Principles of Polymer Science - Bahadur, P Sastry, N - V - 2002 - Pangbourne, England - Alpha Science International, c2002 - 9780849324185 - Anna's Archive

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Principles of
POLYMER SCIENCE
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Principles of
POLYMER SCIENCE
P. Bahadur | N.V. Sastry
CRC Press
Boca Raton London New York Washington, D.C.
¢@)
Narosa Publishing House
New Delhi Chennai Mumbai Kolkata
YEARY LIBRARY
-AREDO COMM. COLLEGE
LAREDO, TEXAS ‘
P. Bahadur
Department of Chemistry
South Gujarat University, Surat
Gujarat, India
N.V. Sastry
Sardar Patel University, Vallabh Vidyanagar
Gujarat, India
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Exclusive distribution in North America only by CRC Press LLC
Direct all inquiries to CRC Press LLC, 2000 N.W. Corporate Blvd., Boca Raton,
Florida 33431. Email: [email protected]
Copyright © 2002 Narosa Publishing House, New Delhi-110 002, India
No claim to original U.S. Government works

International Standard Book Number 0-8493-2418-1
Printed in India
NCT 19 9nne
Preface
One of the most exciting areas in chemistry, chemical engineering and materials
science is the preparation, characterisation and application of polymers. Polymers
(or macromolecules) constitute a group of materials made up of long chains built
up by covalently bonded molecules which include plastics, fibers, rubbers, adhesives
and surface coating materials. Polymers have become the most versatile commodity
in today’s life style. We start our day with tooth brush, wear synthetic polymer
clothing, move on rubberised wheels of the conveyance and go to bed on foamed
urethane mattresses with cosy acrylic blankets.
Polymers belong to a relatively new branch of science (as the concept of
macromolecules was first proposed by German physical chemist Hermann
Staudinger in 1920, much criticised at that time but won him Nobel Chemistry
prize in 1953) although these substances did exist since the first life began on the
earth (proteins and nucleic acids which are the essential components of the cell,
are polymers). There has been tremendous development in polymers in past 70
years or so and as on today it is impossible to think of world without polymeric
materials that we use in our day-to-day life. The use of synthetic polymers is
increasing rapidly year by year and in many applications they are replacing
conventional materials like metals, ceramics, wood, natural fibers such as cotton,
wool etc. In fact, science of polymers has its roots in physics, chemistry, biology,
engineering and technology and medicine and has grown to a full fledged discipline
of science. In polymer chemistry alone all aspects (viz. analytical, organic,
physical, inorganic and biological) have been extensively developed. The
commercial and economic value of polymers is also considerable because nowadays
commodity and specialty polymers have been produced and several industries
are flourishing dealing with them.
Looking into the advances in polymer science in general and polymer chemistry
in particular, it is almost impossible to cover all aspects of polymers in a single
book. :
This book familiarises the reader (who have little or no prior knowledge of
the subject) to this fascinating world of polymers. The level will range from
highly introductory treatment to a bit advanced aspects covering all facets of
polymer science. The book is not intended to provide an in-depth coverage of
many aspects of polymers such as books included in the further reading list, but
rather an overview. One can never do full justice in writing a book on a subject
such as polymer science that has roots everywhere and it may not be surprising
if we have failed in including some important topic or did not do justice by
vi Preface
writing some other with sufficient details. Enough care has been taken to eliminate
typographical errors and make the text available for enjoyable reading. Readers
who have suggestions for improving the book are cordially invited to send them
to us. Polymer chemistry is now an important subject in almost all undergraduate/
postgraduate curricula in science and engineering. The book, aimed for
undergraduate and postgraduate students of chemistry and material science, would
also be useful to engineering students and chemists working in industries.
To cater the needs of students coming from multidisciplinary background, an
introductory course in polymer science should provide information not only on
chemistry especially physical chemistry of polymers but also on other aspects
such as basic information on important application of synthetic polymers as
fibers, thermoplastics, elastomers and technological principles involved in their
production. Mention of not only organic polymers but also natural, inorganic
and specialty polymers should also be made. This book has been formulated on
these lines. The book is divided into four main aspects of polymer science
namely synthesis, analysis and characterisation, important solid and solution
state properties of polymers, technology of polymers and much required emphasis
on natural, inorganic and specialty polymers. These parts are preceded by general
introduction which aims at defining and explaining salient and unique features
such as chain constitution, inter-molecular forces, configurational and
conformational forms in polymer chains and milestones in the development of
modern polymer science, Additional supplementary material such as some common
laboratory experiments, brief bio-sketch and contributions of polymer science
pioneers is given in the appendix part.
The book has been written in simple English and contains neat illustrations
and easily understandable tables. Several questions of different type including
numerical problems, concept based problems, multiple choice questions, etc.
along with their answers have been given in the end. In all this we have made an
ambitious effort in explaining several facets of polymers and we would be highly
satisfied if the book helps the needs of students and teachers alike.
We are grateful to Mr. Saurabh Soni and John George for their skill full
assistance in the art work. The handling of the manuscript at different stages till
its publication by Dr. Mayank Dalal, Dr. Nirmesh Jain and Dr. Alex George is
also gratefully acknowledged. One of the authors PB thanks his wife Anita for
her continued patience, understanding, endless love and faith through out the
enormous task of completion of the book. We can offer here only on inadequate
acknowledgement of our appreciation to Shri N.K. Mehra, M/s Narosa Publishing
House, for his enthusiasm and great patience.
P. BAHADUR
N.V. SASTRY
Contents
é
Preface \
1. Genera! Introduction 1
1.1 Introduction /
1.2 Classification of Polymers 4
1.3 Nomenclature of Polymers J0
1.4 Isomerism in Polymer Chains //
1.5 History of Polymers 1/4
1.6 Industrial Scenario 16
1.7 Intermolecular Forces in Polymers 1/8
1.8 Conformations in Polymer Chains 20
1.9 Polymer Waste Disposal and Remedies 23
2. Synthesis of Polymers 26
2.1 Chain Growth Polymerisation (Addition Polymerisation) 26
2.1.1 Introduction 26
2.1.2 Mechanism of Polymerisation (Free Radical,
Cationic and Anionic) 26
2.1.3 Coordination Polymerisation 33
2.1.4 Ring Opening Polymerisation 34
2.1.5 Kinetics of Free Radical Addition (Chain)
Polymerisation 39
2.1.6 Kinetics of Cationic Polymerisation 42
2.1.7 Kinetics of Anionic Polymerisation 42
2.1.8 Phase Systems in Polymerisation (Techniques of
Polymerisation) 42
2.1.9 Industrial Polymerisation 45
2.1.10 Thermodynamic Aspects of Polymerisation 47
2.1.11 Copolymerisation 49
2.2 Step-growth Polymerisation (or Polycondensation) 54
2.2.1 Mechanism of Polycondensation 55
2.2.2 Phase Techniques in Polycondensation 56
2.2.3 Kinetics of Polycondensation 56
2.3. Synthesis and Application of Some Common
Industrial Polymers 6/
3. Polymer Analysis and Characterisation 85

3.1 Identification 85
Vili Contents
3.1.1 Physical Testing 86

3.1.2 Spectral Methods 88
3.1.3 Chromatographic Methods 95
3.1.4 Identification of Typical Plastic Materials 95
3.2 Testing Methods 97
3.2.1 Thermal 97
3.2.2 Electrical 103
3.2.3 Chemical 106
3.3 Characterisation 11/0
3.3.1 Molecular Weight Distribution 1/0
3.3.2 Fractionation J/5
3.3.3 Determination of Molecular Weight of Polymers 1/7
3.3.4 Molecular Weight Distribution (MWD) Curves 1/28
4. Behaviour of Polymers 135

4.1 Crystalline 135
4.2 Thermal 1/5]
4.3 Dilute Solution 162
4.4 Rheological 1/83
4.5 Chemical /88
5. Polymer Technology 203

5.1 Physical Properties Versus Applications 203
5.2 Plastics 204
5.3 Fibers 206
5.4 Elastomers 2/2
5.5 Adhesives 2/5
5.6 Polymer Additives 2/5
5.7 Polymer Processing 220
5.7.1 Casting 220
5.7.2 Thermoforming 224
5.7.3 Foaming 225
5.7.4 Lamination 227
5.7.5 Reinforcing 228
5.7.6 Processing of Fibers 228
5.7.7 Moulding Processes 23]
6. Natural Polymers 236

6.1 Polysaccharides 236
6.2 Proteins 24]
6.3 Nucleic Acids 243
6.4 Natural Rubber 246
7. Inorganic Polymers 249

7.1 Silicones 25]
7.2 Polyphosphazenes 252
7.3 Organometallic Polymers 256
7.4 Coordination Polymers 257
Contents ix
8. Specialty Polymers 259

8.1 Polyelectrolytes 259
8.2 Ionomers (Ion Containing Polymers) 26/
8.3 Conducting Polymers 262
8.4 Solid Polymer Electrolytes (SPE) 264
8.5 Electroluminiscent Polymers 270
8.6 Block Copolymers 27/
8.7 Polymer Colloids 277
8.8 Thermoplastic Elastomers (TPE) 28]
5.9 Polyblends (Heterogenous Plastics) 28/
8.10 Polymer Composites 283
8.11 Inter Penetrating Network (IPN) Polymers 283
8.12 Thermally Stable Polymers 285
8.13 Liquid Crystalline Polymers 286
8.14 Teiechelic Polymers (Functional Polymers) 286
8.15 Polymer Microgels 287
8.16 Biomedical Polymers 288
8.17 Polymeric Supports for Solid Phase Synthesis 29/
8.18 Polymers for Combating Environmental Pollution 292
8.19 Polymers as Chemical Reagents 292
Appendices
A. Laboratory Experiments 295
B. Pioneers in Polymer Science 3/0
C. Questions 335
D. Glossary 361
E. Trade Names for'Some Common Polymers 368
F. Abbreviated Forms of Some Common
Initiators/Monomers/Polymers/Additives etc. 369
G. Structures of Repeat Units of Some Common and
Specialty Polymers 37]
H. ASTM Methods 379
I._ SI Prefixes. 382
J. Some Fundamental Physical Constants 383
K. Physical Quantities and SI Units 384
L. Important Derived SI Units of Physical Quantities with
their Symbols 385
M. Other Units and Conversion 386
N. Definition of the Basic Units 387
General References 389
Index 39]
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General Introduction
1.1 Introduction
A polymer may be defined as a substance built up of a number of repeating
chemical units held together by chemical bonds. A high polymer is one in which
the number of repeating units is in excess of about 1000. This number is termed
as “Degree of Polymerisation (DP). The molecular weight of a polymer is
often given by the product of the molecular weight of the repeating units and DP.
The compound or compounds, used in the preparation of polymer are called
monomers. The repeating units constituting the polymer molecule are called
constitutional repeat units (or CRU). Fig. 1.1 illustrates the monomer, DP and
CRU for polyvinyl chloride.
(i) Monomer : Vinyl chloride

ape
1
l (ii) DP: 1000

o
i
C
CH
Cl
PVC
(iii) Molecular weight of polymer

= Mol. Wt. of monomer x DP
= 62.5 x 1000
= 62,500
(iv) CRU CH) — CH

Cl
Fig. 1.1 The monomer, DP, molecular weight and CRU in polyviny! chloride (PVC)
It is important to note here that the term polymer was first used by Berzelius
in 1827, but the concept of polymer as molecule with high molecular weight (at
2 Principles of Polymer Science
least few ten thousands) was introduced by the German Scientis Hermann
Staudinger almost a century later (in 1920) which was at that time severely
criticised. A macromolecule is the term interchangeably used for polymers,
more often of biological origin. For example insulin, a protein-like hormone, is
made up of several different amino acids (51 in total) and can be called as a
macromolecule but not strictly as a high polymer. Note all the substances can be
polymerised. It is necessary that a chemical substance can act as monomer only
if it has at least bi-functionality (which could be due to one double bond or two
reactive functional groups).
As stated before, the bi-functionality may result due to the presence of at
least a double bond (like in olefins) or two reactive functional groups (two -OH
groups in ethylene glycol).
H,C=CH, -(CH,— CH2};

Ethylene Polyethylene
HO—CH, —CH,— OH (CH) CH, —0>-

Ethylene glycol Polyethylene glycol
Let us consider following examples to show that bi-functionality in a monomer

is a must for the growth of a polymer chain through the reaction of functional
groups successively. For two compounds each possessing only one functional
group (as in the case of acetic acid and ethy! alcohol), the reaction is complete
in one step leading to the formation of ethyl acetate.
O
ene 3
CH wheat a, HOCH, —CH,
Acetic acid | Ethy! alcohol
O
I
CH C—O
CH s-CH,
Ethyl acetate
For a reaction between two compounds one possessing a monofunctional

group such as a carboxylic group in acetic acid and the other with bifunctional
groups of two hydroxyl groups in ethylene glycol, it can be easily seen that the
reaction completes in two steps leading to a monoester (I) in the first step. In the
second step the pre-formed monoester reacts further with one molecule of acetic
acid to yield a diester (II). Since the diester do not have any more reactive
functional groups on its either sides, no further reactions take place. Thus it can
be seen that when diester or any other intermediate which do not have any
reactive functional groups, are formed no polymer chains are resulted.
| i
HO—CH,—CH,+OH + HO—C—CH,
Ethylene glycol | Acetic acid
|
HO—CH,—CH,—O—C—CH,
Monoester
(1]
General Introduction 3
[I] combines with another molecule of CH,;COOH in the second step to form a
diester [II];
IInd step O
Dees ]
10>
Ci 6 0in4NO.CH—CH,-0—C—CH,
I |
CH3;—C—O—CH,—CH,—O—C—-CH,
Diester
(1)
Now if we consider a reaction between two compounds each containing two
reactive functional groups (e.g. ethylene glycol and malonic acid), it can be
inferred that the addition of each of the monomer to another continues till the
concentration of one of the species is depleted. Then one can have high molecular
weight polymers formed from these bifunctional monomers.
HO=Ch=Ch—0n"+-H0OC=CH.—COOH
Ig
HO—CH,—CH,—-O—C—CH,—-COOH
Monoester
Monoester can combine with either the glycol or the malonic acid at the
corresponding functional group end to facilitate further growth of the chain;
] l
HOj;-C—CH—C=OHu+? HO—CH,=—CH,-0H
+
i
HOs-CH.
CH) —0 CCH GOoH
Monoester
O
| I
Hot Gu, ¢ 9 occ, C0 _cH,_-cH, on
Diester
Thus if n moles of a bifunctional species such as malonic acid is reacted with

the same number of moles of ethylene glycol which has two reactive hydroxyl
groups on both the ends, the esterification reaction occurs step wise forming
mono, di-, tri-, tetra-, multi- and polyesters (see the following scheme).
Qt 71 ND
i i
nHO—C—CH,—C—OH + nHO—CH,—CH,—OH
O
I
HO--CH—CH)—0+6=Ciy==—0)41
Polyester
Thus, the reaction between two bifunctional molecules leads to a linear high
polymer. Further, if we add some trifunctional group, it may form either branched
polymeric chain or a three dimensional network structure.
The reactions between different molecules is schematically shown in Fig. 1.2
Monofunctional Molecules:
—e +x ——_r> —ox
Mono and Bifunctional Molecules:

—e +x——x ——, —e x—KX
|
—e x xX e—
Bifunctional Molecules: Small Molecule
x baer ee
| Nf poh Rs oe X——X @—e® X——-X @—@ X——-X
x x Xx——xX
Nf Linear Polymer Molecule
X——x 5 ign
Bifunctional Molecules in presence of some Trifunctional Molecules:

. ~ x——X e—o X———X
ee
ee
ionx
x Tft x ay
oes
|
Cross linked or Polymeric Network
Fig. 1.2 Reactions between molecules with different functionality
1.2 Classification of Polymers

There are several ways to classify polymers. The classification is based on
several considerations. The source of polymers i.e. natural or synthetic, the type
of polymerisation process used in the synthesis, nature and type of chain and
solid state behavour of polymer chains etc. The different classification schemes
can be outlined as shown in Fig. 1.3.
Natural and synthetic polymers
P ‘
O Addition and condensation polymers
L
¥ Homochain and heterochain polymers
E
R Monodispersed and polydispersed polymers
Organic and inorganic polymers
c Homopolymers and copolymers

Ig
A
S Linear, Branched and cross-linked polymers
S
I
F Charged and uncharged polymers
I
ie
A Thermoplasts and thermosetts
all
I :
O Fibers, plastics and elastomers
N
Crystalline and amorphous polymers
Isotactic, syndiotactic and atactic polymers

Fig. 1.3. Classification of polymers
Most linear polymers take on new shapes by the application of heat and
pressure. They are thus called ‘thermoplastics’ whereas the cross-linked polymers
cannot be made to flow or melt irreversibly and are said to be ‘thermosetting’
resins. The differences between these two types are listed in Table 1 (a). A
polymer may contain monomers of identical or different chemical structure.
Polymers made up of only one type of monomeric units are called ‘homopolymers’
whereas those polymeric compounds which are built up of two different types of
monomer units in their chain are called ‘copolymers’ (or mixed polymers).
Polymers with three different types of monomeric units are some times called
‘terpolymers’. The advantage of such polymeric structures is that a single polymer
molecule can have the properties of both the entities, which cna be selected
suiting to the end use of application. Such possibility hardly exists in simple
molecules.
Copolymers are further classified as alternating copolymers or statistically
regular (where both different repeating monomeric units are joined side by side)
and random copolymers or statistically irregular (where there is no regularity in
Table 1(a) Comparison between thermoplastics and thermosetts
Thermoplastics Thermosetts
They are often formed by addition They are often formed by condensation
polymerisation leading to long polymerisation and three dimensional
linear chain polymers with no network structures are formed
cross-links
They soften on heating readily, They do not soften on heating, On
because secondary forces between prolonged heating, however charring
the individual chains can break of polymers is caused
easily by heat or pressure
en They can be reshaped and reused They can not be reshaped and reused
They are usually soft, weak and They are usually hard, strong and more
less brittle brittle
i These can be reclaimed from wastes They can not be reclaimed from wastes
They are usually soluble in suitable Due to strong bonds and intra- and
solvents interchain cross-links, they are
insoluble in almost all organic solvents
the joining of units of two different monomers). Copolymers can also be of

block or graft types. In Fig. 1.4 are schematically shown structures of different
homo-, co- and ter-polymers made using the monomers A, B and C.
(1) Homopolymers: www AAAAAAAAAAAAA

Awww
(2) Copolymers:
(a) Alternating: Www ABABABABABABABwwv
(b) Random: ww» ABBABAAAABAABAwww
(c) Block (two block): wwww+§ AAA AAAABBBBBBBwww
(three block): Www A AAAABBBBBAAAAWw

www BBBBBA AAAABBBBwwww
(d) Graft: MARA AAAAR BAAR AAI
(3) Terpolymers:) wwwABAACBAACCAABwww
Fig. 1.4 Molecular architecture of homo-, co- and terplymers
Polymers can be classified as linear, branched or cross-linked polymers. High

density polyethylene (HDPE) is a linear polymer, while low density polyethylene
(LDPE) is a branched polymer. Natural rubber has two configurational forms.
The cis form has less density and is available as latex. The other form is the trans
form and is brittle and hard (gutta percha). Further the natural rubber on
vulcanisation (or mastication with sulphur) develops crosslinking and becomes
processable. The various topologies of the polymer chains are schematically
presented in Fig. 1.5.
Lineat polymers) =< > 7
Branched polymers:
Cross linked polymers:

(Network) Sen
Fig. 1.5 Schematic representation of linear, branched and cross-linked polymers
According to the structure of their main chain, all polymers can be broadly
classified as homochain and heterochain polymers. In case of homochain polymers
the main chain is made up of linkages between the atoms of same element e.g.
carbon in organic polymers.
In heterochain polymers, the main chain consists of linkages between different

atoms e.g. between carbon and oxygen in polyester, polyethers, carbon, nitrogen
toftot
and oxygen in polyurethanes etc.
Polymers are also classified as organic, elementoorganic and inorganic polymers.

Organic polymers have chains consisting of C—C linkages and have apart from
carbon atoms, hydrogen, oxygen, nitrogen, sulfur and halogen atoms in the side
chains. Elementoorganic (or hetero organic) polymers include (i) macromolecules
whose chains are composed of carbon as well as heteroatoms (except N, S, O
and halogen atoms) and (ii) inorganic chains in which side groups contain carbon
atoms directly linked to chain. Inorganic polymers are polymers containing no
carbon atoms but have Si—Si, Si—O, N—PX, P—O and B—O linkage e.g.
polysilanes, polysiloxanes, polyphosphazenes, polyphosphoric acid or
polyphosphates and poyboron oxides. Inorganic polymers have been studied to
a little extent so far and it is difficult to provide a classification. However inorganic
polymers posses superior thermal, electrical and mechanical properties over
the organic polymers. Silicones, polyphosphazenes and several organometallic
and coordination polymers are from this class and worth mentioning (these are
described in detail in chapter 7). Soe common inorganic polymers are shown in
Fig. 1.6.
Polysilanes:
fe dele gel ie!
svete Si—Si—Si—Si ann
HoH OH
Polyphosphoric acid:
Polysilicic acid:
OH ne ‘i io
3h. aa cf am a Mee AMAMAMARAAM
OH OH OH OH
Polymeric sulfur:
ways SSS -—S-S-_S_ www
Polyphosphazene:
a « Cl a
cans gutaine cehia Nae N—P www
Cl Cl GI Cl
Polyvinyl crown ether:
~as
CH —CH. 5Wye
Ve an
‘a .SS a,”
N‘ ,‘
‘N \, ‘\
‘,
, ‘\ ‘\
} jo)
Fig. 1.6 Some common inorganic polymers
Polymers in which the side branches are present in every unit, being joined by
different chemical groups with the main polymer chain are known as comb-like
polymers. Branched polymers which resemble a star by their structure are known
as star like polymers. Collinear double chain polymers are known as ladder
polymers. Model structures for various branched polymers are shown in Fig. 1.7.
Polymers can also be classified as (1) natural or (ii) synthetic. The common
natural polymers include polysaccharides (starch, cellulose, gums etc), proteins
(gelatin, albumin, enzymes, insulin), polyisoprenes (natural rubber, gutta percha)
and nucleic acids (RNA and DNA). Natural polymers are sometimes also called
‘Biopolymers’ or “Biological macromolecules’.
Polymers can also be classified further as fibers, plastics, resins and rubbers
So
Suatg Random comb Regular comb
LUM THIET
Fig. 1.7
Ladder Semiladder
Possible model structures for branched and cross-linked polymers
based on the nature and extent of secondary valence forces and mobility among
the constitutional repeat units. Important examples belonging to each class are
shown in Table 1(b).
Table 1(b) Some important polymeric materials useful as plastics, fibers, rubbers
and resins
Form Type Polymeric material
Fibers Natural Cotton, wool, silk and asbestos

Semsynthetic Viscose rayon, acetate rayon and cuprammonium
(Cellulosic) rayon
Synthetic Polyamides, polyesters, acrylics, polyurethanes,
polyolefins, polypropylene, polyvinyl! chloride,
polyvinyl! alcohol
Plastics Cellulosic plastics Celluloid, cellophane
Vinyl plastic Polyolefins-(polyethylene, polypropylene,
polytetrafloroethylene (teflon)), polystyrene,
polyvinyl chloride, polyvinyl acetate,
polyvinylpyrrolidone,
Polyacryloids polyacrylic acid and polymethylmethacrylate
Rubber Natural polyisoprene (cis-1, 4) polydiene (e.g.
Synthetic polybutadiene, polychloroprene and polyisoprene),
butadiene copolymers (e.g. NBR, SBR or
Buna N and Buna S), butyl rubber, polyurethanes,
polysulfides and polsysiloxanes (silicone rubber)
Resins Water Solube Modified starches, cellulose derivatives, polyvinyl!
alcohol, polyvinyl pyrrolidone, polyacrylic acid
and polyacrylamide
Water Insoluble Phenol plasts and amino plasts, polyurethane
resins, silicone resins, epoxy resins and unsaturated
polyesters
Plastics, fibers and elastomers possess different physical properties. While

fibers are crystalline materials, elastomers are amorphous. Plastics lie between
these two extreme cases in physical properties viz. modulus and elongation as
shown in the Table l(c).
Table 1(c) Physical characteristics of polymers
Polymers Modulus, dyne cem~? Elongation, %
Elastomers 105-10" 1000

Plastics 10° 10" 100 — 200
Fibers 10° — 70" 10 — 30
Polymers may be charged or uncharged. Charged polymers have some free

functional groups e.g. polyacrylic acid (anionic polymer) or polyethylimine
(cationic polymer). Charged (or ionic) polymers that are soluble in water are
called as “polyelectrolytes”. Water insoluble charged polymers are often called
“jonomers”’.
Polymers may also be classified as amorphous or crystalline depending
upon their morphological behaviour. These two types of polymers behave differently
as crystallinity influences the properties such as hardness, stiffness and elasticity,
thus making them useful as plastic, rubber, fiber or resin. LDPE is less crystalline
and while HDPE is highly crystalline polymer. However it is important to note
that solid polymers when crystallised hardly attain hundred percent crystallinity.
Thus solid state of polymers is often characterised by both amorphous and
crystalline domains. The two polyethylenes have different properties as shown
in Table 1(d).
Table 1(d) Properties of LDPE and HDPE —- a comparison
LDPE HDPE
Branched (% crystallinity < 50) Linear (% crystallinity > 90)

Density, 0.92 g cm™? Density, 0.96 g cm?
Softening point, 360 K Softening point, 400 K
Tensile strength, 85-136 atm Tensile strength, 205 — 315 atm
Linear low density polyethylene (LLDPE) is now manufactured and has less
branching. The linearity provides the polymer strength and branching gives
toughness.
1.3. Nomenclature of Polymers

Polymers are prepared by addition polymerisation of an unsaturated monomer or
by step polymerisation of monomer (or monomer pair) containing at least two
functional groups. The nomenclature of addition polymers is relatively simple.
Condensation polymers, for example, terylene and nylons are named according
to the repeat unit.
Addition polymers are usually named by prefixing poly- before the monomer
from which the polymer is derived. For example polyvinyl chloride and
polyethylene are synthesised from vinyl chloride and ethylene monomers,
respectively.
Copolymers are named by inserting -co- (or -alt-, -rand-, -block-, or -graft-
if the position of the two monomers is known) as prefix. For example; poly
(styrne-co-butadiene) is a copolymer of styrene and butadiene and poly (styrene-
block-butadiene) is a diblock copolymer of styrene and butadiene. It is also a
common practice to designate a diblock copolymer as styrenebutadiene copolymer
and a triblock copolymer as styrne-butadiene-styrene block copolymer. An AB
block copolymer is also designate as poly (A-b-B) and an ABA copolymer as
poly (A-b-B-b-A). The block sequence arrangement of a diblock copolymer is
also represented by a long dash such as A—block—B and the corresponding
copolymer as poly A—block—poly B.
A wide diversity exists in naming polymers viz. based on source, structure,
industrial names, trivial names and even IUPAC names. The nomenclature of
few polymers has been illustrated in Table 1(e). However no single nomenclature
is universally adopted.
IUPAC names of some other common polymers are polystyrene (poly-(1-
phenylethene)), polyphenylene oxide (poly(oxyl, 4 phenylene)) and polyvinyl
chloride (poly (1-chloroethene)). Similarly IUPAC names for various monomers
are; adipic acid (1, 6 hexandioic acid), acrylonitrile (propennitrile), bisphenol A
(2, 2, bis-4-hydroxyphenylpropane), butadiene (1, 3-butadiene), caprolactam (2-
oxohexamethyleneimine), chloroprene (2-chloro-1, 3-butadiene), divinyl-benzene
(1, 4-diethenylbenzene), ethylene glycol (1, 2,-ethane diol), ethylene oxide (1, 2
epoxyethane), hexamethylene diamine (1, 6-hexanediamine), isoprene (2-methy]
1, 3-butadiene), melamine (2, 4, 6-triamino-s-triazine), methacrylic acid (2-
methylpropenoic acid), styrene (ethenyl benzene), terphthalic acid (benzene-|,
4-dicarboxylic acid) and vinyl chloride (chloroethene). Also, these IUPAC names
given in the parenthesis are seldom used in the polymer literature.
1.4 Isomerism in Polymer Chains

Various types of isomerisms are possible in case of polymers. These can be
grouped as constitutional, orientational, geometrical or stereoisomerism as shown
in Fig. 1.8.
A good example of constitutional isomerism is that of the monomer with the
CRU as C>H,O. Three different polymers viz. polyethylene oxide, polyvinyl
alcohol and polyacetaldehyde are possible, each one has quite different property.
It is not always that a polymer chain possesses regularity; any polymer which
lacks such an ordered arrangement, is called irregular. Polydienes, for example
1, 2- and 1, 4-polybutadienes show chain irregularity. In case of polyisoprenes
(1, 2-; 3, 4-and 1, 4- isomers) are possible. Chain irregularity may be of different
kinds e.g. polymerisation of vinyl polymers gives rise to ‘head to tail’ (major) as
well as ‘head to head’ or ‘tail to tail’ (minor) products as shown in the Fig. 1.8.
The stereo isomerism in polymer chains leads to tacticity (spatial order of
arrangement). Based on tacticity, the macromolecular substances are divided
into three categories as shown in Fig. 1.9.
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Fig. 1.8 Isomerism in polymers
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Fig. 1.9 Isotactic, syndiotactic and atactic polymers
Isotactic polymers — these polymers consist of chain segments, which display

a regular repetition of monomer units with tertiary C-atoms of the same steric
configuration; syndiotactic polymers — the chains of these polymers consist of
regular series of monomer units in which every second C-atom of the chain
possesses opposed steric configuration and atactic polymers — the polymer
chain lacks regularity in the distribution of steric configuration of monomer
units.
The cis-trans isomerism in polymers can be easily seen from the structures of
two natural polymers (natural rubber and gutta-percha). As shown in Fig. 1,10,
both are polyisoprenes but posses different physical behaviour e.g. the former is
elastic whereas the later is hard.
eli an ARS HG. SAI

C=C C=C
H3C f > H www HC “se bsH
cis-polyisoprene trans-polyisoprene
Natural rubber Gutta-percha
Fig. 1.10 Cis and trans 1, 4 polyisoprenes
1.5 History of Polymers

Polymers existed in nature ever since the life originated on earth as the prime
bio-molecules viz. proteins, nucleic acids and polysaccharides, which are all
naturally occurring polymers (biopolymers or biological macromolecules).
Staudinger’s concept of macromolecules (severely criticised initially) got support
from the research works of Hermann Mark and William Carothers. The development
of molecular weight determination methods proved in no uncertain terms that
molecules with longer chains and bigger size do exist. Natural rubber (which is
a polymer of isoprene) was known to man for more than 500 years. Christopher
Columbus on his voyage to explore the world, found Brazilians playing with a
ball-like material made from the sap (or latex) of the rubber trees. however, first
successful application of natural rubber was possible only after 1840 when
Charles Goodyear cross-linked natural rubber with elemental sulphur (the process
is known as vulcanisation). Unvulcanised rubber was gummy material which
creeped of its own weight. Different amounts of sulphur added to natural rubber
made it more and more hard, tough and elastic material. Baekeland made the
first synthetic polymer by the condensation of phenol and formaldehyde (now
known as PF resin or Bakelite). The accidental discovery of cellulose nitrate by
Schonbein and its plasticization with camphor to produce celuloid by Hyatt was
done much before the concept of macromolecules was put forward by Staudinger
in 1920. In the decade of 1920s several new polymers like plasticized PVC,
urea-formaldehyde resins, thiokol rubber and alkyed resins were made.
Polyethylene, polystyrene, polymethyl methacrylate, neoprene rubber, nylon 6,
6, melamine resin and polyesters were soon commercialised. In 1940, Plunkett
at DuPont company in USA accidentally discovered polytetrafluoroethylene
(PTFE, teflon) which is most inert polymer commonly known for its use as a
coating material for kitchen ware particularly in non-sticking frying pans. However,
a very important development in the history of synthetic polymers is the Ziegler-
Natta polymerisation. Karl Ziegler (from erstwhile East Germany) was able to
produce linear polyethylene (now called HDPE) under ordinary conditions of
pressure and temperature. The demands of modern day life for high performing
and speciality polymers has thrown a challenge to polymer chemists, physicists
and technologists to come up with new polymers and also do modifications on
existing polymers.
In earlier days, very drastic conditions were needed for the polymerisation of
ethylene, which yielded branched polymer (LDPE). Both HDPE and LDPE are
now important polymers with varied applications. Using Ziegler’s co-ordination
catalysts, Italian scientist Giulio Natta polymerised propylene with ordered
arrangement of pendant methy] groups. This gave highly crystalline polypropylene,
again a polymer with a great demand in today’s market. Some important dates in
the polymer history are outlined in Table 1 (f). Since 80s so many monomers
were polymerised. Copolymerisation using two or more monomers was achieved.
The discovery of thermoplastic elastomers, thermally stable polymers, conducting
polymers and liquid crystalline polymers can be considered as important landmarks
in the polymer history. Polymer chemistry has shown the fastest development in
Table 1(f) Important events in the polymer history
Period Event
1840-1920 Vulcanisation of natural rubber by Charles Goodyear, Schonbein made

cellulose nitrate, Menard and Hyatt synthesised collodion and celluloid
respectively. Chardonnet prepared regenerated cellulose fibers, Graham
classified substances as crystalloids and colloids, oligomers of ethylene
glycol and amino acids were made, Baekeland prepared the first synthetic
polymer bakelite
1920 Staudinger gave the concept of macromolecules, alkyd resins, plasticised
PVQ, U-F and thiokol resins were synthesised
1930 Synthesis and commercialisation of melamine resins, polymethyl methacrylate
(Perspex, ICI; lucite, DuPont), neoprene, polystyrene, polyethylene and nylon
6.6 (by Carothers at DuPont)
1940 PET and unsaturated polyesters (terylene, ICI; dacron, DuPont) and teflon
(by Plunkett at DuPont) were patented
1950 Synthesis and development of ABS, spandex (polyurethane elastomers),
HDPE (by Ziegler), stereoregular PP (by Natta) and polycarbonates were
reported
1960 Ionomeric thermoplastic elastomers, aramides (kevlar), flame retardant
polymers and carbon fibers (cyclised, dehydrogenated PAN) were developed
1970 Thermotropic liquid crystalline polymers were invented
1980 Polyetherether ketone (PEEK) was made
1990 Development of polymer composites, high performance polymers, design
and synthesis of biodegradable polymeric vehicles for sustained release of
pharmaceuticals and fertiliser formulations, design of hydro- and micro gels
based on water soluble polymers, development of conducting polymers,
polymer solid electrolyte, electro-luminescent polymers and synthesis of
multifunctional star and dendrimers
= WEARERS ST Riese F6 ec he R A T e t
past half century and has emerged as a full-fledged science having its roots in
physics, biology, engineering and technology. Detailed mathematical treatments
have been provided to explain the mechanisms/kinetics of polymerisation and,
for the solid and solution properties of polymers.
1.6 Industrial Scenario

Polymers have now become indispensable materials for us and it is difficult
today to think of daily life without them. Virtually modern synthetic polymers
have replaced the use of metals in many cases. Polymers are in fact engineering
materials and are fast replacing metals in every application. Some of the advantages
and disadvantages in using polymers in place of metals are listed as follows. The
advantages of polymers are (i) they are light weight, (ii) they have good thermal/
electrical insulation capacity, (iii) they are resistant to corrosion effects and are
chemically inert, (iv) polymers have easy workability and their fabrication costs
are low, (v) they have good strength, dimensional stability and toughness, (vi)
they are transparent in appearance, have good dyeability and possess decorative
surface effects and (vii) polymers absorb the mechanical shocks and show resistance
to abrasion effects. The major disadvantages however are (i) polymers are high
cost materials, (ii) they are easily combustible, (iii) they have poor ductility, (iv)
they deform under applied load, (v) they have low thermal stability and (vi)
polymers em-brittle at low temperatures.
One of the most severe disadvantages that has been of recent concern in using
plastic/polymeric materials is associated with the problem of waste disposal.
Several thousands of polymers are now available to use now. These are utilised
as thermoplasts (non-fiber), thermoplasts (fibers), themosetts (cross-liniked
materials used as resins and surface coating materials) and elastomers for a
variety of uses. The major polymers, thus classified are commercially produced
in the proportion shown in Table | (g).
Table 1(g) The percentage composition of commercial polymers from different

classes
Type Percentage Main Polymers
Thermoplastics (non-fibers) ~ 65% Polyethylene, Polyvinyl chloride,

Polypropylene and Polystyrene
Thermoplastics (fibers) ~ 15% Polyesters and Nylons
Thermosetts ~ 10% P-F and U-F resins
Elastomers ~10% SBR, NBR and Polybutadiene
Very few polymers, however are used in producing articles for domestic and
speciality applications. The most important of these along with their production
data are shown in Table | (h). Fig. 1.11 also shows some data for the period
1970-2000. Other commercially available polymers are often produced in smaller
quantities and are used for highly specialised applications. Instead of getting a
new monomer for the production of polymers, the trend is to mix two polymers
(polyblends) or a polymer with some non-polymeric material (composites).
4
Table 1(h) US production of polymeric materials
(In million pounds)

1990 as base year
Thermosetts Phenolics 2900

Urea-F resins 1500
Polyester resms 1300
Epoxies 500
Thermoplastics | LDPE 9700
PVC and its copolymers 9100
HDPE 8100
Polypropylene 7200
Polystyrene 5000
Fibers Polyesters 3200
Nylons 2700
Polyolefins 1800
Acrylics 500
Rayon 300
Elastomers SBR 1900
Polybutadiene 900
Ethylene/propylene copolymers 500
NBR 200
ma LDPE
RVEe
HDPE
PP
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PS P-F resin
2.0
Production
Nylons
U-F resin
Unsat PET resin
Get oa ee cere
Ras ee ane ee ais
aes a Melamine resin
albus eet
ol
1970 1980 1990 ~ 2000

Year
Fig. 1.11 US production (10° kg/year) from 1970 to 2000 of various polymers
Polyblends are just physical mixtures (heterogeneous), often designed to improve

properties like processibility, mechanical strength, abrasion resistance and flame
retardance. The term engineering plastics or performance plastics refers to a
group of polymeric materials possessing the following characteristics: plasticity
at some stage of processing, high load bearing capacity, high mechanical strength,
rigidity, abrasion resistanc,e dimensional and thermal stability, light weight and
high performance properties which permit them to be used in the same manner
as metals, alloys and ceramic materials.
The other thrust aspect of polymer industry has been to produce speciality
polymers for very specialised applications. Many industries are carrying out
trials for synthesising highly conducting polymers, novel conjugated polymers
with light emitting and photo conducting properties. Efforts are also on to synthesise
polymer tubes based on polycatenanes and polyrotoxanes. Supramolecular
chemistry has also been applied in joining small chemical molecules via noncovalent
bonds to develop large physical structures which can be used as polymer tubes
for entrapping biomolecules. Multibranched polymers with a main core having
a trifunctionality and a first generation dendrimer (with up to six to nine end
groups) are also being in the process of commercialisation.
1.7 Intermolecular Forces in Polymers

The main linkage in polymer chains in general is always through the covalent
bond between the terminal atoms of successive CRU units. The covalent bonds
are quite strong having bond energies of about 50 to 100 k cal. The formation of
covalent bonds occurs between the atoms (or elements) having similar
electronegativity and hence by sharing of electrons. When diene monomers are
used, polymer chains with covalent linkages are formed with an even spread of
unsaturation along the chain. Possibility of ionic bond formation for the chain
linkage though is favourable but growth of a long chain during the polymerisation
process is difficult when ionic forces are operating. Besides the intermolecular
linkages, the intra-molecular forces between the units spread along the same
chain or neighbouring chains, is a must for a large molecule to possess properties
unique for a polymer chain. These secondary forces operate at distances of about
3-4 A and can be of different types; hydrogen bonding, dipole-dipole forces and
weak van der Waals forces etc. Fig. 1.12 depicts the various forces present in
polymeric chains.
These forces between the units of chains are source of unit as well as chain
movements due to a special kind of motion present only in polymer chains i.e.
internal rotation. If the ratio between the primary and secondary valence forces
is unity or greater than unity, the structures formed loose typical polymer properties.
For example, in diamond structure, each carbon atom is linked to four other C-
atoms through covalent bonds forming a tetrahedral spatial net work. Secondary
forces between the neighbouring units is almost non existent and hence diamond
type structure sdo not posses polymeric properties. Interestingly, in graphite,
which is, an another allotropic form of carbon, the bond energies between the
atoms in the same plane differs considerably from that of other planes. This
indicates the presence of secondary forces of different magnitudes in different
planes. Thus graphite structures possess typical polymer properties. The
arrangement of carbon atoms in diamond and graphite structure are shown in
Fig. 1.13.
Primary covalent bond: Secondary valence forces:

CH Hydrogen bonding
H 3
www
|
H» C—— (e si coeds www ihe arene os tee Fwww
| |
S 0 Owe C
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S S H H O
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| I
www HC ——C—CH,
www www N+ CH9g- — N—— C— CH 37 —C ww
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Vulcanised rubber Nylon 6, 6
Dipole interaction
Polyviny] chloride
van der Waals forces between two similar chains
CEASE
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4
Polyethylene
Fig. 1.12 Molecular forces in macromolecules
(a) Diamond structure (b) Graphite structure
Fig. 1.13 The arrangement of carbon atoms in diamond and graphite structures
The arrangement of atoms or groups in space gives rise to enormous change

in the properties of macromolecules e.g. starch and cellulose both being the
polymers of glucose (glucose units are joined by ethereal oxygen with carbon at
1tand 4" position) behave differently. While starch is an important food material
for humans where in the body, it gets hydrolyzed to glucose, which then converts
into CO, and HO along with a release of lot of energy which is utilised by the
body in doing work or building up of tissues. On the other hand, cellulose is
difficult to digest but is largely employed in cotton and paper industries. This
difference between two polysaccharides can be accounted by the fact that starch
being the polymer of a@-glucose assumes a helical conformation because of the
ethereal links joining glucose molecules are on opposite side of the ring. On the
contrary, cellulose is a polymer of B-glucose and is believed to exist with fully
extended chains which are bonded into a sheet structure by inter chain hydrogen
bonds. High melting point of nylon 6, 6 (265°C) is due to extensive hydrogen
bonding. H-Bonding and dipole-dipole interaction in fibers like cotton, wool,
polyester, acrylan and polyurethanes provide them strength.
Also, cis and trans polyisoprenes possess different characteristics. The former
is natural rubber with high elasticity, whereas the later form is ‘gutta percha’ and
behaves like a hard plastic.
The structural characteristics that determine the chemical and physical properties
of polymers are shown in Table 1 (1).
1.8 Conformations in Polymer Chains

A polymer chain can acquire several conformations. If it were considered to be
rigid, then a linear polymer chain may acquire a fully extended form of
conformation. Such a fully extended conformation for a linear polyethylene
chain is depicted in Fig. 1.14. Thus the linear chain is composed of Ne chain
carbon atoms with N = Nc — 1, bonds of identical length b. The possible maximum
length of such a chain can be calculated mathematically as Leyain = Nb. This
length has been referred in old literature as contour length. The contour length
Teont Of a chain in fact is given by rgont = N 6 sin (7/2) = Nebe, where N, and b,
are effective number of bonds and effective bond length and T is the bond or
valence angle. Fig. 1.15 shows the physical structure of a macromolecule in an
exended form of conformation.
Thus the contour length equals the end-to-end distance in a fully extended
chain. In vinyl polymers -~-CH;—CHR-),,-, the effective bond length (per CRU)
b, = 0.254 nm since b = 0.154 nm and T= 111.5°. Similarly for polymer with a
degree of polymerisation 2000, the contour length 4, of the chain in fully
extended form would be;
N b sin (1/2) = 1999 x 0.154 sin (111.5/2) = 254 nm, since N = N, - 1

= 2000 - 1 = 1999.
In a fully extended chain, the movement of one unit is considered independent

of its neighbours and hence it is also known as freely jointed chain. A long
polymer chain is often assumes a conformation close to that of a coil. The reason
for this once again the presence of secondary valence forces operating through
out the chains at distances of about 3-4 A. Thus it is not always possible to
calculate the length of various conformers that a polymer chain attains, it may be
Table 1(i) Essential structural characteristics that determine the chemical and
physical properties of polymers
Structural Description and Examples

Characteristics
I. Periodically recurring primary units

(a) Structure « Alphatic, alicyclic, aromatic and heterocyclic
Joining of similar PVC, Teflon, polystyrene, styrene-
primary units butadiene rubber, nylon 6, 6 and nylon 6
(b) Joining of different Copolymers e.g. SBR
primary units
(c) Joining of polymer Block and graft copolymers
segments
II. Nature of the joining atoms of the primary units in the macromolecule
C—O and C-N among ether, ester, amide and
urea groups etc.
Il. Structure build-up of the macromolecule
(a) Linear HDPE, polyesters and polyamides
(b) Weakly branched LLDPE
(c) Strongly branched Glycogen and ovalbumin
(d) Cross-linked LDPE, Phenolplasts, cured epoxy resins,
polyurethanes and polyester resins
IV. Topo-chemical characteristics
(a) Geometrical isomers Cis- and transforms of natural rubber
(b) Optical isomers Polypeptides and polysaccharides
(c) Tacticity Isotactic, syndiotactic and atactic polyolefins
(d) Helical structures Polypeptides, isotactic polymers and starch
(e) Head to tail, head to Polystyrene and polyvinyl chloride
head (or tail to tail)
joining
V. Molecular weight In several thousands
SVC LIENAan NY a
fee on tle RE RT
dy Det ndNe2 doereq nyo.
Fig. 1.14 Extended, planner, zig-zag conformation of polyethylene
useful to calculate end-to-end distance of polymer chain. The end-to-end distance

is the shortest distance between chain ends in the molecule. For branched polymers,
which have several ends, radius of gyration is often used to estimate the size of
the coil. In solutions, the information about these parameters can be obtained
experimentally by light or neutron scattering techniques and also from viscosity
measurements. The experimental results can be compared with theoretical
predictions obtained using realistic models of the chain molecule. Based on
random flight technique and classical statistics, the conformers of polymer
molecules can be better understood. The various possible conformations (see
] SA bea Nc
}~_——__——_—______—- Toont —________—_+|
Fig. 1.15 Chain length and contour length of a polymer chain in fully extended
form of conformation N- = 15 chain atoms, N = 14 chian bonds, N, = 8
effective bonds and ¢ = bond angle
Fig. 1.16) and the root mean square distance can be expressed as shown in Fig.
1.16.
Tr T
Fig. 1.16 A polymer molecule in two different conformations
The root mean square end-to-end distance, (77 )'/? for a polymer chain is
related to number of bonds Nc and bond length b by (77) =Nc'"b. The
polymer chain acquires unperturbed dimensions in @-solvents in which the polymer
chain is assumed to behave like a freely jointed chain. In non-@- solvents, the
chains are described by real chains which differ from the idealistic freely jointed
chains. The ratio between the root mean square end-to-end distance for a polymer
chain in 6- and non-6- conditions estimates a parameter called steric or hindrance
parameter, o. For real chains, o value is more than unity. The first of the more
sophisticated models takes into account the fact that bond angles in molecule are
very nearly constant. It also assumes that rotations about the skeletal bonds are
unhindered. This model is known as the freely rotating chain. For tetrahedral
bonding, this modification approximately doubles the characteristic ratio, to 2.2.
The ratio is generally increased further if it is assumed that different rotational
angles have different energies. The final refinement involves taking into account
the co-operativity of neighbouring rotational isomeric states. In other words, it
assumes that the movement of one unit influences the movement of its neighbour.
Most experimental values of this characteristic ratio are in the range of 4-10.
1.9 Polymer Waste Disposal and Remedies

A huge amount of polymer materials is used al! over the world as plastics, fibers
and elastomers, Fortunately, these materials do not offer serious health hazards.
However, the main problem associated with the polymer waste is its disposal.
Another problem associated with the exceedingly large use of polymers is the
resource problem, as these are produced chiefly from petrochemicals. There are
two ways that can be thought of to combat this problem. Besides cutting down
the use of polymeric materials to a certain extent, recycling of used polymers
and also making them biodegradable could offer solutions. Recycling means
different things. For example, waste PVC can be burnt to give HCI and ethylene
which by suitable chemical reactions can be converted into vinyl chloride monomer
and can finally be polymerised to give back PVC. However, producing the
polymer again by polymerising the monomers obtained from the decomposition
of the polymer waste has to be economic. Moreover a finished polymer product
is often associated with several additives viz. fillers, plasticizers, antioxidants,
thermal and photostabilizers and colourants. Thus for making recyclic process
economically, energetically and technically viable, it is necessary that the used
polymer made from the same lot and brand should be collected separately. This
is possible only when the users are educated thoroughly on this problem and
necessary provision is created by the concerned public authorities for collecting
the used polymer products variety wise. Also, it may be noted that severe problems
can be encountered in making the recycling process industrially viable.
Recycling of glass, paper and rubber has shown promise and the processes
are industrially feasible. Everyone is aware of recycled glass and recycled paper.
Recycling of rubber, for example, rubber tyres used as automotive bumper guards,
capped tyres, fillers, rubber toys, rubber gaskets, tyre hides, hoses and belts etc.
is also almost established. The rubber obtained from waste rubber articles when
recycled gives reclaimed rubber. Though the recycled rubber possesses less
tensile strength, lower elasticity and wear resistance, it is a useful product as it
is very cheap and combats problem of rubber wastes. Recycled polyethylene is
used in making carry bags. There is much focus on polypropylene based products
as it is the single largest material consumed in terms of volume due to its low
cost, good strength and easy moulding. Other recycled plastics such as polystyrene
and polyesters etc. are used to make cheaper items. It is important to note that
the thermosett plastics and crosslinked rubbers can not be recycled. Using
biodegradable polymers also offers an important way to fight against polymer
waste disposal but more research needs to be done in this field.
Suggested Questions
1. What are polymers? Explain why polymer science is relatively new but fastest
growing science?
Name five important events in the history of polymer chemistry.

ie
2 Enlist the contribution of following scientists in the development of polymer
chemistry: (a) Hermann Staudinger (b) Hermann Mark (c) P.J. Flory (d) Hyatt
(e) Carothers (f) Charles Goodyear (g) Karl Ziegler (h) Guilio Natta (i) Henry
Baekeland (j) Fredrick Sanger (k) Merrifield (1) P.G. deGennes.
Define the terms ‘monomer’ and ‘monomer functionality’. Describe briefly how
do polymers behave differently from low mol mass substances. Which important
properties make them useful as material?
Who are the scientists associated with the following which lead them Nobel prize
on polymer research: (i) Concept of macromolecules (ii) Stereoregular
polymerization (iii) Solid phase polypeptide synthesis (iv) Theory of polymer
solutions and (v) Conducting plastics.
Show the structure of repeating units in: (a) Polycaprolactam (b) Polybutylene
terephthalate (c) Polyisoprene (d) Polyisobutylene (e) Polyacrylonitrile (f) Polyvinyl]
alcohol (g) Polyvinylidine chloride (h) Polyacrylamide (i) Teflon (j) Poly-
oxypropylene (k) Polyphenylene (1) Polyoxyphenylene (m) Polyoxymethylene
(n) Polyvinyl acetate (0) Polyvinyl chloride (p) SBR (q) PMMA (r) Poly a-
methylstyrene (s) Polyphosphoric acid
. Write the monomers used in making: (a) Polyurethane (b) Nylon 66 (c) Epoxy
resin (d) SBR (e) Polycarbonate (f) Terylene (g) Thiokol rubbers (h) Silicones (1)
Glyptals (j) Melamine resin.
Write repeating units in: (a) Nylon (b) Nylon 6 (c) Nylon 6, 6 (d) Nylon 6, 10
(e) Nylon 11.
. Write the structure of repeating units in following copolymers:
(a) Poly (divinyl benzene-co-styrene) (b) Poly styrene-block-poly (ethylene oxide)
(c) Poly (ethylene-co-maleic anhydride) (d) Polystyrene-block-poly (ethylene-
co-maleic anhydride) (e) Poly (styrene-graft-isoprene).
Draw structures of the following copolymers considering A and B as monomers:
(a) Random copolymer (b) Alternating copolymer (c) Two block copolymer and
three block copolymer (d) Graft copolymer (e) Radial copolymer.
. Define the following with suitable examples:
(a) Ladder polymer (b) Flame retardant polymers (c) Organometallic polymers
(d) Inorganic polymers (e) Ter-polymers (f) Block and graft polymers (g)
Homopolymers (h) Telechelic polymers (i) Reactive polymers (j) Spiropolymers.
Write the structure of repeating units and the method of preparation of polyviny]
butyral and polyvinyl alcohol.
Write the structure of the following heat resistant polymers: (a) Poly xylyene
(b) Polyphenylene (c) Graphite (d) Polysulphone.
What are the following: (a) Coumarone-indene resins (b) Galalith (c) Ebonite
(d) Shellac
. Write the IUPAC (or structure based names) for; (a) Polyacrylonitrile (b) Polystyrene
(c) Polyethylene terephathalate (d) Polymethy! methar cylate (e) Polyvinyl acetate
(f) Nylon 6.
16. Make an exhaustive chart classifying macromolecules in different possible ways.
ive What are the following polymers? Mention their properties and applications:
. (a) High impact polystyrene (HIPS) (b) Polyimides (c) Crosslinked poly (styrene
sulphonate).
What do the following trade names stand for: (a) Kraton (b) Teflon (c) Thiokol
(d) Pluronics (e) Saran (f) Plexiglas (g) Orlon (h) Nylon (i) Mylar (j) Neoprene
(k) Lucite (1) Bakelite.
Discuss the importance ofinter-molecular forces in polymers with suitable example
for each case.
20. Show schematically the inter-molecular (secondary) forces present in PVC, PAN,
HDPE, Nylon 6, and Terylene.
21. Write structures showing (a) head-to-tail and head-to-head arrangement and
(b) isostactic, syndiotactic and atactic arrangements in polypropylene.
22. Describe giving suitable examples of the following isomerism in polymers:
(a). Constitutional isomerism (b) Orientation isomerism (c) Geometrical isomerism
(d) Stereo-isomerism.
23. Write the structures for the following monomers and the names of polymers they
produce; (a) Adipic acid (b) DMT (c) Bisphenol A (d) Epichlorhydrin (e) TDI.
24. Suggest few remedies that can help make the synthetic polymers eco-friendly.
25. What are natural polymers and how do they differ from synthetic ones?
Suggested Further Readings
Batzer, H., and F. Lohse, /ntroduction to Macromolecular Chemistry. New York: Wiley,
19872.
Billmeyer, F.W., Jr., Text Book of Polymer Science, 3rd ed. New York: Wiley, 1984.
Bovey, F.A., and RH. Winslow (eds.) Macromolecules, An Introduction to Polymer Science.
New York: Academic Press, 1979.
Boyd, R.H., and P.J. Phillips, The Science of Polymer Molecules. New York: Cambridge
Univ. Press, 1994.
Carraher, C.E., Jr., Seymour/Carraher’s Polymer Chemistry—An Introduction, 4th ed.
New York: Dekker, 1996.
Coleman, M.M., and P.C. Painter Fundammentals of Polymer Science. Lancaster, Pa.:
Technomic, 1994.
Cowie, J.M.G., Polymers: Chemistry and Physics of Materials, 2d. ed. London: Blackie,
1991.
Elias, Hans-Georg, An Introduction to Polymer Science. Weinheim: VCH, 1997.
Gowarikar, V., N.V. Viswanathan, and J. Sreedhar, Polymer Science. New York: Wiley,
1986.
Hiemenz, P.C., Polymer Chemistry. New York: Dekker, 1984.
Nicholson, J.W., The Chemistry of Polymers. Boca Raton, Fla.: CRC Press, 1991.
Ravve, A, Principles of Polymer Chemistry. New York: Plenum, 1995.
Rodriguez, F., Principles of Polymer Systems, 4th ed. Washington, D.C.: Taylor and
Francies, 1996.
Rosen, S.L. Fundamental Principles of Polymeric Materials, 2d ed. New York: Wiley,
1993.
Seymour, R.B., and C.E. Carraher., Jr., Polymer Chemistry—An Introduction, 3d ed. New
York: Dekker, 1992.
Sperling, L.H., Introduction to Physical Polymer Science, 2d ed. New York: Wiely, 1992.
Stevens, M.P., Polymer Chemistry, 2nd ed. New York: Oxford Univ. Press, 1990.
Young, R.J., and P.A. Lovell, Introduction to Polymers, 2nd ed. New York: Chapman and
Hall, 1991.
Z
Synthesis of Polymers
2.1 Chain Growth Polymerisation (Addition

Polymerisation)
2.1.1 Introduction
Two major types of polymerisation methods are used to convert small molecules
(monomers) into polymers. These methods were originally referred to as (i)
Addition polymerisation and (ii) Condensation polymerisation. The addition
polymerisation is also called as chain-, chain growth-, or chain reaction
polymerisation. While condensation polymerisation is also described under
headings such as step-, step growth-, or step reaction polymerisation and sometimes
polycondensation.
As has been mentioned before, a monomer needs to have at least bifunctionality,
which may arise from one double bond or two reactive functional groups to
undergo polymerisation. Unsaturated monomers usually follow addition
polymerisation while those, containing functional groups undergo
polycondensation. For example, polyethylene and polypropylene are addition
polymers (as the monomers undergo addition polymerisation) whereas nylons,
terylene etc. are condensation polymers (as the monomer pairs undergo
condensation). Each method has some characteristic and distinguishing features
as shown in Table 2(a) and Fig. 2.1. Some common polymers made from each
method are shown in Figs. 2.2 and 2.3.
2.1.2 Mechanism of Polymerisation (Free Radical, Cationic and Anionic)

The monomers contain at least a double bond that participates in the polymerisation
reaction. The mechanism of this kind of polymerisation is similar to that of chain
reaction involving the halogenation of alkanes. It consists of three steps namely
initiation, propagation and termination. The initiation step comprises of the
reaction of the active species generated from an initiator (or catalyst by its
decomposition) and adds to the C=C bond of the monomer. The active species
generated from an initiator may be a free radical, a cation, an anion or a coordination
complex. These species on reaction with the monomer form new free radicals
such as a carbocation, a carbanion or a coordination complex.
Synthesis of Polymers 27
Table 2(a) Distinction between addition and condensation polymerisation

eee
Addition polymerisation Polycondensation

(Chain-growth polymerisation) (Step-growth polymerisation)
. Monomers are unsaturated Monomers contain two or more

functional groups
2. Nothing is eliminated as a result 6f Usually small molecules like H,O,
this type of polymerisation CH,0H, HCl, etc. are eliminated
3. High molecular weight in polymer High molecular weight is attained
is attained at once only at very high conversions
4. Only monomer and polymer are All possible molecular weight species
present during the course of viz. dimers, trimers, tetramers and
polymerisation multimers etc. are present
5. Only monomers add to the growing All species are reactive
chain
6. Chain grows at active centres Stepwise intermoleculer condensation
7. Polymer molecular weight is equal Not so, some small molecules often
to DP x molecular weight of monomer get eliminated
8. Involves opening of double bond by Involves reaction between functional
active species like free radical or ion groups
9. Examples of polymers are Examples are polyesters, polyamides
polyolefins, polydienes, vinyl and polycarbonates
polymers and acrylic polymers
10. Initiator (catalyst) generates active Most reactions have high AE, and
species that attack monomer (the hence usually heating is required.
active species can be free radical, Un-catalysed or catalysed (e.g. by
anion or cation). The process of acids) processes are possible
polymerisation is exothermic
11. Can be done by bulk, solution, Polycondensation can be achieved
suspension, and emulsion in melt, solution as well as at
polymerisation techniques interfacial boundary between two
liquids in which the respective
monomers are dissolved
12. Can quickly lead to a polymer with Slow stepwise addition process,
very high molecular weight, cross- molecular weight is < 1,00,000,
linking can be achieved by using highly dependent on monomer
monomers with two double bonds stoichiometry, little amount of tri
e.g. divinylbenzene or multi-functional monomers
develops extensive cross-linking
The important characteristics of chain polymerisation are: (i) once the initiation
occurs, the polymer chains form very quickly i.e. in the time scale of 107! to
10° s, (ii) the catalyst concentration needed is very low and that means during
the course of polymerisation only monomers and polymer are present, (iii) the
process is exothermic (see the thermodynamics of polymerisation) and (iv) high
polymers with molecular weights of 10,000 to 10 million can be obtained.
The initiators for chain polymerisation may be different depending upon the
nature of initiation. The initiators commonly used for generating various active
species are listed below;
Addition polymerisation
DP
Polycondensation
Reaction time
So
Fig. 2.1 The addition polymerisation and polycondensation
Free radical Peroxides (e.g. benzoylperoxide, BPO), azo compounds

initiators (e.g. azobisisobutyronitrile, AIBN), redox systems
(e.g. persulphate + bisulphite), light or ionising radiation
Cationic Proton or Lewis acids, carbocations, oxonium ions, high
initiators energy radiations
Anionic Lewis bases, oranic alkalis e.g. sodium + ammonia, butyl
initiators lithium and naphthalene + sodium
Coordination Transition metal complexes
initiators
In free radical polymerisation, the initiator generates free radicals as the

active species through its homolytic decomposition. The different mechanisms
through which initiator species are initially produced are shown in Fig. 2.4. The
decomposition of peroxide type initiators in aqueous systems is generally
accelerated in the presence of a reducing agent. This allows high rates of free
radical formation at low temperatures, for example in emulsion polymerisation.
A typical redox system is that of ferrous ion and hydrogen peroxide. Another
widely used redox system is of persulfate with thiosulfate or bisulfite as reducing
agents.
Cationic polymerisation involves initiators, which produce a cationic species
that interacts with the monomer. More traditional initiators used here include
Lewis acids such as BF3, AICI; etc. Protonic acids like sulphuric acid, perchloric
acid, phosphoric acid and trichloroacetic acids do act as initiators.
However, pure Lewis acids are not effective as initiators and do need a proton
containing Lewis base such as water (called co-catalyst). The Lewis base
coordinates with electrophilic Lewis acid and the proton is the actual initiator.
Anionic polymerisation uses initiators, which produce anionic species. Organo
alkali compounds like butyllithium, electron transfer reagents such disodium-
—+-CH—CH),>,,
| R=H Polyethylene
R R=CH, Polypropylene
R=Cl Polyvinyl! chloride
R=OH Polyvinyl alcohol
R=OCOCH, Polyvinyl acetate
R=CN Polyacrylonitrile
R= CONH, Polyacrylamide
R=COOH Polyacrylic acid
R=CHO Polyacrolein
R=NH), Polyvinyl amine
R=C,H; Polystyrene
ee CO—CH,
R= Ss Polyviny! pyrrolidone
CH,—CH,
sg
= 1,4 Polyisobutylene
CH;
- CH;—CH=CH — CH,}; 1,4 Polybutadiene
ee eS es Polyisoprene
CH;
=--CE>— CE. Polytetrafluoroethylene
ei
+—C—CH3; Polymethacrylic acid
P |
a, *CSOOR
a
+ i— CH; Polymethy! methacrylate
COOCH,;
Fig. 2.2 Some addition polymers
naphthalene complex and NaNH, are common initiators for anionic polymerisation.
Vinyl monomers with electron withdrawing group e.g. acrylonitrile and styrene
etc. are readily polymerised by anionic mechanism. The reaction depends on the
polarity of the solvent, electronegativity of the initiator and the resonance stability
of the carbanion. Monomers with strong electron withdrawing groups may need
only weakly polar initiators like Grignards reagent while monomers with weak
electron withdrawing groups need strongly polar initiators like butyllithium.
Unlike cationic polymerisation, here the stereoregularity is observed. Soluble
anionic initiators in polar solvents at low temperatures from syndiotactic polymers
while in non-polar solvents they give isotactic polymers. The termination step
does not take place itself in anionic polymerisation and the living macroanion
has to be terminated by the addition of some reagents. Szwarc thus used the term
Polyesters (Terylene, Mylar, Dacron):
—-O—CH,—_ Ci, —O—G

i i
C—O)
Nylons (Nylon 6, 6):
I I
—HN—(CH,)¢>—NH —C-€CH,)—- C+;
CH;
Polycarbonates: —¢O O)- c{O)- Ga o>:
CH, O
Polysulfones: —¢O <O)- {O)-0 <O)-{O)
CH; O
Polyurethanes: eae ae a HRN H—-O;
Epoxy resins:
.
+O) aren Nala
CH; OH n
Polyethers; -~-CH,;—CH,—03,
Polyanhydrides ia i
I I I
O O O
Fig. 2.3. Some condensation polymers
living polymers to describe these reactive species and living polymerisation to

describe the anionic polymerisation. The absence of self-termination in anionic
polymerisation is useful in the synthesis of block copolymers.
The reactive species is a coordination complex in case of coordination
polymerisation (Ziegler-Natta polymerisation is a particular case). These catalysts
involve a variety of transition metal complexes. These complexes are usually
based on Ti, V, or Cr type metals and organometallic compounds like (C,H;)3Al.
After the initiation, the second step is propagation, where the newly generated
‘active species’ adds to another monomer in the same manner as in the initiation
step. This procedure is repeated over and over again until the final step of the
polymerisation process ‘termination’, occurs.
The termination step is one when the growing chain with active species reacts
with other growing chain or by the spontaneous decomposition of the active site.
The termination follows either coupling or disproportionation mechanism. The
detailed mechanism of free radical polymerisation is shown in Fig. 2.5.
Thermal decomposition
C,.Hs
1
ste C—O—O—C—C;H,
1 —— 2C,H5 TE CO,
Benzoyl peroxide
CH, CH; CH,

é
es Wey eee ——— a +N,
CN CN CN
Azobisisobutyronitrile (AIBN)
(O;S—O—O—SO,)** —» 280;
Persulfate
CH; CH;
CéHs—C—O—OH —> Cols —C—0* + OH*

CH; CH;
Hydroperoxide
Redox systems
(i) S,03+ S,07 —» so?+ so}
Persulfate §Thiosulfate
(ii) Fe** +H,O, ——» Fe**+ + OH* + OH™

Fig. 2.4 Formation of free radicals from initiators
Initiation: CH )= CH) + *R —*» *CH)—CH)—R

Propagation:
CH)>=CH) + *CH,—CH,»—R —* *CH)—CH)—CH)—CH)—R
CH —=CH> + *CH>—CH>—(CH),-R ——® *CH>—CH>—_{CH
ino R
Chain transfer: CH,=CH2 + *CH2,—CH2—-¢CH};R
*CH)—CH3 + * Ho CH —+CH7}7R
Termination:
(a) Combination: R--CH;};CH;—CH; + *CH,—CH)-(CH3},R
R-(CH;}; CHp—CH)—CH)—CH)-CHaR
(b) Disproportionation:
R+CH3;CH);—CH)*” + *CH)—CH (CHR
CH )= CH-€CH)}-R + CH3—CH)-€CH)),;-R
Fig. 2.5 Mechanism of free radical polymerisation

32. Principles of Polymer Science
The cationic polymerisation takes place in presence of catalysts such as pretonic

acids viz. HCl, HCIOy, H,SO4, CCI,;COOH and H3PO, and Lewis acids such as
BF;, AICI; and SnCly. It proceeds with the following steps as shown in Fig. 2.6.
Initiation: BF; + HJO —— H+ (BF30H)-
(F3BOH)- Ht + CH2=C = CH,—C* ~(HOBF3)

CH, \ CH;
Isobutene (monomer)
Propagation:
CH3;—C* ~(HOBF3) + n CHC

CH, | CH;
A CH; A CH;
H-(CH,—C},CH,—C* ~(HOBF3)
CH, CH;
Termination .
Anion atgohannn yr Aughenien abstraction
Jods Ag LH JE
H-+CH»—C}; CH2—-C—-OH H-(CH2—C}, CH»— ‘a
CH, CH, CH, CH;
+ BF,
Fig. 2.6 Mechanism of cationic polymerisation
The salient features of cationic polymerisation are: (i) the required activation
energy is small and the polymerisation may occur at low temperatures, (ii) the
similarly charged macrocations and also carbocations would repel, thus the final
termination process cannot take place by combination, (iii) the mechanism depends
on the nature of the solvent, electrophilicity of the monomer and the nucleophilicity
of the counterion generated and (iv) the polymerisation order in the olefin monomers
follows; isobutene > propene > ethene.
Anionic polymerisation has following specific features: (1) monomers with
electron withdrawing groups e.g. - CN and — COOH are readily polymerised,
(ii) termination is to be deliberately achieved as it does not take place by itself.
Hence it is also known as living polymerisation, (iii) it can be used in synthesising
tailor made block copolymers and (iv) soluble anionic initiators at low temperatures
in polar solvents yield syndiotactic polymers and in non-polar solvents produce
isotactic polymers. The various steps i.e. initiation, propagation and termination
involved in anionic polymerisation are depicted in Fig. 2.7.
Initiation:
CH, oie ae :NHz sae Aaa aes
CN CN
monomer catalyst carbanion
Propagation:
pee Te CH + nCH, uibga
CN | CN
H,N-ECH,—CHt; CH) —CH
CN CN
Termination: Does not take place by itself and the living
chains are made to terminate e.g. by adding ammonia.
H,N-ECH)—CHi;
CH; —C-H
CN CN
[NHs
H,N-{CH._-CH CH —CH + :NH>
CN CN
Fig. 2.7 Mechanism of anionic polymerisation
2.1.3 Coordination Polymerisation

Before 1050, the only available commercial polymer, polyethylene, was a branched
polymer and was manufactured at extremely high pressure. Karl Ziegler in the
early 1950s, prepared linear polyethylene at low pressure and ambient temperatures
using TiCl4/(CHs)3A1 mixture as a catalyst. Using such complex catalysts, Giulio
Natta in 1955 produced crystalline polypropylene. Soon the industrial usefulness
of the process was known and the manufacture of linear PE, isotactic PP, ethylene-
propylene copolymers, cis-1, 4 polydienes was started. Ziegler and Natta for
their outstanding work on using coordination catalysts for the synthesis of polymers
shared Nobel prize in Chemistry for the year 1963. A number of coordination
catalysts can be used to polymerise olefins. The polymerisation as such is referred
to as coordination polymerisation. In general, a Ziegler-Natta catalyst may be
described as a transition metal compound coming from group IV to VIII and
orgonometallic compound of a metal from group I to III of the periodic table.
The transition metal compound is customarily called a catalyst and the
organometallic compound a cocatalyst. The most commonly used catalyst system
is R3Al + TiCly. The typical catalyst components are given in Table 2(b).
While the technique is highly developed, it is still not perfectly clear to what
mechanism exactly the polymerisation follows. The characteristic features of
this process are:
(i) the polymerisation of non-polar monomers is easy and is stereo-selective.
The extent of stereo-selectivity depends on the amount of exposure of the
active site,
(ii) the reaction has the characteristics of anionic polymerisation and
Table 2(b) Ziegler Natta catalyst components
Organometallic compound Transition metal salt
Triethylaluminium Titanium tetrachloride

Diethylaluminium chloride Vanadium trichloride
Diethylaluminium chloride Triacetyl acetone vanadium
Diethylaluminium chloride Triacetyl acetone chromium
Diethylaluminium chloride Cobalt chloride-pyridine complex
Butyllithium Titanium tetrachloride
Butyl magnesium iodide Titanium trichloride
Ethyl aluminium dichloride Dichlorodicyclopentadieny] titanium.
(iii) the catalyst is usually heterogeneous and the reaction takes place on a
solid surface.
The most generally accepted mechanism is shown in Fig. 2.8. The olefin is
believed to first co-ordinate via 7-bonding with vacant d-orbitals on the transition
metal (complex). The availability and stability of these co-ordination sites are
highly influenced by the metal alkyl. In the usually considered monometallic
mechanism, the co-ordination species undergo a cis-rearrangement to provide
stereo-regular placement as well as to create new vacancies in the transition
metal structure, which co-ordinates with the next monomer unit (the propagation
step).
The monomer gets inserted between Ti atom and the terminal C atom in the
growing chain. The polymerisation is thus also called insertion polymerisation.
The extent of stereo-regularity depends on the amount of exposure of the active
sites. At least 98% isotactic polypropylene is formed by the polymerisation at
ambient temperature. Low temperatures favour syndiotactic polymer.
The AI/Ti ratio (in AIR3 and TiCl4) controls the cis- or trans-structure of
polydienes. For example if ratio Al/Ti > 1, 95%, cis-polyisoprene is formed
whereas for the ratio, Al/Ti < 1, 95% trans-polyisoprene is formed. The molecular
weight of the polymer is regulated to some degree by chain transfer by monomer
or with the co-catalyst. Hydrogen is often added in the commercial process for
causing the chain transfer.
A comparison in terms of a schematic representation of propagation steps
involved in free radical, cationic, anionic and co-ordination polymerisations is
given in Fig. 2.9.
2.1.4 Ring Opening Polymerisation

Some polymers can be prepared by reactions involving ring opening. Few typical
examples of monomers for ring-scission polymerisation are lactones, cyclic ethers,
lactams, cyclic anhydrides and N- carboxyanhydrides. Fig. 2.10 illustrates some
useful polymers made by ring opening polymerisation.
The polymerisation of such cyclic compounds can follow the kinetics and
mechanism resembling to both chain polymerisation and polycondensation. For
example, the monomer is added to form a chain (chain polymerisation), the
polymer growth is through step wise addition and thus molecular weight of the
Initiation
R ee oe R, cl
ee ee — = 4 :
(e' cl
tH) R=C3Hs
| Coordination electron
deficient bridge complex
/CHg ve CHs
ie ee eee.
“CH Coe R—CH
: insertion o: p A f is
Al iC monomer wets Ti? —> ar Ti

Cl Cl 10)
Transition state (II)
ring structure Same as [I] with
monomer inserted
Propagation
CH 3 H3C Hi CH
R—CH SGHCH, \R
CH, Ck
Nar’ he, al H,C=CH—CH, Ar Lae insertion of
<a “set” SX Consequent steps as Dae “st” “SX more monomers Stereo polymer
“cl shown between
Iand II ‘Cl
Termination
(i) By an active hydrogen compound
Mt ae ae amin: + R‘'H > Mt—R’ + en Bee coe
(ii) By transfer with monomer

Mt CH,—CH [ CH,—CH],R + HyxC =CH — Mt CH;—CH) + H;C =C +CH,;—CH}-R
\ { { hes |
(iii) By spontaneous internal transfer
Mt Cie CH Ce Cae — Mt—H + H2C nk ee R
x x x x
Mt = Ti, Mo, Cr, V, Ni or Rh
Fig. 2.8 Bimetallic mechanism for Ziegler-Natta polymerisation
polymer increases during the course of reaction (polycondensation). Thus

monomers can be polymerised by different methods. The choice of a particular
method for given polymer synthesis depends upon several factors viz. ease of
method, desired molecular characteristics such as total molecular weight, molecular
weight distribution and type of chain etc.
The polymerisation of ethylene oxide leading to a high mol. wt. polyethylene
oxide (PEO) can be accomplished by different ways.
Free radical:
H a s| H H
WY * ue aN = oo anna c—c&
Wf OX H X
Cationic:
H H H H
www © ae —_— wowwwnC—CO
H 4 H XxX
Anionic:
H H H H
www 2 + Nc£cZ7 — mmm va C— CO
H7 X Xx NX
H Pe
Coordination:
wn.Neg! —. mabe H
H7
H
Xx
H
H
H
x
Fig. 2.9 Propagation steps in different chain polymerisations (* free radical, ®
carbonium, © carbanion, CL) vacancy for a pair of electrons)
nCH,—CH, ——» -¢CH,—CH,—O},
O
Ethylene oxide Polyethylene oxide
NH i
C=O ——» -+NH4CH),CH
Caprolactam Nylon - 6
oO.
m a ) ——> +CH,—O+
O O
ga
Trioxane Polyformaldehyde
oe
%
is 2 ork
Plastic sulfur
2 S S
Sah
Rhombic sulfur
Fig. 2.10 Ring opening polymerisation
The utility of different polymerisation methods is shown in Table 2(c).

Lewis acids provide low mol. wt. polymers while anionic polymerisation
yields high mol. wt. PEO. The three steps of chain polymerisation namely initiation,
propagation and termination are shown in Fig. 2.11.
Basically, polymerisation kinetics suggests that the rate of polymerisation
Table 2(c) Preferred methods of polymerisation of monomers

SS a a ee 2 | ee eee ee eee
Monomers Polymerisation method
Free radical Anionic Cationic Co-ordination

a eh ey ee I
Ethylene ~ + +
Propylene + +
Styrene ent’ 2 + + +
Isobutylene +
1, 3 Butadiene + + +
Isoprene + + +
Vinyl pyrrolidone ~ + oa
Methyl methacrylate + + +
Acrylonitrile + -
Initiation:
H,C—CH, + MtA7 —> A—CH,—CH,—O" M*
‘i Initiator
Ethylene oxide
Propagation: A—CH,—CH,—O-
M* + ee
A—CHy—Chs—-O-—-CH—
CH, —_O7M*
A~CCH)—CH}-0) =|CH)>—CH,—O7M* + HG —CH
A-€CH,—CH ,—O},-CH;—CH,—O" M*
Termination: Many of these polymerisation reactions have the characteristics of living
* polymerisation and thus have no termination step
Fig. 2.11 Mechanism of ring opening polymerisation
will depend on several factors and will also be proportional to the first power-of
the monomer concentration and square root of the initiator concentration. Thus,
doubling the initiator concentration means that the rate increases only by a factor
of 1.4. This has been experimentally confirmed and the detailed kinetics is
described later.
The Gel Effect (Tromsdorf effect, auto-accelaration)

In some polymerisation processes, after a certain percent conversion, the
polymerisation appears to accelerate rather rapidly. This is because of the increase
in viscosity, often leading to gels, which decreases the termination rate constant.
Since the rate of polymerisation is a function of propagation and termination rate
constants, an acceleration effect is observed. This sudden increase in viscosity
particularly in bulk polymerisation some times leads to explosions.
The Chain Transfer

Often the growing chain terminates before it fully grows by interaction with a
small molecule say RH in such a way that a portion of the small molecule
terminates the active chain and at the same time produces a new radical R. The
chain transfer is acommon feature of solution polymerisation. The chain transfer
reaction can be shown as follows.
mawM* + RH > »uMH + R*

The chain transfer can be done by the monomer itself (though difficult as the
removal of hydrogen atom or other atom from the monomer is not easy), through
solvent, from initiator (though insignificant as the concentration of the initiator
is always very low) or from polymer. It can also be intentionally done by adding
substances called chain transfer agents or chain modifiers. The chain transfer
during the polymerisation leads to low mol. wt. polymers (sometimes desirable
and at some other times undesirable). The capability of chain transfer agents can
be expressed as the ratio of the rate constant for chain transfer reaction, K,, to the
rate constant for the propagation reaction, K,, which is called the chain transfer
constant, C,, which is thus defined as C,, = K,,/K,. The chain transfer constant
depends upon the temperature and the nature of monomer being polymerised.
Usually, it increases with increase in temperature. In Table 2(d) are shown chain
transfer constants for polymerisation of styrene monomer.
Table 2(d) Chain transfer constant, C,, of some

solvents for polymerisation of styrene
at 60°C
Chain transfer agent C.,,« 10?
Benzene 0.029
n-Heptane 0.42
m-Cresol 11.0
CCl, 90.0
CBr, 22,000
n-Butylmercaptan 2,10,000
The extent to which the molecular weight or degree of polymerisation decreases

by different chain transfer agents can be examined by measuring degree of
polymerisation or mol. wt. as a function of the concentration of chain transfer
agent. Under the conditions when the chain transfer is due to the chain transfer
agent only i.e. no transfer from the initiator, monomer, or the polymer, the Mayo
equation holds;
1/DP = 1/DPy + C,, - [transfer agent]/[monomer] (2.1)
To determine the degree of polymerisation for a particular monomer in the

presence of varying concentrations of the chain transfer agent, a plot between 1/
DP and [transfer agent]/[monomer] can be constructed (see Fig. 2.12).
A linearly in the behaviour can be seen through Mayo equation. The slope of
the straight line gives chain transfer constant. The values of chain transfer constants
are shown in the parenthesis. It is clear that benzene is not effective as chain
transfer agent whereas butylmercaptan is highly effective.
Butylmercaptan (210000)
CC1,(90)
ec
;
[aw m-Cresol (11)
a
> n-Heptane (0.42)
1 Benzene (0.03)
DPo [Transfer agent]/[Styrene]
Fig. 2.12 Effect of chain transfer agents in the polymerisation of styrene
2.1.5 Kinetics of Free Radical Addition (Chain) Polymerisation

As has been discussed in the mechanism part that the polymerisation is a chain
reaction that involves three steps viz initiation, propagation and termination. In
the first part of the process, free radical is generated from the initiator, which
combines with the monomer generating new free radical. The initiator undergoes
thermal, photo- or high-energy radiation decomposition and produces free radicals
(free radicals can also be generated by chemical reaction). The rate of decomposition
of initiator follows first order kinetics and depends upon temperature and the
solvent. The rate constant for decomposition of initiator varies with temperature
in accordance with the well known Arrhenius equation, K = Ae““®". The rate
constant and energy of activation for the decomposition of two initiators are
given below:
Initiator Solvent Temp., °C K, s! E,, k cal mol"!

