION OF PHOSPHORUS IN POLYMERS.

ACID DIGESTION - SPECTROPHOTOMETRIC METHOD.
89.1 SUMMARY
This acid digestion - spectrophotometric method determines phosphorus in

amounts down to 0.5% in polymers.
89.2 APPARATUS
Hot plate capable of maintaining a temperature of 250 - 300°C.

Fume chamber connected to water vacuum pump.
Pyrex flasks, 100 ml.
Spectrophotometer with matched cells (I cm).
Small glass sample cups, with ground glass lids.
89.3 REAGENTS
Ammonium molybdate, 10% waqueous.

Ammonium vanadate, 1% w/v in 2 N.HN03 •
Perchloric acid, 70% A.R.
Sulphuric acid, A.R.
Standard phosphate solution, 0.1 mg P/cm3•
89.4 METHOD
The sample is decomposed and oxidized in sulphuric acid-perchloric acid. After

cooling, water, ammonium vanadate and ammonium molybdate are added to form the
yellow phosphovanadomolybdate complex, which is measured colorimetrically at 430
nm.
Weigh out a suitable amount of polymer (ranging from 25 - 50 mg at the 0.1 to

0.5% phosphorus level to 3 - 5 mg at the 20% phosphorus level).
403
Place the weighed sample in the flask. Add 3 cm3 of concentrated sUlphuric acid,
then 0.5 cm3 perchloric acid and digest on the hotplate at 250 - 300°C. After about 15 s
the perchloric acid decomposes with formation of dense white fumes and the solution
becomes yellow. Heating is continued for a further two m.
Remove the flask from the hotplate, allow to cool and then cautiously add a few
drops of water and mix. Dilute to about 50 cm3 with distilled water.
89.5.2 Spectrometric Evaluation.
Add 5 cm3 of ammonium vanadate solution, followed by 10 cm3 of ammonium

molybdate solution, make up to 100 cm3 and mix. Allow 15 m for colour development
and read off the optical density at 430 nm. Carry out a blank determination.
89.5.3 Preparation of Calibration Curve.
Transfer by use of pipettes or a burette 0, 2, 5, 8,10,12,15 and 20 cm3 aliquots of

standard phosphate solution into separate 100 cm3 volume reaction flasks. Add 3 cm3 of
concentrated sulphuric acid and 0.5 rnl of 70% perchloric acid.
Add a small glass bead to each flask and boil off the water by heating on the
hotplate. Continue heating until the dense cloud of decomposing perchloric acid appears
and then for a further two minutes.
Cool, add water cautiously to a volume of 50 - 60 cm3• Add 5 cm 3 ammonium
vanadate solution followed by 10 cm3 of ammonium molybdate, make up to 100 cm3 and
leave for at least 15 m.
Read off the optical densities of the solutions using 1 cm cells at 430 nm. Plot
milligrams of phosphorus/cm3 against optical density. The average factor (F) may be
calculated from the expression:
F = mg P per cm1
a.D. reading
89.5.3 Calculation of Results
Phosphorus, % w = (O.D' I - O.D.?) x F x 100

W
where:
a.D' 1 = optical density of test solution.
O.D'2 = optical density of blank.
F = factor obtained by standardisation against known concentrations of standard
phosphate solution.
W = sample weight in mg.
This method is capable of determining total phosphorus in polymers in amounts

down to 0.5% and up to 20% with an accuracy of ± 5%.
404
CHAPTER 7.4
COMPOSITIONAL ANALYSIS
Methods 90 • 97
METHOD 90 • DETERMINATION OF NATURAL RUBBER, STYRENE-

BUTADIENE RUBBER AND ETHYLENE·PROPYLENE DIENE TERPOLYMER
IN COMPOUNDED RUBBER STOCKS. PYROLYSIS - GAS
CHROMATOGRAPHY.51
90.1 SUMMARY
This pyrolysis - gas chromatography procedure enables the determination of

monomer units such as butadiene, isoprene and propylene to be determined in natural and
synthetic rubbers in amounts down to 0.5%.
90.2 APPARATUS
Pyrolysis unit. Loenco Division Infotronics Corp, Altadene, Calif. this Unit,
Model 260 uses a 3" x 1/8" quartz U-tube as the pyrolysis chamber. It is heated by
sliding a thermostatically controlled heated furnace over it for a fixed time. A sliding gas
valve arrangement in the unit allows uninterrupted carrier gas flow through the gas
chromatographic column while the sample chamber is being reloaded or purged with
helium.
Stripping and backflushing valve. A Carle Micro Volume Eight Port Gas
Chromatography Valve No. 2012 (Carle Instruments, Fullerton, Calif.) is used to avoid
the introduction of high boiling pyrolysis products onto the chromatographic column. It
is connected to the columns and the gas chromatograph. The pyrolysis products are
allowed to go onto the main column for the first 15 minutes only, (Figure 7.27).
Gas Chromatograph. The pyrolysis products are analysed with an F & M 1609
gas chromatograph equipped with a flame ionization detector. The chromatographic
peaks are recorded at electrometer range of 100 and a chart speed of 112 inch per minute.
The area measurements are made by the triangulation method (peak height x width at half
peak height). The main column was aluminium tubing 40 ft x 3/16 inch o.d. 0.032 in
wall thickness. It is packed with 10% tricresylphosphate on 60-80 mesh Chromosorb P,
the stripper and restrictor columns are 10ft lengths of the 2/16 inch aluminium tubing
packed as the main column. The columns are operated at 35°C. The injection port and
the detector block are maintained at 175°C. The helium, hydrogen and air pressure are 30
psi (flowrato at 4.0), 15 psi (flowrato at 7.50) and 20 psi (flowrato 9.0) respectively.
Relative retention data for the pyrolysis products are shown in Table 7.45.
40S
Clockwise Position - Stripper In
s ,.,..---...,
Main
,
stream I 2 8 ~~-.-.-.-.+ Vent
f) R \... \
~ <t'-'~'-'7~ }
Auxiliary \ • I Me
Helium ~ ._._.~~4 5 6 I • • . --+ Detector
,
L-_ _ _ _-'-.:... ..... ____ "
/
~
Counter Clockwise Position - Backrtushing

S "..----,
~.-.-.-.~.-.~ "
Main • / Z 1 "'S~'-'-'-'-'+- Vent
Stream 1 8 \
: R \
I I (~-~'I.----,..-6) :
. I ,
! \ " M.e.
Auxiliary
Heliu m -+ y-' - .-.~..... 5 6@-,,4---"'VV'I'\.-t- Detector
--'-.-'-'~.:..-'-:e ---_ ... .""
Figure 7.27. Stripping and backflushing valve connections.
M.C. Main cQlumn, 40 ft x 3/16 in. 10% tricresylphosphate on 60-80 mesh Chromosorb P.
S. Stripping column 10 ft x 3/16 in. 10% tricresylphosphate on 60-80 mesh Chromosorb P.
R. Restrictor column 10 ft x 3/16 in. 10% tricresylphosphae on 60-80 mesh Chromosorb P.
From Krishen with permission." Americal Chemical Society.
Table 7.45 - Peak Identification and Relative Retention Data. (tricresylphosphate column
at 35°C)
Peak no. Compound Relative Retention
in Figure Nonane = 1.0000
1 Methane 0.0009
2 Ethane + Ethane 0.0082
3 Propane 0.0268
4 Propene 0.0347
5 2-Methylpropane 0.0849
6 Propadiene + Butane 0.0948
7 I-Butene + 2-Methylpropene 0.1048
8 Trans-2-Butene 0.1409
9 Cis-2-Butene 0.1649
10 1,3-Butadiene 0.1769
11 2-Methyl-l-Butene 0.2074
12 I-Pentene 0.3038
13 2-Methyl-l-Butene 0.2074
14 Trans-2-Pentene 0.3848
15 Cis-2-Pentene 0.3993
16 2-Methyl-2-Butene 0.4476
17 Isoprene 0.5397
From Krishen31 • American Chemical Society
406
90.3 REAGENTS
Tricresylphosphate stationary phase.

Chromosorb P, 60-80 mesh.
Methanol, Analar.
90.4 METHOD
A methanol extract of a weighed portion of the polymer is pyrolysed at 700°C and

the pyrolysis products swept on to a gas chromatograph and then determined. For
example if a styrene-butadiene copolymer is being examined then determination of 1,3
butadiene in the pyrolysis products enables the bound butadiene content of the copolymer
to be determined. The procedure is calibrated against copolymers of known composition,
or, alternatively against injections of the pure monomers.
The cured rubber samples are subdivided into small pieces. A 0.1 to 1 gram
sample of these pieces is extracted with methanol in Underwriters' extraction apparatus
for 8-12 hours. The solvent is completely removed from the rubber by placing the sample
in a vacuum oven at 60°C for 30 minutes. A 500 to 800 ug sample of the dried rubber is
weighed on the microbalance and carefully placed inside the quartz pyrolysis tube. Small
borosilicate glass wool plugs are put on each end of the U-tube. This tube is then
installed in the pyrolyser unit, purged with a helium flow of 30 ml per minute for 2
minutes, and then heated for 30 seconds at 700°C by positioning the furnace over the
tube. At the end of 30 second, the furnace is move away; the pyrolysis tube is connected
in series with the column carrier flow using the appropriate valve on the pyrolysis unit;
and the start of the chromatogram marked on the recorder chart. At the end of about 60
seconds, the carrier gas flow through the pyrolysis tube is terminated by sliding up the
valve on the pyrolysis unit. The tube is removed from the pyrolysis unit, glass wool
plugs are removed and the tube cleaned by heating it thoroughly in a burner flame to bum
off all combustible material. Another weighed sample is then placed in the tube and it is
installed in the pyrolysis unit as before ready for the next run. After 15 minutes, the flow
of the carrier gas through the stripper column is terminated and the restrictor column
placed in series with the main column by turning the Carle valve knob to the counter
clockwise position. The stripper is back flushed while the chromatogram is being
recorded. At the end of the chromatographic run, the Carle valve knob is turned back to
the clockwise position and the apparatus is ready to accept the next run.
Peak identification and retention data are given in Table 7.45 for a range of
pyrolysis products.
Krishen'l quantitatively analysed the gaseous pyrolysis products from natural
rubber, styrene-butadiene rubber and ethylene-propylene diamine terpolymer rubber by
gas chromatography. He showed that the 2-methyl-2-butene peak was linear with the
natural rubber content of the sample. Styrene-butadiene rubber was determined from the
407
peak area of the 1,3-butadiene peak. The ethylene-propylene-terpolymer content was
deduced from the I-pentane peak area of the pyrolysis products.
This method is capable of determining down to 0.5% of monomer units such as

bound butadiene and isoprene in synthetic and natural rubbers with an accuracy of ± 5%.
METHOD 91 - DETERMINATION OF THE BOUND ETHYLENE IN

ETHYLENE-PROPYLENE COPOLYMERS (>95% PROPYLENE). INFRARED
SPECTROSCOPy.52
91.1 SUMMARY
This infrared spectroscopic procedure determines bound ethylene in propylene

rich ethylene copolymers in amounts down to 0.1 %.
91.2 APPARATUS
Fourier Transform infrared system at four wavenumber resolution in double beam

operation. Standard double precision computer software were used to present data
properly scale expanded in absorbance form.
91.3 METHOD
Determination of infrared spectra of moulded films of the polymer at 732 cm'l

enables the propylene unit content of the polymer to be determined. The absorbance is
measured of the 732 cm'· infrared band, attributed to gamma.. (CH2)3 is characteristic of
an ethylene unit isolated between two head to tail propylene units. The method is
calibrated against known copolymers of similar constitution to the copolymers being
analysed.
Infrared spectra are obtained on moulded films of a nominal I mm thickness.

Approximately 0.52 g of sample is placed between 31.8 rom diameter aluminium foil
disks on a I mm brass spacer of 19.0 rom i.d. and 31.8 rom o.d. resting in a Buehler 20-
2112 specimen mould. The temperature of the assembled mould is maintained at 175°C
by a standard thermocouple temperature controller. After the sample is pressed to 6000
psig in a Buehler 1315 AB specimen mould and cooled to 35°C under pressure, the film
is removed and mounted in a holder, Five measurements with a micrometer are averaged
to provide a film thickness for the ethylene calculations. Since small variations in
thickness introduce substantial errors in final calculations, the film is discarded if the
readings varied by more than 0.05 mm and another sample is moulded.
Infrared spectra are obtained on a Digilab Model 15 Fourier Transform system at
four wavenumber resolution in double beam operation. An adequate signal-to-noise ratio
408
resulted from 1000 scans. Standard double precision DigilablData General computer
software are used to present data properly scale expanded in absorbance form. The
absorbance of the 732.1 micron infrared band, attributed to gamma r (CHJ3 is recorded.
The equation relating the infrared absorbance to the ethylene content is:
Y = 2.465 X + 0.451
where Y is the infrared absorbance at 732 wavenumbers divided by the film

thickness in centimetres and X is the wt% ethylene. The standard errors are 0.110 and the
intercept 0.051 for the slope.
The infrared absorbance at 732cmol is sufficiently sensitive to the ethylene
incorporation to determine the wt% ethylene within 0.1-0.2% at the 95% confidence
level. From the 13-C NMR data, it can be concluded that the propylene units occur in
predominantly isotactic, heat to tail sequences and that the ethylene units are incorporated
as isolated units only. Thus, this structural prequisite is a requirement for application of
this method because it has not been tested on copolymers containing propylene
configurational irregularities or ethylene sequences two units and longer.
The infrared absorbance at 732cmol is sufficiently sensitive to the ethylene

incorporation to determine the wtl'.4 ethylene to within 001 - 0.2 % at the 95% confidence
level.
This method enables down to 0.1 % propylene to be determined in ethylene rich (>
95% propylene) ethylene-propylene copolymers with an accUracy of ± 5%.
METHOD 92- DETERMINATION OF ETHYLENE IN ETHYLENE-

PROPYLENE COPOLYMERS (>95% PROPYLENE). NMR SPECTROSCOPy.52
92.1 SUMMARY
This NMR method is capable of determining down to 0.1 % propylene units in

propylene rich (>95% propylene) ethylene-propylene copolymers.
92.2 APPARATUS
NMR Spectrometer Varian, XLOI00 15 NMR equipped with Varian FT-100

pulsed NMR Fourier transform system and disc accessory or equivalent.
92.3 REAGENTS
1,2,4 trichlorobenzene.
Perdeuterobenzene.
409
92.4 METHOD
A 1,2,4 trichlorobenzene - perdeuterobenzene solution of the polymer is examined

on a NMR spectrometer to evaluate methine resonances. The method is calibrated
against known copolymers of similar constitution to the copolymers being analysed.
NMR spectra are measured from polymer samples dissolved in a mixture of 1,2,4-
trichlorobenzene and perdeuterobenzene at concentrations between 10 - 15 wt %.
Sufficient perdeuterobenzene is added to maintain a lock signal on the NMR spectrometer
at a temperature of 125°C. The 13-C NMR spectra is obtained utilizing the following
conditions for the pulse sequences:
pulse angle 90° transients accumulated 2000 - 5000

pulse delay 8.5 s spectral width 5000Hz
acquisition time 1.5s no signal enhancement used
A pulse interval of lOs is sufficient to satisfy the spin-lattice relaxation time, T of

the methyl group, which is the slowest relaxing nucleus with a Tl of 2 s at 125°C. The
number of transients accumulated depended upon the ethylene content and in each case,
accumulations are allowed to continue until a satisfactory signal-to-noise ratio was
achieved. Each 13C NMR spectrum is recorded with proton noise-decoupling to remove
unwanted 13C - I H scalar couplings. No corrections are made for differential nuclear
Overhauser effects since these have been shown to be constant for the major resonances
in low ethylene - propylene copolymers. s3
The best results are obtained using methine resonances 4 and 5 (Table 7.46) to
determine copolymer composition. This is because the methine carbon resonance is the
least sensitive towards configurational differences and also the least affected by overlap
from neighbouring resonances. Similar results are obtained whether one uses peak
heights or peak areas.
From the NMR data it can be concluded that the propylene units occur in
predominantly isotactic head to tail sequences and that the ethylene units are incorporated
as isolated units only. The NMR method can be used to provide reference standards for
the less time consuming infrared method (Method 91). Provided the infrared method is
calibrated in this way excellent agreement is obtained between the infrared and NMR
methods for copolymers containing >95% propylene.
410
METHOD 93 - DETERMINATION OF BOUND STYRENE IN STYRENATED
ALKYL RESINS. INFRARED SPECTROSCOPy.54
93.1 SUMMARY
This infrared spectroscopic method is capable of determining bound styrene units

in styrenated alkyl resins in amounts down to 1%.
93.2 APPARATUS
Infrared spectrometer equipped with 0.062 cm path length liquid cell with
potassium bromide windows.
93.3 REAGENTS
Tetrahydrofuran.
Acetone, AR.
93.4 METHOD
A tetrahydrofuran or acetone solution of the sample is run on an infrared

spectrometer and the true absorbance of the 700 cm·\ absorption calculated. The method
is calibrated against styrenated alkyl resins of known composition.
To determine styrene units, solutions of the polymers are prepared in volumetric

flasks by dissolving known weights of the dried polymers in tetrahydrofuran or acetone.
The infrared cell is rinsed twice with the sample solution before use. A liquid cell,
having potassium bromide windows and a path length of 0.062 cm was used. The
optimum region for performing quantitative infrared analysis is between 0.3 and 0.6
absorbance unit. Typical polymer concentrations were 3 to 8 wt«'10 within the optimum
region. Before scanning the spectrum, the filled infrared cell is placed in the instrument
for 15 minutes to allow the sample to reach temperature equilibrium. The region of the
spectrum between 15.38 and 13.33 micron is scanned at 17 cm -J/min and the absorbance
of the 13.33 micron band is determined using the "basic line technique".
93.5.1 Determination of Absorbtivity Value.
Polystyrene solutions are prepared between 10 and 60 gil, and their infrared
spectra determined 15.38 to 13.33 microns. The true absorbance of the 14.28 micron
band is then calculated using the following equation:
A=Ar-Ao
where
A = true absorbance.
411
Ar = the total recorded absorbance of the absorption maxima.
Ao = the general beckground absorption at the absorption maxima.
The true absorbance of the 14.28 micron styrene band is then plotted against
sample concentration. Using Beer's law an absorptivity value is readily calculated. The
absorptivity values determined in acetone and tetrahydrofuran are given in Table 7.47.
93.5.2 Determination of Styrene Content.
By knowing the absorbance, cell path length and absorptivity value, the
concentration (gil) of styrene is a solution is calculated using the equation:
c=Alab
where
c = styrene concentration (gil) in the solution.
A = true absorbance of 14.28 micron band.
b = cell path length (cm).
a - absorptivity (l/g cm)
The concentration of styrene in the polymer is calculated using the equation:
% styrene = !;, (l00

W
where
C = styrene concentration (gil) in solution.
W = sample concentration in solution (gil).
The absorptivity values determined in acetone and tetrahydrofuran are given in

Table 7.47.
93.7 DISCUSSION
The accuracy of this method on typical acid modified styrenated acrylic polymers is
shown in Table 7.48. In the 5 to 70% styrene range, determined values are better than
95% relative.
METHOD 94 - DETERMINATION OF STYRENE AND METHACRYLATE

UNITS IN STYRENE METHYL-METHACRYLATE AND STYRENE-N-BUTYL
METHACRYLATE COPOLYMERS. NMR SPECTROSCOPy.55
94.1 SUMMARY
This NMR method determines styrene and methacrylate units in styrene-methyl

methacrylate and styrene-n-butyl methacrylate copolymers in amounts down to 0.5%.
412
Table 7.46 - Observed and Reference \3C NMR Chemical Shifts in ppm for Ethylene-
Propylene Copolymers and Reference Polypropylenes as Measured with Respect to an
Internal TMS Standard
Resonance Carbon 3/91 EIP 9113" Sequence Reference Amorphous

Line EIP' EIP Assign- Crystalline Polypropylene
ment Polypropylene
alpha 46.4 46.3 PPPP 46.5 41.0-41.5 r

aiphaCH2 46.5m
2 alpha 46.0 45.8 PPE
aiphaCH2
3 alpha 31.8 31.8 PPEP
gammaCH2
4 CH 30.9 30.1 PPE
5 CH 28.8 28.1 PPP 28.5 28.8mmm
28.6mmmr
28.5 rmmr
28.4mr+rr
6 beta 24.5 24.4 PPEPP
betaCH2
1 CH, 21.8 21.6 PPPPP 21.8 21.3-21.8 mm
20.6-21.0 mr
19.9-20.3 rr
8 CH, 21.6 21.4 PPPE
9 CH, 20.9 20.1 PPPEP
CH, 19.8 19.8 EPE
CH 33.1 33.1 EPE
aiphaCH2 31.4 EPE
betaCH2 EPE 21.3
(CH2). 29.8 29.8 EEE
From Paxton and RandaUS2. American Chemical Sociey

• As measured
Table 7.47 - Absolute Absorptivity Values Obtained for Styrene
Component Absorptivity Value Solvent

IIcmg
Styrene 1.903 Acetone

Styrene 1.911 Tetrahydrofuran
From Anderson et al. 54 American Chemical Society
94_2 APPARATUS
Proton NMR spectrometer, Joel C-60H Mhz spectrometer used in original work
or equivalent.
94.3 REAGENTS
Deuterated chloroform.
Trimethylsilane.
413
Table 7.48 - Infrared Analysis for Bound Styrene in Styrenated Acrylic Polymers
Styrene
Sample Calculated % Observed %
1 5.0 5.0,4.9
2 7.5 7.1,6.9
3 10.0 19.6,19.5
4 24.3 24.4,24.3
5 24.3 25.6,24.6
6 25.0 25.1,25.8,24.2'
7 35.0 36.3,35.6
8 35.0 34.7,35.2
9 40.0 28.9,40.1
10 60.7 59.1,60.3,59.7"
II 70.0 69.3,70.3,69.5'
From Anderson. s4 American Chemical Society

, Percent styrene values, determined in tetrahydrofuran. All the remaining values were determined using
acetone as the solvent.
94.4 METHOD
A deuterated chloroform solution of the polymer containing trimethylsilane

internal standard is run on the proton NMR spectrometer. Integration of peak areas at
delta 8 and 1-4 delta respectively gives a measure of signal strengths from aliphatic
protons (methacrylate units) and aromatic protons (styrene). These areas can be used as a
basis for calculating the methacrylate and styrene unit contents of the polymer.
The proton NMR spectra are obtained using a Jeol C-60H MHz spectrometer.
Sweep width of 50 Hz and sweep time of 2.5 min are employed. For integration, sweep
time is increased to 1.25 min. Deuterated chloroform is used as a solvent and
trimethylsilane is used as an internal standard. The spectra are run at ambient
temperature using 10-15 wt% solutions. Small variations in room temperature do not
affect the precision of spectra as demonstrated by 1% standard deviation. Solutions of
10-15 wt% of copolymer are used since this gives the best spectra. If the number average
molecular weight (Mn) of a copolymer is high, a lower wt% gives better results and vice
versa. The sample size is optimized by varying the sample concentration to obtain the
best possible spectra. Too high a concentration dampens the signals. One can easily
differentiate the aromatic protons from the aliphatic protons since the former absorb at 8
delta whereas the latter absorb between 1-4 delta. Areas under these peaks are integrated.
The integrated areas are related to either the aliphatic or aromatic protons of the
copolymer under study. These areas can then be converted to weight per cent of the
monomers using simultaneous equations.
414
This procedure enables down to 0.5% styrene and methacrylate units to be

detennined in styrene methyl methacrylate and styrene-n-butyl methacrylate copolymers
METHOD 95 - DETERMINATION OF STYRENE AND METHACRYLATE

UNITS IN STYRENE-METHYL METACRYLATE AND STYRENE N-BUTYL
METHACRYLATE COPOLYMERS. PYROLYSIS - GAS
CHROMATOGRAPHY.55
95.1 SUMMARY
This pyrolysis gas chromatography method determines styrene and methacrylate

units in styrene-methyl methacrylate and n-butyl methacrylate copolymers in amounts
down to 0.5%.
95.2 APPARATUS
The pyrolyser. Chemical Data System Pyroprobe Model 100 are used as the
pyrolyser. Quartz sample tubes, 30 mm long and I mm i.d. are placed in the platinum coil
heating probe. Pyrolysis conditions are varied until the most reproducible pyrograms
were obtained. The optimum operation conditions are interface temperature, 120°C;
ramp, 20°C; interval, 20 s; final tempemture 600°C. The ramp indicates rise in
tempemture °C/m. Interval indicates the period for which the final temperature is held.
The gas chromatogmph. Hewlett Packard 5750 gas chromatograph with 12 ft x
liS inch stainless steel column packed with S0l100 mesh Chromosorb P (Applied
Science) coated with 10% W-9S2 are used. Opemting conditions: helium flow 25
mlImin; injection port tempemture, 150°C; detector tempemture, 250°C; flame ionization
detector range 10 with 4 x attenuation; oven tempemture programmed from 70-270°C at
SOC/min.
95.3 REAGENTS
Methylene dichloride.
95.4 METHOD
A methylene dichloride solution of the polymer is pyrolysed and the integmted

areas of the styrene and acrylic monomers obtained from a gas chromatographic scan.
The ratio of these two monomer peak areas proportional to the styrene and methacrylate
unit contents of the original polymer is compared with that obtained for standard
copolymers of known composition, and, hence the composition of the sample obtained.
415
The copolymer material (100 mg) is weighed in a 10 ml volumetric flask and

dissolved in 10 ml methylene chloride. Two microlitres of this solution are placed at the
centre of a quartz sample tube and allowed to dry. The sample tube is placed inside the
platinum coil of the pyrolysis probe which is then inserted into the heated interface.
Before initiating the run, 10 min are allowed for any entrapped air, residual solvents or
monomers to escape.
For calculation of percent styrene and methacrylate in the sample, the ratio of
integrated areas of acrylic monomer to that of the styrene monomer is obtained from the
gas chromatographic scan. This ratio is then compared to the one obtained from a
standard copolymer of known composition which is prepared by 100% conversion of the
starting monomers.
The analysis of comonomer composition does not appear to be significantly

affected by the extent of randomness observed for these materials. The difference
between NMR and gas chromatography pyrolysis results are in the range of 0.4% and 0-
4.8% for styrene-n-butyl methacrylate and styrene-methyl methacrylate, respectively.
The difference in carbon analysis and pyrolysis gas chromatography results is also in the
same range for both the copolymers. Standard deviation for pyrolysis gas chrom-
atography ranges from 1.2-2.1 %. Precision for NMR analyses is better than 1%.
Pyrolysis of methyl methacrylate-ethylene dimethacrylate copolymer gives only
once major peak (methyl methacrylate) using a hot filament detector. The composition of
methyl methacrylate-ethylene dimethacrylate copolymer can, however, be determined by
pyrolysing a weighed sample and using the ratio of sample weight to area of the methyl
methacrylate peak for obtaining a standard analysis curve. Under favourable conditons
and with careful control of pyrolysis column, and detector variable, constituents can be
determined within ± 0.5%.
The differences in the pyrograms of block and random copolymers allows
estimation of the comonomer distribution. Random copolymers of ethylene with methyl
acrylate or methyl methacrylate yield on pyrolysis a lower ratio of methanol/methyl
acrylate or methyl methacrylate, respectively, than block polymers of the same
composition. Differential thermal analysis measurements give a first-order transition for
block polymers only, and by measuring the area under the transition an indication of the
minimum chain length between acrylate units can be obtained.
METHOD 96 - DETERMINATION OF COMPOSITIONAL ANALYSIS OF

METHYLMETHACRYLATE- METHACRYLIC ACID COPOLYMERS.
FOURIER TRANSFORM Be NMR SPECTROSCOPy.56
96.1 SUMMARY
This Fourier transform 13C NMR method determines the compositional analysis
of methylmethacrylate-methacrylic acid copolymers.
416
96.2 APPARATUS
13C NMR spectrometer, various CFR-20 pluse Fourier transform spectrometer

used in original work, or equivalent.
96.3 REAGENTS
Pyridine: pyridine ds, 1:1 v/v.
96.4 METHOD
A pyridine-pyridine ds solution of the polymer is run ofa 13C NMR spectrometer

and acidic (methacrylic acid) and ester (methyl methacrylate) group resonances
evaluated. The procedure is calibrated against standards of known composition.
Samples are prepared by dissolving or swelling ca. 0.3 g of copolymer in 2 g

solvent - both components being weighed directly into a 10 mm NMR sample tube. A
50150 mixture of pyridine and pyridine ds is used as the solvent and provided the
deuterium intemallock for the spectrometer. Spectra are obtained on a Varian CFR-20
pulse Fourier transform spectrometer operating at 18.7 kg (20.0 Mhz l3C frequency).
The pulse power delivered to the single coil 10 mm o.d. probe is sufficient to rotate the
l3C magnetization by 90° in 15 us. Probe temperature under these conditions was 38°C.
Spectrometer parameters for the determination of spectra are: ca 65 degree (10 us) pulse,
4 Khz spectral width, 1 second data acquisition time and 3 seconds delay between
repetitive pulses (ie. a total experiment recycle time of 4 seconds). Typically 12,000-
15,000 free induction decays (FID) are accumulated (ie. an "overnight" run mode was
employed) for each quantitative determination. The accumulated FID is digitally filtered
with a time constant that produces a 1.7 Hz line broadening. The 8 K data table is then
Fourier transformed to yield a 4 Khz spectrum defined by 4K real points (ie. digital
resolution ca I Hz).
Spin lattice relaxation times (T I) for the carbonyl carbides are estimated from
180-5-90 pulse sequences and found to be in the range 0.8-1.1 seconds for ungassed
solutions. It should be noted that the solutions were not degassed and that the presence of
dissolved oxygen may influence the observed relaxation rate. If samples were degassed,
the carbonyl relaxation could be longer in which case a longer delay between repetitive
pulses would be required. The imposition of a 3 second pulse delay and employment of a
65° pulse ensured the recovery of the carbonyl magnetization during the recycle time,
thus eliminating possible errors in quantitation resulting from differential relaxation
times. Spectra are obtained under fully proton decoupled conditions using a gated-
decoupling scheme in which the proton decoupler was off during the 3 seconds delay
time and gated on at the start of the 1.0 seconds acquisition period. In this manner,
problems associated with differential nuclear Overhauser enhancements (NOE) for
different carbonyl carbons are avoided.
A method of checking that the spectrometer conditions are sufficient to yield
quantitative data is to compare the total integral of the carbonyl region with those
obtained for alpha-CH3>C< CH2 since all integrals should be the same under quantitative
417
quantitative conditions. In all cases the integral values for all four resonance regions are
within 2-3% with the deviations being random from sample to sample - ie. in one case the
carbonyl might be the greatest of the four in magnitude and in another case the lowest.
A 13C NMR spectrum of a polymethylmethacrylate - methacrylic acid copolymer
demonstrates the acidic group and the ester group resonances.
In Figure 7.28 is shown the fully proton decoupled 13C spectrum obtained in
pyridine at 38°C of a (MMAlMAA) copolymer of ca. 33% acid composition. While the
spectrum resolves into alpha CH3, CH2, OCH3 >C<, and C = 0 regions, the structural
similarity of the comonomers results in resonance overlap (at 20 Mhz) between ester and
acid carbons in all regions but the carbonyl. The complete structure in the carbonyl
region arises from the sensitivity of the carbons to the microstructural features of the
copolymer chain, ie. sequence and tacticity effects. To assure these effects do not lead to
overlap of ester and acid carbonyl resonance, chemical shifts of both homopolymers and
homosteric copolymers were examined with the result that the carbonyl resonance region
does separate into distinct acid and ester regions in pyridine.
In order to test the reliability of compositional results obtained by the 13c NMR,
analyses of several copolymers were carried out by both 13c NMR and titration.
Titrations were carried out in 50010 aqueous ethanol medium to the phenol phthalein end-
point using 0.15 N aqueous potassium hydroxide as the titrant. As evidenced in Table
7.49 there is an excellent correlation between the compositional analysis by NMR and
titration (correlation coefficient = 0.998) with most of the comparative analyses differing
by 2% or less.
METHOD 97 - DETERMINATION OF HEXAFLUOROPROPYLENE AND

VINYLIDENE FLUORIDE UNITS IN POLYHEXA FLUOROPROPYLENE -
VINYLIDENE FLUORIDE CO POLYMERS. PYROLYSIS - GAS
CHROMATOGRAPHY.51
97.1 SUMMARY
This pyrolysis - gas chromatography method determines hexafluoropropylene and

vinylidene fluoride units in polyhexafluoropropylene-vinylidene fluoride copolymers in
amounts down to 0.5%.
97.2 APPARATUS
Curie point pyrolyser (Figure 7.30).

Gas chromatograph, (Hewlett Packard HP5750 or equivalent, Figure 7.29,
equipped with gas sampling valve). Magnetic induction coil located near to injection
port. The solenoid gas valve is operated by a switch on the control panel. The HP-5750
gas chromatograph is equipped with a gas sampling valve and the solenoid valve is
connected in place of the sample loop. With the gas sample valve open, the solenoid
valve can be used to divert the carrier gas flow either directly through the injection port or
through the pyrolysis chamber.
418
Table 7.49 - Comrositional Analysis ofPoly(inethyl methacrylate-co-methacrtylic acid)
by Titration and ' C NMR
Acid Content
Test Sample Number Base Titration % '3CNMR%
1 14 13
2 15 15
3 21 22
4 23 24
5 23 26
6 24 27
7 24 24
8 25 27
9 24.5 23.5
10 25 24
11 25.S 25.5 .
12 29 28
13 33 33
14 36 33
15 48 48
16 48 49
17 45 49
18 50 49
19 97 100
From Johnson et a1 56 • American Chemical Society
Gas chromatography conditions. Gaseous pyrolyzate separated on a 10 foot x 1.8

inch o.d. stainless steel column packed with beta,beta'-oxydipropionitrile Porasil C
Durapak (Waters Associates), 80 to 100 mesh. The carrier gas is argon flowing at the
rate of 15 cm 3 min-' The temperature of the column oven is initially 90°C; 3 min after
pyrolysis, the temperature of the column oven is raised to 120°C and maintained there.
The flame ionization detector is optimized for fluorocarbons. The complete elution of all
fragments takes 30 min.
Hypodermic needles. Huler point 24 gauge with syringe fitting removed and
replaced by 3 mm od quartz tubes sealed with epoxy resin suitable for use in vacuum
systems.
97.3 REAGENTS
Acetone, reagent grade.
97.4 METHOD
An acetone extract of the polymer is injected into a pyrolysis unit and the
pyrolysis products swept into a gas chromatograph. The copolymer composition is
calculated from the amount of vinylidine chloride and trifluoromethane produced during
pyrolysis. The procedure is calibrated against standard polymers whose composition has
been determined by 19F NMR analysis.
419
«I
."
C
o
0-
."
«I
L.
L.
«I
-0
I-
o TMS
o
CII
0::
H
"C-
H
I i
.50 .oa 50 o
Figure 7.28. The 20Mhz 13C NMR spectrum of p(MMA-co-MAA)-33% acid dissolved in (50/50) vlv
pyridine pyridine-d,. The I,H,S notation refers to isotactic, heterotactic and syndiotactic stereochemical
triads: A and E refer respectively to acid and ester. From Johnson et al with permission." American
Chemical Society
7.16
F H CF 3 F H F F F H F
I I I I I I
-c-c-c-c-c-c-
6H
-. CF3H + - C - C·
I +
III
·c - c - c - c-
I I I I I I
F H F F H F
I I
F H
II II
F F H F
A 10% solution of each hexafluoropropylene-vinylidene fluoride copolymer is

prepared by dissolving 10 g of polymer in 100 ml of reagent grade acetone. A vial 58
mm high is filled with the sample solution. A pyrolysis wire, previously cleaned in a
bunsen burner until red hot, then cooled, is dipped into the vial. The dipped wire is then
dried in a vacuum oven at 90°C for 30 min. Use of lower drying temperatures or shorter
times results in an acetone peak in the pyrogram. This is due to mechanically trapped
420
GAS
IAM'L,"'G
VALV!
INDUC-
TION
COIL
A, ANALYTICAL COLUMN
GAS CHROMATOGRA'"
CURl' POINT 'YROLYZU
Figure 7.29. Schematic of the coupling of the Curie point pyrolyser to the gas chromatograph.
The induction coil was positioned as close as possible to the injection port. The solenoid valve and the gas
sampling valve were mounted directly on the gas chromatograph. From Blackwell with permission.'7
American Chemical Society.
TEE
NUT
~ 0 PVROL VSIS W'"E C::;=::::J~.....- HUBER P()tNT
SEPTUM " NEEDLE.
(POleY
SEAL
BUS"'NG ..
Gas TUBING
TO
SOLENOID
VALvE
Figure 7.30. Schematic of the pyrolysis chamber. From Blackwell with permission.'7 American Chemical
Society
421
acetone being liberated. This procedure will provide a pyrolysis wire coated with a thin
film of unifonn thickness and reproducible length.
97.5.2 Procedure.
Pyrolysis conditions are varied until the most reproducible pyrogram is obtained.
The coated wire is placed in the pyrolysis chamber and allowed to come to equilibrium
for 5 min with the carrier gas flowing throught the chamber. The samples are pyrolysed
at SOODC for 4 seconds. The gaseous pyrolyzate is separated on a lO foot by liS inch o.d.
stainless steel column packed with beta, beta' oxydipropionitrile Porasil C Durapak
(Waters Associates), SO to 100 mesh. The carrier gas is argon flowing at the rate of 15
cm 3 min. The temperature of the column oven is raised to 120DC and maintained there.
The flame ionization detector is optimized for fluorocarbons. The complete elution of all
fragments takes 30 min.
The components of the pyrolyzate are identified by mass spectrometry. The Curie
point pyrolyser is coupled to the gas chromatography system (which utilizes a Varian
IS00 GC) in the same way as it was coupled to the HP-5750 gas chromatograph. The
first three peaks are identified as vinylidene fluoride, trifluoromethane and hexafluoro-
propylene respectively. The other peaks are identified as oligomers or hexafluoro-
propylene and vinylidene fluoride. The output from the HP 5750 is integrated by a
computer system. The relative peak areas for vinylidene fluoride, and hexafluoro-
propylene is calculated.
Two calibration plots are made, one of the sum of the relative peak areas for
trifluoromethane and hexafluoropropylene produced during pyrolysis against the weight
per cent of hexafluoropropylene calculated from 19F NMR data and the other of the
relative peak area for vinylidene fluoride produced during pyrolysis against the weight
per cent vinylidene fluoride calculated from 19F NMR data. A least square fit was
calculated for each calibration plot and the slope and intercept were detennined.
The two calibration plots demonstrate a linear relationship between the pyrolysis
products and the NMR data. The slopes of the two calibration plots are close to 1, the
slope for weight per cent hexafluoropropylene is 0.99 and that for vinylidene fluoride is
0.97.
The monomer composition of the series of copolymers was calculated from the
pyrolysis data and compared to that calculated from the NMR data. These data are
summarized in Table 7.50. The difference in weight per cent calculated for the two
techniques, averaged for hexafluoropropylene ± 6.0% and for vinylidene fluoride ±
0.S5%.
The components of the pyrolyzate can be identified by mass spectroscopy. The

Curie point pyrolyzer is coupled to the gas chromatograph system (which utilizes a
Varian 1800 GC) in the same way as it was coupled to the HP-5750 gas chromatograph
(see Figure 7.29). The first three peaks are identified as vinylidene fluoride,
trifluoromethane and hexafluoropropylene respectively. The other peaks are identified as
oligomers ofhexafluoropropylene and vinylidene fluoride.
422
The reproducibility of the pyrolysis step, achieved by the Curie point pyrolyser
permitted the monomer composition to be determined with a reproducibility of ± 1%.
Table 7.50 - Comparison of the Monomer Composition ofHFPNF2 Copolymer as

Calculated by Pyrolysis Data and NMR Data
Weight%HFP Weight % VF2 StdDev
For Curie
Point
Pyrolyser
19FNMR 19FNMR
Pyrolysis Pyrolysis
28.6 28.8 0.2 71.4 70.9 0.5 1.04

29.0 28.8 0.2 71.0 71.0 0 0.34
34.79 36.04 1.25 65.21 62.63 2.58 0.52
36.46 36.73 0.27 63.96 62.91 1.05 0.82
37.24 37.33 0.11 62.76 62.61 0.15 0.39
39.04 39.07 0.03 60.96 60.88 0.08 0.67
39.04 38.35 0.69 60.96 61.55 0.59 0.63
39.82 38.46 \.36 60.18 61.89 1.71 0.30
40.10 39.45 0.65 59.90 61.49 0.57 0.10
42.4 43.2 0.8 57.6 56.7 0.9 0.39
44.8 46.2 0.2 55.2 53.8 1.4 0.48
44.8 45.4 1.4 55.2 54.3 0.9 0.59
47.3 47.0 0.3 52.7 52.8 0.1 0.92
49.95 49.45 0.50 50.05 50.55 0.50 0.30
423
CHAPTER7.!
ADDITIVE MIXTURES
Methods 98 - 108
METHOD 98 - DETERMINATION OF MIXTURES OF ADDITIVES IN