BPO benzene 30 4.8 x 10°8 27.8
AIBN benzene 40 5.4 x 1077 30.7
The decomposition of the initiator (/) can be explained as follows:

Considering one initiator molecule decomposing to give two free radicals, the
rate of decomposition reaction can be shown as:
1 “43 2R* (2.2)

and R,=-d{IVat = KA] (2.3)
where / is initiator, R* is free radical generated, K, is the rate (or decay) constant
and R, is the rate of decomposition. The freeradicals so generated attack onto the
monomer, M, and produce a new free radical (initiation step):
R* + M — RM* (2.4)
and R; = — d[M)/dt = d[RM*)/dt = K,{R*][M] 235)
where K; is the initiation rate constant and R; is the rate of initiation. The rate of
initiation is rate controlling step and is related to the efficiency of production of
two free radicals from each initiator molecule. Thus,
R; = 2Kq°f: (1) (2.6)

where f is the efficiency factor and is equal to unity when all the free radicals
generated by the decomposition take part in the initiation. The free radicals can
sometimes recombine and in such a case f may be < I.
The free radical RM* so obtained (by initiation) leads to the chain growth by
combining with more and more monomers. The propagation step is thus a
bimolecular reaction and can consist as many steps with a propagation rate
constant K,, which is independent of chain length:
RM* + M — RMM* (2.7)
RMM* + M > RMMM* (2.7a)
R —M* + M > R—MM* (2.7b)
So, the rate of propagation, R, will be
R, = — d{M)/dt = K, [R—M*][M] (2.8)
or [R—M*] = R,/K,[M] (2.8a)
In the third step, where the termination occurs, e.g. by coupling
R—M* + *M—R — R—MM—R (2.9)

termination rate constant R, is given by
R, = — d|M*—R)/dt (2.10)
= 2K,[M*—R]*
where K, is the termination rate constant.
Using steady state approximation 1.e. considering the rate of initiation equal
to rate of termination, it can be written that
R;=R, (2.11)
or 2KafUl] = 2K,[M*—R]* (2.11a)
or [M*—R] = {Ka +f: VK} (2.11b)
Substituting the [R—M*] value in the equation of propagation rate, propagation
step can thus be written as
R= Kk (fk ays (2.12)

= K[M){1)'”
where K=J[K2 Ky fikgll”
This equation shows the propagation as the first order with respect to monomer
concentration and half order with respect to initiator concentration.
Limitations: The kinetic expression is good for head to tail polymerisation, when
termination is by coupling and when auto-acceleration is absent. The degree of
polymerisation DP can be written as
DP = R,/R; = {K,(M\(Kq° f : (D/K,)""}/2K

(1D (2.13)
= K,(M\/2(Kq: K,- f- )'”)
or = ((M}/[I]"") * (K,/2)(Ka * Ky - f)!?
= (MVE) * K”
where Koh IQGK, Ky fy (2.13a)
Thus, the degree of polymerisation or the molecular weight is directly proportional
to [M] or (1/{1]'”). The characteristic features of free radical addition polymerisation
thus can be summarised as
(i) Rp e<[M] and [1]!?
(i) R, x [1]
(iii) DP <[M] and [/]7'?
(iv) The monomer concentration steadily decreases during the course of
polymerisation and become zero in the end.
Increase in temperature increases the [/] and thus the rate of reactions, but
decreases the average mol. wt. No polymerisation will take place above a certain
temperature called ceiling temperature e.g. this temperature for styrene monomer
is 310°C. The kinetic chain length v is defined as the average number of monomer
molecules consumed by each free radical generated. Thus
v= R,/R;, = R,/R, (2.14)
so v=K,- (KY7/K,")(f >W'71M} - (/Kaf (0) (2.14a)
= K,[MV(2(KaK,
fU)"”) (2.14b)
Thus degree of polymerisation DP = 2v (for termination by coupling) and DP =
v (for termination by disproportion). Table 2(e) lists some of the kinetic parameters
for free radical polymerisation.
Table 2(e) Typical kinetic parameters for free radical

polymerisation
Rate constant Activation energy/k cal mol!
Kgl0 se 30 to 50
K,/10° liter mol! s™! 5 to7
K,/10° liter mol s 4 to 10
K,/107 liter mol! s™! 0 to 6
The chain growth polymerisation, proceeds via contraction of volume and

thus the kinetics can be conveniently examined dilatometrically (a method that
measures the changes in specific volumes). The increase in molecular weight
during the course. of polymerisation can be monitored viscometrically or
turbidimetrically.
2.1.6 Kinetics of Cationic Polymerisation

As discussed in the mechanism part before, the cationic polymerisation begins
when the initiator releases a proton that combines with the monomer in the
initiation step on the polymerisation. Considering BF; as the catalyst and H30 as
the cocatalyst, the different rate equations can be written as:
Initiation: M + H*BF,;0H > HM* + BF;0H™

R; = K;{C"][M], where C = catalyst or cocatalyst
Propagation: R, = K,(M][M"]
The rate depends on the dielectric constant of the solvent. The solvents with
high dielectric constants speed up the rate as this promotes the separation of
carbocation and counterion. The rate is assumed essentially same for all the
propagation steps.
Termination: Re At ag
This first order process simply involves the dissociation of the macrocation-
counterion complex to BF3;, H,O and dead polymer molecule.
Assuming steady state, i.e. R; = R, one can get
K;[C][M] = K,[M*] and [M*] = K,[C][M\/K, (2.15)

The overall rate of polymerisation is thus expressed as
R, = K,[M][M"] = (K,Ki/K){C][M"] = constant [C][M’] (2.16)

DP = R,/R, = K,(M)[M*\/K,[M"] = constant [M] (2.17)
2.1.7 Kinetics of Anionic Polymerisation

Here the propagation species are carbanions as described in the mechanism part.
Considering the polymerisation of acrylonitrile by KNH)
: NH, + CH; =CH—CN > H,N—CH, —CH—CN
the initiation step can be written as R; = Kj[C][M] where [C] = [:NH)]
for the propagation step R, = K,([M][M]
for the termination step R, = K,{NH3][M]
assuming steady state, it can be written as
R; = [R, - M} = (K;/K,) - (C][M\/[NH], (2.18)

thus R, = constant [C][M]*/[NH3] (2.19)
and DP = (constant) {[M]/[NH3]}. It can now be seen that the rate of propagation
and DP are inversely related to the concentration of ammonia.
2.1.8 Phase Systems in Polymerisation (Techniques of Polymerisation)

Based on the different methods of preparation, polymerisation can be classified
as:
Bulk (or mass) polymerisation

Solution polymerisation
Precipitation polymerisation
Suspension polymerisation
|
2
oSEmulsion polymerisation
1. Bulk Polymerisation ‘
The polymerisation reaction is carried out within the monomer itself. The reaction
is catalysed by additives (like initiator, transfer agents etc.) or uhder the influence
of heat or light. Since polymerisation is a highly exothermic process, the process
is difficult to carry out and the polymer obtained is generally of non-uniform
molecular mass distribution. If the polymer is insoluble in its monomer, it is
obtained as a powdery of porous solid. Since the recipe contains primarily the
monomers, the polymer formed is usually pure. Bulk polymerisation on large
scale is carried out with vinyl chloride, vinyl accetate and acrylic esters.
2. Solution Polymerisation
When both the monomer and the polymer produced are soluble in a suitable
solvent, the polymerisation reaction is carried out with the monomer in solution.
Such a polymerisation is referred to as ‘solution polymerisation’ and has the
advantage of easy dissipation of heat evolved as a result of exothermic
polymerisation reaction. The polymers so formed have low degree of branching
and relatively uniform molecular weight, but the disadvantage is that solid polymeric
product can only be isolated in pure form from the solution with great difficulty
or some times not at all. It is because the solvent is occluded and firmly traps the
polymer. For this reason solution polymerisation is mainly applied when solutions
of polymers are required (for ready-made use) for technical applications e.g. as
lacquers, adhesives etc. The products obtained by this method are usually relatively
low molecular weight because of the possibility of chain transfer to solvents.
3. Precipitation Polymerisation
In such a polymerisation reaction, the monomer is soluble in the solvent and the
polymer precipitates out as a result of polymerisation (polymer being insoluble
in solvent unlike solution polymerisation). The so precipitated polymer can be
separated in the form of a gel or powder by centifugation or simple filtration.
Further there is no problem in heat dissipation and the degree of polymerisation
is also hgih. Polyethylene, polyvinyl esters, polyacrylic esters are obtained
commercially using hydrocarbons as solvents. Polyacrylonitrile is prepared using
water as solvent.
4. Suspension Polymerisation (or Pearl. Polymerisation)

In suspension polymerisation, the monomer containing initiator, modifier etc. is
dispersed in a solvent (generally water) by vigorous stirring. For a stable suspension
of monomer in the solvent some stabilisers are added. These may be protective
colloids (e.g. carboxymethyl cellulose, polyvinyl alcohol), finely divided inorganic
solids (e.g. hydroxides of various metals) or surfactants. The polymerisation
takes place within the dispersed (or suspended) monomer particles and the
agglomeration of which is prevented by stabiliser. After the reaction is completed,
the polymer is separated by centrifugation or filtration, washed and dried.
5. Emulsion Polymerisation
In emulsion polymerisation, the liquid monomer is dispersed in an insoluble
liquid, which in turn gives an emulsion. For most of the polymerisation reactions
under this head, the dispersion medium is water. So the monomer-in-water emulsion
(containing catalyst and stabilised by emulsifying agents e.g. surface active
agents) is then used as the polymerising mixture. The events that occur in emulsion
polymerisation are schematically shown in Fig. 2.13.
Monomer drop
Micelle with
solubilized monomer
Swollen polymer
Emulsifier molecule
particle
(or ions) in aqueous
solution
Fig. 2.13 Emulsion polymerisation
A typical recipe for emulsion polymerisation is monomer, water (monomer is

immiscible with water), emulsifier (a surfactant at concentration above critical
micelle concentration) and a water soluble initiator. The monomer, though insoluble,
has some limiting solubility in water. Thus it remains as (i) the large dispersed
droplets stabilised by surfactant adsorption, (ii) solubilized in the hydrophobic
core of the micelle and (iii) in the molecularly dissolved state in water. The latter
is initiated by the water soluble initiator e.g. benzoy! peroxide or a redox system.
Polymerisation thus takes place within the surfactant micelles (size about 10
nm) which grow in size at the expense of dispersed monomer droplets (size
about 1000 nm). In the end a latex (or a polymer colloid) with dispersed polymer
(size about 100 nm) is left.
Once the polymerisation is complete, the polymer can be isolated either by
evaporation of water in a spray drier for example, or by the coagulation of the
polymer latex and subsequent filtration and drying. The polymers of varying
degree of purity are obtained depending upon the finishing treatment; the spraydried
product contains emulsifier, catalyst, modifier and other foreign substances; the
separated product can be washed before drying. The degree of polymerisation is
usually high since there exists only a few possibilities of chain termination of a
growing polymer chain within the micelles. Table 2(f) shows the comparison
between different polymerisation techniques.
Table 2(f) Comparison of various polymerisation techniques
Method Advantages Disadvantages
Homogeneous
Bulk Low impurity level, casting Thermal control difficult
(batch) possible
Bulk Improved thermal control Isolation is difficult and requires
(continuous) devolatilization
Solution Improved thermal control Difficult to remove solvent,
solvent recovery costly and chain
transfer may limit molecular weight
Heterogeneous
Suspension Low viscosity, simple Highly sensitive to agitation rate,
polymer isolation, easy control of particle size is difficult,
thermal control and may yield _ possible contamination by
particles of desirable size suspending agent and washing,
drying, and compaction are
necessary
Emulsion Low viscosity, Good thermal Emulsifier, surfactants and
control, latex may be directly coagulants must be removed and
usable, 100% conversion with high residual impurity level may
high MW at high rates and affect certain polymer properties,
small particle size can be high cost, washing, drying and
obtained. compacting may be necessary.
2.1.9 Industrial Polymerisation

The polymerisation of most of the monomers by using different methods can be
carried out at laboratory scale using simple reaction vessels. These vessels are
usually thick walled standard glass mono, two- and three-necked flasks, and
long tubes etc. At the laboratory scale the monomer concentrations or quantity
taken is very low and hence the elimination of effects due to heat generation,
viscosity build up and heterogenities that are developed during polymerisation
process, is achieved by continuous and controlled stirring. But at Industrial scale
production, the quantity of monomer feed and other reagents are very high. Thus
high viscosities, low diffusivity and large heats produced because of polymerisation
process, are to be considered while designing reactors for large scale polymer
production. The polymer engineer, takes into account the flow rates, temperatures
and composition, while designing the geometry and other requirements of a
reactor.
Reactors
Several types of reactors have been used in polymer industries. Among them
three types of reactors namely batch reactor, tubular-flow reactors, stirred-tank

reactor and cascade reactors are most commonly employed. A brief description
of these reactors is as follows.
Batch Reactor
These reactors are of simplest in design. They are designed such that the reactor
withstands maximum temperature and pressure that can be built up. These reactors
are highly useful, when the polymerisation is conducted batch wise. The reactants
containing monomer, initiator, stabiliser and other chemicals are mixed by agitation
and polymerisation is initiated by applying heat from the external sides of the
reactor. The initial heat generated at early stages of the polymerisation facilitates
the further continuation of the process. The control of heat is achieved by allowing
the refluxing of solvent media. The major disadvantage of batch reactors is that,
termination of a process needs to be done either by quenching the contents or
transferring or pouring the product to other containers before the viscosity of the
system becomes too high.
Tubular-Flow Reactors
The objective of this type of reactors is to provide a progressive flow of the
monomer into the reactor and separating the polmer and un-reacted monomers.
This allows the maintenance of uniform distribution of thermal exposure and
residence times. The operation of such a process is not easy. Usually, radial
mixing and flow redistribution are achieved by number of stationary techniques
such as coiling the tube into a spiral and utilisation of temperature and pressure
gradients that are developed along the tube. Another way of achieving radial
mixing is to use extruders and casting slips. A typical stationary tubular-flow
reactor is shown in Fig. 2.14. This type of reactor is commonly used for
polymerising olefins at high pressures.
Oz
CH, = CH,
2,000 atm
Unreacted
monomer
Polymer
Fig. 2.14 Tubular-flow reactor for ethylene polymerisation
Stirred-Tank Reactor
This type of reactor is sturdy and also known as autoclave. They are designed
mainly to easy and faster dissipation of heat, by initiating the reaction and
controlling the heat by appropriate controlled cooling. The reactor’s design is
such that the monomer feed and other agents are mixed throughout the volume
of the reactor by setting up the agitation system reasonably constant. This minimises
the temperature and composition variation in the reaction media. The yield of
polymerisation is affected when there is a gel formation. Similarly the nature of
mixing affects the molecular weight distribution. It has been shown that when
the life time of a growing chain is long compared to residence time, as normally
observed in step growth polymerisation, the molecular weight distribution achieved
is very broad, even if perfect mixing is ensured. On the other hand when chain
life is short, the distribution is narrowest with perfect mixing. This is especially
true in case of polyaddition reactions employing free radicals.
2.1.10 Thermodynamic Aspects of Polymerisation

Whether a monomer will polymerize or not depends upon polarizability of the
double bond. The symmetrical monomer molecules polymerise with difficulty
(e.g. ethylene). Unsymmetrical monomer molecules polymerise easily (e.g.
propylene, isobutylene and styrene). Monomers with polar substituents polymerise
(e.g. arylonitrile, acrylic acid) readily. A non-polar monomer that polymerises
with great difficulty or even does not polymerise at all may be copolymerised
with a polar monomer. The polymerisation process can be explained
thermodynamically. A process may occur spontaneously at constant temperature
and pressure if the free energy change is negative i.e. the free energy of polymer
is less than the free energy of monomer. The free energy change is given by the
relation, AG = 4H — TAS.
The formation of macromolecules from randomly arranged monomers results
in their ordering i.e. the entropy of a polymer is less than the entropy of monomers.
For most of the chain polymerisations, AS falls in a narrow range of —25 to —30
cal mol”! K7! (thus does not favor polymerisation).
Polymerisation of monomers with double bonds involves breaking up of the
double bond and formation of two single bonds e.g. in ethylene
CH,=CH, —-+CH,-—CH) tr
Now since C=C bond energy is 145.5 k cal mol” and C—C bond energy is
84 k cal mol"!; the enthalpy of polymerisation can be calculated as 145.5 — 2(84) =
— 22.5 k cal mol™!. AH and AS along with the calculated values of free energy
values for several monomers are shown in Table 2(g).
An increase in polymerisation temperature increases TAS term whereas AH
does not change significantly. This decreases the magnitude of AG and at a
certain temperature a condition is achieved when AH = TAS, 1.e. AG = 0. This
means that above this temperature no polymerisation can occur. The temperature
at which AG = 0 is called ceiling temperature 7... Table 2(h) lists the ceiling
temperatures for several commonly used monomers.
For cyclic monomers undergoing ring opening polymerisation, the ease of
Table 2(g) Enthalpy and entropy and free energy of polymerisation of some
monomers at 25°C
Monomer —AH —-AS —AG

k cal mol"! cal mol! k! k cal mol"!
Ethylene 22e) 24.0 15.5
Propylene 20.5 ‘ 27.8 122
Styrene 16.7 25.0 9.2
a-Methylstyrene 8.4 24.8 1.0
Butadiene 17.4 20.5 Wire)
Acrylonitrile 18.4 26.0 10.6
Methyl! methacrylate 13.5 28.0 aye
Vinyl acetate 21.0 26.2 |
geyee)
Tetrafluoroethylene S72 26.8 2972
Table 2(h) Ceiling temperature for common

liquid monomers
Monomer f
bregiel ©
Styrene 310
a-Methylstyrene 61
Methyl methacrylate 220
polymerisation can be explained on thermodynamic basis considering strains in

the rings. The six membered ring systems have’ least strain and hence hardly
undergo ring-opening polymerisation. Whereas the ring systems having other
than hexagonal symmetry have more strain and can be easily opened up. Thus
for non-strained rings, the ring opening has no effect on the change of bonds and
thus AH = 0. Ring opening is accompanied with an increase in disorder i.e.
entropy and for a ring opening, the term TAS = 2.5 k cal mol”!. Since AH = 0,
AG = 0 for non-strained rings, polymerisation is not thermodynamically favored.
However, for strained rings, ring opening is accompanied by energy generation,
thus AH is negative and consequently AG < 0. This means that the polymerisation
of cyclic monomers with strained ring is thermodynamically favored. Table 2(i)
lists the thermodynamic parameters for the different ring systems.
Table 2(i) The thermodynamic parameters for the different ring

systems
No. of carbon atoms in the AH/k cal mol"! AG/k cal mol"!
ring system
3 — 27.0 — 22.1
4 — 25.1 — 21.5
5 — 5.2 —2.2
6 + 0.7 + 1.4
7 — 5.2 -49
2.1.11 Copolymerisation
The process of polymerising two or more than two monomers together is called
copolymerisation. The term copolymer is better referred to addition polymers.
The copolymers often possess the properties shown by the homopolymers made
from the constituent monomers of the copolymer. Instead of searching new
mnomers for the production of polymers to obtain the product with desired
properties, it is often desired to achieve this by copolymerisation using the well
known inexpensive monomers like styrene, ethylene, propylene, butadiene, vinyl
chloride and other common vinyl and acrylic monomers etc. Some very useful
and commercially important copolymers are SBR and NBR—the copolymers of
butadiene with styrene or acrylonitrile. These copolymers are ideal elastomers
and possess properties superior to polybutadiene rubber. Block copolymers of
styrene and butadiene are excellent thermoplastic elastomers.
High impact polystyrene (HIPS) is a similar copolymeric plastic. Copolymer
of butadiene with styrene and acrylonitrile together (ABS) is a useful plastic.
Polyvinyl chloride has high T, and less soluble. This rigid PVC is not useful
when flexibility in the end product is desired. It is for this reason viny! chloride
monomer is copolymerised with small amount of vinyl acetate. Copolymers of
vinyl chloride with vinylidene chloride (Saran—film or filament) and with
acrylonitrile (vinyon, dynel fiber) are well known.
Ethylene copolymerised with propylene (EPM) and with propylene and diene
like butadiene (EPDM) are plastics resistant to oxygen, ozone and heat. Copolymers
of ethylene with methacrylic acid (ionomers) are good transparent adhesives.
However, the properties of the copolymer depend upon the relative amount of
the two monomers present in the copolymer and its type. The kinetics of
copolymerisation is well understood and on its basis one can predict the composition
of a copolymer and its nature when the two different monomers are copolymerised
in different mole ratios in the feed. The kinetics of copolymerisation is described
below:
When two monomers say M, and M) are simultaneously polymerised, both
will from free radical RM; and RM3 as aresult of the initiation reaction between
the initiator free radical, R*. Now there are four propagation steps as described
below which will determine the reactivity of a monomer free radical with the
same monomer or the other.
(i) RM; +M,—> RM,M; [propagation reaction (PR) type 11]

(ii) RM; + M,— RM,M3 [PR type 12]
(iii) RM} +M,— RM,M; [PR type 21]
(iv) RM} +M,— RM)M3 [PR type 22]
Assuming that all the four types of addition take place, the growing chains
ending with My or M3 will have the possibility of all the four types of propagation.
Now, the rates of these four propagation reactions are as follows,
M;+M,> MM; Ry = ky (MFM
M; +M,—> M,M3 Ry = ky2(M7 ][M2]

M3+M,—> MM; Ry, = ko [M3 ][M2]
M3 +M,— M2M3 Ry = ky2 [M3 ][M2]

The basic assumption is that the reactivity of any growing chain depends only
on the end monomer unit carrying the free-radical site and not on the number of
type of monomer units already added to the chain. The rate at which the monomers
M, and M, are consumed during the course of propagation can be expressed as
follows:
— d{M\/dt = ky, (My {My} + ky (M2 1M) ] (2.20)

— d{M)\/dt = ky2[My [Mp] + koy[M3][M] (2.21)
Now, assuming a steady state, wherein the rate of particular chain end (say, M,)
disappearing is equal to the rate of formation of the same chain end, we can write
kyo
My [M2] = ko [M21[M)] (2.22)
[Mi] -_ kilMr] Din
A combination of all the foregoing equations gives the ‘copolymer equation’,
d|M, | m RTT eae (2.24)

d|M, | [My ][M,]
+ (k22/ko1 [M2]
Z [M,] ry[M,] + [M2] 2.24

a LARCARARAGAl iain
The terms k,;/k,2 (denoted by r,) and k22/k2,; (denoted by r,) appearing in this
equation are two important terms, known as the reactivity ratios for any given
pair of monomers M, and M). These ratios (7, and rz) indicate whether a growing
chain carrying a free radical on a particular monomer unit would prefer to add
its Own monomer species or the comonomer species. In other words, the
composition of the copolymer formed at any given instant is dependent not only
on the concentration of the monomer species present in the system at that instant
but also on théir reactivity ratios. The point to be noted is that r; and r, for any
given pair of monomers are dependent purely on the nature of other parameters
such as the solvent, initiator and chain transfer agent. The latter, however, will
have a pronounced influence on the molecular weight and the molecular weight
distribution of the polymer formed. The chemical composition of the copolymer
formed depends exclusively on the monomer concentration and their reactivity
ratios by the equation, which can be rewritten in the following form:
[mm] — (My) |tM) + [M2]

(2.25)
[m2] [M2] |mn[M2] + [Mj]
where [11]/[m] gives the ratio of the monomers M, and Mj entered into the
copolymer formed. If we express the monomer components [m,] and [mz] in

terms of mole fraction instead of molar concentration, the mole fraction of
monomer M, in the copolymer can be given by
[m] dM) =nh= 1 - no (2.26)

[m]
+ [m2] d[M,]
+ d[M)]
where n, and nq are the mole fractiops of monomers M, and M3, respectively, in
the monomer formed. Similarly, the mole fractions of monomer M ; In the monomer
feed can be given by
[M;]
=N,=1-N, (2.27)
[M,] + [M2]
where, N, and N, are the mole fractions of the monomers M, and M3, respectively
in the monomer feed.
Now, the ‘copolymer equation’ can be expressed as,
ry (N,)?
+ N\N>
iy) = — oO, (2.28)
"71 (N,)2 + 2NNo + (No)?
By knowing r, and r, and also the monomer feed ratio, one can easily predict
the instantaneous molar composition of the copolymer formed. There are
experimental methods by which the reactivity ratios can be determined.
Determination of Reactivity Ratios

In order to predict composition of the monomers in the copolymer formed, the
values of r; and r, for a given pair of monomers are required. Experimental
determination of r, and r, can be achieved by copolymerising the two monomers
at different mole ratios to low conversion (upto less than 10%) and then analyzing
the copolymer formed. Low conversion minimises the effect of change in monomer
mole ratio as the copolymerisation progresses.
Either of the following two procedures can be employed to get the reactivity
ratio. In Mayo-Lewis scheme the copolymer equation can be transformed into
the following simple form;
ry = r(A7/B) + [(A/B) — A] (2.29)

where A = [M,]/[M>] and B = [m,]/[m]
Since [M,] and [M)] are known (as taken during polymerisation at varying
concentration) so that several values of A and [m,] and [m ] are determined for
the copolymer formed to give B for corresponding values of A. Now using the
above equation for each set of A and B, giving different values to r, arbitrarily,
the corresponding values of r, are calculated. Thus plotting the r2 on y-axis and
r, on x-axis, a linear plot will be obtained (satisfying above straight line equation).
For different sets of A and B values, different lines will be obtained; each would
intersect at one fixed point. The coordinates of this point will be the actual r; and
ry values for that monomer pair. It is illustrated in Fig. 2.15.
The other procedure is Fineman-Ross method, (see Fig. 2.16) which uses the
copolymer equation of the form,
ry
Fig. 2.15 Mayo-Lewis method to obtain r, and r,
(+)
Fig. 2.16 Fineman-Ross method to obtain r; and r,
(A — (A/B)) = — ry + r,(A7/B) (2.30)

where A = [M,]/[M)] and B = [m,]/[m,] as considered above. Thus a plot between
A — (A/B) versus (A’/B) shown below will be linear with intercept equal to — r,
and slope r}.
The Q-e scheme proposed by Alfrey and Price, established a semi quantitative
relationship predicting the reactivity behaviour of one monomer to another standard
monomer. In this method they considered the resonance stabilisation and
polarisation characteristics of a given monomer. Assume that a monomer M,
adds onto a radical My and the rate constant for the propagation reaction after
the addition can be written as,
ki2 = PQ) exp (— ee) (2.31)

where P, is a factor that characterises the state of the radical My at the growing
chain and Q) is the resonance stability in the structure of monomer Mj i.e.
reactivity measure for M), e; and e, refer to the polarisation characteristics of
monomer M, and Mas well as radicals Mj and M3. The rate of propagation or
addition of a M, to its non radical i.e. k,,; can be defined as
ky; = P,Q exp (— ee) (2.32)

By definition r; = k,;/k,2 and rz = ky2/ky, or
_ PQ: exp —ee; )

ry
~ P,Q> exp (— ee ) Gi?)
thus, r; = Q)/Q» exp [— e,(e; — e2)] andr, = Q,/Q, exp [- e,(e7 — e)].
The value Q; and e; have been assigned to several monomers based on styrene,
which in considered as reference or standard because it has been experimentally
proved that styrene undergoes copolymerisation with most of the other monomers.
Thus, r; and rz values for a given monomer M, and styrene (M>) have been
determined by the methods previously described. Knowing the values of r, and
ry for a given pair of monomer and styrene and assuming standard values of Q
= | and e = — 0.8 for styrene, Q and e values for the monomers have been
obtained by using above given relations. Thus by knowing Q-e values for different
monomer pairs, r, and r, values can be calculated by using the above mentioned
relations. The general conclusions drawn from the Q-e scheme are, (i) monomers
do not copolymerise when the values of Q for individual monomer differ largely,
(ii) when the e values for a given pair of monomer differ widely, alternating
copolymers are formed, (iii) the ideal or azeotropic copolymerisation is achieved
with monomer pairs, when the Q values and e values are roughly equal or
identical. The Q-e values of various monomers are listed in Table 2(j).
Table 2(j) Q-e values for monomers
Monomers 0) e
Acrylic acid Iles 0.77

Butadiene 2.39 -1.05
p-Chlorostyrene 1.03 —0.33
Ethyl acrylate 0.52 0.22
Ethylene 0.015 -0.02
Maleic anhydride 0.23 ILI)
Methyl methacrylate 0.74 0.40
Propylene 0.002 -0.78
Styrene 1.0 —0.80
Vinyl acetate 0.026 —0.22
2-Vinylpyridine 1.30 —0.50
In some simple cases of reactivity ratios, we discuss here how can the copolymer
composition be predicted based on monomer reactivity ratios.
1. When r, =r, = 0. Here reactions 11 and 22 would not occur and therefore
Mf; will react with M, to form M} which in turn would react with M,. Thus
an alternating copolymer would form irrespective of the monomer ratio
taken in the feed.
2. When r; =r, = 1. Here all the four propagation steps are equally possible.
Thus the copolymer formed will have the same ratio as the monomers in the
feed. Thus the copolymer composition can be adjusted by changing the
monomer ratio in the feed. It can thus be said as an ideal polymerisation.
Also, since the copolymer composition is uniform through out the process
and it is called azeotropic copolymerisation.
3. When r, > | and ry < 1. Insuch a case a look into the four propagation steps
will clearly show that the copolymer will be richer in M@,. Furthermore, if
the two reactivity ratios differ much, it would be difficult to incorporate Mj
in the growing chain and the copolymer will essentially be homopolymer of
M,. For the reverse case i.e. when r; < 1 and r, > 1, the copolymer would be
rich in M).
4. Whenr, > 1 andr > 1. In such cases the mixture of two homopolymers can
be expected.
The reactivity ratio for some monomers in free radical polymerisation are
listed in Table 2(k).
Table 2(k) Reactivity ratios for typical monomers employed in free radical
polymerisation
Monomer- 1 Monomer-2 ri 12 iro
Arcylamide Acrylic acid 1.38 0.36 0.5

Acrylic acid Styrene 0.25 0.15 0.04
Acrylonitrile Butadiene 0.25 Os 0.08
Acrylonitrile Styrene 0.04 0.41 0.16
Acrylonitrile Vinyl chloride 3.28 0.02 0.07
Butadiene Methyl methacrylate 0.70 0.32 0.22
Butadiene Styrene 1.39 0.78 1.08
Maleic anhydride Methyl] acrylate 0 Phe) 0
Maleic anhydride Styrene 0 0.02 0
Maleic anhydride Vinyl acetate 0.003 0.055 0.0002
Methyl methacrylate Styrene 0.50 0.50 0.25
Methyl methacrylate Vinyl acetate 20 0.015 0.30
Methyl methacrylate Vinyl chloride | aes 0 0
a@-Ethylstyrene Maleic anhydride 0.038 0.08 0.003
a-Methylstyrene Styrene 0.38 oS 0.87
Styrene p-Chlorostyrene 0.74 1.025 0.76
Styrene Vinyl acetate 55 0.01 0.55
Styrene Viny! chloride 17 0.02 0.34
Vinyl acetate Vinyl chloride 0.23 1.68 0.39
Vinyl chloride Vinylidene chloride 0.3 Din 0.96
2.2 Step-growth Polymerisation (or Polycondensation)

Polycondensation may be described as a simple condensation reaction carried
out repeatedly. For example, polyesterification to get terylene is same as a simple
esterification of an alcohol with carboxylic acid, the equilibrium of which can be
shifted to the ester side by the removal of the by-product water either by simple
distillation or as an azeotrope. However, a polycondensation process differs
from the simple condensation in that the high molecular weight polymer produced
in the former increases the viscosity of the reaction mixture if the polymer is
soluble in it and if not, the polymer precipitates. Thus, powerful stirrers and a
strong polymerisation vessel are needed to accommodate viscous masses.
Polycondensation is a result of reaction between functional groups in bifunctional
monomers e.g. the formation of polyesters by the reaction of diols with dibasic
acids. The low molecular weight intermediates called ‘oligomers’ are first formed.
An oligomer for example in polyesterification can have two terminal—OH groups,
two terminal-COOH groups, or one of each. The hydroxyl groups can react
further with dibasic acid and the carboxylic groups with diol. Alternatively, two
oligomers can condense. The repetition of such reactions yields final polymer.
The polycondensation reaction canbe stopped at any time and low molecular
weight polyesters (hydroxyl or carboxyl group terminated) are isolated. This is
in strong contrast to chain polymerisation in which the reaction cannot be stopped
to get intermediates.
Usually, small molecules like water, alcohol, hydrogen chloride, ammonia,
carbon dioxide are liberated during the course of polycondensation reaction, but
this is not always so. Formation of polyurethane by the reaction between disocyanate
and diol, the formation of epoxy polymers by the reaction of epichlorhydrin with
diol, the formation of nylon-6 from é-caprolactam are the examples of step
growth polymers which do not yield small molecules (the formation of nylon-6
from caprolactam using initiator may well be described as addition polymerisation
process).
In polycondensation, the monomer concentration disappears early in the reaction
because of ready formation of low molecular weight oligomers. The molecular
weight of a given polymer chain increases successively throughout the course of
reaction, and thus long reaction times build up high molecular weight product.
Thus, again in contrast to chain polymerisation, in polycondensation process,
there remains neither monomer nor fully grown polymer after an early stage of
reaction. Instead there is a wide distribution of slow growing oligomers.
2.2.1 Mechanism of Polycondensation

Polycondensation reaction follow essentially the similar mechanism as proposed
in general reactions of functional groups in low molecular weight organic
compounds. For example, nylons, the polyamides do form via a simple SN? type
Lewis acid-base reaction, involving the attack of Lewis base for example a
nucleophilic amine on the electron deficient site of electrophile carbonyl group
followed by a loss of proton. In the process elimination of small molecules
occur. Similarly one can envisage identical mechanism for polyesterification.
The following scheme depicts the mechanism of nylon and polyester formations.
Mechanism of nylon formation
5-
aque | | | |
bangecsye + pee== www RT N—C ow SS ew R—N—Cmw
WH” /> C|
Ho H O
Hf | jot y rw R
wmwR—OL + CR ® | Rv
ee R-O—C— = ow R—O—C—
® |
OH °
|
HOH + *”"R—C—O—Rso === wweR—C—O—Row
2.2.2 Phase Techniques in Polycondensation

The polycondensation involves the reactions of the functional groups and therefore
for the reaction to occur the reactant need to be in fluid phase. This can be
achieved either by melting the reacting monomers (melt polycondensation) or
by dissolving them in a suitable inert common solvent (solution polycondensation).
A third technique is called interfacial polycondensation. This polycondensation
technique uses the solutions of the two monomers prepared separately in
two solvents immiscible with each other. When these two solutions are
brought in contact, the polycondensation reaction begins at the interface separating
the liquids. The three polycondensation techniques are described in the Table
2(I).
2.2.3. Kinetics of Polycondensation

Consider a reaction of two substances each containing two functional groups
(e.g., ethylene glycol and terephthalic acid) to give a polymer,
SA Xb Ve Dat ae A ae ee
Both the monomer are taken in equal molar concentration, and let the initial
concentration of each is Cp. Since the number of functional groups in each
reactant is 2 and therefore if the functional group concentration is expressed as
No, then ng = 2Cp. For kinetic consideration it is assumed that the reactivity of the
functional groups is independent of chain length (i.e. for dimers, tetramers etc.)
and remains same. Now after time fo, if the concentration is C and if p is assumed
as the extent of reaction at time f, then
Table 2(1) Comparison of requirements of different polycondensation techniques

a
ec ee
Requirement Melt Solution Interfacial
i ee ee ee LN
Temperature High Usually up to a temperature below b.pt.
of solvent media or liquid monomers
and up to m.pt. of solid monomers
Stability to heat Necessary 7 Unnecessary Unnecessary
Kinetics Equilibrium, Equilibrium, Non-equilibrium,
stepwise stepwise polyaddition on a
macroscopic level
Reaction time 1 hr. to several Several minutes Several minutes to
days to 1 hr. 1 hr.
Yield Necessarily high Low to high Low to high
Stoichiometric Necessary Less necessary Often necessary
equivalence
Purity of Necessary Less necessary Less necessary
reactants
Equipment Specialized often Simple, open Simple, open
sealed
Pressure High, low Atmospheric Atmospheric
C=C (1 - p) (2.34)
n= nol - p) (2.35)
where n is the moles of functional groups left after time f.
The average DP of polycondensation polymer formed at time ft can be written
as, DP = [initial number of functional groups]/[number of functional groups
after time f]
= ndo/n = [Co]/[C] (2.36)
= [Co]/[Co](1 — p)
= 1/11 —p)
Thus the degree of polymerisation is dependent on the extent of conversion p
and increases as p increases. This equation is known as Carothers equation. The
DP can be seen to vary with p in the following manner.
P 0.50 0.90 0.95 0.99 0.999 1.0

DP 2 10 20 100 1000 eo
The polycondensation reactions may be non-catalysed or catalysed. For non-

catalysed reactions, e.g. of ethylene glycol and terephthalic acid, the acid itself
acts as a catalyst (as well as one reactant). Hence, the polyesterification reaction
rate will be proportional to the square of the concentration of the carboxylic acid
group and to the first power of the hydroxyl group, 1.e.
d[C\/dt = K[X -A - X]*: [Y-B-Y] (2.37)

= K{CP- [cl
as the concentration of acid and alcohol are same i.e. [C],
~ d{C\{dt}* = K{C} (2.38)

or — d{C\/[C}° = Kadt (2.38a)
Integration of the above equation yields
2Kt = I/[C}* — 1/[Co] (2.39)
as [C] = [Co]U — p)
2Kt = 1/[Co]7U. - p)? — 1W{Col* (2.40)
or 2K[C]*t + 1 = 1/(1 — p)* (2.40a)
This equation shows linear behaviour between 1/(1 — p )* and t.
Also, since DP,, = 1/(1 — p) one can get
DP? = 2K[Cy]* + 1
Thus, DP,, appears as the second power and time as the first power. This
means that the polymer molecular weight increases slowly with time. For acid
catalysed polycondensation (e.g. by mineral acids), the following equation can
be written,
— d(C\/dt = K[X —-A - X]|[Y-B-Y] (2.42)
= K{C][C]
= KICy
(the reaction is first order with respect to each reactant)
Upon integration, one gets
Kt = 1/[C] — 1/[Co] (2.43)

or Kt = 1/[Co](Q — p) - IWC] (2.43a)
or Kt[Co] = 1/1 —p)-1
and DP,, = K[{Co]t + 1 (2.44)
These equations indicate a linear relationship between ¢ and 1/(1 — p) and 1/

(1 —p)’. The kinetics of polycondensation can be studied by titrating the unreacted
monomer using a suitable reagent at different intervals of time. Alternatively, the
polymer formed at these time intervals can be precipitated/dried/weighed. Typical
plots of variation of DP with time for catalysed and uncatalysed polycondensations
are shown in Fig. 2.17.
It is important to note that the rate constants for reactions of monofunctional
substance is essentially the same as that for di-functional compounds and, therefore,
these can be used for polycondensation reactions. Also, a similar increase in rate
DP
1/-p)
=
Time Time
Fig. 2.17 Schematic plot of DP versus time for the reaction between ethylene
glycol and terephthalic acid (a) acid catalysed and (b) non-catalysed
polycondensation
constants (obtained from Arrhenius plots) for condensation of mono- and di-
functional compounds are comparable.
Control of Polymer Molecular Weight

As has been discussed before that the polycondensation is a quite rapid process
which proceeds to almost completion, a very high mol. wt. polymer will thus
result. The mechanical properties of a polymer remain almost constant after a
critical mol. wt. and the melt viscosity increases exponentially. The very high
melt viscosity of high mol. wt. polymers offers problems in its processing and,
therefore, polymers with very high mol. wt. are not often desired. Figure 2.18
describes the general variation in the mechanical properties and melt viscosity
with molecular weight.
viscosity
Melt
Mechanical
property
Molecular weight
Fig. 2.18 Variation of melt viscosity and mechanical properties with

molecular weight of polymers
The mol. wt. can however, be controlled by adjusting the concentrations of

reactants (one having a slightly low mole composition as compared to the other)
or by using a small amount of a monofunctional reactant.
The distribution functions, number fractions (i.e. number fraction of n-mer in

the total number of polymer molecules), N,, and weight fraction, W,, for different
values of p and DP are shown in Fig. 2.19.
0.024
25
0.016
0.008
p=0.99
0 50 100 150 200 250 0 50 100 150 200 250

DP DP
Fig. 2.19 Distribution functions (a) number fraction, N, and (b) weight fraction,
W,, as a function of DP at different conversions during polycondensation
The Criterion of Monomer Purity

Most vinyl monomers often contain small amounts of substances called inhibitors,
which are intentionally added to prevent self polymerisation of the monomer
during storage or transportation. Such substances must be removed prior to
polymerisation. It can be achieved either by distilling the monomer or washing
it with dilute alkali solution. The presence of traces of monofunctional or
polyfunctional impurity in the monomers during polycondensation process
drastically influences the DP and should therefore be avoided.
Numerical Exercises
Ex. 1. If M,, for LDPE is 1,400,000, what is the value of DP?
Ex. 2. At the end of the polymerisation of p-hydroxybenzoic acid, IR analysis shows

0.2 mole% unreacted COOH. Calculate the molecular weight and categorise it.
Solution. 99.8% of the COOH is reacted, so the extent of reaction p = 0.998: DP =

1/(1 —p) = 1/0.998 = 500. Repeat unit is -OC,H,CO- and hence its mol. wt. = 180. Hence
mol. wt. of polymer = DP x (mol. wt. of monomer) = 500 x 180 = 90,000.
Mol. wt. calculated is number average type because it is based on the estimation of
reacted functional groups.
Ex. 3. The monomer OH(CH)),4COOH is used to prepare a polymer of number average

molecular mass of 24,000. Neglecting the effect of end groups, calculate the percentage
conversion to polymer necessary to reach this MW.
Solution. The repeat unit is—+- (CH );4,-COO+,, monomer unit mol. wt. = C,5H gO, =
240 g mol"', DP = mol. wt. of polymer/mol. wt. of monomer unit = 24000/240 = 100 DP =
100 = 1/(1 — p) and hence extent of reaction p = 0.990.
Ex. 4. What is the functionality of a mixture consisting of 0.7 mol. of ethylene glycol,
0.05 mol of ethanol and 0.25 mol of glycerol.
(Ans. 2.2)
Ex. 5. What is the M,, of a polymer prepared by the self polycondensation of

HO— > >—cooH, if the 99.5% of the functional groups react.
Repeat unit = (O— <> >—CO), p = 0.995, DP = 1/(1 = p) = 1/(1 - 0.995) = 200, the
molecular weight of repeat unit is 120 and hence the mol. wt. of polymer = 120 x DP =
120 x 200 = 24,000 g mol"!
Ex. 6. The fractional conversion in an ester interchange reaction is 0.99999. What would
be the DP of the polyester produced?
Degree of polymerisation = 1/(1 — p) = 1/(1 — 0.99999)
Ex. 7. If 2% molar excess of bisphenol A is used with toluene diisocynate for making a
polyurethane, what will be the maximum DP obtained?
(Ans. 9)
Ex. 8. An equimolar mixture of two monomers | and 2 is copolymerised. If the reactivity

ratios are r; = 4 and r, = 0.5, calculate the average sequence lengths for residue | and 2:
Here [m,]/[m] = 1
ny = 1+ {r,[m,]/[m2]} "I +r, = 1+4=5
ipa bavi = iG St 10518

Ex. 9. What is the percentage conversion of a monomer OH(CH;),4COOH to a polymer
of average molecular weight 2400? (Ans. 99.0%)
Ex. 10. Determine the degree of polymerisation of a polyester made from equimolar
quantities of PTA and ethylene glycol in the presence of 1.5 mol% of acetic acid for p =
0.999? (Ans. 133)
2.3 Synthesis and Application of Some Common Industrial

Polymers
Polyethylene
The manufacture of polyethylene began around 1930 when ethylene was
polymerised at high pressure (1000-300 atm) and temperature about 250°C
using free radicals. The so obtained polymer was a branched one and had less
bulk density. It was only in 1953, Karl Ziegler polymerised ethylene at pressure
just above atmospheric pressure by using organo-metallic catalysts in conjunction
with transition metal halides. The polyethylene so obtained was a linear polymer
with high molecular weight. The polymer, being linear, is closely packed
(crystalline) yielding dense structure (high density) with a greater rigidity and
higher softening temperature.
Polyethylene is chemically very inert. Both high density and low density
polyethylenes differ in physical properties. The low density polyethylene LDPE
(branched polymer), due to its flexibility, high tensile strength and resistance to
moisture and chemicals is generally used as film or for foil packaging containers
and electrical insulation material as sheathing for wires and cables. The high-
density polyethylene HDPE (linear polymer chain synthesised at low pressures)
with its stiffness and high tensile strength is used for piping, tubing and a whole
range of objectives and vessels.
CH)2=CH, —* -+CH)—CH2t;
Polyethylene
Polypropylene
High molecular weight, isotactic and highly eed polypropylene is generally
similar in properties to high density polyethylene. Isotactic polypropylene is
harder and stronger and softens at about 160°C. The monomer propylene is
inexpensively obtained in large quantities from the cracking of petroleum
hydrocarbons and the high molecular weight isotactic polymers are formed in
the presence of the stereospecific catalysts.
CH; CH;
Ziegler catalyst
sicas 50-120°C
-+CH,—CH+;
Polypropylene
The crystalline polypropylene is about 90-95% isotactic and has high strength,
exceptional flexing resistance to stress cracking. Polypropylene is used in preparing
moulded and excluded articles and films. Copolymerisation of propylene with
ethylene or other monomers is frequently advantageous in order to reduce the
tendency towards the cracking at low temperatures, or to enhance the dyeability
of fibres.
Polyisobutylene
The monomer isobutene is obtained by cracking petroleum hydrocarbons and
can be readily polymerised by cationic process in the presence of acid catalyst,
such as boron tetrafluoride or aluminium chloride.
CH3 ies
AICI
GC - tee
CH3 CH;
Polyisobutylene
Major use of polyisobutylene is as its copolymer with 24% isoprene, which

is known as butyl rubber. For its impermeability to gases and resistance to
ageing butyl rubber is largely used in automobile tires and tubes.
Polystyrene
Styrene is produced by the dehydrogenation of ethyl benzene, which in turn is
obtained by the alkylation of benzene with ethylene as shown in following in
reaction,
CH,—CH3
CH= cH, + O sc @f
Al
Ethylene Benzene Ethylbenzene
Me) so-sure
CH=CH,
Cent
Styrene
Styrene polymerises to polystyrene,
CH=CH) +CH—CH)+;
peroxide
Polystyrene is a hard, transparent, glass like thermoplastic resin. It is

characterised by excellent electrical insulation properties, relatively high resistance
to water, high refractive index, clarity, and low softening temperature. Polystyrene
may also be fabricated in the form of rigid foam, which is used in packaging,
food-service articles and insulating panels.
The high-molecular-weight homopolymers, copolymers and polyblends are
used as extrusion and moulding compounds for packaging appliance and furniture
components, toys and insulating panels.
Polydienes
Butadiene, isoprene, and 2-chlorobutadiene are widely used dienes. Butadiene
can be obained by the thermal cracking of n-butane and also as a by product of
other cracking processes.
eC ie Ce re
CH, CH —_-CH=CH,
1, 3 Butadiene
Isoprene is readily available by cracking processes. Chloroprene is obtained

from acetylene via dichlorobutene as shown below.
2HC=CH “2+ CcH>=CH—CH=CH)

Acetylene 1, 3 Butadiene
|e
Cl vi
|
CH)>=C—CH=CH, <—“ ClCH,—CH—CH=CH)
Chloroprene Dichlorobutene
Butadiene and 2-chlorobutadiene have long been used in the production of

synthetic rubbers by free-radical catalysis.
Special stereospecific catalysts are useful in the polymerisation of butadiene

and isoprene. Natural rubber consists largely of cis-polyisoprene, and is
characterised by high elasticity and low internal friction. The polymers of butadiene
and isoprene formed by free radical polymerisation contains mixtures of the cis
and trans forms together with some 1, 2 or 3, 4 structures in the case of polyisoprene.
The presence of the trans 1, 2 and 3, 4 structures causes the rubber to have a
lower elasticity and high internal friction.
Ca aeaig — seks Tact aaa
R R
1, 3 diene 1, 4 polydiene
R=H, butadiene, R=Cl, chloroprene, R= CH3, isoprene
The copolymer of styrene and butadiene was the major synthetic rubber of
World War II. During 1940s, the redox system for polymerisation was developed
in which the presence of a reducing agent caused the peroxide to yield free
radicals more rapidly at lower temperatures. At the lower temperature used in
redox polymerisation, a more linear copolymer called cold rubber is obtained in
high conversion with improved physical properties. Styrenebutadiene copolymers
are still used for automobile tyres and in various rubber articles. High molecular
weight styrene-butadiene copolymers (containing more than 50% styrene) are
resinous rather than rubbery. The latex as produced by emulsion polymerisation,
has achieved wide usage in water based paints.
Copolymers of styrene with 20-30% acrylonitrile may be used when a somewhat
higher softening point is desired without sacrifice of transparency. By sulfonation
of the copolymer of styrene and divinylbenzene, an insoluble resin is produced.
This product in the form of its sodium salt is employed as a cationic exchange
resin, which is used for water softening.
Blending of polystyrene with polybutadiene gives high impact polystyrene
(HIPS). Other complex polyblends and copolymers of styrene, butadiene, and
acrylonitrile in various combinations (ABS resins) are important. Besides many
applications of styrene in combination with other materials as in rubber and
paints, the homopolymer and the polyblends are employed in the injection moulding
of toys, panels, novelty items and also in the extrusion of sheets. The sheets are
used for panels or they may be further shaped by vacuum forming for uses such
as liners for refrigerator doors.
Polyvinyl Chloride and Polyvinylidene Chloride

The vinyl chloride monomer (VCM) is prepared from chlorine, acetylene and
ethylene by following any of the routes.
Cl
CH,=CH, —— Cl—CH,—CH>,—Cl
Ethylene
Dehydrohalogenation
Cha CHCl. + HCl

Vinyl chloride
HCl
HC=CH ——* CH)=CH—Cl
Acetylene Vinyl! chloride
The polymerisation of vinyl chloride gives PVC
peroxide
nS CH ——+ -CH,—CH}
|
as Cl
Vinyl chloride Polyvinyl chloride
Polyvinyl chloride (PVC) is a tough, strong thermoplastic material, which

has an excellent combination of physical and electrical properties. The products
are usually characterized as plasticized or rigid types. Polyvinyl chloride is one
of the most versatile plastics. The plasticized polymer is somewhat elastic material
and is used in shower curtains, floor covering, rain coats, dish pans, dolls, wire
insulation and films etc.
Rigid PVC is used in the manufacture of photograph records, pipes and
chemically resistant liners for chemical reaction vessels etc. The monomer
vinylidene chloride is normally prepared by the pyrolysis of 1, 1, 2 trichloroethane.
The latter is obtained by the chlorination of 1, 2 dichloroethane which in turn, is
formed by the addition of chlorine to ethylene.
Cl
cl c ly |
CH,=CH, ——> bissaiea2 ——s rare + HCl
Ethyl
id Cpu*Ci Ge IG
1, 2 Dichloroethane 1, 1, 2 Trichloroethane
Heat
CH) = + HCl
Cl
Vinylidene chloride
Polyvinylidene chloride is a tough, horny thermoplastic with properties generally

similar to those of polyvinyl chloride. In comparison with the latter, polyvinylidene
chloride is softer and less soluble; it softens and decomposes at lower temperatures,
crystallises more readily and is more resistant to burning. Because of its relatively
low solubility and decomposition temperature, the material is most widely used
in the form of copolymers with other vinyl monomers, such as vinyl chloride.
The copolymers are employed as packaging film, rigid pipe, as filaments for
upholstery and window screens etc.
Fluoropolymers
Polyvinyl Fluoride
Polyvinyl fluoride is a tough, partially crystalline thermoplastic material, which
has a higher softening temperature than polyvinyl chloride. Films and sheets are
characterised by high resistance to weathering. The monomer is obtained by
catalytic hydrofluorination of acetylene.
HC=CH + HF
HgCl)-BaCl
———— + CH)=CH
[
Acetylene ’ Vinyl fluoride
Polymerisation can be effected in the presence of oxygen and peroxidic catalysts.

Because of the low boiling point (-88°C) and high critical temperature of the
monomer, polymerisation is accomplished by use of pressure techniques similar
to these employed in the high-pressure process for polymerising ethylene.
peroxide
n ipieeerlat a oieeae oe
F 5
Vinyl fluoride Polyvinyl! fluoride
Films of PVF are used in industrial and architectural applications. Coatings

made of PVF for example on pipe are resistant to highly corrosive media.
Polyvinylidene Fluoride
The monomer is prepared by the dehydrohalogenation of 1, 1, 1
chlorodifluoroethane or by the dechlorination of 1, 2 dichloro- and 1, 1
difluoroethane. The polymer is inert and possesses low dielectric constant and
thermal stability (up to about 150°C). It is used in electrical insulation, piping
and process equipment and as a protective coating in the form of a liquid dispersion.
r
-HCI
seails anc OT eae CH)= CF,
FB
F
ay
SP, es Buy aes So aR CH)= CF,
Polytetrafluoroethylene (PTFE)
The monomer tetrafluoroethylene can be polymerised readily and conveniently
by emulsion polymerisation under pressure, using free-radical catalysts such as
peroxides or persulfates. The polymer is insoluble, resistant to heat (up to 250°C)
and chemical attack, has the lowest coefficient of friction of any solid.
Polytetrafluoroethylene is a useful polymer for applications under extreme
conditions of heat and chemical activity. Polytetrafluoroethylene bearings, valve
seats, packagings, gaskets, coatings and tubing can withstand relatively severe
conditions. Because of its excellent insulating properties, it is useful when a
dielectric material is required for service at a high temperature. The non adhesive
quality is often turned to advantage in the use of polytetrafluoroethylene to coat

articles such as nonsticking frying pans and other kitchenware.
Polyvinyl acetate
The monomer vinyl acetate is conveniently prepared by the reaction of acetylene
with acetic acid. Acetaldehyde is produced by the oxidation of olefins or
hydrocarbons. ‘
OCOCH,
Hg2Cl2
HC=CH + CH,COOH ——*> H.C = CH
Acetylene see Vinyl acetate
aci
Vinyl acetate is largely polymerised by emulsion (or suspension) polymerisation.
OCOCHs OCOCHs
CH,>=CH ——~ +CH,—CH}
Vinyl acetate Polyvinyl acetate
Aqueous dispersions (latexes) produced by the emulsion polymerisation are

used for treating textiles and paper, as adhesives and as water based paints. The
water based paints prepared by pigmenting vinyl acetate polymer and copolymer
emulsion achieved wide usage because of low cost, ease of application and
resistance to weathering. As water is removed from the latex by evaporation or
absorption, the suspended polymer particles coalesce into a tough film.
Polyvinyl acetate is a leathery, colourless thermoplastic material, which softens
at relatively low temperatures and which is relatively stable to light and oxygen.
The polymers are clear and noncrystalline. The chief applications of polyviny]
acetate are as binders for water based or emulsion paints.
Polyvinyl alcohol
The monomer vinyl alcohol, HyC=CHOH can not be isolated as it transforms
into the tautomeric acetaldehyde. However, the polyvinyl] alcohol can be produced
commercially from polyvinyl acetate.
OCOCHs OH o
+~CH,—CH}, + H-OH —» +CH)—CH}; + CH3—C—OH
Polyvinyl acetate Polyvinyl alcohol Acetic acid
The hydrolysis of polyvinyl acetate can be controlled to get the product with
different degree of hydrolysis. Highly hydrolysed polymers may be plasticized
with water or glycols and moulded or extruded into films, tubes and filaments
which are resistant to hydrocarbons; these can be rendered insoluble in water by
cold drawing or heat or by the use of chemical cross-linking agents. It is used in
grease resistant coating and paper adhesives, for treating paper and textiles and
as emulsifiers and thickeners.
The partially hydrolyzed products crystallise with difficulty. These materials

are used as emulsifying solutions in adhesive formulations and textile sizes and
in preparation of water soluble films. Polyvinyl alcohol is a tough, whitish
polymer which can be formed into strong films, tubes and fibres that are highly
resistant to hydrocarbon solvents. Although polyvinyl alcohol is one of the few
water soluble polymers, it can be rendered insoluble in water by drawing or by
the use of cross-linking agents.
Polyvinyl acetals
These are relatively soft, water insoluble thermoplastic products obtained by the
reaction of polyvinyl alcohol with aldehydes. Properties depend on the extent to
which alcohol groups are reacted. Polyvinyl butyral is rubbery and tough and is
used primarily in plasticized form as the inner layer and binder for safety glass.
Polyvinyl formal is the hardest of the group; it is used mainly in adhesive, primer
and wire coating formulations especially when blended with a phenolic resin.
Polyvinyl butyral is usually obtained by the reaction of butyraldehyde with
polyvinyl alcohol.
I
-f CH»—CH—CH7—CH+ + C3H7—C—H
a poe Butyraldehyde
Polyviny! alcohol |
Hy —CHy CH + H,O
|
O O
\ a was 4
i
C3H7
Polyvinyl butyral
Polyvinyl pyrrolidone
Polyvinyl pyrrolidone is a water soluble polymer of basic nature which has film
forming properties, strong absorptive or complexing qualities for various reagents
and the ability to form water soluble salts which are polyelectrolytic in nature.
The polymer can be prepared by free radical polymerisation in bulk or aqueous
solution reaction.
lied
CH, C=O ——
Free-radical
"+
iiPibS
i
CH, C=O
mit catalysts os a
| |
CH=CH) ++CH—CH)+;
Vinyl pyrrolidone Polyviny! pyrrolidone
Isotonic solutions of PVP were used in Germany during World War II as

extenders for blood plasma. The main uses of PVP, today however are as solubilizing
agents for water based medicinal formulations such as iodine and as semi-
permanent setting agents in hair sprays. Certain synthetic textile fibres containing
small amounts of vinylpyrrolidone as a copolymer have improved affinity for
dyes.
Polyvinyl ethers
The monomers may be prepared by the reaction of alcohols with acetylene in the
presence of alkali.
OC>Hs
ae at C)H,OH/C,H,OK e se
>= __ —
180°C 2
Acetylene Vinyl ethy] ether
By careful choice of conditions, it is possible to achieve stereoregular

polymerisation, which yields partially crystalline polymers that are tougher than
the amorphous products.
cationic
nCH, =CH —C
2 | initiators £CH2 lAth
OC>Hs OC Hs
Vinyl ethyl ether Polyvinyl ethy! ether
The alkyl vinyl ether polymers are insoluble in water. Copolymers of vinyl
methyl ether with maleic anhydride are useful in textile applications.
Polyvinyl carbazole
Polyvinyl carbazole is a tough, glassy themoplastic with excellent electrical
properties and the relatively high softening temperature of 120—150°C. Its uses
have been limited to small scale electrical applications requiring resistance to
high temperatures.
}
CH=CH)
}
+CH—CH)+,
Vinyl carbazole Polyvinyl carbazole
Polyvinyl carbonate
Vinyl carbonate polymerizes to polyvinyl carbonate, which is a solid polymer
with m. pt. around 200°C. It forms fibers with high tensile strength. Its copolymers
with vinyl chloride or vinyl acetate or vinyl thiocyanate are known. Poly (vinyl
carbonate-co-vinyl thiocyanate) protects tissues from high energy ionising
radiation.
Polyacrylates
Useful polymers are made from a variety of acrylic monomers, such as acrylic
and methacrylic acids, their salts, esters, amides and the corresponding nitriles.
The most important monomers are shown below.
Tot
HoC=C—C—OCH,;
it
H,C=C—C—OC,H; H,C=C—CN
i
Methyl methacrylate Ethyl acrylate Acrylonitrile
Polymethyl methacrylate is a hard and transparent polymer with good resistance

to the effects of light and weathering. It and its copolymers are useful for lenses,
transparent domes, skylights, dentures and in protective coatings.
The monomer is usually made by the dehydration and methanolysis of acetone
cyanohydrin as in reaction,
II Vw
CH. C—CH, CHa
Acetone tis
Acetone cyanohydrin
CH,OH | H,SO,
CH30
[itera]
H,cC=C—C—OCH,
Methyl methacrylate
Polymerisation may be initiated by free radical catalysts such as peroxides, or

by organometallic compounds such as butyl! lithium. The free radical
polymerisation, which is used for commercial production can be carried out in
bulk, in solution, and in aqueous emulsions or suspensions. Depending on catalyst,
temperature and solvent used in polymerisations, isotactic, syndiotactic, or atactic
forms can be obtained. Although solution polymerisation is not commonly used,
bulk polymerisation usually with co-monomers is frequently employed in various
casting operations such as in the formation of sheets, rods, and tubes in the
mounting of biological, textile and metallurgical test specimens and in dental
applications. Solutions of polymethy! methacrylate and its copolymers are useful
as lacquers. Aqueous latices formed by the emulsion polymerisation of methyl
methacrylate with other monomers are useful as water based paints and in the
treatment of textiles and leather goods.
Polyethyl acrylate is a tough and somewhat rubbery material. The monomer
ethyl acrylate is used mainly as an internal plasticizing or softening component
of copolymers. Ethyl acrylate is usually produced by the dehydration and
ethanolysis of ethylene cyanohydrin, which can be obtained from ethylene
oxide.
HyC—CH ei@uy H2C—CH

om
Ethylene oxide
OH CN 4
Ethylene cyanohydrin
C)H;OH |H,SO,
sas |
H,C = C—C—OC Hs
Ethyl acrylate
Modified acrylic resins with high impact strengths can be prepared by blending
with polyvinyl chloride. Copolymers of ethyl acrylate with 2-chloroethyl viny|
ether are useful rubbers. Butyl and octyl esters of acrylic acid are rubbery materials
and when fluorinated have been used as oil-resistance rubbers. Polymers of
alkyl, cyanoacrylates make excellent adhesives. Copolymers of methylacrylate
or acrylamide are water soluble and useful as sizing and finishing aids. Addition
of polylauryl methacrylate to petroleum lubricating oil improves the flow properties
of the oil.
Polyacrylonitrile
The monomeric acrylonitrile can be produced using any of the following methods.
(i) Catalyzed addition of hydrogen cyanide to acetylene
H
HC=CH + HCN “+ H,C=C—CN
2 1
(ii) Reaction between hydrogen cyanide and ethylene oxide
H
|
HyG—CH + HCN ——* H,C=C—CN + H,0
O
(iii) Reaction between ammonia and propylene
2H;C—CH=
CH) + 2NH3 + 30)
Propylene |
H
|
2H»C= C—CN + 6H,0
Acrylonitrile
Polyacrylonitrile (PAN) is largely used in fibers. An acrylic fiber contains at

least 85% acrylonitrile; a modacrylic fiber may contain 35 to 85% acrylonitrile.
The high strength, high softening temperature, resistance to weathering, chemicals,

water, and cleaning solvents; and the soft wool like feel of fabrics have made
PAN popular for many uses such as in blankets and various types of clothing.
Commercial forms of the fiber probably are copolymers containing minor amounts
of other vinyl derivatives such as vinyl pyrrolidone, vinyl acetate, maleic anhydride
and acrylamide.
Copolymers of acrylonitrile with butadiene, often called NBR (formerly Buna
N) rubbers, which contain 15-40% acrylonitrile are well known rubbers. The
NBR rubbers are resistant to hydrocarbon solvents such as gasoline, to abrasion,
and in some cases show high flexibility at low temperatures.
ABS resins are made by blending acrylonitrile and styrene copolymers with
a butadiene-acrylonitrile rubber or by interpolymerizing polybutadiene with styrene
and acrylonitrile. The ABS resins combine the advantages of hardness and strength
of the vinyl resin component on one hand and with toughness and impact resistance
of the rubbery component at the other. ABS resins due to their high impact
strength are used in pipes and sheets for structural uses such as industrial ducts
and components of automobile bodies.
Polyesters
Polyesters are the condensation polymers made by the reaction of an acid and an
alcohol each containing at least bi-functionality. The commonest example of the
polyesters is that obtained from ethylene glycol and terephthalic acid which is
known as terylene, dacron and mylar etc.
Ethylene glycol Terephthalic acid
--O—CH? —CHy—O—¢ ; + H,O

O O
Polyethylene terephthalate (Terylene)
The linear polyester is formed with the release of water. However, in place of
terephthalic acid, its dimethyl ester (dimethyl terephthalate, DMT) is used, as
the former is difficult to purify. The polycondensation between ethylene glycol
and DMT is a kind of trans esterification and in this case methanol is the by
product in the place of water. This polyester, commonly known as PET melts at
around 265°C and is resistant to heat, moisture and chemicals. It has good
mechanical strength up to temperatures around 175°C. PET is extensively used
in fibres (e.g. terycot is a blend of terylene + cotton). Ethylene glycol is obtained
by the oxidation of ethylene while terephthalic acid by the oxidation of p-
xylene.
CH2z=CH, ——~ HO—CH7—CH»7—OH

Ethylene Ethylene glycol
yA
HCO) cH —»> HO—C COn

I |
p-Xylene O O
Terephthalic acid
Branched and cross-linked polyesters are obtained if small amount of a

polyhydric alcohol is used. For example, alkyd resins called glyptals form when
glycerol (trifunctional monomer) is’ used. Glycerol needed is manufactured by
the catalytic hydroxylation or hypochlorination of allyl alcohol. The latter is
produced from acryldehyde (acrolein) which is obtained by the oxidation of
propylene. Glycerol is also obtained as the byproduct during soap manufacture.
Unsaturated polyesters
Linear unsaturated polyesters often called prepolymers are obtained when the
dicarboxylic acid used is unsaturated e.g. maleic acid or its anhydride. These
polyesters may be dissolved in styrene and used as cross-linked resins for the
production of fibrous glass reinforced plastics. Maleic anhydride is a by product
of phthalic acid manufacture by the oxidation of xylene. It can also be obtained
by the oxidation of benzene and by the vapour phase oxidation of crotonaldehyde
or butene.
Polyamides
Commercially useful polyamides are made by the reaction of dicarboxylic acids
with diamines. The most common commercial aliphatic polyamides known by
the generic name nylons are nylon 6, 6; nylon 6; nylon 6, 10; nylon 11 and nylon
£2;
Nylon 6, 6 is prepared by polycondensation reaction of hexamethylenediamine
(6 carbon atoms) with adipic acid (6 carbon atoms). By heating equimolar
proportions of the two reactants, a polymeric salt is formed.
n HO—C-(CHy)C—OH + n H)N+CH3};,NH)
O O
Adipic acid Hexamethylene diamine
[N*Hs-€CH2)5 —N*H30"—C-(CHz},C—O] A*
O O
Nylon 6, 6 salt
ee HIN-(CH},NH—C-4CH2), i +H)0
fe) O
Nylon 6, 6
The starting material adipic acid is manufactured from benzene. Oxidation of

benzene gives cyclohexane, which oxidizes to cyclohexanone. It on further oxidation
by 50% HNO; at 55°C undergoes ring scission and produces adipic acid. The
other monomer hexamethylenediamine is obtained from the reduction of
adiponitrile or adipamide.
Nylon-6 can be obtained by the self condensation of €-aminocaproic acid.

Nylon-6 can also be produced by the polymerisation of the lactam of €-
aminocaproic acid. The lactam process is generally preferred for commercial
operation because it is easier to make and purify the lactam than the € -aminocaproic
acid.
HaN{ CH C— OF =" EHN(CHsCh
O
€-Aminocaproic acid Nylon-6
NH
C=O ie THN HN-(CH>}='C--

(CHS C4,
\ Trace H,O catalyst
= Sgae erFa pana
O
Caprolactam Nylon-6
The monomer caprolactam is prepared by the following synthetic route,
OH O
i i es
N—OH
NH
iaet) Beckmann
rearrangement
Caprolactam
Nylons are strong and tough materials. Their mechanical properties depend
on the degree of crystallinity. Because of good mechanical properties and
adaptability to both moulding and extrusion, nylons are often used for gears,
bearing, and electrical mountings. Nylon bearings and gears perform quietly and
need little or no lubrication. Nylon resins are used extensively as filaments,
bristles, wire insulation, appliance parts, and film. Reinforcement of nylons with
glass fibers results in increased stiffness, lower creep and improved resistance to
elevated temperatures. The aromatic polyamide (aramides) e.g. one prepared
from terephthalic acid and 1, 3 phenylene diamine (known as kevlar) have very
high melting points and are thus used in places where this property is desired.
Polyimides
Polyimides are polymers that can withstand high temperature (~ 425°C).
Pyromellitic anhydride and p, p’ diaminodiphenyl ether, for example on
polycondensation in dimethylformamide produces polyimide. The process involves
two stages. The first stage gives polyamic acid at around 50°C.
O O
| |
COL > om -O-G-=

gu Sips
b Lh |
1
Io G)—oG)-
ope.
Polyamic acid
Polyamic acid film on heating to 300°C in nitrogen atmosphere result into

polyimide by the removalof water molecules.
Polyimide
Polyamides are extensively used in electrical industries and in suspersonic

aircraft coating materials.
Polyformaldehyde
Cationic polymerisation of formaldehyde or trioxane gives polyformaldehyde.
The polymer is highly unstable and depolymerizes to monomer and therefore
has to be stabilised. It’s high m. pt. (185°C) and fibrous character (SO-80%
crystallinity) makes it useful as an engineering plastic.
| BF,/H,O
H-C-H —++ HO+CH)—0).H
CH>-—@G
We : > HClO,
CH, ———_ HO-€CH>—
0}, H
\cu,—0
Phenol-Formaldehyde Resin
This important thermosetting resin was first developed by Henry Baekelund and
is knownas bakelite. It is formed by the condensation of phenol with formaldehyde.
There are two reactions for the formation of the resin. The intial reaction is the
introduction of amethylol group (-CH,OH) at the ortho- and para-positions of phenol
by condensation of formaldehyde with phenol in the presence of a basic catalyst.
7 cHAOH
+ H—C—H —~>
o - Hydroxy benzyl
alcoho! CH20H
p - Hydroxy benzyl
alcohol
The second primary reaction is the condensation of the methylol group with
other molecule of phenol at its ortho- or para-positions.
OH OH HO OH
CH OH hoe
+ wa
OH
HO
The phenolic resins for moulded products are usually prepared by a two stage
process. The initial process is the condensation of formaldehyde with a slight
excess of phenol in the presence of an acid catalyst. This reaction produces
linear thermoplastic polymer, which is known as novolac. Novolacs contain no
methylol groups and probably have the diphenylmethane type of structure.
The monomer phenol is manufactured from benzene (Raschigs process) or
from isopropylbenzene (Cumene process).
OH OH OH OH
t CH) CH) CH) CH)
+ H—C—H ——~
Novolac
ASS
BEMBr
Novolac ial
Bakelite
The second stage is the reaction of novolac with more formaldehyde in the
presence of a basic catalyst results in a hard infusible thermoset resin called
bakelite.
Urea-Formaldehyde Resin
Urea reacts with formaldehyde under slightly alkaline or neutral conditions to
give compounds known by their trivial names such as monomethylolurea and
dimethylolurea depending upon the ratio of the two reactants.
HIN—C—NH, + H—C—H
7 NC
| |
sal ee a a ee ae
OH O OH O OH
Monomethylol urea Dimethylol urea
These further condense with urea to give final resin in the following manner,
BON HORT
C=O + C=O
HN (hi HOH,CHN”
HOH,CHN\ | |
C=O + H,0 andsoon
H)»NOC—NHCH>NH io
or $
n HCHO + n NH>CONH, ——> H-[NH—CO—NH—CH>}_OH

The hydrogen atoms in the imide group in this linear polymer can be further
replaced with methylol groups by using excess of formaldehyde to finally form
a cross-linked resin. Polymeric resins are then formed as a result of
polycondensation. The monomer urea is prepared by the reaction of carbon
dioxide with ammonia.
Melamine-formaldehyde resin
Melamine and formaldehyde react to give hexamethylol-melamine, which on
heating in presence of acids gives cross-linked polymer called melamine resin.
The resin is resistant to heat and moisture and is used in making dinnerware and
decorative table tops (Formica). The monomer melamine is prepared from calcium
cynamide.
NH) NHCH20H
<5 “a
“i lg ¢bSGICHO! seb le A
H>N~ Sn~ SNH) HOH,CHN~ Sj~ “NHCH>OH
Melamine Methylol derivative
The methylol derivative is further condensed with melamine to give a linear

polymer. The latter when reacts with excess of formaldehyde produces a cross-
linked melamine-formaldehyde resin.
NHCH)NH™™ NHCH NH
KA
N~ “N
|
HNH>,CHN Ay HNH ,CHN
NS mit
N~ “N
we le
N
ye N
swe HNHCHN AY zh NHCH,NH™
Polyurethanes
Polyurethane (or polyisocyanate) resins are produced by the reaction of a
diisocyanate with a compound containing atleast two active hydrogen atoms
such as a diol or diamine. Toluene diisocyanate (TDI) is most frequently employed.
The diisocyanates are prepared by the reaction of phosgene with the corresponding
diamines.
CH3 CH3
NH) NCO
+ Sea ——- + 4HCl
O
NH} NCO
2, 4 Diaminotoluene Phosgene 2, 4 Toluenediisocyanate
Linear and fiber forming polymers are prepared by the addition of diisocyanates
to diols while cross-linking is made possible by the use of polyols or isocyanates
having more than two functional groups. Resins can be produced in different
forms varying from hard, glossy, solvent resistant coatings, to abrasion and
solvent resistant rubbers, fibers, and flexible to rigid foams. The polyurethane
foams or U-foams have found the widest use. The more flexible foams are
employed as upholstery material for furniture, insulation and crash pads. The
more rigid foams are employed as the core material in structural and insulating
laminates and as insulation cover in refrigerated appliances and vehicles.
The flexible polyurethanes may be used for coating rubber articles to give
them additional resistance to abrasion and solvents. Wire insulated with
polyurethane resin can be soldered directly. Among these various applications,
the uses of the foamed products developed is extensive because their density and
flexibility can be varied easily and they have good resistance to ageing by
solvents.
Polyureas /
Polyureas are polyamides of carbonic acid and contian -NH CONH—as a part of
repeat units. These can be obtained by the reactions of diamines with diisocyanates.
H»N—{CH3)¢NH> + OCN {O)}-nco

De SER eae CH;
| 2, 5 Toluenediisocyanate
{CH jgNH—C-—NH vac}

n
CH, O
Polyureas have higher melting points than the corresponding polyurethanes
and polyamides.
Polysulphides
Alkyl dihalides on reaction with sodium polysulphides produce polysulphide
elastomers commonly known a thiokol rubbers,
jana + NajS, ——» —CH,—CH)—S,
3,+ NaCl
CCl
Polysulphides have excellent oil resistance and low permeability for the gases.
These are mainly used to make sealants, balloons and gaskets etc. Polysulphides
on mixing with inorganic oxidisers (e.g. ammonium perchlorate) function as
solid propellants for rockets.
Polethylene Glycols
Polyethlene glycols can be obtained by self polycondersation of ethylene glycol.
The same polymer, usually with high mol. wt. when obtained by ring opening
polymerisation of ethylene oxide is called polyethylene oxide. These are water
soluble as well as soluble in inorganic solvents. PEGs of different molecular
weights are waxy solids commercially known as Carbowax. These are widely
used in cosmetics, textile and pharmaceutical industries.
Polyparaphenylene
Polyparaphenylene can be obtained from dibromobenzene, which on reaction
with activated copper powder at high temperature yields the polymer.
BO) Bre Cu Koy + CuBr>

n
Due to the rigid backbone made of aromatic rings, the polymer is very bittle,
insoluble and can withstand temperature upto 550°C.
Polysulphones
These are the polymers which contain sulfone groups in the chain, as well as a
variety of aromatic or aliphatic constituents such as ether or isopropylidene

groups.
CH3
n(NaO 4O-¢ <O)- ONa)
co,
oO) Ora
+
O
h=—
=
{O-O-°-O--O}
CH3 = O
CH b
Polysulfones based on aromatic backbone constitute a useful class of engineering
plastics owing to their high strength, stiffness, and toughness together with high
thermal and oxidative resistance.
Polyethers
Polyethers of polyoxyethylene like polyethylene oxide and polypropylene oxide
are well known in detergent industries. The monomers ethylene oxide and propylene
oxides are made from ethylene and propylene, respectively.
Cpa — HO}
CH; CH;
CH; CH,
Polyphenylene oxide is produced by the oxidative coupling of 2, 6 disubstituted

phenols and is used in making airline beverage cases, solar energy collectors and
window frames. Polyphenylene oxide is a high temperature resistant polymer.
Epoxy Resins
These resins are commercially known as araldite and epon and can be made by
the polycondensation of epichlorhydrin with bisphenol A.
Epoxy prepolymers are cured by alkylene polyamines or cyclic anhydrides to
give curved epoxy resin. These are widely used for moulding, laminating and
surface coating resins. The monomer epichlorohydrin is prepared by the
dehydrochlorination of glycerol.
™
4
Ho {O)-¢-{O)-on WAC et eel FC

| Rea
CH; O
ie
fo-OLO cover
CH; 2
Polyetheretherketone (PEEK)
It is a polymer with a T, of 145°C with the following repeat unit. It finds use as
blow moulded containers for nuclear waste, printed circuits, electrical applications
and wire coatings.
to
6-6 O
| oe
C
n
Silicones
These are the polymers of silicon and constitute a very interesting class of
commercially available products with wide range of materials as oils, greases,
plastics, elastomers and resins. These are discussed in detail in chapter 7.
Polyphosphazenes
Polyphosphazenes are also inorganic polymers containing nitrogen and phosphorus
and find several biomedical applications. These are described separately under
the heading Inorganic Polymers (see chapter 7).
Suggested Questions
1. Distinguish clearly addition polymerisation and polycondensation reactions. Give

the names of 5 commercial polymers each made by addition polymerisation and
polycondensation. Write the structure of monomers and the repeat units in polymers
in each case.
2. Write a detailed account on mechanism of polymerisation. Name initiators used
in free radical/ionic and co-ordination polymerisation. Explain initiation,
propagation, termination and chain transfer steps.
3. Write mechanism of Ziegler Natta polymerisation. How is the growing chain
terminated? Why are stereo-regular polymers are obtained from it? Write different
isomeric forms of polypropylene and polyisoprene.
4. (a) Describe kinetics of chain polymerisation by free radicals. Obtain expression
for rate of polymerisation and degree of polymerisation. (b) Describe mechanism
of cationic polymerisation. Derive an expression for rate of polymerisation. (c)
Name some catalysts for cationic polymerisation. What are its characteristic
features?
. Describe various phase techniques used for polymerisation. Mention merits and
demerits of each of the technique. Which type of polymers are obtained by bulk,
solution, emulsion and suspension polymerisation? Give two examples for each.
What are polycondensation reactions? How are polyurethane, epoxy-polymers,
polyester, polyamides, polysulfide, alkyd resins synthesised? Give only the names
of monomers used.
Write a detailed account on polycondensation reactions describing mechanism.
Describe the kinetics of catalysed and non-catalysed polycondensation.
(a) What are copolymers? Obtain expression for the kinetics of copolymerisation.
How does the reactivity ratio of monomers affect the copolymerisation reactions?
Explain what do the following abbreviations stand for, (a) SBR, Buna N, ABS
resin and HIPS, (b) What is Copolymerisation? Give some examples of useful
copolymers and mention their advantages over the constituting homopolymers.
What are different types of copolymers? Explain each one. (c) Discuss various
copolymers of styrene. Mention their properties and applications, (d) Describe
the methods for the determination of reactivity ratios in general and Q-e scheme
of Alfrey and Price in particular.
What are block copolymers? How are they synthesised by anionic polymerisation?
Write various heterogeneities that exist in block copolymers. Describe their solution
behaviour and solid state properties. Give various applications of block copolymers.
Explain the mechanism of emulsion polymerisation. Which polymers are usually
obtained by this technique?
. Name two initiators for each; anionic; cationic and free radical polymerisation.
Show how do they generate ions/radicals.
. Identify all the possible structural and stereoisomers that can result from the
addition polymerisation of chloroprene.
. Mention three examples of ring scission polymers. Write their names and structure
of monomers and repeating units.
Write the synthetic routes for the following condensation polymers; (a)
Polyurethanes, (b) Polycarbonates, (c) Epoxide resins, (d) Alkyd resins (e)
Melamine-formaldehyde, (f) Polyethylene terephthalate, (g) Nylon 6, 6, (h) Nylon
6, (i) Polyphenylene, (j) Polyphenylene oxide, (k) Thiokol rubber.
. Show the condensation reaction steps between phenol and formaldehyde resulting
to novolac, resole and resitole. How can the bifunctionality in phenol and
formaldehyde be ascertained?
16. Answer the following; (a) explain the dependence of mol. mass of the polymer on
initiator concentration, (b) explain the dependence of kinetic chain length on
initiator concentration, (c) explain the dependence of rate of polymerisation on
initiator concentration.
we Give an account on thermodynamics of polymerisation.
18. Define the terms “Ceiling temperature” and “Floor temperature”. Why do these
definitions generally apply one to closed systems?
19. Which cyclic monomers are easily polymerised? A three membered or six membered
ring compound. Give reasons.
20. Comment on (i) why does anionic polymerisation result to a polymer with low
polydispersity? (ii) why is a minimum bifunctionality in the monomers necessary?
dhMe Show the formation of anion from naphthalene/sodium. How does anionic
polymerisation of styrene proceed?
Liles Explain the term “Inferfacial polycondensation”. Give an example of a polymer
made by this process.
23. Write short notes on (a) ring opening polymerisation, (b) coordination
7
polymerisation, (c) precipitation polymerisation, (d) plasma polymerisation, (e)
photopolymerisation, (f) living polymerisation, (g) Trommsdorf effect, (h)
telomerisation, (i) redox polymerisation, (j) chain transfer, (k) inverse emulsion
polymerisation.
24. Construct tables to show clearly the comparison in (a) bulk, solution, suspension
and emulsion polymerisation, (b) addition and step polymerisation, (c) free radical,
anionic and cationic polymerisation (d) melt, solution and interfacial
polycondensation é
25. Comment on: (a) Living anionic polymerisation yields polymers with low
polydispersity and tailored block copolymers, (b) Micelles but not dispersed
monomer droplets are the centres where polymerisation takes place in emulsion
polymerisation, (c) Polyvinyl alcohol is not made by the polymerisation of vinyl
alcohol but is made by the hydrolysis (or alcoholysis) of polyvinyl acetate, (d)
Free radical polymerisation of ethylene is more easier than that of polyisobutylene.
26. In the monomer R-CH = CH, if R is an electron donating group, cationic
polymerisation is favoured whereas for R is an electron withdrawing group anionic
polymerisation is favoured. Why?
27. Discuss the manufacturing process of: (a) HDPE, (b) stereoregular polypropylene,
(c) nylon 6, (d) polyimides, (e) carbon fibres
28. Show using chemical equations how the following monomers are synthesised
industrially: (a) hexamethylene diamine, (b) toluene diisocynate, (c) vinyl chloride,
(d) w-caprolactam, (e) adipic acid, (f) bisphenol-A, (g) phenol
29. Show the mechanism of generation of free radicals by the decomposition of
following initiators: (a) Benzoyl peroxide, (b) azobisisobutyronitrile, (c) persulphate
and (d) Fe*?/H,O,
30. Define the following terms: (a) Functionality of monomer, (b) degree of conversion,
(c) kinetic chain length, (d) initiator efficiency, (e) branching coefficient.
31. How are the following polymers made? Write the chemical equations: (a) carbon
fibres, (b) polyimides, (c) polyvinylbutyral and (d) cross-linked polystyrene
sulphonate.
General Fundamentals:
Allen, P.E.M. and C.R. Patrick, Kinetics and Mechanism of Polymerisation Reactions,
New York: Halsted-Wiley, 1974.
Brunnelle, D.J. (Ed.), Ring-Opening Polymerisation, Munich: Hanser, 1993.
Elias, H.-G., Macromolecules, Synthesis, Materials and Technology, 2nd ed., New York:
Plenum, 1984.
Erunsalimskii, B.L., Mechanisms of Ionic Polymerisation, New York: Plenum, 1986.
Kucern, M., Mechanism and Kinetics of Addition Polymerisation, Amsterdam: Elsevier,
1982.
Leng, R.W., Organic Chemistry of Synthetic High Polymers, New York: Interscience,
1967.
Odian, G., Principles of Polymerization, 3d ed., New York: Wiley, 1992.
Remp, P., E.W. Merrill, Polymer Synthesis, 2d ed., Basel: Hultig and Wept, 1991.
Free Radical Polymerisation:

Eeisenberger, J.A., D.A. Sebastian, Principles of Polymer Engineering, New York: Wiley,
1983.
Blackley, D.C., Emulsion Polymerisation: Theory and Practice, New York: Halsted, 1975.
Cationic Polymerisation:
Natyjaszewski, K., (ed.), Cationic Polymerisation, New York: Dekker, 1996.
Coordination Polymerisation:
Frink, G., R. Mulhaupt, H.H. Britzinger, (eds.), Zeigler Catalysts, Berlin: Springer, 1995.
Kissin, Y.V., [sospecific Polymerisation of Olefins, Berlin: Springer, 1986.
Copolymerisation:
Ham, G.E. (ed.), Copolymerisation, New York: Interscience, 1964.
B
Polymer Analysis and Characterization
3.1 Identification
Synthetic polymers are widely used today as plastics, rubbers, fibers, adhesives
and surface coating materials with or without trade names. It is important to
identify the polymer in a commercial product. After the polymer is identified
and analyzed, its physical characteristics in general and molecular weight (MW)
and molecular weight distribution (MWD) in particular are to be determined.
The knowledge of the last two parameters is highly essential because they greatly
influence the physical properties of the polymers. Table 3(a) describes important
parameters that need to be determined for the total analysis and characterization
of polymers either in their virgin form or in an end product form.
Table 3(a) Parameter for the analysis and characterization of polymers
Structural parameter Information obtained
Chemical composition Homopolymer or copolymer, percentage of the monomers

and their arrangement in the compolymer
MW and MWD Number and weight average mol. wt. and thus the
polydispersity index
Stereochemistry Microstructure, cis/trans, isotactic/syndiotactic/atactic
Topology Linear/branched/cross-linked
Morphology Structure in solid state, crystallinity and crystallizability
Miscellaneous Identification of additives present
The following discussion concerns with the analysis and characterization of

the polymers. The analysis of the polymers mainly involves the physical and
spectral identification of either (virgin) polymers or a polymer in end-use or
finished product. Besides this examination and isolation of polymers, they are to
be characterized for the type of molecular weight distribution present and evaluation
of their total molecular weight. One is always confused with words analysis,
identification, testing and characterization as applied to polymers, because all
these attempts are based on measuring either some property or monitoring the .
behavior of polymers. This discussion on individual properties such as solid
state or solution state is closely linked to the analysis of polymers. One more
difficulty associated with the analysis of polymers especially in finished products
is the presence of additives, which can interfere with the methods used and
hence the results of analysis. Similarly, other factors such as solvent quality,
temperature, concentration and other conditions such as moisture and humidity
have large effects on a given measurement. Thus one should be cautious in
drawing conclusions. ;
3.1.1. Physical Testing

It involves the examination of polymer material for knowing about its appearance,
feel, hardness and density and monitoring the effects of heat, combustion and
solubility etc. A very quick guess can be made using the foregoing statements.
Pure polystyrene, polymethyl methacrylate, polycarbonate are transparent polymers.
Teflon is milky opaque. A light colored material can not be a phenol-formaldehyde
polymer. Polyetheylene and polytetrafluoroethylene have soft waxy feel. Rubbers
and thermophlastics like polystyrene, PMMA, polyethylene, PVA, PVAc are soft
enough to be scratched by a nail. A sharpened knife gives a soft cut to thermoplasts
but a hard cut to thermosetts. Elastomers like natural rubber, SBR, butyl rubber,
nitrile rubber are compressible and can be stretched.
Polymers such as polyethylene (both LDPE and HDPE), natural rubber have
density less than 1 g/cm? and float over water surface. The density of
phenolformaldehyde, PMMA, PVC, polyvinyl acetate, polystyrene ranges between
11.34 g/cm? and these polymers sink in water but float over saturated magnesium
chloride solution. PVC, UF resin, cellulose nitrate/acetate possess density around
1.5—2 g/em? and sink even in saturated magnesium chloride but float over saturated
ZnCl, solution. PTFE and urethane polymers have density more than 2 g/cm’,
Linear polymers melt on heating. Thermosetts are infusible plastics. Polyethylene
and polypropylene burn like a wax candle. PVC and PVDC are self-extinguishing.
Polystyrene burns with a sooty flame. Acrylic polymers are hard to decompose
and burn slowly. Polyesters burn with smoky flame, melt and darken. Nylons
also melt and darken.
Chemical tests for the detection of elements like nitrogen, sulphur and halogen
(as done in organic qualitative analysis) using sodium fusion extract can be
conducted to ascertain the presence of these elements and their proportion.
Solubility of a polymer in different solvents can provide some definite clue to
identify it. The general behavior ‘like dissolves like’ is followed by polymers.
Usually, a polymer whose solubility parameter value is close to that of a liquid,
will dissolve in that liquid. The solubility parameter concept will be discussed in
detail while discussing the polymer solutions. Table 3(b) lists the solubility
parameter values for some common polymers and solvents.
Cross-linked polymers do not dissolve in any solvent and may swell only to
a limited extent. Crystalline polymers are often soluble at temperature above
their melting temperature, T,,,, or in strongly interacting solvents i.e. good solvents.
Thus, polyvinyl alcohol, polyethylene oxide, polyvinyl pyrrolidone, polyacrylic
acid with polar pendant groups are soluble in water. Polystyrene, polyolefins etc.
dissolve in hydrocarbon solvents. Nylons, which have strong intermolecular
Polymer Analysis and Characterization 87
i
Table 3(b) Solubility parameters of some common

polymers and solvents
Polymers/Solvents Solubility parameter, H
Polystyrene 91
Polypropylene SR
IENKE ‘ 97
PMMA DE
PET 10.7
Nylon 6, 6 13.6
Acetone 10.0
CCl, 8.6
Cyclohexane See
Dioxane 05
Chlorobenzene Of
Diethy] ether 7.4
n-Hexane Thee
Acetonitrile 11.9
DMF 1A
Xylene 8.3
Pyridine 10.7
hydrogen bonding (which imparts crystallinity) dissolve in strongly interacting

solvents like phenols, conc. H,SO4,.
Table 3(c) and 3(d) provide some important information about the physical
properties of polymers useful in their identification. The test methods that can be
used for identifying and characterizing the polymers or polymeric materials are
mostly based gn the measurements of either typical responses shown by them to
a given condition or by measuring literally all the physical properties which may
include thermal, electrical, crystallinity and mechanical properties. In fact the
Characterization of polymers is mainly based on the structure-property relationship.
Following tests based on mechanical property measurements are routinely doen
to predict the performance of polymers and these can also be used to identify and
characterize them. These tests are briefly described below:
Tensile Strength
It measures the ability of a polymer to withstand pulling stresses. It is usually
determined by pulling a dumb-bell shaped specimen of the plastic. The ultimate
tensile strength is equal to the load that caused failure divided by minimum
cross-sectional area (ASTM D638).
Flexural Strength
It is a measure of the bonding strength or stiffness of a test bar specimen used as
a sample beam. The flexural strength is based on the load required to rupture a
sample beam before its deflection is 5% (ASTM D790).
Impact strength
It is a measure of toughness or ability of a specimen to withstand a sharp blow
Table 3(c) Physical properties of polymers and their possible identity
Type of Observation Possible identification of polymer

measurement
1. Appearance transparent PS, PMMA, PC

milky opaque PTFE
light PF absent
2 reel soft and waxy PE and PTFE
3. Hardness scratching by nail Rubbers and soft thermoplasts
cutting by sharp
knife PS, PMMA, PE, PVC and PVAc
soft cut Thermoplast
hard cut Thermosett
hot needle melt Thermoplast
compress to stretch NR, SBR, Butyl R, NBR
4. Specific gravity <l PE, NR
1-1.34 PF, PMMA, PVC, PVAc, PS,
(float over sat. MgCl,)
1.34-2.01 PVC, UF, cellulose acetate and
cellulose nitrate (sinks in sat. MgCl,
but float in a sat. ZnCl»)
>2,.01 PTFE
mn Heating and Linear polymers melt on heating
combustion Thermosets are infusible plastics
PE,. PP burn like a wax candle
PVC, PVDC are self extinguishing,
PS burns with sooty flame. PET burns
with smoky flame, darkens upon
heating. Nylons melt and darken
such as the ability to withstand a given object being dropped from a specific
height (ASTM D256).
Shear strength
It is a measure of the load required to cause the failure in the area of the sheared
specimen (ASTM D732)
3.1.2 Spectral Methods

Spectroscopic methods that have been successfully applied to polymers are
ultraviolet (UV), infrared (IR), nuclear magnetic resonance (NMR), electron
spin resonance (ESR), x-ray, raman, mass and microwave spectroscopy. Commonly
employed methods for the analysis and identification of polymers, however, are
based on IR and NMR spectroscopy. UV-visible (UV- VIS) and Raman spectroscopy
are also used sometimes to provide useful information. ESR is used to a limited
extent; it is principally used to detect the free radicals generated during degradation
or pyrolysis.
Polymer Analysis and.Characterization 89
Table 3(d) Densities of some polymers
Polymer Density g/cm?
Unfoamed PS 1.04-1.06
Teflon DED,
Polyacrylates oo N04
Nylons ‘ 0.97-1.15
Polyesters 1235
Alkyds 1-1.4
Polycarbonate 125
Cellulose eS
Cellulose acetate 1.3
Cellulose nitrate 1.4
Natural rubber 0.92
Ebonite (30% S vulcanized rubber) 1.1-1.3
Polybutadiene 0.9
Butyl rubber 0.93
UF, MF resin LS.
PF resin 1.2-1.35
Epoxy resin ey
Polyacrylonitrile Nig?
Silicones 0.96-1.5
Infrared Spectroscopy (IR)

Most polymers absorb electromagnetic radiation in the IR region (1-500 um)
because their molecules undergo transitions between vibrational states of different
energies causing absorption and emission. The infrared spectra are generally
used as qualitative finger prints for the identification of polymers, since they
rarely identify specific bonds. The infrared spectrum of polymers is often
surprisingly simple. The simplicity has its origin both in the unique nature of
molecular arrangement in the polymer chain and also on the utility of selection
rule in identifying the bands in the IR spectrum. Since polymer chains are made
of same repeating units spread monotonously along the chain, the many expected
IR vibrations occur almost at the same frequency. The use of IR technique is
relative in nature because, the spectrum of a given polymer with unknown structure
is often compared with the reference collection of spectra of several other polymers
of known structures. Some of the wave numbers that can be assigned with
reasonable certainty are given in Table 3(e).
The bands in the range of 8.7 to 9.7 um are characteristic for hydrocarbon
polymers and are called finger print region. Typical C—H stretching vibrations
are observed at 3.8, 3.4 and 3.5 ym, and out of plane bending of aromatic C—
H bonds are at 11.0 and 14.3 um. Characteristic C—C stretching vibrations are
noted at 6.2 and 6.7 um. The C—H bond stretching vibrations of the methylene
(—CH,—) group appear close to 3000 cm! which may be symmetric or
asymmetric as illustrated in Fig. 3.1.
These vibrational frequencies appear in the spectra of almost all hydrocarbon
polymers. Thus, they are of no use for diagnostic purpose. The deformation
Table 3(e) Useful IR bands for the identification of polymers
Wave number, cm™! Chemical bond
3550-3070 O---H or N---H

3100-3000 C—H (aromatic)
3000-2800 C—H (aliphatic) — absent in PTEE
1820-1680 C—O
1680-1620 C—C
1650-1500 N—H
1470-1370 C—H, absent in PTEE
1420-1330 S—O
1440-1250 O—H
1300-1000 C—O
1250-1100 C—F
700-800 C—D
(H) (H)
Symmetric stretching 2926 cm"! Asymmetric stretching 2853 cm7!

(3.42 um) (3.51 sm)
@ ®) ny
Scissoring deformation 1468 cm7! Wagging deformation 1350 cm”!
(7.41 um) (6.81 jum)
+ -_
Twisting deformation 1305 cm=! Rocking deformation 720 cm=!