POLYMERS. THIN-LAYER CHROMATOGRAPHY - INFRARED AND
ULTRAVIOLET SPECTROSCOPY.
98.1 SUMMARY
This thin-layer chromatography - spectroscopic procedure is capable of identify-

ing and detennining a wide range of additives in polymers in amounts down to a few
hundred ppm. Several additives can be evaluated during the same analysis.
98.2 APPARATUS
Thin layer plates. Plates (20 cm x 20 cm and 20 cm x 5 cm) coated with 250 u
thickness of Merck silica gel 0 254 or OF 254 (ultraviolet fluorescent). These plates can
either be prepared in the laboratory using an adjustable spreader or prepared plates can be
obtained commercially.
Alumina type D5F (Fluka), fluorescent MN cellulose powder 300 F254 (Mackery
Nagel and Co), fluorescent silica gel HF 254 + 366 (Merck) fluorescent.
The glass used to prepare plates in the laboratory should be cleaned with chromic
acid, then with deionised water avoiding detergents and dried in an air oven prior to
coating with silica gel in a clean laboratory atmosphere; conditioning in an air oven for
30 min at 120°C in a vertical position should be followed by storage in a desiccant box
until required for use. The plates should preferably be used within 1 - 2 h of preparation
so that their activity does not change appreciably and to. reduce the possibility of
contamination of the silica gel layer by volatile impurities in the laboratory atmosphere
which might interfere in the subsequent evaluation of the plates.
Volumetric flasks, 0.5 and 1 cm3•
Automatic sample applicator, for applying polymer extracts to thin-layer plates
capable of applying 35 cm band of extract to plates.
Ultraviolet lamp, shortwave (254 nm) and longwave (366 nm).
Electrically heated copper wire.
Stylus.
Extraction thimble, sintered glass, see Figure 7.31.
Elution column, see Figure 7.32.
Infrared spectrometer, with beam condenser and ultramicro cavity cells.
Ultraviolet spectrometer with rectagular microcells (Figure 7.33)
424
E
E
N
10
Eluting solvent
Absorbent
No. 2 sinler disc ----I~~(J
-1r~1.0.
Figure 7.31. Filtration apparatus for extracting separated additives from adsorbent isolated from thin-layer
chromatography plates.
:::=::: ==-
(a) Pasteur type disposable pipette (BKH No.53039, 9 inch length)
~ijr
AdlOrbent
~ GI.UWool ~
~~~;;~~~~~;.;;,.,;;;;.;~;;;;;;~====C=.'=2=5"t.mm/
I' aI. 50mm
To be cut here
I
~. 45'
'-S.c.,
(b) Pipette modified and ready for elution
Solution /
~~--------/'------,
(e) Capillary before evaporation
Residue #
::~/======-'
(d) Capillary after evaporation
Figure 7.32. Steps in preparation and use of elution column used for OLC fraction collecting; (a) pasteur-
type disposable pipette (CKH No. 53039, 9 in length); (b) pipette modified and ready for elution; (c)
capillary before evaporation; (d) capillary after evaporation.
425
Elution columns, disposable, made from Pasteur-type pipettes (230 mm size) as
shown in Figure 7.32. Pack a glass wool plug firmly into the larger half of the tapered
section as shown in Figure 7.32. A more retentive pad is obtained if the glass wool pad is
dampened with a few drops of the elution solvent to be used just before use. Excess
liquid is removed by drawing air through the column.
Infrared spectrophotometer fitted with a beam condenser and "ultramicro" cavity
cells.69
Centrifuge.
Micromanipulator, Microchemical Specialities Co., Berkeley, Calif., No. 5020, or
equivalent.
Hair dryer
98.3 REAGENTS
Acetone.
n-hexane.
Carbon disulphide.
Tetrachloroethylene.
Carbon tetrachloride.
Toluene.
Benzene.
Chloroform.
Methyl cellosolve.
Dioxan.
Ethylene dichloride.
Ethyl acetate.
Nitromethane.
Acetone.
Methyl alcohol.
Ethyl alcohol, absolute.
Petroleum ether 40/60.
Spray reagents, see Tables 7.51 and 7.52.
98.4 METHOD
A suitable extract of the polymer is applied to a thin layer plate and the plate migrated
with suitable development solvents to separate the individual polymer additives present.
Examination of the plate under an ultraviolet light or the application of spray reagents
reveals the separated additives. A second plate is now prepared and the bands of plate
which contain the separated additives are removed and each band is separately extracted
with a suitable solvent to extract the additives. These extracts are then concentrated and
dissolved in suitable spectroscopic solvents for infrared and/or ultra-violet spectroscopy
to identify and/or determine each additive.
426
Quartz mieroeell
(The Ullracell Co., Emerson.
N. J .• 2 mm inside widlh.
code 518-120)
Bevel edges
10 30' Mask with pin
included
angle Make from '116" brass sheel.
bevel edges of slot from side
with pin to leave sharp edges
2'/S' of dimensions shown on other
0~78" slol side. Hand file outside edges
(centred) as necessary for snug, sliding
bevel from fit in groove of cell holder.
this side Blacken with dull enamel or
'/'6" ink.
-
0·31'"
0-47"
1 em cell holder
(Applied Physics Corp .•
Monrovia, Calif" Part.
No. 1443150. ribs on
top not shown)
Figure 7.33. Microcell, mask and cell holder used in ultraviolet spectroscopy.
98.5.1 Premigration of Plate.
Thin-layer chromatographic grades of silica gel usually contain traces of inorganic

impurities. If, during the development of the chromatogram these impurities migrate to
regions of the plate which coincide with the Rf values of separated additives then the
impurities will interfere with the interpretation of the plate following application of spray
reagents. A plate premigration procedure for overcoming such interferences is discussed
in Note l.
The following procedure is suitable for the premigration of adsorbent impurities
from thin-layer plates prior to the use of the plates for separations of polymer additives.
427
In the case of silica gel, at least, methyl alcohol is the recommended solvent. Methanol is
poured into a glass tank with a ground glass lid to a depth of 1 - 2 cm and the walls of the
tank are lined with sheets of filter paper dipping into the solvent. The tank is left for 30 -
60 min in a draught-free area until the interior has become saturated with solvent vapour.
The coated 20 cm x 20 cm plate is then supported vertically in the methanol layer and left
until solvent has ascended to the top of the plate. The plate is then removed from the
tank, conditioned at 120°C (for 30 min) and the top 5 - 10 cm of adsorbent containing the
impurities scraped off with a sharp instrument and thrown away leaving the remainder of
the adsorbent coating free from impurities. Plates should be used as soon as possible
after activation. Plates prepared in this way are virtually free from ultraviolet and
infrared absorbing impurities. Premigrated plates should always be reactivated by
heating for 30 min at 120°C immediately prior to use in the chromatography of polymer
extracts.
Ultraviolet fluorescent grades of silica gel absorbent, discussed later, usually
contain manganese activated zinc silicate as a fluoroescening agent, ego Merck GF 254
Merck G and Camag silica gel G (SG-05F). This compound is not extracted from the
adsorbent in the methanol premigration procedure.
98.5.2 Applitation ofPoiymer Extrad to Plate.
Regular application of the sample is particularly important for successful

separations. In this procedure the sample is sprayed on to the layer as a band by means of
an automated applicator.
In order to minimize washing-out of the sprayed solution at high sample volumes
the most volatile solvent possible is chosen, ego diethyl ether or methylene dichloride.
Where appropriate the plate may be warmed beforehand so as to achieve rapid
evaporation of the solvent.
A convenient trial sample size of solvent solution of a polymer extract for
application as a band on a 250 u thick 20 cm x 20 cm plate is I cm3 of a 1% solution, ie.
IOmg.
98.5.3 Seledion of Chromatographit Elution Solvent.
Chromatograph an unknown mixture with solvents of different polarities to obtain

an idea of the types of compounds on the plate, see Note 2.
In order to avoid 'missing' any sample components it is highly advisable to apply
the sample location techniques described in the last section to chromatograms of the
sample obtained using several plate materials such as silica gels and alumina, and with
each adsorbent to use as wide a variety as possible of different types of development
solvents. These steps reduce to a minimum mistakes brought about by supposedly pure
separated compounds consisting, in fact, of two or more unresolved compounds and
enable a suitable development solvent to be selected.
98.5.4 Detedion of Separated Compounds on the Plate.
Detection techniques should be carried out immediately after the chromatogram

has been developed, in order to reduce to a minimum any opportunity for volatile sample
constituents to be lost by evaporation from the plate. Detection of the separated
compounds on the plate is achieved by examination under ultraviolet light which locates
428
Table 7.51 - General Spray Reagents for Location of Compounds on 20 cm x 20 cm
Silica Gel Coated Thin-Layer Chromatography Plates
A. Reagents Applied to FO 254 Plate Without Subsequent Heating·
Potassium pennanganate(O.1 N) in aqueous sodium carbonate

(5%w/v)
2 Potassium pennanganate (2% w/v) in aqueous sulphuric acid
(6%v/v)
3 Potassium pennanganate 0.1% w/v in sulphuric acid (96%)
4 Antimony pentachloride (2% w/v) in carbon tetrachloride
5 Phosphomolybdic acid (3% w/v) in ethanol, then expose plate
to amonia vapour
B. Reagents Applied to 0254 Plate with Subsequent Heating·
Sulphuric acid aqueous

(20010 w/v) 5-15 minutes at 120·C, then 5 minutes at 150·C
2 As (2) under A 5-15 minutes at 120·C, then 5 minutes at 150·C
3 Phosphoric acid (10010)
methanolic 5-15 minutes at 120·C, then 5 minutes at 150·C
4 Perchloric acid (2%)
methanolic 5-15 minutes at 120·C, then 5 minutes at 150·C
5 As (4) under A 5-15 minutes at 120·C, then 5 minutes at 150·C
6 Phosphomolybdic acid (20010 5-15 minutes at 120·C

w/v in methanol or methyl
cellosolve, then expose
plate to ammonia vapour
• Spray 20 em x 2 cm wide sections of plate with each reagent using an aluminium or glass mask with
suitable aperture
some, but not all, types of compounds and by spraying with a range of general or specific
spmy reagents. (Tables 7.51 and 7.52 and Note 3).
98.5.5 Removal of Separated Compounds from Plate.
The next stage is to run a chromatogmm on fresh 20 cm x 20 cm plates using a

suitably sized sample (say I cm3 of a I % solution) and mark off with a sharp stylus the
bands corresponding to the known positions of the separated compounds. No detection
reagents are applied to these plates although they may be examined under the ultmviolet
light to precisely locate any components which show up under these conditions. The
simplest method of removing the zones containing the separated compounds (after
allowing solvent to evapomte from the plate) is to hold the plate vertically its side resting
on a sheet of paper and to scrape off the desired zone with a spatula. For substances
which are not sensitive to oxidation, the zones may be sucked from the layer directly into
an extmction thimble by using a small 'vacuum cleaner,.72 Each separated adsorbent
band can then be bottled off in 5 ml polyethene stoppered tubes and retained for further
examination.
Each portion of adsorbent is transferred from the storage tube to a small sintered
glass extraction thimble (Figure 7.31) and the organic compounds leached out with a
suitable solvent such as anhydrous absolute ethanol, diethyl ether or methylene dichloride
(see Note 4).
429
Table 7.52 - Chemical Analysis of Additives in Plastics: Specific Spray Reagents for
Locations of Compounds by Thin-Layer Chromatography
Additive Type Spray Reagent Reference
Phenolic antioxidants 1. 2,6-dichloro-benzoquinone chlorimine (1-2% in 75 - 77

ethanol followed 15 mins later by 2% borax in 40"10
aqueous ethanol)
2. Alpha, alpha'-diphenyl picryl hydrazyl (0.1% in 95% 77
aqueous ethanol)
3. Palladium chloride (mix 150 ml palladium chloride 77
with 100 ml of2 N hydrochloric acid)
4. Diazotized p-nitroaniline (mix 5 ml O.S% p- 74
nitroaniline in 2 N hydrochloric acid with O.S ml S%
sodium nitrite until colourless and 15 minutes later add
15 m120% sodium acetate)
Amine antioxidants Diazotized p-nitroaniline (mix 5 ml 0.5% p-nitroaniline 74
in 2 N hydrochloric acid with O.S ml S% sodium nitrite,
until colourless and IS minutes later add IS m120"1o
sodium acetate)
Dialkyl thiodipropionates Potassium platinoiodide (mix S ml S% platinum 77
tetrachloride in I N hydrochloric acid with 4S ml 10%
potassium iodide and 100 ml water)
Phthalate ester plasticizer Resorcinol. (Spray with 20"10 aqueous resorcinol in 2% 78,79
aqueous zinc chloride and heat to 1SO"C. Then spray
with 4 N sulphuric acid and heat for 20 minutes at
120"C. Spray with 40"10 potassium hydroxide to produce
orange spots). Phthalic acid and phthalates also react
Acids and bases Bromocresol green (O.S% in SO"lo aqueous ethanol) 80,81
Bromocresol purple (O.S% in SO% aqueous ethanol)
Bromophenol blue, Methyl red (O.S% in SO% aqueous
ethanol) 80,82,83
Carboxylic acids, Aliphatic Sodium dichlorophenolindophenol (1% ethanolic). 84
(primary, secondary, tertiary) Cobalt thiocyanate 109 Co(NO])z6H20 and 109
amines, long chain ammonium thiocyanate made up to 100 ml. Produces
quaternary salts and amine blue clour
oxides
Alkanolamines Ninhydrin, heat plate for 5 minutes at II O"C, spray with 79

0.2% ninhydrin in acetone and heat S minutes at IIO"C
to produce colours. Further colours then produced upon
spraying plate with 0.2% alizarin in acetone
Alkyl phenols Phenols coupled as p-nitrophenol azo dyes applied to
plate of silica gel impregnated with alkali. Separated azo
dyes located as yellow/red colours upon exposure of
plate to ammonia vapour
Carbonyl compounds Carbonyl compounds in sample converted to 2,4- 8S
dinitrophenylhydrazones, applied to thin-layer plate and
plate developed. Separated 2,4-DNPH compounds
located as yellow or brown colours upon spraying plate
with 2% sodium hydroxide in 90"10 ethanol
Organic peroxides Hydriodic acid (spray plate with a reagent comprising 40 86
ml glacial acetic and 0.2 g zinc dust added to 10 ml of
4% aq. potassium iodide, then spray with fresh I % starch
solution). Peroxides (and certain other types of
oxidizing agents) revealed by liberation of free iodine.
Alternatively use 2,6-dibromobenzoquinone chlorimine
• Spray 20 cm x 2 em wide sections of the plate with various reagents using an aluminium or glass mask
with suitable aperture
430
98.5.6 Preparation onnfrared Spectrum of Separated Additives.
Evaporate the low boiling solvent from the solution obtained in the previous
section and dissolve the residue in a suitable spectroscopic solvent (chloroform, carbon
tetrachloride or carbon disulphide). Transfer this solution into an ultramicro cavity cell.
The infrared spectrum of the solvent solution can then be obtained by normal
infrared spectroscopic techniques.
Alternatively, especially if the compound is insoluble in the usual spectroscopic
solvent, the solid can be dispersed in well-ground solid dry potassium bromide using a
dental mixing machine and the mixture pressed into a I mm thick 5 mm diameter disc.
This disc can then be mounted in a cardboard or plastic holder and used to prepare a
spectrum.
98.5.7 Preparation of Ultraviolet Spectra of Separated Additives.
Measure the absorbance of the solution at the desired wavelength or record its
spectrum using small volume microcells. Either air or the elution solvent may be used as
the reference. Blank determinations which were carried through the entire procedure,
including chromatography, should always be made and measured or recorded. It is
important that the sections of adsorbent eluted for the blanks come from chromatograms
prepared and handled in the same manner as the sample chromatogram and that they
represent the same areas and locations of adsorbent. This is necessary because impurities,
if present, are not distributed uniformly on the chromatogram. Removal of impurities
from the region of the adsorbent layer to be used for the sample separation by washing
the layer prior to migration of the sample using the methanol premigration technique
described earlier is a convenient and effective method of reducing blank absorption.
Standards. When quantitative determinations are desired using this technique, it

is necessary to known or to determine the absorptivities of the particular compounds.
This is done by preparing and measuring solutions of known concentration of the pure
compounds. It is also advisable to chromatograph known amounts of the pure compo-
unds to verify the applicability of the technique to the particular compounds. This is
recommended because unexpected errors can occur if compounds have enough volatility
to escape from the adsorbent or are unstable and change during the chromatography and
drying.
Note 1. Premigration of plate. Thin-layer chromatographic grades of silica gel

ususally contain traces of inorganic impurities. If, during development of a
chromatogram, these impurities migmte to regions of the plate which coincide with the
Rf values of separated additives, then the impurities will interfere in the interpretation of
the plate, following spmying with aggressive detection reagents, such as concentrated
sulphuric acid and antimony pentachloride, as the organic impurities in the adsorbent may
also react with these reagents and show upon the spmyed chromatograms. Also the
impurities absorb strongly in the ultraviolet region, especially below 250 nm. The
adsorbent impurities do not have an appreciable absorption in the infrared region. As
organic and inorganic impurities are extracted from the silica gel with organic solvents
such as diethyl ether, ethanol, acetone, benzene, chloroform and many others, they could
occur as contaminants in some of the fractions of separated additives isolated from the
plate by solvent extraction of the gel and consequently interfere in the interpretation of
the spectra of the additives, particularly in the case of additives which absorb below 250
431
in the ultraviolet. For this reason an identical blank chromatogram (only sample absent)
should always be run in parallel with the sample chromatogram in order to check whether
such interference effects exist.
Ultraviolet absorbing impurities in adsorbants are influenced by the nature of the
migration solvent. Depending on the polarity of the migration solvent used the impurities
migrate to a greater or lesser extent up the plate towards the solvent front with the result
that the lower part of the chromatogram nearer the baseline is cleared of impurities and
the impurities become concentrated in the upper section of the plate nearer the solvent
front. Subsequently, when a section of the absorbent is removed and eluted with a further
solvent to recover a separated compound the amount of impurities contaminating the
compound will depend on the location of the compound on the chromatogram (Rf values)
and contamination may range from negligible to substantial.
In circumstances where slow moving compounds are being separated, the
impurities may move away from the polymer additives towards the solvent front and thus
not interfere in the subsequent examination of the separated compounds. This behaviour
leads to a convenient method for moving the impurities beyond the section of the
chromatogram to be used for the separation of polymer additives by migrating the
chromatogram with appropriate washing solvents before applying and migrating the
sample mixture. If this premigration washing covers a longer distance on the plate than is
to be used in the sample migration then it is possible to move interfering impurities out of
the way.
Note 2. Selection of chromatographic solvent An unknown mixture should be

first chromatographed on 20 cm x 5 cm plates with solvent of different polarities to
obtain an idea of the polarities of compounds present in the sample and to reduce the
possibility of missing any of the sample components. Solvents of low polarity, such a n-
hexane, tetrachloroethylene and carbon tetrachloride, cause polar sample constituents to
migrate more readily. Solvents of intermediate polarity such as toluene, benzene,
chloroform and methyl cellusolve have a greater elutive effect on polar sample
components, whereas highly polar solvents such as dioxan, methylene dichloride, ethyl
acetate, nitromethane, acetone, lower alcohols and water elute polar sample constituents
towards the solvent front, ie. Rf values near unity. Mixtures of 40/60 petroleum spirit
and up to 10% (v/v) ethyl acetate are very useful general solvents for the separation of
unknown mixtures.
Note 3. Detection of separated compounds on the plate. Alumina and cellulose

powders are both available in fluorescent forms, respectively, alumina Fluka type D5F
and MN cellulose powder 300 F254 (Macherey Nagel & Co.). Exposure of plates to 254
nm radiation permits visualisation of substances on the plate which absorb above 230 nm
as a dark area on a blue fluorescent background. Fluorescent indicators which are
activated by long-wave length ultraviolet light may also be incorporated in the adsorbent.
The sodium salts of hydroxy-pyrene-sulphonic acids are particularly suited for this
purpose. The separated polymer constituents show on the chromatogram, partly as dark
zones, partly as zones which fluoresce brightly. The Merck silica gel HF 254+366
contains two fluorescence indicators, long and short ultraviolet light sensitive. To incite
fluorescence, apparatus is needed which will allow a choice of short or long wave
ultraviolet radiation. The non-fluorescent silica gel, Merck 0254, reveals the presence of
polymer constituents which have an intrinsic fluorescence under short wave (254 nm) or
long wave (366 nm) ultraviolet light.
432
A further general test for organic compounds on the plate involves holding an
electrically heated 25 cm long copper wire, set at red heat, at a few millilitres above the
plate along the length in which the chromatogram has been developed. After a few
seconds exposure, many types of organic compounds reveal themselves by charring or
otherwise discolouring.
Note 4. Removal of separated compounds from the plate. The extraction solvent
must: (1) be a good solvent for the additive, (2) be sufficiently polar to desorb the additive
from the absorbent (successive desorption with different solvent may be necessary at this
stage), (3) have a low boiling point to facilitate subsequent removal of solvent and reduce
to a minimum evaporation losses of any volatile sample constituents, and/or, (4) not
interfere in the subsequent spectroscopic examination of extracts.
Provided the desorption solvent is sufficiently powerful and polar, it should
recover between 50 and 100% of the additive present in the silica gel fraction and provide
sufficient material for examination by ultraviolet or infrared spectroscopy.
During the solvent elution of compounds from the isolated bands of adsorbent, the
elution solvent effectively displaces the components from the adsorbent so that all of the
component is contained in the first liquid emerging from the sintered glass thimble. Loss
of the component by its failure to elute is not usually serious, provided that the eluant
selected is one which would elute the particular compounds to the solvent front (ie. R f
near unity) on a thin-layer plate. In fact, the behaviour of the component on the plate
with plate elution solvents is a good guide to the selection of an appropriate solvent for
desorbing the same component from the isolated gel in the extraction thimble. If the
elution solvent used is less effective than this, then losses can be expected of the
compound at the adsorbent extraction stage.
In extractions from silica gel, care should be taken to ensure that, according to the
solvent used, components of the adsorbent are not coextracted with polymer additives.
Silica gel and cellulose powder adsorbents containing gypsum as a binder cannot be
extracted with water or with aqueous organic solvent mixtures because calcium sulphate
is quantitatively extracted at the same time. A significant extraction residue is obtained
even using chloroform, benzene or acetone as extractants. A significant inorganic
extraction residue is also obtained from gypsum-free silica gel to which silicon dioxide of
particle size less than 40 nm is added as a binder; this extract decreases with decreasing
polarity of the extraction solvent. The extract solution should, therefore, be filtered
through a hardened filter at the base of the extraction thimble (Figure 7.31) and/or
through short columns of Celite. Alternatively, the solvent extract can be evaporated to
dryness and the silica contaminated residue contacted with a good solvent for the polymer
additive and a bad solvent for the silica.
The method was applied to a polymer suspected to contain one or more of the
following additives; (I) Topanol CA (4,4',4" - butylene -1,1 3 tris (trimethyl-6-tert butyl
phenol). (2) DLTDP (dilauryl thiodipropionate) and (3) lonox 330 (1,3,5 tri methyl.
2,4,6-tri (3,5-di-tert-butyl)-4-hydroxy benzyl) benzene.
Additives were removed from 30 g of each of the polymers by Soxhlet extraction
overnight with diethyl ether. The extract residue was made up to 10 cm3 with chloroform
and portions of these solutions and of solutions of the trace additives mentioned above
were spotted on to silica gel plates. Viewing the developed plates under 254 nm
433
ultraviolet light located Ionox 330 and Topanol CA but not DLTDP. All three additives
were however located with aggressive spray reagents and with a reagent for phenols (2,6
dibromo benzoquinone-4-chlorimine) which gives a strong colour with hindered phenols
and also a yellow colour with DLTDP. Polymers I and 2 both contained DLTDP and
Ionox 330, polymer 2 also contained Topanol CA, and polymer 3 contained DLTDP and
Topanol CA. Both of the aggressive spray reagents revealed the presence of low
molecular weight polymer at the solvent front. These reagents also revealed the presence
in Topanol CA of impurity which appears at the solvent front. Obviously, this impurity
is of low polarity and is not phenolic as evidenced by the fact that it does not produce a
colour with the phenol reagent. It is probably a hydrocarbon.
. The method was also applied to the identification of an ultraviolet light stabiliser
and an antioxidant in a sample of a polyolefin. Again the polymer was extracted with
diethyl ether to isolate total additives and a portion of a chloroform solution of the extract
run on a silica gel coated plate in parallel with various known light stabilisers and
antioxidants commonly used in polymer formulations.
The polymer contained two additives appearing at Rf 0.6 and 0.85 which
coincided in Rf value and in the colour obtained with 2,6 dibromobenzoquinone -4-
chlorimine with known specimens ofUV 531 (2-hydroxy-4-n-octoxy benzophenone) and
lonol CP (2,6-di-tert butyl-p-cresol). Spraying the plate with 2,6 dibromo benzoquinone-
4-butyl chlorimine also revealed an additional orange coloured spot at Rf 0.8 (degraded
lonol) which did not coincide with any of the known additives tried. All three
compounds showed up under ultraviolet light.
In Table 7.53 are summarized the results obtained in some experiments carried
out to determine the recovery from thin-layer plates of compounds adsorbing at shorter
and longer ultraviolet wavelengths, respectively, di-n-butyl phthalate (222 nm) and lonox
330 (277 nm). These compounds were carried through the whole series of operations
involving application of sample to a silica gel plate, solvent development, separation of
adsorbent from plate and finally, solvent extraction of the compound from the adsorbent.
lonox 330 has a low Rfvalue with 4:1 cyclohexane:benzene development solvent hence,
during solvent development, ultraviolet absorbing adsorbent impurities are swept well
away from this compound to the solvent front. Premigration of the plate with methyl
alcohol was unnecessary and not used, therefore, prior to application of Ionox 330 to the
plate. Premigration of the plate with methanol before sample application was however,
carried out in the case of di-n-butyl phthalate. This was because this compound has a
fairly high R fvalue with the 9:1 iso-octane:ethyl acetate development solvent used, with
consequent possible contamination of the di-n-butyl phthalate band with ultraviolet
absorbing adsorbent impurities near the solvent front.
434
Table 7.53 - Reproducibility of Recovery from Polypropylene ofIonox 330 and di-n-butyl phthalate from Thin-Layer Plate (Silica Gel G254)
Compound Absorbance No. of Sample Sample Development Plate Section Solvent Adsorbtivity Recovery Standard
Maximum Plates Size Coneen- Solvent Dry- ofadsob- used to of Standard of Com- Deviation
Prepared (ul) tration ing entrem- Desorb Solution of pound
(%w/v) Time oved Compound Compound
(h) from from (titres gem)
PIateRf Adsorbent
lonox
330 277u 10 4:1 cyclo- 18 0.03 - Methanol 8.0 100 1.2
bexane:benzene 0.14 (extract
made up
to 1 ml)
Di-n-butyl-
p-phthalate 222u 5 5 9: 1 iso-octane: 18 Methanol 29.0 99.6 1.2
ethyl acetate (extract
made up
to 1 ml)
~
METHOD 99 - DETERMINATION OF ADDITIVES IN POLYETHYLENE AND
PVC. ruGH PERFORMANCE LIQUID CHROMATOGRAPHY.5I
99.1 SUMMARY
This hplc procedure is capable of determining a wide range of types of additives

in polyethylene and PVC in amounts down to 0.01 %.
99.2 APPARATUS AND EXPERIMENTAL PROCEDURE
99.2.1 Apparatus
The high pressure liquid chromatogrpahic system is shown in Figure 7.34. The
unit employed in this particular method was a Whitey Micro-regulating high pressure
feed pump (Whitney Research Tool Co. Oakland, Calif) equipped with a II mm plunger,
capable of a maximum flow rate of 7.3 cm3 per h and output pressure of 5,000 psi. The
solvent reservoir is placed a few feet above the pump since a slightly positive inlet
pressure was required for operation. The degassed solvent is slowly stirred by means of a
magnetic stirrer and heated externally slightly above room temperature to keep the
solvent degassed. A Whitey Union Bonnet Bar stock valve is placed on the high pressure
side of the pump to aid in priming the pump or to shut off the solvent flow when required.
A Circle Seal (Circle Seal Co., Anaheim, Calif.) adjustable relief valve set at 5,000 psi is
placed on the high pressure side of the pump for safety in case a blockage occurred
upstream. A Hellicoid Pressure Gauge 0 - 5,000 psi with a snubber and cleaned for
oxygen is used to monitor the output pressure. Downstream from the pressure gauge, the
entire system is connected with 0.04 in i.d. 0.063 in o.d. stainless steel tubing to ensure a
minimal dead-volume in the system which is particularly desirable when changing
solvent or solvent programming. Up to 2,500 psi output pressure on ALC-lOO LC pulse
damper (Water Associates, Framingham, Mass.) are used.
The system is operated at ambient temperatures. The system is shielded from
drafts and the components beyond the pulse damper are insulated with glass wool which
was wrapped with several layers of aluminium foil. This procedure eliminated short
term, localized temperature fluctuations and appeared to be satisfactory as far as system
stability was concerned. No base-line drift occurs under these conditions.
To ensure saturation of the carrier liquid when doing liquid-liquid chromat-
ography, a pre-saturator column is placed before the chromatographic column. It consists
of a 8 in x 3/8 in o.d. stainless steel tube packed with 62 - lOO micron Porasil A. (Waters
Asssociates) loaded with 5% by weight of the same liquid phase used in the
chromatographic column.
When necessary, the liquid flow can be split between the analytical column and
the reference column. A valve placed before the reference column permits the flow rate
through that column to be completely shut-off or varied depending on the requirements of
the system. This is particularly useful when using the refractive index monitor at higher
flow rates. For column flow rates up to 2 cm3 min· t good stability could be obtained by
careful balance of flow. The reference column was either filled with the same liquid-
liquid support employed in the analytical column or merely filled with uncoated glass
beads. With the ultraviolet detector the reference column is not used. Column head
pressures are read on 1 - 3,000 psi or 0 - 5,000 psi standard gauges.
436
Reservoir
MagnetIC
stirrer
Pn!ssure
gouge
/
Figure 7.34. Schematic of high pressure liquid chromatographic system. From Majors with permission.~R
Preston Publications Inc., New York
A six-port rotary liquid sampling valve is used for high pressure injections in the
continuous mode of operation. The basic design of the valve is that of Scott et al 73 but
with the volume reduced by careful machining to approximately a hundredth of that in the
original specifications. The ports are constructed with 0.010 in ie. 0.063 in o.d. stainless
steel tubing and the slots in the plastic cylindrical sleeve which rotates to permit injection
of the filled sample loop are drilled with a 0.010 in drill to the smallest possible depth.
Because of the extremely close tolerances of the internal connections great care is needed
to avoid the introduction of particulate matter which may accidently enter the stream and
clog the tiny holes. Immediately before the eluent-in port, a high pressure stainless steel
filter with a 5 micron frit is placed. Likewise, the sample loop is filled at ambient
pressure by connection to a five cm3 Luer-Iok syringe equipped with a Millipore Filter
holder. A five micron PTFE Millipore membrane is used as the filter material. These
precautions permitted the valve to be used for hundreds of injections with a wide variety
of sample without any clogging of the ports or internal sleeve.
The sample loop is connected to the valve with zero-dead volume Swagelok
stainless steel capillary unions. The size of the loop can be varied depending on the
injection size desired. For the minimum sample size, a three inch piece of 0.01 in i.d.
tubing is used.
Since a six-port valve rotates to divert the eluent stream through the filled sample
loop, there is a small internal volume (ie. the volume of the valve without the sample
loop) which must necessarily be injected. This internal volume can be determined by
filling the sample loop with a solution ofN,N-dimethyl-p-phenylazoaniline dye dissolved
in benzene and injecting the contents into a volumetric flask. The solution is diluted to
volume with benzene and the dye concentration determined spectrophotometrically. The
sample loop is calibrated externally in a similar manner. The volume of the small sample
loop (4 ul) is subtracted from total volume injected to give the true sample injected
volume (2 - 10 ul).
The columns used by Majors58 were 2.1 mm Ld. x 0.125 in o.d. precision bore
stainless. steel. The columns were normally one metre in length and were rinsed
thoroughly with dilute hydrochloric acid, water and acetone in that order and dried, prior
to filling. A special stainless steel modified Swagelok union was constructed for
437
connection of the column to the injection valve and to the detector. A capillary union
was sawed in half and was welded into a Swagelok union also sawed in half as shown in
Figure 7.35. To connect columns in series one only needs to add a short length of
capillary tubing fitted with the male portion of the capillary unions. A very similar union
can be purchased from Crawford Fitting Co. (Solon, Ohio) as Part No. 200-6-1-GC-316.
The detectors employed in the system are: (1) a refracto-monitor model 1103
(Laboratory Data Control LDC, Danbury, Conn.) with a cell volume of 3 microlitres and
interchangeable prisms to cover solvent refractive indices from 1.31 - 1.55 and (2)
Monitor Ultraviolet Absorbance Monitor (LDC) with a 8 microlitre cell volume and
minimum absorbance range of 0.02 o.d. units. Only the ultraviolet monitor was used by
Majors. s8 The detector output was monitored by a 10 mv recorder.
A fraction collector may be employed when sample collection is necessary.
In the entire system, only 3=6 stainless steel, glass, PTFE and a small amount of
polyacetal in the injection valve contacted the solvent.
Chromatographic supports. (20 - 30 microns). E.I. du Pont de Nemours and Co.,
Wilmington, Delaware.
Corasil I and II (particle range 37 - 50 microns), Waters Associates, Framingham,
Mass. (solid glass bead with either single (Type I) or a double (Type II) porous silica
layer).
DurapaklOPN (36 - 75 microns), Waters Associates.
99.2.2 Column Packing Procedure.
Two small discs of Millipore PTFE filter (0.125 in in diameter) are placed inside
an end fitting and the fitting placed on the column. Regular 118 in Swagelok stainless
steel nuts and ferrules are used to attach the column to the end fitting. A short extension
of 118 o.d. tubing is added directly to the top of the column by the use of a Swagelok
union which was bored out internally to a 0.125 in diameter. A smaIl funnel is used to
add small, incremental amounts of packing and the bottom and sides gently trapped
during the addition. Once the entire length has been filled, the column is tapped for an
additional ten minutes. Finally the column with the small extension is connected to the
outlet of the pump and the chromatographic solvent allowed to flow slowly through the
column in an upward direction to sweep out air bubbles. As the liquid emerged from the
column, the pressure is gradually increased to approximately a thousand pounds above
the pressure at which the column would be used. The liquid is permitted to flow at this
pressure for about 5 min. This final treatment insured that the column is packed to its
maximum density. The extension was removed and the upper end fitting with a small
disc of Millipore filter carefully pressed into the column end of it was attached to the
column. Then the column is affixed to the chromatographic system.
99.2.3 Coating of the Support.
For liquid-liquid chromatography, the liquid phase is dissolved in a sufficient

amount of dichloromethane to give Z-factor of 1.4. The Z-factor is defined as the ratio of
the volume of solvent to the weight of support. The solution is added to the dry support
in a round bottom flask. The volatile solvent is slowly removed by evaporation in a
stream of dry nitrogen while slowly rotating the flask.
438
~LI,..m",,,,,·nk 0.09"
One-holf of"'-
lIS" union
Figure 7.35. High pressure column chromatography. Low dead-volume column end fitting (not to scale).
From Majors with permission. 5• Preston Publications Inc., New York.
To determine Irganox 1076, CAO-40, and Santonax R antioxidants in

polyethylene the additives were extracted from the polymer by grinding them in a freezer
mill then extracting with diethyl ether in a Soxhlet extractor for two days. The ether was
then evaporated off and the residues dissolved in 25 cm3 of 1% by volume of isopropanol
in hexane. Using the chromatographic system of a 1% isopropanol in hexane solvent and
Corasil II adsorbent (surface area 14 ± 2' m2g- l ) and the conditions outlined below the
amount of hindered phenolic antioxidant in the ether extract of the polymer was
determined. Column 1000 Qllll x 2.1 mm, i.d.; packing: 37-50 u Corasil II (activated at
110°C) carrier 1% (v/v) iso-propanol in hexane; flow rate - 0.95 ml/min.
Calibration curves over the concentration range of interest were obtained for the
antioxidants known to be present. Figure 7.36 shows the separation achieved of three
phthalate plasticizers used in poly(vinyl chloride). The separation of all three is obtained
in less than 8 minutes on Zipax with HETP values less than a millimeter as summarized
in Table 7.54. At the same flow rate the separation times on Corasil are considerably
longer and the plate heights greater although not excessive. .
The method is capable of determining a wide range of antioxidants and other

polymer additives in polyethylene and PVC extracts in amounts down to 0.01% with an
accuracy of ± 5%.
METHOD 100 - DETERMINATION OF 0.01 - 0.1 % ADDITIVES IN

POLYPROPYLENE. CHEMICAL IONIZATION MASS SPECTROMETRy.59
100.1 SUMMARY
This chemical ionization mass spectrometric technique determines down to 0.01 %

additives in polypropylene without the necessity of a prior solvent extraction of the
additives from the polymer.
439
T
a.aaSAs
Didecyl
phthalate Oibenzyl
1
phthalate
Oecyl
benzyl
phthalate
Solvent
impurity
g
c
...
.c
o
OIl
.c
«
ri..\.--_-..J IrJ v
I I I I I I
o 2 4 6 B 10
Time, min
Figure 7.36. Separation of phthalate plasticisers using Zipex support column 1000 mm x 2.1 mm Ld.,
Zipax support, carrier-iso-octane; flow rate 0.50 mllmin sample - 10.6 ul ofa mixture of 0.40 ullml each of
didecyl phthalate and decyl benzyl phthalate and 0.35 mglml of dibenzy\ phthalate in heptane.
From Majors with permission. 51 Preston Publications Inc., New York.
100.2 APPARATUS
Mass spectrometer, Dupont 492B used in original work or equivalent modified for
chemical ionization operation.
Computer with data system, Hewlett Packard 210-MX used in original work or
equivalent.
Capacitance Manometer, MKS Instruments Burlington or an instrument used in
original work or equivalent.
100.3 REAGENTS
1.1 % ammonia in methane mixture.
100.4 METHOD
A small pellet of the sample is placed in the heatable glass probe and spectra
produced evenly using the computer and data system. The identity and concentration of
antioxidants present in the polymer is obtained from the profiles for the additives being
determined.
440
Table 7.54 - Evaluation of Solid Core Supports for Phthalate Plasticizers
Zipax Corasill Deactivated
Corasil
Solute VRoml HETP,mm VRoml HETP,mm V~I HETP,mm
Didecyl
Phthalate 2.0 0.38 3.11.9 3.1 1.8
Decyl Benzyl
Phthalate 2.4 0.93 5.13.3 4.7 2.7
Dibenzyl
Phthalate 3.8 0.51 11.6 1.9 8.4 2.5
From Majors. 51 Preston Publications Inc, New Yark
l00.5EXPE~NTALPROCEDURE
A small slice of a polypropylene pellet (l - 2 mg) is placed in the well of a

heatable glass probe.S4 The probe is placed into the source of a mass spectrometer and
heated from 30° C to 350° C at 20 or 30° C/min. Spectra are obtained every 6 s with the
computer and data system. Spectra of the pure additives are also obtained by introducing
the samples withthe heatable glass probe. The ion accelerating voltage is approximately
1750 V. The source repeller voltage is kept at 0 V to maximize the ionic residence times.
A mixture of 1.1 % ammonia in methane is used as the reagent gas at 0.5 torr, with the
source temperature kept at 225° C for the pure additives and 240°C for the polymer