(7.66 Lm) (13.89 pum)
Fig. 3.1 Stretching and deformation vibrational modes of methylene group
vibrations due to the bending of bond angles or scissoring motion appear at

lower frequencies, giving a large band near 1500 cm™!. Wagging and twisting
modes of CH; occur near 1300 cm”! and rocking deformations occur at the low
energy end of the spectrum. The carbonyl (C=O) stretching band near 1700 cm”,
the C=C stretching band near 1600 cm”! and the olefinic C—H bending bands
between 900 and 10007 are also particularly important.
The polymer sample for IR analysis can be prepared in various forms i.e. in
the form of a thin film, a pellet of the powdered compound with KBr, a nujol
mull or as a solution in chloroform or carbon tetrachloride held in a NaCl cell.
In a double beam infrared spectrophotometer having matched cells, one can
compensate the absorption for the solvent also, if a solution has been used for
recording the spectrum.
Most monomers and several polymers may be identified by IR spectrocopy in
which the energy is associated with molecular vibrations and vibrationrotation

spectra of polymer molecules. IR spectra for polymers may some times be
complex to interpret due to presence of repeat units. IR spectra of some polymers
Transmittance
|
3000 2000 1000 700
Wave number, cm!
Fig. 3.2 Transmission IR spectra of (a) polyethylene, (b) polypropylene,

(c) polyisoprene and (d) polystyrene (the ordinate in all the spectra
is to be taken as 0-100%)
It can be seen that the —CH—stretching vibrations of methylene (—CH,—)

group are found in the narrow frequency range from 2880 to 2900 cm! in all the
four polymers (polyethylene, polypropylene, polyisoprene and polystyrene). The
local chemical environment effects the position of a principal absorption band in
the spectra. The simple wagging and wagging deformation of (—CH,—) group
appear in the frequency range 1345-1470 cm™!. The band due to the rocking
deformation of (—CH,—) group at a frequency of 720 cm”! is apparent in
polyethylene, but interestingly shifted to left hand side in polypropylene,
polyisoprene and from (—CH,—) to a and to = and to
CH; <
“CHC Hs from PE to PP, to PI and to PS respectively. The IR spectrum of

polystyrene possesses some characteristic features and is used as standard for
checking instrumental operation. The repeat unit in polystyrene is CgHg and thus
contains 16 atoms. Since it has no symmetry, all vibrations are active i.e. 3° each
of rotational and translational freedom and 42° of vibrational freedom (3n-6).
Fig. 3.3 shows the IR spectra of pure polyvinyl chloride and dioctylphthalate
plasticized PVC sample. The spectrum of pure PVC shows the characteristic
C—Cl band which is apparent near to the right hand edge and the C—H band is
also evident near to the left hand limit. The spectrum of plasticized polyvinyl
chloride using dioctylphthalate shows the characteristic C=O band at 1740 em.
Transmittance
<.
3000 2500 2000 1800 1600 1400 1200 1000 800 600
Wavenumber, cm”
1
Fig. 3.3 IR spectrum of (a) pure PVC and (b) PVC plasticized with dioctylphthalate
An example of the use of IR method in distinguishing polyvinyl acetate from

its hydrolysed product namely polyvinly alcohol can be seen from Fig. 3.4.
Polyvinyl acetate has characteristic bands at 1700 cm™! (C=O) and at 1240 cm”,
1010-1040 cm! (C—O—C) while polyvinyl alcohol at 3200-3500 cm7! (O—
H). IR absorption of a polymer is significantly altretd when it crystallizes. Thus,
information on crystallinity can be obtained from IR. Usually, intensity of some
IR bands increases and some others decreases as the crystallinity increases.
Transmittance
4000 3000 1500 1000 800 650

Wavenumber, cm!
Fig. 3.4 IR spectra of (a) PVA, (b) PVAc and (c) PVA + PVAc
The ratio of intensity of a band to that of some reference band thus provides
a measure of crystallinity. For example, the ratio of intensity of a band at 846
cm to that of a band at 1171 cm for polypropylene as a function of temperature
slowly decreases and drops to zero at the melting point of the polymer (around
170°C) when the crystallinity in the polymer vanishes. Similarly, the ratio of
absorption bands at 635 cm™! to 615 cm™! in PVC has been found to increase
with the increase in crystallinity (as “ g|

found from density measurements) (see Fe ~
Big.3.5), 2 z
a =
Nuclear Magnetic Resonance
:
=
35
(NMR) 8 5
It is an excellent method for resolying &
the environment of protons in molecules
a 16 Crystallization time, min.
and can also be used to detect °°C, ‘°N,
17 19 Fig. 3.5 Plot showing ratio of intensities
O and "F. . of IR bands at 635 cm™ to 615
Studies based on nuclear magnetic cm and the percentage of
spectroscopy are made on polymers crystallinity as a function of
with the objective of ascertaining and crystallisation time
establishing chain configuration,
sequence distribution and microstructure. 'H NMR technique is particularly
advantageous in that it allows study of the motion and location of protons, which
is not that readily accomplished by other approaches of study and analysis. As
a distinctive and powerful analytical tool, this technique allows independent
confirmation of isomeric structure (isotactic and syndioctatic sequence and their
random combination giving atactic structure) and evaluation of copolymer
composition including the composition of selected copolymers.
In NMR spectroscopy, a strong magnetic field is applied to a material containing
above said nuclei which splits the energy level into two states with the spin
parallel and antiparallel to the field. The chemical shift (in the scale of 0 to din
the form of unit ppm), is helpful in determining the amount of the respective
nuclei in the component. A good illustration of the use of NMR measurements
to determine polymer microstructure is polymethyl methacrylate (PMMA). The
NMR spectra of methylene protons for two samples of PMMA as obtained in
CDCl, at 220 MHz are shown in Fig. 3.6.
If the polymeric chain is syndiotactic, the two protons on the #-methylene
groups are equivalent and therefore there should be a single resonance. However,
if the chain is isotactic, the local environment of the two protons varies due to
electron cloud shielding and one expects four principal resonances due to spin—
spin interaction. On similar lines the NMR spectra of amorphous andcrystalline
polypropylenes in which the polymer chains have predominantly atactic or
predominantly isotactic configurations, are expected to be different (as shown in
Fig. 3.7).
Polymers particularly containing conjugated multiple bonds also absorb in
UV-VIS region and thus UV-VIS spectroscopy can be used to identify them. It
is also used to identify the additives like antioxidants present in the polymeric
material.
Raman spectroscopy is frequently used as a complementary technique to IR
because certain vibrational modes which are inactive in IR are found in Raman
spectra.
(a)
(b)
WS 7.6 Vel 7.8 79 8.0 8.1 8.2 8.3 8.4 8.5

r)
Fig. 3.6 ‘HNMR spectra of &-methylene protons for (a) predominantly syndiotactic
and (b) predominantly isotactic PMMA samples
(a) CH
CH; CH,
() CH,
CH, CH
50 40 30 20 10 0
PPM
Fig. 3.7 Bc NMR spectra of (a) amorphous and (b) crystalline polypropylene
3.1.3 Chromatographic Methods
Pyrolysis Gas Chromatography

It is another important technique used in the identification of polymers and is
often coupled with mass spectrometry. The polymeric material on strongly heating
degrades into smaller gaseous components, which are detected by the gas
chromatograph. This technique may be used for qualitative and quantitative
analysis. Later requires calibration with known amount of standard polymer,
pyrolyzed under the same conditions as used for the unknown. Further, this
procedure enables to identify the presence of volatile additives in polymers.
In gas chromatography, the mobile phase is a gas and solutes are separated as
vapours. The separation is feasible by partitioning of sample between mobile gas
phase and thin layer of nonvolatile high boiling liquid held onto solid support. In
contrast gas—solid chromatography employs a solid sorbent. In GC, the volume
of carrier gas necessary to convey a solute band through full length of a column
is retention volume and is the fundamental quantity measured in gas
chromatography.
3.1.4 Identification of Typical Plastic Materials
Thermoplastics
Acrylonitrile—butadiene—styrene (ABS)
It is an amorphous terpolymer with a specific gravity of 1.04. It shows very good
solubility in toluene and ethylene chloride. IR spectroscopy can be used to
identify the ABS because one can detect the vibrational bands due to characteristic
groups such asxsC = N,—CH = CH— and ofcourse C—H stretching vibrations of
methylene (—CH,—) group. The percentage of each monomer in the terpolymer
can be estimated from IR spectroscopy method. ABS polymer burns with a
yellow flame and it continues to burn after the removal of heat source with black
smoke. Soot and drippings are formed in the air.
Acrylics
Acrylic is a common generic name used to represent whole lot of polymers
formed by methyl methacrylate and its analogues. Most of the acrylic polymers
are amorphous with a specific gravity of ~ 1.18. These polymers burn with a blue
flame with a yellow tip. They produce no smoke while they burn. Upon burning,
acrylics give off fruity odor. Acrylic polymers are soluble in acetone and aromatic
hydrocarbons. IR spectroscopy is the best means to identify the acrylic polymers.
Polyfluorocarbons
This class of polymers include FEP (elastomeric copolymer of tetrafluoro-ethylene
and hexafluoro propylene), CTFE (polychlorotrifluoro-ethylene), PTFE
(polytetrafluoroethylene) and PVF (polyvinyl fluoride) and PVDF (polyvinylidene
difluoride). The unique characteristic features of all these polymers are that
(i) they do not burn when exposed to flame, (ii) they are practically insoluble in
any organic or inorganic solvents, (iii) they have high melting point, (iv) they
have specific gravities > 2.0 and (v) they can be easily identified by a copper
wire test-in this test, the tip of the copper wire should be heated to red-hot
temperature in a flame and with the hot wire small amount of polymer is picked
up and then heated in the flame. A green colored flame is observed when polymers
contain chlorine and or fluorine atoms.
Polycarbonate
It is one of the transparent and toughest polymers. It has got a specific gravity
around 1.2. It is soluble in methylene dichloride and ethylene dichloride. The
polymer burns with an yellow or orange flame and gives off a black smoke along
with soot formation in the air. The polymer has an odor of phenol and can be
easily identified by IR method.
PVC
Polyvinyl chloride is a self extinguishing amorphous polymer with specific gravity
of 1.2-1.7. When burnt, PVC gives a yellow flame and white smoke. It gives off
an odor of hydrochloric acid when burnt. Since PVC contains Cl atom, copper
wire test gives a bright green flame. PVC is highly soluble in solvents such as
tetrahydrofuran and methyl ethyl ketone.
PE and PP
Polyethylene (PE) is one of the most common crystalline plastic in use. The
specific gravity of PE range fromk 0.91—0.96 and PE floats on water. PE is
insoluble in most of common organic solvents but is soluble in hot aromatic
hydrocarbons such as toluene and benzene. PE burns like a candle and small
drips are formed with a paraffinic odor when burnt. IR method is most useful in
identifying the polymer. Polypropylene (PP) has characteristics similar to PE,
but burns with an odor similar to diesel fumes.
PS
Polystyrene (PS) is also another widely used amorphous plastic with a specific
gravity of 1.09. It burns like a candle with drips formation and thick smoke and
soot in the air. The drops also burn continuously. Polystyrene is soluble in wide
variety of solvents such as benzene, toluene, methyl ethyl ketone, acetone and
carbon tetrachloride.
PPO
Polyphenylene oxide (PPO) is another phenyl! group containing polymer and has
self extinguishing property. It gives off phenolic odor when burnt and does not
form drippings when flamed. A yellow-orange flame is observed upon exposing
the polymer to flame. IR spectroscopy method can be easily used for identifying
the polymer. The polymer dissolves in toluene and dichloroethylene.
PU
Polyurethanes (PU) ignite quickly upon burning and a yellow flame with a faint
odor of an apple is given out. PU burns with a black smoke. PUs are soluble in
tetrahydrofuran and dimethylformamide.
Nylons
Different types of nylons (nylon-6, nylon 6,6 nylon 6,10 nylon 11 and nylon 12
etc.) have varying specific gravities in the range of 1.04—1.17. They have different
melting points and solubility characteristics. All nylons burn with blue flame
with a burnt wool or hair odor. Interestingly nylons burn only when they are
flamed and self extinguish when the flame is removed away. Phenol, m-cresol
and formic acids are solvents for nylons. The solubility and specific gravity data
combined with IR method are used for identifying different nylons.
Thermosetts
Epoxy resins
The various epoxy resins have specific graity ranging from 1.10—2.10. These
resins produce yellow flame with a pungent amine odor upon burning. A black
smoke is given off when they are burnt. Both thermal and IR spectral methods
are useful in identifying the epoxies.
PF resins
Phenol-formaldehyde (PF) resins are soluble in acetone and acetic acid. They
burn with yellow flame and pungent odor of phenol. Different PE resins have
specific gravity ranging from 1.30—1.90.
UF resins
Urea-formaldehyde (UF) resins burn with yellow flame releasing typical strong
odor of formaldehyde. The brittleness of UF resins causes swelling and cracking
as they burn. They are not self extinguishing.
MF resins
The melamine-formaldehyde (MF) resins are self-extinguishing. These burn with
yellow flame and characteristic fish like odor. The material also swells, cracks
and turns white while burning.
3.2 Testing Methods
3.2.1 Thermal
The thermal behavior of polymers, especially plastics is rather complex. Unlike
metals, plastics are extremely sensitive to temperature changes. The ultimate
performance of a plastic for a particular use depends upon its response to the
changes in temperature. Several factors, structural as well as molecular, contribute
to the final thermal response of a given plastic material. These factors can be
listed as crystallinity, molecular orientation, the spatial arrangement, molecular
weight, intermolecular forces, cross-linking and polymer compositional variations *
(viz. copolymers, graft polymers and branched polymers etc.).
The design and selection of a plastic material for specialty application purpose
is always based on the available thermal property data. Mainly, the thermal
evaluation of plastics is done by two types of test methods. These methods are
based on long term and short-term effects of temperature on thermal response
properties of plastic materials. The results of these tests help polymer technologist
to select a suitable plastic material for elevated temperature performance.
Short-term Tests
In these tests plastic specimens are exposed to elevated temperatures for shorter
duration of time and the changes in the thermal responses are noted. Three main
tests of this category are widely employed by plastic technologists. They are;
(a) Heat deflection temperature

(b) Vicat softening temperature
(c) Torsion pendulum test
Heat Deflection Temperature (HDT)

Heat deflection temperature is defined as the temperature at which a standard
test specimen deflects 0.010 inches under a stated load of either 66 or 264 psi.
The basic requirements for this test are standard test bar, oil bath with heating
and cooling devices such as dial recorder etc. The test bars are either molded or
cut from extruded sheets and should have 5 in. (length), 0.125—0.5 in. (width)
and 0.5 in. (depth). Care should be taken to keep the surface of the cut specimen
flat and smooth and free from excessive ink marks. The desired pressure on
specimen during the testing is usually applied by means of a dead weight.
Common laboratory manual heat deflection measuring devices and automatic
heat deflection temperature testers are available.
The actual test procedure is described and recorded in ASTM D 648. The
specimen mounted on standard support, temperature and deflection measuring
devices are lowered into the oil bath, kept initially at room temperature. Then the
desired load value of 66 or 264 psi is applied by a fiber stress. After 5 min. the
dial pointer is adjusted to zero and the temperature of the bath is raised at the rate
of 2 + 0.1°C/min. The temperature in the oil bath at which the test bar has
deflected 0.010 in. on the dial indicator is noted as heat deflection temperature.
There are several precautions, one needs to take care before accurately recording
a HDT for a plastic material. Also, the residual stress (normally expected in high
degree molded-in articles), thickness of the specimen, and the type of molding
etc. have large influence on test results. Usually accurate test results are recorded
by taking pre-annealed, thin and compression molded specimens.
Heat deflection temperature is a single point measurement and does distinguish
between those materials, which become flexible in narrower temperatue range.
The behavior of plastic material at elevated temperatures and for longer period
of time cannot be predicted from HDT data.
Vicat Softening Temperature

The Vicat softening temperature is defined as the temperature at which a flat
ended needle of 1 mm‘* of circular cross section will penetrate a thermoplastic
Polymer Analysis and. Characterization 99
specimen to a depth of 1 mm under a specified load using a selected uniform rate

of temperature rise. The test apparatus designed for deflection temperature under
a specified load can be used for Vicat softening temperature with minor modification
in the assembly.
A needle rod or indenting tip is allowed to rest on the specimen, which is
molded or cut from a sheet with minimum thickness and width of 0.12 and 0.50
inch, respectively. The test procedure is recorded in ASTM D1525. The specimen
mounted on the steel support is exposed to a needle rod, which rests initially on
the former before test procedure begins. The temperature of the bath is increased
at the rate of 50°C or 120°C/hr uniformly and the temperature at which the
needle rod penetrates into the specimen by | mm is noted and recorded as Vicat
softening temperature. All the precautions in the preparation of test specimen as
taken in HDT measurements are needed to be taken. The Vicat softening temperature
data are highly useful for comparing the heat softening qualities of thermoplastic
materials. However, this test is not recommended for flexible plastic materials
such as PVC or ethylcelluose etc. which have a wider softening range.
Torsion Pendulum Test

The behavior of plastic materials at elevated temperatures is too complex and too
varied. They undergo deformation at elevated temperatures and their properties
profoundly vary at the temperature range of glass transition in case of amorphous
materials and by the melting temperature in case of semicrystalline plastics.
Mechanical and thermal properties are very sensitive to deformation and hence
to temperature. The performance of plastic material at elevated temperatures
cannot be judged by simple tests such as heat deflection and Vicat softening
temperatures carried under load. In order to understand the elevated temperature
capability of plastic materials, the knowledge of full temperature-modulus plot
especially, dynamic modulus is highly essential and useful. Dynamic mechanical
analysis which determines the temperature dependence of shear modulus by
forced oscillations or by damping free oscillations, offer best means of testing
the plastic specimens at elevated temperatures. Of all the experimental techniques
available to study the dynamic mechanical properties of plastics, torsion pendulum
technique is the simplest and widely used in plastic industries. This technique is
based on obtaining a plot of short time modulus as function of temperature (from
room temperature to the temperature of melting and degradation).
The apparatus for the torsion pendulum test is designed as per the ASTM
procedure D 2236. It consists of an insulated chamber with heating and cooling
facilities and a rigidly fixed clamp at one end. The movable clamp is attached to
an inertial disk or a rod with a known moment of inertia. The angular displacement
of the oscillating specimen versus time is recorded by using differential transformer
and stip chart recorder. Specimens for the test are prepared either in a rectangular
or cylindrical shape and different length. The thickness of the specimen needs to
be specified because it influences the dynamic results. To carryout the test, the
clamped specimen is put into oscillation, after placing the assembly into the
chamber, which was preconditioned to a desired temperature of test. The period
and rate of decay of amplitude of socillations are measured. The elastic shear
modulus is calculated from specimen dimensions, moment of inertia of the

movable member, I and the frequency of oscillation. The shear modulus is given
by;
Ee 12 2a doef acks\ue rps G.1)

Ss ales 6 AC PREC
where | = free length of test species, b = test piece width, h = test piece thickness,
m= tensile force on test piece, g = acceleration due to gravity and C = correction
factor (or shape factor) defined by the ratio of both. A quantity log decrement,
A is defined as the natural logarithm of the ratio of the amplitude of successive
oscillations in the same direction i.e. A = In (A,/A,4,). The log decrement-
temperature profile is shown in Fig. 3.8.
1.0
°
Onset of transition Onset of transition
A
decrement,
Log
—40 0 40 80 120 160 200

Temperature, °C
Fig. 3.8 The log decrement-temperature profile of a typical semicrystalline

thermoplastic (nylon-6)
It is evident that a dramatic drop in shear modulus occurs at a particular

temperature (corresponding to glass transition region). This temperature is regarded
as the maximum usable load bearing temperature as applicable to test plastic
material. In addition to these two other long term tests at elevated temperatures
are also recommended; (i) long term heat resistance test (ASTM D794) and
(ii) underwriters laboratories index.
Thermal Conductivity
The replacement of metals and ceramics with synthetic plastics has been occurring
at a faster rate. The tremendous success of plastics as a material for cooking
utensils, thermal automobile parts and cellulose plastic insulation devices etc. is
mainly due to their low thermal conductivity. This property measures the quantity
of heat flow in unit time across unit area of a sheet of substance of unit thickness
with unit temperature gradient between its faces. In the thermal insulation devices,
the observed thermal resistance is not due to plastics but for the entrapped gases.
There are several methods for measuring thermal conductivity of plastic materials.
These are divided into two main groups: steady state and transient methods.
Steady state methods employ steady state conditions, i.e. the temperature at
any point does not change with time. Based on sample geometry, four steady
state methods are used for determining the thermal conductivity of plastic materials.
These are unguarded hot plate, guarded hot plate, and coaxial cylindrical and
quasi-stationary methods. In transient methods, the time dependent temperature
distribution is measured. It encompasses line source and plane source methods.
Among all these methods, the guarded hot plate method is widely used. The
equipment used in this methods is quite complex and expensive. ASTM C 177
lists the procedure for guard hot plate method. A schematic representation of the
general arrangement in gurarded hot plate method is shown in Fig. 3.9.
Thermocouples to measure sample

surface temperature
Outer shround
Sample test area
Top heat sink
heater
Y Bottom
Bottom heat sink VI
> \'Q'='powerito
main heater
Fig. 3.9 Schematic assembly of the guarded hot plate
The assembly shows that the heat source is surrounded by a guard heater,
which is connected to an independent power supply. The test sample is then
sandwiched between the heat source and heat sinks from the above and below.
The temperature in the heat sink is controlled by circulating a liquid from a
constant temperature thermostatic bath.
A known power is supplied to heat source and at the same time the power to
the guard is adjusted such that the heat source and the guard are maintained at
the same temperature. This ensures that the heat from the heat source flows
normally through test samples. Two thermocouples are used to record the
temperature drop across the samples. Then thermal conductivity, K of test specimen
is calculated using equation K = gx/A AT, where K is the thermal conductivity

(BTU/(h) ( ft”) (°F/in.); g the time rate of heat flow (BTU/h); x the thickness of
test specimen (in.); A the area under the test (sq.in.) and AT the temperature
ditference between hot 7,/°F) and cold surfaces (T>/°F) of the specimen.
ASTM procedure recommends specifications for accurate thermal conductivity
measurements. Accordingly, the apparatus dimensions are usually 30 mm square,
the sample thickness range from 6 mm to 50 mm, and the gap between the heat
source and guard heater is about 2 mm. Table 3(f) lists thermal conductivities of
some plastic materials of common use.
Table 3(f) Thermal conductivity of different materials
Polymer K
BTU/(h) (ft?) (°F/in.)
Polystyrene (medium impact) 0.29-0.87
Polystyrene (high impact) 0.29-0.87
Polystyrene (heat resistant) 0.29-0.87
Polystyrene (general purpose) 0.70-0.96
Polyethylene-polypropylene copolymer 0.58-1.20
Polypropylene 0.81
Polycarbonate 1.40-1.50
Polyvinyl chloride (flexible) 0.99
Polyvinylidene fluoride 0.87
Polyurethane 0.11-0.52
Thermal Expansion
Polymeric materials when subjected to thermal changes tend to expand and
contract from five to ten times more than other materials such as metals and
ceramics. The possibility of segmental motion in a long polymer chain and also
temperature induced movement along the chain as a whole, are the two main
factors that are responsible for the sensitive changes in volume (expansion or
contraction) of a polymeric material with the application of heat. The temperature
dependent volume changes in a polymeric material are expressed in terms of
(i) coefficient of linear thermal expansion and (ii) coefficient of volume expansion.
The coefficient of linear thermal expansion, @, is defined as the fractional change
in length or volume of a material after application of an unit change of temperature.
Following expression gives the values of @.
a= 1/ (AU/0T), (3.2)
where / is the length of the specimen, 7 the temperature and p is the pressure.
The range of values of coefficient of thermal expansion observed for polymer
materials means the expansion develops internal stresses in the polymer. The
coefficients of volume expansion or coefficient of thermal expanision Bis given
by the expression
B= 1/V (OVIOT), (3.3)

where V is the volume of specimen
ASTM D 696 provides a method for determining the coefficient of linear

thermal expansion. This method uses a fused quartz tube dilatometer, temperature
controlled bath, linear volume displacement transducer (LVDT). Wide range of
temperatures can be covered. Fig. 3.10 illustrates a schematic assembly of quartz
tube dilatometer.
LVDT transformer
Specimen Quartz rod
Quartz tube Low-force spring

Fig. 3.10 Schematic assembly of quartz tube dilatometer
The test measurement involves the placement of a preconditioned polymeric

specimen of length between 2 and 5 inch in the dilatometer. The dilatometer
containing the specimen and the measuring devices are lowered below the liquid
level in the bath. The temperature of the liquid bath is varied as desired and the
change in the length is recorded. The coefficient of linear thermal expansion is
calculated as follows;
at = All, AT (3.4)
where Al = change in length of the specimen due to temperature increase or
decrease, /,, = length of the specimen at room temperature and AT = temperature
difference in °C over which the change in length of the specimen is measured.
A liquid-in-glass dilatometer (ASTM D 864-52) is used for measuring
coefficient of cubical thermal expansion of polymeric materials. The sample is
placed in the dilatometer and then a known amount of liquid (mercury) is filled.
The dilatometer is then suspended in a temperature controlled bath. After reaching
the initial thermal equilibrium, the height of the liquid meniscus in the capillary
of the dilatometer is noted by using cathetometer. Then the temperature of the
bath is changed and the changes in the height of the mercury meniscus as a result
of expanision of polymeric material is recorded at predicated temperatures. After
making necessary corrections to the expansion of dilatometer and mercury liquid,
the volume expansion of the polymeric specimen is measured.
3.2.2 Electrical
The electrical testing of polymeric macerials is based on some measurable dielectric
and electric properties. Polymeric materials especially plastics have been used in
many electrical applications which are related to their insulation capacity. Although
plastics can be made to conduct electricity by:adding dopants such as carbon
black and iodine etc, the extensive use of polymer i.e. materials in electrical
application is due to the following factors; ease of fabrication, low cost, light
weight and of course excellent insulation properties. The emergence of high and
super performance engineering plastic materials has extended the use of polymeric
materials to specialty applications, which requires the material to show extreme
resistance to high temperatures, corrosive chemical environment, high humidity
and high mechanical stress etc. The major electrical application of polymers is
as insulator. Use of polymers as insulators in place of other media viz. air or
vacuum, is highly preferred because polymers act not only as effective insulators
but also provide good and well needed mechanical support for the field carrying
conductors.
Thus electrical test results on both the semi finished products such as sheet,
film and tape etc. and on finished products, cables, cases for household appliances
and coated kitchen ware etc., are highly essential and useful in selecting a
particular polymer for a specific requirement. The important electrical properties
of interest for electrical test purpose are dielectric strength, dielectric constant
and dissipation factor, volume and surface resistivity and arc resistance. These
are briefly discussed below.
Dielectric Strength
It is a very important characteristic property of an insulating material, because it
measures the electrical strength of a material. Higher the electrical strength or
resistance of a material for electrical flow, the larger the insulating capacity. The
dielectric strength of the material is defined in terms of maximum voltage the
material withstands and beyond which the dielectric nature of the material is
lost. It is thus expressed in voltage per unit thickness 1.e. V/mm. ASTM D 149
procedure is routinely used for testing the dielectric strength of an insulator. This
method recommends three basic procedures; (i) the short time method, (ii) slow
rate of rise method and (iii) step by step method. In all these three procedures,
the basic set up remains the same. A test specimen is sandwiched between the
electrodes, connected to a variable voltmeter. The thickness of the specimen is
not fix but commonly 0.05—0.06 inch thickness is preferred. A schematic
representation of set up used for dielectric strength is shown in Fig. 3.11.
Short Time Method

In this method the voltage is raised uniformly from zero to maximum value (till
the breakdown i.e. actual rupture or decomposition of the material occurs). The
rate of rise in the voltage generally employed is 100, 500, 1000 or 3000 V/sec
until the failure occurs.
Slow Rate of Rise Method

In this method an initial voltage equal to half of the breakdown voltage (as
determined from short time method) is applied and is then followed by further
uniform increase in voltage until the breakdown occurs.
Polymer Analysis and (Characterization 105
Electrodes
Fig. 3.11 Block diagram for dielectric strength test
Step by Step Method

In this method, initially the voltage equal to fifty percent of breakdown voltage
as established by short time test results is applied. Then, after the increase in
voltage is affected not only in uniform increment values but also for specific
period of time. The dielectric strength (V/mm) is calculated as the ratio of
breakdown voltage (V) to specimen thickness (mm).
Several factors affect the test results. These can be listed as specimen thickness,
temperature, humidity, composition and geometry of electrodes, time of application
of voltage and other factors such as residual mechanical stress and defects (if
any) during the processing of material.
Dielectric Constant and Dissipation Factor

Dielectric constant of an insulating material is defined as the ratio of the capacitance
induced by two metallic plates with an insulator sand-witched between them and
the capacitance of the same plates without the material i.e. with a vacuum
between them’ The knowledge of dielectric constant of an insulating polymer
material is highly desirable because, it measures the storage capacitance of
electrical energy. Thus the suitability of a given insulator for a given electrical
application can be judged priorily, if its dilelectric constant is known.
The test procedure for dielectric constant measurement is quite simple. It
consists of placing a thin film or a pelette of a polymeric dielectric material
between two metal electrodes and the capacitance is measured by an LCR bridge
or a Dielectrometer which can cover wide range of capacitances. Similarly, the
capacitance of metallic plates without sample 1.e. with air as medium is measured.
Then the dielectric constant or relative permittivity of the material is calculated
from the ratios of capacitance observed when specimen and air are placed between
electrodes. A schematic block diagram or dielectric test is shown in Fig. 3.12.
Dissipation factor
The dissipation factor of an insulating material measures the amount of electric
loss and in other words the dissipation factor is defined as the ratio of the
conductance of a dielectric material to its susceptance. The product of dissipation
factor and dielectric constant of the same insulating material is known as loss
factor.
Power ass
Re — _ Dielectric material GL Metal
“on pale ee
Fig. 3.12 Block diagram for dielectric constant test (ASTM D 150)
Arc resistance test

Most of the insulating polymeric materials are exposed to high voltages carried
by the conducting carriers around which the insulator material is strapped. The
action of high voltage on an insulator is measured in terms of time till the surface
of the insulator material gets carbonized or burnt and rendering it to loose its
insulating property. The applied high voltage causes arcing on the surface of the
insulator material, leaving a carbonized path in the form of a wiry line along the
surface and between the electrodes. The more time a material withstands the
arcing, the better arc resistance it has. The arc resistance is thus capacity of the
insulator material to with stand high voltages for a specified time without getting
damaged. Resistance to arcing by the polymer materials depends upon the type
of plastics used. For example, PF-resins tend to get carbonized easily and on the
other hand alkyd resins, melamine resins and fluorocarbon polymers have excellent
arc resistance.
Acrylic plastics though do not leave any tracks on arcing but get decomposed
to ignitable gases and thus show a failure at high voltage in a short time. Since
the arcing is the phenomenon initiated at the surface of the material and the
plastic materials have fillers as additives, the determination of arc resistance has
always been a problem.
ASTM D495 procedure recommends the measurement of arc resistance of an
insulating material in clean and dry laboratory conditions, by applying the voltage
intermittently and in a stepwise increase till the failure occurs. However, the
result of this test may help in initial screening of material, its reliability is not
high since the actual use conditions are affected by so many factors such as
moisture, fog, dust and other wet conditions. That is why the tracking on the
~ surface of an insulator material has also been monitored (i) in conducting the test
in a fog chamber and after coating the surface of the material with standardised
dust, (11) in partially immersing the specimen in an aqueous solution of ammonium
chloride and a wetting agent, and (iii) in developing tracks or erosion on the
surface by discharging electrolyte on the surface of the material.
3.2.3. Chemical
These test methods are basically meant for estimating the resistance of the
synthetic polymers against attack by chemicals. The resistance of polymers

especially plastics to chemical (the typical chemical substances of interest and
importance are staining agents, coloring agents, surface active agents, hydrogen
sulfide and other organic solvents etc.) mainly depends upon the (i) structural
characteristics of its repeat units (type of bond linkage, bond length and bond
energy), (ii) nature of polymer chain i.e. linear or branched and (iii) the packing
of polymer chains i.e. degree of crystallinity.
Chemical resistance tests are conducted mainly by four different ways;
(i) immersion test, (ii) strain-resistance test, (iii) solvent stress cracking resistance
and (iv) environmental stress cracking resistance. Besides the results from these
tests, one should consider other factors such as test temperature, solvent media,
exposure time and nature and composition of additives in polymers etc. before
reporting the final assessment.
Immersion Test
This is one of the simplest methods used in chemical industry to screen the
unsuitable material for a given end use application. The test consists of preparing
a specimen, of any size and shape depending upon the material at hand, immersing
it in a bath containing a particular solvent and maintained at controlled atmosphere
and temperature. ASTM D 543 specifies that the specimen should be kept totally
immersed for seven days. Then the specimen is taken out and changes ranging
from its physical appearance to mechanical properties are recorded. The physical
appearance includes loss of weight, change in shape and other surface characteristics
such as transparency etc. The results of a test specimen are compared with
another reference standard of the same material but not immersed in the bath.
The contrasts obtained for immersed and non-immersed specimen would halp
observe the folowing: loss of gloss, swelling, clouding, tackiness, crazing and
bubbling etc. Also, the results reported are highly dependent upon duration of
immersion, temperature/atmosphere of the container bath and concentration of
reagent/solvent media.
Staining Resistance of Plastics

Plastic materials are not only composites but also heterogeneous in nature. The
end used form of thermoplastics/thermosetts consists of the polymer, filler, coloring
agents, stabilizers and other additives. The wide usage of plastic materials in
domestic applications exposes them to different staining reagents found in the
domestic consumables. These agents are chemical substances that can react with
some of the additives in the plastic material and cause staining or development
of a color-coat on its surface different than the original. The staining of a plastic
material may result in loss of its aesthetic appearance. The staining agents present
in common consumable items such as food items, beverages, cosmetics, solvents,
detergents, jelly, tea, coffee, bleach, shoe-polish, lipstick and nail polish remover
and other solvents cause the staining resulting in the decoloration of plastic
container in which they are used. Hence the staining resistance tests for the
plastic has been usually carried out before the plastic containers are sent to the
market.
The test specimen can have any size but it should have a flat, smooth and
large surface, so that visual examination of a stain caused can be made. The
specimen should be thoroughly cleaned and dried before it is kept in a applicator
container in which the staining agent is applied so that a thin coat is formed on
the specimen. Usually, the specimen is dipped in the staining agent taken in a
glass container. The container in closed condition and along with the specimen
is kept in an oven, at 50 + 2°C for 16 hours. After the exposure period is over the
excess solvent is removed and the specimen is visually examined for appearance
of any stain against an unexposed standard specimen of the identical dimension
and from the same specimen. This test is more effective, when conducted on the
finished products, which directly enter the market.
One of the very reactive staining agents that is found in industrial fumes and
rubber items is the sulfide. When sulfide in the form of hydrogen sulfide comes
in contact with the plastic material, which usually contains the salts of lead,
copper and antimony as stabilizers, fillers and pigments, the former stains the
plastic materials very easily. ASTM D 1712 recommends a procedure for testing
resistance of plastics to sulfide staining. In this procedure, the plastic test specimen
is immersed in a freshly prepared hydrogen sulfide solution for 15 min. along
with control specimen with a known susceptibility to sulfide stain. After 15 min.,
both the specimens are removed and a comparison is made between control and
test specimen to judge the stain resistance of a given plastic material against
sulfide agents.
Solvent Stress Cracking Resistance

The selection of a proper plastic material to a given application depends on its
resistance to chemicals besides other considerations. It has been observed that
plastic materials are attacked by chemicals when they are under stress. The
chemical agents may not have any effect on unstressed parts. The effect of
chemicals on plastic materials under stress is called stress cracking or solvent
stress cracking. There is an inherent stress left in the finished plastic product
during its processing. Thus results from simple immersion tests always are not
sufficient to measure the solvent resistance of a plastic material. Solvent stress
cracking has been found to occur in almost all plastic materials. The stress in a
plastic material can be due to external or internal conditions. Though the complete
elimination of internal stress is impossible, the stress effects can be minimised
by using proper design of the mold and processing method.
Under stress, the cohesiveness of polymer-polymer bond is weakened and
due to solvent attack new polymer-solvent bonds are developed. This causes
disturbance in the packing and arrangement of polymer chains. If the disturbance
caused exceeds the cohesive strength within the polymer chains, the rupture of
polymer-polymer bonds can take place. It has been observed that plastic materials
undergo solvent stress cracking only when they are subjected to either minimum
internal and external stress, below which the solvent has no effect or does not
penetrate into the bulk of the polymer. This minimum stress is known as ‘critical
stress’. Critical stress is defined as the amount of stress at which cracking of
polymer occurs due to solvent attack in a defined environment. There are two
Polymer Analysis and,Characterization 109
methods through which critical stress for a given polymer under a specified
chemical attack can be measured. These are known as calibrated solvent stress
and solvent stress cracking tests.
Calibrated solvent test uses a specimen cut from a plastic specimen, that is
used in real conditions, preferably in bar form (dimensions such as thickness and
the area depends upon the type of plastic to be tested) and subjected to a known
tensile stress by stretching. Just-after stretching, the specimen is exposed to
chemical either by a spraying or dipping process. The exposure time is fixed for
one minute and thereafter the specimen is examined for any crazing that might
have been developed due to solvent/chemical penetration. If no crazing is noted,
a fresh specimen of the plastic material is cut into identical dimensions and is
once again subjected to increased tensile stress and exposed to solvent for observing
any craze. The test is repeated every time with a fresh specimen and increasing
tensile stress till the crazing on the surface is recorded. The material is considered
to show high solvent stress cracking resistance, if no crazing is observed till its
yield point i.e. the maximum stress value at which the material is broken.
One of the major disadvantages of this test is that it requires large number of
pieces of the specimen and the test results are highly dependent upon the time of
exposure of the material to a given chemical. Long exposure time is not suitable
for visible examination of cracking. Thus another alternate method is suggested.
In this method, which is known as standard solvent stress cracking test, a specimen
of 4 x 1 x 0.03 inch dimension is strapped in an ellipsoidal jig and the specimen
along with the jig is immersed in the solvent or a chemical reagent. Because of
the geometrical variations in the jig, the specimen experiences different stress
levels. Thus a contrast in the crazing from different parts of the specimen can be
developed. The test is repeated at different time intervals. The time at which the
crazing stops+in the specimen is noted and it is considered as critical Stress
Point.
Environmental stress cracking

This test is specially designed for polyethylene samples, which are highly
susceptible to agents such as detergents, water, sunlight and oil etc. It has been
found that polyethylene specimens, which perform well in the ordinary laboratory
conditions, very rapidly develop severe cracks, when they are exposed to lubricants.
It has also been established that the chemical agents have severe effects on
polyethylene, when the specimens are under high stress. So following test method
is developed for judging the failure limits of a polyethylene sample against
chemical agents. A specimen of 1.5 x '/, inches dimensions is cut precisely into
rectangular shape. A nick of a fixed length and depth is inflicted onto the specimen
using a nicking jig. Then the specimen is bent exactly by 180° so that the nick
made is at right angles to the line of bend. Then the bent specimen is mounted
onto a sample holder. The holder with the specimen fixed is lowered into a test
tube filled with fresh solution of a non ionic detergent or any other lubricant. The
test tube is placed in a thermostat bath maintained at a constant temperature of
50°C or 100°C. Then the test specimen is removed after a specified time and is
examined for crazing. The time at which crazing is observed is noted. The stress
crack resistant polyethylene samples can be prepared by increasing molecular

weight, decreasing the molecular weight distribution and increasing the crystallinity
in the virgin polymer.
3.3. Characterisation
3.3.1 Molecular Weight Distribution

Many properties of a polymeric material e.g. solubility, melt and solution viscosity,
moldability etc. depend on its molecular weight. The knowledge of the mol. wt.
of polymers is thus very important. Several experimental methods are available
to determine the molecular weight of polymers and these will be described here.
Howerver, unlike low molecular weight substances, a particular polymer can
have different molecular weights. For example, polyethylene of varying mol. wt.
can be made. Furthermore, it is also important to know that a polymer sample
always contains molecules of different sizes and thus never has a fixed value of
mol. wt. The different sized chains in a polymer sample result as the polymerization
is a Statistical process and the growing chain can terminate at any instant. If
termination happens soon after the chain start to grow, then obviously, the chain
will be short. If the growing chain evades termination for a while, it will be
longer. Because of this, polymers are usually characterized by a distribution of
molecular weights. This distinguishes them from their low molecular weight
analogues. Thus for these polydispersed polymers, it is necessary to describe
their molecular weights as relative mol. wt. or an average molecular weight.
There can be in principle different ways to average the relative mol. wt. for
describing the mol. wt. in a justified manner, the two most common ones are
number average and weight average mol. wt. The various average molecular
weight expressions are shown in Table 3(g).
Table 3(g) The different molecular weight averages in polymers
Mol. Wt. average Expression
—
M, 2 NM;
pollit ee 2 W;
XN; XW, /M,;
re 2Ni;M? _ 2WiM,
* x N;M; x W,
a: 2 N,M3 . 2 W,M?
’ 2N;M? XW,M;
+ l/a
= = N,M;**
: = NM;
In the expressions given in Table 3(g), the terms N; and W; represent the
number of moles of molecules with a molecular weight of M; and weight of
molecules with molecular weight M;, respectively. The weight, W; of molecules
_ Polymer Analysis and Characterization 111
with molecular weight M; is then equal to W; = N; M,. Before we understand the

concept of M,, and M,,, let us consider the foregoing definitions. It has already
been mentioned that the polymerisation process yields several chains each having
a definite number of molecules and thus a definite molecular weight. Such non-
uniformity in the chains prevents us from describing the polymers in terms of a
single degree of polymerisation. So one resorts to average degree of polymerisation.
The averaging of degree of polymerisation is done over the molecules with
various degree of polymerisation Dp; according to their number based statistical
entities. These statistical entities can be the number n,, the amount of substance
w; = n;/N,, where N, is the Avogadro number. Or the number fraction
x, =nfd>,n; = wld; w;
Thus, one can write number average degree of polymerisation as
Dik = Xin; Dp; te 2 iw; Dp; (3.5)

2 ny LW :
= LixDp;
where x; is now the mole fraction of i molecules.

From the above definition for expressing an average quantity, let us now
consider that a polymer sample has total, N number of molecules out of which
a fraction N, has molecules with molecular weight M,, another fraction N, has
molecules with molecular weight M, and similarly ith fraction has molecules N;
with a molecular weight M;. Then by simple mathematical consideration we can
write the total number of molecules N = ¥; N; and the number of molecules
in fraction 1 = N, and in fraction 2 = N, and in fraction 3 = N3 and in fraction
i= N,;
The molecules in a given fraction relative to the total number of molecules
can be expressed in terms of molecular number fraction.
Then for the fraction 1, the molecular fraction would be equal to N,/¥; N; and
for fraction 2, the same is written as N/>, N;. and so finally for fraction i,
the molecular fraction is guiven as N,//;N; When a molecular weight of a
polymer sample is determined by any method, the value obtained considers all
the fractions present in the polymer. Thus one needs to calculate the molecular
weight contribution of every fraction present to the total molecular weight of
polymer.
The molecular weight contribution of each individual fraction will be the
product of molecular weight M; and molecular number fraction N,/ %; Np tee Ny
M,/3; N;, No Mo/; Ni, N3 M3/%; N;, and so on till N; Mj/D; N;. Thus the total
molecular weight of polymer sample containing several fractions would be simply
an additive quantity, i.e.
i —o
2; NiM;
n XN; (3.6 )
Similarly, the molecular fractions can be expressed in terms of weight fraction

i.e. weight of each tth fraction having a molecular weight Mj. The weight of
fraction | will be W,, fraction 2, W2 and for ith fraction, W;. The weight fractions
W, to W; are simply defined as N;M, to N; M; because, by definition, weight is
equal to no. of moles multiplied by molecular weight. Then we can write
Weight of fraction W; = N\M,

Weight of fraction W, = NM,
Weight of fraction W; = N;M;
The weight fraction for the individual polymer fractions, | to 7 relative to total
weight of polymer W = >; N,M, would be
NiM,
Ww
N2M>z
Ww and
Ni M;
NiM, N»M>, Bhd Ni M;

x,NiM; 2, NM; 2 NiM;
Before one expresses the total molecular weight of polymer containing several
fractions in terms of weight average molecular weight, M,,, what needs to be
done is simply calculate the molecular weight contribution of each fraction and
summate all the contributions. Thus the molecular weight contribution of weight
fractions, W,, W, and W; etc. are
NiM, _N2M2_Mt:
= TM, d >, Mi
SM de Cee
or
NiM? = -N2M3
1 —eran nas YY —_—_ an
a rs
M?
XNiM;’ 2 N{M; x NM,
whose overall summation defines weight average molecular weight of polymer
M,, as
trl
M =
seMP
~ LN; ou
As shown in Table 3 (g), the average molecular weights of polymers are also
expressed by another two ways i.e. M, and M ,, in addition to above discussed
M,, and M,,. The terms M, and M,, are measured based on sedimentation
equilibrium experiments and flow behavior (or viscosity) of polymer solutions,
The symbol z in M_ comes from German word Zentrifuge = centrifuge. Both
M. and M, are used for expressing the molecular weights of larger molecules.
Since M; > 1, the expression given in Table 3 (g) implies M, > M,, = M, > M,,.
The superscript, a, in M, expression is a variable with its value ranging from
0.5 to 1 depending upon the solvent quality. The @ value is defined by Mark-
Houwink equation, which will be discussed in the later part of this chapter.
Thus it is clear from foregoing discussion that the molecular weight of polymer
is not an absolute quantity and the value of a given polymer may vary with the
method of its determination. The different experimental methods are described
later in the chapter. Each method or group of methods defines the molecular
weight depending upon the statistical weight that is measured. Suppose that the
molecular weight of two polymers of same chemical constitution is determined
to be same, but both of them may possess different properties. This is because
the two samples might consist fractions that are not identical in terms of number
of molecules/moles, weight of molecules and of course in molecular weight. But
still, the averaging of all the fractions yield same final value. That is why not
only the averaged molecular weight but the dispersity of molecular weight from
smaller to larger fraction is to be known. Such an analysis is normally done by
expressing or mapping the molecular weight distribution curve. Such a curve is
developed easily from the experimentally derived data and simply is a plot
showing the variation of number (or mole fraction) N; of molecule (having a
molecular weight M,) against the corresponding molecular weight M,. Such a
curve for polymer having a hypothetical distribution of fractions with different
molecular weight is shown in Fig. 3.13.
M,
————
Fig. 3.13 The different molecular weight averages
A perusal of the shape of the curve in the figure reveals not only interesting
but also important information. It can be seen that the number of molecules (or
moles) having particular molecular weight passes through a maximum i.e. it
increaes initially with respect to molecular weights. This means the statistical
weighing factor predominantly shifts to weight and size of fraction at high
molecular weights. So this explains that the experimental methods need to be
changed for determination of molecular weight of a same type of polymer but
differing in molecular weight. The pattern shown in the above figure also reveals
that M, <M, <M, <M,.
Molecular Weight Distribution

The subject of mol. wt. distribution is of great practical as well as fundamental
importance. For example, a small amount of a fraction of either very high or
very low mol. wt. can greatly change the solid and solution state properties, and
thus affects the processing characteristics of a polymer. It is therefore necessary
to develop quantitative ways to obtain mol. wt. distribution. Figure 3.14 shows
the mol. wt. distribution of three polymer samples with almost same number
average mol. wt. It can be seen from the curves that polymer sample | is highly
polydispersed than polymer 2, while polymer sample 3 is less polydispersed
than the other two. The polydispersity index, P.I. for polymers is defined as the
ratio= M,,/M,,. As mentioned earlier, the polydispersity of the molecular weight
in the polymer fractions is mainly due to variation of degree of polymerisation
in each fraction formed during polymerisation process. Hence the values of P.I.
are highly dependent on the type of polymer process. For a monodispersed
polymer, P.I. value is unity.
M,
M,
——
Fig. 3.14 Molecular weight distribution in polymers
The polydispersity index in polymers prepared using different techniques are

shown in Table 3(h).
Table 3(h) The polydispersity index (P.I.) using different polymerization methods
Technique/conditions M,,/M, il
Free radical polymerization

with precise temperature control 1.5-2
moderate temp. control (e.g.in bulk polymn.) 2-5
without temp. control (e.g. with autoaccelaration) 8-10
Ionic polymerization
with homogeneous catalyst < 15
with heterogeneous catalyst > 10
Polycondensation 2-3
Coordinate polymers and polymers with many branches >20
SS
3.3.2 Fractionation A
The fractionation of polymer means separating a polydispersed polymer sample
into several fractions each with a molecular weight distribution as narrower as
possible. Most methods used for this purpose are based on the fact that polymer
solubility decreases with increase in mol. wt. some common fractionation methods
are described below.
Fractional Precipitation
In this method, the polymer sample is dissolved in some suitable solvent. The
concentration of polymer solution is fixed around 0.1% (g dl”'). To this dilute
solution of the polymer, a non-solvent is added drop wise with vigorous stirring.
As a result of the addition of a non-solvent, the portion of the dissolved polymer
that contains molecules with largest size becomes insoluble first. The insoluble
materials is removed as the fraction of highest molecular weight. To the clear
solution, more non-solvent is added when the portion with next highest mol. wt.
precipitates out and is separated as the second fraction. This procedure is repeated
several times to obtain various fractions with decreasing molecular weight.
Fractional Elution
In this method, polymer is extracted from solid into solution. The method used
is to pack a column with, for example, glass beads which are coated with polymer.
The column is eluted with solvent/non-solvent mixtures of gradually increasing
solvent power. Here, the lowest mol. wt. portion will elute first from the column,
followed by fractions containing gradually increasing mol. wt. as the proportion
of the solvent in the solvent/nonsolvent mixture is increased.
Gel Permeation Chromatography (GPC)

An elegant method used for the fractionation of polymers is gel permeation
chromatography. The technique when applied by biologists for the separation of
proteins from a mixture is called gel filtration chromatography and by colloid
chemists to separate colloidal dispersions according to size is called size exclusion
chromatography.
It is a liquid-solid elution chromatography that separates polydispersed polymer
into several fractions by means of the sieving action of a cross-linked polystyrene
gel. The gel material acts as stationary phase and is commercially available with
a wide distribution of pore size (1-10° nm). This is an expensive technique but
provides a very quick information on fractionation and MWD. A single run can
yield the value of all the averages together with the distribution of relative
molecular weights. The GPC column is packed with above mentioned insoluble
polystyrene or polystyrene—polydivinylbezene gels. The solvent is forced
continously through the sets of columns at a controlled rate of about 1 ml/min by
a high pressure pump. The polymer solution is injected at a position upstream of
the column. The detector is located downstream of the column and responds
sensitively to the presence of the polymer in a small volume of eluent. A variety
of detector techniques are used. The common ones measure differences in refractive
index, UV absorption or light scattering.
The basic principle underlying the separation of different fractions of a

polydispersed sample is based on the size of individual polymer molecules that
explore the pore system of the column material. Large molecules are excluded
from small pores and can only diffuse into a restricted part of the pore system
within the beads while smaller ones would enter into the pores of the bead. Thus
large molecules would have less residence time and would emerge first. Fig.
3.15 schematically illustrates the principle of GPC.
Separation
o@
beginning
Partially
separated
Fully
separated
Elution
Fig. 3.15 Schematic presentation of the basic principle involved in GPC
A calibration curve is necessary to obtain information from GPC. Several

samples of narrow dispersed polymers
like polystyrene, polyethylene oxide etc.
of varying mol. wt. (these are available
commercially) are first eluted separately
from the column and the retention time
(or volume) for each sample is Log M
determined. This procedure provides a
calibration plot, which can be used to
obtain the mol. wt. of an unknown
polymer fraction. A GPC run of the
Elution volume
sample provides a plot between record
output versus elution volume. Another Fig. 3.16 Calibration plot of log molecular
plot between log mol. wt. versus elution weight versus elution volume for
volume is then constructed which is a narrow dispersed polymer of
linear as shown in Fig. 3.16. known molecular weight
. Polymer Analysis and Characterization 117
Now the unknown polymer is run in the column and with the help of different
fractions eluting and the calibration plot MWD curves can be constructed.
3.3.3. Determination of Molecular Weight of Polymers

Different methods that enable the mol. wt. determination of polymers are based
either on the colligative properties or estimation of size of polymer chains. As
expected, the former methods will yield number average mol. wt. and while the
later give weight average molecular weight. In addition to these two methods
another method based on estimation of chemical functional groups present as
end groups in polymer chains is also used to get M,,. The details of the above
mentioned methods are discussed as follows.
End Group Analysis

This method concerns with the determination of the number of the end groups
present in a given mass of the polymer (provided it has a given number of
functional groups) using any standard analytical method. For example, if a polyester
contains one end COOH group per chain which can be estimated by the titration
using standard solution of NaOH solution. The procedure is for example as
follows. Suppose | g of the solution of the polyester needs ‘a’ ml of 0.01 M
NaOH, then moles of NaOH needed to neutralise the polyester solution will be,
[‘a’/1000] x 0.10 = 107° x ‘a’ mole. Therefore the number of moles of COOH
groups will be (107°) x ‘a’. Since there is only one functional group per polyester
chain, the number of mole of the polymer in 1 g of it would be 107° x ‘a’. So the
number average molecular weight of the polymer will be 10°/‘a’.
Colligative Properties and Molecular Weight

The two common methods for the determination of the mol. wt. of low molecular
weight substances ar based on properties viz. depression in freezing point
(cryoscopy) and elevation in boiling point (ebulliometry). As these two properties
are colligative (i.e. depend only on the number of moles of a solute present in a
liquid and not on their nature). The measurement in the decrease in freezing
point or increase in boiling point of the liqid on addition of a given mass of a
solute can simply be used for the determination of the mol. wt. of the solute
material. However, the magnitude of this change in b.pt. or f.pt. is very small and
can be measured precisely using Beckmann thermometers, which measure small
changes in temperature. These two techniques are highly sensitive to the mol.
wt. Substances with low mol. wt. would give the measurable changes in b.pt. or
f.pt. For polymeric substances, particularly when the mol. wt. is more than few
thousands, these techniques are seldom used.
The other two colligative properties viz. osmotic pressure and lowering in
vapour pressure can however be conveniently used for the mol. wt. determination
in polymers. The later property is again limited to mol. wt. up to few thousands
only. Since all the methods mentioned above are based on the number of molecules,
the experimentally determined mol. wt. they would offer will be the number
average mol. wt. Table 3 (i) shows the comparison between changes in various
colligative properties upon dissolution of a low mol. wt. (1000) and high mol.
wt. (10,00,000) substances ina suitable solvent. It is clear that for high mol. wt.
sample, the only useful method that can provide number average mol. wt. is
membrane osmometry which is based on measurement of osmotic pressure.
Table 3(i) The subitability of methods based on colligative properties versus mol. wt
Property M,, = 10,000 M,, = 10,00,000

Depression in f.pt. 0.012 K 0.00012 K
Elevation in b.pt. 0.006 K 0.000006 K
Osmotic pressure 600 mm solvent 6 mm
Vapour pressure lowering 0.018 mm Hg 0.00018 mm
The details of osmometric methods (vapour pressure osmomety, VPO and

membrane osmometry) are described below.
Vapour Pressure Osmometry

This technique is governed by the principle that the vapour pressure of a liquid
is lowered on addition of a solute and this lowering is dependant on the number
of the solute molecules present and is based on the idea of isothermal distillation.
The construction principle of a vapour pressure osmometer is schematically
shown in Fig. 3.17.
Solvent » Solution
droplet droplet
Fig. 3.17 Block diagram of a vapour pressure osmometer
In this method, drops of solvent are placed using syringes in an insulated

chamber as in proximity to thermistors T; and 7. As both the drops are of the
solvent, equilibrium is achieved. The two thermistors form a part of a Wheatstone
bridge and the balance point is established. Now on one of the thermistors, a
drop of solution is introduced with the help of syringe. The thermistor probe
would register the temperature difference, AT arising due to the faster evaporation
of the molecules of liquid from solvent drop than from solution drop.
This temperature difference can be accurately measured as a function of the
bridge imbalance output voltage, AV and is related to the molecular weight of the
polymer by,
aA
AV/C
= K/M,, + KBC (3.8)
where K is the calibration constant that can be determined by doing the similar
experiment with any polymer sample of known molecular weight. Thus a plot
between AV/C versus C gives a linear behavior, the intercept of which would
provide M,,. This method needs calibration, which involves the determination of
calibration constant K. It is obtained by measuring AT for a relatively low mol.
wt. polymer of known mol. wt. and low polydispersity. The measurements at
different concentrations when plotted as AV/C versus C would give the intercept
as K/M,,. Substituting the value of M. n» K is estimated. The advantage of the
method is its quick determination of molecular weight using only a small amount
of the sample. The disadvantage is that it is limited to determination of low
molecular weights (less than 30,000).
Membrane Osmometry
The membrane osmometer apparatus basically measures osmotic pressure of
polymer solutions of known concentration, say | g dI-!, which can be correlated
to the number average mol. wt. of the polymer. Since polymer solutions even in
dilute regime usually behave nonideally, the osmotic pressure is measured at
several concentration, C, and an extrapolation to zero concentration is made
from the linear plot of reduced somotic pressur (7/C) versus C. Using the van’t
Hoff equation, the intercept of this linear plot (see Fig. 3.18) can be considered
equal to RT/M,,.
A static membrane osmometer works on the principle that if the polymer
solution is separated from the pure solvent through a semipermeable membrane
(that allows passage of only small solvent molecules but not large polymer
molecules), then due to the difference in the chemical potetial in the two
compartments, the solvent molecules transport from the solvent compartment to
the solution compartment. If the two compartments have columns containing the
capillaries in each compartment and if initially the two compartments have
liquids at the same heights in the capillaries, then due to the passage of solvent
molecules across the membrane (osmosis) the level in the capillary in the solvent
compartment will show a gradual decrease while that in the solution compartment
will show an increase. It would continue for some time till the equilibrium is
reached due to the osmotic head working in the solution compartment does not
allow any more solvent molecules to migrate from solvent compartment to solution
compartment. In principle, the difference in the level of capillaries of the two
compartments, after the equilibrium is achieved can be taken as the osmotic
pressure.
The membrane osmometry (static) suffers with a disadvantage that often long
time (several hours for a single measurement of mol. wt.) is required as the
achievement of equilibrium is a slow process. Also, since no membrane can be
perfectly ideal, small sized molecules of a polydispersed polymer sample can
pass through the membrane causing error in the mol. wt. determination. A modified
version, the dynamic osmometer reduces the time problem. In this method, the
counter pressure required to prevent the transport of solvent molecules through
the membrane is measured. In high speed osmometers, an optical system in the

solvent chamber detects flow through the membrane and automatically adjusts
pressure by an electro-mechanical device to prevent any flow. In the absence of
any flow the whole process completes in few minutes. Also since the time is
reduced, there is virtually no possibility of the migration of even smallest polymer
molecules that causes errors in static method.
As already mentioned the van’t Hoff law forms the basis for the determination
of number average molecular weight, M,,. Following equation gives the relation
ship between osmotic pressure, 7 of polymer solution to M,, of the polymer,
mC
= RT [A; + AoC + A3C’ + A,C’+....] (3.9)
where Aj, A, and A; are the first, second and third virial coefficients, Cy is the
concentration of polymer solution and R and Tare the gas constant and temperature
respectively. The first virial coefficient, A, is equal to 1/M,,. Thus the above
equation can be written as,
mIC
= RT [1/M, + AoC +.A3C2 + AgC? +....] (3.10)
For very dilute solutions (typically less than 1 g dl~'), the concentration terms
containing higher order powers can be neglected and hence it can be written that
m/C = RT{1/M,, + AC] (3.11)

Thus a plot of (7/RTC] versus C should yield a straight line with an intercept
of 1/M,, and slope equal to A (see Fig. 3.18b). The value of A3, the second virial
coefficient is often used as a measure of polymer-solvent interaction. As the
quality of the solvent worsens the slope of the line decreases. The slope is
practically zero i.e. the line is parallel to the concentration axis in solvents called
theta solvents. In order to have better results on mol. wt. by osmometry, the
solvent used should not be very good for the polymer as a large increase in the
osmotic pressure would be observed with concentration of the polymer and this
Good solvent
m/C
Solution | Solvent = Poor solvent
(a) Concentration, g di“!

Pee
SR LST
(b)
Fig. 3.18 (a) The working principle of a membrane osmometer and (b) a plot of
reduced osmotic pressure versus concentration
would cause difficulty in extrapolation of the line to obtain precise intercept. In

Table 3(j) are given some solvents, which behave as theta solvents for some
polymers at the specified temperature. In membrane osmometry, determination
of mol. wts above a million is essentially impossible because there are too few
particles in a given weight of polymer. On the other hand, polymers with mol.
wt. less than 20,000 can cause problems by their diffusion through the membrane.
Thus membrane osmometry is ideally suitable for determination of molecular
weights in the range from 20,000 to 1,00,000.
Table 3(j) Theta solvents for some polymers
Polymer Solvent Temperature, °C
Polystyrene Decalin 31
Polypropylene Isoamy] acetate 34
PVC Benzyl! alcohol 155
PVAc 3-Heptanone 29
Polyacrylic acid 1,4-Dioxane 30
Polyisoprene Propy! ketone ~20
PMMA (atactic) n-Butyl chloride 35.4
Polyisobutylene Benzene 25
Polydimethy] siloxane Butanone 20
Dilute solution viscosity method for molecular weight determination

This method involves the measurements of viscosity of dilute polymer solutions
over a concentration range (usually up to 2 g di~'). The measurements do not
require any sophisticated instrumentation
and are thus used routinely in molecular
weight determinations. The presence of
small amount of a polymeric material
dissolved in a solvent significantly
increases viscosity of the solvent. Such
an increase in viscosity is dependent on
the concentration and molecular weight
of the polymer and its interaction with
solvent. In order to determine the mol.
wt. of a polymer, viscosity of polymer
solutions at different concentrations
relative to that of the solvent is measured.
Since only relative measurements are
required, capillary viscometers are well
suited. The most convenient viscometers
are Ostwald viscometer and Ubbelohde
viscometer. In the latter the additional
advantage is that dilutions of the solution
can be done in the viscometer itself. The
design of an Ubbelohde viscometer is
Fig. 3.19 The Ubbelohde viscometer
shown in Fig. 3.19.
A polymer solution of about 2 wt % (2 g di) concentration is transferred into

bulb B after meticulosuly cleaning the viscometer. The viscometer is then vertically
immersed in a constant temperature bath. The end of the tube attached to bulb C
is closed by a finger and suction is applied at A end so that the solution comes
above level m,. Tube C is then opened till the liquid in the bulb A is drained and
the pressure at this end of the capillary remains at atmospheric levels. Thereafter,
the suction at end A is released and the time (r) taken for the solution to fall from
level m, to mz is measured by a stopwatch. The flow occurs only along the walls
in bulb C and flooding is totally avoided by the bell-shaped design of the capillary
end. After reproducible results are obtained, a known amount of solvent is added
to bulb B to dilute the solution and the viscometer is gently shaken by hand. The
flow times for polymer solutions at several concentrations are thus obtained with
a single filling only. Ubbelohde viscometers are available in several sizes and the
one which gives flow times of about 200 to 400 s for the solution to be studied
should be chosen to reduce shear errors. The viscosity is then given by the
equation 1) = ¢ [At — B/t], where the first term on the right represents the Hagen-
Poiseuille law and the second term gives the correction for the kinetic energy of
the fluid leaving the capillary. Usually, the constants A and B are either supplied
by the manufacturers or can be obtained by calibration using standard liquids
like water and cyclohexane at two different temperatures. Normally, B is a small
number and in case A and B are unknown, one takes 7 as proportional to t. The
relative viscosity can be obtained by dividing the flow time ofthe solution by the
flow time of the solvent (since the solutions of polymers are very dilute, the
density of the solution and that of solvent can be considered same). Also, since
t > fo, the relative viscosity would always be greater than 1. Thus a new ‘term
specific viscosity is defined as a positive quantity by subtracting 1 from relative
viscosity. Specific viscosity is then divided by the corresponding concentration
to give reduced viscosity. When the reduced viscosity is plotted on ordinate (y-
axis) against polymer concentration on abscissa (x-axis), a straight line behavior
is observed. The extrapolation of reduced viscosity to zero concentration gives
intrinsic viscosity. Another way is to plot inherent viscosity versus concentration,
which also shows linear behavior with extrapolated value to zero concentration
as intrinsic viscosity. The different viscosity terms are shown in Table 3(k). For
calculating different terms given in the above table, the concentration of the
polymer is usually in g per 100 ml i.e. g di! or wt. %, t and f, are the times of
efflux for the solution and the solvent through the viscometer. Intrinsic viscosity
of a polymer solution at a particular temperature is obtained by the use of either
Huggins or Kraemer equation. The forms of the equations are as follows:
Table 3(k) Viscosity terms and their definitions
Viscosity term Definition Unit
Relative viscosity Nred n/N, t/t,

Specific viscosity Nsp = 1-1 (Nn - No)/No (t —1,)/t,
Reduced viscosity Ned (n,,/C) dl g"!
Inherent viscosity Ninh (In Mey)/C dl g!
Intrinsic viscosity [7] (Nsp/Qcso OF (IN Ne W(C)es dl g"!
Nsp/C =n] +k [nC Huggins equation (3.12)

(In Ney/C = [n] + k’ [nC Kraemer equation (3.13)
The representative plots using both the equations are shown in Fig. 3.20.
Nsp/C
NrevC
In
Cuz di}
——_—_>
Fig. 3.20 The typical Huggins and Kraemer viscosity plots
If the higher terms of C are neglected, both the lines should intersect at the
ordinate to correspond to zero concentration and the constants should satisfy the
condition, k’ + k” = 0.5. The intrinsic viscosity is related to the mol. wt. by the
Mark-Houwink-Sakurada equation,
[n] = kM“ (3.14)

where &k and & are empirical constants and are characteristic for a polymer-
solvent pair at a given temperature. Typical values of k are of the order 10 and
a about 0.7. The values of k and @ are obtained from the known values of
molecular weights for well defined fractions of given polymer dissolved in a
solvent and measured intrinsic viscosities for the same pair. When log [7] is
plotted against log molecular weight, a linear relation results (based on Mark-
Houwink and Sakurada equation). The slope of the plot gives @ and the intercept
yields the value of log k. Table 3(1) provides the values of k and q& for several
polymer-solvent pairs at 30°C.
Although, viscometry measurement provides an indirect method (as it needs
the values of constants of k and @ for the determination of molecular weight of
a polymer), it is still the most convenient way for routine determination molecular
weights of polymers, due to the simplicity of the set up. Wide range of molecular
weights for all the polymers having solubility in any of the solvents are obtained
by this method. However, there are some limitations of the method. It gives
errors in molecular weight in branched polymers and copolymers. Because, the
values of k and @ are highly dependent upon the degree of branching in branched
copolymer and compositional variations in the statistically regular or irregular
copolymers such as block and graft copolymers or random copolymers. One
more limitation of the method is that the polymer solutions used have to be very
dilute so that the chain entanglements, drag effect and adsorption onto capillary
inner surfaces are eliminated maximally.
Table 3(1) The constants k and aof the Mark-Houwink-Sakurada equation at 30°C
Polymer Solvent k x 10° ml/g a

Polypropylene (atactic) benzene 27.0 0.71
Polyvinyl alcohol Water 45.3 0.64
Polyvinyl acetate acetone 10.2 0.72
benzene 56.2 0.62
methanol 31.4 0.60
Polystyrene benzene Wh Fs) 0.73
toluene 11.0 0.72
Polyvinyl chloride THF 83.3 0.83
cyclohexanone 16.3 0.77
Natural rubber benzene 18.5 0.74
SBR toluene S79 0.71
cyclohexane 31.6 0.70
Polyethylene oxide water 16.6 0.82
benzene 40.0 0.70
acetone 32.0 0.67
Polyacrylamide Water 68.0 0.66
Polyvinylpyrrolidone water 39/3 0.59
methanol 23.0 0.65
Polymethyl methacrylate acetone 6,2 0.72
benzene 4.0 0.77
Polyacrylic acid 1,4 dioxane 76.0 0.50
Polyacrylonitrile DMF 20.9 0.75
Nylon 6 m-cresol 320.0 0.62
Nylon 6,6 m-cresol 240.0 0.61
Light Scattering
When a beam of light is passed through a colloidal solution, it is scattered. This
is well-known Tyndall effect, which results from the scattering of a prat of the
beam of light by the colloidal particles in all directions (see Fig. 3.21). Since
polymer solutions can be considered as colloidal (lyophilic) solutions and as the
intensity of light scattered depends on the size of colloidal particles (or polymer
molecules), the scattering phenomenon can be used for the determination of
molecular weight of polymers. Light scattering measurements thus provide the
weight average molecular weights of polymers.
Solution
hv
Detector
Fig. 3.21 Light scattering from a polymer solution
Debye, in 1944, correlated molecular weight of polymer with the intensity of

light scattered by its solution by the equation (now known as Debye equation)
which holds good only for particles which are smaller than the wavelength of
light used for the scattering experiment as
KC/ Roy = HC/t = 1/M,, + 2 BC (3.15)

where B is the second virial coefficient, C is the concentration of the solution,
and Roo is the Rayleigh ratio at 90° observation angle. This ratio in a generalized
case is represented as Rg i.e. the Rayleigh ratio is determined at an observation
angle of 90°, Rg = Roo.
Ro=iarlly V (3.16)
where ig is the intensity of the scattered light per unit volume, V, of scattrering
material which is observed at a distance r and at an angle of @ with reference to
the incident beam, and Jp is the intensity of the incident beam. The turbidity Tis
defined as, e-™ = I/Ip. The constants K and H are light scattering calibration
constants and are defined by the following equations,
_ 22?n?(dn/dC)*
K (3.17)
A4N«
where n is the refractive index of the solution, (dn/dC) is the specific refractive
index increment, i.e. the change of refractive index with concentration, A is the
wavelength of the incident light and N, is the Avogadro number.
_ 32m3n* (dn/dC)* (3.18)

H
3A4N4
For polymer solutions where the molecules are larger in size compared to the
wavelength of light, the equation needs to be modified to,
BO 5H Ag le ORG (3.19)
Ro tT M,- P(@)
where P(@) is the particle-scattering factor. It represents the angular dependence
of the scattered light by following equation,
Evh2 he Ea (52) sin?| 2] (3.20)

P(@) 342
where (57) is the mean square radius of gyration of the polymer random coil.
Substituting this value of P(@) in eq. 3.19 we get,
2 oe
beh Sat 5 a | +|aoe dons |<5?) aie[8 +2BC (3.21)
3A7M,,
P(@) is considered as a correction factor to the scattered intensity at different

values of 0, such that P(@) = 1 at @=0. Similarly, BC = 0 at C = 0. Now, above
equation can be rewritten in the following forms:
fe]
KC
— =
oat atin |
—
1 16s
+ |———
[m2
|(S°) sin
2 (0/2) (3.224)
AC) = <1 42BC (3.22b)

Ro Io 49 My
AC en (3.22c)
Ro C,60 M,
Light scattering technique has developed a fastest tool for molecular weight
determination of polymer due to the availability of laser radiation sources. Light
scattering measurements traditionally require extremely clean, dust-free samples
in order that erroneous scattering may not be generated. The presence of any gel
like, semi-dissolved or associated polymers cause large errors. The light scattering
measurements are usually valid between molecular weights of 10,000 and
10,00,000. Below 10,000, there are interference effects from solvent molecules
and dust particles. Above 10,000,000, there are interference effects from other
polymer molecules.
Use of equations 3.22(a) and 3.22(b) is made either by Debye method or
Zimm method to determine the molecular weights of polymers. Debye method
is also known as disymmetry method. It requires measurements of the scattered
intensities at three angles, which typically are 45°, 90° and 135° and at several
different concentrations. A disymmetry ratio, z can be defined as z = I (45°)/I
(135°). Since z value is concentration dependant, in usual practice the value of
z at different concentrations is plotted in the form of (z— 5 ie versus concentration
plot and the intercept is obtained as value of z at zero concentration. Then the
particle scattering factor P(@) i.e. P(90°) and (S%) are calculated from the
known values using models developed for describing the scattering systems.
These models are derived for a particular conformational state i.e. sphere, random
coil, rod and disk etc., Once P(90°) is known, M,, can be calculated from the
intercept of plot of KC/Rigg») versus concentration (eq. 3.22a) by simple
extrapolation to zero concentration.
The main disadvantage of this method however is that a model for the polymer
chain in dissolved state is to be pre assumed. That is why another method is
developed by Zimm, which does not need any advance information on the
conformational state of polymer chains in solution.
Zimm method is based on a double extrapolation procedure (see Fig. 3.22).
Both the extrapolations of plots of KC/Rg versus sin” (0/2) + kC (where k is a
constant chosen arbitrarily) to zero angle and to zero concentration, are made.
Then from the intercept and slope, the molecular weight of polymer and second
virial coefficients can be determined by use of equations 3.22(a)—3.22(c).
Low Angle Laser Light Scattering (LALLS)

The conventional light scattering instruments use light from high intensity mercury
lamp. In recent years, the mercury lamp source is replaced by a laser source.
» Polymer Analysis and Characterization 127
4
C;
Cy
C
Sin? 6/2 + kC
Fig. 3.22 The double extrapolation Zimm plot
Mostly, helium — neon (He — Ne) lasers (with A = 6328 A) are used. The advantage
of the laser source is that, the high intensities of the light emerging from them
permit scattering experiments at much smaller or low angles (which typically may
vary from 2° to 10°) and also much lower polymer concentration solutions can
be studied. At very low angles and low concentrations, eq. 3.22 effectively reduces
to the classical Debye equation derived for small spherical particles,
== == +2BC (3.23)
M,,
Thus, one can construct linear plots between KC/Rg versus C at a single 6 value
and different concentrations to get
intercept which yields the reciprocal
of molecular weight, M,,. The slope
of the line gives the value of second
virial coefficient, B. Such a general plot
of KC/Rg versus C at low angles is KC/R,
shown in Fig. 3.23.
Ultracentrifugation
Polymer solutions are lyophilic colloids C, g drt
and these can be made to settle down fig. 3.23 Plot of Rayleigh ratio versus
on the application of centrifugal force. concentration from low angle
The rate of the settling (sedimentation laser light scattering
rate) of polymer molecules depends on
the size of the molecules. Then, this property can be applied to experimentally
determine the molecular weight of polymers. Two methods viz, sedimentation
velocity method and sedimentation equilibrium method are used for this purpose.
The sedimentation velocity method involves the determination of sedimentation
coefficient, S on applying a very high gravitational field using an ultracentrifuge
which can provide spins as high as 65000 rpm. With the help of the predetermined
paramters like diffusion coefficient, D, specific volume of the polymer in solution,
V.» and the density of solvent, d, the mol. wt of the polymer is obtained using
Stokes law which correlates the sedimentation coefficient and diffusion coefficient
by
Mol. wt. = SRT/D(1 — d Vp) (3.24)
Where R and 7are the gas constant and temperature in Kelvin scale. The above
equation is known as Svedberg equation. In practice both the sedimentation and
diffusion coefficients are measured at different polymer concentrations and the
values extrapolated to zero concentration are used. The sedimentation equilibrium
method as the name suggests concerns with the setting up of equilibrium during
sedimentation. The merits and limitations of the various mol. wt. determination
methods are shown in Table 3(m).
Table 3(m) Different molecular weight determination methods: A comparison
Method Type of average Mol. wt. range
Ebbuliometry or Cryoscopy M,, < 10,000

Vapour pressure osmometry* M, < 25,000
Memberane osmometry M, 1500—100,000
Dilute solution viscosity** M, 15,000—1000.000
Light scattering My, 2000-—10,000,00
Ultracentrifuge M,,,M., MWD 2000-10,000,00
Gel permeation chromatography* M,,,M,, MWD up to 50,00,000
*Relative methods and need calibration from standard polymers samples

**Indirect method and needs values of & and q@ for particular polymer — solvent system
3.3.4 Molecular Weight Distribution (MWD) Curves

The mapping of a MWD curve for a given polymer system can be done by
following steps: (i) synthesis of polymers, (ii) fractionation of polymers (by any
methods from fractional precipitation,
partial extraction or size exclusion
chromatography), (iii) determination of
molecular weight of each of the fraction
and its weight and finally (iv) by plotting
either simple or integral or differential |
distribution curves. In the fourth step, =
a simple distribution curve can be
obtained by using information obtained
in step (iii). i.e. by plotting the weight
of each fraction against its molecular
weight. If the fraction form and M,
separated form differ in molecular “the@
Fig. 3.24 Plot of weight fraction W,;
weight by same value successively, one
versus its molecular weight M;
can easily obtain a simple and smoothed for simple representation of
distribution curve as shown in Fig. 3.24. MWD
But in real experiment and practice, getfing such uniform fractions is extremely
difficult. When one plots a distribution curve between the weight of each fraction
and its molecular weight (as obtained
in actual experiments), the curve
looks like as shown in Fig. 3.25.
Figure 3.25 shows that the spread
of fractions with a given weight and
molecular weight is uneven. The
MWD shown in Fig. 3.25 has least
utility and convey very little
information on the dispersity.
Tackling of the data as shown in
Fig. 3.25 is done either by (i) plotting
the cumulative weight fractions (i.e. M;
—_—
each successive fractions are added Fig. 3.25 Actual MWD curve
continuously) against a molecular

weight of preceding fraction. The
curve thus resulted is known as
integral distribution curve and looks
as shown in Fig. 3.26, or (11) by taking
the slopes at as many points as
possible from the integral curve and
the slopes at each point corresponding
to a particular W; are plotted against
M,; (see Fig. 327). This methods yield
M; the differential weight percentage of
$
Fig. 3.26 Integral distribution curve molecules of particular molecular
weight in the whole polymer sample.
Fig. 3.27 Differential distribution curve of a real polymer sample

Numerical exercises
1. Equal number of molecules with M, = 1,0,000 and M, = 1,00,000 are mixed.

Calculate M,, and M,,.
Solution Let n,; = ny = 10 (say), then,
— nM,+n.M, — (10x 10,000)

+ (10 x 100,000)
M, = —————— =
ny, +n (10 + 10)
10° + 10° _ 10°(1+10) _ 11x 104 a -1

7 x0 SNL ie 10 GL Pe = 55,000g mol
_ mM? +n,\M3 _ [10 x (10,000)}+[10 x (1,00,000)?]

s| ~ nM, +mM, [10 x 10,000] + [10 x 1,00,000]
_ 10? +10" — 10°(1+ 100) _ 101 x 104
~ 105 +10 ~105(1+ 10) 1
= 91,818 = 92,000 g mol"!
2. Equal masses of polymer molecules with M, = 10,000 and M-2 = 1,00,000 are
mixed. Calculate M, and M,,.
Solution Let m, = mz = 2,00,000 (say), then number of moles n, and ny are
a, = mass. my _ 2,00,000 _ 20
1 = Tnolar massM, 10,000 —
mass m) 2,00,000
ny = = =i
molar mass M, — 1,00,000 ~
_ mM,+n,M, _ [20x 10,000] + [2 x 1,00,000] _ 10° + 10°

hie ny + Ny 20 + 2 ni 1]
5
= ait = 18,182 ~ 18,000gmol"
7.< niM? +m,Mz _ [20 x (10,000)?]

+ [2 x(1,00,000)?]
nM, - nM, i (20 x 10,000] st (2 x 100,000]
10° (1
ih al ie 10* = 55,000 g mol”!
2x 10° 2
3. Calculate M,,M, andM, for a polymer consisting of three fractions with
molecular weights, 1 x 10°, 2 x 10° and 3 x 10°. The mole fractions of each of
these fractions are found to be 0.1, 0.5 and 0.4, respectively.
Solution M,, =X nM/&Xn;, M, = XnjM?/XnjM; and M, = Xn,M}/Zn,M?.

Introducing the values of n; and M; namely 0.1, 0.5 and 0.4 and 1 x 10°, 2 x 10°
and 3 x 10° into the relation of M,,, we get
+o08 ((0.1 x 1 x 10°) + (0.5 x 2x 105)

+ (0.4 x 3 x 105)]
ony (0.1 + 0.5 + 0.4]
4
A (1,00,000) + (10,00,000) + (12,00,000)
1
= 2,30 x 10° ¢ mol!
. Calculate M, and M,, and M, for a polydispersed polymer composed of the
following mixture of fractions (mass % and molecular weight of each of the
fractions are given):
4
Mass % 20 30 50
Mol. weight 50,000 1,00,000 2,00,000
Solution The mass fraction W; for each of the fractions would be 0.2, 0.3, 0.5
respectively. In terms of mass fractions,
M, => W,/d (W,/M)), M,, =X W,M/> W; and M, = = W,M?/= W,M, and so

77. — U.0.2x 50,000) + (0.3 x 1,00,000) + (0.5 x 2,00,000)]
ie 0.2 + 0.3 +0.5
= 1,40,000 g mol"!
ack [0.2 + 0.3 + 0.5]
" ~ [(0.2/50,000) + (0.3/1,00,000) + (0.5/2,00,000)}
= 1,05,263 = 1,05,260 g mol"!

and M, can also be calculated in the similar way.
. Calculate M, and M,, for a polymer which contains a mixture of following
amount of fractions (with respective mol. wts. given in parenthesis). 1 g (20,000),
2 g (50,000) and 0.5 g (1,00,000).
Hint Calculate the mass fractions of each of them as 1/(1 + 2 + 0.5); 2/(1 + 2 +
0.5); 0.5/1 + 2 + 0.5), i.e. 0.285 (= 0.30), 0.571 (= 0.6) and 0.142 (= 0.1). Then
estimate 4, and M,, in the usual manner.
. Two fractions of polymers with mol. wts. of 10,000 and 1,00,000 are mixed in the
ratio 0.145: 0.855 by mass. Calculate the ratio M,, /M py.Comment on the nature
of distribution.
. The intrinsic viscosity of myosin is 217 cm? g'. Calculate the approximate
concentration of myosin in water, which would have a relative viscosity of 1.5.
Solution [1] = (Nyp/C)c-40 = 217 cm? g™! and ney = 1.5, Since Nop = Mei - 1 =
1.5-—1=0.5, so introducing 7,, as 0.5 in (1),)/C) and equating the whole term to
217 cm? g ~, we get 0.5.C = 217 cm? g"!; C = 0.5/217 = 2.30 x 10° g cm”.
_ The intrinsic viscosity of a solution of polyisobutylene at 20°C is 180° cm? g™.
If [7] is related to the viscosity average molecular weight M,, by the expression,
[n] = 3.60 x 10 (M°%), calculate the molecular weight M,, of the polymer.
Solution [n] = 3.60 x 104 (M,)°% or 180 cm. g! = 3.60 x 104 (M,)°%,
(M, )° = 180 cm? g-'/3.60 x 10 = 5.0 x 10° taking the log form, 0.64 log M, =
log (5.0 x 10°) and hence M, = 8.03 x 10° g mol.
. The following data were obtained for intrinsic viscosity of some polyisobutylene
samples in CCl, solutions at 30°C. Verify by a suitable plot that the data fit to the
equation [7] =k (M,)*. Determine the constants k and @
[n], cm? g™! M,, g mol

430 12,60,000
206 4,63,000
78 1,10,000
73 92,700
43 48,000
15.1 10,000
13.8 9,550
11.5 7,080
Solution Since [n] = k(M,)%, In[n]=Ink+ @ In M,, one can plot In [7] versus
In M,,. It will be found that slope = a@= 0.70 and intercept = In k = — 8.245 and
hence, k = 2.63 x 10~.
Calculate the intrinsic viscosity of a polystyrene sample in toluene from the
following relative viscosity data obtained at 25°C:
C x 10°, kg m? 0.002 0.004 0.006 0.008 0.010

n, 1.102 1.208 1.317 1.430 1.548
Calculate M, if the Mark-Houwink constants are @ = 0.69 and k = 1.7 x 10-3
m? kg7.
Solution Mark-Houwink equation is given as [n] = k (M,)* where, M, is the
viscosity-average molecular weight of the polymer, [7] = the intercept for the
plot of (7,-1)/C versus C. From the above data of 7), calculate 1-1 = Nesp
and 7,,/C versus C. It would be equal to 50.1 x 10° m* g!. Then M, can
be calculated from the equation 50.1 x 10 = 1.7 x 10° M2 -M, would be
135 kg mol! or 1,35,000 g mol".
. For a2% aqueous solution of apolymer with molecular weight 50,000, calculate
at 27°C (a) the depression in freezing point (A7;), and (b) the elevation in boiling
point. Given that molal depression in freezing point of water = Ky = 1.85 and
molal elevation in boiling point of water = K, = 0.52.
Solution molality of 2% solution i.e. 2 g in 100 ml or 20 g in 1 lit. =m =
20/50,000 = 4.0 x 10 m. Thus calculate au = Ky: m = 1.85 x 4.0 x 107 =
0.00074 and AT, = K, - m= 0.52 x 4.0 x 10“ = 0.00021.
The following data were obtained on the osmotic pressure of solutions of
B-globulin in 0.15 M NaCl at 37°C:
C, g/100 ml 19.27 12.53 5.81
m, mm H,O 453 253 112
Calculate the molecular weight of the polymer.

Solution 100 ml = 0.1 litre = 0.1 dm?. Obtain 7/C values (e.g. 453 mm H,0/192.7
g dm~ =2.35 mm H,O dm’ g“!) and tabulate the data for all the three concentrations
as below:
C(g dm?) 192.7 125.3 58.1

m/C (mm H,O dm? g™') 235 2.05 1.93
Plot 2/C versus C to obtain a straight line. It would be seen from the plot that the
intercept (2/C)c_,9 = 18.6 mm H,O dm? g™!. Given that (1/C)c_59 =
RT/M,,;M,, = RT/(2/C) c-49 where R = gas constant = 0.08206 lit atm K~! mol"!
= 0.08206 x 760 x 13.56 mm H,0 dm? K! mol"! and hence R = 845.67 mm H,O
dm? K™! mol"!, then
i.F; - 845.67186x 310 a= 1.409

x 10°5 g mol Li
13: Use the following data to calculate the number average molecular weight and the
second virial coefficient of the solutions of collagen at 25°C.
C(g m-) 2.4 4.1 5.0 a5 G4

m/CRT (10% mol. kg~!) 3.7 4.2 4.2 42°" 49
Solution According to the van’t Hoff osmotic virial equation
mICRT = E + ByC +B;C? a

M n
Where, M,, is the number-average molecular weight. Thus, a plot of 2/CRT

versus C will be a straight line with intercept = 1/M,, and slope = B3. If we plot
the data, we find that M, = 1/.1 x 10 mol kg!) = 320 kg mol"! B, = 2.5 x
10-* mol m? kg?
The excess Rayleigh ratio, Rig of a polymer dissolved in dioxane was determined
as a function of concentration by low angle laser light-scattering measurements
per the data given below;
C x 10° g mr! Ro x 10° cm!
0.503 0.239
1.007 0.440
1.510 0.606
2.014 0.790
2:517 0.902
If the refractive index, (nj) of dioxane is 1.4199, the refractive index increment
(dn/dC) for the polymer in dioxane is 6.297 x 10 cm? g!, the wavelength (A)
of the laser light is 6328 A, calculate the weight average molecular weight of the
polymer and second virial coefficient (Az). The following equation is employed
for determining the molecular weight from light scattering data;
+
Ea Lah opRe
Ro Joo My
2n*n? (dn/idC)?
and the constant K is calculated from the relation, K =
AtNa
By introducing the values of ng = 1.4199, dn/dC = 6.297 x 10°? and A = 6328 A
(6328 x 10° cm we get K = 1.66969 x 10-°. Then calculate KC/Rg for different
concentrations and obtain a plot between KC/Rg versus C. It would be seen that
the intercept of the above plot is 0.33 x 10~° and hence M,, will be equal to 1/
intercept and that is equal to 3.030 x 10° g mol"!. The slope of the line would be
0.05333 and the second virial coefficient A, would than be one half the slope that
is 2.66 x 10°? cm? mol g™’.
. (a) What is the value of the exponent in Mark-Houwink equation in theta condition?
(b) The solubility parameter of water is 23.4 H. What is the value of CED?
(c) What would be the value of AG at theta condition? (d) What is the value of
the exponent in Mark-Houwink equation for a rigid rod? (e) What is the value of
the ratio of weight average mol. wt. to the number average mol. wt. for proteins?
(f) If we use a 2% molar excess of bisphenol with TDI for making polyurethane,
what would be the maximum DP of the polymer? (g) How many amino groups
are present in each molecule of nylon 6,6 made with an excess of

hexamethylenediamine? (h) What»would be the second virial coefficient at theta
temperature? (i) What would be the value of interaction parameter in poor and
good solvents?
Ans. (a) 0.5 (b) (23.2)? = 543.6 cal cm™ (c) 0 (d) 2 (e) 1 (f) 9
(g) 2 (h) O (i) 0.5, less than 0.5.