samples. The source pressure is measured with a capacitance manometer through a
hollow glass probe connected directly to the ion source.

Using this technique Rudewicz and MunsonS9 determined Ionox 330 and Irganox
168 antioxidants and UV 531 ultraviolet absorber in polypropylene. Figure 7.37 shows
two ion profiles when a 2.0 mg sample of polypropylene containing 0.15 wt % Irganox
168 (mlz 647 (M + H +) and 0.05 wt % Ionox 330 (M/z 792 (M + N~)+ is heated at 30°
Clmin. Both additives begin to vaporize rapidly at temperatures near the melting point of
polypropylene, about 176°C. The two additives, however, can clearly be distinguished by
their different masses and their very different heating profiles. The lower molecular
weight additive gives a relatively sharp peak with a maximum at approximately 210°C
and the higher molecular weight additive gives a broader peak that maximizes near
300°C.
It is possible to identify these additives from a small set of likely compounds from
the masses of their characteristic (M + H)+ or (M + N~)+ ions in the ammonia chemical
ionization spectra. However, greater confidence' in the identification would be provided
by spectra obtained with a more reactive chemical ionization reagent gas, like methane,
which gives significantly more fragmentation than does ammonia. The ammonia
chemical ionization spectrum of Ionox 330 contains (M + H)+ as the most abundant ion
and abundant fragment ions at mlz 569, 319,203 and 163. This compound may be
readily identified in a simple mixture, by noting that these ions have the same
temperature profiles. Similarly, the methane chemical ionization spectrum of Irganox
168 contains a reasonably abundant (M + H)+ ion, the base peak at mlz 441 and another
441
-
c
or
",Z-647
N
8=
~
~
~:
~
li
500
gY>
~
GO
N
55 72 89 114 168 222 276 330 350 350

PII)BE TEMPERATURE (C)
Figure 7.37. Heating profiles for (M + H)+ for Irganox 168, m/z 647, and (M + NH4f for Ionox 330, m/z
792, from polypropylene. Probe heating rate was 30 C/min. From Rudewicz and Munson with
D
permission.'9 American Chemical Society.
fragment ion at mlz 147. Similar temperature profiles for these ions indicate the presence
of this additive. One could probably identify the additives from a limited set of likely
possibilities by comparing temperature (or time) plots of characteristic ions, even when
several additives are present.
This procedure enables additives to be determined in polypropylene in amounts

down to 0.01% with an accuracy of ± 5%.
METHOD 101 - DETERMINATION OF ADDITIVES IN POLVPROPYLENE.

LIQUID CHROMATOGRAPHY - MASS SPECTROMETRY,'l
101.1 SUMMARY
This liquid chromatography - mass spectrometric system enables additives to be

determined in polypropylene in amounts down to 0.01%.
101.2 APPARATUS
Quadrupole mass spectrometer, Finnigan MAT Model 4165 or equivalent

equipped with moving belt LCIMS interface.
High performance liquid chromatography dual pump gradient system with
ultraviolet detector (variable wavelength) and 0.5 ml flow through cell.
442
Absorbance detection was done at 280 nIn. Chemical separations were achieved
on a 118 o.d. x 2.1 mm i.d. x 25 cm long column packed with 5 urn diameter ODS
particles (Alltech Associates Inc., Deerfield, I.L.O.). Sample injections were made with a
Valco injection valve equipped with a 10 ulloop. A precolumn filter was used to remove
particulate material from the injection sample.
101.3 REAGENTS
Standard stock solutions made up in acetonitrile with enough tetrahydrofuran

(THF) added to dissolve the compounds.
Acetonitrile, HPLC grade.
Tetrahydrofuran, freshly distilled.
101.4 METHOD
Applicable to any acetonitrile extract of the polymer. Separation of additives

were achieved using an acetonitrile - tetrahydrofuran gmdient elution system and the
separated additives were detected using an ultraviolet detector. This method was
calibmted against standard solutions of the additives put through the analytical procedure.
101.5.1 Chromatography
Approximately 1 g of plastic shavings is extracted overnight with 5 cm3 of

acetonitrile at ambient temperature in a sealed amber vial with constant stirring. The
extract solutions are filtered prior to analysis. The gradient elution scheme shown in
Table 7.55 is used for the Ii~uid chromatographic separations. The grodient controller is
set for a flow rate of 0.2 cm IminO!. At this flow rate, it takes approximately 10 min for
the mobile phase in the solvent mixing chamber to reach the column inlet. Therefore,
injections were not made until the gradient controller was 7.0 min into the gradient
elution programme. This reduces the amount of computer time and disk space required to
record an LCIMS chromatogram.
101.5.2 Mass Spectrometry.
Mass spectrometric detection was achieved with a quadrupole mass spectrometer

which was equipped with a moving belt LCIMS interface. Methane chemical ionization
is used. The ion source is pressurized to 0.3 torr with methane reagent gas, which is
ionized with 70 eV electrons. Solutes are desorbed from the polyimide LCIMS interface
belt at 230°C. The ion source temperature is 120°C. Chemical ionization spectra from
rn/z 200 to 1200 are recorded repetitively at 3 slscan. Electron ionization spectra are
recorded from rn/z 50 to 800 at 3 s/scan.
The LCIMS moving belt interface was modified so that the column effluent was
deposited on the belt in a fine spray. With this system, the LCIMS interface is capable of
efficient opemtion with the mobile phases used at flow rotes up to 0.2 cm3/minol • There
is no significant loss of resolution or efficiency in going from the absorbance detector to
443
Table 7.55 - Gradient Elution Scheme
Time,min. % Solvent A' % SolventBb
0 100 0
10 60 40
20 0 100
30 0 100
32 100 0
From Vargo and Olsen6i. American Chemical Society

• Solvent A 75% acetonitrile and 25% water. b Solvent B 50% THF and 50% acetonitrile
the mass spectrometer when the two detectors were used in series. When the absorbance
detector and mass spectrometer are operated in series, a 20 cm length of 0.01 in Ld.
stainless steel tubing is used to connect the absorbance detector outlet to the LCIMS
interface.
The procedure was used to characterise additives in polypropylene samples of

unknown composition. Butylated hydroxy toluene and Irganox 1076 were identified in
the extract of an automative component moulding. In addition, several other additives
were identified (palmitic acid, dioctylphthalate, stearic acid and octadecanol).
The procedure enables additives to be identified and determined in polypropylene

in amounts down to 2 mg (0.01 % in polymer) with an accuracy of ± 5% to 10%.
METHOD 102 - IDENTIFICATION AND DETERMINATION OF ADDITIVES IN

POLYMERS. PHOTOLYTIC DEGRADATION-GAS CHROMATOGRAPHIC
METHOD. 62
102.1 SUMMARY
This photolytic degradation technique enables additives to be identified and

determined in polymers in amounts down to 0.01%.
102.2 APPARATUS
Photolytic degradation apparatus, see Figure 7.38.

Capillary crusher, model 81-4 solid samples, (Hewlett Packard).
Potassium bromide press.
Gas chromatograph, with flame ionization detector.
Flame photometer, providing light at 360.0 nm.
Hydraulic press, 30 ton.
Gas chromatographic column, 10% w/w SE-30 on 80/200 chromo-ports.
444
102.3 METHOD
Films of the polymer are irradiated with light at 360 run. The photolysis products
are then examined by gas chromatography to identify them. The structure of the polymer
additive is elucidated from the nature of the photolysis products.
Pure polymer samples are prepared for photolysis with the apparatus shown in
Figure 7.38. A sample of up to 50 mg is placed between two plane glass microscope
slides which are then inserted between the two large aluminium blocks. The temperature
of the blocks is maintained slightly above the glass transition temperature of the polymer
(usually ca 150·C) by controlling the voltage to the 65 watt cartridge heaters. The 3/8
inch machine screw is tightened and the sample flattened into a thin film rapidly (about 5
s) to preclude thermal degradation of the polymer. The resulting film is placed between
two glass plates with one edge slightly protruding and sliced into strips ca. 0.8 mm wide
with a scalpel. These strips are weighed and transferred to 1.0 mm i.d. quartz capillaries,
previously sealed at one end. The capillary is evacuated for 5 min to remove air and is
then sealed.
To prepare samples of known composition for calibration purposes, weighed
amounts of additives are mixed with pure polymer samples prior to casting into thin films
with the apparatus shown in Figure 7.39. A stainless steel cylinder kept at a temperature
slightly above the glass transition temperature of the polymer is placed under the top stop
of 30 ton hydraulic infrared laboratory KBr pellet press. The film is placed on the
cylinder and compressed until it forms a disk, the diameter of which equals that of the
cylinder. The pressure is released, the cylinder withdrawn, and the sample is further
mixed by folding and compressing several times with a small spatula, after which it is
recompressed with the hydraulic press. Small portions of the disk thus formed are cast
into thin films between glass slides as above. The film is attached to the burner mounting
of a Heath flame photometer module, the position of which can be varied by a
micrometer adjustment system. Heath light source, photomultiplier tube and
monochromator modules are used to isolate light at 360.0 run. The light beam from the
exit slit is focused to dimensions of ca. 0.2 mm wide and 1.0 mm high. Absorbance
measurements are made at 1.8 mm intervals across the full 18 mm diameter of the disk.
102.4.2 Sample Irradiation.
To provide maximum ultraviolet intensity for photolysis in the solid phase, an

irradiation apparatus using an Engelhard Hanovia Type 612C medium-pressure mercury
source was used. Photolysis period of 5 minutes were used in quantitative determinations
of polymer additives. The irradiation cavity is of an elliptocylindrical shape in which the
source and sample are positioned at the foci. The cavity was formed by placing a
cylinder of spring brass, 13 cm high and 0.22 mm wall thickness within four upright
posts arranged in a rectangular pattern of 8 x 14 cm. The brass cylinder assumes the
shape of an ellipse having major and minor axes of 18 cm and 14 cm respectively. A
lining of highly reflecting aluminium foil concentrates a large percentage of the emitted
radiation on the sample.
445
"-0;'
-'"~
-'-1.17
o
1/4.20 I 2 V2"
WATT
RTRIOGE
AHR
Figure 7.38. Heated compressing unit for rapid preparation of polymer films prior to photolytic
degradation and GC analysis.
Compression time, 5 sec. Temperature maintained above polymer glass transition temperature (usually
150"C). From Juvet et al with permission. 62 American Chemical Society.
The water jacketed sample compartment consists of an inner 2 mm i.d. quartz tube
surrounded by a 25 mm i.d. quartz tube with sidearms for cooling water circulation.
Directional irregularities in light intensity are minimized by rotating the sample with a 1
rpm synchronous motor.
102.4.3 Product Separation and Identification.
After irradiation, the samples are introduced onto the chromatographic column
with a capillary crusher to accommodate 1.0 mm i.d. quartz tubing.
A gas chromatograph with flame ionization detector was used to obtain
chromatographic data using a 6 foot 118 inch o.d. stainless steel column packed with 10%
w/w SE-30 on 80/300 mesh Chromport S. The injection port temperature is maintained
at about 150°C. A tem~erature programming rate of ca 6°/min-\ and a helium carrier gas
flow rate of ca 30 cm3 min-' are employed. Products can also be separated, either
isothermally or under temperature programmed conditions, on a 6 foot 114 inch o.d.
stainless steel column containing 15% wlw Carbowax 20M on silane·treated 60/80 mesh
Chromosorb P. Retention data are reported as Kovats retention indices. Peak area
measurements are made with a planimeter and are reproducible to ± 0.1 cm2 •
446
POLYMER
SAMPLE
C---J-==-~
f
I
~~ I
.THERMOCOUPLE
I I
30-TON 165 WATT

HYDRAULIC ARTRIDGE
PRESS HEATER
I
/
r
'T-~
. I
I lIZ· I \
STAINLESS \ \
\ \
-
STEEL
,'
CYLINDER \ \
TO VARIAC
"" ---
=-----
Figure 7.39. Heated compressing unit for use with IR-Iaboratory KBr pellet press for preparation of
polymer mixtures of known composition. From Juvet et al with permission.62 American Chemical Society
To aid in the determination of the retention indices of the photolysis products an

iron constantin thermocouple device is used which automatically indicates column oven
temperature on the recorder chart during temperature programming. With proper
calibration, the column oven temperature is indicated on the chart of aimV recorder and
can be read directly in degrees centigrade. A mixture of n-hydrocarbons from n-pentane
to n-pentacosane is chromatographed daily from which a calibration curve of column
oven temperature vs Kovats retention index is prepared. The retention indices of eluted
compounds are obtained by graphical comparison of the retention temperature with the
calibration curve.
Juvet et al62 found that with low concentrations of additives, the photodegradation
pattern of a polymer is not affected and new products appear from photolysis of the
additives. As an example Table 7.56 lists the retention indices on SE-30 for the
additional photolysis products from two similar sample, 1.0% dilaurylthiodipropionate in
polyethylene and 1.0% distearylthiodipropionate in polyethylene. No difficulty is found
in differentiating between these two additives by photolysis gas chromatography although
they are of closely related structure; indeed the similarity in structure is readily apparent
from the constant difference of 600 I units in the homologous peaks of these two
additives. The product from dilaurylthiodipropionate eluting at I = 1690 was identified
447
from retention data and mass spectrometry as dodecyl propionate. The overlapping
doublets which elute at I = 995 - 1000 and I = 1194 - 1200 on SE-30 are resolved in
Carbowax 20M and the individual products elute at I values of 1000, 1045, 1200 and
1242. These four products were identified, respectively, as n-decane, n-decene, n-
dodecane and n-dodecene. Considering the kinetic data presented in this figure, the
decomposition of dilaurylthiodipropionate is very likely to follow the mechanism:
7.17
C16H 32
(I =
1000)
Addition of 1.0% dilaurylthiodipropionate to poly(methyl methacrylate) has no

effect on the basic polymer photolysis pattern, but the formation of C 10 and C 12
hydrocarbons relative to the peak at I = 1690 reduced to ca. om and 0.02 respectively.
In this matrix the concentration of the product eluting at I = 1690 increases continuously
throughout a two-hour irradiation further strengthening the argument that the
hydrocarbon fragments obtained in the polyethylene matrix are secondary photolysis
products which show a decrease in quantum yield in the methyl methacrylate matrix
toward production of the hydrocarbon fragments.
102.5.1 Quantitative Determination of Additives.
Quantitative measurements are carried out by irradiating the sample for a carefully
controlled time period usi,ng a light source of constant intensity. In the analysis of the
antioxidant, dilaurylthiodipropionate in polyethylene an irradiation time of 5.00 ± 0.02
min was chosen and a calibration curve constructed by plotting the peak area of the
product peak, dodecyl propionate at I = 1690 vs the per cent LTOP in the sample. The
average relative mean deviation of the 11 points used in constructing the graph is 2.7%.
Since the product peak tails to a small extent under the chromatographic conditions used,
the error in peak area measurement is increased somewhat and is thought to be the major
source of error in this determination.
As a typical example of the determination of plasticizers, dinonyl phthalate at
concentrations up to ca. 9% was studied in a poly (methyl methacrylate) matrix. The mte
of formation of seveml photolysis products from samples containing 4.30% dinonyl
phthalate is shown in Figure 7.40. The peaks at I < 500, I = 756 and I = 812 are
irradiation products of the polymer and the product eluting at I = 658 is from dinonyl
phthalate. The nonlinear calibmtion curve produced using irradiation times of 15.0 ± 0.1
448
Table 7.56 - Photolysis Products of Antioxidants and Polyethylene
Additive Concentration % Additional Products, Relative Peak Area
I Values on SE-30 for 30 Minutes
Irradiation
Dilaurylthio- 1.0 995~1000 ±4" 0.22

dipropionate 1100 + 6 0.09
±
1194- 1200 4" 1.00
1690-1200 + 5 0.21
Distearlylthio- 1.0 1592-1602±4" - 0.21
dipropionate 1700+6 0.34
1792-1805 ± 6" 1.00
2298±8 0.50
From luvet6Z• American Chemical Society

" Overlapping doublet peaks
min was prepared. It is interesting to note that dioctyl phthalate in poly (vinyl chloride)
shows linear dependence on concentration as high as 19 weight per cent for the
decomposition product peak appearing at I = 796 (probably n-octane) on SE-30 liquid
phase when an irradiation time of 5.00 ± 0.02 minutes is used. In the case of dinonyl
phthalate, variation in plasticizer concentration affects the relative amounts of the
polymer photolysis products at I = 756 and I = 812. Since the relative product yield from
the basic polymer is altered it is apparent that the matrix in which photolysis of the
additive occurs in changing with plasticizer concentration.
This technique enables additives to be identified in polymers and to be determined

in amounts down to 0.01% with an accuracy of± 5% to ± 10%.
METHOD 103 - IDENTIFICATION OF ADDITIVES IN POLYMERS. GAS

CHROMATOGRAPHY - INFRARED SPECTROSCOPy.63 .
103.1 SUMMARY
This gas chromatography infrared spectroscopic procedure enables a wide range

of additives to be determined in polymers in amounts down to 0.01 %.
103.2 APPARATUS
The fraction-collecting apparatus is used in conjunction with gas chromatographic

columns operated under reduced pressure and with katharometer detection.
Apparatus involving a column thermostatically controlled within the range oOe to
1300e and a katharometer at room temperature. This apparatus is used for separating
mixtures when the highest boiling constituent boils below 1600 e at atmospheric pressure.
If the polymer constituent boils between 160 and 2500 e then the column should be
thermostatically controlled in the range 100 - 200oe.
449
.so
.!M
ca.
e
CII
lit
CII'
$
-
e
u
IrJ
en
Z
0 50
0..
en
IrJ
a:
o 7.5
IRRADIATION TIME (MINUTES'
Figure 7.40. Radiation kinetics for 4.30% dinonyl phthalate plasticizer in poly(methylmethacrylate).
Radiation products peak at I = 658 from dinonyl phthalate; others from the polymer matrix. Retention
indicies measured on a Carbowax 20M column at 85°C. From Juvet et al with permission. 62 American
Chemical Society
Infrared spectrometer with 9 cm3 cavity cells, length 10 cm, height 1.5 cm width
0.6 cm. (Figure 7.43).
The trap shown in Figures 7.41 and 7.42 has been successfully used for the
condensation of substances boiling in the range 100° to + 160°C. The packing used is
small Dixon rings held in place by a small loose fitting piece of glass rod. The efficiency
of this type of trap varies between 8S and 95% depending on the chemical class of
substance. The trap is connected to the exit of the katharometer by means of the
minimum length of stainless steel tubing (internal diameter 1 mm) brazed into a metal
cup. This in turn is cemented to a glass socket with Araldite cement. The exit ends of the
four traps are connected via rubber tubing ancJ separate stopcocks to a vacuum manifold.
The traps are partly immersed in liquid nitrogen contained in dewer flasks.
Having condensed the desired component in a trap it has to be decided whether to
record the spectrum in the vapour state (method 1 below) or the liquid phase (method 2
below).
103.3 METHOD
The sample is heated in a trap device and the volatiles produced transferred to an
infrared gas cell. Examination of the infrared spectrum provides information on the
identity of volatile additives present in polymers which boil between 0 and 250°C.
450
P'l
Figure 7.41. Pipette for transferring liquid to micro infrared cell.
From Anderson with pennission. 63 Royal Society of Chemistry. London.
,
I
f
I
•
Figure 7.42. Micro infrared cell for liquid samples.
From Anderson with pennission. 63 Royal Society of Chemistry. London
103.4.1 Method 1 - Liquids of Boiling Point up to 60°C.
Figure 7.43 shows how the low-boiling component is transferred to a 9 cm3

infrared gas cell. No heat is applied to the trap.
In order to attain optimum light transmission, such a cell is inserted at a point
where the area of the spectrometer beam is least; this will be where a focus of the beam is
451
fonned in the centre of the cell. At a few centimetres on either side of the focal position
the beam is rectangular. Condensation of liquids boiling up to 100°C may occur on the
walls of a 9 em3 cell at pressures above 80 nm.
The image to be found in the centre of the cell should nonnally have the length
and width of the entrance slit of the spectrometer. Knowing the f number of the
instrument, it is possible to calculate the size of the rectangular aperture required to admit