Identification and Testing of Polymers
Bark, L.S., and N.S. Allen (eds.) Analysis of Polymer Systems, New York: Elsevier
Applied Science, 1982.
Braun, D., Simple Methods for Identification of Plastics, 2d ed., Cincinnati, Ohio: Hanser-
Gardner, 1986.
Brown, R.P. (ed.), Handbook of Plastic Test Methods, 2d ed., London: George Goodwin
Ltd., 1981.
Craver, C.D., and T. Provider (eds.), Polymer Characterisation: Spectroscopic,
Chromatographic and Physical Instrumental Methods, Washington D.C.: ACS, 1990.
Shah, V., Handbook of Plastics and Testing Technology, New York: Wiley-Interscience,
1984.
Characterization Methods
Barth, H.G., and J.W. Mays, Modern Methods of Polymer Characterisation, New York:
Wiley, 1991.
Bern, B.J. and R. Pecora, (eds.), Dynamic Light Scattering, New York: Plenum, 1976.
Chu, B., Laser Light Scattering, New York: Academic Press, 1974.
Dillinghan, N.C., Molar Mass Measurements in Polymer Science, New York: Wiley,
1977.
Flory, P.J., Principles of Polymer Chemistry, Chap 8, Ithaca, New York: Cornell Univ.
Pressyd 9536
Frankuskiewicz, E., Polymer Fractionation, Berlin: Springer, 1994.
Gloskner, G., Polymer Characterization by Liquid Chromatography, New York: Elsevier
Higlin, M.B. (ed.), Light Scattering from Polymer Solutions, New York: Academic Press,
1972.
Kratochvil, P., Classical Light Scattering from Polymer Solutions, New York: Elsevier
Peebles, L.H., Jr., Molecular Weight Distributions in Polymers, New York: Wiley-
Interscience, 1971.
Smith, C.G., W.C. Buzanowski, J.D. Graham, and Z. Iskandarani, (eds.), Handbook of
Chromatography, Polymers, Boca Raton, Fla: CRC Press, 1982.
Slade, P.E., Jr., Polymer Molecular Weights, (2 vols.), New York: Dekker, 1975.
Wu, C.S., (ed.), Handbook of Size Exclusion Chromatography, New York: Dekker, 1995.
Yau, W.J., J.J. Kirland, and B. Bly, Modern Size Exclusion Liquid Chromatography,
New York: Wiley, 1979.
Behaviour of Polymers
4.1 Crystalline
High molecular weight substances due to the entanglements of the long chains
and polydispersity are not perfectly crystalline unlike low molecular weight
crystalline solids. Generally, no polymer can be regarded to have 100% crystallinity.
The degree of crystallinity varies from polymer to polymer and many polymers
are non-crystalline (i.e. amorphous). The presence of crystalline and amorphous
regions together in polymers can be accounted by “Fringe micelle model” as
depicted in Fig. 4.1. The model presumes that the ordered and disordered domians
are intermingled with no clear cut demarcation between the two regions. The
ordered and disordered arrangements shown in the figure can be equated to the
crystalline and amorphous regions as observed in packing of small molecules.
The ordered crystalline regions in a polymer physical structure are called as
crystallites.
Fig. 4.1 The fringe micelle model showing crystalline and amorphous regions
The crystallites along with the inseparable amorphous regions in polymer

chain packing, form shallow pyramid like structures called “spherulites”. Besides,
these morphologies, it is also observed that ordered polymers may form single
(or lamellar) crystals with a thickness of 10-20 nm in which the polymer chains
are folded back upon themselves. Single crystals are perfect and possess internal
order that can be revealed from x-ray or electron diffraction studies.
The crystallizability i.e. ability to undergo crystallisation in polymers depends

on several factors such as regularity in the chains, thermodynamic chain flexibility
and possibility of close packing. The pre-thermal history of the amorphous
polymers plays not only an important but also decisive role in deciding the
ordered arrangement in polymer solids. Higher degree of crystallinity in polymers
can be developed by using the proper method of polymerisation. Polymerisation
of ethylene at ordinary temperature and pressure can be carried out using special
catalysts (Ziegler — Natta catalysts). As discussed in the second chapter, the
Ziegler Natta catalysts consist of a combination of metal halides (e.g. titanium
tetrachloride and an organometallic compound e.g. trialkylaluminium) dissolved
in inert solvent such as hexane. Polyethylene obtained using Ziegler’s catalyst
and at low pressures, is a linear polymer (with few branches) and has higher
degree of regularity or ordered arrangement in the chain. The polyethylene thus
obtained has high density and melting point and upon crystallisation forms very
good single crystals. The crystalline polyethylene (HDPE) is similar to crystalline
hydrocarbon wax (petroleum product). It is interesting to note that polyethylene
obtained by free radical polymerisation and at high pressure, is strongly branched
which results into lower crystallinity and density. This form of polyethylene is
known as low density polyethylene (LDPE). The copolymers of ethylene and
other alkenes such as butene, hexene etc. hardly have linear structures and can
not be crystallised. When the proportion of ethylene in these copolymers is
major, they are called as LLDPE (linear low-density polyethylenes).
The replacement of H atom of ethylene by other hydrocarbon groups yields
polymers e.g. polypropylene, polyisobutylene or polystyrene, in which the close
packing of the chain becomes difficult due to the presence of the bulky groups
and thus these polymers are amorphous with very low crystallinity, if any. The
presence of a polar group along the back bone of the hydrocarbon chain increases
inter-chain attraction an makes the polymers hard and brittle. These polar polymers
have high melting points (e.g. polyvinyl chloride melts at 273°C). The introduction
of amide linkages in the hydrocarbon chain (e.g. nylons) increases inter-molecular
attraction due to the hydrogen bonding between the oxygen of —CO- group and
hydrogen from —NH— group. The chains of these polymers crystallise with ease
and higher degree of ordering 1s obtained.
Crystallinity of polymers has a direct bearing on their physical properties and
application as fibers, plastics or elastomers. Generally, fibers possess high degree
of crystallinity and tensile strength. Plastics are often amorphous and un-oriented.
The crystallites present in a crystalline polymer such as nylon are usually un-
oriented. However, when the fiber material is stretched at room temperature
Fig. 4.2 Crystallites oriented upon cold drawing

Behaviour of Polymers 137
(cold drawn), the molecules slip across oné another and become oriented. Stretching
of amorphous polymers may also induce some crystalline regions in them.
Elastomers are amorphous polymers with very low glass transition temperature.
However some crystallinity can be induced in elastomers under the influence of
stress. For example the crystallinity in a stretched rubber band can be observed
from its opaqueness and warmth it produces when touched by lips. Similarly, the
fiber forming polymers which age predominantly in amorphous form can be
stretched along the axis of their orientation under stress. Then the fibrous chains
are drawn in a desired direction of their orientation Fig. 4.3 depicts the effects in
an elasotmer upon its stretching.
: @uyg* eVaneeuuend
Under tension e
ESS oF og co8 PPP Pp oeccce®
Tension released
Relaxed form Stretched form

(disordered state with high entropy) (ordered state with low entropy)
Fig. 4.3 An elastomer on stretching develops crystallinity
The crystallinity in elastomers has pronounced effect on its mechanical

properties. In Fig. 4.4, the general variation of mechanical properties in an
elastomer is shown as function of
crystallinity. The mechanical strength,
for example, increases sharply after the
development of some _ ordered
arrangement and shows a continuous
increase at higher crystallinity.
Isotactic polymers are more
crystalline and thus have high melting Mechanical
strength
point and density as compared to the
corresponding atactic forms. Syndio- % crystallinity
tactic polymers have a tough cohesive
Fig. 4.4. Mechanical properties of
structure because of the interlocking natural rubber with different
of the side chains which project above degree of crystallinity
and below the carbon backbone.
X-ray diffraction method is commonly used to study crystallinity in polymers.
Concentric rings are observed in the x-ray diffraction powder photograph of
crystalline polymers similar to low molecular weight solids. Since most polymers
have some amorphous regions, these rings are not usually $0 sharp. For amorphous
polymers, the x-ray diffraction pattern is quite diffused and an amorphous halo
(characterised by dark shaded portion in the centre of the photograph) has been
invariably observed. It is possible to obtain information about the conformation
adopted by the polymer chains in the crystallites. Many polymers crystallise in
helical conformations. The percentage of crystallinity of a partially crystalline
polymer can be determined by x-ray crystallography, calorimetry, dilatometry
and infrared spectroscopy.
Factors affecting crystallinity and thus physical properties of polymers

There are several factors which affect the crystallinity in polymers and thus their
physical properties. These are the molecular length of the chain, the secondary
valence forces, polymer configuration and conformation, and the nature of chain
packing in polymer molecules. Some of these factors have already been considered
earlier. These factors influence important physical properties such as impact and
tensile strength, melting point, melt viscosity and even the solution properties of
polymers.
Molecular weight
One of the most important properties of a polymer moleculer is its molecular
weight. This characteristic property alone distinguishes a polymer molecule
from its low molecular weight analogues. The physical properties of polymers
such as tensile strength and impact resistance are intimately related to the molecular
weight and molecular weight distribution of the polymer chain. Low molecular
weight substances tend to be brittle and possess poor mechanical strength. Usually,
the mechanical properties in a polymer develop after a threshold molecular
weight is reached. Above a certain molecular weight these properties are almost
unaltered. However, the melt viscosity at first increases slowly and then rapidly
after the polymer has attained a certain molecular weight. The value of threshold
molecular weight varies from polymer to polymer. For example, polyolefins
exhibit such behaviour at a DP value around 5000 whereas for polyamides the
value is only 200 on account of hydrogen bonding between the different chains.
The effect of molecular weight of polymer on its mechanical strength is shown
in Fig. 4.5.
Perfect crystalline
Hard, brittle Stronp) tit

2 No effect of} hard
ed crystallinity
= on mechanical isteeeeeeneenecetsnreceneees 7Aprniad Seat het ae
EF properties: :
e Sah wax Hard, brittle,
: y limp or flexible
Amorphous < 10,000 > 10,000

Molecular weight
Fig. 4.5 Effect of mol. wt. and crystallinity on the mechanical strength
of polymers
It may be pointed out that not all the physical properties of polymers are
dependent on the molecular weight or for that matter on the magnitude of the
intermolecular interactions. For example, the refractive index, colour, density,
hardness and electrical properties are independent of the molecular weight of the
polymer. Due to very high melt viscosity, extremely high molecular weight
polymers become tough and intractable and cannot be easily handled. Thus,
such extremely high molecular weight polymers are not desired for end use
purpose.
Behayiour of Polymers 139
4
Secondary valence forces
The secondary valence forces e.g. van der Waals and dipole-dipole forces in
polymers are similar to those present in small molecules. In polymers, however,
many types of electrostatic forces may be present that act among different parts
of the same chain. The strength of these forces increases with the increasing
polarity and decreases sharply with increasing distance between such polar groups
along the chain. The cumulative effect of thousands of the bonds spread along
the polymer chain results in large attraction. The inter-molecular bonds formed
in polymers are described in the introduction part of this book. The physical
properties of polymers thus drastically change with inter-molecular forces. This
has been illustrated using some examples. Polyethylene, due to the presence of
only very weak van der Waals forces between the chain segments (as it is non-
polar) is a soft waxy solid. Nylons and cellulose chains have extensive inter-
molecular hydrogen bonding and are strong fibers. Dipole-dipole interactions in
polyester and PVC make them tough plastics. Markedly different properties can
be seen in polyethylene and nylon 11, which may be considered some what
structurally similar as shown in the Fig. 4.6.
ATP, re oe hen tes ENN 7h CHa.
H.C CH, tee a

dam CHC gr CH, Pe
med CH BLO gem

per CHC pers CHC
es CH, sth Die
7h CHC aah CHa
H,¢ ‘ CH, Eee vn

ct, CH, ee ae
oS
ae ath AG CH)
Doh CHS oe CH
elegy oda jig CH, CH,
8 Nylon 11 Polyethylene
Tn = 180°C T,, +.130°C
Fig. 4.6 Structural similarities in nylon 11 and polyethylene
Chain flexibility
A polymer chain is considered to be flexible if the chain segments can rotate
with respect to each other with sufficient freedom. Thus, polybutadiene and
polyethylene have flexible chains whereas polystyrene and polymethy! metacrylate
have rigid chains. The flexibility of a polymer chain depends on factors like
potential energy barrier to rotation, molecular weight of the polymer, nature and
size of the substituents and cross-link density etc. These are briefly described
below.
The potential energy barrier is the minimum energy needed for chain molecule
to undergo a conformational change via a special kind of motion i.e. internal

motion. It depends mainly on the strength of intta-molecular and inter-molecular
interactions. For example, isolated chains of polyacrylic acid and polymethacrylic
acid should be rigid due to strong intra-molecular interaction of their COOH
groups. In the condensed phase, the intra-molecular interaction of carboxylic
groups lowers the potential energy barrier, the chains become flexible and assume
a coiled globular structure. Conversely, chains that are flexible in the isolated
state become more rigid in the condensed phase due to strong inter-molecular
interaction.
The introduction of substituents containing polar groups in a polymer molecule
intensifies the intra- and inter-molecular interactions. The most polar groups are
the —CN, —NI,, —OH, groups. The distance between polar groups in a polymer
chain has a profound effect on the flexibility of the chain. For example, in a
copolymer of butadiene and acrylonitrile, containing 18 percentage of acrylonitrile
on mole basis, the flexibility of the chain is close to that of polybutadiene. As the
amount of acrylonitrile is increased in the copolymer, the flexibility decreases
and the chain becomes more rigid. Polytetrafluoroethylene and polyvinylidene
chloride have flexible chains even though a large number of polar groups are
present in the chains. This is due to the fact that polar substituents (halogen
atoms) are arranged symmetrically on a C atom. Molecular weight, in a homologous
series of polymers, has a very little effect on the potential energy barrier but as
the chain length increases, infinite number of conformations are possible which
can change the conformation of the chain from a coiled form to a rod like shape
even though there may be high energy barrier.
Bulky substituents such as phenyl groups in polystyrene make the chain less
flexible and consequently rigid at insufficiently high temperature In butadiene
and styrene-buadiene copolymer (SBR), if styrene is randomly distributed in the
chain and its percentage is small, the chain is flexible. As the amount of styrene
is increased the chain flexibility decreases. The presence of two substuents on a
carbon atom decreases the chain flexibility. For example, polymethyl methacrylate
contains two substituents, e.g., —CH; and —COOCH; whereas polymethyl
acrylate has only one such substiuent, a—-COOH; group. Polymethy! methacrylate
is more rigid than polymethyl acrylate.
The flexibility of natural rubber which has been vulcanised by the addition of
2—3% sulphur based on the rubber content is comparable to that of unvulcanised
rubber. However, if rubber is highly vulcanised, a rigid network structure is
formed and the mobility of the unit is decreased considerably. Consequently, the
chains are said to have high-link density and become rigid.
Some common observations on the crystallinity can be listed as follows:
Linear polymers are more crystalline than their branched counter parts (HDPE
is more crystalline than LDPE). trans 1, 4-Polyisoprene is more crystalline than
cis form (natural rubber). Poly #-glucose (cellulose) is crystalline whereas poly
a- glucose (starch) is amorphous. Stereoregular polymers are crystalline. whereas
poly a@-glucose (starch) is amorphous. Stereoregular polymers are crystalline.
Polarity in the chain develops crystallinity. Nylons and polyesters are crystalline.
The terms crystallinity and crystallizability are interchangeably used but they
have quite different meaning. Crystallinity means the relative proportion of

crystalline and amorphous regions in a polymer sample (degree of crystallinity)
at a particular temperature and depends on conditions like rate of cooling, residence
time, temperature of the molten polymer, heat dissipation at which the crystallisation
take place. Crystallizability refers to how a polymeric substance can be obtained
in the crystalline form from melt or solution. It refers to the maximum crystallinity
that a polymer can achieve at a particular temperature and depends on the chemical
nature of the chain, its geometrical structure, molecular weight and molecular
weight distribution. Regarding the crystallizability of polymers, the following
general comments can be made. Homopolymers are more easily crystallised
than copolymers. Alternating copolymers are more easily crystallised than random
copolymers. Polymers with bulky pendant groups are crystallised with great
difficulty. For example, polyvinyl carbazole is amorphous.
Like low molecular weight substances, polymers crystallise into various
morphological forms i.e. physical structures. These include single crystals to
polycrystalline spherulite formations. The comparison of the size of crystallites,
spherulites and single polymer crystals with those of simple molecules is shown
in Table 4(a)
Table 4(a) Structural units and their sizes
Morphological minimum size maximum size
forms A A
Molecules 2-5 10°-10°
Crystallites 20-100 100-500
Single crystals 100 10°-10°
Sphemulites 10°-10’ > 10’
Depending upon the dimensions and symmetry of the simplest crystalline

units and the manner of their mutual arrangement, the macroscopic physical
structure in a crystallised state may consist of single crystals and when they are
formed, the physical structure is built by the translation of identical unit cells.
There are several types of single crystals, which vary in the mutual arrangement
of units in the space and the symmetry of ultimate structures. For example,
polyethylene may crystallise into orthorhombic structures. The chains of
polyethylene are arranged in a planar zig-zag manner along four edges and in the
centre of the orthorhombic unit cell (see Fig. 4.7).
When the linear chains with bulky side substituents are crystallised, the unit
cells formed are characterised not by a planar zig-zag arrangement but by helical
conformations with different loop lengths depending on the size and nature of
side substituents. The various possible ordered helical structures in isotactic
polymers are shown in Fig. 4.8.
Three basic single crystal structures namely lamellar, fibrillar and globular
single crystals result when polymers are crystallised from dilute solutions. Also,
these formations differ in dimensions and shape of unit cell and in regularity of
arrangement of the chain. The formation of particular single crystal depends on
(b)
Fig. 4.7 (a) Conformation of a polyethylene chain and (b) arrangement of chains
in a crystalline cell
(c) (d)
(a) e = —CH,; etc., (b) ¢ = —CH,—CH—(CH3),,

(c) e =—CH,—(CH;), (d) ¢ = —CsH;—F
Fig. 4.8 The helical ordered structures in isotactic polymers
molecular characteristics of polymers as well as crystallisation conditions. The

temperature of crystallisation, nature of solvent, concentration of solution and
cooling rate etc. When the crystallisation is carried out in concentrated solutions
or from polymeric melts and under real conditions (high viscosity, high temperatures
and applied mechanical pressures) that are encountered during the processing of
various polymeric articles such as films, casts and fibers, spherulite structures,
unique only in polymers are formed. These structures can be seen by the naked
eye or viewed as maltese-cross like formation under a polarised microscope.
Crystallisation of polymers
By crystallisation, an ordered arrangement is obtained from a disordered one
which is usually present in a melt or solution. For example, when a molten
polymer is cooled below its T,,, there isan inherent tendency for the randomly
tangled molecules in the melt to align and form small ordered regions. Such
regions are called nuclei, which are stable only at temperatures below T,,, (and
are disrupted above T,, by the thermal motion). Once the crystal nuclei are
formed, they do show crystal growth by addition of further chains. Thus,
crystallisation is an over all process consisting of nucleation and crystal growth.
Nucleation may be homogeneoys (i.e. where the nuclei do form randomly
throughout the polymer melt) or heterogeneous (where foreign particles such as
dust and impurities form part of nuclei besides the amorphous polymer molecules).
Nucleation is temperature dependent. At high under-coolings, many nuclei are
formed along with a large number of spherulite structures. Crystal growth can
take place in one, two or three dimensions leading to variety of geometrical
shapes for the crystals ranging form rods, discs and spheres, respectively. The
growth takes place by the incorporation of polymer chains within the crystals,
which are normally lamellar.
The change in size for a unidimensionally growing entity is generally linear
with time at a given temperature of crystallisation. For example, a spherulite
radius r will change with time ¢ through the relation r= vt, where vis the growth
rate. This relation is valid only at initial stages of spherulite growth (i.e. until
they are not very large and touch one another). The growth rate depends upon
the molecular weight of the polymer (it decreases with increase in molecular
weight) and temperature (often a peak is seen). These effects are shown in
Fig. 4.9. The temperature dependence of v showing a peak may be explained
due to two competing effects. A decrease in temperature will increase the
thermodynamic driving force for crystallisation. At the same time, decrease in
temperature gives rise to increase in viscosity that offers obstacles in transporting
the molecules to the point where crystal growth occurs.
hr!
Rate,
-60 -50 -40 -30 -20 -10 0 10 , 20

TG:
Fig. 4.9 Effect of temperature on the crystal growth
rate for natural rubber
Kinetics of crystallisation
As discussed earlier, the crystallinity in polymers has tremendous effect on
structure-performance relationship of polymeric materials. It is therefore necessary
to study the kinetics of crystallisation and provide a molecular mechanism
to the process. This can be done by considering some asumptions such as:
(i) nucleation is homogeneous, (ii) at a given temperature the number of nuclei
formed per unit time and per unit volume is a constant (say N) and (iti) there 1s
no impingement of spherulite structures already formed. Now, if a molten polymer
of mass Wp is cooled below the crystallisation temperature, spherulites will
nucleate and grow over a period of time. The total number of nuclei formed in
time interval (say df) will then be N Wo dt/p,,, where p, is the density of the
molten polymer.
After time rf, suppose these nuclei grow into spherulites of radius, r, the mass
of each spherulite wil be 4/3 zr? p, where /, is the density of spherulite.
Now since r = Vt, so te mass of the spherulite material (dW,) present at time
t and grown in time interval dt will be
dW, = 4/3 nu°tp,.N Wo/p,dt (4.1)
where N is the number of nuclei, Wo is the initial mass of the polymer melt, 9,
is the density of the grown crystal at time f.
The total mass of the spherulite formed after time ¢ from all nuclei N is,
4/3nv3t30,NW,
W, (4.2)
3p;
or
W, mVv°t*p,
— = 4.2a
Wo 3p; ee
If W, is the total mass of liquid left after time ¢, then Wp = W, + Wj, and
Ws mVv * 0,
W, = 1 3p, (4.3)
Equation 4.3 predicts the essential features of spherulite crystallisation and it

further predicts that mass fraction of the crystals should depend initially on fr’.
The above equation is derived on the assumption that the nuclei are grown
independent of any impingement that may occur during the growth process.
However, it is logical to expect that the growth of a nuclei may get impeded if
impingement of growing nuclei is taken into consideration. In case of impingement
of spherulites, the following equation can be obtained
i ee= exp(—kt*
Wo 4) (4.4)
This equation is called Avrami equation. It can be seen that for small t, both the
eqs. 4.3 and 4.4 have the same form. If the nucleation and crystal growth follow
some other types, a general equation that can be written is
Wy P
Wet exp(—kt” ) (4.5)
where n is known as Avrami coefficient, k is the constant which includes terms

such as nucleation frequency, growth vector, shape factors and densities of

crystalline and amorphous phases. The crystallisation can, however, be monitored
by measuring change in specimen volume rather than the mass of grown spherulite.
This can be done dilatometrically. Defining the volume terms as
Vo = Wo/pi (4.6)
Va= Wolps « (4.7)
V, = W,/p; + WJps (4.8)
= Wd/p,; + (W,(1/p; — 1/p,))

Introducing Vp and V, from eqs. 4.6 and 4.7 into eq. 4.8, we get
Vs = Va + Wi((Vo/Wo) — (Val Wo)) (4.9)

or
WwW, = V, én Ve pt ery:
Writ Va exp(—zt” ) (4.9a)
Thus, the value of Avrami coefficient n can be determined from the slope of log-
log plot of volume terms and time.
A typical plot of log eparaMesversus

Vo -— Va
log t is shown in Fig. 4.10.
The Avrami equation provides a
satisfactory account of polymer
crystallisation rate but does not give &
any insight into the molecular
mechanism involved in nucleation and
growth. Several theories have been put log t
forward to explain the phenomenon but
Fig. 4.10 Log volume change ratio
none has so far been found to be perfect.
versus log time plot
Supramolecular structure of polymers

Polymeric solids are unique. Some special solid state characteristics of these
molecules are already discussed. The diverse physical and mechanical properties
that are observed in polymers no doubt not only depend upon their chemical
characteristics but also on their physical structure. Owing to the large size and
presence of long chains besides smaller units, the spatial arrangement of
macromolecules into separable elements out of which the entire structure is
built, assumes great significance. The way of chain packing, dimensions and
shape of the its constituent elements and the relative arrangement of elements
constitute the supramolecular structure of polymers. There are three main methods
for investigating the supramolecular structure. They are visual methods, interference
and diffraction methods and measurements of properties, which are related directly
or indirectly to the physical structure.
Visual methods
The visual methods are based upon examination of either transmitted or reflected
electromagnetic radiation from the specimen. Thus, in order the above phenomenon
to occur, the electromagnetic radiation must have wavelengths far smaller than
the sizes of structural elements, for example of unit cells in a crystalline body.
The application of these methods enables to discern the information on the
shape, geometry, size and other specific features in the specimen under observation.
Two common visual methods namely optical and electron microscopy are used
in observing the morphological features of polymer solids.
(a) Optical microscopy

This method is based on the formation of a magnified image (of the specimen)
when polarised visible light is thrown on it and the incident light either gets
transmitted or reflected. Since the wave length of visible light range from 400 to
800 nm, the optical microscopy methods can be easily applied even on the
specimens having dimensions as large as several to hundred microns. Another
advantage with this method is that it requires no special sample preparation and
thus it can be easily applied. Samples in the form of thin films or slices (from the
bulk bodies) with thickness ranging from several to hundred microns can
conveniently be studied. The optical microscopy technique utilising the reflected
light passing through the films of the samples cast on a microscope glass slide,
is used for analysing the morphological and structure related studies. The polarised
light and the phase contrast microscopy methods are also employed in analysing
the polymer molecular aggregates containing domains differing in refractive
indices. Besides obtaining information on morphological features, the optical
microscopy methods are widely used for monitoring: (i) changes in the order of
molecular rearrangement during the crystallisation process, (ii) kinetics of
crystallisation and (iii) effects on physical structure under the influence of various
thermal and mechanical variations.
(b) Electron microscopy

In electron microscopy, electron beam emanating from cathode ray tube is made
to fall on the specimen. Modern electron microscopes operate at accelerating
voltages of 100-300 kV, use electrons with wave lengths ranging from 0.03 to
0.06 A. Thus it is possible to study the structural elements, whose dimensions
range from several angstroms to few microns. Moreover, electron microscopy is
a powerful technique because its resolution power is 3-20A and magnification
of image by 3 x 10° to 1 x 10° times possible. The images obtained from an
electron microscope are not called photographs but as electro-micrographs. The
image formed is not only due to optical phenomenon but also involves the
contribution from the interaction of an electron beam with the sample. The
variation in the scattered electron intensities from different regions of the sample
develops contrast and with the amplification facility, images with high magnification
are formed.
Unlike optical microscopy methods, electron microscopy requires stringent
procedures for sample preparation. The thickness of transmitting layer is confined
to 1000 A because of strong interaction of electrons with the sample being

examined.
In actual practice, the samples thinner than 1000 A are used. Thus, the method
allows studying the structure even in very thin films or fractures of the polymer
samples. Polymer single crystals can be easily examined under an electron
microscope. As already mentioned, the contrast in electron micrographs depends
on the electron scattering ability of the nuclei of various atoms present in the
sample. Atoms of heavier metals scatter the electrons to a greater extent in the
sample Atoms of heavier metals scatter the electrons to a greater extent and
hence metal shadowing of polymer specimens is often employed in electron
microscopic methods.
Scanning electron microscopy (SEM) has been developed as special technique
in which a fine electron beam is scanned across the surface of an opaque and
nonconducting polymer specimen coated with a conducting film of metals such
as gold and copper. The sample is illuminated by parallel electron beams and the
scattered electrons are measured by Gieger—Muller counters. The scattered electron
intensities are then converted into cathode ray beam whose intensities vary with
the initial intensity. This variation in the intensities develops a contrast and the
image of the sample under observation is formed on the screen. The images
formed have greater depth of field and excellent three dimensional appearance.
SEM method is used in the studies of (i) phase morphology of polymer blends,
graft and block copolymers (ii) surface features or textures of natural and synthetic
fibers and (iii) monitoring the surface or fracture failure in plastics, elastomers
and composite materials under the applied mechanical stresses such as tensile,
abrasion and dynamic loading etc.
Electron microscopy is also a powerful tool to investigate the unique
characteristics of amorphous state in polymers. It is found that amorphous polymers
are not perfectly disordered but are poorly crystalline and have some order of
arrangement among its structural elements. A special technique called dark field
electron microscopy has been developed to detect the ordered regions in otherwise
amorphous polymers. This method is based on isolating the scattered Bragg
reflexes from a specimen. In this method the entire useful field becomes dark
and the ordered regions from which the scattered electrons which produce Bragg
reflexes are examined. The use of this technique has shown that like in crystalline
polymers, amorphous state in polymers is characterised by the presence of some
degree of order (in the form of domains) of 30-100 A. These domains are
thought to be formed by the chain folds.
Interference and Diffraction methods

These methods are based on interaction of the electromagnetic radiation with the
ordered ensembles of structures as encountered in crystalline bodies of a material
and following the scattering pattern by using suitable detectors. The wavelength
of the radiation used is either of the same order or much larger than the characteristic
size of the structural elements in the ordered bodies. The diffraction or interference
pattern of x-rays from the ordered structures of a specimen provide information
on wide variety of quantitative physical structural characteristic such as shape
and dimensions of the entities, distance between scattering centres and the extent
of order or repeat distance in a given structural arrangement. Small angle and
large angle x-ray diffraction, electron diffraction and neutron diffraction are
some powerful analytical techniques employed for understanding and elucidating
the structure of crystalline, drawn or oriented polymers.
When monochromatic x-rays are passed onto a rystal, whose structure consists
of layers in which its constituent atoms or molecules are arranged perodically
with the spacing as that of the same magnitude as the wavelength of x-rays used,
simple reflection and scattering of incident rays would occur. The interference
coming from the reflections caused by the atoms/molecules in the same plane or
from the neighbouring planes severely affects the ultimate intensity reflected
beam. Bragg, W.H. and Bragg, W.L. (father and son, both shared Nobel physics
prize; the son at the age of 25) gave the condition for a constructive interference.
The incident x- ray beam can be represented with all the waves in phase i.e. their
electrical and magnetic vectors are same all along the path of their propagation.
For some special angles, 0, the reflected x-rays coming out from particular
planes separated with a periodic ‘d’ spacing are also in phase with each other.
Under this condition the reflected waves will then add or reinforce each other,
giving a net resultant wave with double of its intensity in comparison to incident
beam. This phenomenon is known as constructive interference or diffraction.
Fig. 4.11 shows a constructive interference pattern of x-rays at certain angles of
reflections, 6 from the planes stalked with spacing ‘d’. Bragg and Bragg further
established that the constructive interference pattern is observed whenever the
phase difference of reflected x-ray beam (from successive planes) differ by an
integral multiple of wave lengths. This is summarised in well known Braggs
equation given as, nA = 2d sin 0, where n = 1, 2, 3,...
The diffracted x-rays are measured classically from the strong blackening of
a photographic film used as detector. Modern x-ray diffractometers use photoelectric
counters for measuring the intensities of diffracted x-rays. The type, size and
geometry of crystal unit cells are discerned from the position and intensity of
diffracted beams. There are three basic methods of x- raying that are widely used
Net reflection
d Sa ge Constructive
x interference
Fig. 4.11 Constructive interference (diffraction) pattern of scattered x-rays

for structural determination of ordered formatons, (a) Laue method, (b) rotating
crystal method and (c) Debye-Scherrer powder method. Laue method and rotating
crystal methods are not employed for studying the solid polymers because both
of these methods need single crystals of large dimensions for observing strong
diffracted reflections for further analysis. Polymers hardly form single crystals
and even if formed, their size is too small for x-ray diffraction experiments using
the above two methods. Thus Debye-Scherrer powder method is of the great
importance and widely used for investigation of oriented polycrystalline samples.
Most of the polymer crystals are polycrystalline and lattice layers are ordered in
each crystallite but the crystallites themselves are not perfectly ordered. Debye-
Scherrer method originally used for crystal powders suits well for polymer
crystalline materials also. When monochromatic x-ray beams are incident on
these ordered layers arranged along one- or two- or even three-dimensional
directions, they find sufficient lattice layers for possible reflections that satisfy
the Braggs condition. The multitude of orientation of layer lattices for example
in a stretched polymeric fiber, generates a coaxial cones of diffracted x-rays,
with a common origin at the centre of the specimen. Each spot generated by the
vertex angle of each of the cones is equal to 20. When the photographic film is
unfoled or straightened and developed, one observes the vertical cross section of
the system of cone, which translates into a number of concentric rings or ellipses.
Powdered pattern of diffracted x-ray from semi crystalline isotactic polystyrene
and atactic or amorphous polystyrene are shown in Fig. 4.12.
(a) (b)
Fig. 4.12 Powder diagram of x-ray diffraction pattern for (a) amorphous or atactic
polystyrene and (b) semi-crystalline isotactic polystyrene
The x-ray diffraction analysis using powder method reveals that three basic
structural orders exist in polymer solids. These are small period. helical pitch
and large period. These three types of periodicities have their own characteristic
Bragg angle. For small period and helical pitch whose size ranges from 1-20A,
the @ values vary from several degrees to some tens of degrees. Thus, the diffraction
observed from these regions is called large angle x-ray scattering. The large
period, which is characterised by the presence of both ordered and disordered
regions along side each other and as inseparable entities, have dimensions as
large as hundred of angstroms. The diffracted angles ftom these large structures
are low i.e. from several minutes to 1—-2° and the method of diffraction is known
as small angle x-ray scattering (SAXS).
The observed x-ray diffraction patterns are quantitatively processed by trial
and error method. In this approach, an hypothetical model is pre-assumed of a
particular arrangement in the specimen under observation and the expected
diffraction patterns are calculated. Then the observed and expected calculations
are compared. The comparisons are continued till a close or perfect match between
expected and observed patterns are obtained. With the advent of modern computers
this approach has been highly successful. The x-ray diffraction analysis has
made it possible to decipher the helical conformation in deoxyribonucleic acid
(DNA) and proteins, which is one of the important discoveries. The relative
proportion of ordered and disorderd regions that is typically found in polymer
crystals is calculated from the x-ray diffraction pattern.
The orientation (full or partial) of chains especially in fibers and its changes
under external effects viz. temperature, magnitude and direction of stress etc.
can be easily ascertained from the characteristic changes observed in diffraction
pattern. The formation of cracks or fractures in solid polymer materials are also
detected from the x-ray diffraction analysis. The changes in crystallisation
conditions such as crystallisation temperature, heating and cooling rates, nature
of solvent and the presence of nucleating agent etc. can profoundly affect the
macro conformations and packing of chains in crystals. These changes lead to
‘polymorphism’, which means several crystalline geometries are possible for the
same polymer, when it is crystallised under different conditions. The existence
of such a phenomenon can only be monitored by x-ray diffraction pattern.
Electron diffraction
The principle employed in electron diffraction is essentially same as that used in
x-ray diffraction. The major advantage being that the wavelength of electrons is
smaller than x-rays and hence structural information on specimens of smaller
dimensions or from a part of larger domain can be obtained. However, care must
be taken of the fact that electrons, when bombarded cause structural modifications,
even induce fragmentation and scissioning of polymer chains producing macro
free radicals, which then form macroscopic cross-linking network structures.
That is why the intensity of electrons and time of their exposure to the specimen
have to be controlled. In order to avoid the absorption of electrons by the specimen
samples, diffraction experiments are normally conducted under high vacuum.
This requirement of experimental condition, however, is very beneficial because
samples in the form of fine films produced on a substrate can be scanned to elicit
structural information.
Neutron diffraction
The theory of neutron diffraction essentially follows the same principle as scattering
of light by macromolecular chains in dilute solutions. Neutrons are uncharged
unlike x-rays and electrons. The slow neutrons produced in a nuclear reactor get
scattered by the nuclei of atoms in the substance. The scattered intensities of
monochromatic neutrons depend mainly ‘on the mass of nuclei. Good contrasts
are developed due to the difference in scattered neutron beam intensity emerged
from nuclei of different mass. The wavelength of neutrons is dependent on their
energy. Cold neutrons have wavelengths in the range of 1.61.8 A. In the actual
experimental practices, the systems investigated include the polymer chains
containing certain amount of deuterated molecules in the medium of hydrogen
containing molecules or vice versa. Since the source of neutrons is nuclear
reactors, this facility is not widely accessible to users. The neutron diffraction
analysis has been widely used to investigate the phase states at microscopic and
macroscopic level in imperfect solid polymers especially in glassy state.
Besides the above discussed direct methods, an independent group of methods
can also be used for studying the physical structure in polymer solids. These
methods are called as integral methods and are based on the measurement of
dependence of any physical property, which is sensitive to the structural order.
These methods are based upon; (i) measurements of heat capacity and temperature
induced transition points, (ii) measurements of deformational and relaxational
properties, (111) measurements of electrical permeability, dielectric loss and electric
conductance, (iv) measurement of density and density related properties and
their change with time and (v) special spectroscopy methods particularly infra-
red dichroism. All the above mentioned methods are known as indirect methods;
they measure changes in specific properties with variation in crystallisation
conditions.
4.2 Thermal
Polymeric materials differ from low molecular weight substances when they are
subjected to heat. While low molecular weight substances on heating show sharp
melting and boiting points, the situation is different when a polymer is subjected
to heat. An amorphous polymer, for example, on heating becomes flexible above
a certain temperature (usually a small range) and then melts on further heating
(again over a small range of temperature). Furthermore, polymers decompose
before the boiling is noticed and therefore, do not exist as vapours. Melting
temperatures of most low molecular weight substances are very easy to detect
since solid, crystalline materials, fuse together to become melts with low viscosities
at these temperatures. The distinguishing features in two classes of substances
when subjected to heat are shown in Fig. 4.13.
Amorphous polymers are known to exhibit two distinctly different mechanical
properties. Some polymers like polystyrene, polyvinyl chloride, polymethyl
methacrylate are hard and rigid glassy materials at room temperature whereas
some others like polybutadiene, polyisoprene and polyisobutylene are soft, flexible
and rubber-like. However, glassy plastic materials can exhibit rubber-like properties
on heating to a certain degree and conversely, rubbery materials become glassy
on cooling. Thus, all amorphous polymers undergo a change from glassy state to
rubbery state and vice versa at a certain temperature known as glass transition
temperature, T,. Each polymer has a characteristic T, value. By definition, glassy
plastics will fave T, values above room temperature and rubber like materials
will have a T, vate below room temperature.
Low molecular weight substances

Sharp change Sharp change
solid gas
Tn T;
Polymeric materials
Narrow range Narrow range
A A A
pa Ga ae ————~ No gaseous state and
Glassy Flexible Melt polymers decompose
into small units
b Tn
Fig. 4.13 Distinct features of low and high molecular weight substances on heating
The thermal transitions in a polymeric material may be described as follows.

An amorphous polymer at lowest temperature behaves as a brittle glassy solid.
Since it is not crystalline, it has no long range order of crystalline solids. Glassy
state of a polymer can be considered as super cooled liquid state. Above a certain
temperature called 7,, the polymer attains flexibility and rubber-like nature; the
segmental motion ses in the constituent units, while the entire chain as a whole
is at rest. In other words, it can be said that the internal Brownian motion begins
but without external Brownian motion. On further heating, the polymer melts at
its T,, when the motion in the whole chain begins (i.e. the external Brownian
motion sets in). Fig. 4.14 depicts the effect of temperature on phase changes in
amorphous and crystalline polymers.
The glass transition temperature of a polymer depends upon several factors.
This can be illustrated taking some examples. Increasing inter-chain interaction
as well as chain stiffness and cross-linking raise T, value. Polyacrylonitrile
because of very strong secondary bonding forces has T, value even higher than
its decomposition temperature. Higher T, for poly a-methylstyrene than polystyrene
is due to extra steric hindrance to rotation. Very high T, values for ladder polymers
e.g. polyimides are due to chain stiffness.
T, of a polymer can be lowered with the help of plasticizer, a chemical
substance deliberately added to the polymer to reduce interchain forces thus
facilitating the movement of chain segments. A hard and tough polymeric material
polyvinyl chloride becomes flexible at room temperature (T, decreases) in the
Amorphous ; Crystalline
Molten liquid Molten liquid
Flexible thermoplastic
Temperature
Crystalline and glassy

domains
Fig. 4.14 Temperature effect on the amorphous and crystalline polymers
presence of the commonly used plasticizer dioctyl phthalate (DOP). The flexible
PVC has several end uses e.g., in making rain coats etc.
Several methods can be used to determine glass transition temerature of
polymers. Since T, involves thermal transitions, any physical property when
measured as a function of temperature would yield a break point at T,. The
specific volume method (dilatometery) and thermal analytical methods (DTA
and DSC) are most commonly used. The dilatometric method requires the
measurements of specific volume at different temperatures. A dilatomerter is an
all glass apparatus as shown in Fig. 4.15. The bulb of the apparatus contains the
polymer sample along with a confined liquid. With the expansion or contraction
of the polymer with temperature, the liquid is displaced and the quantity displaced
can be measured in a graduated capillary tube. The specific volume so obtained
is thus plotted against temperature. The inflection point in the specific volume—
temperature curves can be used to determine 7, for most amorphous polymers.
A typical plot of specific volume versus temperature is also shown in the same
figure. When the polymer sample is perfectly crystalline i.e. degree of crystallinity
Specific
volume
Liquid
Solid polymer
Temperature
(a) (b)
Fig. 4.15 (a) Dilatometer and (b) Graphical determination of T, from dilatometric
measurements
is hundred percent (which however is very rare in polymer solids), the plot
shows a reflected Z type relation with sharp point of transition. The specific
volume abruptly increases indicating direct melting. The sharpness of transition
points is decreased with the presence of disordered or amorphous regions. In this
case melting is preceded by glass transition.
Fig. 4.16 shows typical plots of specific volume versus temperature for
amorphous, partially crystalline and crystalline polymers.
z Amorphous Partially crystalline Crystalline

= ;
£ | Glassy
v
‘=
5 t : p
e :Rubbery ; Melt
zs y Y !
ie if iy Tp Li
Temperature
Fig. 4.16 Dilatometric data for amorphous, partially crystalline and crystalline
polymers
It can be seen that, for crystalline polymers the glass transition is not detectable.
Though the specific volume versus temperature plots are simplest means of
determining 7, values of polymers, the data from more sophisticated methods
such as DSC are needed for the final assignment of glass transition temperatures.
Table 4(b) lists glass transition temperature, 7, values for some common polymers.
Table 4(b) 7, values for some selected polymers
_ Polymer Ty K
Polystyrene 373
Polyvinyl] alcohol 358
Polyvinyl acetate 301
Polymethy! methacrylate (isotactic) 378
Polyvinyl! chloride 354
Polypropylene (isotactic) 378
Polypropylene (atactic) 255
Cellulose triacetate 430
Cellulose acetate butyrate 320
Low density polyethylene 148
Polyacrylonitrile 378
Nylon 6, 6 330
Terylene 342
Polydimethylsiloxane 150
1, 4-cis Polybutadiene 165
1, 4-trans Polybutadiene eho$s:
The following are some important points regarding the glas transition tempeature:
(i) T, is an inherent property of amorphous polymers originating at the onset of
segmental motion in the chain, (ii) T, and the melting temperatures are related
as follows: T, = 1/2 T,,, for regular polymers and = 2/3 T,,, for amorphous polymers,
(i11) Plastisizers decrease T, (Plastisizers are low molecular weight, non-volatile
substances mostly consisting of organic liquids based on alkyl di-esters. They
decrease T, because their molecules penetrate into the polymer matrix and establish
polar attractive forces between them and polymer and thus decrease the inter chain
attraction. This affects segmental motion and thus lowers T,), (iv) Small amount
of a monomer is often added to decrease the T, of a polymer during its formation.
This is called internal plasticization., (v) T, of copolymers usually lies between
the T, values of the individual homopolymers, (vi) For block copolymers, two T,
values one corresponding to each block are seen.
From the view point of the physical structural changes in a polymer with an
increase in temperature, the segmental motion in a polymer chain though plays
a key role, monitoring of the changes in energy based thermodynamic parameters
as function of temperature gives characteristic transition points. Below glass
transition temperature, the polymer segments are rigid and do not have enough
energy to undergo a rotational rearrangement and hence the material is brittle
and glassy. As the sample is heated further, a small increase in volume and
energy is noted until at T, and above T, the chains become more flexible and
mobile. The nature of the material changes from brittle glassy to flexible plastic
and even rubbery. Further heating provides conditions highly conducive for
crystallisation because the segments and units of the polymer chain have sufficient
energy and undergo rearrangement or ordering. At temperatures higher than this,
the polymer melts and gets into molten state. These characteristic changes are
schematically represented in Fig. 4.17. It can be seen that transition from glassy
to liquid state is highly dependent on the rate of heating and cooling.
4
+
Liquid
Glass
Fast heat and cool
T, 1 T,2 Th,
Tee
oo
Fig. 4.17 Schematic representation of energy changes for a polymeric material

with increase in temperature
The change in the heat flow as a function temperature during the above
transitions is shown in Fig. 4.18 for different polymers. The curves shown are
the results based on DSC measurements. The gradual decrease followed by
Endo
flow,
Heat
0 50 100 150 200

TPC
—_—_—_—_>
Fig. 4.18 DSC tracings for various polymers; (PC = polycarbonate, EP = epoxy-
resin, PS = polystyrene and PVC = polyvinyl] chloride)
sudden endothermic changes in the heat flow indicates that polymer has undergone
glass transition. The value of temperature corresponding to the minimum in heat
flow is taken as glass transition temperature. The value of T,, however, depends
greatly on the heating and cooling rates used in the DSC runs. If the sample is
heated at very low rate of 0.1 K/min, the 7, observed is low, say 90°C and the
same value is reproduced again if the sample is cooled back at the same rate.
Nevertheless, if the sample is heated and cooled at much faster rate of 20 K/min,
the T, is noted at 95°C or even higher. Now imagine what happens when the
heating and cooling rates are not the same. The sample cooled at a rate of 0.1 K
min undergoes glass transition at 90°C and if its is then heated with the rate of
20 K/min, no T, would be observed till 95°C. This means by employing non
uniform cooling and heating rates, the sample is allowed to absorb more energy
to reach rubbery state from initial brittle and glassy state.
The above results when combined together, give an endotherm, a distinct
peak indicating absorption of energy by the sample at the transition temperature.
Thus, DSC runs with non uniform heating and cooling schedules yield thermograms
with well defined and accurate glass transition temperature. A typical DSC curve
for polystyrene cooled at 0.2 K/min and then heated at 5 K/min is shown in Fig.
4.19. It can be seen that a sharp 7, appears as an endotherm in the figure.
Thermal methods of analysis in polymers

The thermal responses in polymers are not only confined to measure various
phase transitions and phase transition temperatures but also provide wide range
of useful information on the nature and mechanistics of thermally induced processes
such as dehydration, degradation, curing and decomposition etc. Four basic
thermal methods namely thermogravimetric analysis (TG or TGA), derivative
thermal gravimetric analysis (DTG), differential thermal analysis (DTA) and
differential scanning calorimetry (DSC) are widely used in analysing the
temperature induced responses in polymeric materials. A brief mention of the
ae
flow,
Heat
Endo
90 100 110 120 130 140

UAE:
—————_»
Fig. 4.19 A DSC trace of polystyrene
basics of these methods and some applications are discussed here. The reader
should refer specialised literature for further details.
Thermogravimetric analysis (TGA)

This technique is based on measuring the mass (to be precise, mass loss) of a
sample specimen as a function of temperature. The sample can be kept in a
defined environment and the changes in the temperature are tuned to pre-
programmed rate. The equipment for TGA measurement consists of four major
parts (i) the electrobalance and its controller, (ii) the furnace and temperature
sensor, (111) the programmer or a computer and (iv) data acquisition device or
recorder or plotter. TGA measurements are carried out mostly on solids. Samples
should be ideally small, powdered and need to be evenly spread in the crucible.
The crucible is usually a platinum pan. The initial mass of the sample taken
range from 7-8 to 10-11 mg. The mass of the sample is to be measured at utmost
accuracy of + 0.001 mg with help of micro-balance. The environment of the
furnace can be Changed as desired for example air, nitrogen or inert atmosphere
of Ar etc. by using the gas inlet and outlet chutes. Both dynamic and static
modes can be employed. The results from TG measurements are represented in
the form of TG curves (or traces) in which the variation of the apparent mass of
the sample is plotted as a function of temperature. The mass is generally expressed
in terms of mass loss (Wp — W,), where Wo is the initial mass and W, is the mass
at a given temperature. The typical plots are usually of one, or two or three or
even multi-step upturned S$ type curves.
In order to ascertain the steps in TGA traces, the derivative thermogravimetric
(DTG) curves are frequently constructed. The DTG curve is represented by a
plot of rate of mass change per pre-slected temperature interval, dm/dt as a
function of temperature. The typical general TGA and DTG curves are shown in
Fig. 4.20. It can be seen that DTG curve has well defined peaks superimposing
on the rapid fall in the mass loss as observed in TGA curve.
The TGA/DTG curves provide information on the nature of any process that
may take place when a polymer sample is subjected to heating. The analysis of
the curves helps in understanding, for example, degradation process in polymers.
A proper treatment of data would provide the kinetics and mechanism of the
process. Also polymers with flexible chains need less energy and hence show
low thermal resistance and melt and decompose at lower temperatures. While
TG
loss
Weight
DTG
dm/at
Wat
a
Fig. 4.20 Typical multi-step TGA and DTG curves
polymers with rigid chains absorb and withstand more energy and undergo
phase transitions or decompositins at higher temperatures. Thus, thermal stability
of a series of polymers of same chemical constitution with different molecular
characteristics or polymers of different chemical constitution with identical
molecular characteristics can be compared from this analysis.
When heated, in an inert atmosphere, polymeric materials (depending upon
their mode of polymerisation and heat of polymerisation) depolymerise or
carbonise. Polymers such as polymethyl methacrylate and polystyrene (whose
monomers are highly reactive) have low enthalpy of polymerisation, may
sequentially depolymerise back to the monomers. The linear chain hydrocarbon
polymers such as polyethylene undergo the chain scission, which may occur
randomly. This random scission of chain fragments produces unsaturated
hydrocarbons of varying carbon chain length butenes, hexenes and dienes. The
substitution of alkyl groups in the main chain (for example polypropylene) degrades
the chain at lower temperature and while introduction of polar substituents like
fluorine as in polytetrafluoroethylene, enhances the thermal stability and shifts
the decomposition to higher temperature. The thermal decomposition scheme
for polyvinyl chloride (PVC) is shown in Fig. 4.21.
R-+CH;—CH>;R’ ——» R-(CH=CH>3;R’ + HCl

Gi
R-(CH)—CH) 35.1. Cte...
Fig. 4.21 Scheme for the degradation of PVC
PVC and PAN undergo decomposition first by elimination of small molecules,

formation of unsaturated links in fragments and build cross-linking among the
scissioned fragments before finally degrading by complex reaction to a char. The
polymers containing hydrophilic polar groups such as polyamides may absorb
water and when heated loose water below 100°C before they decompose. The
complex polymers such as celulose, polyester resins and phenol-formaldehyde
resins decompose through several complex reactions and finally to coke or char.
Behavjaur of Polymers 159
The intermediate or residual polymer fragments are highly active and hence
form peroxides or other oxidised products when heated in air. The decomposition
profiles of several polymers are shown in Fig. 4.22.
10
20
nNoO
weight
%
loss
PVC
PP PE
100
100 200 300 400 500 600 700
Ee
—_—_—_—_—__»>
Fig. 4.22 TGA curves for polymer samples with initial sample weight 1.0 mg, heating
rate of 50 K/min (under static air conditions)
Differential Thermal Analysis (DTA)

Whenever one needs to know the purity and stability of a material against a
known reference substance, TGA measurement would not suffice. Suppose one
wishes to know the melting point of a sample sharply against reference whose
properties are known, it can not be done by TGA, because melting involves no
mass loss. Therefore, another thermal technique, which can record the temperature
difference between a sample and reference material simultaneously, is needed.
This technique is known as DTA.
Based on similar lines, another important thermal method of analysis called
differential scanning calorimetry (DSC) has been devised. The basic difference
between DTA and DSC is that the later technique measures the difference in heat
flow to a given sample and to a reference. Thus, heat is applied to the sample and
to the reference material and then the temperature sensor output signal in terms
of difference in heat flow of both is recorded as a function of temperature. A
typical general DTA or DSC curve is shown in Fig. 4.23.
The peaks going up the base line are called as endothermic (indicating the
absorption of heat by the sample) and down the base line are denoted as exothermic
(heat is liberated). The value on x-axis corresponding to the peak maximum
AVE
Fig. 4.23 Typical DTA/DSC trace
represents the temperature at which the given process has occurred. The temperature
scale in both the instruments has to be calibrated for obtaining accurate results.
Various chemical substances are used as standard or reference materials for DTA
and DSC instruments. Table 4(c) lists such materials.
Table 4(c) Calibration substances for DTA and SDC instruments
Substance Temperature Enthalpy

{Gs J/g
Cyclohexane (rt) -83

(m) 7
1,2-Dichloroethane (m) —32
Phenylether (m) 30 120.41
Biphenyl] (m) 69.3
Polystyrene (T,) 105
Potassium nitrate (t) 128 28.71
Indium (m) 156.6 56.06
Tin (m) 231.9
Potassium perchlorate (t) 300 111.18
Zinc (m) 419.4
Quartz (1) 573
Potassium chromate (1) 665
Barium carbonate (t) 810
(t) = crystal transition, (m) = melting, T, = glass transition temperature.
There are many and wide range of DTA and DSC aplications in the study of
polymeric materials. These are broadly classified into the types, (i) physical
changes and thermal transitions and (ii) study of chemical reactions such as
dehydration, degradation, and curing etc. The utility of DSC method for estimating
T, of polymers is already discussed. Other important applications are mentioned
here.
(i) Determination of percentage crystallinity

The integrated areas of the peaks observed in DSC/DTA measurements are used
to calculate the instrument sensitivity constant, K (J/cm) by using the relation;
K = AH,M./A, where AH, is the enthalpy of fusion of reference material (J/g), m,
Behavigur of Polymers 161
4
= mass of the reference sample (g) and A, is the peak area (cm). Thus, knowing
the value of instrument constant and a reference material the percentage of
crystallinity can be calculated as
Area of the sample melting peak x(% crystallinity of standard)

%© crystallinity
crystallinity = Area of standard melting peak
As discussed, polymeric solids do not crystallise to hundred percent crystallinity.
Thus the reference material in such measurement is a polymer with known and
maximum crystallinity and has chemical structure identical to the sample.
(ii) The Heat Capacity Measurements

Heat capacity is one of the most important prameters needed for adjudging the
polymers especially as insultators or building materials etc. The ordinate in a
DSC where represents the differential rate of supply of heat energy (or heat
flow). By knowing the y-axis deflection from the base line to peak point, Ay, the
heating rate (dT/dt), the heat capacity of a polymer sample can be calculated as;
C, poly = K-Ay/(dT/dt), where K is the instrument sensitivity constant.
(iii) Compositional analysis of polymer blends

If two polymers having characteristic melting points and crystallinity are blended
DSC and DTA techniques can be used to detect their individual presence and
their amounts in the blend.
(iv) Monitoring of polymer degradation and recycling

The thermal degradation in polymers always occurs in different steps because
degradation is not a simple decomposition process. Elimination of certain small
molecules produced because of quick alignment of some atoms present in the
repeat units is quite possible before the polymer chain gets scissioned into smaller
fragments. Similarly, the small fragments show some chemical reactivity before
they finally melt and decompose to char. DTA curves for the oxidative
decomposition of polyvinyl chloride (PVC) and polypropylene are shown in
Figs. 4.24 and 4.25, respectively.
AT ———
Exo
0 200 400 600 800 1000

ae
od
Fig. 4.24 DTA curve for polyvinyl chloride
An interesting observation can be made by comparing the two DTA curves

shown in Figs. 4.24 and 4.25. PVC powder shows a small deflection at around
AT
Exo
0 100 200 300 400

TAS
(a
Fig. 4.25 DTA curve for polypropylene
80°C indicating its glass transition temperature and further heating shows small
endotherm near 300°C followed by a large exotherm, which peaks at around
550°C. In contrast, the decomposition of polypropylene (PP) is characterised by
a smooth peak. The initial single endothermic peak shows the melting followed
by a large oxidation peak. The presence of several peak in DTA curves indicates
that the degradation of PVC takes place in multi steps with loss of HCI and other
volatile substances followed by oxidation products.
Besides the above described applications, DTA and DSC methods either
individually or sometimes combined simultaneously with FTIR (Fourier transform
infrared) and MS (mass spectrometry), are also used for (a) monitoring the
curing of epoxy resins, (b) oxidative stability of polymers, (c) polymer blend
analysis and (d) curing and thermal degradation of phenol-formaldehyde resins.
4.3 Dilute Solution
Polymer dissolution
The dissolution of polymeric substances in solvents is also different from that of
low molecular weight substances. The distinguishing features of the solutions
for low molecular and high molecular weight substances are shown below in
Table 4(d).
Swelling of polymers
Swelling of polymers is a slow process involving the penetration of solvent
molecules into the polymer matrix there by increasing its mass and volume.
Swelling may be limited or unlimited. The diffusion of solvent molecules into
polymer solute structures depends upon polymer — solvent interaction, which
leads to the unwinding or expanding of the polymer surface and allows the
penetration of the solvent molecules. Thus the polymer chain containing diffused
solvent molecules is known as swollen chain. The swelling may reach a
thermodynamic equilibrium. For solutes which form molecular solutions in solvents
the swelling is unlimited and continues infinitely until the chains are completely
separated from each other and finaNy acquire mobility and diffuse back into the
bulk of solvent state (forming molecular solutions). For limited swelling i.e.
when thermodynamic equilibrium exists between polymer — solvent systems,
the polymer does not dissolve to form molecular solution.
Table 4(d) Distinct features in dissolution behaviour of low and high molecular
weight substances
eee
Systems Features
EEE SENS CEPT ON ES) REET) SEIS HEN Be > TE Tesi AE Sia SUR Ea)
Solvent + low molecular
weight solutes; Immediate dissolution
Reaches a saturation limit above which no further
dissolution occurs
Viscosity of solution is similar to that of solvent even
at fairly high concentration of solute
Solvent + polymefic solute Polymer swells before dissolution begins
No saturation limit
High viscosities are built up with increase in polymer
concentration and may prevent further dissolution after
certain limit depending upon the total molecular weight
of polymer molecule
Very dilute solutions may also be markedly viscous
Swelling can be treated thermodynamically as the phenomenon involving

two processes namely mixing and expansion. The diffusion of solvent into the
polymer matrix is a type of mixing phenomenon where as the expansion due to
swelling is similar to an elastic deformation. For systems showing limited swelling,
a parameter known as degree or amount of swelling can be defined. It is expressed
as the amount of liquid sorbed by unit mass or volume of the polymer and is
determined both gravimetrically and volumetrically. For example, a known mass
of a polymer is kept in a solvent till equilibrium is established. The mass of the
swollen polymer gel is measured after separating it from the bulk solvent. Then
the amount of fhe swelling can be expressed as (m — mo)/mo, where mpg is the
mass of the solid polymer and m is that of swollen polymer.
Swelling and dissolution of polymers in suitable solvents constiute very
important phenomenon in solution chemistry and applications of polymers. These
two successive processes are influenced by several factors viz. chemical nature
of polymer and solvent, molecular weight of polymer, chain flexibility of polymer,
packing density in solid polymer, phase state and temperature etc.
The nature of polymer/solvent system is often described in terms of polymer-
polymer, polymer-solvent and solvent-solvent interactions. The molecular weight
effect on swelling degree for given polymer-solvent systems is an important
factor in fractionation of polydispere polymers into fine fractions. Highe is the
molecular weight, finite the swelling would be while the low molecular weight
polymers swell infinitely. The flexibility i.e. the ability of the polymer chains to
undergo conformational changes due to special kind of motion called internal
rotation, has remarkable influence on the degree of swelling in polymers. Noh-
polar polymers which as a rule are more flexible usually form solutions in non-
polar solvents. Rigid or less flexible chains offer problem in swelling and dissolution
because lot of energy is required to unwind the polymer-polymer segmental
contacts. This makes the dissolution of rigid polymer chains thermodynamically
less favourable. Amorphous polymers containing bulky polar substituents readily
swell in polar solvents but do not form solutions at room temperature. Similarly
crystalline polymers with close packing between the chain segements do not
easily dissolve and need high temperatures so that the crystalline order is broken
to fcilitate the individual segment-solvent contacts. Thus, crystalline polymers
usually form solutions above their melting temperature. Similarly, more the
cross-linking among the chains, poorer would be their solubility and highly
cross-linked polymers do not show swelling even above melting temperatures.
Dimensions of polymer molecules in solution

The shape of low molecular weight solute molecules in solution can be considered
as spherical and for this reason, their molecular size is expressed in terms of
collision diameter. However, it is not always so in case of polymers, except for
polymers with flexible chains which remain in solution as coils. Also, polymers
even with most rigid chains do not remain in fully extended form. So one uses
the terms, full contour length and extended length in describing the polymer
chain in solutions. A full contour length can be treated as the product of length
of the monomer (b) and the number of monomers (N) where as the extended
length can be treated as Nb sin 6/2, where @ is the bond angle between the chain
links.
A polymer molecule may be considered to exist as a thin long chain as shown
(see Fig. 4.26).
For C—C chains Contour length = Nb

Extended length = Nb sin 0/2
Fig. 4.26 The polymer molecule showing extended length
However, in reality a polymer molecule exists as random coil with large

number of conformations that rise as a result of segmental motion and internal
rotation among the units. Chain segments constituting a polymer molecule (one
segment usually consists of a few monomer units) are capable of rotating around
fixed angles at links between successive segments. The segmental conformations
are governed by random flight probability. The polymer molecule thus assumes
innumerable conformations. The probability is that two chain ends would be
separated by a distance rg (which is extremely small as compared to the size of
the polymer molecule). The parameter rg (which is often expressed as root mean
square end-to-end distance (77 )? | thus gives an idea of the size of the polymer
coil.
In branched polymers, which contain several chain ends, the root mean square
end-to-end distance does not provide correct information on the size of the
polymer coil. In such cases, a new term called radius of gyration (sy) is considered
which is also expressed as root mean square value (5? )'” and is defined as the
average distance between molecular coil’s centre of gravity and the chain ends.
The end-to-end distance for linear polymers and radius of gyration for branched
polymers are shown in the Fig. 4.27.
(tan
me yi
(53 yl2
Linear polymer Branched polymer
Fig. 4.27 The dimensions of polymer coils in solution
For linear polymers, the size of polymer coil can be expressed by any of the
above two quantites. These are related to each other as (7)? = 6(52)"?
When a polymer is dissolved in a solvent, different types of interactions exist.
For example, one is the cohesive force between chain segments of the polymer
molecule, which tightens the polymer coil. Also, strong interaction between
chain segment and solvent would operate and loosen the polymer coil. Basically,
these two opposing forces would then determine the actual size of the polymer
coil. The polymer molecules are thus more and more expanded as the polymer-
solvent interaction strengthens (quality of the solvent goes on improving). The
end-to-end distance thus increases. When the polymer coil has no interaction
with the solvent molecules; it acquires what are known as unperturbed dimensions.
The solvents in which polymer coil acquires unperturbed dimensions are called
theta or Flory solvents. The temperature at which the polymer molecules are just
held in solution or are held at the threshold of precipitation is called theta
temperature (or Flory temperature).
The average dimension of the polymer coil in real solutions is therefore
different from the unperturbed dimension. In good solvents, for example, the
root mean square end-to-end distance, (7)? can be written as,
(7*)"? = a(7)'*. The end-to-end distance of a polymer coil in any solvent
compared with the same in theta solvents provides the value of the chain expansion
factor, a. In very dilute solutions, isolated polymer coils do exist which are
independent of their neighbouring molecules. In moderately concentrated solutions
the polymer coils may interpenetrate and entangle with each other. In more
concentrated solutions, viscoelastic swollen gels do form as the coils are aggregated.
The determinations of the rms end-to-end distance in theta solvents should
therefore provide the size of the polymer chain identical to that can be simply
calculated for an undissolved polymer coil. Dilute solution viscosity measurements
are used for determining the rms end-to-end distance for a polymer coil in theta
solvents. The ratio between the calculated rms end-to-end distance to the
experimental value gives an idea about the stiffness of the chain. For flexible
polymer chains, the ratio is close to 1.0 and while rigid chains with hindered
rotation among its segments as well as units (rigid or stiff chains), are characterised
by a ratio more than 1.0. The values of chain stiffness ratio for some polymers
are shown in Table 4(e) : .
Table 4(e) Chain stiffness ratios for some polymers
Polymer Chain stiffness ratio
Natural rubber ' iNet

Polyisobutylene 19
Polystyrene 2.4
Polyacrylonitrile 3.0
Cellulose nitrate 4.5
Cellulose butyrate eo)
Besides chain stiffness ratio, another important parameter known as chain

expansion factor can also be estimated from the calculated and measured dimensions
of polymer coils. For example, the root mean square end-to-end distance of a
polymer coil ina @-solvent, (7° )'’* and the same dimension for the polymer coil
in a non theta solvent, (7,” )'”? can be related by; (7) = a(7”)"”*, and thus
the ratio between the two is given as @, which provides the value of chain
expansion factor. The utility of the value of @ is that based on its magnitude the
solvent quality is decided for a given polymer. For example, a value for the a
greater than unity indicates better quality of solvent (good solvent). Value less
than unity is observed for poor solvents and a value of unity is noted in 6-
solvents.
Thermodynamics of polymer dissolution

Thermodynamics principles governing the dissolution of low molecular weight
substances and polymers are essentially the same. The dissolution of a solute
involves a change of state and, therefore, depends on the changes in entropy and
enthalpy of the system. Whether or not a polymer dissolves (mixing of polymer
with solvent) in a solvent can be examined from the well known Gibbs relationship,
AG mix = AA max — TAS pix. For the thermodynamic feasibility of the dissolution of
polymer in the solvent, the free energy change of the solution (mixing) i.e.
AG pix. Should be negative. The entropy change, AS,,;, for any dissolution process
is always positive because of the increased randomness of the molecules in
solution. However, the magnitude of entropy change for the mixing of a
macromolecule in a liquid is far less as compared to the mixing of alow molecular
weight substance in a liquid. Since AS,,;, is positive, (though small in magnitude)
and T is always positive, the quantity TAS,,;, will always be positive and will
favour the dissolution of polymer. Now AH,,;, can be either positive or negative.
For a negative value of AH,,;,, the terms, AH,,;, — TAS,ix = AG pix Will be large
negative and therefore the solute solubility will be very high. A negative AH,,.,
means the existence of specific interactions such as hydrogen bonding between
the polymer solute and solvent molecules. If AH,,;, to be positive, the solution is
possible only if AH,,;, < TASpix (ie. AG pix is negative). A positive AH,,,, means
that the polymer and solvent ‘prefer their own company’ i.e. these are in lower
energy state. Thus when AH,,,;, is small, the sign of AG pix is governed by AS nix.
Hildebrand, however, gave the following empirical equation for the estimation
of AA mix:
AH mix = Vs%s%p(6; — 5p)” (4.10)

where @, and @, are the volume fractions of solvent and polymer, respectively. V,
is the molar volume of the solvent gnd 6, and 6, are the solubility parameters for
solvent and polymers, respectively. The solubility parameters are estimated as
the square root values of cohesive energy density (CED), which is a measure of
the magnitude of inter-molecular attraction. Further, the cohesive energy density
is defined in terms of the molar energy of vaporisation, AE,, by the relation;
6 = (CED)'” = (AE,,)!7/V (4.11)

By convention, these values are always positive and irrespective of their magnitude;
the term (6, — ON will also be positive. Thus, AH,,;, will always be positive.
Now as discussed before TAS,,;, is very small in magnitude; for the condition
favouring polymer solubility, i.e. AH pix < TAS pji,, a Minimum positive value of
AH pix can be upset by matching the polymer and solvent such that their solubility
parameters are as close as possible. To a rough approximation a polymer and
solvent differing in solubility parameters by (A; — 62) < 0.5 will form the solution.
Solubility parameter of solvents can be experimentally determined easily
from the values of molar internal energy change on vaporisation. Solubility
parameter for polymer can not be obtained by this method as they decompose
long before reaching vaporisation temperature. But 6 values for polymers can be
indirectly determined. The basis to do this is that the solvent which shows
maximum swelling of a lightly cross-linked polymer has the same solubility
parameter value as polymer. Thus degree of swelling for a given polymer is
determined in various solvents to obtain the solubility parameter of the polymer.
In Table 4(f) are shown solubility parameter values for some selected solvents
and polymers.
Table 4(f) Solubility parameters of some polymers
Polymer Solubility parameter

H
Polystyrene 9.1
Polyethylene T9
Polypropylene 9.2
PVC Bal
PMMA 9:5
PET 10.7
Nylon 6, 6 13.6
Hildebrand’s solubility parameter approach is simple and in common practice

even today to select a solvent for a polymer. Since the solubility parameters can
have only positive values, the AH,,;, as defined by below given equation 4.12 is
obtained always positive (i.e. endothermic mixing). Flory introduced a term
which eventually known as Flory interaction parameter y (which can take positive
or negative values), to explain the dissolution process in systems (both exothermic
and endothermic) of solute-solvent pair systems. The enthalpy of mixing is
defined as
AH mix= 5:5p1RT (4.12)
where ¥ = Z Aw RT and Z is the number of nearest neighbour (or coordination
number) and Aw will yield large y (which is dimensionless) and thus large
positive values to AH,,;, and would not favour dissolution (or phase separation
would result). Small positive or negative values of y would explain the spontaneity
of dissolution process. Table 4(g) lists interaction parameter for some polymer-
solvent pairs.
Table 4(g) Flory interaction parameter values for some polymer-solvent systems
Polymer Solvent Temperature Flory parameter, 7

i
Polyvinyl acetate n-Hexane 100 1.93

Benzene 100 0.37
Chloroform 100 0.11
HDPE n-Decane 150 0.18
LDPE n-Dodecane 120 0.18
Natural rubber n-Hexane 25 0.53
n-Heptane 25 0.50
n-Octane 25 0.48
Benzene 25 0.46
Toluene 25 0.35
Thermodynamics of Solution
Before we attempt to develop relations for explaining the thermodynamics aspects
of plymer solutions, it is highly essential to consider the following thermodynamic
principles derived for solutions of simple molecules.
Solutions of simple molecules

A simple example for a solution of small molecules would be a binary system
consisting components | and 2 and formed by mixing n, and ny moles (N, and
N> molecules) at constant pressure, P and temperature, T. The total free energy
of such simple systems is given as
Gy2 = nGP + n2G} + nm RT In(p;/p?) + np RT In(p2/p)

where GP and G9 are the free energies of pure components, p? and p9 are the
vapour pressures of pure components and p, and p, the partial vapour pressures
of pure components in solution, respectively.
Raoult’s law defines the partial vapour pressure of the pure components in
ideal solutions as
Pi =XPy (4.14)
P2 =x2p) (4.15)
where x; and x2 are the mole fractions of the respective components such that
xX, + x2 = 1 and x, = (1 — x2) = nj/(n, + np). Thus
Giz =mGP + n»G? +n, RTInx, + nz RTInxy (4.16)

or ‘
Giz — (m GP + ngG)) =n, RT In x, + ny RTInxy (4.16a)

or
AG pix= Ny RT In x, + nz RT In x, (4.16.b)
or
AGwix = RT Dn; In x; (4.16c)
Differentiating eq. 4.16b with respect to temperature, we can write
OAG pix/OT = ny RT In x; + nz RT In x, (4.17)
— VAG pix/0T = AS mix = — Ny RT In x; — ny RT In x, (4.18)
Combining eqs. 4.16b and 4.18, we get
AGIEE = ASKem (4.19)

or
ALK =0
For non-ideal or real solutions, however, eqs. 4.14 and 4.15 should be modified
to give allowance to the nonideality by introducing a term for activity coefficient.
Then
Pi =%1Y1PY (4.21)
P2 =X2Y2Ps (4.22)
Now for real solutions the free energy, entropy and enthalpy of mixing can be
expressed in terms of
AG mix = RT Xn; In x; + RT YX n; In y, (4.23)
AS mix = —R YX nj In x; - R Xn; in y; —RT LY n; ( In ¥,/07) (4.24)
AH nix= RT” Yn; (0 In 7;,/0T) (4.25)
Defining an excess function as the difference between the change in it upon
mixing over its value in ideal state, we can write
G? = AGnx, — AGS = — RTI; ny; (4.26)

S¥ = ASmix — AS =—-RIn; Iny; -RTXn;(Olny;/0T) (4.27)
H® = AH pix — AH = RT? En; (9 In y;/0T) (4.28)

The utility of excess functions is manyfold in explaining the solution behaviour
in simple and complex systems. It can be seen from eqs. 4.26 to 4.28 that the
excess functions namely G®, S®, and H® are zero for ideal solutions. In case of
nonideal solutions, the values deviate from zero either by a positive or negative
magnitude. Similarly one expects either positive or negative deviation from
Raoult’s law when applied to real solutions;
G* > 0 positive deviation from Raoult’s law
G* <0 negative deviations from Raoult’s law
Thus solutions showing positive deviation from Raoult’s law undergo immiscibility
or phase separation only if G* = AG‘! Taking into consideration the well
known Gibbs relation, G’ = H* — TS®, the following can be written for regular
as well as for non ideal solutions;
SE =0, G’ = HF (4.29)
Mixtures containing components of same size and polarity show such behaviour.
For example for the system benzene + CCly, G’ = 82 J mol!, H® = 115 J mol"!
and S© = 0.11 J mol! K7! at 298.15 K. When S® > 0, positive deviation is
expected from Raoult’s law and since S* > 0, then G’ > 0, AGI" < 0. Thus, no
phase separation occurs when G* > AG/S*"!. For S® < 0, negative deviation is
expected from Raoult’s law and since S* < 0, mixtures have more orderliness
than their respective pure components (due to hydrogen bond formation or
any other specific interaction etc.). For S* <0, H® <0, so also G* <0, ice. all the
three functions are negative (e.g. benzene + tetrahydrofuran systems with
G* =— 131 J mol+H® = -271.1 J mol and S* = -0.47 J mol! K™').
By applying statistical thermodynamics and assuming certain models the
relations for the fundamental thermodynamics functions of mixing can further
be refined. For example, using Boltzmann relation, the entropy of mixing can be
expressed as
AS mix= k In Q (4.30)
where Q2 is the number of distinguishable arrangements of N, and N> molecules
in N, + Nj sites in a lattice (see Fig. 4.28) and defined as
QQ. = (N,; + Nz)!/N;! No! (4.31)
AS mix = k In (N; + N2)!/N,! No! (4.32)

Introducing Stirling’s approximation N! = (N In N) —N, we get
AS mix = — k [Ny In {Ny/(N, + Nz)} + Nz In (ND/(N, + No)}] (4.33)
For expressing the number of molecules N in terms of either the moles n or

mole fraction (X), we can define ny = N,/N4, nz = No/Nag, X, = nj/(ny + np) and
X7 = n»/(n, + nz) and also writing the term kN4= R, one obtains
AS mix = — R [ny In X; + ny In X3] (4.34)

since for ideal solutions AH,,;, = 0, the free energy of mixing can be written as
AG pix = TAS pix.= RT [rn In X, + ng In Xp] (4.35)
Thermodynamics of polymer solutions

Polymer solutions are mostly nonideal. At concentration above a few percent,
the deviations from ideality are so large that the Hildebrnd’s law is of very little
significance for predicting the thermodynamic properties of polymer solutions.
The heat of mixing is zero and the entropy of the mixing is simply given by the
ideal combinatorial entropy that results from the mixing of two types of solid
spheres of the same size for ideal solutions. For athermal solutions the heat of
mixing is zero but the entropy of mixing is larger than the ideal combinatorial
entropy by an excess entropy of mixing. But in theta solution, the heat of mixing
just compensates the excess entropy of mixing at a certain temperature. The
deviations from ideality are mainly attributed to the small values for the entropy
of mixing. Also, the simple lattice model for calculation of AS,,;, given by eq.
4.34 is not only insufficient but also invalid as the polymer solute and low
molecular weight solvent differ in size by several decades of magnitude. Flory
and Huggins independently proposed the calculation procedures for the estiamtion
of AG ae, AS vix and Ales.
Flory Huggins theory

The theory takes into consideration of modified lattice model as shown in Fig.
4.28. It is assumed that each space in the lattice is occupied by either one solvent
molecule or one chain segment. Also polymer chains are divided into segments
based on thei ease of internal rotation. These segments are known as
thermodynamic or Kuhn segments. A freely jointed chain is characterised by
segments of equal size and identical internal rotation. Also, each site occupied
by a polymer segment has two adjacent polymer sites so that there is a continuous
path of polymer segments. The solution is assumed to be concentrated enough
that the occupied lattice sites are randomly distributed as shown in Fig. 4.28b. A
small entropy of mixing for polymer solutions as compared to larger values for
low molecular weight solutes in solvents, can be qualitatively understood here.
There will be fewer ways in which the same number of lattice sites can be
occupied by polymer segments.
Now, if there are N; solvent molecules and N, polymer molecules and each
polymer molecule is made up of x segments, then the total number of lattice sites
will be [N, + xN>]. The calculation of configurational entropy of mixing in this
case is more complicated than for the solutions of low molecular weight solutes.
but was independently derived by Flory and Huggins in 1942 by simple equation:
AS nix = — KIN, In {N,/ (Ny + xN5)} + No In {x No/(N, + XN3)}] (4.36)

AS mix = — R[n, In O, + n In @,], (4.37)
where Q, = N/M, + XN >) and %» = xN,/(N, ait xN>) (4.38)

Fig. 4.28 Model of quasicrystalline lattice (a) at low concentration (b) at high
solvent concentration. 1—polymer units connected into segments
and 2—free polymer units
It should be noticed that the entropy contribution that may be present as a result
of specific interaction between polymer and solvent molecules is not considered
here. The Flory-Huggins theory also allows the simple calculations of entropy of
mixing. It assumes that AH,,;, is not equal to zero because the polymer-solvent
interaction energies in solution are different from the polymer-polymer and
solvent-solvent in the pure unmixed state. Considering uncharged polymer and
solvents, the interaction energy is primarily governed by the three types of
contacts viz. solvent-solvent, solvent-polymer and polymer-polymer. Let these
be given the name w,,, w,, and w,,. Now for every two polymer-solvent contacts
taking place in solution, one solvent-solvent and one polymer-polymer contacts
of the pure components are broken. Thus the energy difference per polymer-
solvent contact, Aw, between the mixed and unmixed states will be
Aw = Wy, — 1/2[w,, + Wp] (4.39)
Using the liquid lattice model, it can be shown that the number of such contacts,
p, is given by
p=xN2z 9, (4.40)
Here z is the coordination number of lattice. The enthalpy of mixing, AH mix 1S

simply the product of the energy per contact and number of contacts.
AH mix = xN7 z9, Aw (4.41)
but xN>@, = Ny %,
so AH mix= Nizd,Aw (4.42)

Flory and Huggins theory introduced a dimensional quantity known as interaction
parameter, 7, which represents the interaction energy per solvent molecule divided
by kT
x = zAwlkT (4.43)
AH pix= XN12G)KT = 11 XRT (4.44)
Now knowing entropy and enthalpy contribution, the free energy of mixing can
be obtained as
AG mix = RT [n; In Q, + nq In Q + 11 0,H) (4.45)
This equation becomes similar to that of ideal solutions when x = 1 and y = 0.

The free energy contribution arises from two entropy factos; one due to the
contact between polymer segments and solvent molecules and the other due to
conformations of polymer molecules. Thus, the overall free energy of mixing
AG mix = AG conform + AG contact (4.46)

These two contributions are
AG conform = RT[In(1 — ¢,) + (1 — L/n) @,] (4.47)
AG oun = Rion (4.48)
AGpix = RT[In(1 — ¢,) + (1 — I/n)g, + X19; | (4.49)
when ¥ exceeds some critical value ¥,, the system will separate into two phases.
It can be derived mathematically
wy ee arn lin? + 1/2 (4.50)
Although Flory-Huggins theory is an important improvement over ideal solution
theory, it has certain serious drawbacks to fully account dilute polymer solutions.
The theory suffers from its limitation because of the following:
(i) the occupation of lattice sites is purely statistical and ignores the tendency
of polymer molecules to form isolated coils specially in dilute solutions and
(ii) does not consider specific interactions between the polymer and solvent.
Determination of Flory interaction parameter from

osmotic pressure measurements
The reduced osmotic pressure, 77/C, is related to molecular weight of polymers
by
m/C = [RT/M](1 + A2C) (4.51)
where A; is the second virial coefficient. The magnitude of A, is related directly

to the extent of deviation from ideality. Thus, we can derive a relation between
A, and Flory interaction parameter ¥. The osmotic pressure 7 is related to the
free energy term by
nV, = -AG mix (4.52)

where V, is the partial molar volume of the solvent
-nV, = RT[Ing, + (1 — I/n)g, + x9; |
or -1V,/RT= In , + (1 — I/n)o, + XO;
=In(1- ¢,) + (1 - I/n)o, + 107

For very dilute solutions @, << | and
In(1 — @)) =-[, + 07/2 + @3/3 +...] (4.55)

= -— >, - o; /2 and we get
1V,/RT = -b, — 0712 + by -— dy/n + XO, (4.56)

= —[¢,/n + ¢(1/2 - x)]
Now, since
dy = NyV_/Vs = Ny Py (4.57)
= C(V,/M) py (as n, = CV,/M),

also d, = NyV,/V, = CV,/M = C/p, (pp = density of polymer) (4.58)
Thus 2V,/RT= CV,/M + C? (1/2 - %)/p? (4.59)
m/CRT:= 1/M + (1/2 — x) C/V,p2 (4.60)
m/C = RT(1/M+ ((1/2 — x) CV,p; )) (4.61)

= RT(1/M + A,C)
where Ay = (1/2 — x) V, pp
It becomes clear that when ¥ = 0.5, the second virial coefficient A, is zero. Thus,
osmotic pressure measurements can also be utilised to estimate the interaction
parameter, y and (@ sovent/temperature) for a given polymer-solvent system.
Second virial coefficient (A) is a measure of polymer-solvent interaction which
depends on several factors such as (i) the temperature (increase in temperature
leads to a decreasing value of A), (ii) the molecular weight and molecular
weight distribution of polymer and (iii) the tacticity of polymer.
Phase Separation
Figure 4.29 shows the plots between total free energy of mixing against volume
fraction of solute @) (for convenience can be taken as x2). At high temperature,
the free energy of mixtures is less than the sum of the free energies of the
AG®
Fig. 4.29 Schematic representation of variation of free energy of

mixing with the composition of solute
constituting components and thus; AG,,;, is negative at all compositions and

hence a homogeneous solution is always formed. At lower temperatures (see
Fig. 4.29), AG jxis positive in the composition range @ and @;’ and negative in
the ranges 0 — @ and ¢,’ — 1. Thus,
the occurrence of phase separation in
the composition range @y and ¢;’ and
a homogeneous solution in rest of the
composition is quite evident. The phase
diagram for a typical polymer is thus
expected to have the feature shown in
Fig. 4.30, where both the upper critical
solution temperature (UCST) and lower
critical solution temperature (LCST)
boundaries of solubility and phase
separation are depicted.
The inflextion observed in free Fig. 4.30 Phase temperatures in
energy versus composition plot can be polymer solutions
mathematically formulated as
(0? AG pix /067 )= 0 and (07

AG pix/00;)= 0 (4.62)
also, the chemical potential of the solvent in the solution {; can be related to
AG mix H = (AG mix/On;) When temperature T and number of moles of solution n,
are constant. The critical conditions for miscibility can be written in terms of
chemical potential as
(dA; /0¢2) = 0 and (07

Au /003 ) = 0 (4.63)
I/RT (dAU, 1002) = 0/0 [In ¢, + O2(1 — I/n) + OFX) (4.64)
=-(1-2)° +7
Further differentiation with respect to @ yields

I/RT(OApy/09s) = — (1 — 7 + X (4.65)
Setting the equation 4.64 to zero under critical conditions:
T= ‘ie iy = Pr,» Ki te
20Xe + (1 — In) — (1 — &),)' =.0 and (4.66)

24. - (1 - &.)* = 0 (4.67)
thus, 2v7.=(1-@,)” (4.68)
So, >M1 — b,)* — (1 — & 1 + 1 = 1 /n or (4.69)
[O2,/(1 -— O2)]°= In (4.69a)
or d= (1+ nl?! (4.69b)
For r 4 ©
o>. = In!” (4.70)

2%, = (l= Gy)? (4.71)
= (1 — n'y
270% 1+ an’? of (4.72)

In!” = x, - 1/2 (4.73)
Thus, the maximum appearing in free energy plot at critical composition 7?
is related to the number of segments, n. An increase in ‘n’ (i.e. increase in
molecular weight) rapidly diminishes v2. Furthermore, under critical condition
whenn— -, y-'? = 0 and x, = 1/2 or Thus, for polymer-solvent pair at a given
temperature, when Flory interaction parameter y > 1/2, the polymer will be
insoluble. Since, the condition y. = 1/2 is valid for a polymer with infinite
molecular weight, i.e. for M > «, T. + @. This implies that @ - temperature
equals to CST for polymer with infinite molecular weight.
Viscosity of polymer solutions and size of the polymer coil

Generally, as would be expected the viscosity of polymer solutions increase with
increase in concentration and decrease in temperature. However, the opposite
behaviour is shown in few cases. For example, the viscosities of dilute aqueous
solutions of polymers with ionisable group increases on further dilution (this is
called a polyelectrolyte behaviour). Such an effect as discused in details elsewhere
(chapter 8) is primarily due to the increased repulsion between like charges on
the same chain, which is further enhanced due to greater ionisation in more
dilute systems. A very high viscosity of phenol-formaldehyde liquid resin in
solvent at elevated temperature can be explained due to the formation of cross-
links.
The viscosities of motor oils can be effectively controlled to a constant value
over wide temperature range, using polymers, for the purpose of all weather
lubricants. While the viscosity of the oil will decrease at hi gher temperatures, as
is the case with most simple organic liquids, the presence of dissolved polymer
will have opposite effect. As the polymer coil will expand with increase in
temperature (making oil with better solvent power), viscosity of solution is
increased rather than usually expected decrease in viscosity with rise in temperature.
The viscosity of molten polymer also varies with molecular weight. Thus,
molecular weight dependence of vjscosity provides highly useful information in
the processing of polymes. The viscosity becomes very high above the threshold
molecular weight making the processing very difficult and, therefore, often
polymers with extremely high molecular weight are not easily processible. Fox
gave following equation relating viscosity and molecular weight (as applicable
at low shear rates above a threshold molecular weight (or degree of polymerisation,
DP));
log n = K + 3.4 log DP (4.74)
For most polymers this DP is around 600. A log-log plot between melt viscosity
and molecular weight for polymer is shown in Fig. 4.31.
log
n
log My
Fig. 4.31 Variation of melt viscosity with molecular weight of polymers
Intrinsic viscosity and dimension of a polymer coil

Contrary of low molecular weight substances which do not show significant
increase in the viscosity of their solution even at fairly high concentrations,
polymeric materials markedly show enhanced viscosity in very dilute solutions.
Such an increase in viscosity of liquids in the presence of polymers can be
explained as follows. When a liquid flows through a capillary, it moves in several
layers with different velocity. The dissolved polymer molecules show translational
motion of both the random (Brownian) and directional (diffusion and sedimentation)
types due to large size. The single polymer molecule occupies position in different
layers of solvents (moving with different velocity) which results in rotational
motion of the molecules. These translational and rotational motions of polymer
moleculs with respect to the static liquid phase produce friction. This leads to
high viscosity even in dilute polymer solutions.
A polymer molecule has been considered to remain as curled coil in solution

(i) from which the solvent molecules can pass (free draining model) or (ii) which
takes up a few solvent molecules to form swollen impermeable gel. In both these
cases the polymer molecules can be treated according to hard sphere model. For
colloidal dispersions with non-interacting dispersed particles, the Einstein equation
relates the specific viscosity 7,, to the volume fraction, @ as
eT (4.75)
A polymer solution can thus behave similar if the total number of polymer
molecules N are present in a given volume V, then @ is defined as
@ = Volume of one molecule x N/V (4.76)
If the polymer molecule is considered as a spherical coil of radius r, then the

volume of a polymer molecule is 4/3 zr?, thus
= 4/32r/V or (4.77)
Nesp & NV (4.77a)
Conventionally, the number of molecules, N can be expressed as
N = WN,/M (4.78)
where W is the weight of the polymer of molecular weight M and N, is the
Avogadro’s number. Thus,
Nsp & WNar'/MV (4.79)

oc CN4r'/M where W/V = concentration ‘C’
Nsp/C c Nar'/M or (4.80)
Nep/C o¢ 7/M (4.80a)
or for dilute solutions, the intrinsic viscosity
[n] = (Np/C)c-0 = P/M (4.81)

Now, r which is the radius of the polymer coil (or the radius of gyration) can be
related to the root mean square end-to-end distance (77)! (i.e. r = radius of
gyration (57 )"? and (77)'? = 6(57)",
The intrinsic viscosity thus can be shown as
[n] = K(r?)*2/M (4.82)

~ where K is proportionality constant, the product of intrinsic viscosity and molecular
weight of the polymer is directly proportional to the 3/2 power of the size of the
polymer coil, i.e.
[N]M« (77)*? (4.83)

The end-to-end distance of a polymer coil in a solvent is related to the similar
, wis a 2 as 7 = . P :
value in @-conditions; (7)? as (F7)"* = a(72)"?, where a is Flory’s chain
9
expansion factor. Thus,

[n] = Kae (7 yiMy2 x M2 (4.84)
The ratio i )/M remains constant for a given polymer [as increase in M
increases (7,” )]. So
[n] = K’ om"? (4.85)

Under 6-conditions, the expansion factor @ = 1, ie. (72)? = A Oebe
[7] my M2 (4.86)
This is the well known Mark-Houwink equation. The exponent value of 0.5
has ben verified for number of polymer solutions in theta solvents. K’ was
erroneously treated as an universal constant with a value of 2.84 x 107!. The ratio
of intrinsic viscosity in a good solvent to that of in theta solvent, [7]g can be
written as [7]/[N]o = oe.
The viscosity of dilute polymer solutions thus depends on several factors like
molecular weight of polymer, nature of solvent, polymer concentration and
temperature. The concentration dependence of polymer viscosity can be represented
by several equations as proposed by Huggins (4.87), Kraemer (4.88), Martin
(4.89) and Schulz-Blaschke (4.90). These equations are written as,
Nsp/C = [nN] {1 + kxlm1C} (4.87)

(In ,)/C = [n] {1 - & [n]C} (4.88)
(In Nsp/C) = In [N] + ky [N]C (4.89)
Nop/C = [n] {1 + kKspncp} (4.90)

Thus, the inttinsic viscosity needed for determining the molecular weight of
a given polymer can be estimated by respective plots of viscosity functions of
polymer solutions. A typical Huggins plot showing the dependence of reduced
viscosity on concentration is shown in Fig. 4.32. Thus, the dilute solution viscometry
Nsp/C
Concentration
Fig. 4.32 Typical Huggins plot of reduced viscosity Vs concentration

has proved to be an important technique employed for obtaining viscosity average

molecular weight of polymers.
Determination of intrinsic viscosity in theta conditions

Theta solvents are known for limited polymers. A slight change in temperature
may transform a theta solvent into good or poor solvent making the estimation
of intrinsic viscosity less reliable. Thus, correct value of intrinsic viscosity
corresponding to nearly 6-conditions has to be found. There are two ways to
obtain the correct [1] from the viscosity functions data as obtained from common
solvents. In one such method, intrinsic viscosities of a given polymer are determined
in a solvent/nonsolvent mixture for different compositions. The compositions of
solvent and nonsolvent are varied such that polymer gets precipitated at particular
proportion. The intrinsic viscosity obtained in a composition close to precipitation
of polymer solute is then determined (see Fig. 4.33). This value is supposed to
be identical with [7)]9. Another way to obtain intrinsic viscosity in theta conditions
is to measure its value for a given polymer in different good solvents and then
extrapolating the respective reduced viscosity plots beyond the zero value of
concentration i.e. to the left of the abscissa to a common intersection point
where all the plots converge. Then the value of intercept from the concentration
base line to the common intersection point gives the [7]o. Such a procedure is
depicted in Fig. 4.34.
oe ae = zone
(7)
Precipitation point
Non-solvent/solvent Cc
Fig. 4.33 Intrinsic viscosity versus Fig. 4.34 Extrapolation of reduced
solvent/non solvent viscosities at zero
composition concentration from
different solvents
Intrinsic viscosity and unperturbed dimensions of polymer coil

The dissolution of a polymer solute takes place by swelling of polymer chains in
the solvent. The degree of swelling as expected, is highly dependent upon solvent
quality. Polymer chains swell to a large degree in good solvents because of
excellent permeation of solvent molecules into polymer chains (as strong solute-
solvent interactions are expected in polymer solute-good solvent systems) while
the polymer chain are least swollen in poor solvents due to very poor interaction
between the polymer solute and poor solvent molecules. In 6-solvents, however,
where the pure solute-solute and solvent-solvent interactions are equally balanced
by solute-solvent interactions, polymer chain, as explained earlier acquire
unperturbed dimensions. Thus hydrodynamic measurements can be of great utilitiy

in evaluating unperturbed state of polymer chain or @-condition. The relation
between intrinsic viscosity and the size of an unperturbed coil has been theoretically
shown to be
Fe
[Me = 90 yy (4.91)
and the same relation in non ideal (or non-theta) condition becomes
(F 1/2
[n] = 0 ~ xa (4.92)
where parameter @ is an universal constant for all polymers equal to 2.84 x 107!.
The disadvantage of above relation is that it requires the accurate determination
of viscosity function in 6-solvents. Finding a @-solvent in a useful and measurable
temperature is highly difficult. Hence, attempts have been made to develop
relations useful for computing the unperturbed dimensions from the measurement
of viscosity functions in solvents under normal conditions. Out of several such
attempts, the relation proposed by Stockmayer and Fixman has been found to be
more popular. The relation is given as
[n] = KoM'” + 0.51 %BM (4.93)

where Kg is the constant determined in 6-solvent, M the molecular weight of
polymer and B the quantity related to Flory-Huggin’s interaction parameter 7 by
the relation
B=Vo(1- 2x)/ViNa (4.94)

Where V,, is the specific volume of a polymer, V; the molar volume of the
solvent and N, the Avogadro’s number.
Rearrangement of eq. 4.93 gives
[nV/M'? = Kg + 0.51 ¢ BM? (4.95)
Thus, knowing the molecular weights of a series of fractions of a polymer and
their corresponding intrinsic viscosities in a single solvent at a selected
temperature, the constants Kg and B can be evaluated from the intercept and
slope of [7]/M'” versus M'” plots. Then the root mean square end-to-end distance
in @-condition (7)? for a polymer chain can be calculated from the relation
=2 \32
6
Ko = | =|
o| — ? (4.96)
4.96
Determination of 6-temperature/solvent
Several methods can be used to determine the theta temperature for a given
polymer-solvent system.
(a) Phase equilibrium method

In this method, the maximum critical precipitation temperature 7, for a polymer
of different molecular weights is determined by slubility method. The plot of

1/T, and M"” is linear with an intercept equal to 1/0.
(b) Second virial coefficient (Az) as obtained from osmometry measurements

From membrane osmometry, one obtained the reduced pressure, 7/C for a given
concentration of polymer solute dissolved in suitable solvents. Then, a plot of
m/C versus concentration is constructed to yield an intercept and slope values.
The magnitude of slope depends highly on the quality of solvent. Such a plot
for solutions of polymer solute in different solvents is shown in Fig. 4.35. The
solvent in which the slope is zero (Aj = 0) corresponds to 6@-solvent at that
temperature.
Positive slope: Aj > good solvent
S eee ————_—____ Zero Slope: Ao = Olis O-solvent
Negative slope: A < 0 poor solvent
ie
Fig. 4.35 Reduced osmotic pressure versus concentration plot for
polymer solution in different solvents
(c) From viscosity-molecular weight relationship

The dependence of intrinsic viscosity [7] on molar mass of polymer chains is
given by the empirical Kuhn-Mark-Houwink-Sakurada equation as
[n] = K,M° (4.97)

This equation is valid for macromolecules with wide range of molar masses. In
the above equation K, and @ are polymer solute-solvent system specific constants
that depend on the constitution, configuration and molar mass distribution of the
polymer as well as on the quality of solvent and temperature. The exponent &
value is dependent on the shape of the polymer molecules and segmented
distribution. It is generally predicted by theory that the value of @ = O for
spheres, @= 0.5 when the polymer chain acquires unperturbed dimensions (in 6-
solvents) @& = 0.764 for perturbed coils (in good solvents) and @= 2 for infinitely
thin rigid rods. Thus, from the measurements of viscosity functions for several
fractions of the same polymer with different molar masses and in wide variety of
solvents, and using eq. 4.97, the value of a for each polymer solute-solvent
system is determined. Also, the system in which @is close to 0.5 can be regarded
to exist in @-conditions.
(d) Titration (cloud appearance) method

Polymer solutions of different concentrations are titrated with a non-solvent till
the first appearance of turbidity. The log [nonsolvent] versus log [polymer] plot
- on extrapolation to 100% turbidity gives the composition of solvent/non-solvent
mixture corresponding to 6-conditions.
Table 4(h) gives 6-conditions i.e. 6-solvents and 6-temperatures for various
polymes.
Table 4(h) 6-Conditions for various polymers
Polymer Solvent Theta temp., K

Polyethylene Biphenyl 398
Polypropylene Isoamyl acetate 307
Polystyrene Cycohexane 308
Polystyrene Decalin 300
PMMA 4-Heptanone 307
PVG Benzyl alcohol 428
Polyacrylic acid Dioxane 297
4.4 Rheological
Rheology is the science of deformation and flow of material (rheos in Greek
means flow; the term was coined by Bingham who is known as father of rheology).
The basic aspects of material deformation involve melt flow and hence are
important from the view point of polymer processing. Low molecular weight
solids and liquids exhibit the characteristic flow behaviour according to Hooke’s
equation (elasticity of solids) or Newtonian equation (viscosity of liquids). A
polymeric material is often visualised as viscoelastic (that can act as both solids
and liquids).
Bi
Hooke’s equation
The elastic component is dominant in solids and hence their mechanical properties
are described by Hooke’s law, which states that ‘applied stress’ (S) is proportional
to the resultant strain y but is independent of the rate of the strain (dy/dt). Many
metals, rubbery materials etc. display elastic behaviour at load (stress) levels
below elastic limit.
The behaviour of an ideal elastic solid can be represented by the elongation
versus time plot as shown in Fig. 4.36.
The application of load at a certain point
of time t elongates the material by a
certain length, which remains same as
long as the load is retained. Releasing
the load say after time ft, leads the
material to restore its original length
instantaneously. Such a_ time
independent behaviour is called elastic
deformation (or elasticity) and is shown ty h
by the linear stress-strain plot. The Tine
elastic behaviour of solids can be fig, 4.36 Elongation versus time plot.
compared with a spring that elongates instantaneously on applying load but

recoils to its original shape on unloading.
Fig. 4.37 shows the typical elastic deformation and Hooke’s spring model.
Spring
fy
(a) (b)
Fig. 4.37 (a) Behaviour of elastic solid under strain and
(b) Hooke’s spring model
The stress, strain and modulus are defined as: stress S = force/area, strain
y = change in length/original length, modulus elasticity E = stress/strain = S/y.
The E values in psi (pound/inch’) for some materials are: glass = (10 x 10°),
nylon 6 = 6 (1 x 10°) and polyethylene = (4 x 10%).
Newton’s equation
Like in liquids, the elongation versus time plot obeys Newton’s law which states
that’ the applied stress S is proportional to the rate of strain dy/dt but independent
of strain y(the strain rate is some times written as y). Thus, S= 7: dy/dt, where
1 is proportionality constant and equals the viscosity of liquid. The viscosities
(in Pa.s) of various materials for example in liquid state are; water (107%), glycerin
(10°), polymer melt (107-10°) and glass (107!). The variation of yand t and S and
y are shown in Fig. 4.38. The application of load at a certain point of time rf, to
a viscous liquid (say honey, coal tar etc.) which then starts elongating and
continues to do so until the force is released at time t, when the flow stops but
the material does not recover its original length. Such a permanent and time
dependent deformation is called as viscous flow. This behaviour can be compared
to the movement of a piston inside a cylinder filled with a viscous liquid (the
liquid does not allow the piston to move fast).
Many low molecular weight systems display laminar flow behaviour as described
by Newton’s viscosity equation and hence are called as Newtonian fluids. Such
behaviour is graphically shown in Fig. 4.39. Polymer melts and concentrated
solutions often deviate from this linear behaviour.
Two types of deviations from Newton’s flow are commonly observed. Some
non-Newtonian fluids exhibit shear thinning. Shear thinning is a reversible decrease
in viscosity with increase in shear rate that results from the tendency of the
applied force to disturb the long chains from their favoured equilibrium
conformations and cause elongation in the direction of shear. The opposite effect
in which the viscosity increases with increasing shear rate is called shear thickening.
This phenomenon is very rare in polymer solutions.
Behavjaur of Polymers 185
(b)
Newton’s piston model

Fig. 4.38 Variation of (a) strain versus time, (b) stress versus strain and
(c) schematic representation of Newton’s model
Slope A = Newtonian viscosity

Shear
stress
~
dy/dt or y
Fig. 4.39 Newtonian variation of shear stress as a function of shear rate
Viscoelasticity is the property of both a solid and liquid and since polymeric
materials are viscoelastic solids, combination of the above Hooke’s model of
elasticity and Newton’s model of viscosity can be used to demonstrate the
deformation resulting from the application of stress. Maxwell put forth a
combination of the above two models in series to explain viscoelasticity. He
assumed that the contributions of both the spring and dash pot to strain were
additive and that the applications of stress would cause instantaneous elongation
of the spring followed by a slow response of the piston in the dash pot.
According to Maxwell’s model for viscoelastic deformation the shear rate is
ZiVEN AS Yiotal = Yelastic + YWiscous: Maxwell model assumes the following dependence
of S on y(see Fig. 4.40).
Another model to explain the viscoelasticity proposed at the same time is
called Voigt-Kelvin model (see Fig. 4.41) which combines a spring and dash pot
in parallel. In this model, the applied stress is shared between the spring and the
a
(a) : (b)
Fig. 4.40 (a) Variaton of S and y in viscoelastic liquids (b) Maxwell model for
viscoelastic deformaton
ae
dash pot and thus the elastic response is retarded by the viscous resistance of the
liquid in the dash pot.
(a) (b)
Fig. 4.41 (a) Stress-strain relation and (b) Voigt-Kelvin model for representing
viscoelasticity
Stress-strain behaviour in polymers

High E values mean rigid materials since stress will be very large and elongation
small. Based on thypical stress-strain behaviour, polymers are classified as:
(a) soft and weak: low E, low yield point and moderate time dependent elongation,
Poisson ratio (contraction/elongation) ~ 0.5, similar to liquids, e.g. polyisobutylene,
(b) hard and brittle: high E, poorly defined yield point, little elongation before
failure, Poisson ratio ~ 0.3, e.g. polyethylene, (c) soft and tough: low E, high
elongation, a well defined yield point, Poisson ratio ~ 0.5—0.6 e.g. plasticized
PVC, (d) hard and strong: high E, high yield strength e.g. rigid PVC, (e) hard
and tough: moderate elongation prior to the yield point followed by nonrecoverable
elongation e.g. ABS resins. In all the cases, the behaviour piro to yield point is
Hookean. The reversible recoverable elongation prior to the yield point is called
4
elastic range. A graphical sketch on the stress- strain behavour in above mentioned
classes of polymers is shown in Fig. 4.42.
(a) Soft and weak (b) Hard and brittle (c) Soft and tough
a
8 ‘
7)
Strain
(d) Hard and strong (e) Hard and tough

f—— Elongation at yield point
eases ee
2
a | |
5 Elongation at break
Se)
i ultimate strength
yield stress
|
Strain
ee
Fig. 4.42 (a—e) Stress-strain behaviour in various polymers baed on
their viscoelastic characteristics
The stress-strain behaviour of typical classes of polymers is shown in

Fig. 4.43. The typical rubbers, plastics and fibers show a varied response to high
stresses. A reinforced or crystallizable rubber exhibits a relatively low value of
breaking stress, but high elongation. A ductile plastic such as polyethylene exhibits
yielding, drawing and at high elongations, some strengthening due to orientation.
A brittle plastic such as polystyrene does not yield much and breaks at high
elongation.
Fiber
Brittle plastic
Flexible plastic
Stress
Elastomer
Elongation
Fig. 4.43. The stress-elongation behavour of typical classes of

polymers (*—point at which failure occurs)
A fiber exhibits the highest strength, high stiffness and low elongation. In all
the three cases, the shae and position of the stress-strain curve are determined by
the balance struck between cohesion and segmental mobility at the testing rate
and temperature concerned. As with the low stress behaviour discussed above,
behaviour is sensitive to these last two parameters.
Thus a polymer that is brittle at room temperature may. become ductile on
raising the temperature and lowering the testing rate. Similarly a normally ductile
polymer becomes brittle at low temperatures and high testing rates.
4.5 Chemical
Various transformations and chemical reactions can be carried out by polymers
but the number of such reactions is very limited unlike low molecular weight
substances. Polymer degradation and cross-linking are the examples involving
reactions in polymer backbone in solid state. polymers, like low molecular weight
substances may react in selected solvents, provided the reaction sites are accessible
in polymer molecules. Some of the typical reactions of polymers involving
functional groups are described below:
Class-I
Polyvinyl alcohol is obtained by the hydrolysis of polyvinyl acetate as shown in
scheme-1.
¢CH2—CH — ~¢CH)—CH + nCH;COOH

H,0
OCOCH; OH
Polyvinyl acetate Polyviny] alcohol
Scheme 1
No direct method for the polymerisation of the vinyl alcohol monomer is possible
(as this monomer is not stable). Polyvinyl acetate is water insoluble and its
hydrolysis can be controlled to a definite degree. Increased hydrolysis makes the
polymer more hydrophilic; the fully hydrolysed polymer, polyvinyl alcohol
possesses excellent water solubility. Polyvinyl alcohol can be sulfated or
phosphorylated to obtain polyelectroytes with desired ionic content.
Class-II
Cellulose can be etherified or esterified resulting into useful products. The free
hydroxyl groups of cellulose react with alkyl halide forming ethers e.g. ethyl]
cellulose, carboxymethyl cellulose. The hydroxyl groups of cellulose react with
acid groups of inorganic or organic acids forming esters. Nitrocellulose, cellulose
acetate are such examples. Scheme-2 gives various reactions that can be carried
out on cellulose to get useful products.
Class -IIl
Polyacrylates and polyacrylamide are hydrolysed (partially or completely) to
yield polymers with characteristics properties (see scheme-3)
ONO, CH,ONO,
Cellulose nitrate
, HNO,
CH,0OCH,;CH,CN =OCH,CH,CN CH,OR OR
On =0 O O
OCH,CH,CN OH OR OH
4. O O O
OCH,CH,CN CH,OCH,CH,CN OR CH,OR
n
Cyanoethy! cellulose Alkyl cellulose
CH>=CH—CN NaOH, R-Cl
CH,OH OH
acy ecm
O O
OH OH
OH CH,OH |,
Cellulose
CH,—CH), Ac,O
xe ie AcOH
O
O
|
CH,OCH,CH,OH OCH,CH,OH
(ORT eo
Ge Faas OH
O
OCHYCH,OH CH,OCH,CH,OH e OCCH; CEOs
Ethyl! cellulose NaOH | CICH,COONa
Cellulose acetate
)
OCH,GONs CHLOCH,CONa
Carboxymethy] cellulose
Scheme 2. Reaction of cellulose giving useful products
hydrolysis
thule aaah a a in aes
x COOH
X =CN, COOR, CONH), Polyacrylic acid
Scheme 3
Class-IV
Aldehydes react with the pendant —-OH groups e.g. in polyvinyl alcohol and form
polyacetals which have useful properties (see scheme - 4).
Gaia rage va
OCOCH3; OCOCH3 OCOCH3
Polyvinyl acetate
H,O
CH ye CH shed
‘a is i Ye
OH OH OH OH
Polyviny! alcohol
C,H;CHO
(butanal)
CH) CH) CH)

>. i Pe LD
= ig hy vi
0. O O. O
we im
‘ea ‘i
CoH, C3H,
Polyvinyl butyral
Hydrolysis of polyvinyl acetate and the formation of polyviny] butyral
Scheme 4
Class -V
Polyacrylonitrile on heating cyclises and forms a ladder like polymer. It is called
carbon fiber and is obtained by the cyclization of the pendant nitrile group. The
formation of carbon fiber is depicted in scheme-5.
Class -VI
The aromatic pendant group of polymers shows all the characteristic reactions of
benzene e.g. alkylation, acylation, nitration, sulfonation and halogenation. For
example, polystyrene can undergo sulfonation to yield sulfonated polystyrene
useful for ion exchange resins. Polyaminostyrene is obtained by the reduction of
polynitrostyrene (formed by the nitration of polystyrene) and is useful for making
CH5 CH, CH>
\ \ NS \
: EK SS
N
SS
N
SS
N
Polyquinizarine (Carbon fibre)
Cyclization and dehydrogenation of polyacrylonitrile

Scheme 5
polymeric dyes. The various possible chemical reactions of polystyrene are

shown in scheme-6.
Some other well known examples involving chemical reactions are the formation
of styrene-maleic acid copolymers by the hydrolysis of styrene-maleic anhydride
copolymer, hydrogenation of styrene-butadiene block copolymer to styrene-butene
block copolymers, formation of polyimides by heating polyamides and
transformation of naturla rubber into useful derivatives. These all are illustrated
in schemes-7-10 respectively.
Cross-linking
Cross-linking means the formation of bonds between different chains of linear
polymers leading to three dimensional network structures. Though the cross-
linking can result due to secondary bonds (e.g. H-bonding), chemical cross-
se CH—CH)},
Cl
Chlorinated polystyrene
Heath CEE Clit
~(CH—CH?>;
SO3H
Sulphonated polystyrene
Polystyrene
-CH—CH)+;
HNO,
Reduction
NH)
Polyamino styrene
O +~CH—CH)),
|
Polyvinyl cyclohexyl benzene

Scheme 6
issues CH,— CH=—= CH — cite

n
Styrene — butadiene copolymer
H, catalyst
8c 08 chy Chi}
n
PS — hydrogenated PB block copolymer
Hydrogenation of styrene-butadiene block copolymer

Scheme 7
| n
|
dehydration
eee N{O)-0
+ Scheme 8
linking involves covalent linkages, which is by nature irreversible. A chemically

_ cross-linked polymer becomes a thermosett which does not melt on heating and
does not dissolve in any solvent. A typical network formed due to cross linking
of linear polymer chains is shown in Fig. 4.44.
Cross-linking in an elastomer (Vulcanisation)

Addition of some reagents develops cross-linking in linear polymers. The best
known example of such cross-linking is of vulcanisation—a process which was
discovered by Charles Goodyear in 1839. Mastication of natural rubber with
sulphur develops cross-links thus improving processing and utility of rubber.
Although the mechanism of vulcanisation appears quite complex and still not
known in detail. The cross-linking as earlier thought is not an auto-accelerated
process. It is not initiated by free radicals but by organic bases and acids, thus it
is probably an ionic (cationic) process. The sulphur added as a cross-linking
agent, itself is a multimer of 8 atoms i.e. cyclooctasulphur Sg. The probability is
that the Sg disociates into S® and S,, ions in the initial stages of vulcanisation.
The sulphur cation S® reacts with a diene molecule of rubber to give I. This
cation adds to another polydiene molecule to give II and III. The allylic carbonium
NH HOOC COOH
oe
HN |
H 2N NH)[
goto
[enn
Aromatic polybenzimidazole (PBI)

Scheme 9
Cl
|
CH) —C—CH—CHp%
CH;
HCl Rubber hydrochloride
Cl Cl
Cl, Db
+ CHy—C—CH—CHp 9
CH,
maa eka 2:
Chlorinated rubber
CH3
Natural
atural rubb
rubber THe egCH,—
awe ) aie
Cyclized rubber
(it.
~ i Ane
8 Vulacanised rubber
wwwCH=C—CH—CHmw
cn,
Scheme 10
e Cross-link
Fig. 4.44 A typical cross-linked network
cation III reacts with Sg to form IV and this adds to polydiene to form V via a
sulphur bridge. Form V also has a cation, which undergoes a transfer reaction to
polydiene, which regenerates III, and the cycle or curing will go on. The scheme-
11 as given below depicts various steps during the vulcanisation process.
To /H Le
ws sng Sg age”aad se rr na
4 Sg Ss
I II
CH; CH3
awww CH—C=CH—CHwwe aw CH= CH—CH, ww
Hl Ss IV
GH,
wens @pide CH—CH,
S,
wr CHS CH CH
CH
Vv
Vulcanisation of natural rubber
Scheme 11
Cross-linking of thermoplasts (Curing)

Low molecular weight polymers usually those containing either reactive functional
groups or double bonds in their molecule which can be cross-linked to obtain a
three dimensional polymer. This process is called curing (see scheme-12). The
low molecular weight polymer, which is liquid-like, is called prepolymer.
Substances, which develop cross-links, should have at least bifunctionality and
are called curing agents. An important example of curing reactions are described
below.
aww CH=CH CH=CH» + CH=CH?

(Unsaturated) prepolymer
Styrene
|rradical
Aw (SH — CH ws(CH as
Cured (or cross-linked polymer)

Scheme 12
An unsaturated polyester resin made as prepolymer by the polycondensation

of ethylene glycol with maleic anhydride, which is liquid-like and yields a
polymer upon curing. This polyester is linear and has unsaturation in the polymer
chain which comes from maleic anhydride. The curing agent used is styrene,
which in the presence of free radical develops chemical cross-links in the
prepolymer producing a network structure.
Polymer degradation
Polymeric materials undergo decrease in their molecular weight during fabrication
and/or long term use, by chemical and/or radiation attack. The loss of molecular
weight is mostly undesirable (however desirable at times) and is called polymer
degradation. The degradation is caused by the scission of the backbone by certain
agents like heat, light and other ionizing radiations, water and bacteria etc.
Degradation in polymer chains is described under several titles depending on the
factor/agent that induce degradation in a polymer chain. Several possible types
of degradation are schematically represented in Fig. 4.45.
The degradation can also be caused by mechanical force, high energy radiation
and ultrasound wave etc.
The degradation takes place in two different ways. In the first chain scission
takes place at random points where the polymer molecular weight decreases
drastically. In the other case the chain begins to break from its ends. In this case
a slow decrease in molecular weight is noticed and the monomers are liberated.
This type of degradation is called unzipping and is reverse of polymerisation. It
is therefore also called depolymerisation. Polymer degradation can be studied
Qa gy
Die are es
Thermal degradation Photodegradation
By oxygen By poo aa
4 By water
Biodegradation
Hydrolytic degradation
Fig. 4.45 Types of polymer degradation
using thermal methods of analysis, spectroscopy and by chromatography. Since

the degradation is accompanied by a decrease in molecular weight, routine
determination of intrinsic viscosity would serve a better way to investigate polymer
degradation. Agents like antioxidants, photo stabilisers are added to the polymers
to prevent the unwanted degradation. Thermal degradation of polymers is practically
important and it may follow either unzipping or random scission. Since many
polymers contain C—C bonds in the main chain (backbone), the thermal stability
of a polymer would thus depend on the stability of C-C bond. Several factors
influence the C-C bond stability. Introduction of methyl substituents in the
polymer decrease the bond stability and it is for this reason Polyolefins show the
following order in thermal stability; polypropylene > polyisobutylene. For the
same reason the following trend in the thermal stability of polymers can be
understood: palyethylene > polystyrene > poly a@-methylstyrene.
High thermal stability of teflon is the exception to this rule. Introduction of
aromatic ring in the polymer main chain increases thermal stability of polymers.
Polycarbonates, polyphenylenes, aromatic polymides are fairly stable to high
temperature. Branching or introduction of oxygen atom in the polymer chain
decreases the thermal stability of polymers. Polyethylene oxide is degradable
while polyethylene is stable. In some cases, the polymer chain remains intact but
the pendant groups are eliminated. For example, polyvinyl chloride degrades at
around 200°C with the elimination of HCl.
Numerical exercises
1. Estimate the contour length and root mean square end-to-end distance of
polypropylene chain with DP = 5000. The end-to-end distance between carbon
atoms is 0.126 nm.
Solution — The contour length = 2 x 0.126 x 5000 = 1260 nm, the root mean
square end-to-end distance = r = nl!” = 0.126 x (2 x 5000)" = 0.126 x 100 =
12.6 nm.
2. The enthalpy change for the polymerisation of methyl methacrylate monomer is
-57 kJ mol"!. If the ceiling temperature for this monomer is 434 K, what would
be the value of entropy change in polymerisation?
Solution At ceiling temperature the equilibrium between monomer and
polymer is established and thus free energy change is 0. Since AG = AH — TAS,
O = — 57 — 434 AS or AS = - (57/434) kJ K7! mol". = 131.3 JK™ mol.
3. The intrinsic viscosity of a polymer is measured in THF and in CHC]. The
intrinsic viscosities are in the ratio [Q] nur/[M]cuciy = 1.7. Calcualte the ratio of
the mean-square end-to-end distances.
Solution Intrinsic viscosity, [7] is proportional to r’, hence [(F?) in THF]/
((F2)! in CHCL] = {[n] in THF/[n] in CHCI;}"? = {1.7}'? = 1.2.
4. Two samples of polystyrene with mol. mass 1 x 10° and 1 x 10° g mol"! in a @-
solvent have intrinsic viscosities of 0.26 and 0.83 dl g™', respectively. A third
sample of the same polymer in similar condition has intrinsic viscosity of 0.50 dl
g'. Calculate the mol. mass of the third sample.
Solution [n] = KM"?, for polymer solvent pair in @-conditions. Thus 0.26 =
K (1 x 10°)!” and 0.83 = K (1 x 10°)”. Solve the equations to get a K value of
8 x 10 dig"!. Then for the third sample, we can write 0.50 = (8 x 10~)M'” and
its molar mass, M is 3.6 x 10°.
5. The intrinsic viscosity for a polyethylene oxide sample in aqueous potassium
sulphate under 6-conditions (K = 130 x 10~) is 0.82 dl g~'. For this sample in
water (K = 16.6 x 107°, @ = 0.82), calculate the chain expansion factor and rms
end-to-end distance of the macromolecular coil.
Hint — Calcualte M value from equation, [N]g= K M°° = 130 x 1079 M°5 = 0.82.
Now calculate [1],yater from equation (using calculate value of M).[
1] water =
KM“ = 16.6 x 107° M®*?, Evaluate chain expansion factor a from of = [n]/[n]o.
Now obtain n or degree of polymerisation = M/44 and N = 2 x n. Calculate
(72) = b[2N]'? (here b = C—C bond length, 1.54A). Calculate rms end-to-
end distance of PEO in water from the relation (7)? x a.
6. Polyethylene oxide (PEO) in water and 0.1 M K,SO4(,q) at 25°C has the following
Mark-Houwink constants, K and a;
Kx 10° a
Water 16.6 0.82
Calculate the chain expansion factor for a PEO sample of mol. mass 50,000.
Solution a= 0.5 for aq. K,SOy, since it is a 6-solvent. Hence, [N]g = KM®% =
130 x 10° x (50,000)°° = 29.1 dl g"!. For water, [)] = K M% = 16.6 x 10° x
(50,000)°*? = 118.4 dl g!.
Chain expansion factor, a = ({n]/[n]¢)!? = (118.376/29.069)'? = (4.072)! =
1.597.
7. A PMMA sample in acetone at 30°C gave intrinsic viscosity of 0.565 dl g™!.
Calculate the mol. mass of the polymer when K = 6.2 x 10° dl g™! and @= 0.72.
Also calculate rms end-to-end distance if under @ conditions the intrinsic viscosity
of the polymer is given by relation [7] = 4.8 x 10*M®>°,
Solution [n] = KM*=0.565 = (6.2 x 10°) M°”? or M= 3, 16,000 g mol~!. Now,
[n]o= 4.8 x 10 x (3, 16,000)°* = 0.269 dl g'. The chain expansion factor @ =
((in\/{nl¢)]'3 = (0.565/0.269)'? = 1.280. The repeat unit in PMMA has a mol.
mass of 100. Thus, n = 3160 and N = 6320. Hence (72)"2 =bV2N =
1.54 V12640 = 173A. In acetone, (F?)"? = a(7?)"”? = 1.279 x 173 =221 A.
8. Calculate (i) the contour length and (ii) the extended chain length and (iii) rms
end to end distance for polyethylene of mol. weight 1,00,000.
Solution The polymer is made up of —(CH;—CH;),— repeat unit. Thus C—C
bond length = b = 1.54 A and C—C—C bond angle @= 109.5°, mol. wt. of repeat
unit = 28 and thus
Contour length =2 xn x b, 2 x (100000/28) x 1.54 = 11000
Extended length = 2 xn x b sin 0/2
= 2 x (100000/28) x 1.54 sin (54.75)
= 8983 A
rms end-to-end distance for freely jointed chain = bV2N = 1.54V2 x 100000/28
= 130 and rms end-to-end distance with bond angle restriction = bV2N.
Suggested Questions
IK Describe briefly some factors that affect the solubility of polymers. Define:
(a) Good solvent (b) Poor solent
(c) 6-Solvent (d) Selective solvent
(e) Hildebrand’s regular solvent
Indicate how solvent “power” (good solvent versus poor solvent) influences:
(a) The intrinsic viscosity of the polymer sample
(b) The molar mass of a polymer sample as determined by membrane osmometry
Write units of
(a) Intrinsic viscosity (b) Solubility parameter
(c) Partial specific volume (d) Second virial coefficient
(e) Modulus of elasticity
(i) What is the value of free energy change for mixing at the 6-temperature?
(ii) What is Hildebrand’s solubility parameter? How is it important in dissolution
of polymers in solvents? (iii) Ethyl benzene is soluble in methanol but not
polystyrene, why? (v) Addition polymers are normally not crystalline, why?
Explain the terms:
(a) Rheopectic (b) Viscoelastic
(c) Thixotropic (d) Isotropic
(e) Microgels (f) Newtonian and non-Newtonian low
Write notes on
(a) Slubility parameter (b) Dimensions of macromolecular coil
(c) Polymer chain flexibility
Explain the terms
(a) Chemcial heterogeneity (b) Polymer chain flexibility
(c) Radius of gyration (d) Ideal and regular solutions
What are polyelectrolytes? Explain viscosity behavour of a polyelectrolyte in
water and aqueous salt solution.
Describe the dissolution process of polymers in solvents. Discuss thermodynamics
of polymer dissolution. How do the following factors influence the polymer
solubility?
(i) Increase in molecular weight (ii) Crosslinking (iii) Crystallinity
Describe the Flory-Huggins theory of polymer solutions. Obtain the necessary
derivation.
Lie Comment on the limitations of Hildebrand solubility parameter equation. How is

the solubility parameter related to the heat of mixing?
12. Explain the terms Flory’s interaction parameter and give its importnace. Describe
the method which can be used to determine its value for:
(a) soluble polymers (b) cross-linked polymers
13. Answer the followings:
(a) How does the crystallinity of polymers influence the film and fiber properties?
(b) How does the tacticity influence the Solution and solid state properties of
polymers?
14. Explain the differences in (a) Plasticization and vulcanisation (b) Newtonian and
non-Newtonian flow (c) Amorphous and crystalline polymers (d) Maxwell and
Voigt model of viscoelsaticity
1yay What effect do the crystalline polymers have*on the solid state and solution
properties? Picturise the ‘Fringed micelle model’ of the crystalline-amorphous
structure of polymers.
(a) Draw schematically the stress-strain curves for different plastics with varying
hardness and toughness (b) Draw schematically the stress-strain curves for plastics,
fibres and elastomers
Define: (a) 0-Temperature (b) Ceiling temperature (c) Glass transitiion temperature
(d) Softening temperature (e) Critical solution temperature
Expalin the term polymer chain flexibility. What factors influence it? How is the
chain flexibility related to end-to-end distance?
Comment on the following:
(i) The polymers of @-amino acids are termed as ‘nylon n’, where n is the number
of consecutive carbon atoms in the chain (general formula+~NH-—CO-(CH)),,_;+.
The polymers are crystalline and do not dissolve in either water or hexane. They,
however, absorb solvent when immersed in each liquid.
(11) Polyvinyl alcohol is made by the hydrolysis of polyvinyl acetate because the
monomer vinyl alcohol is unstable. Hydrolysis can be controlled anywhere from
0-100%. Polyvinyl acetate is insoluble in water, polymer with increased hydrolysed
character becomes more and more soluble and 100% hydrolysed polyvinyl acetate,
i.e. polyvinyl alcohol is very soluble in water. Explain its solubility behaviour.
(iii) Cellulose and starch, both are polymers of glucose, yet cellulose does not
dissolve in water whereas starch is soluble. Comment why methyl! cellulose is
more water soluble than cellulose.
(iv) Crystalline polymers can be dissolved only above their 7, in the presence of
strongly interacting solvent.
20. The chemical reactions shown by polymers are few as compared to those by low
molecular weight substances. Why?
2x What are various chemical transformations in polymers? Describe in detail polymer
degradation, cross-linking and stabilisation.
22 How can the following polymer transformations be carried out?
(a) Polyvinyl acetate to polyvinyl alcohol (b) Styrene-isoprene block polymer to
styrene (ethylene/propylene) block copolymer (c) Polyacrylonitrile to carbon
fiber (d) Cellulose to acetate rayon. Mention the usefulness of these transformations.
Crystalline Behaviour of Polymers

Alexander, L.E., X-ray Diffraction Methods in Polymer Science, New York: John Wiley,
1969.
Balta-Calleja, FJ., and C.G. Vonk, X-Ray Scattering of Synthetic Polymers, New York:
Elsevier, 1989.
Geil, P.H., Polymer Single Crystals, New York: John Wiley, 1963.
Glatter, O., and O. Kratky, Small Angle X-Ray Scattering, New York: Academic Press,
1982.
Hemsley, D.A., The Light Microscopy of Synthetic Polymers, New York: Oxford Univ.
Press, 1985.
Kakudo, M., and N. Kasai, X-ray Diffraction by Polymers, Amsterdam: Elsevier 1972.
Keinath, S.E., R.L. Miller, and J.K. Rieke, (eds.), Order in the Amorphous State of
Polymers, New York: Plenum, 1987.
Mendelkern, L., Crystallisation of Polymers, New York: McGraw-Hill, 1964.
Rhodes, G., Crystallography Made Crystal Clear. A Guide for users of Macromolecular
Models, New York: Academic Press, 1993.
Sandman, D.J. (ed.) Crystallographically Oriented Polymers, Washington, D.C.: ACS,
1987.
Sawyer, L.C., and D.T. Grubb, Polymer Microscopy, New York: Chapman and Hall, 1987.
Sharples, A., Introduction to Polymer Crystallisation, London, Edward Arnold, 1966.
Tadakoro, H., Structure of Crystalline Polymers, New York: Wiley-Interscience, 1979.
Ward, I.M. (ed.), Developments in Oriented Polyme, 2 Parts, New York: Elsevier Applied
Science, 1982 and 1987.
Woodward, A.E., Understanding Polymer Morphology, Munich: Hanser, 1995.
Wunderlich, B., Marcomolecular Physics, (3 vols.), New York: Academic Press, 1980.
Thermal Behaviour of Polymers:
Mathot, V.B.F., (ed.), Calorimetry and Thermal Analysis of Polymers, Munich: Hanser,
1994.
Turi, E.A., (ed.), Thermal Characterisation of Polymeric materials, 2nd ed., New York:
Academic Press, 1982.
Wunderlich, B., Macromolecular Physics, Vol. 3, Crystal Melting, New York: Academic
Press, 1980.
4
+
Solution Behaviour of Polymers:

Barton, A.F.M., CRC Handbook of Solubility Parameters and Other Cohesion Parameters,
Boca Raton, Fla.: CRC Press, 1983.
Bohdanecky, M., and J. Kovar, Viscosity of Polymer Solutions, Amsterdam: Elasevier,
1982.
Flory, P.J., Principles of Polymer Chemistry, Ithaca, New York: Cornell Univ. Press, 1953.
Fujita, H., Polymer Solutions, Amsterdam: Elsevier, 1990.
Jannik, G., and J. des Cloizeaux, Polymers in Solutions, Oxford: Oxford Univ. Press,
1990.
Kurata, M., Thermodynamics of Polymer Solutions, New York: Gordon and Breach, 1982.
Morawetz, H., (ed), Macromolecules in Solution, 2nd ed., New York: Wiley-Increascience,
1975.
Tanford, C., Physical Chemistry of Macromolecules, New York: Wiley-Interscience, 1961.
Tompa, H., Polymer Solutions, New York, Academic Press, 1956.
Yamakawa, H., Modern Theory of Polymer Solutions, New York: Harper and Row, 1971.
Rheological Behaviour of Polymers:

Aklonis, J.J., W.J. MacKnight, and M. Shen, Introduction to Polymer Viscoelasticity, 2nd
ed., New York: Wiley-Interscience, 1983.
Alfrey, T., Mechanical Behaviour of high polymers, New York: Interscience, 1948.
Brydson, J.A., Flow Properties of Polymer Melts, Lancaster Penn.: Technomic, 1981.
Cogswell, F.N., Polymer melt Rheology, New York: Halsted-Wiley, 1981.

Deanin, R.D., Polymers: Structure, Properties and Applications, Boston: Cahners, 1972.
Ferry, J.D., Viscoelastic Properties of Poymers, 3d ed., New York: John Wiley, 1980.
Mashelkar, R.A., A.S. Mujumdar, and R. Kamal, (eds.), Transport Phenomenon in Polymeric
Systems, Englewood Cliffs, New Jersey: Prentice Hall, 1989.
Severs, E-T, Rheology of Polymers, New York: Reinhold, 1962.
Chemical Behaviour of Polymers

Cassidy, P.E. Thermally Stable Polymers, New York: Dekker, 1980.
Guven. O, Crosslinking and Scission in Polymers, Dordrecht: Kluwer, 1990.
Grassie, N., and G. Scott, Polymer Degradation and Stabilisation, Cambridge: Cambridge
Univ. Press, 1988.
Mark, J.E., B. Erman, and FR. Eirich, (eds.), Science arid Technology of Rubber, 2nd ed.,
San Diego: Academic Press, 1994.
Moore, J.A. (Ed.) Chemical Reactions of Polymers, New York, Wiley-Interscience, 1964.
Hoe)
Polymer Technology
5.1 Physical Properties Versus Application

After the synthesis, identification and characterisation in terms of evaluation of
molecular weight and molecular weight distribution, crystallinity, glass transition
temperature and the determination of other physical properties (in solid state and
in solution), the polymers are then processed into a material which is in useful
form for a direct application. The processing of polymers is not straight forward.
Usually, polymers with very high molecular weight offer problems in processing
due to enormous increase in melt viscosity (see Fig. 5.1).
Melt viscosity
i Mechanical strength
Property
Molecular weight
—_—_—_ —
Fig. 5.1 The mechanical properties and melt viscosity of polymers as

a function of molecular weight
Depending upon various applications most polymeric materials can be classified

into major groups such as plastics, fibers, elastomers, coating materials and
adhesives. The materials belonging to these different groups vary in many properties
especially in solid state properties. One of the most important physical properties
i.e. mechanical properties differ to a great extent and also play a decisive role in
classifying the industrial polymers. The typical responses of rubbers, plastics
and fibers to large stresses are depicted in Fig. 5.2. Areinforced or crystallizable
rubber exhibits a relatively low value of breaking stress, but high elongation. A
ductile plastic such as polyethylene exhibits yielding, drawing and at high elongation
some strengthening due to orientation. A brittle plastic such as polystyrene does
not yield much and breaks at a low elongation; a fiber exhibits the highest
strength, high stiffness and low elongation. In all these cases, the form of the
final curves i.e. the shape and position are determined by the balance struck
between cohesion and segmental mobility at the respective and concerned
temperature and testing rate. The strain behaviour under applied low stress is
very sensitive to the temperature and testing rate. A polymer that is brittle at
room temperature may thus become ductile on raising the temperature or lowering
the testing rate. Similarly, a normally ductile polymer becomes brittle at low
temperatures and high testing rates.
Brittle plastic
Flexible plastic
Elastomer
Stress
Elongation, %
re
Fig. 5.2 Stress-elongation behavior of typical polymer
The characteristic features of plastics, fibers, elastomers and adhesives are

discussed in the following manner.
5.2 Plastics
The word plastics is commonly used for a material that usually consists of
organic polymers. The term plastic is nowadays refers to all thermoplastic polymers.
These are the macromolecular compounds which, within a more or less wide
temperature range, pass over from the solid state into a plastic mouldable state
without having undergone chemical changes. This process is reversible. The
thermoplastic behavior of polymers is due to the absence of cross-linking. Examples
of plastics include polymeric hydrocarbons (e.g polyethylene, polypropylene,
polyisobutylene etc.), vinyl polymers (e.g. polystyrene, polyvinyl chloride,
polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, etc.), acrylics
(polyacrylamide, polyacrylates, etc.). Many fluorine containing polymers (e.g.
Polymer Technology 205
teflon, polychlorotrifluorethylene and polyviny! fluoride etc.) polyacrylonitrile

and polymethyl methacrylate are well known examples of plastics.
The synthesis, properties and applications of these substances have already
been described in previous chapters. Plastics are divided into two types,
thermosetting and thermoplastic materials. The difference between these two is
that thermoplastics become fluid upon heating above a certain temperature called
heat distortion temperature and en cooling they again restore elastic or solid
state. The process can be repeated many times without any effects on its chemical
structure. Thermosetts can be heated to fluid state only once and the reverse
process is not possible, because of the change in their chemical structure upon
heating. Such plastics can not be re-softened because of cross-linking that takes
place during the course of first heating. Some of the examples of thermoplastics
are polyamides, polyesters, polyolefins and polystyrenes. Cured unsaturated
polyesters, condensation products of urea-formaldehyde(UF) and melamine-
formaldehyde(MF), phenol-formaldehyde(PF) and epoxy resins etc. are
representative of thermosetts. Table 5(a) describes the typical properties of various
thermoplastic materials.
Table 5(a) Physical properties of some common thermoplastics
Property PS LDPE HDPE PP PMMA PTFE
Elongation
% 1.2-2.5 90-800 20-1000 200-700 2-10 200-400
Tensile
strength 5-12 0.6-2.3 3.1-5.5 4.3-5.5 7-11 2-5
(10° psi)
Impact
strength 025-0.4 16 0.5-2.0 0.5-2.0 0.3-2.0 3.0
(ft.lb/inch
of notch)
Tensile
Modulus 4-6 0.2-0.4 0.6-1.8 1.6-2.3 4.5 0.58
(10° psi)
Burning slow very very slow slow none
Rate slow slow
Effect of attacks resistant resistant resistant attacks very
alkalis resistant
to acids
Effect of resistant resistant resistant very
organic soluble (below (below (below soluble resistant
solvents 80°C) 80°C) 80°C)
Clarity transpa- opaque opaque opaque transpa opaque
rent rent
Specific
gravity 1.4-1.09 0.91-0.92 0.94-0.96 0.90-0.91 1.17-1.2 2.14-2.2
Thermosett materials are also often called as resins. The term resin was
applied originally to naturally occurring amorphous organic solids such as amber,
copal, dammar, shellac and rosin etc., but is now commonly used for synthetic
polymeric materials similar to natural resins in physical properties and used for
surface coatings. Resins differ from linear polymers in having cross-linked
structures that produce three dimensional network. Thermosetting resins change
irreversibly on heating from a fusible and soluble material to infusible and
insoluble mass; such a conversion results into a thermally stable network. These
materials are used for variety of purposes. Some common physical properties of
thermosetting resins are listed in Table 5(b). A few examples of commercially
important thermosetts are (i) phenolic resins, (11) amine resins, (iii) epoxy resins
(iv) unsaturated polyester resins (v) polyurethane resins (vi) silicone resins, and
(vii) alkyd resins etc.
Table 5(b) Physical properties of some common thermosetting (cross-linked) resins
Property ele Polyester Epoxy silicone
Elongation (%) 1-1.5 3 3-6 100-300

Tensile modulus
(10° psi) 7.5-10 3-6.5 a5 0.1
Impact strength
(ft.lb/inch of 0.2-0.35 0.2-0.4 0.2-1 —
notch)
Burning rate very slow burns slow self-extinguishing
Effect of organic resistant attacks resistant attacks
solvents
Specific gravity 1.25-1.3 1.1-1.45 1.1-1.4 1-1.5
All resins are attacked by strong acids or alkalis and they are transparent in
appearance. However, reinforced polymers are opaque and have modified
properties.
5.3 Fibers
Fibers by definition are macromolecular substances, which have length to diameter
ratio of at least 100: 1. To qualify as a useful textile material, a polymer has to
meet the following requirements, (i) high degree of polymerisation, (ii) high
degree of orientation of molecules relative to longitudinal axis, (iii) high melting
(or softening) point, (iv) fair elongation to break, (v) elasticity and (vi) chemical
stability. Different polymer materials are used as fibers. Fibers can be broadly
classified as natural, semi-synthetic and synthetic types. As expected natural
fibers are derived from naturally available sources. Semi-synthetic fibers are
produced by modifying the otherwise naturally occurring material. Synthetic
fibers are, however, produced exclusively by the laboratory process. Cotton, silk
and wool are the well-known natural fibers. Rayons are cellulose based semi-
synthetic fibers. Among the synthetic (man made) fibers, the most common are
nylons, polyesters and acrylic fibers. These are described below.
Natural Fibers
Cotton
Cotton is a vegetable fiber and is essentially made of cellulose, which is a linear
polymer of #-glucose. Cellulose has a sheet like structure and is the principal
structural component of plants. The strong intermolecular hydrogen bonding
between hydroxyl groups gives cedlulose a high degree of crystallinity and thus
strength of cotton. For the same reason, cellulose despite containing a large
number of hydroxyl groups is insoluble in water. However, the water uptake is
high enough and therefore cotton clothes take long time to dry up. Fibers derived
from cellulose ate called rayons. The viscose rayon, cupraammonium rayon and
acetate rayon are the derivatized celluloses which are used as fibers. These
useful fibrous materials are called cellulosic (semi-synthetic) fibers. An early
process for producing regenerated cellulose fiber involved treating cellulose
with solution of ammonical copper sulfate and the resulting solution was then
forced through spinnerets into an acid bath to produce cellulose as long filaments.
An alternative method of regeneration is to dissolve cellulose in a solution of
sodium hydroxide and carbon disulphide. The resulting solution is called viscose
and it is then forced through a spinneret into an acid solution. This form of
cellulose is also called regenerated cellulose and can be further processed into
fibrous form. It is known as viscose rayon and is a major commercial textile
fiber. Cellulose acetate (acetate rayon) can be prepared by heating cellulose with
acetic anhydride and acetic acid in the presence of sulfuric acid. It is also used
in making films and lacquers in addition to fibers.
Wool
Wool is an aninial protein fiber. Like all other proteins, wool is also made up of
a-amino acids. The amino acids are joined end-to-end in the form of peptide
chains making long chain molecules. These polypeptide chains are joined through
cross-linkages which give wool many characteristic structural and tensile properties.
Polypeptide chains in wool occur normally in folded form and these chains can
be unfolded on stretching the fiber. The folded form as 6-keratin. Two sulfur
containing @-amino acids found in wool as well as in other keratins are cysteine
and methionine. Many of the physical and chemical properties of wool are due
to the disulfide bonds formed by covalent cross-linking of the cysteine molecules.
Any chemical that weakens or destroys disulfide bonds may cause structural
break-down of the fiber. Many other acidic and basic side chains are also present
in the polypeptide chain of wool. The presence of these side chains causes the
formation of “‘salt-linkage” which are responsible for the amphoteric nature of
wool, i.e. it behaves both as acid and base. The peptide chains are held together
also through hydrogen bonds which are responsible for the elastic properties of
individual wool fiber.
Dry wool fiber swells up when placed in water. The degree of swelling depends
on factors such as the temperature and strain on the fiber. In cold or luke-warm
water, the fiber swells to about 10% in diameter, but on drying, the fiber usually
returns to its original size. This recovery is thought to be due to reversibility of
hydrogen bonding transformation. This explains the important property of elasticity

of wool. Fibers dried in extended state do not recover to their original size. When
wool is heated in dry air at 100°C to 105°C over a long period, it loses moisture
and the fibers become harsh, if returned to moist air, the fiber rapidly reabsorbs
moisture and regains its softness. Wool, when burnt emits a characteristic odor
like that of burning of hair or feather, probably due to the presence of nitrogen
and sulphur in the keratin. The vapors coming off during burning have an alkaline
reaction and probably contain ammonia and sulfur compounds. Although it burns,
wool is fire resistant. When removed from the flame, wool fiber assumes a knot
or charred globule on its end but does not continue to burn. Oxidizing agents like
hydrogen peroxide, KMnOy,, K,Cr,07, attack cysteine disulfide bonds, resulting
in decreased sulfur content, strength and fiber weight. The main use of oxidizing
agent is in bleaching. HO; is the most common bleaching agent for wool and
imparts permanent white colour. When wool fiber is exposed to light in the
presence of water, reaction between water and cysteine linkage takes place. This
photochemical reaction is responsible for the yellowing of woollen fabrics. So
white woollen garments should not be dried in bright light. Wool is more
hygroscopic than other textile fibers. This characteristic feature confers a number
of advantages on wool as a clothing and furnishing fabric.
Silk
Silk is a natural protein fiber produced by the insect, silk worm. It has all the
desirable qualities of fiber such as softness, strength, elongation, etc. Besides,
silk has a bright lusture. It is lighter than other natural fibers and has the specific
gravity of 1.25—1.27. Silk is an excellent insulator of heat, hence it is warm in
winter and cool in.summer. Depending upon the atmospheric conditions, silk
can absorb about 20-25% moisture without becoming wet, which makes it
comfortable to wear. Silk is a polypeptide made up of only four amino acids,
glycine, alanine, serine and tyrosine. Glycine and alanine are present in 2 : 1
ratio and cover more than 75% mole percent of the silk. The fiber can be made
to form a continuous filament about 300-700 metre long. Silk is noted for its
strength, toughness and smooth soft feel. It is a poor conductor of heat and
electricity. After proper cooking, the cocoons are deflossed mechanically to get
the continuous filament. Several cocoons are fed per end of the reeling machine
to produce silk yarn of a particular thickness. These yarns are then twisted or
doubled and used for fabrication to get the bright silk cloth.
Synthetic Fibers
The first synthetic fiber was produced by Carothers by the reaction of
hexamethylene glycol and adipic acid. The molten polyester thus obtained gave
a long filament like material that could be stretched several times of its original
length. Since then, there has been a phenomenal growth in the production of
synthetic fibers. In 1950, production of synthetic fibers was 0.73% of the total
fibers while in 1980 it rose to 37% and presently it is estimated around 55-60%.
The increasing trend will still continue. Polyesters, nylons and acrylic fibers are
produced in major quantities. An important development in the synthetic fiber
industry is the production of staples of short length that can be blended with
natural animal or other synthetic fibers. The advantage of such composite or
blend fibers is that the properties of individual components complement each
other. For example, a blend of polyester-cotton (67: 33) is superior and exhibits
more comfort than that of its individual components. Many drawbacks of synthetic
fibers such as low moisture absorption, accumulation of static charges, easy
soiling, metallic lusture, and lack pf ideal warmth and comfort can be overcome
by blending them with other fibers.
Synthetic fibers are produced from highly pure monomers under strictly
controlled reaction conditions. The following steps are generally involved for
the manufacture of fibers; (i) conversion of monomer into a polymer, (ii) polymer
to granules or chips, (iii) pressing the melt or dope of the polymer through
spinning jet to form filaments, (iv) development of morphological fine structures
and (v) modification of filament to suit the end use. Synthetic fibers are produced
in a batch or continuous process. Some of such fibers are described below:
Polyester (polyethylene terephthalate)

Polyethylene terephthalate is produced by the condensation of ethylene glycol
(EG) and dimethyl terephthalate (DMT) or terephthalic acid (TPA)..The
condensation of DMT and EG is carried out in two steps namely trans-esterification
and polycondensation. The catalyst for trans-esterification process consists of
acetates of sodium, manganese, zinc or cobalt or a mixture there of. Antimony
trioxide or acetate is used as a polycondensation catalyst. The polymer melt is
spun into ribbons or bands that are granulated. The granules are dried under
reduced pressure till the moisture content reaches to 0.05% since polyester is
hydrolysed in the presence of trances of water. The dried chips are melted and
the molten mass is spun into filaments. The appropriate spin finish is applied and
the filaments or tows are collected in a drum.
The technology of staple manufacture is slightly different from that of filaments.
Many filaments are brought together to form a thick tow. The tow is passed
through water to remove the spin finish, squeezed, heated and stretched before
crimping, drying, heat set and cut into stable fibers of desired length. The stretched
tow is used for yarn spinning. The staples are pressed into bales and marketed.
The polyester staples are directly spun into filaments or blended with cotton
before spinning into fibers.
Polyamides (Nylons)
Among the large number of polyamides (nylons) only two, i.e. nylon 6 and
nylon 6, 6 could get commercial importance. Nylon 6, 6 is synthesised by the
condensation of hexamethylene diadipate salt (HD Salt). The salt is produced by
the condensation of equimolar amount of hexamethylene diamine and adipic
acid. The salt is relatively insoluble in methanol and crystallises out on cooling.
The crystals are separated, purified and dissolved in water to get a 50-60%
solution. Acetic acid (5%) is then added as viscosity stabiliser. The solution is
heated in an autoclave when a pressure of 15—20 kg / cm? builds up. The pressure
is slowly released and heating is continued to remove all water by distillation.
The autoclave is evacuated to facilitate the removal of water from highly viscous
molten polyamide mass. The melt is spun into filament or fibers by conventional
methods. The filaments are cold drawn 3-4 times of their original length to
improve the mechanical properties.
Polyamides (nylon 6)
6-aminocaproic acid or caprolactam is the raw material for the production of
nylon 6. Caprolactam, water and acetic acid are charged to an autoclave preheated
to 250°C under pressure ranging from 12—15 kg/cm”. The steam is slowly released,
nitrogen is flushed and vacuum is applied to remove last traces of water. The
reaction never reaches to a state of completion. The melt is extruded and granulated
in water. The granules are extracted with hot water to remove 10% low molecular
weight compounds, containing unreacted monomer and oligomers, in a counter
current manner. After the extraction, granules are washed with fresh water and
vacuum dried. They are then spun at 270—280°C. Nylon 6 is invariably spun into
filaments because its staple fibers could not get any commercial importance.
Acrylic Fibers
World wide demand for the substitute of natural wool led to the invention of
acrylic fibers. It was in 1940, when Du Pont produced first acrylic fiber that was
difficult to dye. After 1955, cationic dyeable fibers were produced. Copolymers
of acrylonitrile with other monomers were synthesised in the presence of few
radical catalysts such as potassium persulfate. Presently available acrylic fibers
are the copolymers of acrylonitrile and other vinyl monomers. In such polymers
the amount of acrylonitrile is not less than 85%,and rest 12% may be constituted
by one or two monomers.
The most common monomers used with acrylonitrile are vinyl acetate, methyl
acrylate. Such monomers reduce glass transition temperature of polyacrylonitrile
from 104°C to 80-90°C, thereby facilitating the dyeing at boil. The acidic
comonomers such as acrylic acid, aliylsulfonic acid, and itaconic acid impart
cationic dyeability to acrylic fibers. The fibers containing basic comonomers
such as vinyl pyridine, or ethylene imine are dyeable with acid dyes. The
commercially available fibers are used as substitute for wool because of their
wool like feel and inertness to chemicals, bacteria and resistance to humidity etc.
Acrylic polymers do not melt before decomposition and are therefore not
melt spun. The acrylic polymers are wet spun. In such a process, polymer is
dissolved in a suitable solvent such as dimethylformamide, dimethylacetamide,
dimethylsulphoxide. The polymer dope is carefully prepared to avoid jet formation
and forced through spinnerets having 5,000 to 70,000 holes. The fiber is passed
through a series of coagulating baths to remove the solvent. The coagulating
baths are filled with dilute aqueous solutions of the solvent. The major fraction
of the solvent diffuses out from the fibers and the residual solvents are removed
by washing with water during the the process of hot stretching. The stretched
tow is crimped and heat set (annealed by steam and cut) into stample fibers.
Polypropylene
Stereoregular, high molecular weight, fiber forming polypropylene is synthesised
using a Ziegler-Natta catalyst by anionic mechanism. Both batch and continuous

polymerisation plants are under operation to make polypropylene. The reactor is
filled with monomer, diluent and catalyst. The polymer is produced by heating
the mixture. The heat of reaction is controlled by the addition of fresh propylene
in order to produce a homogeneous product. The slurry thus obtained is passed
into the flask, which is maintained at relatively low pressure wherein monomer
and diluents are flushed out. The catalyst is deactivated by the addition of alcohol
and is removed from the main polymer. The polymer is centrifuged, washed and
dried. Paraffins, cycloparaffins or their mixtures are used as the inert medium.
The filaments are produced from the polymer by melt spinning at temperatures
of 100-150°C higher than its melting point because it exhibits high melt viscosity.
The spinneret jet holes are also larger (higher length to diameter ratio) than those
used for PET or nylon spinning. Polypropylene fibers have excellent properties
and are used for various purpose. Since the fiber has low moisture absorption,
wet and dry strengths are the same. It has lowest fiber density of all the commercial
fibers. Polypropylene is extensively used in ropes, netting, industrial fabrics and
carpets.
The main problem of polypropylene fiber is its low softening point (160°C).
Fabrics having more than 30% PP can not be exposed to temperatures higher
than 125—130°C as they become harsh due to shrinkage. However, PP fiber is
chemically inert to most chemicals, acids, alkalis and oxidising agents. In the
Table 5(c) are given some physical properties of common fibers.
Table 5(c) Summary of some characteristics of synthetic fibers
Polyesters Polyamides Acrylics
Acidic at room + Inert to alkalis. Have good resistance to

temperature. Disintegr Dissolve in strong weak alkalis. They
ate on boiling in strong mineral acids, are have excellent resistance
alkali solutions but bleach resistant, have to sun light, to bleaches
resistant to bleaches little or no effect of and common solvents.
and organic solvents. most organic solvents. Can be dyed using
Have good resistance They are soluble in cationic, dispersed, acid
to sun light on glass phenols. The fibers and vat dyes
support but prolonged show marked loss in the
exposure results into a physical strength on
decrease in strength. prolonged exposure to
Can be dyed using sun light. Can be
dispersed and cationic dyed with dispersed and
dyes acid dyes
Properties of synthetic fibers

Synthetic fibers are characterised by high strength, superior abrasion resistance,
good crease recovery, low density and resistance to moth and bacteria. Synthetic
fibers are very durable compared to natural fibers such as cotton, viscose and
wool. The main problems with synthetic fibers are the low moisture absorption,
development of static charges, easy soiling, poor comfort and loss of aesthetic
properties during their use. The synthetic fibers burn before they melt.
Most of the synthetic fibers melt before burning. Synthetic fibers recover
well from crosses formed during wear. However, pleats and creases set in the
fibers at high temperatures remain almost through out the life of the garments.
Synthetic fibers have good resistance to chemicals. Polyester and acrylic fibers
are attacked by hot alkaline solutions. The stability against the light and UV
radiation is better than those of natural fibers. Synthetic fibers have a tendency
to shrink in hot water and are usually heat set during the process of manufacturing
to avoid the shrinkage during their use. After heat setting, nylons and polyesters
do not shrink. Acrylic fiber is heat set in the presence of moisture or preferably
by steam.
Synthetic fibers are produced in different deniers as staples and yarns. The
denier of a fiber measures its size and is defined as the weight in grams of 9000
m of the fiber. The size of the fiber is also expressed in many other measures, but
the denier is the most common of all. The size of the fiber measured in deniers
is proportional to its density and to its cross sectional area. One measures the
tensile strength of the fiber from deniers when the later is expressed as weight
per unit length. The yarns are directly used for weaving the garments whereas
staples of different cut lengths are blended with other staple fibers and the blend
is spun into yarns before the processing, weaving or knitting. Variable cut lengths
of staples are common in acrylic fibers. Fibers with different cross sections are
produced by changing the spinnerets having different types of holes. Trilobal,
multilobal yarns of nylon, polyester are used for various purposes and exhibit
different types of lusture and comfort depending upon the dimension of the cross
section. Some important properties of synthetic fibers are listed in Table 5(d).
Table 5(d) Physical properties of some typical fibers
Fiber Tenacity Tensile strength Elongation

g /denier (10° psi) %
Cotton 2.1-6.3 42-125 3-10
Viscose rayon 0.7-3.2 28-47 15-30
Acetate rayon 1.2-1.4 20-24 25-45
Wool 1.0-1.7 17-28 20-50
Silk 2.8-5.2 45-83 13-31
Polyester 2.4-7.0 39-106 12-55
Polyamide (Nylon 6,6) 2.3-6.0 40-106 25-65
Polyacrylonitrile 2.3-2.6 32-39 20-28
Polyurethane 0.7-0.9 11-14 400-625
Polypropylene 3-4 35-47 80-100
Glass 30-50 0.5-2.0
5.4 Elastomers
Natural rubber is a polymer of isoprene that has pronounced elasticity (high
extension and low modulus of elasticity). In other words, a rubber-like state is a
state in which a polymeric material is capable of undergoing very great recoverable
deformations that occur under the influence of very small loads. Elastomer is a
general name given to synthetic polymers with rubber-like elasticity. The formation
. . ¢ . . . . .
of rubber from its monomer isoprene is as follows;
<p tel at a eel SP n
CH, CH;
Isoprene 7 Polyisoprene
(natural rubber)
The charcateristic property of rubbers or elastic materials is that they possess

little or no crystallinity. The extension and contraction is only possible if the
polymer is in amorphous state and at an operating temperature above its glass
transition temperature. Under these conditions, segments of polymer chains are
able to move so that the material can extend or contract rapidly. However, chains
must not slip past each other on stretching, otherwise the material will not regain
its original shape. Slipping of chains (creep) can be prevented by introducing
cross-links into the material, a process known as vulcanisation. An elastomer
can thus be described as an amorphous polymer, which is above its T,, and
contains cross-links to prevent slipping of chains. Table 5(e), (f) and (g) describe
some important properties of elastomers.
Table 5(e) Molecular weight dependence of physical properties of natural rubber
Mol. wt. range Appearance Solubility in benzene (1%)
Upto 700 Thick liquid Quickly dissolves without swelling

700-7,000 Sticky elastic Soluble without swelling
7,000-—35,000 Tough and elastic Soluble with weak swelling
35,000—2,00,000 Very tough and Soluble with strong swelling
high elastic
Table 5(f) Typical properties of elastomers
Elastomer type Tensile strength Elongation

(10° psi) (%)
Natural rubber 210 700
Styrene-butadiene rubber 28 800
Acrylonitrile-butadiene rubber 42 600
Thiokol 21 300
Neoprene 245 800
Butyl rubber 210 ; 1000
Polyurethane elastomer 350 600
The properties of natural rubber drastically change upon hardening. Even the
appearance and physical states are immediately imminent. Natural or raw rubber
is in latex form (dispersion) and the vulcanised forms of rubbers are however
rigid and in glassy state. A contrast of different properties for natural raw and
vulcanised rubber is shown in Table 5(h).
Table 5(g) Upper and lower use temperatures of typical elastomers
Elastomers Use temperature limit (°C)

Upper Lower
Natural rubber (polyisoprene) 80 -50

SBR [butadiene-co-styrene (25%)] 110 —SO
Nitrile rubber [butadiene-co- ' 120 =50
acrylonitrile (25%)]
Butyl rubber [isobutylene-co- 100 —50
isoprene (5%)]
Fluorinated rubbers 230 —40
Polysulfide (thiokol) 80 —50
neoprene (polychloroprene) 100 -50
Table 5(h) Raw versus vulcanised rubber
Property Raw rubber Vulcanised rubber
Tensile strength (10° psi) 0.2 2.0

Elongation at break (%) 1,200 800
Rapidity of retraction good very good
Water absorption large small
Swelling in organic infinite (soluble) large, but limited
Solvents
Tackiness marked slight
Useful temperature 10 to 60°C —40 to +100°C
Range
Chemical resistance very poor much better
Elasticity very high (300 to Low, depending on degree
1,000 %) of vuicanization
The chains of a stretched elastomer revert to the highly coiled state on the
release of tension. This is due to the fact that highly coiled polymer system has
a higher degree of disorder, i.e. higher entropy than a stretched oriented sample.
Thus, the elastic behaviour is a direct consequence of the tendency of the system
to assume spontaneously a state of maximum entropy. Since free energy, enthalpy
and entropy are related by well known Gibbs equation, AG = AH — TAS, a
stretched rubber band immediately held to the lips is warm.
Several elastomers have been commercialised. These include styrene-butadiene
rubber, butyl rubber (copolymer of isoprene and isobutylene), neoprene
(polychloroprene), nitrile rubber (copolymer of acrylonitrile and butadiene),
thiokols (polysulfide), silicone rubbers and polyurethane rubbers etc. The synthesis
and application of these rubbery materials and the production of the monomers
used for making them are already described in Chapter 2. Some newly
commercialised elastomers include ethylene/propylene copolymers, polypropylene
oxide, copolymer of epichlorohydrin with ethylene oxide, copolymers of ethylene
and vinyl acetate.
5.5 Adhesives i
Adhesives are the substances, often polymeric (natural or synthetic) that are
used to glue two surfaces together. Plant exudates have been known in use as
adhesives by Egyptians for about 6000 years for bonding ceramic vessels. Starch
and sugar, casein (from milk) and glue from animals and fish have been used for
4000 years. The adhesives often work on the principle that they form either
primary covalent bond or interact with the surface through physical forces
(secondary bonds). There are several types of adhesives. Solvent based adhesives
are dissolved in solvent and the solvent is then allowed to evaporate in the
presence of surface to be glued. The evaporation of the solvent that leads to the
formation of a thick or thin solid coating. Latex adhesives (which are directly
used as the dispersion of the polymer made by emulsion polymerization) must
have low T,. It gives a flow and good surface contact on evaporation of water
from a water based latex. Pressure sensitive adhesives are viscous polymer melts
at room temperature. The adhesives flow on applying pressure and thereafter on
releasing the pressure the high viscosity of the polymer provides the adhesion.
Hot melt adhesive works on similar principle except here the material flows on
applying heat. Important and highly effective of all the adhesives are reactive
adhesives which are low molecular weight liquid polymers and solidify due to
the cross-linking. Cyanoacrylates, phenolic resins, silicones, epoxy polymers
and unsaturated polyesters are some examples of this class.
5.6 Polymer Additives

Only few polymers like PMMA, polystyrene, gums and some fiber forming
materials etc., are used as pure polymers (virgin polymers). Many plastincs, for
example formaldehyde resins (PF, UF and melamine-formaldehyde resins) which
are highly useful materials would have been of no commercial value in the
absence of substances like wood flour, cotton and other textile fibers, glass wool
etc. Most polymers often contain a variety of substances which are added during
their preparation or processing. Chemical additives are often used in plastics to
produce some desired characteristic. For instance, antioxidants protect a polymer
from chemical degradation by oxygen or ozone; similarly, ultraviolet stabilizers
protect against weathering. Plasticizers make a polymer more flexible, lubricants
reduce problems with friction, and pigments add colour to polymeric materials.
The other important additives namely flame retardants, antistatics and antibiocides
etc. are also added for specific functions.
Many plastics are manufactured as composites. This involves a system where
reinforcements (usually fibers made of glass or carbon) are added to a plastic
resin matrix. Composites have strength and stability comparable to that of metals
but generally with less weight. Plastic foams, which are composites of plastic
and gas, offer bulkiness with less weight. Additives are thus essential functional
ingredients of polymers and their proportion in the material should be optimum
in order to obtain high quality materials. Table 5(1) lists various types of additives
along with the suitable examples. Each one plays a definite and distinctive role.
Table 5(i) Some polymer additives
Function of additives Examples
1. Fillers Cellulosic and lignin products, carbon black, silica products

and silicates, métals, metallic oxides and carbonates
2. Plasticizers Paraffin oils, n-dialkyl phthalate, tricresyl phosphate and
camphor etc.
3. Antioxidants Phenol derivatives, e.g. di (t-butyl) p-cresol
4. Heat Stabilizers Organic phosphides, toxic lead, barium and cadmium salts
5. UV Stabilizers Benzotriazoles, phenyl] salicylate
6. Flame Retardants Halogen and phosphorus compounds, antimony oxide
7. Colorants Inorganic pigments (iron oxides, lead chromate, zinc
chromate, prussian blue, ultramarine blue, carbon black),
organic pigments (phthalocyanines, and dyes of the class
triphenylmethane, anthraquinone etc)
8. Curing Agents Benzothiazoles (e.g. 2-mercaptobenzothiazole), zinc butyl
xanthate
Fillers
Fillers are often used in substantial amount. A filler is an inert material added to
a plastic to modify its strength and working properties or sometimes to lower its
cost. Besides reducing the cost, a filler helps in improving physical properties
viz. high heat resistance, high mechanical strength, low moisture absorption,
good electrical characteristics. Fillers are supposed to be available abundantly at
cheaper cost. These should be compatible with the polymer and other additives
and should not have abrasive or chemical action on the mould. Cellulosic products
(wood, paper, fibers viz. cotton and jute), carbon, inorganic materials such as
silica (sand, quartz etc.), silicates (asbestos, clay, mica, talc etc.), glass, metals,
metal oxides (alumina, titania, magnesia and zinc oxide etc.) and even synthetic
fibers (nylons, polyesters and orlon) are the commonly used fillers. Fibrous
fillers greatly enhance the mechanical strength in the polymers. Such a fibrous
reinforcement is much more effective than spherical fillers. The effect of a
fibrous filler depends on the fiber length and the interfacial bond between it and
the continuous resin matrix.
Plasticizers
Many synthetic polymers and cellulose derivatives are often obtained as white
powders or horny tough materials as a result of which they do not flow to a
significant level on heating or under pressure. This makes their processing difficult.
Such thermoplastic materials are thus modified by adding some substances called
plasticizers. Plasticizers are non-volatile liquids, decrease T, of polymers and
thus impart flexibility. Tricresyl phosphate, dialkyl phthalates, camphor, glycerol,
paraffin oils etc. are well known plasticizers. Since plasticizers are essentially
non-volatile liquids, they would be compatible with the polymer if the solubility
parameter of the two matches (as discussed in Chapter 4). Thus the difference in
the solubility parameter of plasticizer and polymer should not be more than 2.
Dioctyl phthalate (DOP) is widely used for plasticizing PVC (whose solubility
parameter is 9.66 H). It is interesting that a plasticizer when used in small

amounts often functions as anti-plasticizer i.e. increases the hardness and decreases
the elongation of polymers. Structures of some commonly used plasticizers are
shown below;
OC,H,CH, cH
| COOC,H;; ati
H;CH,C,O ileal g OC,H,CH; ‘ |
P CHOH
| COOC;3H,; |
O CH,OH
Tricresyl phosphate Dioctyl phathalate Glycerol
(5= 8.4 H) (6 = 7.9 H) (6 = 9.3 H)
(6) Cl
COOC,H,
idea ba @) 6) a Cl
COOC,H,
Cl Cl
Paraffin oils Polychlorinated biphenyl! Dibutyl phthalate
(6 = 7.5 H) (6 = 9.3 H) (5 = 8.8 H)
Fig. 5.3 Structures of some common plasticizers
Plasticizers function by reducing intermolecular forces between the polymer

chains (and decreasing the glass transition temperature of polymer taken) and
thus makes it flexible at lower temperature. Camphor has long been used as
plasticizer in the manufacture of celluloid from cellulose nitrate. PVC and cellulose
esters are often plasticized by dialkyl phthaiates. The development and applications
of plasticizers have been associated with the toxicity. The use of highly toxic
polychlorinated biphenyls (PCB) has been discontinued. Also, plasticizers are
often leached out after a prolonged use of the polymeric material which as a
result becomes brittle. One usually notices the inner surface of buckets used in
the bath rooms becoming greasy and sticky after water storage. This is essentially
due to the leaching out of the plasticizer. Also, it is a common experience that
plastic buckets get cracked and broken after their life time. The flexibility of a
polymer can also be increased by internal plasticisation. For example, flexible
PVC can be obtained if vinyl chloride monomer is copolymerized with small
amount of vinyl acetate.
UV Stabilizers and Absorbers

A part of UV radiation in the wave length range 280-400 nm reaches earth’s
surface. This is associated with the energy of 100—72 kcal and is strong enough
to cleave covalent bonds and thus causes yellowing and embrittlement of organic
polymers. UV stabilizers protect the material from preferentially harmful high
energy UV radiation emanating from sun. An UV absorber usually dissipates the
absorbed energy by transferring it to its surroundings as heat or by remitting it
at higher wave length (or harmless low energy) radiation. Carbon black can
function as UV absorber but is restricted to articles where colour is not a criterion
of choice. Many commercial UV absorbers have alkoxy groups at the 4th positioned
carbon of the phenyl] group. Pheny!] salicylate, 2-hydroxy, 4-octoxy - benzophenone,
a-hydroxy-3, S5di-alkyl benzotriazole are commonly used UV-stabilisers.
Antioxidants
Several polymers undergo degrandation during their fabrication or on prolonged
use when they come in contact with air, light; heat etc. Antioxidants are substances
that protect the deterioration of polymeric materials by thermal-, photo- and
oxidative degradation that leads to ageing, weathering and fatigue. Antioxidants
oppose oxidation and in many cases oppose undesirable reactions promoted by
oxygen or peroxides. Some examples of antioxidants are di(t-butyl)p-cresol,
phenyl #naphthylamine, diphenyl-p-phenylenediamine, dif-naphthyl-p-
phenylenediamine.
An antioxidant (XH) interacts with reactive radicals like P*, PO*, POO*,
OH*, which are formed as a result of the attack of oxygen and produces stable
substances as described below.
PY + AH => Pirie A*
PO* + XH — POH + X*
POO* + XH — POOH + X*
OH* + XH — HOH + X*
A typical behaviour of a polymer with or without antioxidant is shown in
Fig. 5.4.
Degradation
behaviour
Without With
antioxidant antioxidant
Time
Fig. 5.4 Comparative behaviour of two samples of a polymer with and
without antioxidant
Flame Retardants
Most organic polymers like other organic compounds have the tendency to burn
at elevated temperatures. While burning, the polymeric materials would melt
(thermoplastics) or decompose giving smoke and even toxic gases like HCl,
HCN and CO etc. Since polymers are often used as building materals and many
household items are made of polymers, it is thus important that they have good
fire resistance. Flame retardants are chemicals added to a polymer to minimise
fire hazards. Inorganic phosphates like ammonium phosphate have been used as
flame retardants in wood, paper and cotton. Tricresyl phosphate, 2-chlorethyl
phosphate, (CICH,CH,O); P = O, antimony trioxide (Sb,O3), aluminium oxide
trihydrate (Al,03 3HO), mixture of borax and boric acid are few examples of
flame retardants.
Colorants
Colouring gives the material a better look and therefore most polymeric materials
are sold as coloured articles. The polymers do not have the colour of their own
but are intentionally coloured for aesthetic appearance. Several dyes and pigments
are used to impart colours to polymeric products. Inorganic pigments (Rutile,
TiO) (for white), lead chromate (for yellow), ferriferrocyanides or prussian blue
(for blue), Carbon black (for black) and organic pigments, phthalocyanines (for
blue) are common. Dyes are often more compatible with polymers and are
therefore used to get transparent coloured products. Acid and basic dyes such as
rhodamine red, victoria blue, anthraquinone dyes such as flavanthrone yellow,
dioxazine dyes such as carbazole violet etc. provide yellow to red range of
colours.
Curing agents
The use of curing agents began with the accidental discovery of vulcanisation of
hevea rubber with sulphur by Charles Goodyear in 1838. Curing of phenol-
formaldehyde resins is another early example. The low mol. wt. substances used
to cross-link plastics (usually liquid prepolymers) to obtain useful resins are
called curing agents. These substances chemically react with the polymer through
functional groups and develop cross-links.
Shaping and Finishing

The techniques used for shaping and finishing plastics depend on three factors:
time, temperature, and flow (or deformation). Many of the processes are cyclic
in nature, although some fall into the categories of continuous or semi-continuous
operation. One of the most widely used operations is extrusion. The extruder is
a device that pumps a plastic through a desired die or shape. Extrusion products,
such as pipes, have a regularly shaped cross section. The extruder itself also
serves as the means to carry out other operations, such as blow moulding and
injection moulding. In extrusion blow moulding, the extruder fills the mould
with a tube, which is then cut off and clamped to form a hollow shape called a
parison. This hot, molten parison is then blown like a balloon and forced against
the walls of the mould to form the desired shape. In injection moulding, one or
more extruders are used with reciprocating screws that move forward to inject
the melt and then retract to take on new molten material to continue the process.
In injection blow moulding, which is used in making bottles for carbonated
beverages, the parison is first injection moulded and then reheated and blown.
Compression moulding uses pressure to force the plastic into a given shape.
Another process, transfer moulding, is a hybird of injection and compression
moulding: The molten plastic is forced by a ram into a mould. Other finishing
processes include calendering, in which plastic sheets are formed, and sheet
forming, in which the plastic sheets are formed into a desired shape. Some
plastics, particularly those with very high temperature resistance, require special
fabrication procedures. For example, polytetrafluoroethylene has such a high
melt viscosity that it is first pressed into shape and then sintered—exposed to
extremely high temperatures that bond it into a cohesive mass without melting
it. Some polyamides are processed by a-similar process.
Health and Environmental Hazards

Because plastics are relatively inert, they do not normally present health hazards
to the maker or user. However, some monomers used in the manufacture of
plastics have been shown to cause cancer. Similarly, benzene, which is an important
raw material for the synthesis of nylon, is a carcinogen. The problems involved
in the manufacture of plastics are parallel to those of the chemical industry in
general. Most synthetic plastics are not environmentally degradable; unlike wood,
paper, natural fibers, or even metal and glass, they do not rot or otherwise break
down over time. (Some degradable plastics have been developed, but none has
proven compatible with the conditions required for most sanitary land-fills).
Thus, there is an environmental problem associated with the disposal of plastics.
Recycling has emerged as the most practical method to deal with this problem,
especially with products such as the polyethylene terephlalate bottles used for
carbonated beverages, where the process is fairly straight forward. More complex
solutions are being developed for handling the mixed plastic scrap that constitutes
a highly visible, albeit relatively small, part of the problem of solid waste disposal.
5.7 Polymer Processing

Polymeric materials are needed for a variety of uses in the form of rods, tubes,
sheets, foam, coatings, adhesives and in other different moulded forms. It is
therefore not surprising that several moulding and fabrication techniques are
used in polymer processing to obtain a finished product. The polymer processing
methods however depend on the nature of the material i.e. thermoplastics,
thermosetts, fibers etc. Fibers are processed in altogether different way. In the
foregoing discussion the processing techniques used for thermoplastics, thermosetts
and fibers are described. The polymeric material is often first mixed with necessary
additives, other polymers (polyblends or polymer alloys) or other inorganic or
fibrous materials (composites or reinforced plastics). This process is called
compounding. The compounded polymer is then subjected to various processing
methods that yield films, sheets, tubes or the finished moulded articles.
5.7.1 Casting
It is one of the cheapest and simplest processes by which polymers can be
shaped into a desired solid form. Both the thermoplastics and thermosetts can be
moulded by this process. In case of thermoplasts, the solid polymer powder is

compounded with other additives such as filler, curing agent, colorants, antioxidants
and plasticizers and the compounded mixture is dissolved or swollen or gelled in
a suitable solvent. Then the mixture is poured into dies or moulds. When thermosetts
are to be casted, usual practice is that the polymerisation mixture at prepolymer
stage is separated from the reaction vessel and then mixed with curing agents,
plasticizers and other additives, which impart color and smoothness. Then the
whole mixture is poured into a mould or a die. The mould or die is prepared out
of plaster of paris, lead or even glass and designed into a given shape with a
particular cross section and depth. The different designs of the mould or die
enable one to get sheets, tubes, rods or even thick films.
The die loaded with the compounded mixture of a thermosett or thermoplast
is then subjected to heating at a programmed schedule, to allow the complete
curing of poured semi-solid mixture into a well shaped solid form. Once the
polymerisation or curing is complete, the die is taken out of the oven and cooled.
The inner lining of the die or mould is often coated with mould releasing agents.
This facilitates easy separation of articles from the mould cavity. The casting
process has following advantages: (i) the mould costs are low, (ii) good surface
finish of the product can be obtained, (iii) the process needs to be conducted
only at ordinary conditions of temperature and pressure, (iv) the whole process
is economically and energetically cheap, (v) large parts with thin to thicker cross
sections can be shaped or solidifed. However, major disadvantages of the casting
process are, (i) only limited shapes can be obtained, (ii) some of the thermoplasts
and thermosetts cannot be casted, (iii) the method is uneconomical when large
volume production is desired, because this process is rarely automated.
Casting process can be divided into three types: (i) die casting, (ii) rotational
casting or slush, moulding and (iii) film casting.
Die Casting
This process is a simple one and as discussed above involves the transfer of the
polymer (thermoplasts in compounded and solution form and thermosetts at
prepolymer stage) plus added curative agents, catalysts and other additives to the
cavity of the pre-designed and pre-shaped die. Then, the die is subjected to
further reaction conditions. The reaction conditions mainly involve the change
in temperature, because casting process seldom involves application of pressure
or vacuum. However, in the case of certain thermoplast and complex parts,
casting has to be done either under applied pressure or in vacuum. To make die
casting energetically and economically viable, following criterion should be
adopted. Free flowing plastics with low surface tension and viscosity can be
casted into intricate shapes easily. The low viscosity of the precast plastic mixture
is highly preferred because bubble free articles can be obtained. However, to get
casted articles with better physical properties viz. mechanical strength, and
transparency etc., the precast mixtures with high viscosity are highly desirable.
But handling of high viscosity mixture is difficult and expensive. Moreover, air
can be trapped into highly viscous mixtures causing voids in the final product.
The selection temperature of casting must be based on the following simpler
considerations. The curing or further polymerisation reaction is usually exothermic

and the heat evolved is dependent upon the shape and thickness of casted article.
When the thin articles with the large exposed surface area in relation to the total
volume of the plastic taken are to be casted, the heat of the process is dissipated
rapidly and thus the cast temperature is not very high. Thus, the thin sections of
the plastics can be casted at room temperatures. When low viscous and free
flowing mixtures are used, one can obtain almost crack free casts of thinner
dimensions. The amount of heat liberated is high when highly viscous and thick
sheets are to be cured during casting process. Thus the proper heating rate has to
be applied for getting bubble- and crack-free articles under this condition. In
such cases, heat sinks or heat pipes are used for absorption or transfer of heat
from one side to another side of the die. Different liquids and bulk graphites can
be used as heat sinks. Heat pipes consists of long tubes with a working fluid
flowing through it. This fluid cna be vaporized by application of external heat
and thus generated heat can be transferred from one part to another. Similarly,
the liquid can adsorb the heat generated during the curing process and eliminate
the excess heat in the die.
Formation of air entrapments and bubbles is the chief drawbacks of casting
process. So extreme care must be taken from calendering stage to final removal
of hardened plastics from the mould. All the ingredients used are to be properly
deaerated and their mixing has to be carefully controlled during calendering to
keep the amount of air entrapped to minimum. The die should be carefully
designed to avoid sharp corners and provision of adequate number of air releasing
outlets must be made for its free circulation. High speed mixers and vortexing of
material has to be avoided. Application of desired level of vacuum during mixing
and pouring eliminates the entrapment of air completely.
Die casting is widely employed in the formation of thin or thick sheets, rods
and other shapes from acrylic, epoxy, polyester, urethane and phenolic polymer
materials. The cast acrylic products in the form of rods, tubes, lenses, spheres
and other intricate shapes are available with high transparency, in wide range of
colors, rigidity, moderate impact strength, good thermal and chemical resistance
and excellent weatherability. From 1930’s acrylic products are being die cast.
The casting of acrylic products has been highly preferred because bulk and
solvent free radical initiated polymerisation of acrylic monomers is possible in
the cavities of moulds made of either plaster of paris, reinforced plastic, wood or
even concrete moulds, which have adequate heat transfer and surface release
characteristics. Transparent, long and thick acrylic sheets are obtained by allowing
the polymerisation of monomers mixed with free radical catalysts for few hours
by heating in a die made up of two thick glass or metal plates with rubber gaskets
fitted in between. Once the polymerisation is complete, the die is cooled gradually
under controlled cooling rates and sheets with better optical characteristics are
separated. The casting process just described is known as batch casting.
This method of casting can be made continuous by taking solutions of already
formed thermoplasts or monomer syrups with catalysts added on and the mix is
then rolled through continuous conveyer belts passing through a controlled
temperature environment adequate for polymerisation process. Though the
continuous casting process is economically cheaper, bath casting yields sheets

of better quality.
Rotational Casting
For obtaining articles such as toys, hollow balls, rain boots and doll heads etc.,
a specialised apparatus based on rotational casting procedure is used. The apparatus
is designed such that the mould which is usually a hollow tube with a desired
shape can be rotated simultaneously along its breadth and length. The mould is
filled either with a fine powder of a thermoplast or plastisol (a dispersion of
thermoplastic polymer in a liquid plasticizer) with additives such as stabilizers,
coloring agents and antioxidants. etc. and closed. The uniform distribution of
suspension mixture is ensured by initial heating and rotation. The mould is then
chilled after a specified time period when it is still under rotation. By this way
the thermoplast is melted first and cooled to a solid into a desired shape. Instead
of a thermoplastic, if one takes a prepolymer of thermosetting resin and curative
and stabilizing agents mixture, the curing is done at elevated temperatures and
chilling step is avoided. In both the cases the conveyor belt is taken through an
oven (kept at appropriate temperature range) and excess liquid plasticizer is
drained out of the mould. When plastisols are to be casted, the conveyor belt is
rotated and passed through another oven kept at higher temperature for final
curing. This process is widely used for PVC, epoxy, and phenolic resins and
unsaturated polyesters.
Film Casting
Films of thermoplastic polymers can be cast on highly polished drums, belts or
bands that are driven by drums. A thermoplast solution in a suitable solvent and
with an appropriate concentration is allowed to be poured on a moving drum or
belt. The movement of the drum or belt is controlled by motors. The continuous
movement of casting device allows the solvent to be evaporated leaving behind
a polymeric film. The polishness on the surface, drying time and speed of the
moving drums all contribute to the quality of films formed. Longer drying time
and slow speed of moving device produce thinner films. The belt method yield
thicker films and high production rates can be achieved. The films formed are
simply stripped, if needed dried further to remove residual solvent. The different
varieties of photographic films and cellophane tapes or sheets are produced by
this technique at commercial levels.
Besides above mentioned casting techniques, there are several other methods
through which casting of polymeric materials for specialised to very specialised
applications can be carried out. These are embedding, encapsulation, potting and
impregnation etc. Embedding usually means complete encasement of a device or
an assembly in a polymeric sheet matrix. For example, various components and
electronic circuits that are used in devices such as television sets, computer
monitor or any other display systems or even the instrument circuits, need special
mechanical support for their optical functioning. Polymer materials offer not
only best mechanical support but also possess other requirements such as better
insulation, better resistance from attacks of oxygen, moisture, temperature, current
flash over and leakages, salt spray, radiation, solvent, chemicals and microorganisms
etc. The polymeric materials usedas embedding matrices are either liquids,
granular solids or powder solids made of epoxies, silicones, polyurethanes,
polyesters and polysulfides etc. The selection of a particular polymer and its
form depend highly on its resistance to various factors as mentioned earlier.
Encapsulation is just a modification or an extension of embedding in which
the part or item to be encapsulated is dipped into a highly viscous or thixotropic
material. Then a thin coating of the polymer material is achieved around the part
by keeping it at required temperature for scheduled time. Caution is always
taken to minimise the internal stress in the die during the process to avoid any
crack in the coated film.
Potting is another form of encapsulation, in which firstly, the part is embedded
in a plastic matrix. Then the whole embedded item along with the plastic is
encased in the mould. Thus, potting is a special embedding where a double
coating takes place on a piece of mould. The part of the mould in which the
encasing is done can be used directly for specialised devices.
Impregnation is another specialised method of embedding in which a liquid
plastic is forced into the bulk of acomponent, which is usually porous in nature.
In the extreme case of impregnation, a liquid like prepolymer with a catalyst is
poured into a small hold made in the device and then allowed to cure in an oven.
5.7.2. Thermoforming
Thermoforming is the process in which the thermoplastic material, which is
usually in a sheet form, is first heated till it softens. So obtained flexible plastic
material is pressed into moulds having desired shape and dimensions. The die
used in the process in fact consists of two parts besides clamps. A male part and
a female part combine together to form the die. The male part is used to press the
warm and flexible plastic material against the female part, which has a dug in
cavity and acts as a store for the hardened material. The hardening or solidification
of softened plastic is usually achieved by cooling process. The way the warm
and softened plastic is pressed against the female part of the die classifies the
thermoforming into four main types: (i) matched-mould forming, (ii) slip forming,
(iii) air blown forming and (iv) vacuum forming. In matched-mould forming, as
the name suggests, the male and the female parts of the die match with each
other but face one opposite another, only a male fold is used in slip forming, the
air is blown into the sheet while it sits in the female part of the mould in air
blown forming and finally vacuum is applied to the sheet before it is pressed into
the cavities of a female part of the mould.
Two important factors are to be considered in processing operation in general
and in thermoforming in particular. These are heat transfer and the changes
caused in the heated material under stress (i.e. rheological responses). The transfer
of heat to the specimen can be achieved by several means, for example by
conduction, convection, radiation, or some combination of these. However, when
already formed thermoplastics or pre-polymer stage thermosetts are to be processed,
the method of heat transfer has to be carefully selected. Since these materials are
made up of chemical linkage between small monomer units and also contain
several additives that may vary from simplé molecules such as catalysts, plasticizers,
antioxidants and colorants to complex molecules such as fillers. The means of
heat transfer plays a crucial role in achieving the targetted curing or hardening
or solidifying processes.
Exposure of plastic mix to radiation for a scheduled and programmed time
period in the mould has been proved more suitable among many other means.
Polymeric materials depending upon their optical properties i.e. transparent,
semi-transparent and opaque etc. interact with radiation differently, hence one
can obtain different heat rates by using the same amount of radiation dose. The
stretching undergone by a flexible polymer during the thermoforming, can affect
the mechanical properties of the article produced. So one must be cautious in
choosing the press rates during the thermoforming.
5.7.3 Foaming
Foaming is a process, in which the density of a plastic material is decreased by
entrapping air or gas into specially created cell type structures in the material.
Thus foaming process results into expandable or spongy materials. Sponginess
is due to creation of numerous cells through out the mass of the material. Thus
foamed plastics can be considered as two phase systems consisting of a gas
phase entrapped in a continuos solid polymer phase. Foamable polymers are of
wide variety types. Virtually any thermoplastic or thermosetting polymers can
be foamed. The usual and most common foamable polymers are polyurethanes,
polystyrene, polyethylene, polypropylene, silicones, epoxy, PVC and styrene
and acrylonitrile (SAN) copolymers etc. The foam structure consists of either
interconnecting or non interconnecting individual cells. The non interconnecting
cells are known as closed cells and the other type are known as open cells. The
closed cells are not accessible to the surrounding air or fluids, while the open
cells can be filled in by surrounding air or fluids. Foaming process essentially
uses the above mentioned cell structures for expanding the polymer materials.
There is a wide variety of methods for obtaining the foamed articles: (i)
whipping of air into a molten thermoplastic or its solution or a prepolymer stage
thermosetting resin, and then heat cure the expanded product, (ii) dissolution of
a gas in a molten polymer kept under pressure and expand the gas into solid melt
matrix by releasing the pressure, (iii) heating the compounded polymer mixture
which contains a liquid plasticizer, till the latter is volatilised. The volatilised
liquid vapor molecules take up the positions in the open cells and (iv) another
technique similar to (iii), makes use of the volatilization of water produced
curing reaction, within the polymer mass.
However, foaming is usually enhanced by adding foaming or blowing agents.
These agents are of two types viz. physical blowing agents and chemical blowing
agents. Physical blowing agents consist of compressed gases (N7 and CO) etc)
and volatile liquids (n-pentane, n-hexane, toluene and isopropyl! ether etc.). The
chemical blowing agents are generally solid materials and may come from both
inorganic and organic origin. The inorganic agents include carbonates of sodium
and zinc. Organic blowing agents are usually hydroquinones, surface active
agents, acids, bases and peroxides. The physical blowing agents create the cell
structures, which act as reservoirs for storage of gas molecules by a physical

process. This process involves the injection of a physical blowing agent into a
molten flexible plastic material kept under pressure and then slowly the melt is
released to atmospheric pressure or even to lower pressures. Then the surrounding
gas expands into flexible polymer matrix and creates foamed structures. The
solvents that are used as physical foam agents have low boiling points and thus
under above conditions liberate large volumes of gases.
Organic blowing agents are typical in the sense that they decompose at a
defined temperature range and produce voluminous gases. The decomposition of
these agents can be achieved either by changing the temperature or pressure or
both. The decomposition temperatures are usually between 100°C to 400°C.
When the decomposition temperature is high, several chemical substances called
activators are added to pre-empt the decomposition at faster rate and at low
temperatures. Typical activators are zinc oxide, acids, bases and peroxides. Besides
the above, the selection of chemical blowing agents is based on following
consideration: (i) release of gases over a controlled temperature and pressure
range, (ii) the gases produced should not have any harmful effects on the quality
and processibility o plastics, (iii) the gases evolved should be as less toxic as
possible, should not have bad odor and decolorise the plastic, and (iv) the density
of the gases produced should be such that the structure of the cells created in the
plastic material should be uniform and the foams formed must be stable and
their entrapment in the plastic structure must be stable.
The usage of physical or chemical blowing agents can sometimes create not
only problems but is also not feasible especially when the curing process of a
thermosett such as unsaturated polyester using styrene as curator. The curing
does not yield the required temperature for the chemical blowing agents to split
and crack into vapor. In such cases chemical reactions such as oxidation and
reduction of hydrazine derivatives and/or a peroxide can be carried out
simultaneously. Because the reactions produce gases, that can expand the flexible
polymer, which is to be foamed. One of the well known side reactions that
facilitates the formation of polyurethane foams is the liberation of carbon dioxide
by the reaction between isocynate and water. Since diisocynate is one monomer,
along with a polyol taken for producing polyurethanes, an excess amount of it
and some quantity of water are sufficient enough to produce a large amount of
carbon dioxide, which can foam up the polyurethane as it is formed.
Foamed polymers are known by many names such as cellular plastic, plastic
foams, expanded plastic foams, and structural plastic foams. Virtually any
thermoplastic or thermosett can form a foamed structure under proper conditions.
Foamed polymers can behave as rigid, semi-rigid and flexible materials. They
can be coloured or obtained plainly. The foamed polymers can be processed, of
course during their formation into blocks, sheets, slaps, sprayed coatings and
extruded films or sheets. Thus conventional processing aids such as extruders,
injection moulding machine, and reservoir moulding machines can be used for
processing of foams.
Foamed polymer articles have been put to use in wide forms. For example,
foamed polystyrene sheets are useful in building, packaging and insulation
applications, expandable polystyrene, polyethylenes (LDPE and HDPE) are used

for decorative and insulative wall panes. Expandable polyethylene copolymer
which consist of 50% polyethylene and 50% polystyrene resin have been used in
many reusable applications such as handling trays and packaging applications
which require solvent resistant, impact absorbing and superior toughness. Flexible
PVC and polyurethane foams are consumed in large quantities in automobile
and furniture industry and as upholstery (i.e. covers, drapiers, curtains, cushions
and other interior domestic fittings). Rubber and polyurethane foams are used
for mattresses and other cushionable fittings. The rigid polyurethane foams are
used as supports for artifical limbs. Foamed polyvinyl chloride is widely used in
water resistant clothing, flooring, footware, furniture and packagings etc..
5.7.4 Lamination
The word laminate or lamination is in very common usage and usually refers to
heterogeneous materials stick together mostly in a flat sheet. The layers in a
laminate can be of same material or of different materials. The most commonly
used laminates are plywood, formica and micarta. In plywood the layers of wood
(known as veers) are oriented along the linear dimension and hence have good
longitudinal strength, but the strength in the lateral sides is weak. The strength
of the veers in both the longitudinal and radial directions can be made equal by
holding several veers together by bonding them together. Phenol-formaldehyde
resins are used for this purpose. Phenol formaldehyde resins taken out from a
reaction vessel at pre polymer stage can be transferred into the gaps of stalks of
veers and further polymerisation and curing of resins are done under high pressure.
Thus these stalked veers bonded by the phenol-formaldehyde resins, have good
strength. The laminated stalks are known as plywood sheets, which can be made
into different thickness depending upon the number of veers bonded. Besides
proceiding strength, laminates with other special propperties such as less moisture
pick up, less. Swollenness and other improved decorative qualities can be prepared
by stalking the sheets out of inexpensive wood veers, except the top layer which
can made of a rare wood. The modification of inner layers can be done such that
the sheets formed have high resistance to moisture, chemicals and fire proofing
etc.
Other classes of industrial laminates, which vary in reinforcement and in the
binder are produced by using paper, woven or knitted cloth, cotton, glass, asbestos,
nylon or rayon layers with binders of phenolic, melamine, polyester, epoxy or
other thermosetting resins. Laminates can be produced during extrusion. The
process is known as coextrusion. the main advantage of laminates is that
multilayered stalks can be fabricated. Laminate systems with upto seven layers
are put in operation. These multilayered sheets can be chosen such that each of
it or some of them are selected such that it meets special requirements like
chemical resistance, water replellence, high strength and tough and coloured
sheets etc. A four layered sheet or laminate made of ABS, polyethylene, polystyrene
and rubber modified polystyrene is one of the best commercial examples, which
is used as package material for wrapping up of food products. The combination
of ABS and high impact polystyrene sheets achieved by thermoforming is used
to make the inside door and food compartment parts of refrigerator.
5.7.5 Reinforcing
The term reinforcement implies an improvement of some ultimate property.
These properties include all mechanical properties, tear strength and abrasion
resistance or fatigue. The reinforcement consists of the polymer material whose
properties are to improved, the material which needs to be combined with polymer
i.e. reinforcing materials and an appropriate process which can combine these
two and produce high strength material. Almost all the thermoplastic as well as
thermosett polymers can be reinforced. The main reinforcing materials are fibers
which include natural fibers such as sisal, asbestos, jute, coir and remp etc.,
glass, graphite, alumina, carbon, boron or beryllia. Synthetic fibers from aromatic
polyamides and polyesters are also good reinforcing material. The physical form
of the chosen fiber can be anything ranging from chopped fiber pieces, porous
mats, woven fabrics, continuous fabrics or filaments etc. The polymeric materials,
whose properties need to be strengthened by reinforcing process are polyester,
epoxy, polyurethane, phenolics, silicones, melamine, vinyl resins, acetal resins,
polycarbonate, polypropylene, acrylonitrile butadiene-styrene terpolymer (ABS)
and styrene-acrylonitrile copolymer (SAN) etc, Out of all the fibers, glass fiber
is the most commonly used reinforcing material. The glass fiber has following
advantages. It has (i) low coefficient of thermal expansion, (ii) good tensile
strength, (iii) low dielectric constant, (iv) nonflammability, (v) high chemical
resistance, (vi) high directional stability and (vii) low cost of production. The
other materials are used when special properties are to be imparted.
Among all thermosett resins, polyester and polyurethane are used in large
proportion in the form of reinforced plastics. The properties that get improved
after reinforcement are, percentage of elongation, flexural modulus, compression
strength, impact strength, hardness, water absorption and mould shrinkage
percentage etc. Reinforcing process consists of two steps. In the first step, the
fiber is bonded to the polymeric resin matrix and the combined material is cured
under pressure and temperature. The second step consists of any of the general
processing methods. The following processing techniques of reinforced polymers
are widely employed: (i) hand lay up, (ii) spray up, (iii) vacuum bag moulding,
(iv) tooling, (v) cold press moulding, (vi) casting, (vii) architectural panelling,
(viii) centrifugal casting and (ix) pultrusion. Beside these, filament winding,
injection moulding, rotational moulding and cold forming are also used.
A variety of moulds is available for reinforcing process. The type of mould
chosen depends upon the kind, form and amount of reinforcement. The shape of
reinforced polymer can be obtained from very small to extremely large and from
simple to complex. Fiber reinforced plastics (FRP) have high performance utility
because of their remarkable high strength to weight ratio, excellent corrosive
resistance and nonbiodegradability, light weight and easy processibility etc.. The
usage of FRPs range from the body of commercial and military air crafts, space
craft, huge surface and underground acid storage tanks, the boat hulls, fiber
boats and the protection sheets on the road side which can take up high impact
during an accident.
5.7.6 Processing of Fibers

Fibers, both natural and man-made (or synthetic) are produced from polymeric
material by a process similar to extrusioh. However, the extrusion of polymers

through fine holes of a spinneret is called ‘spinning’. The spinneret is a special
kind of plate made of a metal, gold or platinum and has small round or oval
shape holes. There are in principle two ways to obtain fibers. i.e. either from the
molten polymer or from polymer solutions. Since most of the natural polymers
decompose before melting, they are drawn into small fibers or yarn by dissolving
them in suitable solvents. After dissolution, fibers are drawn either by dry or wet
spinning processes. Another method of recent origin is however known as melt
spinnning, in which especially thermally stable polymers such as polyamides,
polyesters and polyolefins are brought to molten state before being extruded
through spinnerets to get fibers.
Dry spinning
This process involves pumping a polymer solution of high concentration through
a spinneret, which is hot. The fine filaments that emerge from the orifices of the
holes of the spinneret are then passed through a zone in which the solvent is
repidly evaporated. The solvent evaporation can be made faster and effective by
pumping nitrogen through the zone in a direction opposite to the emerging end
of the filament. The filaments or fine fibers thus formed are hardened by solvent
evaporation and are directed to a spindle for wounding them up. This process of
spinning is very common and fibers in large quantities can be produced. The
fibers can be wound up at speeds up to about 100 m/min. Two precautions are to
be taken for an efficient dry spinning. The viscosity of polymer solution has to
be optimum for the fibers to be formed. The control of viscosity is achieved by
changing the temperature of hot solution before it is pumped. The whole process
has to be carried out in inert atmosphere to avoid the exposure of hot solution to
the air, which can cause oxidative degradation. Fibers of cellulose acetate are
drawn from its concentrated solutions maintained at 35—40°C, by this method.
Similarly, PAN and PVC fibers are obtained by dry spinning method.
Wet Spinning
Wet spinning also employs a concentrated polymer solution at a higher elevated
temperature. The process for wet spinning is identical with dry spinning for
initial stages. But the filaments emerging from a spinneret containing large
number of holes are directed to a bath filled with a non-solvent. Thus, when the
continuously drawn filaments are passed through the non-solvent, the polymer
gets precipitated from solution. This process is sometimes called coagulation. In
some cases especially, when viscose rayon fibers are drawn, the precipitation
stage can involve a chemical reaction leading to the coagulation and solidification
or hardening of the fiber. The filaments are then collected from the coagulation
bath, washed, dried and finally wound up around the spindles. The coagulation
is a slow process and as a consequence, the conventional wet spinning is by far
the slowest process. The rate of wet spinning (in fact wounding up) is as low as
50 m/min. But since spinneret has large holes for a given area of the plate, the
productivity of fibers is high.
Melt Spinning :
Though melt spinning was developed in the late 1930s for producing nylon 6 and
nylon 6, 6 it has become popular recently. Polymer either in the form of powder,
flakes, chips or granule is heated to a molten state on a heating grid. The polymer
melt is then forced through a spinneret by using a metering pump (which is
operated at a constant pumping rate). The fine filaments that emerge from the
spinneret holes are still hot and are further cooled and solidified by blowing cool
air. The blow rate of cool air is such that, it almost blasts into the container and
by this way the hot filament solidifies at faster rate. The hardened fibers are then
wound up through spindles. One of the utmost cares, that needs to be taken is
that, polymers in hot stage can be cross-linked and form lumps, which can block
the holes of spinneret. Similarly, any exposure to the air in hot condition can
degrade the polymer by oxidation. Hence precautions are taken to guide the
polymer melt through appropriate filters and spinning is carried out in an inert
atmosphere.
Filaments formed from the polymer melt or dope by cooling or coagulation
have poor strength. Their storage stability is also poor and can be stored upto
30-40 hrs. before further processing. Then they are stretched. In this process of
stretching the so called drawn filaments are extended by 3-4 times or more
depending upon various factors whereby the orientation of molecule takes place
in direction parallel to the axis of the filament. The drawing is carried out after
spinning. Simultaneous melt spinning and drawing the filament give moderately
oriented yarn (MOY) or partially oriented yarn (POY). Such yarns are fully
drawn during the texturising process. The POY and MOY have a long storage
life and can be produced in single operation.of melt spinning combined with
stretching. The process of simultaneous production of POY and MOY is called
high speed spinning. In another process, as-spun yarns are kept under controlled
temperature and humidity and are usually subjected to the process of stretching
or drawn-twisting (D/T). Since this process is a two step process and is carried
out at the yarn manufacturer’s site. However, it has become presently an obsolete
technology mainly because of the short shelve life of the as-spun yarn and high
cost of production. Most companies manufacture either MOY or POY filaments
independently.
In the process of drawing or stretching, molecular orientation takes place
along the axis of fibre and can be measured either by x-ray diffraction or
birefringence. Continuous filament or yarn does not have same hairiness, bulk
and warmth of handle as those found in natural fibres or synthetic staples. Some
of such desirable properties are imparted by texturing, wherein the filament is
permanently deformed to add bulkiness by the formation of air spaces. The
properties such as crimps, coils, loops, curls and/or crinkles into filament are
developed by various texturing methods. All texturing processes are mechanical
in nature and do not involve any chemical treatment. The process of texturing is
carried out at certain temperature depending upon the glass transition temperature
of the polymer. Some of the important techniques used for producing textured
yarns are: (i) false-twist process (a) spindle technique, (b) friction-texturing
process, (ii) air texturing process, (iii) knit-de-knit process, (iv) gear crimping
process, (v) knife edge process and (vi) stuffer-box crimping process.
Heat setting, twisting, doubling and céne winding are other processes required
before yarn is subjected to the process of weaving or knitting.
5.7.7 Moulding Processes

Moulding processes are those in which a finely divided plastic is forced by the
application of heat and pressure to flow into the fill and conform to the shape of
cavity (mould). There are five different types of moulding techniques: (a)
compression moulding, (b) injection moulding (c) transfer moulding (d) blow
moulding (e) extrusion moulding
(a) Compression Moulding

It is one of the oldest methods. The polymeric material is put between stationary
and movable parts of a mould. There are two different halves. The lower half
usually contains a cavity and the upper half has a projection which fits into the
cavity when the mould is closed as shown in Fig. 5.5.
Platen
Heat and cooling Mould plunger
Guide pins
Heat and cooling