the radiation cone in terms of the length of the cell. The body consists of rectangular
brass tube (1 mm thick) cut from wave-guide tubing and has the internal dimensions
stated above. A flat brass flange is brazed on each end of the tube, and a short side arm
(stainless steel capillary tubing) is brazed in one side of the body. A glass capillary tap
that will just slide over the side-arm is cemented in place by filling the space between the
two tubes with Araldite resin; by this means the volume of the side arm is rendered
negligible. Two rock-salt windows are attached. to the flanges with Picene wax.
Although this cell is designed for an f 11 system, it will give acceptable perfonnance,
although with some loss of energy, on an f 7 spectrometer.
103.4.2 Method 2 -Liquids Boiling above 60°C.
If the gas chromatographic evidence indicates that the substance boils above 60°C
the fraction condensed in the trap is treated as shown in Figure 7.44. The trap and
contents are held in liquid nitrogen while the apparatus is completely evacuated. After
testing the system for leaks, the source or vacuum is cut off. The flask containing the
liquid nitrogen is removed from the trap and placed over the side-arm so that the bulb is
just immersed in the refrigerant. As the trap attains room temperature, the small amount
of liquid in it distils through the desiccant and is condensed round the sides of the bulb of
the side-arm. The liquid is encouraged into the capillary tip by lowering the vacuum
flask containing the liquid nitrogen until only the last 114 in of the tip is immersed. The
bulb is then warmed with the fingers. During this distillation the trap is not warmed as
this may cause some of the liquid to distil in the wrong direction. The apparatus may be
left for 1 or 2 h in order to achieve complete distillation of higher boiling liquids. Having
. obtained the liquid in the capillary tip. this tip is broken off at the constriction just below
the bulb. Figure 7.41 shows a piece of apparatus which may be used to transfer the liquid
to the micro infrared cell. It has a rubber teat and a very fine internal capillary. The
device has a detachable tip, which is discarded after use and pennits close control over
the transfer operation.
The micro infrared cell design is shown in Figure 7.42. The two rock-salt plates
are about 20 mm x 10 mm x 3 mm in size. Two holes are drilled in one plate with a No.
86 drill; these holes taper inwards, as shown, being 7 mm apart on the inside and 12 mm
apart on the outside of the plate. A gold-foil washer (25 u thick) is cut, the inner space
being 1.5 mm wide and approximately 7 mm in length (just sufficient to clear the edges
of the filling holes); the width of this washer is about 2 mm. The cell is first stuck
together with gold amalgam. The washer is immersed in mercury for a short period and
withdrawn after a layer of jUnalgam has fonned on its surface. The cell is then carefully
assembled in a small clamp and left under pressure for 24 h for the amalgam to set. The
space between the plates outside the washer is then filled with Araldite 700 resin and the
surplus of resin is allowed to bridge the edges of the plates on all four sides.
The cell is fiJled by inserting a capillary needle containing the liquid into one
filling hole. Provided that the thickness of the cell is less than the diameter of the needle,
the liquid will run in to fiJI the cell area. It is essential that no free space be left in the cell
behind the filling holes; such space will not immediately fill by capillary action and air
452
Glass rod
Dillon ring.
To vlCuum_-I~~~§
pump
Figure 7.43. Apparatus for transfer of volatile components from trap to infrared gas cell.
From Anderson with permission. 63 Royal Society ofCbemistry, London.
( Desiccant
Glas. rod_
: _Dixon rings
Figure 7.44. Apparatus for transfer of liquid components from trap to tip of side arm.
From Anderson with permission. 63 Royal Society ofCbemistry, London
453
bubbles trapped here may subsequently run into the useful part of the cell and are most
difficult to remove. When the cell is filled, the outer ends of the filling tubes are covered
by two small squares of nitrile-rubber sheet, held in position by "butterfly" spring clips.
The amount of liquid required to fill the cell by the method described above (as
opposed to the theoretical capacity of the cell calculated from the dimensions) is
determined experimentally by weighing the cell on a microbalance before and after filling
with n-dodecane. With this cell, infrared spectra can be obtained from 0.5 to 1.0 ul
portions of liquid samples.
This procedure enables a.wide range of additives to be determined in polymers in

amounts down to 0.01 % with an accuracy of ±5% to ± 10%.
454
CBAPTER7.6
PRELIMINARY QUALITATIVE IDENTIFICATION
Methods 104 - 108
METHOD 104 - QUALITATIVE DETECTION OF ELEMENTS IN POLYMERS.

OXYGEN FLASK COMBUSTION.64
104.1 SUMMARY
This qualitative oxygen flask combustion method enables nitrogen. fluorine,

chlorine, bromine, iodine, sulphur and phosphorus to be identified in polymers in
amounts down to 0.01%.
104.2 APPARATUS
Combustion unit - the electrically fired combustion unit was used in this work,
although there is no reason why other forms of oxygen flask should not be used, with
appropriate calibration.
Filter paper - Whatman No. 541 filter paper. When not in use, store filter paper in
a sealed container out of contact with the laboratory atmosphere.
Cotton wool- B.P.C. super quality.
104.3 REAGENTS
Sodium hydroxide, N.
Nitrogen.
Resorcinol - AnalR
Acetic acid, glacial.
Ammonium ferrous sulphate - AnalR.
Fluorine.
Reagents. Buffered alizarin and complexan solution - weigh 40 mg of 3-amino-
ethylalizarin-NN'-diacetic acid (Hopkins and Williams Ltd.) into a beaker and add 2
drops of N sodium hydroxide and approximately 20 ml of distilled water. Warm the
solution to dissolve the reagent, cool and dilute to 208 ml. Weigh into another beaker 4.4
g of sodium acetate (CH3COONa3H20) and dissolve in water. Add 4.2 ml of glacial
acetic acid and dilute to 42 ml. Pour this sodium acetate solution into the alizarin
complexan solution and mix to give the fmal buffered alizarin complexan solution.
Cerous nitrate, 0.0005 M - dissolve 54.3 mg of cerous nitrate (Ce(N03MH20) in
water and dilute to 250 ml.
4SS
Chlorine.
Reagents. Ammonium ferric sulphate solution - dissolve 12 g of AnalaR ammon-
ium ferric sulphate in water and add 40 ml of AnalaR nitric acid. Dilute to 100 ml and
filter.
Mercuric thiocyanate solution - dissolve 0.4 g of recrystalized mercuric thio-
cyanate in 100 ml of absolute ethanol.
Bromine.
Reagents. Fluorescein solution - dissolve 0.1 g of fluorescein in 25 ml of 0.1 N
sodium hydroxide and dilute to 100 ml with water.
Sodium acetate buffer solution - mix 100 ml ofN sodium acetate with 15 ml ofN
acetic acid.
Chloramine-T solution - dissolve 12 g of chloramine-T in 100 ml of distilled
water.
Sodium thiosulphate solution - prepare a 0.5% w/v solution of sodium
thiosulphate in 5% w/v sodium hydroxide solution.
Hydrochloric acid, N.
Iodine.
Reagents. Starch solution - dissolve 0.2 g of soluble starch in 100 ml of distilled
watet.
Sulphuric acid, dilute - prepare an approximately 10% w/v solution of concen-
trated sulphuric acid in distilled water.
Qualititative Determination of Sulphur - Barium Chloride Method.

Reagents. Hydrochloric acid, N.
Precipitating reagent solution A - dissolve 0.2 g of peptone in 50 ml of 1 per cent
barium chloride (BaCI22H20) solution. Buffer to a pH of 5.0 with 0.02 N hydrochloric
acid, add 20 g of sodium chloride (Analar) and dilute to 100 ml. Heat on a water bath for
10 minutes, and add a few drops of chloroform. Filter if necessary.
Precipitating reagent solution B - dissolve 0.04 g of gum ghatti in 200 ml of
distilled water by warming slightly. When solution is complete, add 2.0 g of barium
chloride (BaCI22H20). Filter if necessary.
Store solutions A and B separately and prepare the final reagent just before use by
diluting 10 ml of solution A to 100 ml with solution B.
Hydrogen peroxide, 100 volume - AnalaR.
Qualitative Determination of Sulphur -4-Amino -4'Chlorodiphenyl Hydro-

chloride Method
Reagents. 4-amino-4' chlorodiphenyl hydrochloride - peptone solution (solution
A). Dissolve 0.025 g of peptone (Hopkin and Williams Ltd.) and 0.125 g of 4-amino-
4'chlorodiphenyl hydrochloride (L. Light and Co. Ltd.) as completely as possible by
warming with 50 ml of 0.05 N hydrochloric acid. Cool, and filter through a double
Whatman No. 40 filter paper.
4-amino-4'chlorodiphenyl hydrochloride - gum ghatti solution (solution B).
Dissolve 0.20 g of gum ghatti (Hopkin and Williams Ltd., finely ground) and 1.00 g of 4-
amino-4'chlorodiphenyl hydrochloride as completely as possible by warming to about
70°C with 400 ml of 0.05 .N hydrochloric acid. Cool and filter through a double
Whatman No. 40 filter paper.
456
Final precipitation reagent - dilute 10 ml of solution A to 100 ml with solution B.
This solution should be freshly prepared.
Hydrochloric acid, N.
Qualitative Determination of Hydrolysable Phosphorus.

Reagents. Ammonium molybdate solution - dissolve 109 of Analar ammonium
molybdate (NH..M070 244H20) in about 70 ml of water and dilute to 100 ml. Add this
solution with stirring to a cooled mixture of ISO ml of sulphuric acid and 150 ml of
water.
Asorbic acid - B.D.H. laboratory reagent grade.
104.4 MEmOD
Approximately 20 mg of polymer is combusted in an oxygen filled flask over

dilute sodium hydroxide solution. Specific colorimetric tests for nitrogen, sulphur and
phosphorus and the four halogens are applied to reveal the presence or absence of these
elements.
104.5.1 Combustion Procedure.
Weigh out approximately 20 mg of sample and transfer it to the centre of a small

piece of the Whatman No. 541 filter paper weighing approximately O.1g. Fold the filter
paper so that the sample is completely enclosed and before making the final fold, insert a
small wick of cotton wool weighing about 6 mg.
Carry out the combustion using 5 ml of N sodium hydroxide in the bottom of the
flask as absorption solution. Set the flask aside for 15 minutes to allow the gases formed
in the combustion to be absorbed and then wash the contents of the flask quantitatively
into a 25 ml measuring cylinder with distilled water. Dilute the solution to 25 ml and mix
well. This constitutes the test solution, aliquots of which are taken for the detection of
the individual elements by the colorimetric methods detailed below. For comparison
purposes in the tests, prepare a blank test solution by carrying out the combustion
procedure on the filter paper and cotton wool only.
104.5.2 Determination of Nitrogen.
Weigh 0.1 g of resorcinol into a clean dry 50 ml beaker and dissolve in 0.5 ml of
glacial acetic acid. Add 5 ml of the test solution and, after mixing, add 0.1 g of
ammonium ferrous sulphate. Carry out the same test on the blank test solution. The
development of a green colour in the sample test solution, compared with a pale yellow in
the blank, indicates the presence of nitrogen in the sample.
If a semi-quantitative estimation of the nitrogen content of the sample is required,
set both sample and blank solutions aside for 20 minutes. Add 10 ml of distilled water to
each, mix and measure the optical density of the sample solution against the blank at 690
nm in a 4 cm cell. The blank in this test is low, giving an optical density of 0.07
measured against water at 690 nm in the 4 cm cells.
457
104.5.3 Determination of Fluorine.
Transfer 20 ml of distilled water and 2.4 mI of buffered alizarin complexan

solution to a 50 ml beaker. Add 1 ml of test solution and mix swirling the solution.
Finally, add 2 ml of cerous nitrate solution and mix again. Treat the blank solution in a
similar manner. When fluorine is present in the sample a mauve colour will be developed
in the test solution compared with the pink coloured blank solution. If a semi-
quantitative estimation of fluorine is required, set the solutions aside for 10 minutes and
measure the optical density of the test solution against the blank solution at 600 nm in 1
cm cells. Sulphur, chlorine, phosphorus and nitrogen do not interfere in this procedure.
104.5.4 Determination of Chlorine.
Transfer 5 ml of the test solution to a 50 ml beaker and add 1 mI of ammonium

ferric sulphate solution. Mix the solution and add 1.5 ml of mercuric thiocyanate
solution. Mix and dilute to 10 mi. Treat the blank solution in a similar manner. When
chlorine is present in the sample an orange colour will be developed in the test solution
compared with yellow coloured blank solution. If a semi-quantitative estimation of
chlorine is required, set the solutions aside for 10 minutes and measure the optical density
of the test solution against the blank solution at 460 nm in 2 cm cells.
104.5.5 Determination of Bromine.
Transfer 5 ml of the test solution to a 50 mI beaker. Add 1 ml ofN hydrochloric

acid and then 0.5 ml of sodium acetate buffer solution and 1 drop of fluorescein solution.
Mix thoroughly and then add I drop of chloramine T solution. Mix by swirling and set
aside for 30 seconds, then stop the reaction by adding 2 drops of alkaline thiosulphate
reducing agent. Treat the blank solution in a similar manner. When bromine is present in
the sample, a rose-pink colour will be developed in the test solution compared with the
yellow-green blank solution, note: This test is also given by iodine.
104.5.6 Determination oflodine.
Transfer 5 ml of test solution to a 50 mI beaker and add a few drops of starch

solution. Mix the solution and then acidify with dilute sulphuric acid. Treat the blank in
a similar manner. When iodine is present in the sample, the characteristic blue colour of
starch iodide will be developed in the test solution compared with the colourless blank
solution.
104.5.7 Determination of Sulphur (Barium Chloride Method).
Transfer 5 ml of the test solution to a 6" x I" test tube and add 2 drops of 100
volume hydrogen peroxide, add then 1.2 mI of N hydrochloric acid. Mix well and add
2.0 ml of precipitating reagent with continued shaking. A distinct turbidity will be
produced in the mixed solution if hydrogen peroxide decomposable sulphur is present in
the sample; the blank test under the same conditions will be perfectly clear. If a semi-
quantitative estimation of the sulphur content is required, add 5 mI of distilled water to
both blank and test solutions, mix, and set aside for 30 minutes. Mix the solutions and
measure the optical density of the test solution in a 4 cm cell at 700 nm with the blank
solution in the comparison cell.
458
104.5.8 Determination of Sulphur (4 Amino-4'Chlorodiphenyl Hydrochloride
Method).
Transfer 5 ml of the test solution to a 6" xl" test tube and add 1-2 ml of N
hydrochloric acid. Mix well and add 10.0 mI of the prepared fmal precipitation reagent.
A distinct turbidity will be produced in the mixed solution if hydrolysable sulphur is
present in the sample. A blank test under the same conditions will be perfectly clear. If a
semi-quantitative estimation of the sulphur content is required, set the solutions aside for
30 minutes, then mix and measure the optical density of the test solution against the blank
in 2 cm cells at 700 nm.
104.5.9 Determination of Phosphorus.
Transfer 2 ml of the test solution to a 100 ml beaker. Add 40 ml of distilled water

and 4 mI of ammonium molybdate solution. Mix thoroughly, then add 0.1 g of ascorbic
acid and boil the solution for 1 minute. Cool in running water for 10 minutes and dilute
to 50 ml with distilled water. Treat the blank solution in a similar manner. When
hydrolysable phosphorus is present in the sample, a blue colour will be developed in the
test solution as compared with a pale yellow in the blank. If a semi quantitative
estimation of the phosphorus is required, measure the optical density of the test solution
against the blank solution at 820 nm in 2 cm cells.
Nitrogen, fluorine, chlorine ,bromine and iodine, sulphur and phosphorus are
quantitatively detected in polymers in the solution resulting from a single oxygen
combustion. Semi quantitative data can be obtained on the same solutions for nitrogen,
fluorine, chlorine, sulphur and phosphorus.
METHOD 105 - IDENTIFICATION OF POLYMER FILMS. THERMAL

METHODS.
105.1 SUMMARY
Simple burning tests are described for the identification of certain types of
polymers. These tests are of limited value, but taken together with results obtained in
other tests might provide information leading to an identification of the polymer.
105.2 APPARATUS
Heating test.
Bunsen burner.
Pair of tweezers.
Copper wire test.
Copper wire: 1 mm.
459
105.3 METHOD
The polymer sample is held in a flame or heated in. a test tube or on a copper wire
and observations made (colour of flame, smoke, odour etc) to provide information on the
identity of the polymer.
Heating test. Hold a 1 in x 3/8 in specimen of polymer in tweezers over bunsen

burner flame.
What to look for. Colour of flame, visible changes in film sample, smoke
formations.
Interpreting observations. If film shrinks a great deal, this usually means material
was stretched or oriented in production process (see Table 7.57).
What to look for. Green colour in flame indicates presence of halogens, ego
chlorine or fluorine.
Interpreting observations. Caution should be used in interpreting results because
test sample may have been varnished or laminated with halogen containing products. In
such cases, more detailed analysis may be necessary to clarify inconclusive results.
To analyse chemical nature of fumes, insert a strip of wet litmus paper in the
upper part of test tube. Alkaline reaction will turn paper blue, acid reaction will turn
paper red. If acid reaction is very strong, insert a strip of Congo paper. If it turns blue
the acid is mineral (see Table 7.57).
Copper wire test Insert one end of copper wire into a cork. Holding the cork,
heat the wire in flame until only a very slight yellow colour is seen in the flame. Now
melt the film sample onto the wire while it is still hot. Hold the wire in outer part of fully
burning flame.
Characteristic results obtained by these tests are shown in Table 7.57.
460
Table 7.57 - Identification of Polymer Films
Film Type Physical Characteristics 1. Burning Test- 2. Copper-Wire Test - 3. Heating Tests - 4. Solubility Test - Dissolves and
Watch Both Flame and Look for Flame and Check Odour and Acid- May Swell in
Film Film Alkalinity
EXTENSIBLE
Waxy Feel No flame produced, Flame turns green Fumes may be toxic - Virtually inert
Fluorocarbon sample deforms do not inhale
slowly
Polyolefins, (low and Wax-like feel, good Burns freely, None Burnt paraffin wax Tetralin at 275 F
high density PE,PP)" extensibility smokeless, bluish aroma
flame, melts, drips like
wax·
Polyvinyl Chloride Softness range is that of Burns with yellowish Flame turns green Sharp acrid fumes turn Cyclohexane, tetrahydrofuran and
(flexible) rubber, extensibility sooty flame, melts Congo paper blue pyridine, solution turns red in
proportionate to freely to form pearl presence of alcoholic potassium
plasticizer used like drops hydroxide solution
Rubber Hydrochloride Clear and tough, Will not burn, edges Flame turns green Rubber odour, fumes Chloroform, solution shows no
relatively good tend to singe, dark turn Congo paper blue change in presence of pyridine and
extensibility· smoke given off, alcoholic potassium hydroxide
green-blue seam in solution
flame
SEMI EXTENSIBLE
Cellulose Acetate Poor extensibility Melts and drips None Acetic odour Acetone
e
tt->
Table 7.57 (continued)
Cellophaneb Transparent, paper-like Bums like paper, with None Burn paper aroma Schweitzer's reagent (cupro-
feel when dry, crumples light flame ammonia)
easily, poor extensibility
Cellulose Acetate Hom-like feel Melts and drips, None Rancid butter Ketones, lactates, Me, Et propyl
Butyrate drippings may bum chlorides
Cellulose Nitrate Similar to cellulose Bums rapidly with an None Odour of camphor Acetone at high nitrogen content
intense, white flame
Polyamide (Nylon) Opaque to clear, hard Bums with yellowish, None Sour aroma, like burnt Formic acid
feel, poor extensibility sooty flame, melts to hom or hair, fumes tum
form pearl-like drops litmus paper red
Polyester Film, Clear, very tough, non- Ignites, but None Faintly sweet Chlorophenol
(polyethylene tearable, poor extinguishes on
terephthalate type) extensibility removal of flame,
shrinks without
singeing of edges,
melts to form pear-
shaped drops
Polyvinyl Chloride Hard, greasy feel, white Self extinguishing Flame turns green Sharp, acrid olour, Cyclohexane, tetrahydrofuran and
(rigid) fracturing will show up fumes tum Congo pyridine, solution turns red in
in creasing line paper blue presence of alcoholic potassium
hydroxide solution
Polyvinylidene Chloride Either milky or clear Self extinguishing Flame turns green Sharp, acrid odour, Cyclohexane, solution black in
film, softer feel than fumes tum Congo presence of pyridine and alcoholic
PVC paper blue potassium hydroxide solution
Table 7.57 (continued)
NONEXTENSIBLE
Oriented Polystyrene Clear, nonextensible, Bums with luminous, None Repugnantly sweet, like Benzene, hydrocarbons
when crumpled, gives soot-producing flame, artificial illuminating
metallic sound, sharp smoke is dense gas