Mould cavity
Platen
~
Hydraulic pressure Hydraulic

plunger
Fig. 5.5 Diagram of compression-moulding press and mould
The gap between the projected upper half and the cavity in the lower one
gives the shape of the moulded articles. The compression moulding is very
widely used to produce articles from thermosetting materials as well as from
thermoplastics. The mould is closed and heat and pressure and applied so that
the material softens, flows to fill the mould, and becomes a homogeneous mass.
The necessary pressure and temperature vary considerably depending upon the
thermal and rheological properties of the polymer material. Moulding themperature
can be as high as 150°C and pressure applied is usually in the range of 1000—
3000 psi. Slightly excess material is always placed to fill the cavity. As the
mould closes down under pressure, the material is squeezed or compressed
between the two halves and compacted to a shape inside the cavity. The excess
meterial that flows out is known as flash. On cooling or after curing, the moulded
article is taken out by opening the mould parts, which can be separated while the
mould is still hot to release the finished moulded product.
(b) Injection Moulding

The injection moulding process is best suited for producing articles made of
thermoplastic materials. Here the polymer is preheated in a cylindrical chamber
to a temperature at which it flows. The molten material is then forced into a
relatively cold mould under high pressure applied hydraulically where it solidifies
to the shape of the mould. The injection moulding machine has high cost but the
production rate of the articles is high and thus economically advantageous. The
process consists of feeding the compounded plastic materials as granules, pellets
or powder through a hopper at definite time intervals into the hot horizontal
cylinder where it gets softened. Pressure moves the piston to push the molten
material through a cylinder into a mould fitted at the end of cylinder. While
moving through the hot zone of the cylinder, a device called ‘torpedo’ helps
spread the plastic material uniformly around the inside wall of the hot cylinder
and thus ensures uniform distribution. The molten plastic material from the
cylinder is then injected through a nozzle into the mould cavity.
The mould is a two-part system. One part is movable and the other is
stationary. By using a mechanical device, the mould is properly held in position
as the molten plastic material is injected under a pressure as high as 1500 kg/cm?.
After the mould is filled with the molten material under pressure, it is cooled
by cold water circulation and then opened so as to eject the moulded article.
The whole cycle can be repeated several times either manually or in an automated
mode. Figure 5.6 shows schematic drawing of an injection moulding machine.
Nozzle \Gaps dco Feed hoper
ATES wee J
apy
pressure
Fig. 5.6 Diagram of a conventional plunger injection-moulding machine
(c) Transfer Moulding

This method uses the principle of injection moulding for thermosett materials.
The moulding powder is placed in a heated chamber, maintained at the minimum
temperature at which the moulding powder just begins to become plastic. The
plastic material is then injected through an orifice into the mould by a plunger,
working at high pressure. This moulding technique has the following advantages:
(i) since the mix flows into the mould cavity in a highly plasticized condition, so
very delicate articles may be handled without distortion or displacement. Fine

wires and glass fibers may be inserted into the mould, (ii) intricate shapes which
are not attainable by compression moulding, can readily be produced, (iii) article
produced is free from flow marks, (iv) even thick pieces can be cured almost
completely and uniformly, (v) owing to uniform and thorough cure, shrinkage
and distortion rates are at a minimum and hence, the mechanical strength and
density of fabricated piece are higher, (vi) finishing cost of fabricated article is
almost entirely eliminated, (vii) blistering is almost eliminated since air and
excluded gases are expelled in the plasticizing chamber itself and (viii) mould
cost is less since it involves very low abrasive action.
(d) Blow Moulding

Most hollow plastic articles are produced by the blow moulding technique which
is principally similar to very old glass blowing method used in glass industries.
A typical blow moulding process is schematically presented in Fig. 5.7.
Blowing pin
: ill
Parison > a
Parison kept in open mould Mould closed
Es
Air Blow moulded

article
Air
ns ‘ ———_>
Air blown into mould Mould opened
Fig. 5.7 Schematic diagram explaining the steps involved in blow moulding process
In blow moulding, a hot softened thermoplastic tube, usually called ‘parison’

is properly placed inside a two piece hollow mould. When the two halves of the
mould are closed, it pinches and closes one end of the parison and encloses a
blowing pin at the other end. The parison is now blown by pressuring from
within by blowing compressed air through the blowing pin. The hot parison is
inflated like a balloon and goes on expanding until it comes in intimate contact
with the relatively cold interior surface of the hollow mould. Under pressure, the
parison ultimately assumes the shape of the hollow cavity of the mould. The
mould is allowed to cool and the rigid thermoplastic article formed is removed
by opening the mould.
Containers, soft drink bottles and numerous other hollow articles are produced
by this process. Thermoplastic materials such as polyethylene, polycarbonate,
PVC, polystyrene, nylon, polypropylene, acrylics, and ABS plastics can be blow
moulded.
(e) Extrusion Moulding

Extrusion technique produces many common plastic products such as films,
filaments, tubes, sheets, pipes, rods, etc. quite inexpensively. A simple schematic
picture of an extrusion machine is shown below (see Fig. 5.8).
Hopper Main cylinder
Heating elements
Screw
Feed zone | Metering zone

Compression zone
Fig. 5.8 Schematic diagram of a simple extrusion machine
The compounded plastic material is fed through the hopper either as powder
or granules into a cylinder having provision for electrical heating for softening
the material. The hot plastic charge is further worked through the cylinder by a
revolving screw. The temperature of the plastic material rises owing to the frictional
heat produced by the compression of the charge between the rotating screw and
the cylinder surface. There are three different zones through which the plastic
material passes and each zone contributes the overall extrusion process. These
are transport zone (or feed zone), compression zone (or transition zone) and a
metering zone. The feed zone receives the charge from the hopper and sends it
over to the compression zone. In compression zone, the powdered charge melts
due to application of heat. The pasty molten plastic material is then sent to
metering zone, where it acquires a constant flow rate, imparted by the screw. The
pressure built up in this section enables the polymer melt to enter the die and
emerge out of it with the desired profile. The extruded material of the required
profile emerging from the die is quite hot (usually 125°C to 350°C) and has to
be cooled rapidly to avoid de-shaping. Cold air blast and cold water spray are
used for cooling. The product formed is cut to the desired length or wound onto
rolls.
Calendering
Calendering is a processing technique employed for the production of films and
sheets. It, in a simplest form contajns a set of highly polished metal rollers that
rotate in opposite directions with provision of precise adjustment of gaps between
them. Compounded polymeric material is fed between the rollers which are hot.
The material here softens and passes through several rollers to give a smooth
film or sheet which solidifies on passing through cold rollers. The film can be
continuously wrapped on wind up rolls. The schematic drawing of a four-roll
calendering machine is shown in Fig. 5.9.
Plastic mass
x
V
Reg) “tah
Fig. 5.9 Schematic representation of a four-roll calender machine
Agassant, J.F., P. ‘Avenas, J. Sergent, and P.J. Carreall, Polymer Processing: Principles
and Moulding, Cincinnati, Ohio: Hanser-Gardner, 1991.
Astarita, G., and L. Nicolais, (eds.), Polymer Processing and Properties, New York:
Plenum, 1984.
Biard, D.G., and D.M. Collias, Polymer Processing: Principles and Design, Newton,
Mass.: Heinemann, 1995.
Birley, A.W., B. Haworth, and J. Batchelor, Physics of Plastics: Processing, Properties
and Materials Engineering, Cincinnati, Ohio: Hanser-Gardner, 1992.
Chanda, M., and S.K. Roy, Plastics Technology Handbook, 2d ed., New York: Dekker,
1992.
Charrier, J.M., Polymer Materials and Processing: Plastics, Elastomers, and Composites,
Cincinnati, Ohio: Hanser-Gardner, 1990.
Florian, J., Practical Thermoforming, New York: Dekker, 1987.
Griskey, R.G., Polymer Process Engineering, London: Chapman and Hall, 1995.
Klempner, D., and K.C. Frisch (eds.), Handbook of Polymeric Foams and Foam Technology,
Cincinnati, Ohio: Hanser-Gardner, 1992.
Kresta, J. (ed.), Polymer Additives, New York: Dekker, 1988.
Mallick, P.K., Fiber-Reinforced Composites, 2d ed., New York: Dekker, 1993.
Michaeli, W., Plastics Processing: An Introduction, Cincinnati, Ohio: Hanser - Gardner,
1995.
Middleman, S., Fundamentals of Polymer Processing, New York: McGraw-Hill, 1977.
Rosato, D., Plastics Processing Data Handbook, London: Chapman and Hall, 1997.
Walczak, Z.K., Formation of Synthetic Fibers, New York: Gordon and Breach, 1976.
Ziabicki, A., Fundamentals of Fibers Formation, New York: Wiley-Interscience, 1976.
Natural Polymers
Living things exist and reproduce because they contain macromolecules (polymeric
materials). Throughout the subsequent evolution of living organisms, polymers
have been used as protective surfaces, membranes, energy storage systems, skeletal
system, and pathways for electrical condution and for countless of other purposes.
These biological/natural polymers are widely known as polysacchrides, proteins,
nucleic acids and polyisoprenes etc.
6.1 Polysaccharides
They have macromolecular structure built up of many monosaccharide units
joined together with an elimination of a water molecule. Hence, polysaccharides
can be broken down on hydrolysis to form monosaccharides. Polysaccharides
are of almost universal occurrence in living organisms where they perform a
variety of functions. In plant cells, they serve as excellent materials for construction
work e.g. cell wall formation. They also serve as food material for the nutrition
of cell. Cellulose and srtach are amongst the best known polysaccharides.
Cellulose (CoH 1905),

This is a natural polymer of 6-d(+) glucose, most widely distributed in plants
where it is found in wood, cereal, straw up to about 50% in association with
lignin, hemicellulose (polysaccharide of other sugars) and non-cellulose substances.
Cotton which contains almost 95% of cellulose, is the oldest natural fibre and is
in common use till today. The fiber is resistant to alkali and can be easily dyed
using direct, vat, sulfur, reactive or azoic dyes. Filter paper is nearly pure cellulose.
Other fibres like jute, flex, hemp and ramie are very rich in cellulose, which can
be freed from other substances by fermentation process, called retting. Cellulose
can also be produced by bacterial action of certain bacteria in nutrient media
containing glucose.
Plants synthesise cellulose out of one of the most basic of all organic substances-
glucose, a simple sugar (monosaccharide) which is found throughout the vegetable
kingdom and even in the blood of animals. Nature converts glucose into cellulose
(in plants) when thousands of glucose molecules are linked together through
hydroxyl groups at C; and C, in a long chain forming a polyanhydride (giant
Natural Polymers 237
cellulose molecule) and several water molecules (by a process similar to

polycondensation). The following is the structure of the repeat unit in cellulose
(see Fig. 6.1).
CH,OH CH,OH CH,OH

se Oo O O
O OH O OH O OH O
‘ee
n
OH OH OH
Fig. 6.1 Cellulose molecule
Despite containing several hydroxyl groups (three in each monomeric unit),

cellulose is unexpectedly water insoluble. The reason for this is the stiffness of
the chains and hydrogen bonding between two -OH groups on adjacent chains.
Cellulose differs from starch (polymer of a@-glucose) only in arrangement of
hydroxyl group at carbon number one in the monomer glucose unit. Both are the
polymers of glucose. The two polysaccharides in spite of having only slight
difference, possess enormously different properties. Starch being the chief
constituent of diet, gets easily hydrolysed by body enzymes to glucose which
finally yields CO, and H,O along with the energy, the later being used for
sustaining body functions. Cellulose nevertheless is of considerable human dietive
value in that it adds “bulk” to the intestinal contents, thereby stimulating peristalsis
and eliminates food residues. It thus provides indigestible but necessary roughage
in the human diet, and the nourishment for such ruminant animals as sheeps and
cows. Indirectly, therefore it also provides nourishment for humans. Sheeps and
cows digest the cellulose and absorb it into their body tissues and thus when
humans consume meat, cellulose is used up by them.
It has the property of forming long threads and for this reason is largely
incorporated as raw material in textile industries. Celluose is highly stereo specific
macromolecule. Considering the geometry of the polymer molecule, cellulose
can be treated as non-planar molecule, but with a screw-axis and with each
glucose unit being at right angles to the previous one. The free rotation about the
C-O-C link does not occur. This and the close packing of the atoms result to a
fully extended form of conformation. Moreover large intra- and inter-molecular
forces (as result of formation of hydrogen bonds) also favour the close packing
and thus cellulose possesses an unusually high degree of crystallinity. The melting
temperature of crystalline cellulose is far above its decomposition temperature.
The fiber forming properties of cellulose can be accounted by its unique
conformation. The fully extended cellulose chains are further bonded together to
give rise to a sheet structure (see Fig. 6.1). A huge amount of cellulose is used
in the paper manufacture. Besides its use in textile and paper industries, cellulose
finds use as celluloid (a hard plastic), cellophane (film) for various purposes.
These materials are called semi-synthetic, because they are obtained from the
raw cellulose. The synthesis of various cellulose derivatives by chemical reactions
is known as regeneration. The various regenerated forms of cellulose are shown
in Fig. 6.2.
Viscose and |
acetate rayon
Methyl- and Cellulose
oS
ethyl cellulose nitrate
Cellulose
Carboxymethy]
Cellophane
cellulose
Fig. 6.2 Cellulose derivatives
Starch
It differs from cellulose in the configurational arrangement in glucose units.
Starch is a polymer with an @-glucose as the repeat unit and is a widely distributed
polysaccharide. It is a major component of human diet in the form of grains e.g.
wheat, corn, barley, rice and potatoes etc., This dissimilarity in the structure of
strach makes it available as a granular material, with no trace of organised
crystalline structure. Starch is in fact, a mixture of two polysacchrides, the one
a linear macromolecule called amylose (soluble starch) and the other branched
chain called amylopectin in which linear 1—4 linked chains are joined together
by 1-6 linked branching points. Besides, its use as foodstuff, starch is extensively
used in paper sizing and textiles, and for fermentation to alcohol. Dextrins are
partial hydrolytic products of strach obtained by the action of enzyme amylase
in acidic media. These have free sugar group and thus reduce alkaline copper
sulfate solution. The structures of amylose and amylopectin are shown in Fig. 6.3.
CH,OH CH,OH CH,OH

O O O
OH OH OH
wr O O O 0
OH OH OH
Amylose (soluble starch)
CH,OH
O
OH
wwan— O O——GH, CH,OH
OH O O
OH OH
wn. C) O O—a
OH OH
Amylopectin (insoluble starch)
Fig. 6.3 Structures of amylose and amylopectin
Some other natural polymers are briefly mentioned as below.
Glycogen
Glycogen is a polysaccharide, found in animals only. It is an important energy
storing material in the body and is found mainly in muscle and liver. This is a
glucose polymer similar to amylopectin, except that it is more highly branched.
cA
Dextran
It is another polysaccharide prepared by cultured propagation of various
microorganisms on a cane sugar phosphate substrate. It is a useful substitute for
blood plasma. During the formation of dextran by the process of fermentation,
glucose part of sucrose molecule is polymerised to give dextran.
Table 6(a) shows a comparison between various physical characteristics of
some common polysaccharides.
Table 6(a) Comparison of physical characteristics of some polysaccharides
Characteristics Cellulose Starch Glycogen

Amylose Amylopectin
Monomeric units B-glucose a-glucose a- glucose a-glucose

Polymer _ linear linear branchec spheriod
structure (sheet like)
Crystallinity high high low nil
Solubility nil limited limited good
in water (after boiling)
Color in water no color blue violet-red brownish-
with iodine red
Film formation +4 very strong strong brittle films nil
Fiber formation very good poor nil nil
The structures of some commonly occurring three other polysaccharides namely

inulin, levan and mannan are depicted in Fig. 6.4.
Heparin
It is a polysaccharide of animal origin. It is widely spread in animal tissues. The
extra-cellular matrix mainly consists of heparin and chondroitin sulfates. Heparin
is extensively used as anticoagulant for blood and antithrombotic agent. It enhances
the natural thromboresistance of endothelium. The biologically reactive nature
of heparin is exploited for inhibition of growth of smooth muscle cells and
human immunodeficiency virus (HIV), and angiogenesis. The structure of heparin
is shown in Fig. 6.5.
Hyaluronic acid
It is a linear high polymer built up of a disaccharide repeat unit, with molecular
weight in the range of 2 x 10° to 2 x 10°. Gels obtained from this polymer
possess good resistance to compression, and appear as lubricants and shock
absorbing components for the nose and joints. A similar polymer is chondroitin.
CH, ,OH CH,OH CH,OH CH,OH
(a) Inulin
—CH, _O O—CH, _O — CH, —
CH,OH CH,OH
aoe
OH
(b) Levan
CH,OH
OH OH OHO OH or
OH eL
& ian CH,OH

(c) Mannan
Fig. 6.4 Structures of (a) Inulin, (b) Levan and (c) Mannan
COOH CH,OH
a ve O O
O. OH o O,
O
OH NHCOCH,
Fig. 6.5 Structures of heparin
Both hyaluronic acid and chondroitin (as sulfate) are often found in combination
with protein or lipid molecules. The repeat unit structure of hyaluronic acid is
shown in Fig. 6.6.
CH,O0SO,H COOH
NHCOCH,
Fig. 6.6 Repeat unit structure of hyaluronic acid
Chitin
It is a tough and brittle polysaccharide, serves as structural component in insects
and anthropods (for example in crabs) where it forms so called exoskeleton,
playing a role analogous to the protein collagen in higher animals.
Several other polysaccharides help to maintain plant structure. Arabans and
xylans, which provide wood many of its typical properties are, made from the
pentose sugars viz. arabinose and xylose. Pectins found in fruits are highly
branched polymers of glucose, arabinose and galacturonic acid.
Various gums and mucilages from land plants and sea weeds are mainly
polysaccharides with applications as emulsifying, gelling and thickening agents.
6.2 Proteins
4
Proteins are the natural polymers made of o-amino acid units through peptide
(-CO-NH-) linkage. In total about twenty of these amino acids occur in nature
(of which eight are essential to sustain life). Except the simplest amino acid
glycine, all other amino acids are optically active and are of |-series. Aqueous
solutions of amino acid can be neutral, acidic or basic. They also form dipolar
structure and thus are zwitterionic in nature.
Each protein is a monodispersed polymer with a definite number of amino
acids linked with each other in distinct sequence. A simple protein is polyamide
(or polypeptide) whereas a conjugated protein consists of a prosthetic group
linked with simple protein. Glycoprotein lipoprotein, nucleoprotein and
haemoglobin are the examples of conjugated proteins of which a carbohydrate,
a lipid, a nucleic acid or haem are the prosthetic groups.
Proteins catalyse a series of biochemical reactions including hydrolysis, group
transfer, oxidation and biosynthesis etc. In fact all enzymes are proteins. Proteins
are structural elements and function as protective agents in the living systems.
Proteins may be inter-molecularly hydrogen bonded (fibrillar proteins) e.g.
keratin of the hair and nails, collagen of the connective tissues, elastin of the
sinusos and arteries, fibroin of silk thread; myosin, the muscle protein or intra-
molecularly hydrogen bonded (globular proteins) e.g. hormones like insulin and
glucagon, enzymes like trypsin, invertase and papain etc., respiratory proteins
such haemoglobin, myoglobin, albumins e.g. egg albumin, bovine serum albumin
and antibodies. Fibrillar proteins are water insoluble whereas globular proteins
are usually water soluble.
All proteins are hydrolysed finally to a mixture of @-amino acid from which
these were built. The reagent ninhydrin gives characteristic coloration to amino
acids and thus may be determined chromatographically (a method developed by
Nobel laureates Martin and Synge).
The structure of proteins is very complex. Primary structure of proteins shows
the chemical formulae of the amino acids arranged in a definite sequence through
peptide linkage. The sequence of amino acids in the protein molecule was first
successfully examined by Sanger who was awarded two nobel prizes in chemistry.
Secondary structure of proteins describes the molecular shape (or conformation)
of a protein molecule. Nobel laureate Linus Pauling, has demonstrated that a
right handed intra-molecularly hydrogen bonded helical arrangement (@-helix)
is an important secondary structure of proteins when many bulky pendant
groups are present on the main chain. A B-arrangement or pleated sheet
conformation predominates when small pendant groups are present on the chain.
The a- and B-forms of proteins enzyme are shown in Fig. 6.7. The sequence of
amino acids in enzymatic protein lysozyme is shown in Fig. 6.8.
Fig. 6.7. The a-and 6-form of proteins
Tertiary structure designates the shape of folding which results due to the
sulfur-sulfur cross-links between macromolecular chains. The specificity of enzyme
action in fact depends on tertiary structure. Proteins lose their physiological
activity because of the disruption of folded structure (denaturation of proteins).
Individual protein chain agglomerates
in to supramolecular system and this
mode of agglomeration is called
“quaternary structure”.
Although polypeptides can be
synthesised by simply heating @-amino
acids but the products obtained are
random mixtures unless a single amino
acid is used. A solid phase technique
developed by Merrifield (Nobel
&
laureate, 1984) is a novel method to .WEX
KX
synthesise polypeptides with desired
amino acid sequence. ce
In Merrifield synthesis, all reactions
take place on the surface of cross linked
polystyrene beads and the entire reaction
for synthesising polypeptides with many
programmed sequences of amino acids
can be carried out automatically in a
simple vessel with a possibility of neat
isolation of any intermediate products. Fig. 6.8 The lysozyme molecule
Natural.Polymers 243
6.3 Nucleic Acids

These are perhaps the macromolecules of utmost biological importance. Two
kinds of nucleic acids exist in the living cell. They are deoxyribonucleic acid
(DNA) and ribonucleic acid (RNA). Nucleic acids are usually built up of bases
(purine and pyrimidine bases), pentose-a sugar, and phosphoric acid. The purine
bases are adenine (A) and guaning (G) whereas the pyrimidine bases are uracil
(U), thymine (T) and cytosine (C). The bases (A), (G) and (C) are common in
both DNA and RNA but the base (U) is present only in RNA and the base (T) is
present only in DNA. The pentose sugar is ribose in RNA whereas it is 2-
deoxyribose in DNA. The various constituent chemical species of nucleic acids
Sugars HOH,C 7O< OH HOH.C O. OH
OH OH OH
Ribose 2-Deoxyribose
Bases O O NH,
pyrimidine CH
: NH C Neo i SN
Bs O aa O NA O
H H H
Uracil Thymine Cytosine
Purine 4 O NH,
N N SS N
<n Gels
NH
So
N N NH; N N
H H
Guanine Adenine
Fig. 6.9a The constituents of nucleic acids
: H
0 |
H~ yy—H" mS N
‘ hog =
ye ey nal H ea N wigN Sih O ANS Oo N N ‘ai
N |N 2 O g ; | nv T
xe)
ae
Z H™
O N N a
| : fi
(a) (b)
Fig. 6.9b Specific base pairing in (a) adenine-thymine pair and (b) guanine—cytosine
pair
The sugar-base combination is called nucleoside. For example the different

nucleosides with bases A, G, U, C, T are called adenosine, guanosine, uridine,
cytidine and thymidine respectively. Linking phosphoric acid to these nucleosides
through the sugar moiety gives nucleotide (Fig. 6.10). The different nucleotides
are adenylic acid and guanylic acid. Both DNA and RNA are polynucleotides
and consist of chains of repeating units of nucleotides.
wow O — CH, oO Base,
Fig. 6.10 Structure of a polynucleotide
On the basis of quantitative chemical analysis by Chargaff and Franklin, the

structure of DNA was elucidated by Watson and Crick which could explain
several problems that puzzled scientists over many decades. DNA structure is
composed of two right-handed helical polynucleotide chains that form a double
helix around the same central axis. The two standards are antiparallel i.e. their
3, 5 phosphodiester likage are in opposite directions. Furthermore the bases are
stacked inside the helix in a plane perpendicular to the helical axis.
The two strands are held together by hydrogen bonds formed between the
pairs of bases. Since there is a fixed distance (1.08 nm) between the two sugar
moieties in the opposite strands, only certain base pair can fit into the structure
and as such the only two possible base pairs are adenine and thymine (A)-(T)
and cytosine and guanine (C)-(G). The two hydrogen bonds are formed between
(A) and (T) and three are formed between (C) and (G). In addition to hydrogen
bonds, the hydrophobic interactions established between the stacked bases are
also important in maintaining the double helical structure.
The Watson and Crick model has been confirmed with slight correction. X-
ray diffraction studies indicate that the base pairs are planar and that the hydrogen
bonds are almost collinear, their length lying between 2.8 and 2.9 A. Each turn
of the helix contains 10 nucleotide pairs and the diameter of the helix is bout 20
A. The spacing between the adjacent pairs is 3.4 A. The two DNA chains are
complementary to each other i.e. a chain with a given sequence of bases can pair
only with another chain which has the complementary sequence of bases.
Since (A) = (T) and (G) = (C), (A) + (G) = (C) + (T), while on the other hand
there is a considerable variation between species regarding the AT/GC ratio. For
example, in higher plants and animals AT is in excess of GC, whereas in viruses,
bacteria and lower plants it may be the contrary. For example in man AT/GC =
1:52; in E. coli, it is 0.93.
DNA is one of the largest known molecules. For example, the DNA of the E.
coli contains 3 x 10° bases, which corresponds to a sterically specific arrangement
of about 10° atoms. The propagation, i.e. the self doubling of the DNA takes
place by the action of an enzyeme, DNA-polymerase as shown in Fig. 6.11.
Phosphates
Nitrogenous
bases
Deoxyribose
Fig. 6.11 Schematic representation of double helical form of DNA and its reduplication
The parent strands are separated and new complementary strands are formed
from monomers by the building up principle. Deoxyribonucleic acid (DNA) is
the molecule of heredity; the purine and pyrimidine bases carry genetic information,
of whereas the sugar (deoxyribose) and phosphate groups perform a structural
role. The function of a DNA molecule is to carry genetic information of a cell in
such a way that this information can be passed from one generation to the next.
For this to occur the DNA must be a stable molecule, which can be exactly
duplicated so that the two daughter cells arising at mitosis may each, receive
identical copies. The genetic information is transferred from the DNA to the
complementary or messenger ribonucleic acid, m RNA (transcription). This is
further translated during protein synthesis from the four letter language of the m
RNA into the twenty letter language of the proteins by dictating which transfer
RNA with its specific amino acid shall operate next on the growing protein
chain.
6.4 Natural Rubber

The polymerisation of isoprene in the rubber plants to natural rubber is highly
organised and controlled process which always results 1,4 cis product (where the
hydrogen and —CH; groups are on the same side). In certain types of plants,
isoprene gets polymerised to give gutta percha—a hard horny substance with
plastic like properties. The possible scheme of the formation of polyisoprene
from isoprene in rubber trees is depicted in Fig. 6.12. Also shown in the figure
are the cis- and trans-arrangements of polyisoprene.
CH,
1 | 3 4
H,C = C — CH=CH,
Isoprene
CH, HG CH
|
LyBe G
i
HC CH;
CH n
II
n
1,2 polyisoprene 3,4 polyisoprene

(Atactic, syndiotactic and isotactic) (Atactic, syndiotactic and isotactic)
CH,
|
H.C — C=CH ===
1,4 polyisoprene (cis- and trans-)
cis rubber
trans gutta purcha
Fig. 6.12 Probable shceme for the polymerisation of isoprene to polyisoprene in
rubber trees
Rubber occurs in nature in about 200 different plant species distributed over
various countries of the world. Most of the commercial natural rubber is obtained
from the Hevea braziliensis tree which is indigenous to Brazil and is now cultivated
in the tropical rain forest regions of all continents.
Rubber is found in tree in the form of milky white fluid called latex, which
occurs in the bark of the rubber tree. It is not the sap of the trees, as so many
people wrongly believed. It occurs,in ting ducts or tubes which spiral upward
round the tree from left to right in the bark.
Natural rubber is made from this milky white fluid (latex) obtained by cutting
narrow strips from the bark of the rubber tree Havea Brasiliensis. The liquid,
which exudes from the exposed cut, is allowed to flow into plastic or aluminium
cups or coconut shells containing a little preservative and later collected for
processing. The process of obtaining the latex is called tapping.
Latex contains about 30-40 percent of solids and 55-60% of water. On
coagulation or evaporation to dryness, it gives a solid substance containing
approximately 95% polyisoprene, the rest being water and nonrubbery substances
such as proteins, sterols, sugar and minerals. The latex is composed of ting
rubber particles suspended in the liquid called “serum” which is chiefly water. If
is collected from the tree and in coagulated form and de-watered on a roller mill.
The properties of rubber can be improved by heating it with sulphur. This
process is called vulcanisation discovered by Charles Goodyear in 1839. The
possible mechanism for the vulcanisation and structure of vulcanised rubber has
already been discussed in Chapter 4. The vulcanised rubber has greater elasticity
and tensile strength than crude rubber. Though the mechanism of vulcanisation
is not fully understood, it results in a loss of one double bond with one sulphur
atom introduced between two repeat units of neighbouring chains. It is assumed
that one sulphur bridge is formed from about 50 initially present sulphur atoms.
The vulcanised rubber still retains high elastic properties when the sulphur bridges
are spaced sufficiently at long intervals along the chain.
There are two types of vulcanisation processes namely hot (warm) and cold
vulcanisations. The hot process occurs at temperatures ranging 120—160°C. It is
performed in autoclaves and in the presence of chemical agents called accelerators.
For example tetraalkylthiouramedisulphide, zinc dialkyldithiocarbamate and 2,
2-dithiobisbenzothiozole. Various substances promote the vulcanisation. Some
such compounds are called accelerators viz. combination of zinc oxide and salts
of fatty acids.
The vulcanisation of natural rubber with an excess of sulphur (around 30%)
yields a kind of hard and cured rubber known as ebonite. The hardness and the
rigidity is due to maximum cross-linking and minimum residual unsaturation
left in the chains. This process can be carried out both in cold and hot conditions.
Normally sulfur is used as cross-linking agent to vulcanise the rubber at 120—
160°C (the mechanism for such hot stage vulcanisation has been discussed in
Chapter 4 (4.5)). The vulcanisation can even be carried out at room temperature.
Disulfur dichloride (SCI) is used as cross-linking agents and produces mono-
sulfide cross-links as shown in the following Fig. 6.13.
The different applications of rubber for different use purposes demand varying
2 www CH,— CH = CH — CH, www
www CH,— CH — CHC] — CH,~wwww
www CH,— CH — CHCl — CH,~www

Fig. 6.13 Cold vulcanisation scheme for natural rubber
degrees of cross-linking among the chains. Thus one can select any of one of the
above mentioned curing processes for obtaining different grades of rubbers.
About 50% of all rubbers go into type production, 25% for other vehicular
applications and the rest goes in other items such as surgical gloves and thin
walled articles.
Dumitriu, S., (ed), Polymeric Biomaterials, New York; Marcel Dekker, 1994.
Dumitriu, S., (ed), Polysaccharides—Structural Diversity and Functional Versatality, New
York: Marcel Dekker, 1998.
Gilbert, R. (ed), Cellulosic Polymers, Munich: Hanser 1994.
Kremer, O. (ed), Biological and Synthetic Polymer Networks, New York: Elsevier Appl.
Sci., 1988.
Radhakrishna, S., A.K. Arof, Polymeric Materials, chap. 14, New Delhi: Narosa, 1998.
Saenger, W., Principles of Nucleic Acid Structure, Berlin: Springer, 1988.
Vincent, I.V. F., Structural Biomaterials, New York: Wiley, 1982.
Young, R.A. and R.M. Rowell, Cellulose, Structure, Modification and Hydrolysis, New
York, Wiley, 1986.
Inorganic Polymers
Inorganic polymers are high molecular weight substances whose molecules are
made up of covalent likages between several small molecules with the absence
or near absence of hydrocarbon units in the main backbone. Glass, silicones and
polyphosphazenes are some common examples of inorganic polymers of industrial
value. Broadly, inorganic polymers consists of several groups to be listed as
phosphorous based macromolecules, sulfur polymers, boron polymers, silicon
polymers, organo-polymers of silicon, germanium, tin and lead, polymeric metal
alkoxides, organometalloxanes and organometalloxono siloxanes, coordination
polymers and electron deficient polymers etc. Some representative examples of
inorganic polymers are already discussed in Chapter 1. Inorganic polymers can
be classified in a number of ways. Some are based on the composition of the
backbone such as silicones (Si-O), polyphosphazenes (P-N) and polymeric sulfur
(S-S). Other classification is based on the connectivity, i.e. the number of network
bonds linking the repeating units into the network. Thus silicones are based on
R-Si—O-, polyphosphazenes are based on N-PX, and polymeric sulfur has the
connectivity of two, while boric oxide (B03) has the connectivity of three and
amorphous silica has four. This is illustrated in Fig. 7.1.
Sulfur, selenium and tellurium all form high polymeric sulfur is elastomeric
while polymers of Se and Te are generally crystalline. Inorganic polymers have
some unique features, which make them advantageous over organic polymers in
some specialized applications. Some of the special characteristics of linear inorganic
polymers are an higher Young modulus and a lower failure strain compared to
organic polymers. Higher degrees of crystallinity and high glass transition
temperatures are often seen in inorganic polymers. Inorganic polymeric materials
are growing in importance as a result of combination of the following two major
factors, (i) the depletion of the world’s fossil fuel resources (which forms the
basis of petrochemical industries and thus polymer industry) and (ii) ever increasing
demand of modern technology coupled with environmental and waste disposal
problems associated with orgnic polymers. Inorganic polymers are widely employed
in the construction and building materials, as abrasives and cutting tools, as
fibers, as elastomers, as coatings, as lubricants and as catalysts. The unique
properties of inorganic polymers and ever decreasing fosiil fuel resource which
R R ‘R Xx X Xx
| | | ie | |
—Si—0O —Si>0— Si —0 — —P=N—P=N—P=N—
| | | | | |
R R R Xx xX xX
(a) Polysiloxanes (2) (b) Polyphosphazenes (2)
a ge
(c) Polymeric sulfur (2)
fe) O
ry Bo —™B O
werd
|
O74 B inlsapaeOan/
s
il B
. O
oe
/
oscil
Np?
Nao pla \
\O xee
| \ }
Ge hs OW, 0
open, d
—B
So
(d) Polyboric oxide (3)
| | |
p jade onl d
~o O O
Sls / \ hails orabbketty |
/ a ee | iatCole
O pro my O 80D fi Oe
Trey. O Q SsiC 0
si f
mah LA
teers pays
Sal a
taog'
°
| alesbicsPmaga Sa le» 0Losin
\ 0 o_ | /
ioe beset cme (
| + O O
| | |
(e) Silica (4)
Fig. 7.1 Inorganic polymers with varying connectivities (given in the parenthesis)
forms the basic raw material for the synthesis of modern organic polymers, has
led to a new branch of chemistry ‘Organometallics’. The application of chemistry
of polymerisation to organometallic compounds led to the development of
organometallic polymers. When direct organometallic polymers can not be
synthesised, attempts are made to produce novel and new combination of properties
Inorganic Polymers 251
y,
that are not present in classical organic polymers and conventional inorganic
polymers. These attempts resulted into metallation of organic polymers and also
metal filled polymers. The metallation of natural rubber is a case in point.
Similarly, synthesis of exotic mono and multi metal-sandwiched organic polymers
such as poly vinyl ferrocene and its derivatives can also be cited.
Some salient features of most common inorganic polymers are briefly discussed
in the following manner. ‘
7.1 Silicones
Silicone is a popular term used to describe a whole family of organo silicon
polymers based on a backbone or a molecular chain of alternate silicon and
oxygen atoms. Polydimethylsiloxane (PDMS) is a most common example.
CH; CH 3
| |
—si—o-+tsi—o
| | P
CH; CH;
Depending upon the length of the chain and the organic groups attached to the
silicon atoms, the silicone polymers may be like water thin liquids, heavy oil like
fluids, greases, gels, rubbers and solid resins etc. The basic reactions in the
synthesis of silicones are usually the hydrolysis of chloromethylsilanes which
can be produced by the reaction of Grignard reagent with silicon tetrachloride;
R Mg X + Si Cly > R Si Cl; + XMgCl
LR Si Cl; + R Mg X > R; Si Cl, + X Mg Cl
The hydrolysis of dialkyldichlorosilanes gives silicones which subsequently
polymerise to polydimethylsiloxane as shown below (see scheme 1).
Ci CH;
| ce |
cl—Si—cl
—+ HO— Si— OH
| |
CH, CH,
Polymerisation
CH,
|
poh
|
CH, in
Scheme I
When the chain becomes sufficiently long, the reaction can be stopped by
terminating end functional group (-OH) by trimethylchlorosilane (see scheme
II). Such end capped low molecular weight linear silicones are oily materials.
Adding some trichloromethylsilane (a trifunctional compound) during the
polycondensation of dialkylsilanediol results in a crosslinked silicon, which can
be end capped by trimethylchlorosilane to give a silicone elastomer or resin.
Silicones are exceptionally stable and highly bio-compatible polymers. The
characteristic resistance of silicones to elevated temperatures is related to the
siloxane backbone, which has high heat resistance capacity.
CH, CH, CH;

|
H,C—Si—Cl
+ HO+Si—O-++H + CIl—Si—CH,
| <
CH; CH, <n CH;

Polymer
H,C
— Si— 0+ Si— O + Si— CH,
| | |
CH, CH; CH;
Scheme II
The lubricant action and water repellency are related to the pendant lipophilic
alkyl groups, which encase the abrasive backbone. Surface related applications
of silicones include their use as water repellents. Siloxanes modified with polyethers
are now commercially available and possess solution properties similar to
conventional low molecular weight nonionic surfactants. These modified siloxanes
are known as silicone glycols or silicone surfactants. They also undergo aggregation
in aqueous and non-aqueous solutions to yield micelles. Silicone surfactants are
characterized by low surface tension values and are widely used as anti-foaming
agents in one shot process for the manufacture of polyurethane foams. Being
biocompatible, silicones are also used as implant materials in biomedical
applications.
Silicones are often characterized by combination of chemical, mechanical
and electrical properties which taken together are not common to any other
polymers available commercially. Silicones show unique rheological properties
and are inert to most ionic reagents. They behave as liquids at fairly high molecular
weight and possess low freezing point, pour point and boiling point. They have
low T, and possess high compressibility and gas permeability. Silicone rubber is
a thermosetting elastomer produced by the cross-linking high molecular weight
silicone gums and is of great value in medical technology. It can be obtained
over a broad range.
7.2 Polyphosphazenes
These are very important phosphorus containing inorganic polymers.
Polyphosphazenes with linear, cyclolinéar and cross-linked and cyclo-matrix

structures have been produced. Polyphosphazenes have low glass transition
temperature and thus have potential use as elastomers. These polymers show fire
resistant properties (the P—N) chain in these polymers has resistance to
combustion). Polyphosphazenes are synthesized by ring opening reaction of
hexachlorocyclotriphosphazene and subsequent substitution of the labile
phosphorus-chlorine bond with alkoxy or alkylamino groups (see Fig. 7.2).
ClCl
Nee
N a PalN
cy | la
Cl Sn7 Na
Hexachlorocyclotriphosphazene
250°C |Vacuum
Cl
|
P=N
|
Cl n
Polyphosphazene
Rw NH
aval \ew
ArO-Na*
St |
has Oar P=N
*+—-P =N | |
ers P=N OR
N <il n | :
NR (c)
OAr n
(b)
Substituted polyphosphazenes
Fig. 7.2 Synthetic route for polyphosphazenes
The ring opening polymerization mechanism for the formation of

polyphosphazenes is shown in the following steps (see Fig. 7.3).
Polyphosphazenes can also be synthesized through polycondensation. The
reaction between PCl,; and NH3/NH,Cl proceeds in a step wise fashion by
elimination of HCI to first form a monomer [A], then a dimer [B], trimer [C],
tetramer .. . . The cyclization could occur to give cyclic chlorophosphazenes at
any stage beyond dimer as shown in the scheme below.
Cl Cl Cl c1O
nd Sy
eo ea arty
N N Heat | |
cy | yok axararerhclt. l/c!
P. lf
cl” ae Nel cl% aad Nea
(1) (II)
Cl CG] a
NS ~ ‘a
~~. Pe
I \ Pe °=N sib
P
\ /® Cly |R yo
Pea cl a“ Sy a
Cl Cl
(ID) (I)
Clay
See Cl Cl
|eames x
Hi \— Bee a
‘int Heat
N Sel | ~ca — P=N
LE: PB gee |
a a a N et Cl :
Transition complex Polyphosphazene
Fig. 7.3 Mechanism of synthesis of polyphosphazene
® © NH3 ne
pci®rci?
a [PCI,|°[Cl,P =N— PCI; re

Cl,P=N—PCl,= NH
pci@pci?
[Cl,P =N — PCl>= N— PCIs]® [PClg]° — and so on

©
Scheme III
Polyphosphazenes when refluxed with nucleophiles like sodium

trifluoroethoxide or sodium cresylate produce amorphous elastomers as per the
below shown reactions; Several substitutions with possibilities of two or more
different organic groups either simultaneously or subsequently give rise to

polyphosphazenes with useful properties.
Bifunctional reactants such as hydroquinone (or dihydroxybenzene) produce
cross-linking in polyphosphazenes. Polyphosphazenes are usually soluble in
common organic solvents such as CHCl;, THF and can be formed into fibers by
extrusion or into films by solution casting. Polyphosphazenes with
microcrystallinity and high strength can be made by single substitution. these
polymers can be fabricated more easily by solution casting or solution spinning.
The biodegradability of these polymers leads to their biomedical use as specialty
blood compatible implants and as surgical sutures etc. A significant advantage of
polyphosphazenes over other biomedical polymers is the ease with which different
organic side groups can be linked to polyphosphazene chain. Thus by changing
the type of side groups present, it is possible to generate virtually any combination
of properties needed for a particular biomedical use including the ability to
hydrolyze inside the body to nontoxic small molecules that can be metabolized
or excreted. Surface modification of polyphosphazenes can be achieved by the
pendant organic groups and thus polyphosphazenes can be made hydorphilic or
hydrophobic. These polymers are quite useful in the immobilization of biomolecules
such as enzymes, cells and drugs etc. Other useful inorganic polymers are briefly
mentioned below:
Cl n
wine H3C
~O)- ONa
4
OCH,CF; 0
| e- on,
| i | f
OCH,CF; O O)- CH;
Polyphosphates, due to low degree of polymerization in real sense are not

considered as high polymers. Structures of some common polyphosphates are
shown in Fig. 7.4.
Boron polymers are structurally related to graphite and consist of hexagonal
boron nitride (BN) (see Fig. 7.5). These BN polymers possess outstanding chemical,
thermal and dielectric properties. Borate glasses and boron phosphate can be
considered as other examples of boron polymers.
Silicate polymers mainly consist of naturally occurring fiber like asbestos
and sheet like mica. Silicate glass is an inorganic polymer that is formed by the
trans polycondensation of SiO (quartz sand) with the aid of washing soda and
lime. The presence of sodium in glass disturbs the crystalline structure of quartz
and thus they are amorphous under ordinary conditions.
O O O
| ll II é
FA P EeEe ly
2B 5Na
OG p) Rioneap Te we
0g OO
Sodium tripolyphosphate (NasP309)
=x yo O , q
Pp |
of ~o sue OUP sn dcindanh 3Na®
Ox! il 20 bo of few
CeO eee ~oe n
Soluble form (Na3P3;05) Insoluble (Na3P3;05)
Fig. 7.4 Some common forms of polyphosphates
Sulfur nitride polymers [SN], can 7B NC

be prepared by solid phase ro | Dithayg
26
polymerization of dimer S,N, at room tA i »
temperature. these are crystalline frigth afloo| addaAD
polymers, which are superconducting | | leq | wqlon
at 0.25 K. PC cima # le
7.3 Organometallic Polymers
| ema
b ah we oN
et.
Te Td H ' Nita
; Nie t lreneettare
The presence of metal atom in the a Se
polymer molecule may increase the Pee fh LN
stability or rigidity of polymer. If the Ae ‘tae ‘andes teeAE|
metal atom carries easily replaceable oy eee ee
ligands such as carbonyl groups, Ae Luton deeetiog
: ae ; on a
catalytic activity can be achieved. er a Om
Polymers where metal atoms or ions SB we Be
lie close together are electrically oN . a ie
conducting. Methyl methacrylate hae: Be
copolymerized with tributyltinmeth-
acrylate shows piezoelectric and Fig. 7.5 Hexagonal crystal structure of
boron nitride polymer
pyroelectric properties due to the
orientation of dipoles in the influence
of high d.c. electrical field applied above —{CH,—Icii}>
T,. The copolymer is a chief constituent
of anti-fouling paint for ship bottoms.
Ferrocene polymers have structures
|
as shown in Fig. 7.6. These are polymers Fe
made from vinyl ferrocene (ferrocene |
is a class of compound such as di-7-
cyclopentadienyl metal complex,
[(CsHs)2 Fe]). Fig.7.6 Structure of polyvinyl ferrocene
7.4 Coordination Polymers

Coordination (or chelate) polymers are high molecular weight substances whose
main chain is built from units which represent chelate rings. Metals can be
coordinated with organic ligands to form a polymer or to form a coordination
complex with an already formed polymer. These polymers show little flexibility
due to the presence of metal ions. The metal-ligand bonds have enough ionic
character. The coordination number and the stereochemistry of the metal ion
determine the polymer structure. These polymers can be made by the reaction of
preformed metal complexes polymerized through functional groups or by
coordination of metal ion by a polymer containing chelating groups. These
inorganic-organic polymers have exceptionally good thermal stability. A best
known example of coordination polymers is that of phthalocyanine polymers
produced when copper metal is heated with tetracyanothylene. The reaction
scheme is depictod as follows;
NC CN
2n Rae mn Ss + nCu arate Phthalocyanine polymer
NC~ CN
NESS O
HO—R—c* 5 Gn stag R—OH
ga aqua ay
+
O O
| |
cl—C—R’—Cc—Cl
Y N—O ea e- R20 |
S02
|
O—R—CcC
Scheme IV
Polyvinylmacrocyclic ethers form complex with metal ions viz. Zn, Cd, Fe
and Ni etc. These complexes are commonly known as crown ethers and have a
cage structure as shown in Fig. 7.7.
Coordination polymers do form during the tanning of leather where the
coordination of metal ions with the protein (which make the hide) takes place.
These protein-metal ion complexes make leather resistant to bacterial attack,
wear and weathering. The blood protein, haemoglobin, is another classical example
of a coordination polymer.
-fCH,—CH}
,,
/
4C
“ Fe
oey /‘
°
--
2e% s,
Fig. 7.7 Cage structure of polyvinyl crown ether
Barry, A.J., and Beck, H.N., in FG.A. Stone and W.A.G. Graham (eds.), /norganic
Polymers, New York: Academic Press, 1962.
Bhattacharya, S.K. (ed.), Metal Filled Polymers. Properties and Applications, New York:
Marcel Dekker, 1986.
Carraher, Jr. C.E., J.E. Sheats, and Pittman, Jr. C.U., (ed.), Organometallic Polymers,
New York: Academic Press, 1978.
Mark, J.E., H.R. Allcock, Inorganic: Polymers, An Introduction, Englewood Cliffs, NJ:
Prentice-Hall, 1992.
Ray, N.H., Inorganic Polymers, New York, Academic Press, 1978.
Stone, F.G. A., and W.A.G. Graham, /norganic Polymers, New York: Academic Press,
1962.
Wisian, D., H.D. Stenzenberger, and P.M. Hergenrother (eds.), Inorganic and Organometallic
Polymers II: Advanced Materials and Intermediates, Washington, DC: ACS, 1995.
Zeldin, M., K.J. Wynne, and H.R. Allcock (eds.), Inorganic and Organometallic Polymers,
Washington, DC: ACS, 1988.
Specialty Polymers
8.1 Polyelectrolytes
The water soluble charged polymers

Polyelectrolytes are polymers containing functional groups capable of dissociating
into ions in solution e.g. poly (sodium acrylate), poly(styrene sulphonate) (see
Fig. 8.1). Polyacids such as polyacrylic acid, hydrolysed copolymers of maleic
anhydride, hydrolysed polyacrylamide and polybases such as polyvinyl amine,
polythylimine, polyvinylpyridinium halids and polyphosphates are also some
common polyelectrolytes. Proteins and nucleic acids are the biopolymers that
behave like polyelectrolytes in aqueous solutions. It is in fact the solvent that
facilitates the polyelectrolyte like behavior of polymers. For example, polyacrylic
acid acts as a polyelectrolyte in aqueous solution but the same polymer is non-
ionizable in solvent such as dioxane and thus behaves like a normal uncharged
polymer.
+ CH,— CH}
eee
Be CH ety + CH,— CH} |
©® hige © SN
COONa C.H,SO,Na S17 “x
Poly sodium acrylate Polystyrene sulphonate — Polyviny! pyridinium chloride
Fig. 8.1 Structures of some polyelectrolytes
A polyelectrolyte may be anionic or cationic depending on the charge on the

macroion. Due to the compact arrangement of ionogenic groups, polyelectolytes
undergo considerably great electostatic attraction in solution which highly deform
the chains of flexible molecules. This deformation depends upon the extent of
group ionization, which is caused by low molecular weight electrolytes and pH
of the aqueous media. Almost all polyelectrolytes dissolve in polar solvents. The
repeat units in many natural and synthetic macromolecules are acidic or basic
and may therefore be charged or uncharged depending upon the pH of the
solution. It is possible to obtain pure polyacids such as polyacrylic acid which is
negatively charged at high pH and uncharged at low pH. Also, pure polybases
such as polyvinylimine which is positively charged at low pH and uncharged at
high pH. All proteins and some synthetic polymers contain some acidic and
some basic side groups, thus making the molecule amphoteric. Such amphoteric
molecules have a net positive charge at low pH, net zero charge at intermediate
pH (this pH is called the isoelectric point) and a net negative charge at high pH.
A single molecule may have hundreds or even thousands of charged groups on
it at the same time. Most rigid macromolecules and some flexible macromolecules
are incidentally polyelectrolytes in nature. Owing to the attractive forces acting
between chaged groups of different sign, the density of coil will be greater than
for a conformation, which corresponds to the most statistically probable shape
of a macromolecule or to its maximum entropy.
Polyelectrolytes are increasingly used as coagulants and flocculants for colloidal
dispersions e.g. in water treatment and for complex formation etc.. lon-exchage
resins are cross-linked polyelectrolytes and are employed extensively.
The shape of a mcromolecule is affected not only by a change in the pH of a
medium but also by the introduction of an indifferent electrolyte in the solution.
When the amount of electrolyte is not too large, the ionisation of ionogenic
groups is suppressed and then the macromolecule acquires the most statistically
probable conformation. For high salt concentration, their salting out effect reduces
the solubility of polymer and causes the formation of compact macromolecular
coil.
The viscosity behaviour ofdilute polyelectrolyte solutions is usually monitored
by plotting the reduced viscosity as a function of concentration of polymer
solutions. Such dependence of reduced viscosity, 1,/C on concentration is depicted
in Fig. 8.2 for dilute solutions of polyelectrolytes, in different pH and in the
presence of added salts
Ns,/€
~— o
Nsp/C
Wat
ater alia muiboe yl 5.0
0.01 M NaCl 4.0

NaCl 3.0
bet 1 M NaCl
Concentration
Fig. 8.2 Reduced viscosity versus concentration curves for (a) dilute polyelectrolyte
solution in water and at different salt concentrations and (b) dilute aqueous
polyelectrolyte (polyacrylic acid) solution at different pH
The following salient features of the curves are observed: (i) the reduced
viscosity, 1,/C increases with decreasing polymer concentration when only
Specialty Polymers 261
water in used as solvent, (ii) the curves, however, take an upturn by addition of
small amount of salt and become linear with increasing salt concentration and
(ii1) the 7,,/C versus concentration curves for a polyelectrolyte (e.g. polyacrylic
acid) aqueous solutions are highly sensitive to pH of the medium. The -COOH
functional group responsible for the generation of charge, dissociates to different
degree with increasing pH. At lower pH values, most of the -COOH groups are
protonated with no net charge. But af high pH deprotonation followed by ionisation
occurs and polymer chain has fully polyelectrolyte nature. The large increase in
viscosity in lower concentraton is normally attributed to chain expansion due to
electrostatic repulsion among the ionised groups.
Another important application of polyelectrolytes is in destabilisation of
dispersions. Besides making stable dispersions for various applications, the
knowledge of colloid science enables to destroy unwanted colloidal dispersions.
The problem of water, associated with drilled oil as water/oil emulsion is quite
common. Some industries need to eliminate particulate dispersions, for examle,
in the final stage of water purification which is achieved by the neutralisation of
charge (alum is used for this purpose) or by using high molecular weight polymers
(polyacrylamide etc.) which cause flocculation through bridging mechanism.
The long chains of a polyelectrolyte adsorb onto several oppositely charged
colloidal particles making the entire mass sedimenting fast, which causes
coagulation. Polyelectrolytes are also used in coal and nuclear industries too.
The coal dust is eliminated from wash water using polymeric flocculants. The
stable concentrated coal suspensions with desired rheological properties can be
made using polyelectrolytes.
8.2 Ionomers (fon Containing Polymers)
The generic term ionomers has been used for thermoplastics containing ionizable
carboxyl groups, which can form ionic cross-links between the chains. Ionomers,
the ion-containing polymers, are synthetic organic polymers with ionic content
of up to 10-15 mol% and are insoluble in water. These polymers differ from
polyelectrolytes, which have higher ion content and are water soluble where
upon the molecule dissociates into macro-ion and counter-ions. More specifically,
ionomers are ionized copolymers whose major component is a non-ionic backbone
and the minor component is of ionic monomers with associated counter ions.
The ionic groups in the polymer chain can be introduced by (a) polymerizing a
monomer with small quantities of ionic co-monomer or (b) modifying a non-
ionic polymer through appropriate chemical moditiation. Several ionomers are
generated from polymers containing polyethylene and polystyrene backbones.
The presence of ionic groups in the polymer chain has profound effect in the
properties of the non-ionic polymers. The glass transition temperature, mechanical
and rheological properties are greatly modified making polymers useful for
some specific applications. These changes in polymer properties arise due to the
aggregation of ions or microphase separation, which take place within the matrix
consisting of non-ionic part of the polymer. Small as well as large aggregates do
form depending upon the nature of the ionomer.
The T, of a polymer is considerably increased in the presence of ionic groups.

For example, 9 mol % of sodium methacrylate introduced into polystyrene chain
raises the T, of later from 100 to 130°C. Usually, T, increases linearly with
increase in ionic content. Also, the incorporation of ions in non-ionic polymers
significantly increases Young’s modulus. For example, a polystyrene sample
with mol. wt. ranging from 10,000—1,00,000 is liquid at 180°C but with presence
of ~9 mol% sodium methacrylate gives a modulus of ~10° N/m’ at that temperature.
The melt viscosity of polymers also shows an increase with the introduction of
ionic content. The extent to which the properties of a polymer are altered depends
on dielectric constant of the backbone, position and type of ionic group and its
concentration, type of counter-ion and the degree of neutralisation.
At sufficiently high ion content, most ionomers show resemblance to non-
ionic block copolymers and form microdomains due to strong incompatibility of
ions and organic backbone material.
8.3 Conducting Polymers

Most polymers are electrical insulators. Great strides have been made in preparing
polymer films, fibres and single crystals that are electrically conductive or that
can be doped to make them so. Hence, a few polymeric materials made during
past two decades, showed high enough electrical conductivity (> 0.1 S cm).
Some polymers become conducting after incorporation of some ‘dopant’ (usually
an inorganic electron acceptor like AsFs or I,). Such polymeric material which
show electron conductivity are called conducting polymers (sometimes also
called as synthetic metals). The electrical conducting behaviour exhibited by
such polymers and that of copper are shown in Figure 8.3
10’
6
10 Copper metal
polyacetylene doped with AsF,
10°
I, doped polyacetylene
10* liquid mercury
10° AsFs doped poly p-pyrrole
102 Poly pyrrole
10
Polyaniline
0
Fig. 8.3 Conductivity (S m™') range for different polymers and copper metal
The examples of some conducting polymers are given in Table 8(a).

trans-Polyacetylene is a weak semiconductor as such in bulk form but behaves
like conducting when doped with AsFs. The incorporation of AsF; is believed to
Table 8(a) Structures of CRUs of some potential polymers and dopants used to
make them conducting
Polymer Dopant Conductivity

range, S cm
H Heer H
Bosc ral 6 Bry, Ip, AsFs, 10-2
Ya Ne Ne eee HCI1O, and
C=C C=C
H La IS H H va ~S H H2SO, (dopant)
Polyacetylene
KO); AsF, (dopant) 197210

n
Poly p-phenylene
107-10?
ae -
Polypyrrole
104-103
n
Polythiophene
Ferrocenylene polymers
[OOO anes N-+ HCl (dopant) 10-102

| |
H H n
Polyaniline
Photo conducting polymers
| 1
— CH— CH,
H =+(CH=CH}=
n
Poly 2-vinyl carbazole
Poly N-vinyl carbazole
oeeecs E&Y
NO; oe 215 tae 5 9 og
2,4,7-trifluororen-9-one Polyvinylpyrene
give rise to charge transfer complexes at various points along the chains as
shown below; ‘ .
AsF,
I
— CH= CH)}- CH= CH — +AsF; —> -—CH=CH}¥
CH— CH—
The strong electron withdrawing nature of AsF; molecule pulls out electronic
charge from the conjugated chain. The resultant positive charge is stabilised by
its delocalisation over a section of -CH=CH}, with n = 14. Thus, the
positive chage can be considered as the mobile ‘positive hole’ which moves and
transfers electric chage. Interestingly, the conducting behaviour of doped
polyacetylenes increases when it is stretched due to the alignment of the chains.
Doped polyacetylenes offer a particularly high electrical conductivity per unit
density of material (even thrice that of metal). The polymer thus has potential for
use as electric wiring or as electrode material in batteries. Such polymeric materials
may help the scaling down of electronic devices since there is change of current
leakage in the wrong direction. Organo-metallic polymers with novel electrical
and optical properties are being prepared and their mechanical and thermal
characteristics improved for their use as conductors. The disadvantage of using
the conducting polymers is their high cost, problems in processing (due to their
insolubility, in-fusibility and brittleness) and long term instability.
8.4 Solid Polymer Electrolytes (SPE)

Polymer electrolytes are defined as solid ion conductors formed by the dissolution
of inorganic salts in suitable high molecular weight polymer solutions. Such
materials shoud be distinguished from polyelectrolytes and gel electrolytes. In a
polyelectrolyte, as discussed earlier cationic or anionic charged groups are
chemically linked to a polymer chain, while importantly the counter ions are
solvated by a high dielectric constant solvent media (usually water). These charged
groups are free to move or migrate within the matrix formed by chain foldings.
The conductivity shown by a polyelectrolyte solution is a function of water
content and arises du to ion transport through aqueous media in which the
polymer is dissolved. Gel electrolytes are mixed polymer-—solvent —salt systems,
where polymer plays a role of a mechanical support in the solvent media in
which cations and anions are in motion resulting into electrolytic conductivities.
Polymer electrolytes are thus different and consist of a host polymer dissolved
in suitable solvent and additionally an inorganic salt is added to the polymer
solution and excess solvent is evaporated. Thus, solid polymer electrolytes are
complex systems. To act as a successful host, the polymeric material ro an active
part of it must meet the following essential characteristics; (i) the polymer chain
must have atoms with sufficient electron donor capacity to form coordinate
bonds with cations of simple inorganic electrolytes, (ii) the polymer chain must
have repeat units which form segments having as far as possible free and sufficient
rotation or motion within them and (iii) the coordinating centers on the polymer
chain should be suitably placed so that formation of multiple intrapolymer ionic

bonds can take place. A number of polymers satisfy this criterion, but to data
polyethylene oxide (PEO) has been most widely studied. The range of salts that
may dissolve in PEO is large but better and higher conductivities are obtained
when salts of lithium and sodium are employed. For development of practical
devices, it has been found that high molecular weight PEOs have limited
applicability because these polymers are highly crystalline and thus have restricted
segmental motion. This leads to poor conductivities (o ~ 10°Ss cm!) at ambient
temperature. However, it is found that reasonable conductivities in the range of
~ 10° S cm! can be obtained at temperatures close to 100°C, but at this
temperature, the polymer loses mechanical strength and can not provide any
support what so ever to the device, for example a film used in rechargeable
battery. So the technologists face with a tough and typical problem i.e. when
improvement in conductivities is achieved the system loses the necessary
mechanical properties and similarly with good mechanical strength, conductivity
is lost. One has to compromise between these two to optimize the electrolytic
and electrochromic properties of SPEs.
A number of potential polymer hosts for SPEs have been tried. These include
both polyether as well as nonpolyether classes of polymers. Among the polyethers
besides PEO, poltpropylene oxide (PPO), block copolymers of type, PEO-PPO,
PEO-PPO-PEO, siloxane based polymers such as copolymers of dimethyl-siloxane
-ethylene oxide and comb polymers of poly {(@-methoxy oligo(oxyethylene)
ethoxy)methy! siloxane}s have also been successfully tried for reasonable
conductitivites. The nonpolyether polymers mainly include polyesfers such as
polyethylene sebacate, polyethylene succinate and poly /propiolactones and
have shown good promise. Polyurethane linked polyethers networks have also
shown good conductivities when dimethylsiloxane units are incorporated into
network structures. Polyphosphazene based polymers exhibit good ionic
conductivites and they suffer from very low T, values and hence can not be
applied in practical devices. Polyphosphazene polymers with substituted ethylene
oxide units having following structure (Fig. 8.4) have been reported to exhibit
ionic conductivites of two or three orders of magnitude higher than those of pure
PEO based polymers.
O-=¢CH.—CH,—0)}-CH,
|
+~N=Ps
|
O=tCH,—CH,—OMCH,
Fig. 8.4 Structure of polyether modified polyphosphazenes
Table 8(b) lists structures of repeat units of some homopolymer architectures

that have been used as hosts in polymer solid electrolytes. Not only homopolymers
but also polymers of varied architecture have been tried as hosts in solid polymer
electrolytes. Care that must be taken in designing the polymers is that the branches
to the backbone should not add rigidity to the over all chain. Similarly, the added
branches should not have chemical constitutions that will decrease the T,. These
conditions ultimately leave not many alternatives than combinations of polyethers

based on PEO and dimethylsiloxanes. The advances in synthetic polymer chemistry
have enabled the scientists to tailor make several variations in the molecular
architectures of potential polymers that can be used SPEs. Based on these variations,
one can try for example, comb or branched or network copolymers in place of
homopolymers. The constituent components of such heterogeneous polymers
can be chosen in such a way that both the desired electrolytic and mechanical
properties can still be retained. Given below structures of some of the copolymers
which have shown potentiality in the construction of SPEs.
Table 8(b) Molecular architecture of repeat units of some polymers used in solid
polymer electrolytes
Type Name Structure of repeat unit
Homopolymer
Polyethers Polyethylene oxide H—O—CH2;—CH2}-OH ns 150
Polypropylene oxide shisaesdinaad cubic
CH;
O O
| |
Polyesters Polyethylene succinate —¢O—CH;—CH,—O—C—CH,—CH;,—C}
O O
| |
Polyethylene sebacate —-O—CH;—CH;—O—C-{CH)},-C-+ n
O
|
Poly B-propiolactone —{CH,;—CH,—C—0)}-
CH; CH;—CH,
Nonpolyethers
Polyethylimine —(CH,;—CH—N—CH,—CH2—NH+-
Polyphosphazene —-(N=P--
|
Cl
Copolymers (Comb-branched):
Poly(bis-(methoxyethoxy ethoxide)) phosphazene
O-(CH,;— CH,;—0-CH3
-—~N=P>—
Sof CHh-acHyes Oaeten

Poly (dimethylsiloxane-co-ethylene oxide)

CH,
|
+ Si—O—-€CH,—
i —(CH,— CH,— O3--
CH,
CH;
Poly {(@-methoxy oligo(oxyethylen)ethoxy)methyl siloxane}
CH,
|
HASi=09-
|
O-(CH>-0H,_0)
46H,
Poly {(@-methoxyoligo(oxyethylene)ethoxy)propyl siloxane}
CH,
|
26 teOpe
|
(CH2)3
O—(CH,—CH,— 0}-CH;
Poly y-methy! L-glutamate
ae ceolveperrn
(ext,
ok —0-¢CH;—CH,—0O7,-CH,
Ethylene oxide substituted methacrylate polymers
CH;
|
taeda
Ethylene oxide substituted polyitaconate back bone
O=C—O-4CH,—CH;—0}_CH;
|
CH,
|
CHO,
In addition to above mentioned polymer molecular architectures, following

cross-linked polymers based on siloxane structures have also been reported to
show ionic conductivity.
(HC a nage suppose

CH; (CHy)3
(CH,—CH,—0)-H
PEO—(CH}};Si—O—SiCH)},PEO
|
O O
| |
PEO-{CH>},-Si—O—
Si-¢ CH}, PEO
| |
CH,. “CH,
CH, CH,CH,CN CH,CH,;CN
| |
+Si—0}-
Si—O —_{Si—0}{
| |
CH, | CH;
~(Si—0)-Si— 0—Si—0 3
| | |
Formation of polymer—salt complexes

The simplest way of introducing ionic conductivity into a polymer is to solvate
the inorganic ion to the polar groups of polymers. The polar groups in the
polymer are thus known as solvating groups. The most usual solvating group is
an ether oxygen which is invariably found in polyethylene oxide (PEO). The
ether group solvates most of the metal cations by establishing a coordination
link between them. Though several metals can solvate with the ether groups
through such coordination links, the requirement is that the metal coming from
a salt with minimum lattice energy is preferred. Thus most of the reported
studies involve the use of lithium and to a lesser extent sodium salts. Majority of
experiments conducted so far have employed mostly salts based on lithium
perchlorate (LiClO), lithium trifluromethanesulfonate (triflate) (LiCF;SO;),
lithium thiocyanate (LiSCN), sodium iodide (NaI), sodium thiocyanate (NaSCN),
sodium perchlorate(NaClO,) and sodium tetraphenylborate, (NaB(C,gHs),4). Other
wide variety of salts can be used to form soluble complexes depending upon the
molecular architecture of polymer. The solvating power of host polymer and the
extent of dissociation of salt into its constituent ions are very important factors
before an effective solvation complex is formed. The salts with large anions such
as perchlorate and trifluromethanesulfonate have been found to form effective
compleses because these anions have maximum solubility and large quantities
of dissociated ions. The structures of these important ions are shown below;
im F 0® Ri. Oinke
Lit bl lus of I; taal
O«CIl— 0 F—C—S—O F—C—S—N—S—C—F
| lore nit Soma Letevest
O Maeat @) Bao) aN
Perchlorate Triflate TFSI
Synthesis of polymer-salt complexes is achieved by three ways;
(a) Addition of salt to solvating polymer

The two components are dissolved in a common solvent usually acetonitile and
the mixture is homogenised and the solvent is evaporated off. This results in to
a fine film of SPE.
(b) Synthesis of salts of polymeric ions

The ionomers as discussed earlier are ion containing polymers. They can be
soaked in a solution of the appropriate inorganic salt containing a cation other
than sodium (e.g. lithium) for an ion exchange reaction. A modern polymer
material known as nafion (a polymer membrane based on polytetrafluoroethylene)
has following structure;
~¢CE— CREE CF
O—CF,—CF,— O—CF,—CF,— SO3Na*
The Na* can be easily exchanged with other cations by an ion exchange
process in aqueous medium. Water not only acts as solvent but also as a plasticizer
and plays a dual role of enhancing the solvating power of polymer and dissociation
capacity of added salt.
(c) Usage of co-solvents or plastcizers and salts together

Polymers with little or no ion-solvating properties are first dissolved in a co-
solvent which acts as a plasticizer. The co-solvent is absorbed entirely in to
polymer and produces a soft single phase material. This material is then added
to an electrolyte solution for solvation of cations. Polyvinylidene difluoride
(PVDF) can be plastcized with propylene carbonate containing dissolved lithium
perchlorate to give a lithium ion conducting polymer.
Mechanism of ion conductivity

The ion transport in polymer electrolytes may occur by a combination of several
events namely ion motion, local motion in the polymer segments and inter- and
intra-polymer transitions between ion coordinating sites. Thus, ion conductivity
in solid polymer electrolytes depends not only upon ion solvation but also on the
morphology of physical structure, nature of phase states of polymers, transport
properties of ionic species and their mobility. Several macroscopic models are
proposed to explain and understand the ionic conductivity mechanism in polymer
electrolytes. These models are based on liquid like and solid like mechanisms
for the ionic conductivity. In solid like mechanism, the motion of ions is activated
by thermal means, while consideration of liquid like mechanism is based on free
volume concept. From macroscoping point of view, the particle/ionic motion is
due to continuous movements in the matter. This motion consists of discrete and
random jumps. The jump distance is the distance between suitable ion coordination
sites.
Application of SPEs
The SPEs are thought to be ideal medium for a wide range of electronic processes.
They include primary and secondary rechargeable batteries, ambient temperature
fuel cells, electrochromic devices, modified electrodes/sensors, solid state reference
electrode system, super capacitors, thermoelectric generators, high vacuum
electrochemical devices and electrochemical switching.
8.5 Electroluminiscent Polymers

Electroluminiscence (EL) is a phenomenon involving generation of light by
electrical excitation. This is seen in a wide range of semiconductors of low
molecular weight inorganic and to a lesser extent in organic materials. The
process of electroluminiscence occur through recombination of electrons from
one electrode and their capture by the holes from the other electrode and subsequent
radiative decay of the excited electron hole state (exciton).
Electroluminiscence effects in polymers were first reported in 1990. The
structure of some EL active polymers is shown in Figs. 8.5 and 8.6, respectively.
These polymers are basically conjugated polymers and derive their semi
conducting properties by having delocalised 7 electron bonding and 7* antibonding
orbitals from delocalised valence and conduction bands which support the mobile
charge carriers. Poly p-phenylene vinylene (PPV) is synthesised by the so called
precursor route, in which a soluble precursor polyelectrolyte is thermolysed in
situ into PPV. The polyelectrolyte is a bis-sulphonium salt obtained by Wessling
condensation polymerisation of p-xylene halides and base. However, this process
inevitably introduces chemical and morphological effects in the chains with the
result that there is a distribution of effective conjugation lengths and these are far
shorter than the normal degree of polymerisation. To solve the porblem copolymers
in which short phenylene vinylene sequences of determined length are alternated
with inert methylene sequcnce in a multi block architecture (see Fig. 8.7). These
alternating block copolymers have good solubility, are homogeneous in terms of
conjugation length and can be designed to emit any portion of visible spectrum.
One of the major applications of EL active polymers is as light emitting diode
(LED) devices. The LED fabrication is shown in Fig. 8.8. The performance of
(Dr)
en he Caf
Poly p-phenylene vinylene
\ ‘
us i}
LPN x
{I\ y OR
My
R= oy
R = (CH,);CH(Me)(CH,),CHMe,
OR: cy
ch wa
R,0 aK
R = Me, R, =CH,CH(Et)Bu
Fig. 8.5 EL active poly p-phenylene vinylene based polymers
Polydialky] fluorene
4
wy9
Polydioxy ethylene-
thienylene (doped)
SO3H
Polystyrenesulphonic
acid (doped)
Fig. 8.6 EL active non poly p-phenylene vinylene (PPV) polymers
(ee) OCH;
Ses cnt \—CH= CH ee

ee
eae A
soft ; hard
Fig. 8.7 Typical alternating block copolymer structures based on PPV
LEDs meets many of the targeted functions necessary for display applications.
Attempts are made to obtain full color display using EL polymers. The range of
potential applications of polymer LED, would be in backlighting segments displays,
alphanumeric displays, full color graphic display (for computer monitors and
video display) and color pixels in ink-jet printing etc.
8.6 Block Copolymers (Important multiphase polymers)

A block copolymer has a molecular architecture in which a linear arrangement
Poly p-phenylene vinylen
\
Aluminium, magnesium
or calcium
External
Circuit
Indium tin oxide
Glass substrate
Fig. 8.8 Device structure of single layer polymer electroluminescent diode
of two often incompatible blocks is achieved by covalently linking of different

monomers. In this way di-block (A-B). tro-block (A-B-A and B-A-B) and multi-
block (or segmented) copolymers are possible (see Fig. 8.9).
Diblock A-B:
A B
Triblock A—B—A or B—A-B
A B A
B A B
Multiblock (A-B),;: : |
A B a
Fig. 8.9 The different types of block copolymers
Two general methods are used for the synthesis of block copolymers namely
(i) step- and (ii) chain-polymerisations. In the first method, two polymers with
functional end groups are reacted while in the later sequential polymerization
involving initiation of second or third monomer by an active site of a already
formed macromolecular chain of the first monomer is carried out (see Fig. 8.10).
Schwarz developed living anionic polymerization method and it is now possible
to tailor make block copolymers with the desired molecular architecture and low
polydispersity by this method.
*
CEE +mB ee
An
etieemainntine. ~ #—— —
Ay
er
Br
An Bn An Bi
Fig. 8.10 Synthetic routes for block copolymers
Block copolymers possess unique structural features resembling to that of

conventional low molecular weight surface active agents which have two distinct
moieties in their molecule that behave differently. Thus, they do adsorb onto
interfaces and self-assemble to form micelles in solutions and in addition show

microdomain formation in solid state.
This makes these multiphase systems useful for a variety of applications. It is
therefore not surprising that block copolymers have aroused world wide interest
at academic (by physicists, chemists and chemical engineers) and also industrial
level. Several products based on block copolymers are commercialised. These
products are available in the market fpr the users. They are; thermoplastic elastomers
e.g. styrene- diene block polymers (solprene, Philips; kraton, Shell), segmented
polyester-polyurethane (estane, Goodrich, spandex, Dupont) and surfactants,
polyalkylene block polymers e.g. ethylene oxide-propylene oxide (pluronics
BASF, ICI) and ethylene oxide-butylene oxide and ethylene oxide—butylene oxide—
ethylene oxide, Polyols, Dow).
Unique features of block copolymers in solid state

Block copolymers possesses incompatible sequences within their molecule and
exhibit characteristic morphological behaviour and interesting properties.
Incompatible and noncrystallizable A and B blocks form microdomain structures
due to their tendency to microphase separation. Block copolymer morphological
features are reviewed extensively in the literature. The conditions of microphase
separation and equilibrium domain size and their various morphologies viz.
spherical, cylindrical and lamellar are predictable in terms of interaction parameters
and molecular characteristics of the copolymer. The various common structures
are schematically shown in Fig. 8.11.
Increasing A content Decreasing B content
Spheres Cylinders Lamellar Cylinders Spheres

A A A,B B B
Fig. 8.11 The different solid state morphologies in block copolymers
The repulsive interactions between A and B block cause the domain to grow
in thickness (thickness of the lamellar domains and radius of the spherical and
cylindrical domians) so as to reduce surface to volume ratio. This is counter
balanced by two forces of entropic origin, i.e. loss of conformational entropy in
maintaining uniform segment density and the loss of placement entropy in confining
A-B junction in the interfacial region. Partial miscibility in the interfacial zone
depends on the nature of the blocks, type and molecular characteristics of block
copolymer and temperature (see Fig. 8.12).
Morphologies of copolymers with amorphous blocks in general, and styrene-
diene block copolymers in particular as studied by different methods have shown
Fig. 8.12 Schematic representation of microphase separation of diblock (3) and

triblock copolymers (1 and 2)
that segregated microphases can be sphere, cylinder or lamella depending upon

the relative composition of the two blcoks. While lamellae form a regularly
repeating lamellar order, the cylinders arrange themselves in a two dimensional
hexagonal lattice and the spheres into cubic lattice. The domain size for a given
morphology depends on structure, moecular weight and polydispersity, block
composition, temperature, polymer-polymer interaction parameter. For styrene-
butadiene-styrene triblock copolymer (PS-PB-PS), it has been observed that (i)
up to 16% PB in volume, a cubic struture of PB spheres in PS matrix, (ii) from
about 16-18% polybutadiene in volume, an orthorhombic structure formed by
short rods of PB in PS matrix, (iii) from 18-36% polybutadiene in volume, a
hexagonal structure of PB cylinders in PS matrix, (iv) PB and PS alternately
arranged, (v) from about 60-80% polybutadiene in volume, an inverse hexagonal
structure of PS cylinders in PB matrix and (vi) above 80% polybutadiene in
volume, in inverse cubic structure of PS spheres in PB matrix.
Morphological studies on copolymers with amorphous and crystalline blocks
reveal crystalline lamellae formed by one or two layers of folded crystallizable
block. Such structures depend on crystallization temperature, molecular weight
and the nature of amorphous and crystalline blocks. Here, for di- and triblock
copolymers e.g., styrene-ethylene oxide block polymer, well organised periodic
structures have been observed while for multiblock copolymers e.g. segmented
polyurethanes or polyesters, microphase separation without any periodic structure
is noticed. For block copolymers with both the crystallizable blocks, lamellar
structures are obtained but the morphology is more complicated.
At certain temperature when the free energy of mixing of both the blocks is
zero, complete mixing of the phases would occur. Thus order-disorder transition
from microphase separated domains into disordered would occur which can be
clearly observed from mechanical behaviéur. The phase transition is evident for
copolymers when the chains are sufficiently short. With increase in temperature,
thermal agitation predominates and the system gets disordered. At this stage, the
molecules diffuse into the entire volume and the copolymer now accommodates
stresses, by restructuring itself much more rapidly. It behaves like a conventional
viscoelastic polymer liquid. The force required to maintain it in a deformed
shape decreases rapidly in a few milljseconds. The deformation is then permanent.
Block copolymers in solution

Due to the structural resemblance to surface active substances, block copolymers
also exhibit adsorption characteristics and micelle formation in solution. These
two fundamental properties which can be suitably controlled provide unique
application possibilities for block copolymers.
(i) Adsorption from solution

The adsorption of polymers onto surfaces plays an important role in many industrial
processes. When a surface is exposed to a polymer solution, one of two diametrically
different processes generally occurs. In the first, the polymer is enriched in the
surface zone (adsorption), while in the second, the surface zone is depleted with
respect to the polymer. Since the change in entropy on adsorption is negative,
due to the restriction of the translational freedom and of the number of possible
conformations of the polymer, adsorption would occur only if the gain in energy
is larger than the loss in entropy. Thus there is a critical energy of adsorption
which determines whether adsorption or depletion occurs (this energy is generally
quite small, typically a few tenth of a kT due to a large number of adsorption
sites). Polymers are known to adsorb onto surfaces as trains, tails and loops.
Block copolymers, due to their amphiphilic nature are best in that their adsorb
is strongly and extensively onto a large variety of interfaces (see Fig. 8.13).
Loop
Tail
5
aks
Adsorption of diblock polymer Adsorption of triblock polymer

Fig. 8.13 Polymer adsorption at interfaces
While soluble block forms a mantle, the insoluble block acts as an anchor; the
efficient adsorption of block copolymers from solution onto the surface of colloidal
particles provides a long-term stability, Napper has pointed out that the mechanism
of polymeric stabilisation of colloidal solutions is governed by steric stabilisation

or depletion stabilisation. In the former case the particles are stabilised by the
attached or adsorbed polymer. The depletion stabilisation is provided by
unanchored, unattached polymer molecules in the dispersion phase.
(ii) Micellization in selective solvents

Block copolymers in a selective solvent (a good solvent for one block but precipitant
for the other) do aggregate in solution. This aggregation process is analogous
with the micelle formation of conventional non-ionic surfactants (see Fig. 8.14).
(a) (b)
In n-Alkane In DMF, DMA or MEK
Fig. 8.14 Polystyrene-polybutadiene micellar structures (a) micelle core is of
polystyrene block and outer shell is of polybutadiene block and (b) micellar
core is of polybutadiene blcok and outer shell is of polystyrene block
Block copolymer micelles do solubilize substances, which are otherwise

insoluble in the selective solvents. Solubilization of various substances (both of
low and high molecular weight) in copolymer micelles has been investigated.
Applications of block copolymers

The unique architecture of block copolymers allows them to possess some
interesting novel properties that lead to lot of industrial applications. The use of
styrene-butadiene and styrene-isoprene block copolymer as thermoplastic
elastomers in footwear is well known. The other thermoplastic elastomers are
polyether-polyester and polyether-polyamide. Thermoplastic elastomers combine
the properties of a rubber and the processing characteristics of a thermoplastic
which make these materials of great industrial importance. Styrene-diene and
styrene-hydrogenated diene triblock copolymers are reportedly good pressure
sensitive adhesives and are used for bitumen modification. The interfacial
characteristics make block copolymers useful materials as polyblends, as adhesives,
sealants, and binders for laminates, as constituent of coating materials, surface
modifiers for fillers and fibers. Blending of block copolymers with other polymers
provides new polymeric materials with desired properties. Some grades of high
impact polystyrene are such systems. Block copolymer biends with homo- or
copolymers of different kinds (elastomers, thermoplasts and thermsets) lead to
interesting mechanical properties. Block copolymers are used in surfce coating
for metals, glass and in surface modification of fillers like calcium carbonate,
carbon black, silica and different fibers. Surfactant based applications of block
copolymers are as colloid stabilizers, in dispersion polymerization in aqueous
and non-aqueous media (particularly in the later case where the conventional
surfactants fail to perform satisfactorily), in emulsion stabilization, microemulsion
polymerization and polymeric emulsions. EO/PO block copolymers find numerous
applications in medical, pharmaceutigal, textile, cosmetic, detergents and pesticidal
formulation. Their reversible thermorheological feature makes them potential
candidates as vehicles for controlled release of pharmaceutical formulations.
8.7 Polymer Colloids

Lyophobic colloidal dispersions are often desirable in stable form but some
times they are useful in their coagulated state. This makes the understanding of
colloidal stability and instability an important topic. Almost all industrial concerns
often face the problem of stability/instability of colloidal dispersions and
suspensions: A colloidal dispersion (where the particles of dispersed phase are
in the size range 10-°-10’ cm) remains stable due to the surface charge onto the
dispersed particles and offers potential applications. The need of breaking (or
coagulating) a colloidal form arises in several instances e.g. in the removal of
suspended impurities of water from the drilled oil (where it emulsifies with oil
to from water-in-oil emulsions) before sending the oil to the refineries etc.
Stable colloidal dispersions, on the other hand, are required for various cosmetic,
pesticidal, paints, pharmaceutical preparations. It is important here to consider
what contributes to the stability of colloidal dispersions. In fact, the most widely
accepted theory proposed independently in 1940s by the Russians (Derjaguin
and Landau) and Dutch (Verwey and Overbeek) commonly known as DLVO
theory. Considers‘the attraction and repulsion terms between two isolated colloidal
particles and the net interaction between them determines whether the system
would be stable or not. Usually, the repulsive interaction is dominated by the
charge on the colloid surface (measured as zeta potential) and thus the colloidal
systems with high values of zeta potential would tend to be stable as the repulsion
would dominate over attraction. The typical energy profile showing the attractive,
repulsive and net enerty is schematically shown in Fig. 8.15 as a function of
inter-particle distance.
In the foregoing discussion we will see how a polymer influences the stability
Interaction
energy
Inter-particle distance
Fig. 8.15 Energy profile as a function of inter-particle distance

of a lyophobic colloid. Polymers can be conveniently used for both the purpose,
for example, to stabilize a dispersion and to flocculate a dispersion. The mixed
system of a polymer and colloidal disperson together is usually called as polymer
colloid, i.e. colloidal dispersion of particles containing polymers as sensitizing/
de-sensitizing agents. When the surface of dispersed particles is exposed to a
polymer solution, one of the two diametrically different porcesses generally
occur. Either the polymer is enriched in the surface zone (adsorption) or the
surface zone is depleted with respect to polymer. As the adsorption involves
negative entropy change (due to the restrictions of the translational freedom and
of the number of polymer conformations, polymer adsorption would occur only
when the gain in energy is larger than the loss in entropy. Thus there is a critical
energy of adsorption that would determine whether the adsorption or depletion
would occur (the value is however, very small, typically a few tenths of kT, due
to high number of adsorption sites).
Polymer adsorption leads to a drastic change in conformations of its molecules.
A polymer molecule adsorbs on a surface as trains, loops and tails as shown
below (see Fig. 8.16). Whether or not the polymer will adsorb on the surface of
a colloidal particle would depend upon the nature of the polymer molecule (the
lyophobic and lyophilic sites in the polymer), nature of the colloidal particle and
of course more importanly in the quality of the solvent. For polymers dissolved
in good solvents (e.g. xanthan in water) adsorption is very unlikely, in the so
called theta solvents, it is likely and in poor solvents; it is all but certain.
Train Loop
Surface
Fig. 8.16 Conformation outline of an adsorbed polymer chain on a surface
The polymer adsorption onto the surface of colloid particles may impart
stability (or instability) and modifies (hydrophilize or functionalize) surface and
is thus of interest from basic (theoretical and experimental) and applied points of
view. Often basic studies provide information on the amount of the polymer
adsorbed and surface coverage, conformation of adsorbed polymer molecule,
thickness of the adsorbed polymer film, kinetics of polymer adsorption and most
importantly the segment density distribution. Several experimental techniques
have been employed to investigate the polymer adsorption characteristics. However,
modern methods viz. ellipsometry, neutron reflectometry, dynamic light scattering
and small angle neutron scattering, and surface force measurements have provided
valuable information. Among theoretical studies on polymer adsorption, Scheutjens-
Fleer (SF) theory based on mean-field model, in particular has proven to be
successful in predicting adsorption features of polymers.
The situation of polymer adsorption is more complex when the polymer is a
block or graft polymer or a polyelectrolyte. In fact, block and graft copolymers
are most efficiently adsorbed onto surfaces due to their structural analogy to
conventional surface active agents in that each has two dissimilar moieties in
their molecules. Polyelectrolyte adsorption is influenced by the ionic charges
present on the back-bone of the chain and the extent of their dissociation.
When a colloidal solution and a polymer solution are mixed, the dispersion
may be stabilized or destabilized (flocculated). Those polymers which adsorb,
usually at low polymer to particle concentration ratio, instability (also called
bridging flocculation) occurs. For high polymer to particle ratio leading to complete
surface coverage, solvency determines the stability or instability. For nonadsorbing
polymers, flocculation can be seen but a very large amount of the polymer may
be necessary to bring this effect.
Bridging flocculation
As the name suggests the flocculation takes place as a result of bridging of
colloidal particles by polymer molecules. As discussed before, the concentration
of polymer causing bridging flocculation should be very low such that the surface
coverage 1s below its saturation value. Here the polymer molecule adsorbs onto
several colloidal surfaces as shown in Fig. 8.17 and flocculates the dispersion.
Particles
Polymer chain
bee.
Fig. 8.17 Schematic depiction of bridging flocculation of colloidal particles by an

adsorbing polymer chain at low surface coverage
There exists a class of polymers that is widely exploited industrially as

flocculants for colloidal dispersions. These polymeric flocculants may be anionic,
cationic or non-ionic. Use of high molecular weight polyacrylamides in the
domestic and industrial waste water treatment is the widely known example of
bridging flocculation.
Depletion flocculation
The origin of depletion flocculation is quite different from that of bridging
flocculation and does not involve the adsorption of polymer. However, a colloidal
system undergoing depletion flocculation by addition of non-adsorbing polymers
can be re-dispersed on dilution with dispersion medium. The origin of force that
is a responsible for this type of flocculation was first recognised by Asakura and
Oosawa in 1954 who accounted for the fact that the interaction between two
collidal particles would result if the particles approach so closely that the polymer
chains present in the inter-particle region are excluded. This depletion of polymer
chain would be possible if the inter-particle distance is less than the diameter of
the non-adsorbing polymer causing the flocculation (the size of the polymer coil
can roughly be treated as the root mean square end-to-end distance or radius of
gyration). At such separations, the polymer chains can only fit between the
particles by undergoing a significant decreaseiinspatial extension. This compression
is accompanied by a loss in configurational entropy which is thermodynamically
unfavorable. The depletion of the polymer chains from the inter-particle zone,
means that the micro-reservoirs of polymer free dispersion medium are generated
in the bulk. For colloidal systems with dispersion medium working as good
solvent for the polymer, closer approach of the colloidal particles would be
possible due to the migration of dispersion medium from the inter-particle zone
towards the polymer chains outside that leads to the reduction in free energy.
The adsorption and ability of polymers to stabilize or de-stabilize the colloidal
dispersions have been exploited in many commercial and industrial formulations.
Following some of the examples are worth considering.
Adhesives
In order to eliminate pollution problems associated with oil based products, the
trend now is towards water based formulations. It is thus not surprising that
adhesive industries are also shifting to water based adhesives. The most important
of these adhesives is based on poly(vinyl acetate) and its copolymers. These
adhesives have been in commercial use since the 1940s, especially as wood,
paper, and glass adhesives. With modification in the polymerization stage by
copolymerisation and other additions, the material has been made usable in a
large number of plastics applications. A large quantity of latex is consumed as a
textile adhesives and in fabric and carpet backing.
Coatings
Polymer colloids have always been essential materials for the coating industry,
whether the coating is oil-or water-based. The polymer or copolymer in the
latex, the particle size and size distribution of the colloid, and the nature of the
surface functional groups (whether from surfactant or copolymer) are all important
variables, as are the chemical nature of the substrate and the mode of application
that need to be considered for effective coating.
Paper
Paper making and printing processes are also important application of polymer
colloids. When applied to paper they enhance the quality and the printability of
the paper surface.
Pharmaceutical and medical applications

Pharmaceutical coatings have always been important in the manufacture of tablets.
Tablets coated with polymer (e.g. polysaccharides) have been found superior to
sugar coatings. Solvent-based polymer coatings have been important for some
20 years, but the pharmaceutical industry has slowly begun to change to water-
based systems to eliminate the necessity for the use of organic solvents. Now
aqueous colloidal polymer dispersions are used almost exclusively. An interesting
and important extension of the tablet coating by polymer colloids is in controlled
release of tablet composition. When the polymer in the latex particle, for example
is hydrolysable and strong acid groups are present at the surface, self catalyzed
hydrolysis may also occur, resulting in controlled release of the material. Immuno-
microspheres are specially designed colloidal particles that have specific molecules
such as antibodies chemically bound at their surfaces. These particle are capable
of attaching themselves to tissues or cells that contain the corresponding antigen.
These target cells could be viruses or other antigenic agents, and under favorable
conditions no non-specific binding, to other kinds of cells takes place. These
immuno-microspheres may be synthesized to incorporate compounds that are
highly radioactive, intensely fluorescent, magnetic, opaque, highly colored and
pharmacologically active. This type of polymer colloidal particles provide a
multitude of applications in medicinal research, diagnosis, and ultimately in
therapeutical practices.
8.8 Thermoplastic Elastomers (TPE)

These are polymeric materials which function as a thermoplastic during the
processing and as elastomer in the finished product. Several different types of
the polymers belong to this class but each of it has a common feature in that they
are relatively low molecular weight elastomers comprising of hard segments of
sufficiently high molecular weight. These hard segments are incompatible with
elastomer’s part (thus form discrete microdomains) and act as a sort of cross-link
at service temperature. The cross-linking increases the effective molecular weight
many times. These physical cross-liking dissociate at elevated temperatures and
low molecular weight polymer is regenerated and flows under the conditions
encountered in machine used by thermoplastic processing industries. This behaviour
avoids the usual time consuming processing of rubbers (e.g. polyisoprene) through
vulcanization. Thermoplastic elastomers have diverse applications and are in use
as adhesives, reinforcing agents for plastics, shoe soles and elastic bands etc.
The first commercial production of TPEs began by Shell Co. in 1965 and
thereafter other thermoplastic elastomers have entered the market. They include
styrene-diene block copolymers by Shell and Phillips, polyesters by Du pont and
several polyurethanes (TPUs) and several polyolefins (TPOs). These are briefly
described below. The rubbery polymer e.g. polybutadiene is associated with
polystyrene end blocks PS-PB-PS. These end blocks associate to form the hard
phase and provide the polymers strength. These block copolymers with desired
molecular characteristics can be prepared by anionic living polymerisation
technique (Shell-Kraton, Phillips—Solprene). Rigid polystyrene end blocks which
are large in dimension, aggregate or form domains which are joined by the
elastomeric, polybutadiene. At room temperature, these block copolymers behave
almost like cross-linked rubber. However, at temperature above 100°C (T, of
polystyrene), the domains soften and may be disrupted by applying stress allowing
the block copolymer to flow (for more see block copolymers).
8.9 Polyblends (Heterogeneous Plastics)

When two or more polymers are mixed together, polyblends or polymer alloys
are obtained. This physical mixing or blending of two polymers produces an
alloy with quite different properties, which can be potentially useful. Two polymers
are generally noncompatible as they have very low combinatorial entropy of
mixing for the components. This is insufficient to overcome the positive heat of
mixing of polymers to make the Gibbs free energy of mixing negative. Only in
the presence of specific interaction between two polymers (e.g. hydrogen bonding,
acid-base type interactions etc.), heat of mixing is negative that makes the free
energy of mixing a negative quantity and then the mixing is spontaneous. Unlike
the mixing of small molecules, the dictum ‘like likenes like’ does not hold good
for mixing of macomolecules. That is why most polyblends result to incompatible
systems. However, both compatible and incompatible blends are industrially
important materials.
The two polymers may from a compatible blend, which exists as a single
phase. The incompatible blends on the other hand exist as two phase system.
Since most blends combine immiscible components and so the material that
results contains tiny particles of one polymer in a matrix of the other. Controlled
mixing and cooling of the blend makes it possible to form the particles in the
optimum concentration and range of sizes. Blending makes it possible to combine
the good properties of several polymers.
The most direct method to obtain a polyblend is to mix the component polymers
in the molten state (melt mixing). In this case the extent of mixing depends on
the rate of diffusion of the molecules. Since such a mixing requires high temperature,
the polymer may decompose and undergo chemical transformation. It is, therefore,
this mixing process is restricted to thermally stable polymers. Another process
involves the mixing of two polymer latices pre-formed by emulsion polymerisation
technique. The polyblend can be obtained by coagulating the mixed latex system.
A polyblend can also be obtained by mixing the polymers in a mutual solvent
followed by the removal of solvent e.g. by drying.
Usually, blending can be made easier by the incorporation of a block or graft
copolymer containing two moieties similar to the component homopolymers.
For example, styrene-butadiene block copolymer shows adhesion and as a result
act as stabilizer/compatibilizer for a polyblend made by mixing polystyrene and
polybutadiene. Usually, such blends are called ‘polymer alloys’. In compatible
polyblends, the glass transition temperature can be easily altered by varying the
composition of the component polymers and thus desired physical and mechanical
properties can be achieved. For example, a small amount of PVC when mixed
with natural rubber, the product shows improved resistance for heat, light and
chemical substances. Similarly, the presence of small amount of nitrile rubber in
PVC significantly lowers the 7, of the product making it flexible and easily
processible. Polyblends made of polystyrene and polyphenylene oxide
commercially known as ‘Noryl’ are compatible blends, which provide improved
toughness, mechanical properties and heat resistance as compared to polystyrene
alone. Polyelectrolyte blends (often called polyelectrolyte complexes) have
tremendous applications in medical science.
The main use of incompatible polyblends is to impove the impact strength of
brittle and glassy polymers. The most known example belonging to this calss of
polyblends is of high impact polystyrene (HIPS). In the presence of the rubber
phase, the impact strength of polystyrene isconsiderably improved. The inclusion

of rubbery material in the matrix of polystyrene forms fine ‘cracks’. Nylon-
phenolic blends find application as ablative heat shields on space vehicles. A
new class of immiscible blends that has been developed is the so called high
performance blends. A promising example is of polycarbonate blended with
polybutylene terephthalate. Because both the polymers are in almost equal amount,
the two phase coexists in an intricatesinterpenetrating network. It is highly resistant
to heat and solvent and possesses long durability. It is used in place of metals in
automotive components such as bumpers.
8.10 Polymer Composites

A composite, in the broadest sense, is simply a material containing more than
one component. Any such composition that comprise two or more materials as
separate phases, at least one of which is a polymer can be called as polymer
composite. By combining a polymer with another material, such as glass, carbon,
or another polymer, it is often possible to obtain unique combinations or levels
of properties. Typical examples of synthetic polymeric composities include glass-
, carbon-, or polymer-fiber-reinforced thermoplastic or thermosetting resins, carbon-
reinforced rubber, polymer blends, silica- or mica- reinforced resins, and polymer-
bonded or -impregnated concrete or wood. Coating formulations (pigment-binder
combinations) and crystalline polymers (crystallites in an amorphous polymer
matrix) can also be called as composites. Typical naturally occurring composites
include wood (cellulosic fibers bonded with lignin) and bone (minerals bonded
with collagen). On the other hand, polymeric compositions compounded with a
plasticizer or very low proportions of pigments or processing acids are not
ordinarily considered as composites.
Usually, composites have properties superior to the properties (particularly
strength-to-weight) of its components. In polymer based composites, the reinforced
fibres and fillers add tensile strength and stiffness. The dimensional stability
(low shrinkage during parts fabrication) is also improved. The behaviour of
composites depends upon the volume fractions of the phases, their shape, and on
the nature of the constituents and their interfaces. High-modulus reinforcements
can stiff a low-modulus matrix, but fibers and platelets are more effective than
spheres. Rubbery inclusions lower the stiffness through they are inherently less
strong.
8.11 Inter Penetrating Network (IPN) Polymers

IPNs are exciting polymer materials and can be designed as per the intellectual
imagination and practical requirement. IPNs represent a unique topology of
entanglement of two polymers out of which at least one is synthesized or cross-
linked in presence of the other. The entanglement of polymer chains is such that
each of it macroscopicaly or their phases microscopically can not be separated
physically. Thus IPNs belong to a broad class of polyblends but possess unique
and diverse properties than the later. The primary condition for IPN formation is
that the constituent polymers should be compatible with each other and should
not form any chemical links. The IPN network results only by physicl forces.
The first synthetic. IPN reported is based on two polymers of cross-linked
polystyrene and polydivinylbenzene. Over the period of time several synthetic
routes have been developed for preparing IPNs. In fact, IPNs are classified
mostly by the method of their synthesis. Following types can be conidered; (i)
Sequential IPNs—a cross-linked polymer is swollen in a solvent media which it
self is a monomer. Then other active agents such as cross-linking agents and
initiators are added to solvent media. Then the second monomer is polymerized
in situ to get the IPN, (ii) Simultaneous IPNs—the synthesis of this type of IPNs
involves two independent non-interfering reactions that can simultaneously be
run under the same conditions and in the same reaction vessel. The reactions for
example polycondensation and polyaddition which take place with different
mechanisms, are carried out in the same container using different monomers,
IPNs can be formed as a result of physical links between the polymers and (iii)
Semi IPNs—these networks are formed essentially by grafting of polymers to
another linear counter part. Then curing or cross-linking of the grafted part
yields a semi IPN. Semi IPNs in fact are of two types; first type consists of a
semi IPN with polymer I in cross-liked form and polymer I in linear form and
the second type has a semi IPN polymer I in linear form and polymer II is cross-
linked.
Besides the above IPNs, two more additional classes of networks have been
prepared. In the first class an emulsion, (for example) of a elastometric polymer
I is mixed with the emulsion of elastomertric polymer II and then cross-linking
is done by evaporating the solvent media and allowing a film formation on a
substrate. These networks ar called as interpenetrating elastometric networks.
The second class of networks are obtained by emulsion polymerisation of a
monomer II in a original seed latex of already cross-linked polymer I. It is
however essential to add cross-linking agent during the subsequent emulsion
polymerisation for the formation of IPN structures. This type of IPNs are called
latex IPNs.
Most IPNs synthesised so far are based on alkly acrylates, styrene,
divinylbenzene, urethane, urea, acrylic acid or acrylates, dimethylsiloxanes,
propylene oxide and acrylonitrile monomers. However, it is to be kept in mind
that the actual IPN synthesis involves a preformed cured/uncured polymer out of
any of the above monomer and polymerisation of second monomer. The
combination of two polymers is chosen such that both of them should have good
compatibility and phase homogeneity. The pre- and post cross-linking are achieved
in the usual way i.e. either by a cross-linking agent to the unsaturation in the
chain or generating macro free radicals within the chain.
IPNs have great advantage over the other polymer combinations. If in the
IPN, one of the polymers is elastometric and the other is plastic at the use
temperature, the combination of both of them yields synergistic behaviour in
properties. For example, depending upon from the phase composition in the final
IPN, a reinforced rubber or high impact resistance thermoplastic can be prepared.
The factors that play a decisive role in the formation of any class of IPNs are (i)
are compatibility of polymer chains, (ii) weight fracton of each polymer as well
as the mobility of the units within their chains, (iii) relative rate of reaction and
network formation within the chain and (iv) average molecular weight of cross-
link.
Application of IPNs
IPNs represent the zenithal ingenuity of synthetic polymer chemists as well as
polymer technologists. The major advantage of these systems is that the combination
of two dissimilar polymers results into a network with useful properties, which
are not found in the respective individual polymers. The IPNs can be easily
casted into tough films. Several applications have been forecasted out of IPNs.
Table 8 (c) summarises the possible application areas of IPNs.
Table 8(c) Areas of application of IPNs
Area of application Types of IPN
Ion exchange resins (i) Network of polystyrene and polydivinybenzene and

polymethacrylic acid and polydivinylbenzenes
(ii) Network of polyethylene and cross-linked polystyrene
(chloromethylate followed by aminated) and divinylbenzene
polymers
Microencapsulation Hydrogel beads of 2-hydroxymethacrylate and N-viny]
(drug delivery and pyrrollidone copolymers cross-linked with poly n-
carbonless carbon (butylene oxide) swollen in mixture of diisocynate and
paper, etc.) diol and triols to yields polyurethane based IPNs
Semipermeable Anions exchange resins based on polyethylene and
membrances for cross-linked poly (N-vinyl pyridine) and cation
reverse OSMOSIS 4 exchange resins on polyethylene and polystyrene
sulfonates
Electrical application Polyurethane and polymethyl methacrylate or
as insulators polyurethane, epoxy resin and polymethyl! acrylates
8.12 Thermally Stable Polymers

Unlike metals, polymeric materials are not stable at high temperatures and
decompose. However, some polymers can withstand high temperature, and these
thermally stable polymers are quite useful in aeronautic and aerospace industries.
Some requirements of a thermally stable polymer are (a) it should have high
melting point and degree of crystallinity, (b) it should have structural features
that do not allow degradation by low energy process, (c) it should possess high
bond dissociation energy.
Polymers like poly (para-phenylene), polythiazoles, polyimides, polyphenylene
oxide, polyphenylene sulphide etc. are some examples of thermally stable polymers
(for structures see appendix). Thermal stability often results from aromatic rings
in the chain which impart rigidity, high bond energy and low degree of reactivity.
Ladder and spiro polymers (schematically shown in Fig. 8.18) are non-cross-
linked polymers in which two molecular chains are joined to each other.
Such polymers could be soluble and fusible and may possess superior thermal
H +B
HC ‘ 2 | 0 ) O
iG: (
CG)
Be each AiG ne O O O
Fig. 8.18 (a) Ladder polymer obtained from the pyrolysis of polyacrylonitrile
(b) spiropolymers
stability. Among ladder polymers are cyclized/dehydrogenated polyacrylonitrile

(carbon fiber), poly benzimidazopyrolones and polyquinoxalines etc.
8.13 Liquid Crystalline Polymers

The molecules in a liquid crystalline material have a restricted mobility which
maintains a degree of order compared to a true liquid. This results to anisotropy
(i.e. the properties depend on the direction in which they are measured in contrast
to isotropy shown by liquids). Liquid crystals are often called mesomorphic
phases and are apparently between a crystalline solid and a normal liquid. Low
molecular weight substances, which exhibit liquid crystalline behaviour tend to
be rather rigid with rod- or disc- like shapes. The liquid crystalline behaviour
originates in the form of long-range order extending over many millions of
molecules. Here, although the individual molecules are in constant motion, as
those are in liquids, there is a rapid fall off in probability that the axis (or plane)
of any particular molecule will deviate far in terms of the angle from the most
probable direction at any instant.
There are two broad classes of liquid crystals, nematic (have only longitudinal
orientation) and smectic (possess a pronounced layering tendency). Further the
liquid crystals can also be classified by the method of developing the crystalline
order in the material. The materials made by heating a substance are called
thermotropic. Those which do organise into liquid crystalline form (often surface
active agents in concentrated solution form such structures) are called lyotropic
liquid crystals. The organisation of molecules in nematic and smectic classes of
liquid crystalline order is depicted in Fig. 8.19.
Polymeric materials possessing liquid crystalline (LC) behaviour are called
liquid crystalline polymers. The best known example of liquid crystal polymer
is that of an aromatic polyamide, ‘kevlar’. Apart from the liquid crystal polymers
where the main chain is responsible for this behaviour, interest has also been
shown to produce liquid crystal polymers where LC property originates rather
due to its rigid side chains. Liquid crystal polymers have a varied field of
applications.
8.14 Telechelic Polymers (Functional Polymers)

Functional polymers are iow molecular weight (~ 500—10,000) substances and
contain functional groups like -OH, COOH, -SH, -HC=CH,, -N=C=O ete.
Thus they are also called as functional oligomers. These functional groups are
present at the ends of the molecule or distributed over the chain. These substances
rey
(oriented)
noone (layered, oriented)
Fig. 8.19 General representation of liquid crystalline order in (a) nematic and
(b) smectic forms of liquid crystals
can be obtained using known methods usually employed in preparing polymers

by suitably adjusting the reaction, whereby the introduction of functional groups
takes place simultaneously or afterwards. The controlled degradation of high
molecular weight polymers also serves as the synthetic route for functional
oligomers. The introduction of functional groups takes place in free radical
addition polymerisation by using initiators, chain transfer agents and/or by
monomers containing functional groups. For example, an initiator of peroxide or
diazo type can lead to a functional polymer. The polycondnsation method can be
employed for making functional oligomers. The growth of an high molecular
weight chain canbe prevented by the nonstochiometric quantities of two monomers
e.g. a reaction between a diol and a diacid with excess of diol will result in
oligomers with functional hydroxyl groups. These functional oligomers are also
called as telechelic polymers.
Functional oligomers can possess different chain composition and different
end groups. Thus, a variety of chemical reactions are possible. These can be
conveniently used to prepare block copolymers and to develop cross-links. Due
to their low viscosity, low toxicity (free from solvent) and presence of chemically
active functional groups, these oligomers have a large number of applications.
These can be used directly in the synthesis of new polymeric materials. The
polar functional groups make these telechelic polymers behave like amphiphilic
molecules and are used as emulsifiers, dispersing agents, in surface modification
(e.g. of fillers pigments, fibres etc.), to increase compatibility with solvents or
with polymers. The uses of telechelic polymers as plasticizer (due to their low
volatility), in liquid/liquid chromatography for purification of enzymes, in the
synthesis of useful block and graft copolymers, cross-linkable elastomers in
adhesive, paint and printing technology are well known.
8.15 Polymer Microgels

Polymer microgels do form in solution depending upon the structure of polymer
and the interaction of polymer molecules with solvent. The microgel structures
are intermediate between branch and microscopically cross-linked systems. Their
overall dimensions are still comparable with those of high molecular weight
linear polymers. It is difficult to precisely define a microgel but these can be
illustrated well by schematic means (see Fig. 8.20). Such microgels are often
observed for biopolymers like proteins and polysaccharides. Microgels possess
characteristic features such as they dissolve (networks only swell) in certain
er
solvents but their conformation is nearly fixed (unilke linear polymers which
show innumerable conformations) and they can be processed like linear polymers
but the final product shows characteristic network behaviour. Microgels from
synthetic polymers can be obtained by the following two routes.
Linear polymer Branched polymer Microgel Network

Fig. 8.20 Schematic representation of gels of polymer networks
Type A. microgles
The addition of multifunctional monomers to a polymerising system usually
forms network poymers. However, the advantage of network polymers is that
they show gelation when dissolved in solvents even in low concentrations.
Type B. microgels
These can be obtained by cross-linking polymers in restricted volume to avoid
network formation. An easy approach is to do cross-linking in microemulsion
polymerisation where the microemulsion droplets (swollen surfactant micelle,
containing polymer droplets) grow and form microgels. Besides these microgel
structures, which are homogeneous, more complex microgels can also be prepared.
These differ in molecular chemistry and can have different features, each with
potential applications. Such complex structured microgels are schematically shown
in Fig. 8.21.
Homogeneous microgels are filtered for optically transparent ‘high impact’
polymers. These microgels embedded in the matrix of linear polymer stabilise
the whole structure by distributing the mechanical tension. A polymer can be
achieved in different useful topological forms using microgels. Functionalised
microgels are good catalysts in nonaqueous media and act as stabilizers in complex
coating formulation.
8.16 Biomedical Polymers

Polymers have become most active materials and cover a multitude of different
(b) (c) (d)

Fig. 8.21 Structure of (a) hollow micronetwork, (b) macroscopic microgel, (c) core-
shell microgel and (d) functionalised spheres
aspects from inorganic macromolecules to natural polymers; the latter are of

utmost importance for living systems. One needs only to think of natural
macromolecules such as the proteins (enzymes), the nucleic acids (DNA and
RNA), the polysaccharides and others. It is not unlikely that many of the diseases
have their origins actually in abnormal macromolecules, leading to abnorml
reactions in the living systems. Synthetic polymers have gained much medical
interest in recent years and are being used for a variety of purposes viz. as
implant materials, as carriers for biomolecules, as drugs etc.
As implant materials
Several synthetic polymers have been used as implant materials; a few important
ones are polyethylene, polyetrafluoroethylene, polyesters, polysulfones,
polyurethanes, acrylics and silicones. Polytethylene is used for articulation surfaces
in joints, in implants and in repair of chest wall and diaphragm.
Polytetrafluoroethylene, a most inert polymer with lowest frictional coefficient
is used as a+blood vessel replacement and in otology prosthesis.
Polyethyleneterephthalate, the fibrous polymer, is used in knit arterial prosthesis
and as non-absorbable sutures. Polysulfones, which are transparent thermoplastic
material and exceptionally tough and resistant to high temperatures, are used in
heart valve and paces components as well as in neurological implants. Polyurethane
are noted for their high strength, aberration and tear resistance and are employed
as implant materials. Acrylic polymers, e.g. PMMA (better known as Plexiglas
or Lucite), polyhydroxyethylmethacrylate are transparent plastics and often used
as implant in the eye after cataract surgery. These polymers constitute hard and
soft contact lenses. Applications of silicones as implant materials are diversified
due to their nontoxic nature and biocompatibility. Silicone rubber serves a variety
of purposes in eye surgery. Silicone rubber tear ducts can be implanted to serve
as a means of controlling glaucoma. Silicone adhesives are used to cover the
third degree burns and making artificial skin as well. Use of silicones in prosthesis,
e.g. mammary and panile prosthesis is well known. Artifical breast and a totally
implantable hydraulically driven total cardiac prosthesis are constructed with
silicone-urethane copolymers. Carbon fibres, obtained by heating polyacrylonitrile
at high temperatures, find application as implant materials as such or as composites
with high molecular weight polyethylene or polytetrafluroethylene.
As carriers of bioactive substances (Immobilisation of bioactive molecules)

It is known that various bioactive materals like enzymes, pesticides, drugs can
be attached to an inert polymeric carrier without any loss in their activity. Enzyme
attachment onto a polymeric support (immobilisation) is a most fascinating area
of research and has several medical, analytical and industrial applications. The
immobilization not only imparts greater stability to the enzyme but also presents
an excellent method for investigation of enzyme function in metabolic process.
Further, repeated use of immobilised enzyme is possible. The various ways of
immobilisation of enzyme on to a polymeric support are adsorption, cross-linking,
covalent bonding and microencapsulation etc. The polymers which have been
used as support materials are many, a few important of them are cellulose and its
derivatives, agarose, polystyrene, nylon, ethylene-maleic anhydride copolymers
etc. Medical applications of contolled drug release systems also involve polymeric
materials. Polymers are ideal candidates for subcutaneous implants since they
are not absorbed orally and generally have short in vivo half lives. Examples of
subcutaneous implants are of insulin, interferon, growth hormones and vaccines.
Among several polymers used in controlled drug release are nylon, polyacrylamide,
cellulose and its derivatives, biodegradable polymers, like polylactic acid and
polyglycollic acid.
Cell labelling
The influence of polymeric microspheres in the studies of biological systems is
just in the beginning stage. Polymeric spheres to which biological moieties have
been attached are being used as immunoadsorbents for antigen and antibody
purification and labelling at the cell surface. Cell labelling can be achieved by
electrostatic or immunological interaction between the polymeric microspheres
and the cell surface.
Polymeric drugs
With the development of polymer research it has now been possible to synthesize
a tailor-made macromolecule, i.e. a polymer with predetermined structure, discrete
molecular weight and with specific functional groups with desired physiological
activity etc. In spite of many positive results in the investigation on the compatibility
or long lasting activity, no decisive breakthrough for a clinical application of
polymeric drugs has so far been realised. Polymeric drugs are advantageous in
respect that they exhibit delayed action, prolongation of activity, decreased rate
of drug metabolism and drug excretion. A number of polymeric drugs have been
developed as antibiotics such as those based on the structure of penicillin.
Polyvinylpyridine-N-oxide has been put in clinical use to inhibit silicotic fibrosis.
Polyvinyl pyrrolidone is known for its use as blood plasma extender. Many
physiologically active monomers lose their activity in the polymeric form but a
few others exhibit enhanced activity. L-lysine, which has apparently no antibacterial
activity as a monomer, is very active against E. Coli and S. Aureus. Urea-
formaldehyde polymer has been used as antibacterial and antifungal agent.
Polyanionic drugs are very valuable substances. Various surface active polymers,
e.g. nonyl phenyl ether of polyoxyethylene (Tritons) have been tested for
antituberculosis. Table 8(d) lists medicinal uses of some polymeric drugs. In
brief, it can be realised that polymeric materials, both natural and synthetic, play
crucial role in life processes.
Table 8(d) Polymers as drug materials
Drug type examples of polymers

a ee ee eee ee a re ee ee
Antibacterial agent Quaternary ammonium polymers, polyanionic polymers,
polypeptides
Antifungal agent Polyanionic polymers
Antiviral agent Polyanionic Polymers
Anticoagulatns Polyanionic polymers, heparin
Antitumor agent Polyanionic polymers
Plasma extenders Polyvinylpyrrolidone, dextran, gelatin
Antisilicosis Poly-N-oxides
8.17 Polymeric Supports for Solid Phase Synthesis

In 1963, Merrifield introduced a new concept for the synthesis of peptides using
cross-linked polystyrene beads with chlorometly! groups. The first amino acid of
the proposed polypeptide chain was attached by its carboxylic groups to the
reactive site. The second amino acid, with all but one of its reactive groups
protected was coupled to the first amino acid, leaving the protective dipeptide
formerly bounded to the support. This could be filtered and washed thoroughly.
In this way the different amino groups were attached in the desired sequence.
After the desired sequence of amino acids was assembled, polypeptide was
removed from the support materials by selectively breaking the bond that held
the polymer and polypeptide together. Now the polypeptide with desired sequence
of amino acids was free and dissolved in solution, could be removed from the
insoluble solid support and was purified by conventional methods.
The use of polymer supports for organic synthesis can be easily understood
because, the functional group X, linked to the polymeric support can be replaced
by the desired functional group Y, which can be recovered from the reaction
medium for further reaction with other substances.
The solid phase synthesis has the following advantages: (a) excess quantities
of unattached reagents may be employed to obtain high yields, (b) the polymeric
support can be recycled and (c) the reaction is simplified by the insoluble polymer
support. Majority of solid phase synthesis reactions have been carried out using
cross-linked polystyrene (easily and economically prepared by copolymerising
styrene with small amount of divinylbenzene). The stable polystyrene beads can
be conveniently functionalised by halogenation, halomethylation, acylation,
metallation etc.
Merrifield’s solid phase synthesis has resulted to an automatic polypeptide
synthesizer where the synthesis can be achieved at greater ease. This method is
likely to provide large scale mnufacture of polypeptides, like insulin, enzymes
and nucleic acids which have potential applications. These can contribute to the
production of insulin (for treatment of diabetic patients), more efficient synthetic
enzymes for biomedical and industrial use and in the understanding of mechanism
of enzyme action versus their structures. Merrifield’s Nobel prize (1984) winning
work on the synthesis of polypeptides using insoluble cross-linked polymeric
materials as supports has stimulated the use of this technique for organic synthesis
8.18 Polymers in Combating Environmental Pollution

Polymers paly an ever-increasing role in the field of pollution. These are becoming
more prominent in controlling all types of pollution namely water, air and solid
waste. To combat water pollution, polyelectrolytes such as high molecular weight
polyacrylamides are frequently used as flocculants and coagulants. Their use as
ion-exchange resins, e.g. cross-linked polystyrene sulfonate is well known.
Membranes for reverse osmosis (for desalination purpose) are made of polymers
and complex formation between metal ions and polyelectrolytes may provide
good product. In air pollution, with the advancement of adsorption-desorption
process, new polymers are designed with side groups which react very fast with
air polluting gases and releasing them under different conditions for recycling
into respective industrial processes. Pyrolysis of polymers may be useful for
solid waste pollution which is becoming a serious problem.
8.19 Polymers as Chemical Reagents

Polymers are now being used as dehydrogenating agents, as catalysts in dehydration,
antioxidants and decomposition reactions. The advantage of using polymers as
catalyst is that with polymers, no compound other than the dehydrogenated
product is formed. Heat resistant polymers, e.g. pyrolysed polyacrylonitrile (with
condensed pyridine rings acting as strong hydrogen acceptor) are used in
dehydrogenating olefinic compounds in vapour phase at high temperatures.
Pyrolysed polyacrylonitrile causes a double bond shift as well as cis-trans
isomerisation in olefinic compounds such as 1-butane. Polymers with conjugated
double bond or rings are good catalysts for autooxidation reactions as shown in
the following scheme.
CHy CHES CrE SY!‘Qis3Bose RO

Pyrolysed PAN
Chye=C= Chi Cre
-H
Pyrolysed PAN
CH,= C= C=CH,
Pyrolysed PAN
CH,;—CH—CH, —————+
CH, -C— CH,
ll
res
Pyrolysed PAN
( )-on
oyoman,
BYtONEGPAN (0
Polyelectrolytes
Dautzenberg, H., W. Jaeger, J. Kotz, B. Phillip, C. Seidel and D. Stscherbina, Polyelectrolytes,
Munich: Hanser, 1994.
Glass, J.E. (ed.), Polymers in Aqueous Media, Advances in Chemistry Series 223, Washington
DC: Am. Chem. Soc., 1989.
Hara, M. (ed.), Polyelectrolytes Science and Technology, New York: Marcel-Dekker,
19938
Mandel, M., Polyelectrolytes, in Encyclopedia of Polymer Science and Engineering, Vol.
11, 2nd ed. (Mark, H.F., N. Bikales, C.G. Oberberger and G. Menges eds.), p. 739
Oosawa, F. Polyelectrolytes, New York: Marcel and Dekker, 1971.
Selegny, E. (ed.), Polyelectrolytes, Dordrecht, D. Riedel, 1974.
Ionomers
Eisenberg, A., and M. King, Jon-Containing Polymers, New York: Academic Press, 1977.
Hara, M., (ed.), Polyelectrolytes: Science and Technology, New York: Marcel-Dekker,
1993.
Schmitz, K.S., Macroions in Solution and Colloidal Suspension, Weinheim: VCH, 1992.
Conducting Polymers
Blythe, A.R., Electrical Properties of Polymers, Cambridge: Cambridge Univ. Press, UK,
1980.
Dyson, R.W. (ed.), Specialty Polymers, New York: Chapman and Hall, 1987.
Goosey, M.T. (ed.), Plastics for Electronics, London: Elsevier Appl. Sci. Pub., 1985.
Kiess, H. (ed.), Conjugated Conducting Polymers, Berlin, Springer, 1992.
Radhakrishna, S., and A.K. Arof, (eds.), Polymeric Materials, New Delhi: Narosa, 1998.
Salaneck, W.R., I. Lundstrom, and B. Roanby, (eds.), Conjugated Polymers and Related
Materials, New York: Oxford Univ. Press, 1993.
Seymour, R.B. (ed.), Conductive Polymers, New York: Plenum Press, 1981.
Skotheim, T.A., (ed.), Handbook of Conducting Polymers, (2 vols.), New York: Marcel-
Dekker, 1986.
Solid Polymer Electrolytes

Gray, F.M., Solid Polymer Electrolytes, New York: VCH, 1991.
MacCallum, J.R., and J.R. Vincent, (eds.), Polymer Electrolyte Reviews, \st and 2nd ed.,
London: Elsevier Applied Science, 1987.
Radhakrishna, S., and A.K. Arof, (ed.), Polymeric Materials, New Delhi: Narosa, 1998.
Scrosati, B., (ed.), Second International Symposium on Polymer Electrolytes, London:
Elsevier Applied Science, 1990.
Skotheim, T.A. (ed.), Electro Responsive Molecular and Polymer Systems, Vol. 1, New
York: Marcel-Dekker, 1988.
Electroluminiscent Polymers
Friend, R.H., R.W. Gymer, A.B. Holmes, J.H. Burroughes, R.N. Marks, C. Taliani, D.D.C.
Bradley, D.A. Dos Santos, J.L. Bredas, M. Logdlund and W.R. Salaneck,
Electroluminiscene in Conjugated Polymer, a review article, Nature, 397, 121-128,
Loo:
Block Copolymers/Polyblends/Polymer Composites

Folkes, M.J. (eds.), Processing, Structure and Properties of Block Copolymers, New
York: Elsevier, 1985.
Goodman, I. (ed.), Developments in Block Copolymers, Barking: Appl. Sci. Publ., 1982.
Manson, J.A., and L.H. Sperling, Polymer Blends and Composites, New York: Plenum,
1976.
Meier, D.J. (ed.), Block Copolymers. Science and Technology, New York: Harwood Academic
Publ., 1983.
Nohay, A., and J.E. McGrath, Block Copolymers, Over view and Critical Survey, New
York: Academic Press, 1976.
Riess, G.P. Bahadur, and G. Hurtrez, Block copolymers in encyclopedia of Polymer
Science and Engineering 2nd ed. New York: Wiley, 1985
Thermoplastic Elastomers
Legge, N.R., G. Holden, H.E. Schroeder, (eds.), Thermoplastic Elastomers, Munchi:
Hanser, 1987. ;
Liquid Crystalline Polymers

Ciferri, A., W.R. Kringbaum, and R.B. Meyer, (eds.), Polymer Liquid Crystals, New York:
Academic Press, 1982.
Collyer, A.A., (ed.), Liguid Crystal Polymers; From Structure to Applications, New York:
Chapman and Hall, 1992.
Donald, A.M., and A.H. Windle, (eds.), Liquid Crystalline Polymers, Cambridge; Cambridge
Univ. Press, 1993.
Keller, A.M., Warner, A.M. Windle, (eds.), Self Order and Form in Polymeric Molecules,
London: Chapman and Hall, 1995.
For Other Topics

Burchard, W., S.B. Ross-Murphy, (eds.), Physical Networks, London: Elsevier Appl. Sci.,
1990.
Cowie, J.M.G., (ed.), Specialty Polymer, Vol. 1, New York: Plenum, 1981.
Miles, I.S., and S. Rostami, (eds.), Multicomponent Polymer Plastics, New York: Wiley,
1993.
Sperling, L.H., Interpenetrating Polymer Networks and Related Materials, New York:
Plenum, 1981.
Utracki, L.A., and A.P. Plochoko, /ndustrial Polymer Blends and Alloys, Munich: Hanser,
1985.
Utracki, L.A., Polymer Alloys and Blends, Munich: Hanser, 1989.
Appendix A
Laboratory Experiments
I Aim: Preparation of polystyrene by a free radical polymerisation

process
Requirements
Apparatus Balance, heavy walled glass tubes, stopper for glass tube, Buchner
funnel, filtration flask, separating funnel and filter papers etc..
Reagents and chemicals Styrene (monomer), 25% aqueous sodium hydroxide
solution, molecular sieves/drying agents (CaCl, or CaO), benzoyl peroxide,
azobisisobutyronitrile, toluene and methanol.
Procedure
(1) Wash styrene twice with 25 ml portions of 25% aqueous sodium hydroxide
solution in order to remove the inhibitor. Then wash twice with the 25 ml of
distilled water to remove any residual sodium hydroxide (2) Dry thus inhibitor
free monomer using molecular sieves or other drying agents (CaCl,) and store
immediately with a nitrogen blanket in a refrigerator (3) Add 50 ml of inhibitor
freed dry styrene to a heavily galssed test tube. Flush the tube with nitrogen and
add 1.0 g of benzoyl peroxide. Genetly shake the contents of the tube, stopper
and place the tube in an oil bath at 80°C for 1—2 hrs (4) When liquid becomes
syrupy and viscous before it gels, dissolve the contents in 50 ml of toluene and
then pour into 500 ml of methanol in order to precipitate polystyrene that is
formed (5) Isolate the polymer by filtration and dry the product (6) Weigh the
amount of polystyrene and report the yield.
II Aim: Preparation of polystyrene by an emulsion polymerisation

process
Requirements
Apparatus Three necked round bottom flask, mechanical stirrer, nitrogen cylinder
Reagents and chemicals Styrene monomer, triple distilled water, potassium

persulfate, sodium lauryl sulfate and ferric alum
Procedure
(1) Add 12 ml of distilled water, 7 ml of styrene monomer (inhibitor freed and
dried as in Exp. I), 4 ml of 0.7% (w/v) potassium persulfate solution, 10 ml of
4% sodium lauryl sulfate solution to a three necked round bottom flask equipped
with mechanical stirrer (2) Purge the contents of the flask with nitrogen till all
the dissolved air is removed (3) Place the flask on a water/oil bath and raise the
temperature to 80°C and allow the process to go on for three hours with continuous
stirring and to a maximum conversion of monomer to polymer (4) The contents
in the flasks would be quite turbid to milky appearance. Coagulate the emulsion
by adding alum solution to isolate the polystyrene formed. If needed, boil the
mixture for complete isolation (5) Filter the contents, wash with water and dry
the polystyrene powder. Determine the yield percentage based on the weight of
the polystyrene isolated
III Aim: Preparation of polystyrene by an anionic polymerisation method
Requirements
Apparatus Three necked round bottom flask, magnetic stirrer and bar (preferably
glass enclosed), water condenser, thermometer, septum, syringe, Buchner funnel,
Buchner flask, vacuum pump etc.
Reagents and chemicals Pre-dried inhibitor freed styrene monomer, n-butyl

lithium in n-hexane (2.5 mol dm°), tetrahydrofuran, methanol and 2-butanone,
(all the three solvents are to be completely dried and freshly distilled), stoppered
separating funnel with standard point tail
Procedure
(1) Fit the three necked flask with septum, water condenser and thermometer
(through a mercury seal). Add a glass encased magnetic stirring bar (2) Add 6 ml
of dry and freshly distilled THF using a syringe into the flask (3) With a careful
control of temperature around 20°C, add the styrene monomer drop wise (0.2
ml/sec) until 2.0 ml has been added. The reaction mixture turns deep red due to
the formation of styrllithium. Continue adding the remaining styrene at the same
rate. Once all the styrene is added, wait for 10-15 minutes (4) Add 1.0 ml of the
methanol to quench the reaction (5) Precipitate the polystyrene by adding excess
of cold methanol (about 5. ml). Further purification of polystyrene can be done
by dissolving it in 2-butanone and re-precipitating again by addition of cold and
dry methanol. Vacuum dry the purified polystyrene and estimate the yield of
polymerisation.
Note It is very important to keep the equipment and reactants dry as well as
oxygen free during the course of anionic polymerisation, otherwise chain
termination can take place. Solvents and monomer have to be delivered via
syringe and no additions can be made by keeping the flask open to air.
Appendix A 297
IV Aim: To polymerise styrene by cationic polymerisation process
Requirements
Apparatus Two large thick walled test tubes, septum for test tubes, hypodermic
syringe, sintered glass filter, filtration flask, ice water bath, Erlenmeyer flask and
vacuum pump etc.
é
Reagents and chemicals Pre dried and freshly distilled styrene monomer, 25%
(w/v) aqueous sodium hydroxide solution, methylene chloride, stannic chloride
(SnCl4) and methanol.
Procedure
(1) Take two large thick walled test tubes fitted with septum and needle to act as
pressure relief valve. Label them as I and II. To each add 40 and 30 ml of dry
methylene chloride respectively via a hypodermic syringe (2) Lower both the
test tubes into an ice water bath so that they attain a temperature close to 0°C (3)
Inject 0.9 ml of stannic chloride to the tube I. Inject 6.5 ml of styrene monomer
to the tube II and keep it cold for about 15 to 20 minutes at 0°C. Again through
syringe add 4—5 ml of cooled stannic chloride solution from test tube I to test
tube II. This marks the start of cationic polymerisation process (4) After 20-25
minutes remove the test tube II from the ice bath. Precipitate the polystyrene by
taking out the tube II from ice water bath and pouring the polymerised reaction
mixture into methanol (about 10 ml) taken in another flask (5) Dry the product
in a vacuum oven for 30 minutes after filtering and giving methanol washes (6)
Weigh polystyrene and report its yield
V Aim: Preparation of solid epoxy resin
Requirements
Apparatus Three necked flask, water condenser, mechanical stirrer and

thermometer etc.
Reagents and chemicals Bisphenol-A, epichlorohydrin and 10% aqueous solution
of sodium hydroxide
Procedure
(1) Charge the three necked flask with 15 g of bisphenol-A and 5 ml of 10%
aqueous sodium hydroxide. Equip the flask with stirrer, condenser, dropping
funnel and thermometer via a mercury seal (2) Place the flask with its contents
on a water bath. Warm the contents of the flask to 45°C and allow the mixing to
go on for 10-15 minutes (3) Then add 10 g of epichlorohydrin rapidly maintaining
stirring uniform (4) Heat the mixture then to a temperature of about 85°C and
allow the polymerisation to go on for about 1| hr (5) The reaction mixture separates
into two phases. Siphon off the aqueous layer. Wash the solid product with hot
water until the washed water is neutral to the litmus paper. Dry the resin in an air
oven at 130°C and report the yield.
VI Aim: Preparation of liquid epoxy resin
Requirements
Apparatus Three necked flask (500 ml), stirrer, thermometer, vacuum distillation
assembly, water condenser, evaporating dish, dropping funnel and Buchner funnel
etc.
Reagents and chemicals—tecrystallised bisphenol-A, epichlorohydrin (good grade),

sodium hydroxide and toluene
Procedure
(1) Set up the three necked flask reactor on a water bath. Add bisphenol-A
(25 g) and epichlorohydrin (15 ml) with stirring on. Heat the mixture to 70°C by
raising the temperature of the water bath (2) Meanwhile prepare 40-45% aqueous
sodium hydroxide solution and add the alkali to the reactor drop wise through a
dropping funnel over a period of | hr (3) Keep the temperature of the reactor
around 70°C through the addition of alkali. Continue the reaction for another
30 minutes after the addtion of alkali (4) Place the reactor in a cold water bath
to allow the contents to reach room temperature (5) Set up the vacuum pump
assembly through the receiver and water condenser. Heat the contents of the
reactor to 70°C (6) Vacuum distill water and un-reacted epichlorohydrin from
the reaction vessel (7) Disconnect vacuum distillation set up and place the reactor
in cold water bath to bring back the contents to room temperature (8) Add 20 ml
of toluene to the reactor and filter the mixture on a Buchner funnel to remove
precipitated NaCl (9) Place the filtrate back into the reactor and again set up the
vacuum distillation assembly. Raise the temperature of the reactor to 70°C under
vacuum and distill out the toluene completely (10) Transfer the resin left to an
evaporating dish and gently heat it using low Bunsen flame in a fuming cupboard.
Continue heating to 140°C till all the volatile matter disappears. Weigh the
liquid epoxy resin and report its yield.
VII Aim: Determination of epoxide equivalent of the given epoxy resin by

the pyridinium chloride method
Requirements
Apparatus Round bottom flask, water condenser, burette, sample test tubes
(small glass vials)
Reagents and chemicals Epoxy resin sample, 0.2 N pyridinium chloride—

pyridine reagent (by dissolving 17 ml of conc. HCI into 1 liter of pyridine)
standard 0.5 N methanolic NaOH, phenolphthalein indicator solution
Procedure
(1) Dissolve about | g of epoxy resin in 25 ml pyridinium chloride—pyridine
reagent by gentle stirring and if necessary warming (2) Take 25 ml of pyridinium
chloride in pyridine solution in another flask (this set is to be considered as
,». Appendix A 299
blank) (3) Fit the water condenser for both the flasks and reflux the contents for
1 hr (4) Cool the solution with condenser fitted on and add 15 ml methanol. Add
few drops of phenolphthalein indicator and titrate the contents with 0.5 N methanolic
NaOH (5) Calculate the epoxide equivalent using the formula
16 x wt. of the sample in gram

epoxide equivalent = ———H—H——___=—__
gm of oxirane oxygen in the sample
gm of oxirane oxygen in sample = [B — S] x N x 0.016
where B = ml of NaOH used for titration of the blank solution till end point and
S = ml of NaOH consumed for the titration of the sample solution till the end
point, N = normality of NaOH.
VIII Aim: Preparation of polysulphide rubber (thiokol)
Requirements
Apparatus Round bottom flask, water condenser, water bath, boiling chips,
thermometers etc.
Reagents and chemicals Sodium hydroxide, powdered sulphur, 1, 2-dichloroethane
Procedure
(1) Dissolve about 40 g of NaOH in about 800 ml of distilled water. Place the
solution in the round bottom flask and warm it on a water bath with water filled
condenser fitted (2) Add 13-15 g of powdered sulphur to the flask (3) The
contents are heated to reflux temperatures for 30-35 minutes (4) Cool the red
brown solution of NaS, by adding 500 ml of water to a temperature of 65—70°C
(5) Add 2 ml of 1, 2-dichloroethane and place 2-3 boiling chips. A two phase
mixture is formed. Reflux the mixture for 45 minutes by using mild heating
rates. A yellow rubber thiokol is formed (6) Cool the contents to room temperature
and wash the product well with water and dry it.
IX Aim: Preparation of polyacrylamide (PAM) by free radical

polymerisation
Requirements
Apparatus Three necked round bottom flask, reflux water condenser, nitrogen
inlet bent glass tube, nitrogen cylinder and water bath
Reagents and chemicals Recrystallised acrylamide monomer, AIBN, methanol,

ethyl acetate and distilled water
Procedure
(1) Dissolve about 2 g of pure acrylamide monomer in 500 ml of methanol and
place the solution in the round bottom flask. Prepare separately 0.2 mol dm?
AIBN solution in dry methanol. Add 2-5 ml of this solution to acrylamide
solution (2) Flush the nitrogen into the reaction flask with the reflux condenser
fitted on. Heat the contents to 65°C for to 1'/, hours. Intermittently shake the
flask (3) After the polymerisation is completed, poor the mixture into equal
amount of dry ethylacetate with efficient stirring to precipitate the polycrylamide.
The formed polymer is purified further first dissolving it in water and re-
precipitating twice with methanol. Dry the polymer and report the yield.
X Aim: Preparation of methacrylic acid-methacrylamide copolymer by

free radical polymerisation
Requirements
Apparatus—same as for PAM (Exp. IX)
Reagents and chemicals—pure methacrylic acid, recrystallised acrylamide,

potassium persulfate (K,S,Og), ethyl acetate and distilled water
Procedure
(1) Take both the methacrylic acid and methacrylamide monomers in the weight
ratio of 9:1 (total weight of both the monomers may be taken about 15—25 g) in
the three necked round bottom reaction flask. Add about 5 ml of 0.1% aqueous
solution of K,S,Og initiator (2) Flush the contents with nitrogen purging and
conduct the polymerisation by heating the contents to 70°C on water bath for
1 hr (3) The product obtained is cooled and re-precipitated twice with ethyl
acetate for removing the un-reacted monomers. The copolymer formed is then
dried and weighed for reporting yield.
XI Aim: Grafting of acrylamide onto polyvinyl! alcohol
Requirements
Apparatus Three necked reaction round bottom flask, glass water condenser,
mercury seal, thermometer, water bath, electric motor driven stirrer, nitrogen
cylinder
Reagents and chemicals Recrystallised acrylamide, polyvinyl alcohol (mol. wt.

> 30,000), ceric ammonium nitrate, 1N nitric acid, acetone and methanol
Procedure
(1) Set up the reaction assembly on a water bath with three necked flask fitted
with a glass water condenser and electric motor driven stirrer (2) Prepare the
polyvinyl alcohol (PVA) solution by adding 10 g of PVA into 10 ml of distilled
water and gently heating to 80°C. It may take 1—1.5 hours for clear solution to
be formed and hence this solution has to be prepared well ahead of starting the
practical (3) Introduce 10 ml of PVA solution into the reaction flask and purge
the nitrogen gas for about 10 minutes at 25°C. Then add 8 ml of 0.1 mol dm~™
solution of ceric ammonium nitrate prepared in 1 N HNO3. Raise the temperature
of the contents to 45—50°C (4) Allow the polymerisation and grafting for another
1 hour with continuous stirring and under nitrogen atmosphere. The solution’s
,. Appendix A 301
yellow color will then disappear. Stop stirring and allow the contents to cool
down to room temperature (5) Pour the solution with rapid stirring into a litre of
acetone to precipitate the copolymer. The precipitated copolymer is to be washed
with acetone and methanol and finally dried in vacuum at 70°C. Determine the
mole percentage of acrylamide in the copolymer by nitrogen estimation method.
XII Aim: Preparation of polymethyl methacrylate beads by pearl

polymerisation
Requirements
Apparatus Three necked flask, glass condenser, electric motor driven slow
speed stirrer, thermometer (with mercury seal), Buchner filtration apparatus
Reagents and chemicals Methyl methacrylate monomer, sodium hydroxide,

benzoyl peroxide, sodium phosphate, lig. ammonia, calcium chloride, polyvinyl
alcohol, hydrochloric acid and double distilled water.
Procedure
(1) Free the freshly vacuum distilled methyl methacrylate monomer from the
stabiliser by washing it thrice with 20 ml of 2% (w/v) sodium hydroxide aqueous
solutions and with 50 ml of distilled water (2) Set up a three necked reaction
flask in the water bath. Fit the stirrer and glass condenser (3) Place a mixture of
120 ml of distilled water, 3.5 ml of 10% (w/v) sodium phosphate aqueous solution,
5 ml of ammonia in the reaction flask. Stir the mixture with specially designed
thick walled glass stirring rod. The shape of the glass stirring piece is very
important. It should be in the form of a thick glass sheet with two portions out
of which the bottom portion is in oval shape and the upper part is of square
shape. Maintain a speed of 60-100 rpm with the low speed stirrer unit (4) Add
50 ml of distilled water and 7.5 ml of 10% (w/v) calcium chloride solution drop
wise through the dropping funnel over a period of 1.5—2 hours. Add 10 ml of 1%
(w/v) of PVA aqueous solution. Then fill water bath with water at a temperature
of 70°C and raise the temperature to 80°C during the first 30 minutes of
polymerisation (5) Add 100 ml of stabiliser freed methyl methacrylate monomer
drop wise using a droping funnel over a 15 minutes time period in which 1.0 g
of benzoyl peroxide is dissolved. Extreme care should be taken to maintain the
slow speed of the glass stirrer piece, so that a stable dispersion of methyl
methacrylate droplets is formed (6) Allow the polymerisation to continue at a
constant stirrer speed and temperature for a minimum time of 1.5 hours. Care
should be taken that the stirrer does not stop during this time and the suspension
does not gellify. After this time observe visually that small tiny and transparent
beads are formed (7) Dismantle the reaction flask assembly and filter off the
beads of polymethyl methacrylate by means of a Buchner vacuum filtration
apparatus. Wash the beads with 2% (w/v) hydrochloric acid and then with distilled
water and finally dry at 40-45°C in an electric oven. Weight the dried beads and
report the yield.
XIII Aim: Preparation of Polyvinyl Alcohol (PVA)
Requirements
Apparatus Three necked round bottom flask, glass condenser, water bath,
Buchner funnel and thermometer
Reagents and chemicals Polyvinyl acetate (good commercial grade), anhydrous
freshly distilled methanol, potassium hydroxide, calcium chloride, distilled water
and acetone
Procedure
(1) Set up the three necked reaction flask on a water bath. Charge it with 3 g of
polyvinyl acetate (PVAc) and 75 ml of anhydrous methanol. Fit the flask with a
reflux water condenser attached to a CaCl, drying gaurd tube. Reflux the contents
until PVAc dissolves (25-30 minutes). Add 25 ml of anhydrous methanol containing
2 g of potassium hydroxide when the contents of the flask are still warm. Reflux
the mixture further for | hour (2) Polyvinyl alcohol formed due to the hydrolysis
of PVAc slowly gets precipitated from the solution as a fine powder. Collect the
product using a Buchner funnel and wash it with four 25 ml portions of anhydrous
methanol. Dry the powder partially dried PVA to a 300 ml beaker containing 100
ml hot water (80°C). Allow the polymer to be dissolved over another 30 minutes
(4) Add the PVA aqueous solution drop wise to a | litre beaker containing 200
ml of acetone. Stir the contents over a magnetic stirrer while addition is on.
Collect the final precipitated powder and air dry it on a Buchner funnel before
drying it to constant weight in a vacuum oven or desiccator at room temperature
over 24 hours period. Weigh the product and report the yield
XIV Aim: Determination of melting point, storing time and gel time of
phenolic resins
Requirements
Apparatus Melting point, capillary tubes, rubber bands, thermometer, beakers

stop watch, spatula, hot plate (electric), crucible
Reagents and chemicals Paraffin, resin sample (commercial phenol formaldehyde

rasin), hexamethylenetetramine
Procedure
(1) Grind finely a small amount of resin in a mortar and introduce it into a
melting point capillary tube. Attach the resin filled capillary tubes to the bottom
of thermometer and place it in a paraffin bath. Raise the temperature of the bath
by using an electric hot plate or Bunsen burner at a rate of 1°C per minute. Note
down the temperature at which melting starts and completes. Report this temperature
range as melting temperature for the resin (2) Take 10 g of finely powdered resin
sample in a petridash. Place the petridash on the surface of an oil bath (maintained
at 135—150°C) with the help of tongs. Hold the dish firmly. Then gently stir the
»~ Appendix A 303
molten resin with a spatula and note the time between the melting and hardening
of the resin. This time is known as storing time (3) Place finely ground 1 g resin
sample in a crucible and mix 0.1 g of finely powdered hexamethylenetetramine.
Place the crucible on an electric hot plate at 150°C. Move the resin backwards
and forwards with the spatula and note down the time interval between the
melting and gelation. This time is known as gel time.
4
XV Aim: Determination of molecular weight of polymer by amine end

group analysis
Requirements
Apparatus 100 ml three necked flasks with stoppers (glass), micro-burette,

heating mantle and controllers, magnetic stirrer, stirring motor, glass condenser,
small liquid nitrogen flask, small laboratory mill, aluminum weighing pan and
balance capable of measuring 0.0001 g.
Reagents and chemicals Commercially available or laboratory prepared

polyhexamethylene sebacamide (nylon 6,10), reagent grade phenol crystals, dry
methanol, 0.05, 0.1, 0.2, 0.15 or 1.0 N standardised hydrochloric acid, thymol
blue indicator (0.1% in distilled water).
Procedure
(1) The polyamide sample must be broken and ground into fine pieces not longer
than | mm in dimension. This is to be done in a laboratory ball mill. The
procedure takes 2.5 to 3 hours. Hence the sample has to be made ahead of time.
Polyamides and other reagents/chemicals used are extremely sensitive to moisture.
Hence care must be taken to avoid the exposure of sample, reagents and chemicals
to moisture or air. If needed the polyamide material should be cooled in nitrogen
before it is crushed, grounded and milled (2) Place 35 g of phenol and 20 ml of
methanol in each of the three 100 ml three necked flasks. Add finely ground and
accurately weighed (1.5—2.0 + 0.0001 g) three polyamide samples into each of
the flasks. Fit the flasks with stoppers and condenser (3) Reflux the contents till
all the sample is dissolved. Cool the flasks to room temperature and replace the
condenser with stirrer (4) Add 0.2 ml of thymol blue indicator solution to each
flask. Titrate the contents of the flask to a pink end point by fine addition of 0.2
ml of standardised HCI solution. The concentration of HCI solution has to be
selected in such a way that finite titer volumes are obtained. Calculate the amount
of HCI added (5) Calculate the molecular weight
M, = (sample wt. (g) X 1000)/(titre in ml x normality)
Degree of polymerisation = M,/Mp

where Mp is the mol. wt. of repeat unit
Tabulate your results and estimate a mean value of M,, for the sample from
the three calculated values
XVI Aim: Estimation of number average molecular weight by hydroxyl

end group analysis uf
Requirements
Apparatus 250 ml iodine flasks, 50 ml burette,10 ml pipettes, hot plate with

magnetic stirrer, aluminium weighing pan, balance for accurate weight measurement
(0.0001 g).
Reagents and chemicals Polyethylene glycol or any other hydroxy terminated

polymer, potassiumhydrogenphthalate, acetic anhydride (reagent grade), reagent
grade pyridine, phenolphthalein, cresol red and thymol blue indicators and n-
butanol.
Procedure
Hydroxy equivalent: (1) Prepare ahead of time 0.4 N methanolic sodium hydroxide
(one litter quantity). Standardise the solution against potassium hydrogen phthalate
(0.5 N) using phenolphthalein indicator. Prepare the acetylating agent by dissolving
the acetic anhydride in pyridine. For a 250 ml of total volume, dissolve about
68.85 x N ml, where N = the normality of methanolic sodium hydroxide and the
rest is pyridine. Prepare the mixed indicator by adding | part 0.1% aqueous
cresol red to 3 parts 0.1% aqueous thymol blue (both these indicators have to be
neutralized with NaOH) (2) Weigh the 250 ml iodine flasks. Accurately weigh
the polymer sample into 250 ml iodine flasks. The weight of the polymer sample
to be taken depends upon the molecular weight of the sample. Following weights
of sample are recommended for appropriate molecular weights:
M, Weight (g)
400 Lee
800 1.8
1200 2.0
1600 pee
2000 3.0
(3) Carry out the following addition to the two flasks containing polymer sample
and also two other flasks with no sample (to be considered as blank) (i) 10 ml of
acetylating reagent (stopper immediately), (11) 10 ml of distilled water and 10 ml
of pyridine after placing the magnetic bar into the flask and placing the flasks on
a stirring hot plate, (iii) Heat the flasks for 5 minutes at approximately 100°C.
Remove the flasks from the stirring hot plates and cool to room temperatures (iv)
Add 10 ml of n-butanol to each of the cooled flasks. Add 5—6 drops of mixed
indicator. (v) Titrate the contents to a neutral end point with 0.04 N NaOH.
Record the titer values
Acid equivalent: (1) Accurately weigh 2-3 g of polymer sample into each of
the iodine flasks. Consider the other two flasks as blanks (2) Add 25 ml of
pyridine and place a magnetic bar in each of the flasks (3) Heat each of the flasks
»- Appendix A 305
on a hot plate at 105—-110°C until the sample is dissolved. Add 10 ml of distilled

water and heat for further 5 minutes. Cool the flasks to room temperature
(4) Add 10 ml of n-butanol and 5 drops of mixed indicator to each of the flasks
(5) Carry out the titration of the contents of all the flasks with 0.4 N NaOH to
the first blue end point. This end point is sensitive and fades rapidly (6) Calculate
the hydroxyl equivalent, acid equivalent and the average molecular weight of
the sample by using the following «elations,
(blank reading — sample reading) x normality of [NaOH]

y
Hydroxyl yl equivalent
equivalen =
Sample weight (g)
Number average molecular weight = 2000

hydroxyl equivalent + 2 (acid equivalent)
XVII Aim: Determination of viscosity average molecular weight of

polystyrene in toluene by dilute solution viscosity method
Requirements
Apparatus Constant temperature thermostatic bath, Ubbelohde viscometer with
efflux time greater than 120 seconds at 25°C, stop watch capable of registering
flow time up to + 0.1 sec. Sintered G4 and G5 glass funnels, rubber suction bulb,
100 ml volumetric flasks with standard joints, 10 and 25 ml stoppered volumetric
flasks and thermometer etc.
Reagents and chemicals Polystyrene, reagent grade toluene, chromic acid

solution (prepared as saturated potassium dichromate in conc. sulfuric acid)
Procedure $
(1) Prepare a stock 100 ml of polystyrene solution in dry toluene, first by adding
75 ml of toluene to priorily accurately weighed (about 2 g) polystyrene. Stopper
the flasks and agitate it gently. Allow about 24 hrs. time for complete dissolution
with agitation. Once the polymer is fully dissolved, make up the total volume to
100 ml. Magnetic stirring and heating facilitates complete and fast dissolution
(2) Filter the solution with sintered G4 funnel. Prepare 5 more solutions with
concentrations namely 1.5, 1.0, 0.75, 0.5 and 0.25% (w/v) by diluting the stock
solution with toluene. These diluted solutions are to be prepared in 25 ml quantity
of each (3) Clean the Ubbelohde viscometer by filling it with chromic acid over
night and repeated rinsing with distilled water. Dry it in hot oven. Deliver about
20 ml of dry toluene into viscometer. Place the viscometer in a constant temperature
water bath maintained electronically at 25 + 0.01°C. Allow the equilibrium to be
attained for 15 minutes. By using the suction rubber bulb and closing the pressure
relieve tube with a finger, allow the solvent to be sucked through capillary into
upper flow bulbs of viscometer. Then release the pressure and allow the solvent
to flow through. Start the stop watch when the bottom of the liquid meniscus
passes the upper timing mark. Stop the stop watch when bottom of the meniscus
touches the lower timing mark. Repeat this for three times and take the mean
value as the flow time of solvent, fg (sec) (4) Deliver the lowest concentration
solution of polystyrene into viscometer and measure the flow time three times as
described previously for the solvent. Take out the viscometer every time out to
deliver a fresh solution and measure its flow time, t. One can also do direct
dilutions in the viscometer using modified Ubbelohde versions (5) Calculate
various viscosity terms by using the flow times of solvent and each polymer
solutions by: 7, = t/to, Nyy = Nr — 1, Nred = Nsp/C and intrinsic viscosity [7] of
polymer solution is obtained by graphs as per using the Huggin’s relation:
Nop/C = [n] + kK [17] C

(6) Tabulate the results listing the concentration, C, average flow time, t, 1, Msp
and 1),.. Plot the graph of 1,,/C versus C and obtain [7] and k’ from the intercepts
and slopes by extrapolating to zero concentration (7) Estimate the viscosity
average molecular weight of polystyrene using Mark-Houwink relation:
[n] = K M,*
= 1.15 x 10+ M,°” for polystyrene in toluene
Note Mol. wt. of other polymers can be similarly determined by dissolving it

in a suitable solvent and measuring viscosity of dilute polymer solutions at fixed
temperature. For some common polymers, the value of K and @ are given in
Table 3(1).
XVIII Aim: Calculation of dimensions of polystyrene coil assuming a

freely jointed chain and from dilute solution viscosity data
Requirements
Apparatus Balance for accurate weight (0.0001g) measurement, constant

temperature thermostatic bath, Ubbelohde viscometer with efflux time greater than
120 seconds at 25°C, stop watch capable of registering flow time up to + 0.1 s.
Sintered G4 and GS glass funnels, rubber suction bulb, 100 ml volumetric flasks
with standard joints, 10 and 25 ml stoppered volumetric flasks and thermometer
Reagents and chemicals Cyclohexane, benzene, polystyrene, reagent grade

toluene, chromic acid solution (prepared as saturated potassium dichromate in
conc. sulfuric acid) etc.
Procedure
(1) Prepare 2% (w/v) stock polystyrene solutions in benzene (25°C) and
cyclohexane (34°C) (i.e. 6-temperature). Dilute the stock solution to required
concentration in the same manner as described in Exp. XVII. Care must be taken
to keep the polystyrene solutions at 34°C because it defines @conditions for
polystyrene (2) Measure the flow times for benzene (25°C), cyclohexane (34°C)
and polystyrene solutions in benzene (25°C) and polystyrene solutions in
cyclohexane (34°C) by the same procedure as Exp. XVII (3) Calculate n,, Nsps
Nrea and [nN] for both the sets (4) Dimensions of polystyrene chain: (i) calculate
~~ Appendix A 307
chain expansion factor, ‘a from the relation o =[Nben/ [leycthetay» Where [7] ben
= intrinsic viscosity of polystyrene in benzene or non 6-solvent solutions, [N]eyctheta)
= intrinsic viscosity in cyclohexane (34°C) or in @ conditions. (ii) Evaluate the
viscosity average molecular weight of polystyrene from intrinsic viscosities under
@ and non @ conditions by:
[Mlben = }.06 x 10 M,°”

[N]cytheta) = 0.82 x 10° M, KY
(ii1) From the My values in 8 and non @ condition calculate the degree of
polymerisation, DP as DP = mol. wt. of polystyrene/mol. wt. styrene repeat unit
(iv) Calculate number of bonds N in freely jointed chain by N = 2 DP. Then
evaluate the root mean square end-to-end distances ry and r2, by equation,
<7 > = b (2N)'””

where b = bond length = 1.54 A for C-C bond (v) the characteristic ratio of
dimensions, Cy is calculated as
Cy Ser Ce Spl 2
> rn
(vi) Finally calculate the steric or hindrance factor o, which is the measure of
thermodynamic chain flexibility of chain by using the equation
Cy = o°(1 — cos t/(1 + cos 7)

where T = valence of angle for a C-C single bond., i.e. 109.5°
XIX Aim: To qualitatively identify an unknown polymer by

thermogravimetry polymer finger printing
Requirements
Apparatus Thermogravimetric analyser, data acquisition system and recorder
plotter, Dewar flask, gas flow meter, calibrated weight standards, microbalance
(weight measurement accurate to + 0.0001 g)
Reagents and chemicals Source of dry and purified nitrogen, polymer samples
of polyethylene, high density polyethylene (HDPE), low density polyethylene
(LDPE), polystyrene, polymethyl methacrylate of syndiotactic and isotactic type
Procedure
(1) Consult the operational manual for the handling of instrument. Take the help
of specialist/analyst, if available (2) Weigh the pan and record the weight. Add
10-20 mg of polystyrene to the pan and reweigh. Record the weight (3) Run the
polystyrene sample on the instrument following a linear programmed temperature
usually 5/10 or 20°C/min till a final temperature of 550—600°C (4) Get the
recorded TG traces as weight % loss against temperature (This is thermogram).
Once the first run is completed, allow the instrument to cool to room temperature,
clean the pan and sample holders. Repeat the runs for other polymers i.e.
polyethylene and polymethyl methacrylate: Obtain the TG runs of as many
samples of these three polymers as possible. Get all the traces on a single graph
(5) Repeat the whole procedure with an unknown polymer sample freshly and
obtain the TG curve. By comparing the unknown TG trace with known plots,
identify the polymer. Attempt to analyse the thermal behaviour of polymer sample.
XX Aim: Determination of melting temperature, 7,,,, glass transition

temperatures, 7, and heat of fusion, AH; of a given polymer sample using
differential scanning calorimeter (DSC)
Requirements
Apparatus DSC instrument and all the other accessories needed for the gas
flow, accurate weight measurements and cooling system etc.
Reagents and chemicals Polystyrene, polyvinyl chloride and polymethyl

methacrylate
Procedure
(1) Weight out exactly 10-15 mg polymer sample onto the DSC sample container.
Place the sample cell on the plotform with an empty reference cell on the reference
plotform. Consult priorily the instrument manual for its operation, data acquisition
and plotting of results. If necessary, take the help of specialist technician (2) Run
the sample with an heating rate of 25 or 30°C/min. Obtain the DSC thermogram
(3) Look for the sudden change in the heat flow with respective to base line and
identify the exo or endotherms and their transition temperatures. Get the area
under the peak either by the data analyzer or manually by using a planimeter (4)
Calculate the heat of fusion (AH,) using the relation, AH; /(J/g) = (A/m) (BE
Aq,;), Where A = peak area in cm’, m = sample mass in mg, B = time scale in
min./cm, E = cell calibration coefficient at the temperature of measurement, Aq,
= Y axis scaling in mW/cm.
Some useful references for more laboratory experiments
A simple inexpensive molecular weight measurement of water soluble polymers using

microemulsions, J. Chem. Edu., 62, 545 (1985).
Determination of acrylonitrile/methyl methacrylate copolymer composition by infrared
spectroscopy, J. Chem. Edu., 60, 431, (1983).
Polyethylene glycol — A poor chemists crown, J. Chem. Edu., 60, 77, (1983).
Sulphonation of polystyrene-orientation and characterisation of an ion exchange resion in
organic chemistry, J. Chem. Edu., 66, 613 (1989).
Viscometric determination ofisoelectric point of a protein, J. Chem. Edu., 40, 468 (1963).
,. Appendix A 309
Bran, B.J., and Billmeyer, Jr. FW., Techniques of Polymer Synthesis and Characterisation,
Brydson, J.A., and Saunders, K.J., Experimental Plastics Technology, Methven Education
Ltd., 1970.
Collins. E.A., Bares. J., and Billmeyer Jr. RW., Experiments in’ Polymer Science, New
York: Wiley, 1973. i
Ke, B., Newer Methods of Polymer Characterisation, New York: Interscience Pub., 1964.
Mc Caffery E.M., Laboratory Preparation for Macromoleular chemistry, New York:
McGraw-Hill, 1970.
Pearce, E.M., Wright, C.E. and bordoloi, B.K., Laboratory Experiments in Polymer Synthesis
and Characterisation, Pennsylvania State University, Univ. Park, Pa, 1982.
Sandler, S.R., Karo, W., Bonesteel, J.A. and Pearce, E.M., Polymer Synthesis and
Characterisation—A Laboratory Manual, New York: Academic Press, 1990.
Sorenson, W.R., and T.W. Campbell, Preparation Methods in Polymer Chemistry, New
York: Wiley, 1968.
Appendix B
Pioneers in Polymer Science
Modern polymer science owes its development to present level because of original,
innovative and highly intellectual thoughts of many scientists and technologists.
The polymer science has seen many breakthroughs over the last five decades.
The Nobel prize in chemistry, which is considered as the top most recognition of
original and path breaking contribution, has gone five times to distinguished
scientists for their contribution in polymer science. The Nobel prize for the year
2000, once again is bagged by polymer scientists for inventing conducting plastics.
A brief biography of these scientists along with a sketch of their contribution are
mentioned. Besides the Nobel laureates, there are many other popular names
associated with different facets of polymer science. The sketches of some of
these pioneers are also given for the benefit of readers. (Nobel laureates for their
work on biological macromolecules are not included here).
Nobel Laureates
Hermann Staudinger (1881-1965)

Hermann Staudinger was honored with the Nobel Prize in chemistry for the year
1953. He was the first who coined the word ‘Macromolecular’ in 1920.
He put forwarded the concept of existence of giant molecules, which behave
different than then well-known small sized simple molecules. Staudinger published
great number of scientific papers. Since 1920, he has written approximately 500
research papers on macromolecular compounds about 120 of these on cellulose
and about 50 on rubber and isoprene. It is during this period, out of his first hand
experience of working with the cellulose and rubber, he propagated that these
compounds have molecules of a giant size and are different from simpler ones.
His idea was rejected then by the academia. In fact it is said that an academicians
had advised him by saying “Dear colleague, leave the concept of large molecules
well alone ... there can be no such thing as a macromolecule’, after his major
lecture devoted in favor of macromolecular concept. This happened in 1925.
Today, however, it seems impossible to believe that this violent opposition
not only to an original but also totally a new idea or innovative intellectual
imagination, has existed relatively in recent times. The present day polymer
Appendix B 311
Hermann Staudinger
science thus owes a lot to Hermann Staudinger, who can be called as ‘Father of
Macromolecules’.
Staudinger was a prolific author and had written number of books. Some of
these are Die ketene (Ketenes) (Enke, Stuttgart, 1912), Anleitung zur organischen
qualitaten Analyse (introduction to organic qualitative analysis) (Springer, Berlin,
1923 (1st ed.) and 1955 (6th ed.), Tabellen Zu den Vorlessungen uber allgemine
und anorganische Chemie (Tables for the lectures on general and inorganic
chemistry) (Braum, Karlsruhe, 1947 (Sth ed.), Die Hochmolekularen Organische
Verbindungen, Kautschak und Cellulose (The high molecular organic compounds,
rubber and cellulose) (Springer, Berlin, 1932), Organische Kolloid Chemie (Organic
Colloid Chemistry) (Viewweg, Braunschweig, 1950 (3rd ed.), Fortschritte der
Chemie, Physics und Technik der Makromolekularen Stritte (Progress of the
Chemistry, Physics and technique of the macromolecular substances, jointly
with Professor Viewweg and Professor Rohrs, volume I (1939) and (1942)
(Lehmann, Munich) and Makromolekulare Chemie and Biologie (Macromolecular
Chemistry and Biology) (Wepf and Co., Basle, 1947). Since 1947 staudinger has
edited the journal Die Makromolekulare Chemie (Macromolecular Chemistry),
published by Dr. A. Huthig, Heidelberg and Wepf & Co., Basle, Switzerland.
Hermann Staudinger was born in Worms, Germany on 23rd March 1981. He
was educated in Worms, at Halle University and latter at Darmstadt and Munich.
He served many institutes as Professor, Professor of organic chemistry (Institute
of Chemistry of the Techmische Hochschule, Karlsruhe, for fourteen years from
1912), University of Freiburg (1912-1926). He had also served as principal of
the Research Institute of Macromolecular Chemistry, Freiburg, and as Head of

the State Research Institute of Macromolecular Chemistry.
He had received many honours and awards; he is Dr. Ing. H.C. of the Technische
Hochschule, Karlsruhe, Dr. Rer. Nat. H.C. of University of Mainz, Dr. (c) H.C.
of University of Salamanca and Dr. H.C. of University of Torino. Staudinger
married Magda Woit, who was for many years his coworker and coauthor of
numerous publications.
Giulio Natta (1903-1979)

Giulio Natta shared the Nobel Prize in chemistry for the year 1963 with Karl
Ziegler. G. Natta began his career with a study of solids by means of x-rays and
electron diffraction. He then used the same methods for studying the catalysts
and structure of some high organic polymers. His kinetic research on methanol
synthesis, on selective hydrogenation of unsaturated organic compounds and on
oxosynthesis led to an understanding of the mechanism of these reactions and to
an improvement in the selectivity of catalysts. In 1938 he began to investigate
polymerisation of olefins and the kinetics of subsequent concurrent reactions. In
1953, he extended research work conducted by Ziegler on organometallic catalysts
to the stereospecific polymerisation. This led to the discovery of new classes of
Giulio Natta
»: Appendix B 313
polymers with sterically ordered structures viz. isotactic, syndiotactic and diisotactic
polymers and linear branched olefinic polymers and copolymers with an atactic
structure. These studies led to the development of new thermoplastic material,
isotactic polypropylene at industrial scale.
By x-ray diffraction studies, Prof. Natta has also determined the exact
arrangement of chains in the lattice of new crystalline polymers. He has also
synthesized new elastomers based on butadine, and copolymers of ethylene with
propylene. Prof. Natta’s work has also led to the synthesis of optically active
macromolecules from optically inactive monomers and synthesis of crystalline
and sterically ordered alternating copolymers from different copolymer couples.
Prof. Natta’s scientific and technical activity is documented in 700 published
papers out of which 500 concern stereoregular polymers, and by a large number
of patents in many different countries. Giulio Natta was born at Imperia, Italy on
26th February 1903. He graduated in chemical engineering at polytechnic of
Milan in 1924. He has joined as a faculty staff member of Pavia University as a
full professor in 1933. He served also as a director of Institute of General
Chemistry at this university before he was appointed as full professor of physical
chemistry at University of Rome. he had also association with the industrial
chemistry departments of polytechnic of Turin and Milan polytechnic in similar
capacity.
Prof. Natta was honorary member of several international chemical societies
of (Austria (1968), Switzerland (1963), Belgium (1962) and (New York Academy
of Sciences (1958)). He has received several gold medals out of which one from
the town of Milan (1960) is worth mentioning because it was given by the
President of Italian Republic exclusively to meritorious personalities. Several
international universities awarded honorary doctorate degrees to Prof. Natta
(Turin University and University of Mainz).
Karl Ziegler (1898-1973)

Prof. Karl Ziegler has shared the Nobel prize in chemistry for the year 1963 with
Prof. Natta. Prof. Natta’s research work was started in the field of radicals with
trivalent carbon and synthesis of multi-membered ring systems. He has carried
out extensive work over the reactions in chemistry of organoaluminium compounds.
Prof. Ziegler’s Nobel Prize winning discovery, however, has been the organic
mixed catalysts for the polymerisation of olefins (e.g. the synthesis of high
density polyethylene).
Karl Ziegler was born at Helsa near Kassel in Germany on 26th November
1898. He had graduated from University of Marburg/Lahn and served at universities
of Frankfurt/Main and Heidelberg. Prof. Ziegler was the Director of the Max
Planck Institut for Kohlen forschunrg in Mulheim/Ruhr from 1943 till 1969. He
was also the founder director of Gesellschaft Deutscher Chemiker (German
Chemical Society). He held honorary doctorate degrees from Technische
Hochschulen, Hannover and Darmstadt, Universities of Heidelberg and Giessen.
He had been bestowed with many medals out of all the most prominent being the
award of distinguished order by the German Federal Government. He was honorary
senator of the Max Planck Society.
Karl Ziegler
Karl Ziegler was married to Maria Kurtz and has five grand children by his
daughter and five by his son.
Paul J Flory (1910-1985)

Prof. Paul J. Flory was honoured for his fundamental work in the chemistry of
macromolecules or polymers, with an award of Nobel Prize in chemistry for the
year 1974. Prof. Flory had an unique distinction as Nobel laureate because
unlike most laureates who are recognised primarily for either theoretical or
experimental work, Flory was cited for achievements in both areas. Prof. Flory
has contributed almost to every branch of polymer chemistry including studies
of polymerisation mechanism and structures, physical and mechanical properties
both in bulk and in solution, elasticity of fiberous proteins and crystallisation of
polymers from solution. Flory developed simple models to solve problems that
had puzzled the scientists for many years. He himself had said once that neither
simplicity nor complexity is inherent in object of inquiry but that both depend
greatly on the point of view or perhaps insight of the observer.
Flory’s interest in science was kindled by his remarkable teacher Carl W.
Holl, Professor of Chemistry at Manchester College from which he was graduated
in 1931. He then moved on to graduate school of Ohio State University and
completed his dissertation in the field of photochemistry and spectroscopy in
ye Appendix B 315
Paul J Flory
1934. He joined Du Pont Company and assigned to small group headed by Dr.
W.H. Carothers*who invented nylon and neoprene. Flory during his stay at Du
Pont explored the fundamentals of polymerisation and other novel aspects of
polymeric substances. Flory has also participated in the research and development
programme on synthetic rubber, which was short of supply due to second World
War. Flory then joined Cornell University and was offered a professorship in
1948. He then had a productive and satisfying period of research and teaching,
which culminated into one of the originally written books in polymer chemistry
“Principles of Polymer Chemistry”, published by Cornell University Press in
1953.
The well known contribution of Flory has been that his models help in (i)
understanding the polymer chain statistics, (ii) configuration of polymer chains,
(iii) rational interpretation of physical measurements in dilute polymer solution
and (iv) quantitative characterisation of macromolecules. The work on all these
aspects led to the formulation of the hydrodynamic constant called theta and
recognition of theta point at which excluded volume interactions are neutralised.
Experimental methods for monitoring the theta conditions have been proposed.
Very soon many laboratories all over the world confirmed the ideal behaviour of
polymers (natural and synthetic) under theta conditions.
Flory futher concentrated his work on spatial configuration of chain molecules
and the treatment of configurational dependent properties by rigorous mathematical
models. Prof. Flory had a stint at Standord University from 1961 and another
fundamental book titled “‘Statistical Mechanisms of Chain Molecules” was authored
by him. This book summarises the theory and its applications.
Flory got married to Emily Catherine Tabor in 1936 and has three children
(two daughters and a son) and four grand children. His son was named as Paul
John Flory Jr.
Bruce Merrifield
Bruce Merrifield’s name is attached to solid phase peptide synthesis. He has
been honoured by Nobel Prize in Chemistry for the year 1984 for his work on
peptide synthesis.
Bruce Merrifield
Merrifield had college training at Pasadena Junior College and then moved to
University of California at Los Angeles. After graduation he worked at the
Phillip R. Park Research Foundation. He worked as an assistant for Dr. D.W.
Woolley at Rockfeller university on a di-nucleotide and nucleotide growth factors.
He persistently pursued his interests in the subject, which eventually led to the
idea of solid state peptide synthesis in 1959.
Peptides act as proteins which are biocatalysts and control, accelerate or even
inhibit the biological and metabolical processes. Merrifield’s contribution led to
,»: Appendix B 317
the synthesis of peptides with desired sequences of amino acids in the laboratory
conditions. Merrifield was a Nobel guest professor at Uppsala University in
1968 and was elected a member of the U.S. National Academy of Sciences in
1972. He had received several awards (Lasker award for basic medical research
(1969), the Gairdner award (1970), the intrascience award (1970) and American
Chemical Society award (1972)), to name a few. He had also received honorary
degrees from several universities (University of Colarado, Uppsala University,
Yale University and Colgate University).
Merrifield was born in Fort Worth, Texas on 15th July 1921. He married
Elizabeth Furlong and has six children. Mrs. Merrifield, a biologist, spent
considerable time at home for upbringing of the children and later joined her
husband at the Merrifield Laboratory at Rockfeller University.
Pierre-Gilles de Gennes
Pierre-Gilles de Gennes discovered that the methods developed for studying
order phenomenon in simple systems can be generalised to more complex forms
of matter, in particular liquid crystals and polymers. De Gennes began working
initially on magnetic phase transitions, but turned his attention during the period
1960-1980 to other more complicated phenomenon such as (1) transition from:
Pierre-Gilles de Gennes
(a) conducting to super conducting state in certain materials and (b) from an
ordered state to disordered state in liquid crystals, (ii) regularities in the geometrical
arrangement and movement of polymer chains, and (iii) conditions that define
the stability in micro-emulsions etc. De Gennes treated some of the complex
systems, which eluded simple explanations based on generalised mathematical
models that are already in place for studying the ordered and disordered
phenomenon in simple systems.
De Gennes, also known as “The Isaac Newton of our time” for his outstanding
contribution in perceiving common features in ordered phenomenon in very
widely differing physical systems such as magnets, super conductors, liquid
crystals, polymer solutions, gels, porous media and other soft systems. The
proposal by de Gennes, that “scaling laws” can be used for predicting the dynamics
of ordered to disordered transitions or vice versa in the abovementioned complex
systems, stimulated a great deal of theoretical and experimental work. Of all his
studies, understanding of phase transitions in liquid crystals and dynamics in
polymer chains, led to technical and commercial exploitation especially of liquid
crystals in daily used items such as pocket calculators, wrist watches, flat TV
screens and other display systems using colored digital numbers. De Gennes
modelled the behavior of polymer chains in dilute to more concentrated solutions
and even in very high concentrations that are encountered in polymer melts. A
new branch of polymer physics i.e. polymer dynamics has emerged due to the
extensive experimental and theoretical studies by the School of Polymer Physics,
founded and chaired by de Gennes under STRASACOL, a joint project with
physicists and chemists from Strassbourg, Saclay and the College de France. De
gennes proposed “blob” model, which states that a certain typical segment of a
polymer chain can move as if it were free, even in more concentrated solution
and “reptation” model, which describes the segmental motion in polymer chain
in terms of serpentine movement within a tangle or loop of surrounding polymer
chains.
One of the most important discoveries of de Gennes is that “‘order in disorder”
exists in the arrangement of polymer chains in dilute to concentrated solutions
or even in polymeric melts, under some applied conditions identical to those
under whose influence, a system of magnetic movements moves from order to
disorder. De Gennes book titled “The Physics of Liquid Crystals” (1974) and
“Scaling Concepts in Polymer Physics” (1979) became standard and authoritative
publications in the respective subjects.
P.G. de Gennes was born in Paris, France in 1932. He had his education from
Ecole Normale from 1955 to 1959. He was with Atomic Energy Center (Saclay,
France) working mainly on neutron scattering and magnetism under the guidance
of A. Herpin, A. Abragam and J. Friedel. He then worked as post-doctoral
scientist with C. Kittel at Berkeley, USA in 1959 and returned to France to serve
in French Navy. He left the navy in 1961 to take up an academic position as
Assistant Professor in Orsay and founded and established Orsay group on
Supraconductors. He became a Professor at the College de France, Paris. His
interests also kept widening from supracondutors to liquid crystals, interfacial
phenomenon, especially the dynamics of wetting and physical chemistry of
Appendix B 319
adhesion etc. De Gennes received prizes and medals from several reputed
academic societies. Of all these following can be cited: Holweck prize from the
joint French and British Physical Society, the Ampere prize from the French
Academy of Sciences, the Worlf prize from Israel, Gold Medal from the French
CNRS, the Matteuci Medal from Italian Academy, the Lorentz Medal from
Dutch Academy of Arts and Sciences and polymer awards from both American
Chemical and American Physical Societies (ACS and APS). He has also been
honoured with the award of memberships by several prestigious societies such
as French Academy of Sciences, Dutch Academy of Arts and Sciences, the
Royal Society, American Academy of Arts and Science and the National Academy
of Sciences, USA.
Hideki Shirakawa, Alan G. Mac Diarmid and

Alan J. Heeger
The Nobel prize in Chemistry for the year 2000 has been shared by three scientists
A.J. Heeger, A. G. Mac Diarmid and H. Shirakawa for their discovery of conducting
plastics. The work of these three scientists has revolutionized the whole thinking
about plastics or polymers. Because it is well known that polymers and plastics
are used as excellent insulators i.e. chemical substances that cannot conduct the
electricity. In fact, it is everybody’s routine observation that insulating plastic
material made up of polymers is coated around the copper or aluminum wires to
prevent any leakage of electricity being carried by these metallic wires. Thus the
pioneering work of these three scientists has changed the whole concept of
electrically conducting materials, which so far have been confined mainly to
metals.
It all started When Prof. Shirakawa and his co-workers synthesised polyacetylene
way back in 1974, from acetylene by using Ziegler-Natta catalyst. (As already
mentioned K. Ziegler and G. Natta shared Nobel Prize in chemistry for the year
1966 for their invention of insertion or stereo-specific polymerisation.) It is
worth mentioning that, in fact Ziegler and Natta prepared for the first time
polyacetylene in 1958 by polymerising acetylene in n-hexane using a mixture of
triethy] titanium/titanium tetrapropoxide as a catalyst. Thus resulted polyacetylene
was black in appearance and highly crystalline with regular structure. The powder
was very susceptible to air and was infusible and insoluble in almost all the
solvents. But however it was not a good conductor.
Similarly the polyacetylene initially obtained by Shirakawa in 1974 had metallic
appearance but was not a conductor. However in 1977, Prof. Shirakawa, Prof.
Alan MacDiarmid, University of California at Santa Barbara, have combinedly
discovered that the conductivity of polyacetylene films can be improved almost
by 10° times by oxidising the polyacetylene (PA) films with chlorine, bromine
and iodine vapours. This treatment of PA films with halogens is called as doping
in analogy to a similar process through which the conductivity of semiconductor
materials is enhanced. The doped form of PA had a conductivity of 10° Siemens
per meter. This value was higher than for any other conducting or semi-conducting
polymers. Metals such as silver and copper have metallic conductivities of above
10° S m7. Thus for the first time, the three pioneering scientists have been
successful in developing polymer plastic having conductivities of about 10°
times closer to that of highly conducting metals.
The major contribution of prof. Shirakawa is that he effected the polymerisation
of acetylene to polyacetylene at the surface of the catalyst system, taken as
concentrated solution in toluene and in inert atmosphere. Besides this modification,
Prof. Shirakawa used a mixed catalyst system of triethylauminium/titanium
tetrabutoxide.
The PA film, initially obtained by Prof. Shirakawa inside the walls of the
reaction vessel had two forms, as expected in Ziegler-Natta polymerisation. The
PA form, when polymerised in toluene under inert atmosphere and at —78°C,
was copper colored and had all cis configuration(a cis content of about 95%).
similarly, when polymerisation was conducted using the same catalyst but in n-
hexadecane as solvent media and at a temperature of 150°C, Prof. Shirakawa
obtained PA films having all trans configuration. The cis- and transforms of PA
are shown below:
all cis-polyacetylene (copper colored)
VAN ANVANVANV AN
all trans-polyacetylene (silver colored)
The conductivities of all cis - polyacetylene films were 107° — 10’ Sm™! and
while trans - polyacetylene was a better conductor with 1073 — 10°? Sm7!.
Mean while Prof. Alan Heeger and Prof. MacDiarmid were collaborating on
the studies of metallic properties of covalent inorganic polymers. Prof. MacDiarmid
met Prof. Shirakawa in Tokyo, and came to learn about the synthesis of PA films
in cis- as well as transforms. After the fruitful discussion and exchange of ideas
between the two, it was suggested that shirakawa’s group refine the polymerisation
process and Prof. MacDiarmid modify the PA films by doping process. These
proposals were based on a previous observation by Shirakawa’s group that PA
films with all trans- configuration when treated with bromine or chlorine decreased
IR transmission without changing the silvery color of the films. Prof. Shirakawa’s
group mean while refined their polymerisation process and could synthesize PA
films with controlled cis / trans double bonds along the chain. Prof. MacDiarmid,
using the PA films from Prof. Shirakawa’s lab, had collaborated with Prof.
Heeger’s lab. Then many experiments went on. The doping of PA films was done
with I, and ASFs. The group has now established that doping of cis- polyacetylene
with iodine and AsF; increase the conductivities of PA films by a factor of 10!!
Sm'. This value is exceptionally very high and the investigations of these three
scientists have opened up totally a new field of polymers i.e. conducting plastics.
Besides polyacetylene, several other polymers are reported in the literature,
which have potential to act as good conductors in doped form. These polymers,
for example are polypyrrole, polythiopene (and its derivatives), polyphenylvinylene
and polyaniline etc.
,: Appendix B 321
The application areas of conducting polymers are far and wide. One of the
major positive commercial and technological aspects of the polymers is that
transparent, homogeneous films of any thinkness can be fabricated at very low
costs because, such a processing is obten done from solutions. The discovery by
Shirakawa, MacDiarmid and Heeger of conducting plastics, have opened following
major applications of conducting polymers- (i) As electromagnetic shields of
electronic circuits, (ii) As anti-static coating materials on photographic films to
prevent their damage from exposure to electric discharge, (iii) As hole injecting
electrode material in light diode (LED) device, (iv) As candidates for
electroluminiscent displays (for example in mobile telephone, remote control
and other such devices), (v) As facilitators for full color video matrix displays,
(vi) As electrochromic windows (smart windows), (vii) As sensing material in
sensors, (viii) As field effect transistors and microwave absorbing screen coatings.
The brief biosketch of each of the Nobel laureates in chemistry for the year
2000 is as follows:
Hideki Shirakawa
Prof. Hideki Shirakawa is a professor of chemistry at the Institute of Material
Science, University of Tsukuba, Japan. Dr. Shirakawa got his Ph. D. degree from
Tokyo Institute to Technology (Titech) in 1966. Prof. Shirakawa has been a
faculty member, holding different positions at Institute of Material Science,
Hideki Shirakawa
Tsukuba University, for more than last twenty years. It is said that he dedicated
his life to both his research and education.
He started exploring polymer science unprecedently to a newer area of
conducting polyacetylene (PA) films from electrically insulating polyacetylenes.
he had initiated this work, when he was at Tokyo Institute of Technology. What
is more heartening to note that Prof. Shirakawa’s success in converting insulating
PA to an electrical conducting one has resulted from an accidental experimental
mistake. During laborious and lengthy laboratory experiments on refining the
synthesis process of PA, a thousand fold too much catalyst was added in one of
the experimental batch and the result was a fascinating silvery PA material, with
all trans configuration of polymer chain. This beautiful silver film has been
found to possess superior properties (hither to unheard to for other known polymers)
close to metals.
Prof. MacDiarmid, University of Pennsylvania heard about the Prof. Shirakawa
discovery of controlled synthesis of PA films having metal like properties, he
had invited Prof. Shirakawa and worked together with Prof. Alan Heeger, University
of California. The combined efforts of these three brilliant brains have led to the
complete understanding of ways to modify the PA films from insulators to
conductors. Their seminal paper titled “Synthesis of electrically conducting organic
polymers: halogen derivatives of polyacetylene (CH), appeared in J. Chem.
Soc., Chem. Comm., 579 (1977). Dr. Shirakawa was born in 1936 in Tokyo and
can be called as saint scientist, who dedicated his life to the cause of teaching
and research in the frontier area of science and has blessed the humanity with his
pioneering contributions, which may convert the silicon based circuits from
polymer based electronics to nano scale integrated circuits.
Alan G. MacDiarmid
Prof. Alan MacDiarmid is the co-discoverer of the new and epoch making area
of conducting polymers, more commonly known as synthetic metals. If prof.
Shirakawa is responsible for the synthesis of hyper fine and superior quality of
PA films, Prof. MacDiarmid is the scientist, who handled these films and modified
them with electrochemical doping by using all the expertise and innovation
available with him and ultimately developed a proto-type conducting polymer.
Prof. MacDiarmid’s scientific interest has been around the studies on and
rediscovery of polyaniline, which is proving to be not only technologically
important but also foremost industrial conducting polymer. His efforts have
always been to improve the conductivity of polyaniline and its isomeric forms
and enhance their mechanical properties. Other aspects that attracted his attention
are reversible sensors and LED’s based on polymers made from aniline and its
isomeric forms.
Dr. MacDiarmid was born in Masterton, New Zeland in 1927 and is presently
a Professor of chemistry at the University of Pennsylvania. He had obtained his
higher education at the Universities of NewZeland, Wisconsin, Cambridge and
joined the faculty of university of Pennsylvania way back in 1955. He is presently
an US citizen. He is the author/co-author of approximately 600 research papers
»: Appendix B 323
MacDiarmid
and 20 patents €xclusively on conducting polymers particularly on synthesis,

chemistry, doping, electrochemistry, conductivity, magnetic and optical properties
and processing of polyacetylene and polyanilines. Thus Prof. Alan MacDiarmid
in true sense is a real polymer scientist, with qualities and approach of a chemist,
physicist and a technologist, all in one personality. Prof. MacDiarmid is recipient
of numerous awards and honory degrees both nationally (in USA) and
internationally. He was recently honored in March 1999, by American Chemical
Society with an award in Materials Chemistry.
Alan J. Heeger
Prof. Alan J. Heeger is the co-inventor and co-pioneer of new branch of polymer
science i.e. conducting plastics. Prof. Heeger put his masterly expertise experience
on semi conducting and metallic polymers and experimental facilities at the
disposal of Prof. MacDiarmid and Prof. Shirakawa in characterising and analysing
the modified or doped polyacetylene (PA) films.
The trio of polymer scientists, together proved beyond doubt that an insulator
polymer can be modified to possess conducting and mechanical properties close
to metals. Thus this trio of genius brains be called as father group, that invented
electrically active polymers, which are going to revolutionize the electronic
Alan J. Heeger
industry in the coming years. Professor Alan Heeger and his collegues at University
of California, Santa Barbara, have been doing pioneering research in inventing
novel polymer materials that possess electrical and optical properties similar to
conventional metals. The beauty of Prof. Heeger research group is that their
experiments focussing on issues related to transport process in semi conducting
polymer devices, their fundamental electronic structure and light emission properties
have led to the new polymer materials, which can be easily processed and have
equally competing mechanical, optical and electrical properties similar to metals
Prof. Heeger’s group can handle studies on LEDs, light-emitting electrochemical
cells (LECs) and lasers, all fabricated from semi conducting and conjugating
polymers. The characterisation of conducting polymers using broad range of
spectroscopic methods (including ultrafast femtosecond, and time resolved)
quantitative measurements of photo and electroluminescene, quantum efficiencies
and photo conductivity etc. is the hall mark Prof. Heeger’s research group.
Dr. Heeger was born on 22nd January 1936, at Sioux city. He had his B.S.
with high distinction from University of Nebraska, and his Ph.D. from University
of California, Berkeley. His professional life was started in 1962 at University of
Pennsylvania as assistant professor and decorated the position of Professor at the
same place for the period 1967—1982. He has been a professor of physics since
1982 at University of California, Santa Barbara. He is the founder president of
a) Appendix B 325
UNIAX corporation and currently is the chief scientist at this corporation. He

has received several national and international honors in the form of fellow,
prizes awards and honorary doctorate. He had more than 650 scholarly publications
to his credit and had filed more than 40 patents in the area of conducting polymers.
Prof. Heeger is married and has two children.
Source: The sketches of Nobel layreates are extracted from the official website
of Nobel foundation, Stockholm, Sweden through internet
Herman Francis Mark

Herman Francis Mark, Popularly known as Herman Mark is one of the exceptional
personalities in the international scientific/academic world. He had a multi-
dimensional (faceted) personality, in which a deeply committed soldier, an honest
and serious teacher, an innovative and intuitive researcher, accommodative and
commanding administrator and finally a struggling man who had always converted
odds against his own as well as his scientific community favor, all these qualities
combined into one. Herman Mark was widely known as the father of polymer
‘science and his enormous contributions as a researcher and inspiring teacher/
Herman Francis Mark

lecturer are mainly responsible for asserting the place, polymer science has
presently taken in academic and industrial circles.
Another uniqueness of Herman Mark was that he was equally at home, at
universities and industrial laboratories and his pioneering work and deeply
committed efforts have a great influence in (i) phenomenal growth of polymer
industry, (ii) design of curricula for polymer science in academic institutions for
establishing polymers as a discrete branch of chemistry and (iii) laying the
foundation of polymer research journals and specialized monographs in the
field. The credit of being the chief architect of a polymer section of International
Union of Pure and Applied chemistry (TUPAC), goes to Herman Mark. The hall
mark of Herman Mark’s personality was that he was informal and quite cheerful
in his approach, which earned him the nick name “Geheimrat” among his
collaborators and associates.
Herman Mark had to abruptly stop his studies and join Austrian army with the
outbreak of the First World War. As a brave soldier, Mark fought from all fronts
in the battle field, which won him not only fourteen gallantry awards for his
bravery, but also wounded him several times. He was so spirited that, he persuaded
his senior army officer to allow him to lead a counter attack on Italian army to
recapture the Monte Ortigora, which Austrian army lost earlier. He was allowed
to do so and emerged as victor in recapturing the lost mountain peaks. However,
he was captured by the Italian army and kept as a prisoner of war in a convent
near Bari, Italy. To keep himself away from the boredom of prison life, Herman
Mark resumed his study of chemistry, which he had started two years earlier
while recapturing from a battle wound. This unending enthusiasm for pursuing
chemistry, in otherwise patriotic, and soldier Mark, has blessed the scientific
community with one of the brilliant brains that has left indelible mark in the
history of science especially polymer science.
Herman Mark worked with Wilhelm Schlenk for his doctoral thesis on synthesis
and characterisation of the pentaphenylethy! free radicals. Mark impressed his
thesis advisor so much that, Schlenk has invited him to join University of Berlin,
where Dr. Schlenk took the chair previously occupied by Emil Fischer. Mark
then took up the position as director, Institute for fiber Research, upon an invitation
from Fritz Haber, director of Kaiser Wilhelm Institute (KWI). Mark then unleashed
his never ending enthusiasm and conducted research work on the detailed analysis
of x-ray crystollographic studies on celluiose fibers as well as zinc wires. Mark
and one of his associates Michael Polanyi have proved from x-ray diffraction
studies the presence of crystallised and oriented regions along the fiber axis
analogous to crystal orientation existed in metallic wires. The fruitfulness of
Mark and Polanyi research work can be judged by the fact that, they could
establish, (i) crystal structure of hexamethylene tetramine (1923), graphite (1924),
(ii) dimerisation of oxalic acid (1924), (iii) birefringence pattern observed in the
crystal structure of calomel (1926), (iv) the carbon-oxygen bond length from
crystallographic study of carbon dioxide (1925, 26) and (v) structure similarities
of ethane and diborane crystals etc.. Thus an originally trained organic chemist
has directed his efforts to the problems in physics and physical chemistry. The
voluminous x-ray crystallographic data was collected both on simple as well as
Appendix B 327
high molecular weight substances by Mark and his associates has been used to
solve the structural problems in polymeric solids even today.
The turning point in the Mark’s career as well as to the development of
modern polymer science took place in 1926, when Mark had attended the meeting
of Gesselschaft Deutscher Naturforscher und Arzte in German city of Dusseldorf.
He had delivered a lecture titled “Roentgenographic determination of structure
of organic molecules, especially high molecular substances”. He reviewed his
whole work emphasizing the utility of important information that can be gained
from the parameters of unit cells and space groups even if detailed molecular
structure is not known. This was in the backdrop of sever skepticism by the
scientists about the concept of large molecules, envisaged by Nobel laureate
Herman Staudinger. Herman Mark was careful enough in his presentation and
then did not commit to the presence of long chains but indicated that the crystallites
of cellulose fibers behave like a large molecule.
The authority on the physics aspects of cellulose fibers, which Mark gained
in Berlin, has prompted K.H. Meyer, director of I.G. Farbenindustrie (then
Germany’s largest chemical corporation), to invite Mark as director of the newly
established research laboratory on high molecular compounds. Thus Mark moved
to Ludwigschafen in 1926. The company, Mark Joined was a prominent producer
of rayon and cellulose acetate fibers. The conducive environment, Mr. Meyer
offered, led Mark to continue his fundamental studies on elucidation of cellulose
structure. Taking the clue from Mr. Polanyl’s earlier observation that x-ray
diffraction studies on cellulose fibers reveal presence of long chains, Mark and
Meyer came with a pioneering research paper in 1928, solving the diffraction
pattern from cellulose fibers and gave first experimental evidence of presence of
a long chemical chain. Thus Mark and Mayer became the discoverers of first
polymer crystal structure, that has survived the test of time.
After this, Mark has turned his attention to Hevea rubber (natural rubber) and
solved not only its crystal structure but in the process settled for the first time the
question of chemical constitution from the spatial point of view. The diffraction
studies by Mark and Meyer have conclusively proved that the natural rubber i.e.
polyisoprene has a cis- configuration around carbon - carbon double bond. Mark
has also estimated the energy required to break its covalent bonds and based on
his findings could predict the ultimate strength of cellulose fiber. Besides these
studies Mark had collected enormous data from electron diffraction patterns of
simple molecules such as carbon tetrachloride, benzene, cyclohexane, and cis-
and trans- 1, 2-dichloroethylene. These studies led to the knowledge of bond
lengths, bond angles and the angle of rotation. The Mark and Meyer’s association
was so fruitful that they together wrote a first monograph (in 1930) on “Der
Aufbau der hochpolymeren organische Naturstoffe” (“The Structure of High
Molecular Organic Natural Substances”) and another authoritative book titled
“Physik und Chemie der Zellulose (Physics and Chemistry of Cellulose)
independently by Mark. With this work, Mark and Meyer had clearly established
that the pclymer molecules behave like flexible coils due to hindered rotation
around the bonds along the polymer backbone. This finding was however severely
contested by Herman Staudinger, who insisted that polymer molecules were stiff
rods. Not only this, Statdinger bitterly attacked Mark and Meyer, for what he
felt a kind of intrusion by the Mark and Meyer duo into his own original thoughts
on macromolecules, which were almost rejected by scientists in 1926.
Meanwhile, as fate wished German government was taken over by Hitler’s
party and the management of I.G. industries had asked Herman Mark to leave
the job and country at earliest, because Mark’s father Herman Carl Mark was a
jew. This brought Mark back to Vienna, Austria, as Professor of Chemistry at
University of Vienna. Forgetting the bitter treatment he had received in Germany
and keeping the great memories of his achievements in polymers in mind, Mark
had straight away embarked on the design of curriculum in polymer science. He
started his research afresh on the mechanism of polymerisation and viscosity of
polymer solutions. He with E. Guth had developed a statistical theory of elasticity
of a rubber molecule, which explained the elasticity shown by cross-linked
rubber.
Once again unsettlement struck again, and Hitler’s army occupied Austria
and Mark was dismissed from professorship because of his close friendship with
then Chancellor Dollfuss who was later murdered by Nazis in 1934. Herman
Mark then managed through one of his close friends to get out of the jail and
along with his wife and two young sons left Austria to Switzerland and proceeded
to England enroute to Canada. He revived an early offer from director, International
Paper Company, Hawkesbury, Ontario, Canada as a research director for two
years concentrating on the improvement of manufacturing of wood pulp, cellulose
acetate and viscose. The work on viscose was very important because Du Pont,
USA has introduced the viscose fibers in tired cards. This collaboration helped
Mark to go to USA, on a proposal by one of the board members of the Polytechnic
Institute of Brooklyn, (poly) New York, where he was to work on a Du Pont
sponsored consultancy work and also act as a faculty members at Poly. Meanwhile
the war in Europe brought many refugees into USA and Mark was assigned to
the Shellac bureau for testing and chemical characterisation of Shellac. Since
this material was imported from Asia and the war situation demanded a synthetic
substitute and Mark grabbed the challenge. His expanded team of associates
namely A.V. Tobolsky, P.M. Doty, B.H. Zimm, S. Krimm and R:S. Stein, all of
whom had been introduced to polymer by Mark and later became leading nemes
in polymer research.
The intense polymer research activities of Herman Mark’s group led to the
foundation of Institute of Polymer Research, the first graduate program in USA
in 1947. The enthusiastic leadership and enormous scientific contacts of Mark
with scientists all over the world created a congenial atmosphere and forum for
exchange and cross fertilization of ideas among the scientists of Institute with
others. On every Saturday mornings, symposia on subjects related to rapidly
growing advances in polymers, were held. Soon by 1944, Mark was able to
establish one of the world’s outstanding scientific centers in polymers. Mark
meanwhile helped in establishing Weizmann Institute in Palestine and similar
other centers in Soviet Union.
Herman Mark was not deterred by advancing age and continued to give his
annual lectures on “What is new in polymers” till into his eighties. He had
ch Appendix B 329
travelled the world widely in delivering lectures in Universities and Industries.