folds displays mother of
pearl effect
• Oriented. polyolefin films will shrink substantially on initial heating

b Absence of condensation when breathing on film indicates film is unvarnished. To test for commonly applied nitrocellulose varnish, apply several drops of a mixture of one part
diphenyl and 100 parts concentrated sulfuric acid to film surface. Appearance of blue colour indicates presence of varnish. Polymer varnishes are readily identified by the Beilstein
test for halogens
e Extensible> 200% elongation, Semi-extensible 25 - 200% elongation, Non-extensible < 25% elongation
~
METHOD 106 - PYROLYSIS - GAS CHROMATOGRAPHY OF POLYMERS.
CURIE POINT FILAMENT PYROLYSER TECHNIQUE."
106.1 SUMMARY
This Curie point filament pyrolysis technique enables unknown polymers to be

identified.
106.2 APPARATUS AND CONDITIONS
Pyrolyser - Pye Unicam Curie point, attached directly to the column, pyrolysis
temperature 610°C maintained for 10 seconds.
Gas chromatograph - dual columns, twin flame-ionisation detectors.
Columns - standard Pye 5 feet long x 4 mm Ld. glass (silanised).
Carrier gas - nitrogen with a flow rate of approximately 60 ml min.
Column packing - Porapak Q, 50 to 80 mesh or 80 to 100 mesh.
Temperature programme - from 100 to 200°C at 8°C min-l (the temperature was
maintained at 200°C for up to 25 minutes and the programmer started on completion of
10 seconds pyrolysis).
The columns are silanised before being packed by passing a 5 per cent solution of
dichlorodimethylsilane in toluene through the columns and then drying at 100°C.
Packing is facilitated by applying suction from the detector end of the column,
accompanied by gentle tapping. The columns are aged by heating at 250°C for 48 hours,
with a nitrogen flow of 60 ml min-I. The hydrogen and air flows are adjusted to give
approximately the maximum sensitivity.
106.3 METHOD
In this Curie point filament pyrolysis technique the polymer is pyrolysed at a

controlled temperature and the pyrolysis products passed into a gas chromatograph.
Relative retention data and peak height ratio data obtained when compared with
tabulations of data obtained from known polymers provide a means of identifying the
unknown polymer.
The flow rate required for pyrolysis is determined by injecting through the
pyrolyser head 1 ul of headspace gas from a retention time standard comprising methanol
-n-propanol (50 + 50) with the column temperature at 100°C and immediately
programming at 8°C min-I. The flow rate of nitrogen is adjusted to give retention times
of2.6 and 9.1 minutes for methanol and n-propanol respectively.
After fixing the flow rate of carrier gas, the upper temperature limit is adjusted to
give a retention time of 4.2 minutes for benzene or 4.4 minutes for cyclohexane when
these compounds are injected at the upper temperature limit. These two compounds have
retention times of 13.4 minutes (benzene) and 14.0 minutes (cyclohexane) when injected
at 100°C and the oven is programmed as described.
464
The pyrolysis wire is prepared in the following way. A 5 to 10 mm length at one
end of the wire is flattened until the flattened portion is approximately 1 mm wide. A
"hook" is then made by doubling over about 2 mm of the flattened end. At this stage, the
hook end plus a few centimetres of the wire adjacent to it are heated to red heat in a
bunsen flame so as to remove contaminants. The sample is placed in the elbow of the
hook, care being taken not to touch or otherwise contaminate that end of the wire. The
sample is then pressed into close contact with the wire surface by crimping the hook.
In developing a systematic scheme of polymer identification, pyrolysis conditions

must be such that all polymers degrade rapidly. However, at temperatures above 1000°C
the pyrograms will also be less suitable for identification, since secondary reactions
become predominant, leading to increasing amounts of simple molecules such as carbon
dioxide, acetylene, ethylene or benzene which gives less characteristic patterns than those
observed for monomers or primary degradation products. Pyrolysis temperatures
between 500 and gOO°C (optimum 610°C) for 10 s are recommended. AlthOUgh
r.r0grams containing from 30 to 50 peaks (for polyolefios) have been reported (Voigt 7·
) the relative retention times and peak height ratios of three to five major peaks are
usually sufficient for identification. Thus a single set of column operating conditions is
desirable that will give characteristic pyrograms for degradation products of all types of
polymers.
METHOD 107 - PYROLYSIS - GAS CHROMATOGRAPHY OF POLYMERS.

PLATINUM RIBBON OR COIL PROCEDURES (CHEMICAL DATA SYSTEMS
PYROPROBE 190).
107.1 SUMMARY
This platinum ribbon or coil pyrolysis - gas chromatographic procedure enables

unknown polymers to be identified from their pyrolysis patterns.
107.2 APPARATUS
Pyrolysis apparatus, Chemical Data Systems Pyroprobe 190 or equivalent.
107.3 METHOD
A solvent solution of the polymer is applied to the pyrolysis filament and

pyrolysed at a controlled temperature. Comparison of relative retention time and peak
height ratio data for the unknown with that for known polymers enables the unknown to
be identified.
465
107.4.1 The Chemical Data System, Pyroprobe 190 Platinum Ribbon Coil
Pyrolyser.
The two types of pyrolyser probe available are based on a platinum ribbon or coil.
If a sample can be dissolved in a suitable solvent, it is best applied to the ribbon as a
solution. This should be prepared at a concentration of about 10mg/1 ml (approximately
1%). About 1-5 ul (representing 10-50 ug of sample) is applied to the centre of the
ribbon using a micro syringe (this may take several applications). The solution should be
spread as evenly as possible so that the entire sample will experience the same heating
profile during pyrolysis. It is essential to avoid the extreme ends of the ribbon as the
points of attachment to the probe mounting provide a large heat-sink and do not reach the
set pyrolysis temperature.
Before inserting the probe into the injection adaptor, the final'temperature should
be set to a low value (such as 100°C) with an interval of 5 to 10 seconds, so that the
residual solvent is flashed off without pyrolysing the sample. For most samples the
solvent can be flashed off in the atmosphere - but for extremely sensitive materials, the
probe should be located in the injector adaptor prior to solvent flash. After the solvent
has been removed and the detector response has returned to base-line, the sample can be
pyrolysed.
Insoluble but meltable samples should be applied by placing fine particles of
material onto the ribbon and gradually raising the temperature with the interval set a I to
5 seconds until the particles adhere to the ribbon.
Samples that are insoluble and that will not melt should be pyrolysed on a quartz
tube located inside the coil probe. The quartz tube must be inseted into the platinum coil
probe very carefully to avoid distortion and damage.
107.4.2 Application of Sample to the Probe.
Quartz tubes must be inserted into the platinum coil probe very carefully to avoid
distortion and damage. This is best achieved by passing the coil probe in the probe stand
and holding the tube by one end with thumb and index finger, gently inserting it into the
coil, rotating it as it enters. When the tube is through the coil part it can then be gently
pushed all the way in so that the end rests on the base of the coil. After insertion, a
careful check of the element is advisable to ensure that there is not shorting to any parts
of the probe assembly and that the coil is even and not distorted.
Samples can then be inserted directly into the quartz tube and, for best results,
should be between 10 and 50 ug and placed in the centre of the tube. As far as possible,
the sample size should be kept constant from analysis to analysis, but for optinum
repeatability of pyrolysis patterns, better results will be achieved by placing the sample
onto a small amount of quartz wool which is itself located in the centre of the tube.
Sample solutions can also be analysed in this way by injecting 1-3 ul from a microsyringe
of a 1% solution of sample onto the quartz wool. The solvent should be evaporated to
dryness by flashing the coil at loooe with interval set a 1 second. For most samples, the
solvent can be flashed off into the atmosphere but for extremely sensitive material the
probe should be located in the injector adaptor prior to solvent flash. After the solvent
has been removed and the signal from the gas chromatograph has returned to base-line,
the sample can be pyrolysed.
466
The coil probe generally requires a fmal temperature of about 150DC higher than
that required by the ribbon probe.
107.4.3 Cleaning the Probes.
Between each sample the probes should be cleaned in the atmosphere by setting
an interval of 2-5 seconds and a final temperature of 1000DC and pressing the RUN
button.
107.4.4 Selection of Pyrolysis Temperature.
An investigation to determine the lowest temperature at which pyrolysis will

occur for a particular sample can be made with repeated runs on the same sample at
increasing pyrolysis temperatures without removing the probe from the adaptor.
Alternatively, arbitrary pyrolysis conditions may be selected and the sample
pyrolysed. The amount of residual organic material remaining can be determined by
repyrolysing the sample at 980DC for I second for the ribbon probe and 10 seconds for the
coil probe. A large residual peak under these conditions indicates that only a small part
of the sample was initially pyrolysed. A higher final pyrolysis temperature should then
be used.
METHOD 108 - PYROLYSIS - GAS CROMATOGRAPHY OF POLYMERS.

LASER PYROLYSIS TECHNIQUE.1O,71
108.1 SUMMARY
This laser pyrolysis gas chromatographic technique is used to identify unknown

polymers from the pattern of the breakdown products of their pyrolysis products.
108.2 APPARATUS
A Gen-a-lite Model 3R laser (General) (Laser Corporation, Natick, Mass 01760)

and a Focuscope (General) Laser Corporation, focussing device. The laser uses a 3.25"
ruby rod with a maximum energy output of 2 joules with a pulse langth of 600 micro
seconds. The instruments are mounted on an optical rail so that the focused beam entered
a box containing a sample holder and a peak-diverting prism. The prism is mounted so
that the beam can be moved in two directions and can thus be aimed at any desired
portion of the sample. The sample holder is a borosilicate glass tube 6 mm o.d. by 25
mm in length. It is clamped between two Teflon (Du Pont) gaskets so that carrier gas can
sweep through the tube in to the chromatograph. The carrier gas enters the chromato-
graph through a 1116 inch o.d. tube which pierces the injection port septum and extends
into the injection port.
Figure 7.45 is a schematic drawing of the apparatus showing the light paths.
The chromatograph used had a pair of flame ionization detectors. The flame
ionization detectors and the associated duel electrometer were from a Varian Aerograph
(Varian .Aerograph, Walnut Creek, Calif. 94598) instrument. The output signal from the
electrometer is connected to an Infotronics Digital Readout Systems Model CRs-I04
467
(lnfotronics, Inc., Houston, Texas 77042) and the output from this system went into a 10
mV Honeywell (Honeywell, Inc., Philadelphia, Pa. 19144) strip chart recorder.
Column A A 223 em (7 ft) 0.25 em i.d. (3/16 inch o.d.) stainless steel column of
70-80 mesh Anakrom ABS coated with 10% UCW-98. This column is operated at room
temperature for one minute, then heated to 70°C the end of the second minute; its
temperature is increased 20°C/min after a maximum temperature of 210°C is reached.
This temperature is maintained until all of the components are apparently eluted.
Helium is used as a carrier gas at a flow rate of 40-50 mlImin. Hydrogen and air flows
are optimized and maintained at those values.
Column B. 476 cm (15 ft) 0.25 cm i.d. (liS inch o.d.) stainless stee column of 70-
SO mesh Anakrom ABS coated with 10% UCW-9S. It is operated at room temperature
for 2 minutes, at 70°C for another minute, then programmed at 10°Clmin to the end of the
analysis or to a temperature of 260°C which ever came first. Column flow rate is 22
rnl/minute. Detector flows are the same as with the other column. Energy output of the
laser rod is measured with a Quantromix Model 504 energy meter equipped with a Model
500 energy receiver.
108.3 METHOD
The pyrolysis products produced when the polymer is exposed to laser light are
swept into a gas chromatograph. The pattern of the decomposition products is compared
with that obtained with known polymers thus facilitating the identification of the
unknown polymer.
Three different types of sample preparation were used. All samples were run as
solids.
1. None. Small pieces of the sample were run as-is.
2. Coated. Sample pieces were coated with graphite by rubbing them with a 6B
drawing pencil. Gold coating was accomplished in a vacuum evaporator.
3. Added carbon. Weighed amounts of sample and fmely ground permium coke
are melted and intimately mixed in a porcelain dish. In some cases the sample was
ground and mixed with coke before melting and further mixing.
The pow.ner is laser pyrolysed using the conditions described under Apparatus.
Folmer 0,71 studied the effects of different operating conditions and methods of
sample preparation on fragmentation patterns. Clear or translucent samples give
reproducible results if mixed with carbon. The concentration of carbon is critical; it has a
great effect on the fragmentation pattern. Some polymers were run whose pyrolysis
chromatograms show great difference in pattern. Others had patterns which were quite
similar. To better compare these similar patterns and the patterns arising from different
operating conditions, a statistical method was devised. An attempt was made .to correlate
these comparisons of patterns with some of the known characteristics of the polymers.
468
~ EYEPIECE 1'011 allllNI aND 'OCUIIIH'I
lOUlL Y RIFUCTIHe
,RIIII IIOVAILE
IIIRROII
UIER ROD
••C=====::J-II flaSH TUIl
-
IIUECTIOII_r ""--....- .....~
CAI'IiIA . , •• N
IAMPl! HDl.DER
WITH SAM'LE
Figure 7.45 - Schematic drawing of laser pyrolysis apparatus.

From Folmer et al with permission. 70•71 American Chemical Society
469
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473
INDEX
Accelerators, det of in,

Non vulcanized rubbers, 253-256
Polymers, 51-53
Acid units, det of in,
Polyesters, 260-262
Terylene, 27, 28, 260-262
Acrylamide copolymers, det of alkoxy groups, 82
Acrylamide monomer, det of in polyarylamide, 35, 36, 279-281
Acrylate copolymers, det of,
Acrylate ester units, 318-321
Carboxyl groups, 78, 79
Ester groups, 79-82
Epoxy groups, 82
Acrylate copolymers,
Fractionation of, 82
Molecular weight of, 82
Acrylic acid - ~ethacrylic and copolymers, det of,
Acrylic acid units in, 106
Methacrylic acid units in, 106
Acrylic acid monomer, det of, 265, 266
Acrylics, determination of,
Acrylate groups, 315-318
Arsenic, 94
Carboxyl groups, 106
Epoxy groups, 106
Ester groups, 106,318-321
Volatiles, 18, 19
Water, 18, 19
Acrylics, pyrolysis - gas chromatography of, 143
Acrylonitrile monomer, det of, 71, 72, 281-283, 291-300
Additives, det of in,
Copolymers, 70, 71, 86-88
Polyacrylates, 30
Polyesters, 29
Polymers, 3-11,16-23,29,30,41-54,70,71,86,88,424-454
Polypropylene, 436-439
Polystyrene, 16, 17
Polyvinyl chloride, 19-22
Rubbers, 22, 23
Styrene-butadiene, 70, 71
Additives,
Extraction from polymers, 112-115, 131-133
475
Gas chromatography of, 115-117, 125-127
High performance liquid chromatography of, 119-121
Infrared spectroscopy of, 125
Mass spectrometry of, 121-123
Supercritical fluid chromatography of, 121
Thin-layer chromatography of, 117-119
Alkene groups, det of in polyesters, 25
Alkoxy groups, det ofin,
Acrylamide copolymers, 82
Ethylene oxide - propylene oxide condensates, 74, 75
Alkyd resins, det of styrene units, 411, 412
Alkyl groups, det of in silicon polymers, 36, 37
Aluminium, det of, 92, 329-334
Amine antidegredants, det of in rubber, 269, 270
Amine antioxidants, det of in,
Non-vulcanized rubber, 253-256
Polyalkenes, 8,9,188-191,193-197
Polybutadiene, 33, 34
Polyvinyl chloride, 19,20
Rubber, 269, 270
Vulcanized rubber, 256-259
Amino groups, det of in,
Polyamides, 35, 40, 274-279
Polyesters, 26, 40
Polyimides, 31, 35, 40, 274-279
Anhydride groups, det of in octadecane-maleic anhydride copolymers, 83
Antioxidants, det of, 22, 41-47, 51-53, 71
Antiozonants, det of in,
Polybutadiene, 33, 34
Rubber 22, 45,51-53
Antimony, det of, 94
Aromatics, det ofin,
Polystyrene, 206-211, 220-223
Styrene monomer, 220-223
Arsenic, det of, 94, 349-351
Aryl groups, det of in silicon polymers, 36, 37
Atomic absorption spectrometry, determination of,
Arsenic, 349-351
Heavy metals, 343-344
Benzaldehyde, det of in styrene monomer, 229-230
Binox M, det of in polyalkenes, 183, 184
Bis(m-(m phenoxy phenoxy) phenyl ether) pyrolysis - mass spectrometry of, 147, 148
Boron, det of, 137
Bound ethylene units, det of in ethylene-butene copolymers, 102,103
Bound ethylene units in copolymers, det of, 101, 102
Bromine, det of, 137,359-362,455-459
Butadiene monomer, det of, 100, 101,297-300
Butadiene units, det of in copolymers, 72-73
Butane 1.4 diol adipic acid polyesters, det of hydroxy number of, 300-301
Butylated hydroxy toluene, det of, 191-193
476
4,4' butyidene (2 tert-butyl-5-methyl) phenol, det of in polyalkenes, 187
Cadmium, det of, 343, 344
Carbonyl groups, det of, 40
Carboxyl groups, det of in,
Acrylate copolymers, 40, 78, 79, 106
Methyl methacrylate-methacrylic acid copolymers, 40, 105, 106
Polyamides, 35, 40
Polyesters, 25, 26, 40
Polyimides, 35, 40
Catalyst residues, det of, 92, 93
Cellulose, det of water in, 34, 270-274
Chlorine, det of, 96, 137, 353-359, 455-459
Chlorobutyl rubber, det of chlorine in, 358-359
Chromium, det of, 93, 94, 343-344
Cobalt, det of, 94
Copper, det of93, 94, 343-348
Cyasorb UV531, det of in polyalkenes, 10,202-204
Dialkyl tin compounds, det of in polyvinyl chloride, 246-253
2.4 and 2.6 diaminotoluene, det of in polyurethanes, 36, 283-285
Dilauryl thio-dipropionate, det of in polyalkenes, 198-201
Dimers, det of in polyalkyl ketenes, 39
Diorganosulphide antioxidants, det of in polyalkenes, 9-11, 198-201
Distearyl thiodipropionate antioxidant, det of in polyalkenes, 198-199
2,6 ditert butyl-p-cresol, det of in,
Polyalkenes, 10, 179-182
Polybutadiene, 3, 4
4(dodecyloxy)-2-hydroxy benzophenone, det of in polyalkenes, 10
Epoxy groups, det of in acrylics, 40, 82, 106
Epoxy resins, det of volatiles in, 84
Ester groups, det of in acrylics, 40, 79-82, 106
Ethanol, det of in polystyrene, 212, 213
Etherification levels in polyacryl amide, 328
Etherlinkages,detofin,
Polyesters, 26
Polyethylene glycol, 32
Polypropylene glycol, 32
2-Ethoxy ethanol, det of in polystyrene, 212, 213
Ethyl acetate, det of in polystyrene, 212, 213
Ethylene-butylene copolymers, det of bound ethylene, 102, 103
Ethylene-alpha olefin, det of comonomers, 104
Ethylene oxide - propylene oxide condensates, det of alkoxy groups, 74, 75
Ethylene oxide - propylene oxide glycerol condensates, det of hydroxy groups in 73,74
Ethylene oxide - propylene oxide - polyhydric alcohol condensates, det of oxyalkene
groups, 75-77
Ethylene oxide tipped glycerol-propylene oxide condensates, det of hydroxy groups,
302-313
Ethylene - propylene copolymers, det of,
Aluminium, 92
Ethylene units, 101, 102,408-411
Vanadium, 92
477
Ethylene - propylene copolymers, pyrolysis - gas chromatography of, 142
Ethylene - propylene - diene terpolymers, det of butadiene, 101
Ethylene - propylene - diene terpolymers, det in rubber, 405-408
Ethylene - tetrafluoroethylene, det of comonomers, 104
Ethylene units, det of in ethylene - propylene copolymers, 104, 408-411
Ethylene - vinyl acetate, det of comonomers, 104
2-ethyl hexyl acrylate monomer, det of, 297-300
Expanding agents, det of in polystyrene, 13-15
Fatty acid salt heat stabilizers, det of in polyvinylchloride 21
Fluorimetry, det ofUvitex DB, 232, 233
Fluorine, det of, 137, 365-367
Fluoropolymers, det of,
Fluorine, 365-367
Oligomers, 38, 39
Fluoropolymers,
Fourier transform infrared spectroscopy, 158
Fractionation of,
Acrylate copolymers, 82
Fluoropolymers, 39
Organosilicon polymers, 37
Polyacrylates, 30
Polystryene, 17, 18
Polyvinyl chloride, 22
Rubbers, 23
Styrene-acrylonitrile copolymers, 72
Styrene-butadiene copolymers, 71
Gas chromatography of,
Acid units in terylene, 27, 28
Acrylic ester groups, 318-321
Acrylonitrile monomer, 297-300
Carboxyl groups in acrylates, 79
Additives, 115-117
Alkoxy groups in alkylene oxide condensates, 74, 75
Alkyl groups in condensates, 74, 75
Aluminium, 92
Amine antioxidants in polybutadiene, 33
Aromatics in polystyrene, 206-211, 220-223
Aromatics in styrene monomer, 223-226
Aryl groups in silicon polymers, 36, 37
Benzaldehyde in styrene monomer, 297-300
Butadiene monomer, 297-300
Dialkyl tin compounds, 251-253
Dilauryl thiodipropionate, 9, 200, 201
Diorganosulphide antioxidants, 200, 201 2,6 di tert butyl-p-cresol, 10,34
4(dodecyloxy)-2-hydroxy benzophenone, 10
Ester groups in acrylate copolymers, 80
478
Etherification levels in polyacrylamide, 324-328
2-ethyl hexyl acrylate monomer, 297-300
Expanding agents in polystyrene, 13-15
Glycol units in terylene, 27, 28 impurities in polyesters, 29
Impurities in styrene monomer, 15
Isobutane in polystyrene, 213, 214
Isohexane in polystyrene, 215, 216
Isopentanes in polystyrene, 218, 220
Monomers in polystyrene, 69
Neohexane in polystyrene,. 218, 219
N-phenyl-2-naphthalene in polybutadiene, 33, 34
N, N'sec heptyl phenyl phenylene diamine in polybutadiene, 33, 34
Oligomers in polyoxy methylene glycols, 37
Oxyalkylene groups in alkylene oxide condensates, 75-77
Oxyalkylene groups in polyethers, 313-315
Oxyalkylene groups in polyurethanes, 313-315
n-pentane in polystyrene, 220
Peroxides in polystyrene, 17
Polyamides, 274-279
Polyimides, 274-279
Styrene monomer, 206-211, 286-289, 297-300
Ultraviolet absorbers, 10
Vinyl chloride monomer, 297-300
Volatiles in polystyrene, II, 12, 164-168
Waterin polymers, 11, 12, 18, 19,28,164-168,262-265
Gas chromatography of additives, 125-127,449-454
Gas chromatography - mass spectrometry of additives, 123
Gel permeation chromatography of,
Amine antiodegredants, 269-270
Amine antioxidants, 33, 269, 270
Antiozonants, 33
Glycerol alkylene oxide condensates, det of hydroxy groups, 300, 301
Glycol units, det in polyesters, 260-262
Glycol units, det in terylene, 27, 28, 260-262
Halogens, det of, 96
Headspace analysis of,
Monomers in copolymers, 72, 73
Volatiles in polystyrene, 212, 213
Heat stabilizers, det of, 48, 49
Heavy metals, det of, 343, 344
Hexafluoropropylene units in fluoropolymers, 106,418-423
High performance liquid chromatography of,
Additives, 119-121, 123,436-439
Acrylic acid monomer, 29, 265, 266
Acrylonitrile monomer, 36,281-283
Butylated hydroxy toluene, 191-193
Irganox 1010,191-193
Irganox 1076, 191-193
Metals, 93
479
Methacrylonitrile, 36, 281·283
Oligomers in polystyrene, 15
Phenolic antioxidats in polyalkenes, 8
High performance liquid chromatography mass spectrometry, 442·444
Hydroquinone, det in styrene monomer, 238·241
Hydroxy groups, det in,
Butane 1,4 diol adipic acid polyesters, 300, 301
Ethylene oxide·propylene oxide condensates 73, 74, 300, 301
Ethylene oxide tipped glycerol· propylene oxide condensates, 302·313
Polyacrylates, 29
Polyamides, 23, 24
Polyesters, 23, 24
Polyethylene glycol, 30·32, 266·269
Polypropylene glycol, 30·32
Polyvinyl alcohol, 36
Infrared spectroscopy of,
Additives, 125,434, 435
Butyl methacrylate monomer in copolymers, 106
Cyasorb UV 531 in polyalkenes, 10, 202, 203
Dialkyl tin compounds, 246·253
Epoxy groups in polyacrylates, 82
Ester groups in acrylate copolymers, 81
Ethylene units in copolymers, 101, 102, 104,408,409
Phenolic antioxidants in polyalkenes, 7
Polymers, 149·152, 155·157
Silica in polyalkenes, 336·338
Si H groups in silicon polymers, 37
Si OH groups in silicon polymers, 37
Styrene units in alkyd resins, 411, 412
Unsaturation in copolymers, 68, 78
Inhibitors, det in styrene monomer, 17,238·246
Iodine, det of, 137, 359, 362, 455·459
lonol, det in polyalkenes, 175·177
lonox 330, det in polyalkenes, 183·184
Irganox 10 10, det in polyalkenes, 191·193
Irganox 1076, det in polyalkenes, 191·193
Iron, det of, 92·94, 329·332, 343, 344
Isobutane, det in polystyrene, 213, 214
Isohexane, det in polystyrene, 215, 216
Laser ionization· mass spectrometry, 158
Laser pyrolysis· gas chromatography, 145
Lead, det of, 343·344
Lithium, det of, 93, 341·343
Low energy ion scattering spectrometry, 158
Manganese,detot94,343,344
Mass spectrometry of,
Additives, 121·123,439-442
Amine antioxidants, 256·259
Antiozonants, 256·259
480
Dimers in polyalkyl ketenes, 39
Oligomers, 28, 30, 37-39
Phenolic antioxidants, 256-259
Polymers, 154-157
Stearic acid in rubber, 260
Volatiles in polystyrene, 13
Mercaptobenzothiazole, det in rubber, 253-256
Methacrylate units, det in styrene-acrylate copolymers, 412-415
Methacrylic acid groups, det in acrylics, 315-318
Methacrylonitrile monomer, det in polyacrylamide, 36, 281-283
2,2' methaylene bis, (4-methyl-6-tert butyl) phenol, det in polyalkenes, 187
p-methoxy phenol, det in styrene monomer, 238-241
Methyl ethyl ketone, det in polystyrene, 212, 213
Methyl methacrylate - methacrylic acid copolymers, det of carboxy groups,
105, 106,416-418
Methyl methacrylate units, det in styrene copolymers, 105
Molecular weight, of
Acrylate copolymers, 82
Fluoropolymers, 39
Polyacrylates, 30
Polystyrene, 17, 18
Polyvinyl chloride, 22
Polyvinyl pyridine, 39
Rubbers, 23
Silicon polymers, 37
Tert octyl phenol- ethylene oxide condensates, 84
Monomers, det of, 29, 35, 36, 69, 85, 86
2-naphthylamine, det in polybutadiene, 33, 34
Natural rubber, det, 405-408
Natural rubber, det of butadiene, 101
Neohexane, det in polystyrene, 218, 219
Neutron activation analysis, det of silica, 336-338
Nickel, det of, 94, 343, 344
Nitrile groups, det of, 40
Nitrogen, det of, 97, 137,375-398,455-459
N,N' sec heptyl phenyl phenylene diamine, det in polybutadiene, 33, 34
Nonox CI, det in polyalkenes, 193-196
Non-vulcanised rubber, det of,
Accelerators, 253-256
Amine antioxidant, 253-256
Mercaptobenzthiozole, 253-256
2(morpholinothio) benzthiazole, 253-256
Tetramethyl thiuram disulphide, 253-256
Tetramethyl thiuram mono sulphide, 253-256
Zinc diethyl dithiocarbamate, 253-256
Nuclear magnetic resonance spectroscopy of,
Carboxyl groups in polyacrylates, 79
481
Dialkyl tin compounds, 246-250
Ester groups in polyacrylates, 81, 82
Ethylene units in copolymers, 104,409-41 1
Ethylene - propylene copolymers, 102
Fluoropolymers, 106, 107
Hydroxy groups in polyethylene glycol, 31, 32
Methacrylate units in acrylate copolymers, 412-415
Methacrylate units in styrene-methacrylate copolymers, 105
Methacrylic acid copolymers, 105, 106
Plasticizers in polyvinyl chloride, 20
Styrene units in acrylate copolymers, 412-415
Styrene units in styrene - methacrylate copolymers, 105
Unsaturation in olefin copolymers, 77, 78
Vinyl chloride - vinylidene chloride copolymers, 106
Octadecyl (3,5 di-tert-4-hydroxy phenol) acetate, det in polyalkenes, 187
Octadecyl - maleic anhydride copolymers, det of anhydride groups, 83
Oligomers, det of, 15,28,30,38,39,84
Optical brighteners, det in polyalkenes, 9, 10
Organic peroxides, det of, 29, 47, 48
Organosilicon polymers,
8H groups, 37
8i OH groups, 37
Organotin compounds, det of in,
Polyalkenes, 188-191
Polymers, 48
Polyvinylchloride,21
Oxirane groups, det of, 40
Oxyalkylene groups, det of in,
Alkylene oxide condensates, 75-77
Polyethers, 313-315
Polyurethanes, 313-315
Pentaerythritol tetra bis (3,5 di-tert butyl-4-hydroxyhydro cinnamate), det in polyalkenes,
187
Peroxides, det in polystyrene, 16, 17, 233-237
Phenol formaldehyde resin, det of oligomers, 37
Phenolic antioxidants, det in,
Non-vulcanized rubber, 253-256
Polyacrylates, 30
PolyaIkenes, 5-8,169-179, 183-193
Polystyrene, 231, 232
Polyvinylchloride, 19, 20
Vulcanized rubber, 256-259
N-phenyl-2 naphthylamine, det in polybutadiene, 33
Phosphorus, det of, 97,137,398-404,455-459
Photolysis of,
Polymers, 124, 145, 146,444-449
Polyethylene, 146
Polymethylmethacrylate, 146
482
Polystyrene, 146
Photolysis of polymers, 147-148
Pigments, det of, 95, 351-353
Plasticizers, det in polyvinyl chloride, 20, 21, 49-52
Polarography of,
Acrylamide monomer, 35, 36, 279-281
Acrylonitrile monomer, 71, 72, 291-294
Hydroquinone, 241-244
Phenolic antioxidants, 30
Styrene monomer, 71, 72, 291-294
p-tert butyl, perbenzoate, 16,233-235
Polyacrylamide, det of
Acrylamide monomer, 35, 36, 279-281
Acrylonitrile monomer, 281-283
Etherification level, 324-328
Heavy metals, 93
Methacrylonitrile monomer, 36, 281-283
Polyacrylates, det of,
Acrylic acid monomer, 265, 266
Acrylic acid units, 315-318
Additives, 30
Arsenic, 349-351
Hydroxy, 29
Oligomers,30
Water, 29
Volatiles, 29
Polyacrylates,
Polyalkenes, det of,
A1uminium,92,329-332
Amine antioxidants, 8, 4, 188-196
4,4' butylidene (2-tert-butyl)-5 methyl phenol, 187
Cadnrium, 343,344
Chlorine, 353-362
Chromium, 93, 343, 344
Copper, 343-345
Cyasorb UV 531,10,202-204
Dilaurylthiodipropionate, 198-201
Diorganosulphides, 9-11,198-201
Distearylthiodipropionate, 198, 199
4(dodecyloxy)-2-hydroxy benzophenone, 10
Heavy metals, 343-345
lonol,175
lonox 330,183,184
Irganox 1010,.191-193
Irganox 1076, 191-193
Iron, 329-332, 343, 344
Lead,343,344
Lithium, 93, 341-343
483
~anganese,343,344
2,2' methylene bis(4-methyl-6-tert butyl phenol), 187
Nickel, 343, 344
Nitrogen, 97
Nonox CI, 193-196
Octadecyl (3,5,di-tert4-hydroxy phenol) acetate, 187
Optical brighteners, 9, 10
Organotin, 188-191
Pentacrythritol tetrakis (3,5 di-tert butyI4-hydroxy) hydrocinnamate, 187
Phenolic antioxidants, 5 - 8
Polygard, 175
SantonoxR, 169-173, 177-179
Silica, 93, 336-338
Sodium, 93, 338-341
Sulphur, 96
Tert phosphite antioxidants, 9-11, 198, 199
1, I' thiobis-2-naphthol, 198, 199
2,2' thiobis (6-tert butyl-p-cresol), 187, 198, 199
Titanium, 329-332
TopanolOC, 183, 184
Triphenyl isopropyl phosphite, 198, 199
Tri-phenyl phosphite, 198, 199
Tris dinonyl phenyl phosphite, 198, 199
Tris isopropyl phosphite, 198, 199
Ultraviolet absorbers, 9, 10,202-204
Vanadium, 333, 334
Volatiles, 164-168
Water, 164-169
Zinc, 343, 344
Polyalkenes, pyrolysis of, 143
Polyalkyl ketenes, dimers in, 39
Polyamides, det of,
Amino groups, 35, 274-279
Carboxyl, 25, 26
Hydroxy, 23, 24
Polybutadiene, det of,
Amine antioxidants, 33, 34
Antiozonants, 10,33,34
Heavy metals, 94
2,6 di-tert butyl-p-cresol, 10, 34
Polycarbonate, det of oligomers, 39
Polycarbonate, thermal decomposition of, 39
Polydimethyl siloxane, infrared spectroscopy of, 151
Polyesters, det of,
Acid units, 25, 26, 260-262
Additives, 29
Alkene groups, 25.
Amino groups, 26
Ether groups, 26
Glycol units, 260-262
484
Hydroxy groups, 23, 24
Oligomers, 28
Organic peroxides, 29
Vinyl groups, 25
Volatiles, 28
Water, 28, 262-265
Zinc, 95
Polyethers, det of oxyalkylene groups, 313-315
Polyethylacrylate, pyrolysis of, 143
Polyethylene, det of,
Aluminium, 92
Nitrogen, 97
Polyethylene,
Photolysis of, 146
Pyrolysis of, 143, 144
Polyethylene glycol, det of,
Ether groups, 32
Hydroxy groups, 30-32, 266, 269
Polyethylene glycol,
Polygard, det of in polyalkenes, 175
Polyhexafluoropropylene vinylidene fluoride copolymers, det of,
Hexafluoropropylene units, 418-423
Vinylidene fluoride units, 418-423
Polyimides, det of amino groups, 35, 274-279
Polymethacrylates, det ofmethacrylic acid Units, 315-318
Polymethylmethacrylate,
Photolysis of, 146
Pyrolysis of, 145
Polyoxymethylene glycols, det of oligomers, 37
Polypropylene, det of,
Additives, 436-444
Antimony, 94
2,6 di-tert-butyl-4-methylphenol, 179-182
4 subst'd 2,6 xylenol, 179-182
Tinuvin 326, 205, 206
Ultraviolet stabilizers, 205, 206
Polypropylene glycol, det of,
Ether groups, 32
Hydorxy groups, 30-32
Polystyrene, det of,
Additives, 16, 17
Aromatics, 206-211, 220-223
Chlorine, 96
2-ethoxy ethanol, 212, 213
Ethyl acetate, 212, 213
Expanding agents, 13-15
lsobutane, 213, 214
Isohexane, 215, 216
485
Methyl ethyl ketone, 212, 213
~eohexane,218,219
Oligomers, 15
Pentanes,218,220
Peroxides, 16, 17, 233-237
Phenolic antioxidants, 231, 232
Propanol-I, 212, 213
Styrene, 286-289
p-tert butyl perbenzoate, 16, 17,233-237
Unsaturated aromatics, 206-211
Uvitex OB, 232, 233
Volatiles, 11 - 15
Water, 11-15
Polystyrene,
Molecular weight, 17, 18
Photolysis, 146
Pyrolysis, 147
Polystyrene sulphonate,
Fractionation, 38
Molecular weight, 38
Polytetrafluoroethylene, photolysis - mass spectrometry of, 147
Polyurethanes, det of,
Diaminotoluenes, 283-285
Oxyalkylene groups, 313-315
Volatiles, 36
Polyvinyl alcohol, of hydroxy groups, 36
Polyvinylchloride, det of,
Additives, 19-22
Amine antioxidants, 19, 20
Dialkyl tin compounds, 21, 246-253
Heat stabilizers, 21
Metals, 94
Phenolic antioxidants, 19, 20
Plasticizers, 20, 21
Volatiles, 18, 19
Water, 18, 19
Polyvinyl chloride,
Fractionation, 22
Pyrolysis, 148
Polyvinylidene fluoride, pyrolysis of, 148
Polyvinyl pyridine,
Fractionation, 39
Propanol-I, det in polystyrene, 212, 213
Pyrolysis - gas chromatography of,
Acrylics, 143
Acrylic copolymers, 106, 315-318
Ethylene units in copolymers, 102, 103, 142,405-408
Hexafluoropropylene units, 418-423
486
Linseed pentaerythritol-o-phthalate, 149
Methacrylate units, 105
Natural rubber, 405-408
Polyalkenes, 143, 144
Polyethyl acrylate, 143
Polyhexafluoro propylene - vinylidene fluoride copolymer, 107
Polymers, 102, 103, 105-107, 141-149,315-318,405-408,418-423,464-469
Polymethyl methacrylate, 145, 147
Polystyrene, 147
Polytetrafluoroethylene, 147
Polyvinylidene fluoride, 148
Styrene - acrylate copolymers, 104
Styrene - butadiene copolymers, 405 - 508
Styrene - isoprene copolymers, 147, 148
Styrene - methyl methacrylate copolymers, 105
Pyrolysis mass spectrometry, 124, 125, 147, 148
Ribbers, det of,
Additives, 22, 23
Amine antiodegradants, 269-270
Amine antioxidants, 269-270
Antioxidants, 22, 269-270
Antiozonants, 22
Volatiles, 22
Rubber,
Santonox R, det in polyalkenes, 169-173, 177-179, 184-186
Scanning electron microscopy, 158
Si H groups, det of, 37
Si OH groups, det of, 37
Silicon, det of, 93, 137, 336-338
Silicones, det of,
Alkyl groups, 36, 37
Aryl groups, 36,37
Siloxanes, det of,
Alkyl groups, 36, 37
Aryl groups, 36,37
Sodium, det of, 93, 338-341
Sodium stearate, det of, 70, 289-291
Stabilizers, det of in styrene - butadiene copolymers, 71
Stearic acid, det of, 70, 260, 289-291
Styrene - acrylate copolymers, det of,
Acrylate units, 104
Methacrylate units, 412-415
Styrene units, 412-415
Styrene - acrylonitrile copolymers, det of,
Acrylonitrile monomer in, 71, 72, 291-297
Styrene monomer in, 71, 72, 291-297
Styrene - acrylonitrile copolymers,
487
Characterization of, 71
Styrene - butadiene copolymers, det of,
Additives, 70, 71
Monomers, 69
Tert phosphite antioxidants, 70, 71
Sodium stearate, 70, 289-291
Stearic acid, 70, 289-291
Unsaturation, 67, 68
Styrene-butadiene, fractionation of, 71
Styrene-butadiene-acrylonitrile copolymers, det of,
Acrylonitrile units, 100, 101
Butadiene units, 100, 101
Styrene-butadiene copolymers, det of,
Stearic acid, 289-291
Styrene 286-289
Styrene-butadiene copolymers, det of rubber in, 405-408
Styrene-n-butylmethacrylate copolymers, det of,
Methacrylate units, 105
Styrene units, 105
Styrene-2-ethyl hexyl acrylate copolymers, det of,
Monomers, 72, 73
Styrene-isoprene copolymers, det of comonomers, 101
Styrene-isoprene copolymers, pyrolysis-mass spectrometry of, 147, 148
Styrene-methyl methacrylate copolymers, det of methyl methacrylate in, 105
Styrene inhibitors, det of, 17
Styrene monomer, det of in,
Styrene acrylonitrile copolymers, 291-297
Polymers, 286-289, 291-297
Styrene butadiene copolymers, 286-289
Styrene monomer, det of,
Aromatics, 223-226
Benzaidehyde, 229-230
Hydroquinone, 238-244
Impurities, 15
Inhibitors, 238-241
p-methoxyphenol, 238-246
p-tert butyl catechol, 238-246
Styrene units, det of in,
Aklyl resins, 411, 412
n-butyl methacrylate copolymers, 105
Styrene-acrylate copolymers, 412-415
4-substituted 2,6 xylenol, det in polypropylene, 179-182
Sulphur, det of, 96, 137,367-375,455-459
Supercritical fluid chromatography of,
Additives, 121
Oligomers, 28, 37
Supersonic jet spectrometry, det of volatiles, 13
Surface enhanced infrared reflection spectrometry, 158
p-Tert butyl catechol, det in styrene monomer,. 138, 139,240-241,244-246
488
p-Tert butyl perbenzoate, det of in polystyrene, 16, 233-237
Tert octyl phenol - ethylene oxide condensates, det of oligomers, 84
Tert octyl phenol - ethylene oxide condensate, molecular weight of, 84
Tert phosphite antioxidants, det of, 9-11,70,71,198,199
Terylene, det of,
Acid units, 27, 28, 260-262
Glycol units, 27, 28, 260-262
Tetramethyl thiuram disulphide, det in rubber, 253-256
Thermogravimetric analysis of,
Isoprene, 101
Rubber, 22
Volatiles, 13
Thin-layer chromatography of,
Accelerators, 22, 253-256
Additives, 22, 117-119,424-435
Amine antioxidants, 188-191,253-256
Cyasorb UV531, 10,203,204
Dialkyltin compounds, 246-253
Diaminotoluenes, 36, 283-285
Dilaurylthiodipropionate, 9
Peroxides, 16, 17,236,237
Phenolic antioxidants, 7, 8, 120, 184-191,253-256
Santonox R, 184-186
p-tert-butyl perbenzate, 236, 237
2,2' thiobis (6-tert butyl-p-cresol), 198, 199
1, I' thiobis-2-naphthol, det of, 198, 199
4,4' thiobis (6-tert butyl-p-cresol), det of, 187, 198-199
Time offlight static secondary ion mass spectrometry, 1 58
Tin, det of, 95
Tinuvin 326, det of, 205, 206
Titanium, det of, 92, 205, 206, 329-332
Toluene, det of in polystyrene, 212, 213
Topanol OC, det of in polyalkenes, 183, 184
Trietbyl phosphite, det of in polyalkenes, 198, 199
Tri iso propylphosphite, det of in polyalkenes, 198, 199
Triphenylphosphite, det of in polyalkenes, 198, 199
Tris (dinonyl phenyl) phosphite, det of in polyalkenes, 198, 199
Tris (dinonyl phenyl) phosphite, det of in polyalkenes, 198, 199
Tri-p-tolyl phosphite, det of in polyalkenes, 198, 199
Unsaturation, det of, 67, 68, 77, 78, 85, 206-211
Ultraviolet absorbers. det of, 9,10,45,46,202-206,424-435
Ultraviolet spectroscopy of,
Binox M, 183,184
lonox 330, 183, 184
Phenolic antioxidants, 5-8,176-182
Topanol OC, ultraviolet spectroscopy of, 183,184
Uvitex OB, det in polystyrene, 232, 233
Vanadium, det in polystyrene, 232, 233
Vinyl acetate units in vinyl chloride - vinyl acetate copolymers, det of, 321-324
489
Vinyl chloride monomer, det of, 297-300
Vinyl chloride - vinylidene chloride copolymers, sequence length, 106
Vinyl esters, det in polyols, 25
Vinyl fluoride units, det in polyhexafluoropropylene-vinylidene fluoride copolymers
418-423
Volatiles, det of, 11-15,22,28,36,40,41,84-86,164-168
Vulcanized rubbers, det of,
Amine antioxidants, 256-259
Antiozonants, 256-259
Water, det of, 1-4, 11-15,28,29,34,41,164-169,262-265,270-274
X-Ray fluorescence spectroscopy of,
Metals,94,158
Tin, 246-250
Zinc, det of, 92, 94, 95, 343, 344
Zinc diethyl-dithiocarbamate, det of in non vulcanized rubber, 253-256
490

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MANUAL OF PLASTICS ANALYSIS

MANUAL OF PLASTICS ANALYSIS

Springer Science+Business Media, LLC

ISBN 978-1-4899-1405-7 ISBN 978-1-4899-1403-3 (eBook)

© 1998 Springer Science+Business Media New York

Figure 1.2 L, Ho.F.F. Analytical Chemistry 45 603 (1973). American Chemical

Figure 7.11 Frankoski, S. P. Siggia, S. Analytical Chemistry 44507 (1972) .

Figure 7.16 Korenaga, T. Analyst (London) 10640 (1981). Royal

Figure 7.17 Tittareli, P. Zerlia, T. Calli, A. Ferrari, G. Analytical

Figure 7.27 Krishen, A. Analytical Chemistry 44 494 (1972). American

Figure 7.28 Johnson, D.E. Lyeria, lR. Horikawa, T.T. Pederson, LA

Figures 7.29 Blackwell, J.T. Analytical Chemistry 48 1883 (1976). American

Figures 7.38 - Juvet, R.S. Smith, L.S. Li, K P. Analytical Chemistry

Figure 7.6 Crompton, T.R. Myers, L.W. Plastics and Polymers

Figure 7.37 Rudewicz, P. Munson, B. Analytical Chemistry 58 358 (1986).

PART 1, REVIEW OF METHODOLOGY

1.1 Polyethylene and polypropylene 1

CHAPTER 2 COPOLYMERS AND CONDENSATION PRODUCTS

CHAPTER 3 DETERMINATION OF ELEMENTS

3.1 Minor metallic constituents 92

CHAPTER 4 COMPOSITIONAL ANALYSIS

4.1 Styrene - butadiene copolymers 100

CHAPTER 5 ADDITIVE MIXTURES

5.1 Separation methods for additive mixtures 112

CHAPTER 6 PRELIMINARY QUALITATIVE IDENTIFICATION

6.1 Preliminary removal of additives from polymers 131

7.1 POLYMER ANALYSIS

2 Determination of water in polyalkenes. Semi-automated Karl Fischer

3 Determination of Santonox R phenolic antioxidant in polyethylene.

4 Detennination of phenolic antioxidants in polyethylene. p-nitroaniline

5 Determination of lonol phenolic antioxidant in polyethylene. Ultraviolet

6 Determination of Santonox R phenolic antioxidant in polyethylene.

7 Determination of2,6-di-tert-butyI4-methylphenol and 4-substituted

8 Determination of Topanol OC, Binox M and Ionox 330 phenolic

9 Determination of Santonox R phenolic antioxidant in polyolefins.

10 Determination of phenolic antioxidants in polyalkenes. Thin layer

11 Determination of phenolic and amine antioxidants, ultra-violet

12 Determination ofIrganox 1076, Irganox 10to and butylated

13 Detennination of Nonox CI amine antioxidant in polyalkenes. Acid

14 Detennination of amine antioxidants in polyalkenes and other

15 Detennination of diorganosulphide and tertiary phosphite antioxidants

16 Detennination of diorganosulphide antioxidants in polyalkenes. Gas

17 Determination of Cyasorb UV531 ultraviolet absorber in polyethylene.

18 Determination of Cyasorb UV 531 ultraviolet absorber in polyalkenes.

19 Determination ofTinuvin 326 ultraviolet absorber in polypropylene.

20 Determination of aromatic volatiles in polystyrene. Gas chromatography 206

21 Determination of aromatic volatiles in polystyrene. Head-space analysis 209

22 Determination of volatiles in polystyrene. Head-space analysis 212

24 Determination of residual iso-hexane in expandable and expanded

25 Determination of residual n- and isopentane in expandable and expanded

26 Determination of residual neo-hexane in expanded and expandable

27 Solvent-free procedure for the determination of residual n- and isopentane

28 Determination of down to 5 ppm hydrocarbon impurities in styrene

29 Determination of hydrocarbon impurities in styrene monomers.

30 Determination of benzaldehyde in styrene monomer. Gas chromatogmphy 229

31 Determination of phenolic antioxidants in polystyrene. p-nitro-aniline

32 Determination of Uvitex UB ultraviolet absorber in polystyrene.

33 Determination ofp-tert-butyl perbenzoate in polystyrene. Cathode-ray

35 Rapid semi-quantitative tests for inhibitors in styrene monomer 238