He was at home at both the institutions. He acted as editor of Journal of Polymer
Science and was also consultant to many polymer industries and U.S. Government.
It is said that out of about 500 overseas visits by Mark, two of them were highly
memorable to him. He was invited to Japan in 1962 to present a lecture to the
Japanese Emperor, an honour exclusively and uniquely reserved for Nobel laureates,
even through Mark did not belgng to this elite club. Thus Mark’s efforts in
polymer research were honoured befittingly by Japanese scientists. Mark was
one of the first two American scientists, who visited China in 1949 after the
communist government seized the power.
Herman Mark was honoured by many awards, prizes and medals. The
Universities of Leige, Berlin, Uppsala, Vienna, Madrid, prague and Technion in
Haifa conferred honourary doctorates. He was offered memberships of Royal
Institute of Great Britain, National Academy of Sciences. He received following
medals/prizes; Hertz medal (1928), Nichols medal (1960), Gibbs medal (1975),
Humbold award (1978), Wolf prize (1979), Perkin medal (1980) and Michelson-
Morley award (1989).
As always, fate wished, Mark’s personal life was deeply affected by deaths,
he lost his father, he lost his wife Mimi Schramek in 1970 after a long struggle
with angina pictoris, his beloved son Peter in 1979. He lived his last two years
of a long life with his second son Hans, who was Chancellor of University of
Texas. Mark left to heavenly abode on 6th April 1992 thus ending his earthly
life, which began on 3rd May 1895.
Stephanie Kwolek
Stephanie Kwolek has invented one of the modern world’s most readily recognized
and widely used material, Kevlar fiber. We are all aware that polymers are not
hundred percent crystalline and hence it is normally expected that polymers with
high mechanical strength are rare. But Stephanie Kwolek proved otherwise.
Kwolek pioneered low temperature processes for the preparation of condensation
polymers. Her determination and love for the work at hand were so great, that
she had met with a string of success in the search for new and better polymers.
In fact it all happened, when she took up a research position with Du Pont’s
textile fibers laboratory in Buffalo, New York, after completing her BS in chemistry
(1946) from Carnegie mellon University, Pittsburg. She had a deep interest in
science and medicine as a child. She wanted to study medicine, but the weak
financial position of her family did not allow her to enter a medical school. She
has found her job at Du Pont very interesting and challenging and she could
work with all the zeal and enthusiasm, Kwolek has synthesized hundreds of new
polymers, including Kapton polyimide film and Nomex aramide polymer and
fiber.
Not satisfied with her already history creating achievements, she has carried
out her experiments to make stronger and stiffer fibers of tremendous rigidity
and strength. In 1960’s, her efforts led to the discovery of an entirely new branch
of synthetic polymers i.e. liquid crystalline polymers. She had succeeded in
Stephanie Kwolek
synthesizing the first pure monomers to synthesize polybenzamide. But she

found that these monomers were ultra-sensitive to the moisture and heat and too
easily underwent hydrolysis and self polymerisation. Then she discovered an
acceptable solvent and created appropriate low temperature polymerisation
conditions for the intermediate monomers.
Not knowing that, she was to make a new discovery in synthesizing a polymer
that would change the world, she began her work at the superpolymers lab as
usual in one morning in 1964. Under mild and earlier set up polymerisation
conditions, Kwolek obtained an aramid polymer, which was in a fluid and cloudy
form. No other scientists would have realised that this new polymer could produce
fibers with much greater strength and stiffness. But acting on her own instinct,
Kwolek asked for spinning out the product and the result was astonishing not
only for her, and for her company but for the whole world. The new synthetic
fiber produced was very thin but at the same time five times stronger than steel
and had superior properties than any other fibers available. So it is obvious that,
Du Pont was delighted at Kwolek’s discovery and took up the studies for
standardizing the conditions for producing the commercial form of Kevlar fiber,
Kevlar fiber, as we all know now, is used to produce bulletproof vests that
protect the lives of policemen on duty. It has been used as a shield to protect the
important personalities from impending shooting attacks. Kevlar fibers have
many other applications including radial tyres, brake pads (replacing asbestos),
P Appendix B 331
racing sails, fiber optic cables, water-, air- and spacecraft shells and mooring and
suspension bridge cables, skis, safety helmets, hiking and camping gear, suits
for fire fighters, cut resistant gloves and tennis rackets etc. Thus Kwolek’s invention
has ensured the sale of hundreds of millions of dollars per year worldwide.
Kevlar was not the Kwolek’s only invention. She had held about 17 patents on
synthetic polymers by the time she had retired in 1986. One of the patents was
for the feasible spinning methods for the production of commercial aramide
fibers. She has been acting as a part time consultant for Du Pont, even after
retirement. She is also a widely respected mentor to young scientists especially
women. Keeping all the commercial success aside, Kwolek has received numerous
awards including Kilby award and the National Medal of technology. She has
been honoured for outstanding achievements in science by inventor’s Hall of
Fame. In recognition of her own pioneering achievements and for her
encouragement of young generation of scientists, Stephanie Kwolek has been
honoured in 1999 by Lemelson-MIT lifetime acheivement award. In April 1999,
San Francisco’s exploratium had honored her at a special ceremony.
Santi Ranjan Palit (1912-1981)

Santi Ranjan Palit is regarded as father of polymer research in India. Santi
Ranjan was born in 1912 at Calcutta, had his university education in Calcutta.
He had started his professional carrier as a lecturer in Vidyasagar College and
became a very successful teacher. During this time he had authored a book
‘Elementary Physical Chemistry” which was accepted by teachers and students
alike. He joined indian Lac Research Institute at Ranchi as a research assistant
~~
Santi Ranjan Palit

and wrote significant publications. He earned a D. Sc. degree from Calcutta

University and on invitation from Prof. McBain of Stanford University moved to
U.S.A.
He worked on detergents and solubilisation of soaps. Santi Ranjan then joined
Prof. Herman Mark at the Polytechnic Institute of Brooklyn, New York, U.S.A.
He worked on the solvency of high polymers. His stay with Prof. mark left in
him a strong desire to pursue polymer research work back in India. He joined
first as planning officer and later as head of department of physical chemistry at
Indian Association for Cultivation of Science, Calcutta. He had pursued his work
in the physical chemistry of polymers rigorously and published several research
papers, monographs and professional books. He had extensively visited several
universities and laboratories for delivering subject Specific and general lectures.
Santi Ranjan has six children and many grand children.
Leo Baekelund (1863-1944)

Baeklund was Dutch chemistry professor, inventor and enterpreneur. He was a
rare personality having qualities of an-intellectual academic, innovative researcher
and highly successful entrepreneur, all together. He was in search of a synthetic
substitute for shellac, the purified secretions (lac) of the larvae of the insect
‘Kerria laccan’. While working in his Bronx, New York, garage laboratory, he
came upon a phehol-formaldehyde formulation of multiple properties. The resin
once formed was very hard and intractable, could be cut and machined.
It was an excellent electrical insulator, highly resistant to water and other
ae ae
RU wz : _ “
z
Leo Baekelund
J Appendix B 333
solvent attacks. Baekelund immediately recognised its potential applications.

He refined his process of synthesis and production and maximised its unique
properties. He kept the secret of formulation to himself and marketed his invention
in 1909 under the trade name “Bakelite” TM, chosen after himself. Thus the
whole credit of development of modern commercial plastics goes to Baekelund.
Bakelite however is not the first commercial plastic material and this credit is
still with the “celluloid”. The extent of enterpreneurship visioned by Baekelund
can be gazed by the fact that, Bakelite is still manufactured commercially and
used at a level of multimillion dollars per year worldwide.
Wallace Hume Carothers (1896-1937)

Wallace Hume Carothers began his industrial career in 1927 at the DuPont
Company. He was instrumental in launching a research program on fundamentals
of polymer synthesis. He was able to synthesise a large numebr of macromolecules
with interesting properties. Carothers synthesised the polymers step-wise using
known condensation reactions of low molecular weight organic substances. He
studied reaction mechanisms involved in their synthesis and the thermodynamics
of the polymerisation processes. In fact Carothers in 1931 gave a classification
scheme for the types of polymerisations. He distinguished between addition
polymer and condensation ploymers in the following manner. Addition polymers
have composition of monomeric units that is identical with that of monomer
molecules and addition polymers are formed by addition polymerisation.
Wallace Hume Carothers

Condensation polymers are those which have monomeric repeat units that are
not identical with the monomers. These are formed by polycondensation in
which small molecules are eliminated.
Carother’s conclusions were entirely consistent and were complimentary to
Staudinger’s work in Germany. By careful selection of reactants or monomers,
Carothers obtained polymers with molecules of great length compared to their
cross section i.e. fiber forming polymers. After an extensive laboratory trial,
Carothers and his research group were able to develop the polymerisation process
for the production of first commercially successful synthetic rubber and synthetic
fiber nylon. Thus, Carothers is regarded as grand daddy of all modern day
engineering plastics. Unfortunately, the brilliant successful career of Wallace
Hume Carothers came to a tragic end in the form of a suicide in 1937 at the age
of just 41.
References for Further Reading
Seymour, R.B., ed. History of Polymer Science, Washington: Am. Chem. Soc., 1982.
Morawetz, H., Polymers, The Origin and Growth of a Science, New York: Wiley-Interscience,
1985.
Seymour, R.B., ed., Pioneers in Polymer Science, Boston: Kluwer, 1989.
Mark, H.F., From Small Organic Molecules to Large: A Century of Progress, Washigton
DC: Am. Chem. Soc., 1993.
Appendix C
Questions
Questions and Clues Based on Conceptual Understanding

il. Polyacrylonitrile is non-elastomeric. Why?
Strong electron withdrawing ability of the cyano group (—CN) produces negative
charge on the pendant group with a counter balacning positive charge located on
the backbone. This results into dipolar interaction and close packing hence
crystallinity.
Some polymers can be cross-linked by high energy radiation. Why?
A polymer when irradiated with high energy radiation, creates radical sites on the
chains which form cross-links with other chains (PVC is cross-linked this way,
HDPE is difficult to cross-link).
. Some polymers are transparent while others are opaque. Wholly amorphous
polymers may be expected to be transparent. Why?
Optical transparency requires that the material must not be made (at the microscopic
level) of phases of significantly different refractive indexes. Crystalline and
amorphous regions in a polymer have different refractive indices. hence when
polymer is wholly amorphous, it is opaque.
LDPE is a branched polymer. Why?
Due to the internal chain transfer, where the growing end of the chain has tendency
to abstract a H-atom from a —CH,—group from the same chain generates free
radical where the new chains grow, adding branches (back biting).
. Thermal decomposition of polymer of formaldehyde is called unzipping. Why?
The decomposition is reverse of propagation and produces formaldehyde.
Why is the termination process not preferred through coupling in cationic
polymerization?
Same charge on macrocations does not allow coupling.
Vinyl chloride-vinyl acetate coplymer is more flexible and can be more easily
processed than PVC, Why? :
Presence of vinyl acetate units in the chain decreases the regularity in PVC
chains (decreases intermolecular forces) thus lowers T, and consequently produces
flexibility making the copolymers easily processable (internal plasticization).
Isotactic polypropylene(PP) films are less permeable to gas as compared to atactic
polypropylene, Why?
Isotactic PP is more crystalline, possesses high density and low permeability.
Why do aramides possesses high melting point?
Polyamides due to extensive intermolecular H-bonding are highly crystalline.
Aromatic polyamides (aramides) due to the planar benzene ring have even more
favorable effect on 7, because the polymer chains become highly rigid.
Polybutylene terephthalate is more flexible than polyethylene terephthalate. Why?
Decrease in the magnitude of inter molecular hydrogen bonding in the polyester
can be expected for the diol (butylene glycol) as compared to ethylene glycol.
Thus, polybutylene terephthalate is more flexible.
. Ubbelohde capillary viscometer is often preferred over Ostwald viscometer in
polymer mol. wt. determination. Why?
In the former, the bottom end of the capillary is above the level of the liquid and
so the pressure head is independent ofthe volume of the liquid. Thus, successive
dilutions can be done in the Ubblehode viscometer.
Specific heats fo polymers are higher as compared to metals. Why?
Polymers are usually poor conductors of heat.
. Cold cracked rubber does not contract easily. Why?
In cold conditions, the rubber is a glassy polymer without any rubber-like flexibility.
Rubbery state is seen only at T > 7,.
Ethylene is more easily polymerised by free radicals than isobutylene. Why?
Due to absence ofelectron donating group, ethylene is less polar than isobutylene.
Why does solution polymerisation often result to low mol. wt. polymer? Due to
the chaintransfer through solvent.
Why does the 7, of a polymer increase in the presence of a filler?
The intermolecular attraction impedes the segmental mobility and thus 7, increases.
Benzoyl peroxide is usually stored as solution. Why?
Due to its explosive nature.
Zimm plot constructed from light scattering results on polymer solutions provides
usuful information about the characterization and solution behaviour-elaborate
Zimm plot is the double extrapolation method to zero angle and zero concentration
and provides M,,. The conc. dependence at zero angle gives second virial coefficient
while angle dependence at zero concentration gives particle scattering function
which gives radius of gyration.
Polymers obtained by condensation polymerization are more crystalline than
addition polymers. Why?
This is due to the presence of highly polar functional groups, condensations
polymers, e.g. nylon, terylene are highly crystalline and usually do not dissolve
below melting temperature.
Polymers like polyacrylonitrile, polyacrylates are often prepared by anionic
poymerization. Why?
Electron withdrawing (-CN,-COOR) groups reduce double bond electron density
and thus favour anionic polymerization.
. Aqueous solution of polyethylene glycol (PEG) shows decreasing polymerwater
interaction with increase in temperature (inverse solubility relationship). Why?
Though several explanations are provided, a simple one could be the disruption
of H-bonds between etherial oxygen of PEG and water molecules with increase
in temperature.
2d. The solubility parameter value (6) for the solvents n CgH,;7,OH, nCyH OH and
CH30OH show a increasing trend. Why?
n-Octanol (d= 10.3), n-butanol (6= 11.4) and methanol (6 = 14.5) show the order
because the contribution of polar group becomes less significiant as the nonpolar
chain increases.
23 Kevlar (aramide) is more rigid than nylons. Why?
This is due to the delocalised electrons on the benzene ring that make the ring
,. Appendix C 337
rigid. The high electron density in the chains result in stronger intermolecular
attraction between the chains.
24. Thiokols (polysulphides) do not make hard rubbers. Why?
Due to not being vulcanized.
MUSy, The melt viscosity increases fast with increase in the mol.wt. of polymer. Why?
The melt viscosity is proportional to the 3.4 power of molecular weight.
26. Though difficult in processing, ultrahigh mol. wt. (UHMW) polyethylene is used
in making some durable items.
Very high mol. wt. gives toughness to polyethylene.
Dil Why are dust free solutions necessary for the determination of mol. wt. of polymers
by light scattering method?
A single dust particle due to its large size would result in very large scattering
leading to erroneous result.
28. Ethyl benzene is soluble in methanol but polystyrene is not. Why?
The low entropy of polymer solutin reduces its solubility.
29. Natural rubber on heating (masticating) with about 30% sulphur becomes a hard
plastic ebonite. Why?
Extensive cross-linking makes polyisoprene behave like an influsible plastic.
30. Ionomers and polyelectrolytes both contain charged pendant groups but behave
differently. Why?
Ionomers have low content of charged groups and are usually insoluble in water.
Polyelectrolytes are highly charged water soluble polymers.
Sill Only proteins can be considered as monodispersed polymers. No synthetic polymer
is mono-dispersed. Why?
Proteins are built up of @-amino acids where a fixed number of @-amino acids are
arranged in a definite sequence leading to a macromolecule of a definite molecular
weight.
52: Methanolic solution of polyvinyl acetate when treated with MaOH precipitates
out. Why?
The polymer gets hydrolysed to polyvinyl alcohol which is insoluble in methanol.
33; Addition polymers are normally not crystalline Why?
Due to the presence of asymmetric carbon atom in the chain.
34. m/C is extrapolated to zero concentration in the membrane osmometric method ot
obtain M,,. Why?
Even the dilute polymer solutions behave nonideally and therefore the equation
m/C = RT/ M,, holds only at infinite dilution.
3)5) Polystyrene develops yellow colour on uv irradiation. Why?
Abstraction of a hydrogen atom from C atom adjacent to the radical centre is
energetically favourable and results in unsaturation in conjugation with the pendant
aromatic ring. This leads to yellow colour.
36. Cotton is used as a filler to impart mechanical strength to polymers. Why? Cotton
being a fibrous material is quite strong and thus provides mechanical strength to
the polymer. .
Bui Why the threshold molecular weight for polyethylene is higher than that for
nylons?
Strong H-bonding in nylon molecules develops mechanical strength in the material
at low mol. wt.
38. Polyisobutylene does not show stereo-regularity whereas as polypropylene does.
Why?
Polypropylene has asymmetric centres which are absent in polyisobutylene.
39. Carbon tetrachloride and disulphides like RSSH are efficient chain transfer agents.
Why?
C—CI bond in CCI; is weak and the resultant free radical gets resonance stabilized.
In bisulphides C—S bond is weak and breaks easily.
—M* + RSSH > — MSH + RS*
40. Paraffin wax has structure similar to HDPE but lacks in strength. Why?
The critical chain length for the onset of chain entanglement is not achieved for
paraffin wax due to its low mol. wt.
41. The contraction of an expanded rubber band on heating is a spontaneous process.
Why?
Large negative contribution from the entropy factor in the free energy change
makes the process spontaneous.
42. The critical chain length required for the onset of chain entanglement for PMMA,
PS and PIB (no. of monomers in the chain are 208, 730 and 610, respectively) are
different. Why?
The cirtical chain length depends on the polarity and shape of the polymer chain.
. Polyethylene terephthalate is stiffer and has higher m. pt. than polyethylene-
adipate and polybutylene terpthalate. Why?
Presence of more methylene groups makes the molecule flexible and the phenyl
group makes it stiff.
T, and T,, of polystyrene are higher than HDPE, PVC has still higher 7, and T,,,.
Why?
The presence of bulky pendant phenyl] groups in polystyrene restricts rotation of
chain segments. Polar Cl atoms of PVC show dipole-dipole attraction between
chains and thus further have high 7, and 7,
45. Polyviny! alcohol crystallises readily but not polyvinyl acetate. Why?
Ordered polymers with small pendant groups crystallise more readily than those
with bulky groups.
46. The refractive index (dn/dc) increment if not measurd precisely, causes serious
error in M,, by light scattering. Why?
The error in dn/dc is magnified as the light scattering equation uses this terms as
square (dnidc)°.
47. Polymer chemistry is considered as a relatively new branch of chemistry. Why?
Before 1920 when Hermann Staudinger for the first time gave the concept of
macromolecules, no one believed that a compound can have molecular weight as
high as a few thousands. Hence the development of this branch had really taken
place since 1940's.
48. Inter polymer networks (IPNs) form polymer mixtures. Why?
IPNs are obtained by polymerising a monomer in the presence of a polymer. This
gives rise to a multiphase system similar to a polyblend which may be described
as an intimate combination of two polymers.
49. Ionomers are superior to LDPE. Why?
Polyethylene containing methacrylic acid in the chain (or ethylene - methacrylic
acid copolymer with low methacrylic acid content) is an ionomer. Introduction of
methacrylic acid decreases the crystallinity and improves the toughness and adhesive
action. The salt of the copolymer (ionomer) sets as cross-linked polymer at
ordinary temperatures.
50. Small amount of divinyl benzene (DVB) is added in the polymerisation of styrene
for use as an ion-exchange resin. Why?
DBV contains two double bonds and thus cross-links polystyrene.
ot, Halogen containing polymers should not be burnt. Why?
The emission of HCI (for example by burning PVC) is harmful to living beings.
,. Appendix C 339
52 Secondary cellulose acetate is more Widely used than tertiary cellulose acetate.
Why?
Due to its solubility in less expensive solvents like acetone.
53. Coatings containing less solvent or those which are water borne are preferred.
Why?
To minimise the environmental pollution due to the evaporation of nonaqueous
solvents.
54. Polyurethanes and epoxies aré good adhesives. Why?
The presence of strong polar groups makes them good adhesives.
55: Phenol-formaldehyde resin (PF), like melamine resin is not used for dinner ware.
Why?
Bakelite (PF resin) is dark brown in color and it is difficult to impart attractive
colors to it.
56. Plasticised PVC is considered toxic. Why?
Due to the presence of plasticizer and residual monomer.
Di The solubility parameter of aliphatic polar solvents decreases with increase in a
homologous series. Why?
Increase in alkyl chain weakens the contribution of polar group.
58. Styrene when copolymerised with maleic anhydride gives alternating copolymer.
Why?
The reactivity ratio ry(k,;/k,2) is 1 while r(ky9/k>,) is zero. Thus, a monomer free
radical adds to other comonomer.
59) Suspension and emulsion polymerization have no problem of heat dissipation
(polymerization is exothermic). Why?
The inert dispersion medium does not allow the viscosity to increase.
60. Head to tail configuration is preferred over head to head configuration. Why?
Due to the steric factors.
61. Block and graft copolymers are very good stabilizers for colloidal dispersions.
Why?
Due to the presence of two distinct moities in the same molecule, these resemble
to surfactants (soaps and detergents) and thus adsorb efficiently.
62. Single crystals of some polymers can be obtained from crystallization in dilute
solution but not from melt. Why?
If crystallization is achieved from a very dilute solution, single, nearly perfect
crystals may be obtained from many polymers. This revolutionary discovery
stimulated much research on the behaviour of crystalline polymers. In single
crystals the long molecules fold back on themselves every 10 nanometers or so,
so that more or less flat platelets are formed, with the molecules lying perpendicular
to the plane of the crystal. Crystallization from the melt leads to much less
regular structures, for it is very difficult to disentangle long molecules from each
other, and a given molecule may participate in several crystalline units. A melt -
crystallized polymer typically contains regions that are rather well ordered
(crystallites), tied together by uncrystallised segments of molecules.
63. Teflon is an inert polymer. Why?
The most electronegative fluorine atoms provide strong attraction in the molecules
thus make it resistant to chemicals.
64. Chain stiffness depends on chemical structure. Why?
Strongly polar groups, such as those containing oxygen, nitrogen, sulfur, and
other polar atoms exert the strongest attractive forces. Bulky side groups attached
to the main chains stiffen the chains and also by their bulk may prevent a close
fit between chains. Long side chains tend to act as internal plasticizers.
65. Light scattering is ahighly useful technique. Why?

The fact that the amount of light scattered by a solution is a function of the
molecular weight of the dissolved particles has provided a means for the
determination of weight-average molecular weights up to several million. The
light scattering measurement can also yield valuable information regarding the
shape of the molecule in solution.
66. In what ways does the reinforcement affects the properties of rubbers and plastics?
With rubbers, strength and modulus may be increased up to a point by reinforcement
or increased cross-linking, at the expense of elongation, while with plastics, the
modulus is increased, but the strength and toughness are often decreased by these
factors.
67. Plasticizers make the polymer flexible and rubbery. Why?
The addition of plasticizers to a polymeric material makes it to be softer and
more rubbery in character. Plasticizers are held in association with the polymer
chains by secondary valence forces. They separate the segments/molecule of
polymer, thus reducing the effective intermolecular attractive forces.
68. cis-1,4 polydienes make very flexible chains and are rubbery, soft and non-
brittle. Why?
The flexibility of linear polymer chains and of the segments between cross-
linked (cured) products is decreased by the presence of polar group and regularity
in the molecular structure. A non-polar irregular chain should be the most flexible.
Products containing highly flexible chains are rubbery, soft, and non brittle, with
relatively high resistance to impact and to tear.
69. Osmometric method for mol. wt. determination is preferred over dndbaity and
GPC methods. Why?
Osmometry is an absolute method and does not require calibration etc. Automated
high speed osmometers are commonly used. However, osmometry does not provide
any information on polydispersity.
70. Osmometry provides number average mol wt. of polymers. Why?
Osmotic pressure is a colligative property i.e. depends only on the number of
molecules and not on their size or value.
7h. The exponent a@ of Mark-Houwink equation is close to unity for aromatic
polyamides. Why?
The polymer molecules of polyaramides behaves as rigid rod-like, because of the
presence of ring structures followed by semi conjugation along the chain.
72. Above the ceiling temperature, depolymerization is favourable process. Why?
The AG for polymerization is negative as long as AH (exothermic, AH = —ve)
is greater than T AS(AG > Q) at higher temperature and thus the reverse
(depolymerization) process becomes favourable.
aa: Softening temperature of nylon 6, 6, is higher than that of nylon 6, 10. Why?
Increase in the methylene groups along the chain (sebacic acid containing 10
carbon atoms making nylon 6, 10 with hexamethylene diamine, and adipic acid
containing 6 carbon atom for nylon 6, 6) weakens H-bonding between molecules
and thus nylon 6, 10 has lower softening temperature compared to nylon 6, 6.
74. Chain structure of elastomers differs from that of thermoplastics and thermosetts.
Elastomers are usually described as loosely linked network where the intermolecular
linkage are few (thermosetts are fully cross-linked network polymers whereas
thermoplasts are linear) which alows considerable extension without breaking
the chemical cross-linking on applying force (elastomeric deformation).
75. The reduced viscosity versus concentration plot is extrapolated to zero concentration
to obtain intrinsic viscosity needed in the mol. wt determination. Why?
Appendix C 341
Extrapolation eliminates the effect of polymer concentration on viscosity of solution.

76. Under what condition the intrinisic viscosity is considered independent of molecular
weight?
When the polymer behaves as a hard sphere. [)] = KM° = K for (@ = 0). This is
the case for all globular proteins.
Wak. A useful range of mol. wt. varies from 20,000 to 2,00,000 Why?
Below 20,000 the polymer does not possess enough strength (polymers usually
have threshold mol. wt. whendheir mechanical strength becomes maximum and
constant. Very high mol. wt. polymers (>200,000) are not preferred as they possess
very high melt viscosity which creates problems in processing.
78. T, of polyethylene, polypropylene and polystyrene are in the order PE < PP< PS.
Why?
Presence of bulky pendant groups hinders segmental motion and thus increases
Pi:
TE), iGof polyethylene is low as compared to PVC and PAN Why?
The polar Cl and CN groups in PVC and PAN hinder the segmental motion and
thus increase T,.
80. Polyethylene oxide has low T, as compared to polyethene. Why?
The insertion of an oxygen atom between the methylene groups in the polymer
backbone increases internal rotation (thus segmental motion) giving a lower
value of T, for PEO.
81. The 7, ws polystyrene is less than T, of poly @-methylstyrene and that of
poly meviacrylate is less than PMMA. Why?
Additional methyl group hinders the segmental motion and thus increases T,.
82. T, of nylon 6, 6 is about the double to that of polyester of comparable chain.
Why?
Strong interaction (H-bonding) is present in nylon 6,6 but absent in polyester, in
which only dipole-dipole forces operate. This increases T, remarkably.
83. Teflon is a linear thermoplast polymer yet it has ehansotoniatios of thermosett
materials, Why?
Due to the presence of most electronegative F atoms in regular configuration.
84. Natural rubber needs vulcanization. Why?
Linear polyisoprene is tacky polymer with poor strength, poor resistance to solvents
and tittle durability as the chains can slip past. Cross-linking develops strength,
makes the rubber hard and easily processable.
Questions Based on Multiple Choice
Set I
1. Hardening of plastics often involves cross-linking. This process is called
(a) Curing (b) Vulcanisation
(c) Compounding (d) Plasticization
Which of the following classes belongs to polymer:
(a) Phospholipids (b) Steroids
(c) Enzymes (d) Vitamins
In order to obtain a high mol. wt. polymer by polycondensation
(a) The byproducts should be removed during polycondensation
(b) Excess of one monomer in a monomer pair should be avoided
(c) Monomers should be highly pure
(d) Each of the above is essential
4. The synthesis of polymers of low molecular mas using chain transfer agents is
often described as ;
(a) Chain polymerisation (b) Step polymerisation
(c) Emulsion polymerisation (d) Telomerisation
5. The final product of emulsion polymerisation is latex. The polymer can be obtained
from this latex by
(a) Coagulation (b) Non-solvents
(c) Evaporation (d) Crystallisation
6. The mixing of two polymes yields a/an
(a) Block copolymer (b) Alternating copolymer
(c) Polyblend or polymer alloy (c) None of the above
7. Which of the following natural polymers are polysaccharides
(a) Casein, gelatin, collagen, keratins ‘
(b) Gums, agar, heparin, alginates
(c) Urease, @-chymotrypsin, amylase, lipase
(d) Insulin, oxytocin, lipase, ribonuclease
8. Gutta percha is
(a) Cis 1, 4-polyisoprene (b) trans 1, 4-polyisoprene
(c) Vulcanised polyisoprene (d) Ebonite
9. The polymerisation of a vinyl monomer often predominatly involves the
(a) Head-to-tail arrangement (b) Head-to-head arrangement
(c) Both the above (d) Both the above are identical
10. Polyethylene oxide can be called as
(a) Polyethylene glycol (b) Polyoxirane
(c) Polyoxyethylene (d) All of the above
11. Which of the following is a polar polymer
(a) Polyvinyl alcohol (b) Polystyrene
(c) Polyethylene (d) ‘All of the above
12. Which of the following is a non-polar polymer
(a) Polyacrylic acid (b) Polyvinyl! alcohol
(c) Polypropylene (d) Polyacrylonitrile
13. Which of the following is a polyelectrolyte
(a) Polyvinyol alcohol sulphate (b) Polyvinyl alcohol
(c) Polymethyl acrylate (d) Polyacrylonitrile
14. Block copolymer molecules in selective solvent (good solvent for one block,
precipitant for the other) aggregate and thus behave like
(a) Surfactants (b) Dyes
(c) Proteins (d) Drugs
15. The concentration of polymers in solution are often expressed as
(a) g/dl or wt% (b) Molarity
(c) Molality (d) Vol %
16. Plasticisers do not affect
(a) Modulus (b) T,
(c) Dielectric loss (iets
17. Excess entropy of polymer solutions is
(a) Zero (b) Highly positive
(c) Negative (d) Either positive or negative
18. Solution polymerisation in CCl, often leads to
(a) Low mol. wt. polymers (b) High mol. wt. polymers
(c) Cross-linked polymers (d) Polydispersed polymers
19. Relaxation is not affected by
Appendix C 343
(a) Tacticity “ (b) Crystallinity

(c) Plasticizers (d) Molecular weight
20. The lower limit of mol. wt. of about 10,000 for membrane osmometry is due to
(a) The assumption of infinite dilution
(b) Polymer-polymer interactions
(c) Leakage through the membrane
(d) All of the above are true
21s The upper limit of about 5,009 mol. wt. for vapour phase osmometry is due to
(a) The small effect on the solvent activity for higher mol. wt. polymers
(b) The low volatility of higher mol. wt. polymers
(c) Approximations in the theory
(d) Inefficiencies in heat transfer
22 Which of the following is the initiator for suspension polymerisation
(a) Potassium persulphate (b) Benzoyl peroxide
(c) AIBN (d) Lewis acids
PB. In order to see the fluctuations in scattered light intensity in quasi-elastic light
scattering
(a) A laser must be used as a light source
(b) Solute concentration must be very small
(c) The particle size should be less than 1/20 of the wavelength
(d) The scattering volume must be very small
24. Which of the following is a thermoplastic
(a) Ebonite (b) Vulcanised rubber
(c) Bakelite (d) HDPE
25% Pyrolysis GC is not generally applicable to polymers
(a) Thermosett (cross-linked, insoluble)
(b) Block copolymers
(c) Terpolymers
(d) Polymers with heteroatoms (O, N, Cl) in the backbone
26. A “good solvent” is one in which
(a) The second virial coefficient is negative
(b) The polymer will always dissolve rapidly
(c) The solubility parameter of the solvent differents from that of the polymer
by less than 30%
(d) Different polymer molecules do not interact strongly with each other
21s At which temperature will the polymer coil be larger in poor solvent
(a) At theta temperature (b) Below theta temperature
(c) Above theta temperature (d) None of the above
28. Which of the following techniques yields a number-average molecular weight
(a) Viscometry (d) Osmometry
(c) Light scattering (d) Ultracentrifugation
29. Which of the following is a branched chain polymer
(2) DRE (b) Isotatic polypropylene
(c) LDPE (d) Amylose (starch)
30. In copolymerisation, one does not usually oserve that the product of the reactivity
ratios is very large (r;/r2 >> 1). In this case,
(a) no polymerisation takes palce
(b) A perfectly alternating copolymer is formed
(c) ky, is small compared to k>
(d) No copolymer is formed
318 Which one of the following is not a requirement for using a wet chemical (titration)
method to determine the amount of some reactive group in a polymer
(a) The reaction'should be rapid

(b) The reagent needs to be a*small molecule so it can have access to buried
groups in the interior of the polymer coil in solution.
(c) The reaction should be quantitative
(d) Itis necessary to be able to monitor either the product formed or the reagent
consumed.
32. The T, of a polymer can be determined by
(a) IR (b) NMR
(c) Dilatometry (d) TGA
33) Which would be the better solvent for polystyrene
(a) m-pentane (b) benzene
(c) acetonitrile (d) methanol ,
34. In which of the following polymers will hydrogen bonding predominate
(a) Natural rubber (b) HDPE
(c) Cellulose (d) Cellulose nitrate
BS: Which of the following is a monodisperse polymer
(a) Natural rubber (b) Cellulose
(c) Casein (d) Nylon
36. Which of the following is thermosett or cross-linked polymer
(a) Cellulose (b) Univulcanised rubber
(c) Cellulose nitrate (d) Bakelite
Ay Which one of the following polymers can be prepared by anionic, cationic and
free radical polymerization?
(a) Polyethylene oxide (b) Polyvinyl chloride
(c) Poly(vinyl methyl! ether) (d) Polystyrene
38. Which of the following will yield a cross-linked polyester when condensed with
adipic acid
(a) Ethyl alcohol (b) Ethylene glycol
(c) Glycerol (d) Hexamethylene diamine
39: Tetrafluoroethylene is a monomer for
(a) Neoprene (b) Butyl rubber
(c) Teflon (d) Glyptals
40. The intermolecular forces operating only in crystalline polymers like terylene,
nylons, cellulose are
(a) H-bonding (b) Dipole-dipole interaction
(c) Hydrophobic interaction (d) London dispersion forces:
41. End group analysis gives
(a) M,, (b) My
(c) M, (d) M,
42. Which of the following is thermoplastic
(a) Terylene (b) Nylon
(c) Polypropylene (d) All of the above
43. Wool and silk are natural polymers. These are basically
(a) Proteins (b) Polysaccharides
(c) Polyesters (d) Polyethers
Vulcanisation of natural rubber by sulphur makes it
(a) Water soluble (b) Soft
(c) Hard (d) Less elastic
45. The polymer Buna N is a copolymer of
(a) Butadiene and acrylonitrile (b) Butadiene and styrene
(c) Butadiene and ethylene (d) Butadiene and isoprene
pee
Appendix C 345
46. Which of the following will not dissolve in a solvent or melt on heating
Qin bviG (b) Teflon
(c) Bakelite (d) PMMA
47. HDPE differs from LDPE in
(a) Degree of crystallinity (b) Molecular weight
(c) Melting temperature (d) All of the above
48. Camphor, dibutyl phthalate, tricresyl phosphate are all examples of
(a) Antioxidants ‘ (b) Plasticizers
(c) Curing agents (d) UV stabilizers
49. The glass transition is a 2nd order thermal transition in amorphous polymers due
to
(a) Segmental motion (b) Molecular motion
(c) Both (d) None of the above
50. Nylon 6 is obtained from
(a) Caprolactam
(b) Hexamethylene diamine and adipic acid
(c) Amino acids
(d) Chloroprene
Set IT
. Terylene is a
(a) Polyester (b) Polyamide
(c) Vinyl polymer (d) Acrylic polymer
Polydispersity index is often expressed as the ratio
(a) T,/T (b) M,,/M,,
(c) Both (d) None of the above
No synthetic polymer can be monodispersed. Nature’s monodispered polymer is
(a) Starch (b) Cellulose
(c) Insulin (d) Natural rubber
GPC is a chromatographic technique whihc separates polymer molecules in a
sample according to their size and provides
(a) Fractionation (b) Mol. wt. distribution
(c) Molecular weight (d) All of the above
Which of the following thermal methods cannot be used to determine 7,
(a) TGA (b) DTA
(c) TMA (d) DSC
Living anionic polymerisation can be conveniently used to produce
(a) Block copolymers (b) Homopolymers
(c) Thermosetts (d) Thermoplasts
Separation of different low mol. wt. (MWD) distribution samples from a highly
polydispersed plymer is called fractionation which can be done by
(a) Partial dissolution method (b) Partial precipitation method
(c)? GPE (d) All of the above
Which of the following polymers are often highly crystalline
(a) Fibres (b) Plastics
(c) Elastomers (d) Surface coating materials
At temperature above T, but below T,,,, a polymer may be considered as a
(a) Crystalline solid (b) Super cooled crystal
(c) Glassy solid (d) None of the above
10. Which of the following can be used for the synthesis of addition polymers
(a) Free radical polymerisation (b) Ionic polymerisation
(c) Coordination polymerisation (d) All of the above
11. Nylon 6, 6 can be conveniently produced directly as yarn by

(a) Melt polycondensation (b) Solution polycondensation
(c) Interfacial polycondensation (d) All of the above
Addition polymerisation involves the breaking of a 2 bond and formation of 2-0
bonds and is a/an
(a) Exothermic process (b) Endothermic process
(c) Reversible process (d) None of the above
. Polycondensation often involves the elimination of small molecules like H3,
CH;0OH, DCI gas, etc. and these are removed to prevent reversible reaction by
(a) Distillation (b) Fractionation
(c) Crystallization (d) Sublimation
The imperfect crystalline regions made from bundles/aggregates of ordered chain
are called
(a) Spherulites (b) Crystallites
(c) Single crystals (d) Dendrites
The value of @ in Mark-Houwink equation [)] = KM® in theta solvent is
(a) 1.0 (b) 0
(c) 0.5 (d) 0.8
. The value of second varial coefficent (A) in the equation 7/C = [RT/M] (1 + A2C)
for polymer in 6-solvent is
(a) 0 (b) 1.0
(c) 0.5 (d) None of the above
. Which of the following most known polymer scientists did not receive Noble
Prize
(a) Hermann Staudinger (b) Karl Ziegler and Giulio Natta
(c) Herman Mark (d) Paul Flory
. Bakelite was the Ist synthetic polymer made by
(a) Henry Baekelund (b) Charles Goodyear
(c) William Carothers (d) Hyatt
. Atany time when the chain polymerisation progresses, the reaction vessel contains
(a) Only monomer
(b) monomer + polymer
(c) Monomer + dimer + trimer + tetramer, etc.
(d) All of the above
20. Polycondensation involving step-wise addition of monomer/monomer pair is also
called
(a) Step polymerisation (b) Condensation polymerisation
(c) Step-addition polymerisation (d) All of the above
PA Which is not true for polymers
(a) Asmall amount of dissolved polymer increases the viscosity of liquid
(b) Polymer dissolution is a slow process involving swelling
(c) Polymers do not show sharp m.pt. and liquid polymers cannot be changed
into gaseous form on heaing
(d) Polymers sublime on heating
22, Which of the following additives is added during the polymerisation
(a) Plasticizers (b) Antioxidants
(c) Thermal stabilizers (d) Chain transfer agents
Zs What is not true for thermosetts
(a) They are cross-linked polymers
(b) They do not melt/soften on heating
(c) They donot dissolve in any liquid
(d) They do not have very high molecular mass
,. Appendix C 347
24. The property of a homopolymer can be improved by

(a) Copolymerisation with some other monomers
(b) Forming polymer alloys
(c) Adding plasticizers
(d) All of the above
Hips. Polymer solutions can be considered colloidal solutions in that they show
(a) Electrophoresis (b) Light scattering
(c) Coagulation ‘ (d) Peptisation
26. Polymer solutions can be grouped into
(a) Association colloids (b) molecular colloids
(c) Lyophobic colloids (d) All of the above
Qe Starch, cellulose, glycogen are allthe polymers of
(a) Glucose (b) Sucrose
(c) Glucose + Fructose (d) None of the above
28. All enzymes are made of
(a) Proteins (b) Proteins and polysaccharides
(c) Nucleic acids (d) None of the above
29: DP = 1/1-pis the equation for polycondensation that relates degree of polymerisation
(DP) to the extent of reaction, p. It is known as
(a) Carother’s equation (b) Huggin’s equation
(c) Mark-Houwink euation (d) Copolymerisation equation
30. In polycondensation, the extent of conversion, p, approaches unity, the heterogenity
index (M,,/M,,) in the polymer is
(a) 1 (b) 2
(c) 100 (d) 0
Sul The high increase in viscosity of the monomer as the polymerisation proceeds is
often described as
(a) Autoacceleration (b) Trommsdorff effect
(c) Gel effect (d) All of the above are same
32: The kinetics of addition polymerisation shows molecular weight as
(a) Proportional to monomer concentration
(b) inversely proportional to (Initiator conc.)
(c) Both
(d) None of the above
33: 1, 4 Polyisoprene shows
(a) Cis-trans isomerism (b) Tacticity
(c) Both of the above (d) None of the above
34. Polypropylene shows
(a) Cis-trans isomerism (b) Stereoisomerism
(c) Structural isomerism (d) Functional isomerism
35% Polystyrene and poly (p-xylene) are
(a) Cis-trans isomers (b) Structural isomers
(c) Stereoisomers (d) Functional isomers
36. At least two functionla groups are required in the monomer/monomer pair. The
functionality of phenol -a monomer for Bakelite is
(a) 1 (b) 2
(c) 3 (d) 4
a The coil dimension (72)? of a polymer molecule is related to the unperturbed
dimension (72)? by (F?)"? = a(7 )'? . Under 6-condition the value of chain
expansion factor, @, is
(a) 0 (b) 0.5

(c) 1.0 , ‘(d) 2.0
38. In good solvents where solvent molecules processes an affinity for polymer
molecule, the polymer coil
(a) Expands (b) Contracts
(c) Expands or contracts (d) Does not change size
39! The Hildebrand’s solubility parameter is equal to cohesive energy density and
has the unit ;
(a) (cal/em?)'”? (b) cal/em?
(c) J/m (d) None of the above
40. For the dissolution of amorphous polymers in non-polar solvents, solubility
parameter values for solvent and polymers should be
(a) Nearly equal (b) Zero
(c) Largely different (d) None of the above is true
41. What is true for membrane osmometry for the determination of mol. wt of polymers?
(a) It gives M,
(b) Dynamic osmometers provide quick determination of osmotic pressure
(c) The solvent should not be a very good solvent
(d) All are correct
42. Which of the following method only will give reliable estimate of M,, of a
polymer with mol. wt. >1,00,000?
(a) Ebbluiometry (b) Cryoscopy
(c) End of group analysis (d) Membrane osmometry
43. The determination of M,, from light scattering involves a double extrapolation
on the same graph. This grid like figure is called
(a) Zimm plot (b) Chromatogram
(c) Turbidity plot (d) Mol.wt. distribution curve
Ultracentrifuge utilizes the determination of mol. wt. through the measurement
of sedimentation constant and diffusion coefficient utilising equation called
(a) Carother’s equation
(b) Huggins equation
(c) Mark-Houwink-Sakurada equation
(d) Svedberg equation
. In GPC, the stationary and mobile phases are
(a) Solid and liquid
(b) Liquid and liquid
(c) The single liquid acts as both the phases
(d) Solid and gas
46. A thin film of melt crystallized polymer on viewing in optical microscope between
crossed polars, show characteristic structure. These are called
(a) Crystallites (b) Spherulites
(c) Single crystals (d) Dendrimers
47. DTA can be utilized in polymer research for the determination of
(a) T,/T, (b) Degree of crystallinity
(ey PeLe (d) All of the above
48. A polymer with high mol. wt. and high degree of crystallinity would behave as
(a) Soft and waxy (b) Hard and flexible
(c) Hard and tough (d) Soft and flexible
49. The reactivity ratios of monomer 1 and monomer 2 are r, and rp. If r; = r, = 0
(a) A block copolymer will form
(b) An alternate copolymer will form
,.. Appendix C 349
(c) A random copolymer will form.

(d) Two homopolymers will form
50. Termination under control conditions sometimes does not occur in:
(a) Anionic polymerisation (b) Cationic polymerisation
(c) Free radical poymerisation (d) Coordination polymerisation
Set IIT
I Nylon 6, Nylon 6,6 and Protéins all are
(a) Polyamides (b) Polyethers
(c) Polyesters (d) Polyolefins
Natural rubber is a ;
(a) Cis 1, 4 Polyisoprene (b) Trns 1,4 Polyisoprene
(c) 1, 2 Polyisoprene (d) 1, 3 Polyisoprene
Which of the natural polymer is not a condensation polymer
(a) Nucleic acids (b) Polysaccharides
(c) Proteins (d) Natural rubber
Which of the following is not a polysaccharide
(a) Starch (b) Cellulose
(c) Heparin (d) Amylase
Which is considered as a first synthetic polymer
(a) Bakelite (b) Teflon
(c) Neoprene (d) Nylon 6
Which of the following polymers possesses elastomeric properties
(a) Thiokol (b) Plypropylene
(c) Polymethyl methacrylate (d) Polyvinylidene chloride
Which of the following is not a fiber
(a) Polypropylene (b) Polyethylene tereph thalate
(c) polyacrylonitrile (d) Polyurethane
Which of the following is not a cellulose derivative
(a) Cellophane (b) Celluloid
(c) Gum cotton (d) Cellobiose
Which of the following is not a copolymer
(a) SBR (b) Butyl rubber
(c) Saran (d) Teflon
10. The concept of macromolecules was propounded by the Nobel laureate
(a) Staudinger (b) Natta
(c) Flory (d) Sanger
. Solid phase synthesis of polymer was first demonstrated by the Nobel laureate
(a) Ziegler i (b) Merrifield
(c) Herman Mark (d) Paul Flory
. Bisphenol-A is a monomer used in the preparation of
(a) Polycarbonates and epoxy resins
(b) PF and UF resins
(c) Polyurethanes
(d) Alkyd resins
Which of the following is not an initiator for free radical addition polymerisation
(a) Benzoyl peroxide (b) Azobis isobutyronitrile
(c) Lewis acids (d) Persulphates
14. The vulcanization process, i.e. mastication of rubber with sulphur to make it
useful is due to:
(a) Carothers (b) Goodyear
(c) Schonbein (d) Hyatt
15. Which of the following is a thermosett

(a) UF polymer (b) Teflon
(c) PMMA (d) SBR
16. Plasticisers are added to polymers to decrease its
(a) T, (b) Try
(c) Solubility (d) Crystallinity
Le The T, of a polymer can be determined by
(a) Dilatometry (by DTA/DSC
(c) TMA (d) both (a) and (b)
18. Light scattering provides molecular weight, which is
(a) Weight average (b) Number average
(c) Z-average (d) Viscosity average
. Which of the following techniques is not based on colligative properties
(a) Ebblumetry and Cryoscopy (b) Vapour pressure osmometry
(c) Membrane osmometry (d) Viscometry
20. The light scattering intensity and sedimentation velocity of particles depends on
their
(a) Sizes (b) Number
(c) Colour (d) None of the above
ze Which of the following would you expect to be a crystalline polymer
(a) Polybutadiene (b) SBR
(c) Nylon 6, 6 (d) LDPE
esp Which of the following will have highest value of 7,
(a) Polyethylene (b) Polypropylene
(c) Polystyrene (d) Polymethyl styrene
2; Which of the following polymers is difficult to crystallize
(a) Polyesters (b) Polyethylene
(c) Polypropylene (d) Polyvinyl carbazole
24. Carbon fibre is obtained by the cyclisation followed by dehydrogenation of
polyacrylonitrile is
(a) Ladder like polymer (b) Star like polymer
(c) Comb like polymer (d) Branched polymer
-3f The monomer added in small amount in the polymerisation of styrene to cross-
link it for use as an ion exchange resin or as column material for GPC is
(a) Divinylbenzene (b) Butadiene
(c) propylene (d) None of the above
In emulsion polymerisation, the initiator is
(a) Soluble in water (b) Soluble in monomer
(c) Insoluble in both (d) Soluble in both
Ze Which of the following polymerisation techniques offers problem of heat dissipation
(a) Solution polymerisation (b) Bulk polymerisation
(c) Suspension polymerisation (d) Emulsion polymerisation
28. Which of the following is not polymerised alone but is copolymerised with
styrene to yield alternating copolymer
(a) Butadiene (b) Maleic anhydride
(c) Acrylonitrile (d) Vinyl acetate
pAty Polyvinyl alcohol is obtained by the hydrolysis of polyvinyl acetate but not by
the polymerisation of vinyl alcohol monomer because the monomer is
(a) Difficult to purify (b) Converts into acetaldehyde
(c) Difficult to polymerise (d) Water soluble
30. The T, of polymers behaving like rubber should be
we Appendix C 351
(a) Less than room temperature ‘ (b) Higher than room temperature
(c) Equal to room temperature (d) Any of the above
31. Which of the folowing abbreviating forms is a condensation polymer
(a) PAN (b) PMMA
(c) SBR (d) PET
32. Which of the following materials is ued in the production of terylene
(a) DMT (b) VAM
(c) Bisphenol ‘ (d) Glycerol
33. The polycondensation of a monomer pair each having bifunctionality always
gives
(a) linear polymer (b) Branched polymer
(c) Cross-linked polymer (d) Any of the above
34. Which of the following is not a thermosett
(a) Glyptals (b) Bakelite
(c) Epoxies (d) Buty] rubber
35. The most inert polymer, used in non-sticking kitchen ware is
(a) Teflon (b) Melamine resin
@Y IMs (d) PMMA
36. The monomers in a polymer molecule are joined through
(a) H-bond (b) Covalent bonds
(c) Electrovalent bonds (d) Dipole-dipole interaction
37. The polymer used in making buckets, mugs, storage tanks, TV cabinets, etc. is
(a) HDPE (b) Polypropylene
(C)aEBY.C (d) Polystyrene
Answers
SetI
1. (a) Za) 3. (a) 4. (d) Deca)
6. (c) ies il(0) 8. (b) 9. (a) 10. (d)
11. (a) 1255) 13. (a) 14. (a) 15. (a)
16. (d) 17. (a) 18. (a) 195R(c) 20. (c)
21. (a) DIAC) 23. (a) 24. (d) 250A)
2604(C) 27 (C) 28. (b) 29. (c) 30. (c)
Slee) 32:40) 33. (d) 34. (c) 35. (c)
36. (d) Sian) 38. (c) 39. (c) 40. (b)
41. (a) 42. (d) 43. (a) 44. (c) 45. (a)
46. (c) Aimee) 48. (b) 49. (a) 50. (a)
Set II
ae) 2. (b) 3. (Cc) 4. (b) 5S. (d)
6. (a) 7. (d) 8. (a) 9. (d) 10. (d)
11a) Te (a) 13. (@) 14a), SCC)
16. (a) K7at (ec) 18. (a) 19. (b) 20. (d)
21. (d) yor (<9) 23. (d) 24. (d) 25. (b),
26. (b) 27. (a) 28. (a) 29. (a) 30. (b)
31. (d) Sade ae 3a (Cc) 34. (b) 35. (b)
36. (c) 5/ arc) 38. (a) 39. (a) 40. (a)
41. (d) 42. (d) 43. (a) 44. (d) 45. (c)
46. (b) 47. (d) 48. (a) 49. (a) 50. (a)
Set Il
if. (a) 2ea(a) 3. (d) 4. (c) 5. (a)
6. (a) 7. (b) 8. (d) 9. (d) 10. (a)
ide (b) 12a) Laie) 14. (b) 15. (a)
16. (a) 17s (a) 18. (a) 19. (b) 20. (a)
21; (c) 22. (d) 23. (d) 24. (a) 25. (a)
26. (a) Bie (b) 28. (b) 29. (b) 30. (a)
Site (d) 32. (a) B83 i(a) 34. (d) 35; (8)
36. (b) 37. (b)
Fill in the blanks
The term ‘polymer’ was first used by the Swede

The structure that repeats in a polymer molecule is called
Network copolymers require one of the monomers with functionality
Intrinsic viscosity is also known as
Membrane osmometry, unlike vapour pressure osmometry, viscosity and GPC,
does not require
A thermoplastic with regular chain amenable to crystallization on stretching to a
temperature between 7, and T,,,, improves mechanical property. This process is
called
A highly regular type of graft polymer where the grafts are separated by uniform
lengths in the backbone can be called ________ polymer
Liquid crystals show _________ behaviour
Poly (phenylene terephthalamide) or Kevlar shows
H-bonding raises ________ of polymers due to the hindered segmental rotation
. For several common polymers T, is approximately equal to _______ of T,,,,
. In solution polymerization the solvent simply acts as _______ for the dissolved
species like monomer and initiator etc.
equation predicts the polycondensation reaction
is a linear polymer of B glucose with crystalline structure
i A glassy polymer on increasing the temperature changes to a soft, flexible, rubbery
mass at
The first synthetic polymer made by Henry Baekelund is
Depending upon the nature of the a-amino acids, a ________ molecule can be
globular (water soluble) or fibrillar (water insoluble)
Polysaccharides, polyamides, polynucleotides and polyisoprene can be grouped
as ee
Polyacrylonitrile on heating followed by dehydrogenation forms a ladder like
polymer called
polymers can be obtained by polymerising a monomer in the presence
of a polymer
polymers have structural resemblance to surfactants and thus form
micelles and adsorb from solution
can be conveniently used to determine M, of polymers with fairly
high value of molecular weight
pep is used as a coating material in cooking frying pans due to its inert
nature
24. Nature can produce mono-dispersed polymers (no perfectly monodispersed
Appendix C 353
polymers are made in the laboratoryy. The Nature’s mono-dispersed polmers are
Do: Cis-1, 4 polyisoprene is a gummy polymer obtained from the latex of rubber
trees. It could be used commercially only after the discovery of vulcanisation
process first used by
26. Based on the cohesive energy density that measures intermolecular attraction,
Hilderbrand introduced ________ that helps in predicting solubility of a polymer
in a solvent ‘
Pe Styrene-maleic anhydride copolymer has charged carboxylic groups and can be
called
28. can be made simply by physical mixing of two homopolymers and
sometimes possess better properties than the constituting homopolymers
29: At any time during the course of polymer formation, the reaction vessel contains
only monomer and polymer in _______ process
30. are low mol. wt. and low volatile materials that often decrease glass
transition temperature of polymers and thus facilitate in processing and give
desired properties to polymer
Sik. anionic polymerization process is very suitable method for obtaining
block copolymers with controlled mol. wt. and molecular composition/structure
32: The value of a@= 0.5 (in the equation [7] = KM®%) and second virial coefficient A,
= 0 (in the equation 2/C = [RT/M,](1 + A2C) for any polymer in
solvents
33: The ________ of the monomers for a particular monomer pair are important in
predicting the composition of a copolymer
34. An —________ copolymer is one when the concentration of the monomers in the
feed (in the polymerization vessel) is same as that in the copolymer formed
35. was the first to give the concept of macromolecules in 1920 (much
criticized then by the scientists) and was awarded Nobel Chemistry Prize in 1953
36. The polydispersity index of a polymer sample is often expressed as the ratio
_______4 where it is one for a monodispersed polymer
oi, Stereoregular polypropylene is a highly ________ and can be used as fibres
38. The polyethylene produced from the polymerisation of ethene by Ziegler’s catalyst
at mild temperature/pressure conditions gives ________, a polymer with high
degree of crystallinity
30! Poly (sodium acrylate) is an example of a ________ which dissociates in water
to give a macroanion and sodium ions
40. Polystyrene (cross-linked) made by copolymerisation of styrene with small amount
of divinylbenzene on sulphonation gives a polymer which is highly useful as
in water treatment
41. Polycondensation of two pure reactants each with a bifunctionality taken in
exactly equimolar ratio may lead to an extremely _______ polymer
. A polystyrene ball thrown on the floor will shatter like glass into pieces but the
same ball when heated to 100°C prior to throwing will show
. The common polymers like PE, PP, PS, PVC, terylene, nylon, can be recycled
from waste by ______ polymers are not reusable
The dissolution of a polymer first involves swelling. A polymer showing
swelling in a solvent will not form solution
45. A polymer will be a useful ruber if its T, is less than room temperature However,
for excellent elasticity the polymer is desired to have a few
46. Polyethylene oxide, polyvinyl alcohol, poly (sodium acrylate), polystyrene
sulphonate, polyvinyl methyl ether are the examples of _______ polymers
47. Maliec acid does hot polymerize by itself although it contains unsaturation as
well as two functional groups. However, styrene and maleic anhydride can be
copolymerised to give an ________ copolymer
48. Chain transfer agents are often added during the polymerisation if low mol. wt.
polymer is desired. The chain transfer can by itself take place in
polymerisation technique
49. T, of a polymer can be decreased by ________plasticization (without adding any
plasticizer) using copolymerization
50. is a quick, reliable and efficient technique for the fractionation of a
polydispersed polymer as well as for molecular weight distribution analysis
ah The hereditary material DNA, is a polynucleotide containing long repeating units
of base-sugar-phosphate. The DNA molecule exists as a double helix, this
understanding about the structure of DNA is due to investigations by
a2. Glyptals, epoxies, alkyds, formaldehyde resins can all be grouped together as
353 PVC, nylons, polyesters, cellulose, PAN can all be considered having strong inter
molecular forces broadly known as
54. In polycondensation, the molecular weight builds up slowly (unlike chain
polymerisation) but the reaction goes to completion yielding high mol. wt. polymer,
if the both the bifunctional reactants are present in equal amount. The DP can be
controled by using a
DD: Benzoyl peroxide, AIBN, persulphates and redox systems e.g. ferrous ions and
H,O), generate ______ which initiate the polymerisation of unsaturated monomers
56. The important condition for a low mol. wt. substance to form a polymer is that
it must contain atleast bifunctionality. This may arise from the presence of functional
groups or
Polymerisation is an exothermic process. Bulk polymerisation technique often
has the problem of heat dissipation. No such problem is present in solution
polymerisation, but chain transfer by solvent gives, low mol. wt. polymer.
and emulsion polymerisation are thus more advantageous techniques for
polymerisation
Polycondensation can be done by melt, solution and _______ techniques. The
latter technique is quite useful for making nylon 6, 6 directly in the form of
continuous filament
oy Polybutadiene and polyisoprene are not useful as rubbers but their cross-linked
products like vulcanised rubber or _______ like butyl rubber, SBR, NBR are
highly commercialized elastomers
60. A chromatographic technique useful in the identification and detection of monomers,
polymer additives and polymers is called
. Most monomers and polymers may be qualitatively and quantitatively identified
by
. A technique commonly employed to obtain information on the crystal structure
of polymers is
. When two monomers are polymerised together, the process is called
Dextran, dextrin, heparin, starch, cellulose, glycogen are all biopolymers from
the class
. Two polymers or their solutions when mixed and when noncompatible exhibit
66. equation named in honour of the ultracentrifuge inventor and is used

in the determination of mol. wt. of polymers by this instrument
67. The double chain heat resistant polymers are called
»» AppendixC 355
68. is used in the preparation of epoxy resins and polycarbonates

69. Certain polymers particularly thermoplastics in the glassy state undergo a localized
deformation called
70. Trommsdorff-Norris effect or gel effect is also known as
wile The copolymers of ethylene and methacrylic acid are often known by their generic
name
WP, An allotropic form of carbon other than diamond and graphite is called
J Polyvinyl acetate on _____¢_ gives PVA which is a useful adhesive
74. Crystalline polymers are often dissolved in solvents above their
qSy Polymers with filler materials, particularly fibres with improved strength are
called#=es 2 plastics
76. An additive that readily undergoes chain transfer with a macroradical is called
Vile Cross-linked polymers do not form solution and can undergo only
78. Polymers prepared by polycondensation of phenol with formaldehyde under acidic.
conditions are called __-____
i). A measure of mechanical strength of materials expressed as the ratio of stress to
strain is called
80. A thermal analytical method that is often used for the determination of T, of
polymers is
81. Degradation of polymers from chain ends successively is called
82. Jute, wood flour, carbon black, glass, talc, sand and silica products are polymer
additives called
83. Natural polymeric biocatalysts which possess high substrate specificity are called
84. A kind of termination step in addition polymerization other than coupling is
85. polypropylene has all the pendant methyl group on one side of the
chain
86. Latex fram the rubber tree is _______ to extract natural rubber
87. Polymer formation takes place within the _______ micelles in emulsion
polymerisation
88. Pyrolysed polyacrylonitrile is used as a reagent for _______ reactions in organic
synthesis
89. The OH stretching vibrations can be seen in the IR spectrum of PVA at
90. Polymer microstructures can be examined by
91. Formaldehyde resins (e.g. PF, UF) are processed by
92. Colloidal dispersions of solid polymer in a dispersion medium are called
93% Epoxies, alkyd resins, PVA, Polycyano-acrylates are all examples of
94. Polyamides, aromatic polyamide, carbon fibres are examples of ________ polymers
95: Number average molecular weight of a polymer can be conveniently determined
by
96. Low molecular weight polymers with end functional groups can be characterised
for mol. wt. by
ip. Polymer spherulites can best be examined by
98. Water soluble charged polymers are called
Do A polymerisation technique that involves surfactant micelles in a heterogeneous
mixutre is
100. A minimum requirement for a monomer to form a polymer is the ________ in its
structure
Set II
i Linear polyethylene made using Ziegler’s catalyst is often abbreviated as
2, The formation of gel often leading to explosion in the bulk polymerisation of
unsaturated monomers like acrylonitrile is called
m4 The first synthetic polymer made by Henry Backeland is
The useful elastomeric material which is chiefly polyisoprene (with little isobutylene
as a comonomer) is called
. In solution polymerisation, solvent often ‘acts as ________ leading to low mol.
wt. polymer
are often added to make the polymer soft and flexible which interact
with polymer and weaken intermacromolecular attraction and thus decrease T,
Emulsion polymerisation often results into ________ from which polymer is not
separated by is used as such, e.g. in emulsion*paints
On cooling a molten polymer, its ________ viscosity shoots up
The milk protein that has been used to make plastics in olden days is
Polyacrylonitrile when cyclised followed by dehydrogenation forms
. Polymerisation of a monomer in a medium consisting of a polymer leads to a
multiphase system called
can be determined experimentally using any colligative property like
osmotic pressure, lowering in vapour pressure, etc.
are the monomers in abbreviated forms needed for producing polyester
terylene
Natural rubber creeps of its own weight but when cross-linked with sulphur (a
process invented by Charles Goodyear) it becomes useful. The process is commonly
called
The hardening of plastics, often associated with cross-linking and is called **
. Ahighly inert polymer that is used in kitchen-ware and was discovered accidentally
by Plunkett is
provide important information on the composition of copolymers formed
from the two comonomers
is the solvent, when the polymer molecule exists as unperturbed
dimension at a definite temperature
. The polysulphides often used as elastomers are known by the trade name
gives rise to the statistically regular or irregular arrangement of pendant
groups (like methyl group in polypropylene)
are the polymers (like polyacetylenes) that conduct electricity
_________ is a very useful technique employed for the preparation of tailor-made
block gopolymers
. A polymer like ABS built up of 3 different monomer units can be called a
is a technique for processing polymers into continuous films or sheets

. Polyethylene containing a few methacrylic acid monomers along the chain can
be called an
A process where the cellulose is regenerated for use in making rayon is called
. Aromatic polyamides are thermally stable polymers commercially known as
. The T, of polystyrene can be decreased by copolymerising styrene with little

butadiene. This process of decreasing T, is called
. Polymerisation above a temperature, which depends on monomer, is not
thermodynamically feasible. This temperatue is called
Appendix C 357
30. The fully extended length of a pokymer molecule based on bond distance and
bond length is expressed as
Al, An elastomer (e.g. natural rubber) flow of its own weight. This is called
32. Natural rubber when cross-linked with 30% S produces a hard plastic like substance
called
65: The organised malteese like structures observed in polymers under polarised
microscope are called
34. The _______ and ______,_ polymerisation in a monomer CH, = CHX often
lead to stereopolymers
ao The German scientist who in 1920 gave the concept of macromolecules (which
was highly criticised at that time but later won him Nobel Chemistry 1953 prize)
was
36. undergoes ring-opening polymerisation to produce nylon 6
Sis The Nobel laureate _______ is known for his solid phase synthesis of
macromolecules
38. A linear polymer chain exhibits coiling due to ______ arising mainly as a
result of internal rotation around a single bond
39) The Nobel physical chemist who is known for the advancement in the theory of
polymer solution is
40. Cotton clothes are first dipped in NaOH solution to avoid shrinkage was a useful
process developed by John Mercer and is known as
41. Regular coiling of flexible chains of many biopolymers forms _______ structures
42. The dimension of a polymer coil in solution particularly for branched polymers
is often expressed as
43. The viscosity average mol. wt. becomes number average mol. wt. when the
empirical constant of Mark-Houwink equation, a@, becomes
44. Small hole like machine through which a molten polymer or its solution is passed
to obtain fibres is called
45. Styrene-butadiene block copolymers can be grouped _______ elastomers
46. Polymers of silicon compounds are collectively called
47. first prepared linear polyethylene using low pressure technique
48. The high degree of crystallinity in nylon fibres arises as a result of intermolecular
49. is experimentally evaluated in dilute solution viscosity method and is

related to molecular weight
50. is the breakdown of a polymer into simpler components by means of
microorganisms
oyly HDPE can be obtained as ______ by crystallisation from dilute solutions
a2: PMMA and polycarbonates possess high
53: Nylons are the synthetic polymers, which possess ________ structures
54. To obtain high mol. wt. polymer by step-polymerisation, _______ of the monomer
pair must be maintained
Joi While the mechanical properties of a polymer become independent of mol. wt.
above a critical value, a sharp increase in _______ restricts the processing of
very high mol. wt. polymers
56. In emulsion technique, the polymerisaton takes place within the ________ of the
emulsifier
Syit is often observed in solution polymerisation and results fnto low mol.
wt. polymers
58. are obtained when the two comonomers have same reactivity ratios
ap A lower critical solution temperature observed in PEO, PPO, PVME due to their
inverse solubility relationship is often called
60. possess structural similarities with surfactants and thus form micelles
and exhibit efficient adsorption characteristics
Gl All polymer solutions exhibit light scattering and thus can be called
solutions
62. The double extrapolation of light scattering experimental data to obtain mol. wt.
of polymers yield a grid which is called
63. is the most widely used moulding technique for thermoplast involves
the passage of the molten polymer from a nozzle
64. is determined by dilatometry and provides a convenient determination
of glass transition temperature
65. The techniques based on colligative properties, e.g. ______ and _______ are
not convenient for the determination of mol. wt. of polymers
66. in linear polymers makes them thermosetting plastics
67. Glyptals are made by the condensation of glycerol with
68. can be obtained from osmometry or light scattering and provides
significant information about polymer-solvent interaction
69. Flory’s ______ provides information about the polymer-solvent interaction
70. The branched polymer component present in starch is called
Te Proteins undergo ________ on heating, with pH changes or when alcohol, urea,
etc. are added to their aqueous solutions
(p7 synthesised and characterised linear polyesters and polyamides as early
as in 1930
tisk Segmented polyurethane fibres are commonly known as
74. A short plastic tube, which is heated and expanded by air in the blow moulding
process, is called
a is a cellulose derivative known for its use as thickener and antisoil
redeposition agent in detergent formulations
76. Polyimides are _______ polymers
TH are additives that are added to polymers to retard their oxidative
degradation
78. A filled or reinforced plastic of often called
79. Cross-linked polymers with ionisable groups are used as
80. Continuous fibres of nylon 6, 6 can be made by
81. BF;, AICI; are the catalysts used in
82. Reacting the end groups to produce a stable polymer is called
83. Cross-linked resin prepared from trihydric alcohols and dibasic acids are called
84. Pyrolysed PAN (carbon fibre) is an example of _______ polymers

85. The polymer coil in solution under theta-conditions assumes _____ dimensions
86. Resistance to bending of a material is measured as
87. Hardness of materials is often measured in ______ scale
88. are the substances formed by 3-10 monomer molecules
89. The point on a stress-strain curve below which there is reversible recovery is
called
90. Fluids which exhibit lamellar flow can called
OL, The solubility parameter concept was given by
92. The property when a material possesses viscosity of liquid and elasticity of
rubbers is called
53; The phenyl group in polystyrene and chloro group in PVC can be called
groups
94. Chain _______ make a polymer more rigid and thermally stable
,. Appendix C 359
95. The trans-1, 4 polyisoprene is called

96. Fibre reinforced materials are the major type of commercial
97. The Nobel chemistry prize for the year 2000 has been awarded for the polymers
known as
98. Polymers containing other than carbon atoms in the main chain are called
99. Polymeric gels, solid polymer electrolytes and photoconducting polymers are
called _______ polymers
100. Cellulose is water ____,
Answers
Set I
1. Berzelius, 2. CRU, 3. More than two, 4. Viscosity number, 5. Calibration, 6. Crystallisation,
7. Comb, 8. Mesomorphic, 9. Highest mechanical strength, 10. T,, 11. 1/2, 12. Inert
liquid, 13. Carothers, 14. Cellulose, 15. T,, 16. Bakelite, 17. Protein, 18. Biopolymers,
19. Carbon fiber, 20. IPN, 21. Block and Graft, 22. Membrane osmometry, 23. Teflon,
24. Proteins, 25. Charles Goodyear, 26. Solublility parameter concept, 27. Ionomer, 28.
Polyblends, 29. Chain polymerisation, 30. Plasticizers, 31. Living, 32. Theta, 33. Reactivity
ratio, 34. Ideal, 35. Staudinger, 36. M,,/M,, 37. Crystalline, 38. HDPE, 39. Polyelectrolyte,
40. Ion exchange resin, 41. High molecular weight, 42. Elastic behaviour, 43. Thermosett,
44. Limited, 45. Cross-links, 46. Water soluble, 47. Alternate, 48. Solution, 49. Internal,
50. GPC, 51. Waston and Crick, 52. Thermosett resins, 53. Dipole-dipole force, 54.
Monofunctional monomer, 55. Free radicals, 56. Double bond, 57. Suspension, 58.
Interfacial, 59. Copolymers, 60. Pyrolysis chromatography, 61. IR spectroscopy, 62. X-
ray diffraction, 63. Copolymerisation, 64. Polysaccharides, 65. Phase separation 66. Svedberg
equation, 67. Ladder polymers, 68. Bisphenol A, 69. Crazing, 70. Autoaccelaration, 71.
Ionomers, 72. Fullerene, 73. Hydrolysis, 74. Melting temperature, 75. Reinforced plastics,
76. Telogen, 77. Limited swelling 78. Novolacs, 79. Young modulus, 80. DSC, 81. Unzipping,
82. Fillers, 83. Enzymes, 84. Disproportionation, 85. Isotactic, 86. Coagulated, 87. Surfactant,
88. Dehydrogenation, 89. 3200-3550 cm™!, 90. NMR, 91. Compression moulding, 92.
Polymer colloids, 93. Adhesives, 94. Thermally stable, 95. Osmometry, 96. End group
analysis, 97. Polarised microscope, 98. Polyelectrolytes, 99. Emulsion polymerisation
100. Bifunctionality
Set IT
1. HDPE, 2. Tromsdorff effect 3. Bakelite, 4. Butyl rubber, 5. Chain transfer agents,
6. Plasticizers, 7. Latex, 8. Bulk, 9. Casein, 10. Carbon fibers, 11. IPN, 12. Molecular
weight, 13. EG and PTA, 14. Cross-linking, 15. Mastication, 16. Teflon, 17. Reactivity
ratio, 18. Theta solvent, 19. Thiokol, 20. Tacticity, 21. Conducting polymers, 22. Living
polymerisation, 23. Terpolymer, 24. Calendering, 25. Ionomers, 26. Viscose, 27. Kevlar,
28. Internal plasticization, 29. Ceiling temperature, 30. Contour length, 31. Creeping, 32.
Ebonite, 33. Spherulites, 34. Head to head and head to tail, 35. Staudinger, 36. Caprolactum,
37. Merrifield, 38. Chain flexibility, 39. P.J. Flory, 40. Mercerization, 41. Helical, 42. End
to end distance, 43. One, 44. Spinneret, 45. Thermoplastic, 46. Silicones, 47. Kar] Ziegler,
48. Bonding, 49. Intrinsic viscosity, 50. Biodegradation, 51. Single crystals, 52. Transparency,
53. Protein like, 54. Stoichiometry, 55. Melt viscosity, 56. Micelles, 57. Chain transfer,
58. Azeotropic copolymers, 59. Cloud point, 60. Block copolymers. 61. Colloidal, 62.
Zimm plot, 63. Injection moulding, 64. Partial specific volume, 65. Ebulliometry and
Cryometry, 66. Cross-linking, 67. Phthalic acid, 68. Second virial coefficient, 69. Interaction
parameter, 70. Amylopectin, 71. Denaturation, 72. Carothers, 73. Spandex, 74. Parison,
75. Carboxymethylcellulose, 76. Thermally stable, 77. Antioxidants, 78. Composite, 79.
Ion exchange resin, 80. Interfacial polycondensation, 81. Cationic polymerisation, 82.
Capping, 83. Alkyd resins 84. Ladder, 85. Unperturbed, 86. Flexural strength, 87. Mhos,
88. Oligomers, 89. Yield point, 90. Newtonian fluid, 91. Hildebrand, 92. Viscoelasticity,
93. Pendant, 94. Stiffening groups, 95. Gutta percha, 96. Composites, 97. Conducting
plastics, 98. Inorganic polymers, 99. Specialty, 100. Insoluble
Appendix D
Glossary
ABS Copolymer of acrylonitrile, butadiene and styrene

Acetate Rayon A fiber made from cellulose diacetate
Acrilan Fiber based polyacrylonitrile
Addition polymerisation Polymerisation involving chain reactions in which chain
carrier may be a free radical or an ion
AIBN 2, 2’ -azobisisobutyronitrile—a free radical initiator for
polymerisation
Aalternating copolymer An ordered copolymer in which two comonomers are
arranged alternatively in the polymer chain-(-ABAB-)-,
Amino resins Resins obtained from polycondensation of urea (or
melamine) and formaldehyde
Amorphous regions Regions of the polymer sample where the chains are
tangled or disordered
Amylopectin Highly branched starch molecule insoluble in water
Amylose Linear starch molecule soluble in water
Anionic Polymerisation A polymerisation initiated by an anion
Anisotropic Properties directionally dependent
Antioxidant A stabilizer which retards the oxidative degradation of a
polymer
Antistat An additive that reduces the static charges
Aramides Aromatic polymides e.g. Kevlar that are thermally stable
polymers
Atactic A polymer with random arrangement of pendant groups
on each side of the polymer chain
Average mol. wt. Number, weight and Z averages defined as the first, second
and the third powers of av. mol. wt, respectively, in a
polydispersed polymer
Azeotropic copolymer A copolymer in which the composition of monomers is
the same as that of the feed
Beta cellulose Cellulose soluble in 175% but insoluble in 8% aq NaOH
Biopolymers Naturally occurring macromolecular substances e.g.
proteins, polysaccharides, nucleic acids and rubber
Bingham Plastic A plastic that doesn’t flow until the external stress exceeds
a critical threshold value
Block copolymer A linear copolymer with constituent monomer units
arranged in blocks (long sequences) in the chain
Bulk density Apparent density that usually refers to powders and small
particles
Bulk polymerisation Polymerisation method of an unsaturated monomer that
contains monomer and the initiator only
Buty! rubber Copolymer of isoprene and isobutene as a useful elastomer
Calender Equipment with a series of hollow rolls used for fabrication
of films and sheets
Capping The reaction of polymer end groups to prevent the
dissociation of a polymer into monomer
Carbon fiber A highly flame retardant polymer obtained from the
cyclization and dehydration of polyacrylonitrile on heating
Casting The solidification of a liquid resinous composition in a
mould without the use-of pressure
Cationic polymerisation A polymerisation, which is initiated by a cation and
subsequently, propagated by carbonium ion
Ceiling temperature A threshold temperature above which a specific polymer
can not be made
Cellophane Regenerated cellulosic sheet produced from cellulose
xanthate (viscous) solution
Cellulose A natural polymer consisting of repeating beta glucose
unit
Cellulose acetate An ester formed by reaction of cellulose and acetic acid
Cellulose nitrate Obtained after nitration of cellulose and classified as
primary, secondary and tertiary depending on number of
groups in each repeating anhydro glucose unit in cellulose
are nitrated
Cellulose xanthate A product of soda cellulose and CS,
Chain stiffening groups Groups in the polymer backbone which decrease the
segmental motion e.g. amide
Chain transfer agent A substance that destroys the activity of the growing
chain
Chitin A polymer of acetylated glucosamine present in the
exoskeleton of shell fish
Cold drawing Process of stretchting a polymer such that its crystalline
regions become aligned or oriented in the direction of
applied stress
Composite A filled or reinforced plastic
Compounding Process of mixing a polymer with additives
Contour length The fully extended length of a polymer chain
Copolymer A polymer made of more than two monomers
Coupling agent A compound which improves interaction between the
filler and a resin
Creep Cold flow
Cross-link density A polymer network formed when separate linear or
branched chains are joined together along the chains by
cross-links
Crystalline polymer A polymer with ordered structure
Crystalline Regions of crystallinity
Curing Formation of extensive three dimensional cross-links in
the final stage in the production of a resin
Curing agent A substance that causes curing
Appendix D 363
Degradation Decomposition of polymer chain by heat, light, oxygen,

water, bacteria etc.
Degree of polymerisation Number of the repeat units present in a polymer molecule
Dilatometry A technique that measures changes in specific volume,
often used to determine 7,
DNA Deoxyribonucleic acid, a biopolymer responsible for the
hereditary character
DSC Differential scanning calorimetry-a technique that
measures differences in change in enthalpy of a heated
polymer and a reference standard based on power input
DTA Differential thermal analysis—a thermal analytical method
often used to monitor thermal transitions in polymers
Dry spinning Extrusion of polymer solution through the holes of a
spinneret into a hot chamber
Elastomers Synthetic polymers with rubber-like properties
Elastic range The range on stress-strain curve below yield point
Emulsion The colloidal dispersion of one liquid into another which
are imiscible with each other
Emulsion polymerisation A technique to prepare a polymer, often in the form of a
latex; the monomer is dispersed in a liquid (usually water)
that contains the initiator. A surfactant emulsifies the
monomer and its micelles are the focus of polymerisation
End group analysis A method for the determination of number average mol.
wt. of polymers if it contains functional end groups that
can be determined (say by titration)
End to end distance Shortest distance between the chain ends in a polymer
molecule
Epoxy resin A polymer obtained by the condensation of
epichlorohydrin and bisphenol A
Extender An inexpensive filler
Extrusion A processing technique in which viscous plastic mass is
continuously forced through an orifice to produce articles
of various profiles such as tubes, rods etc.
Fiber A crystalline polymer that can be used as a fiber
Filler A solid additive which resricts the mobility of polymer
chains and may also serve as an extender or reinforcing
agent for the polymer
Flame retardants Additives that reduce the flamability of a polymer
Flexural strength A measure of resistance to bending
Flory-Huggins theory Mathematical treatment that predicts the equilibrium
behaviour between liquid phases containing polymer
Fractionation A method to produce several low polydispersed sample
from a highly polydispersed polymer sample
Fringe micelle model A model showing crystalline and amorphous domains
present in polymer
Gel A semi-solid mass that forms usually when concentrated
colloidal substances are stored
Gel effect An enormous rise in viscosity in bulk polymerisation
that leads to a high mol. wt. polymer (Autoaccelaration
or Tromsdorff effect)
Gel point The point at which gelation (cross-linking) begins
Geotextiles Polymeric mats, sheets and textiles employed in the control

of soil, water etc..in geological applications
GPC Gel permeation chromatography—a chromatographic
technique useful in the determination of molecular weight
distribution in polymer
Glass transition temperature A characteristic temperature for a given polymer at which
a polymer transforms from glassy state to rubbery state,
designated by 7,
Glycogen A highly branched polysaccharide which serves as the
reserve carbohydrate in animals
Graft copolymer A special type of a branched copolymer in which the
branches consist of one type of monomer units while the
main chain consists of another type of monomer units
Gutta percha A naturally occurring polymer, trans-1, 4-polyisoprene—
a stiff isomer of natural polymer
Hevea Brazilensis Natural polymer (cis-1, 4-polyisoprene)
HDPE High density polyethylene (also low pressure
polyethylene); a linear polymer obtained using Ziegler-
Natta catalysts
Homopolymer A polymer made of a single type of monomer e.g.
polyethylene
Humic acid Natural polymeric aromatic carboxylic acids
Impact strength The resistance of a test sample to a sharp blow
Inhibitor A chemical used to stop polymerisation
Initiation The first step of chain polymerisation where the free
radicals or ions generated from the initiator attack the
monomer molecule to form new reactive species
Initiator Substance that generates reactive species like free radicals
or ions that participate in the reaction with monomer
molecule
Initiator efficiency The fraction of radical or decomposed initiators that lead
to the formation of active centres
Injection moulding A process in which a heat softened polymer is injected
under pressure into a cool mould where it hardens to
give the desired article
Interfacial polycondensation The process of producing a polymer by the reaction of
the functional group containing monomers at the oil/
water interface for example in the production of nylon
6, 6
Internal plasticization Polymer chain flexibility achieved by reduction of chain
symmetry through copolymerisation
Interpenetrating network A multiphase polymer system that is obtained when a
monomer is polymerised in presence of a polymer
Intrinsic viscosity Reduced viscosity at infinite dilution, a parameter that is
experimentally obtained from dilute solution viscosity
measurements and is related to the molecular weight of
the polymer by an empirical Mark-Houwink equation
Ionomer Polymer that contains only a few charged groups in its
molecule and is insoluble in water. A generic name for
copolymer of ethylene and methacrylic acid
Isotactic Arrangement in space where all the symmetric centres
Appendix D 365
in the molécule have identical (either with d or /

configuration)
Kinetic chain length The av. number of monomers that add to a growing
chain before it terminates (rate of propagation = rate of
termination)
Lacquers Polymer solutions containing pigment—a surface coating
material
Ladder polymer A polymer in which the backbone consists of a double
strand much like a ladder that makes the polymer thermally
stable
Latex Stable dispersion of a polymer in water. For example,
polyisoprene is dispersed in water as the sap of the rubber
tree in a latex
Lignin Non-cellulosic resinous component of wood which acts
as a binder for the cellulosic fiber of wood
Living polymers The product formed at the end of an anionic polymerisation
in which all monomer is consumed, but the active centres
have not been terminated. Addition of monomer (same
or different) will continue the polymerization further
Mark-Houwink equation The equation that relates intrinisc viscosity to molecular
weight of polymers. [7] = KM® where K and @ are the
constants for a particular polymer-solvent pair at fixed
temperaure
Melt spinning A technique for fiber processing in which a molten
polymer is pumped at a constant rate under high pressure
through a plate (called spinneret) containing several holes
Melt viscosity Viscosity of a molten polymer
Microstructure The local organisation of the repeat units in a copolymer
or partially atactic polymer, i.e. sequence distribution
Modulus Ratio of stress (applied force) to strain (elongation); a
measure of stiffness of a polymer
Monomer The starting substance that has minimum bifunctionality
from which a polymer is made
Network A high degree of cross-linking in linear polymers
Newtonian flow A fluid whose viscosity is proportional to the applied
viscosity gradient
Novalac Polymer made by the condensation of phenol and
formaldehyde under acidic conditions
Oligomers Substances usually made up of a few monomer units
Pendant groups Groups attached to the main polymer chain e.g. Cl in
PVC
Plasticizer Substance added to polymer to reduce its glass transition
temperature, thus facilitating segmental motion and
making polymer flexible .
Polyblend Multiphase polymer system consisting of two polymers
Polycondensation Formation of polymer by the reaction of monomers
containing two or more functional groups (also called
step polymerisation)
Polydispersity index The ratio of weight average mol. wt to number average
mol. wt. that is a measure of the distribution of molecules
of different sizes present in a polymer
Polyelectrolyte A polymer containing charged groups that make it water

soluble where it ionises to form a macro ion and counter
ions
Polymer Large molecules built up of thousands of small repeat
units (monomers) which are joined together by covalent
bonds
Polymer pioneers Those scientists who contributed to the advancement of
polymer science and include Nobel laureates, Staudinger,
Ziegler, Natta, Flory, Merrifield, de Gennes and others
like Hermann Mark, Marvell, and Carothers
Polymerisation Process of making polymers from low mol. wt. substances
(chain polymerisation from unsaturated monomers and
step polymerisation from functional group containing
monomers)
Polypeptide An oligomer made up of few @-amino acid units covalently
liked through covalent bond
Pultrusion A process in which filaments are dipped in a prepolymer,
passed through a die, and cured
Radius of gyration rms distances of a chain end from the centre of gravity
of its polymer molecules
Random copolymers A copolymer in which there is no definite ordering in
the arrangement of the two monomers from which the
polymer is made
Rayon Regenerated cellulose filament
Reclaimed rubber Recycled rubber
Retarder A substance that competes with the monomer for free
radical during radical polymerisation. Decreases both
the rate of polymerisationm and DP and is less reactive
than inhibitor
Shellac Resin secreted by coccid insect
Solubility parameter Numerical value equal to the square root of the cohesive
energy density. It is used to predict polymer solubility
through matching the solubility parameter of the polymer
to that of solvent
Solution polymerisation A polymerisation technique in which the monomer is
dissolved in an inert solvent and then polymerised. It
overcomes the problem of heat dissipation encountered
in bulk polymerisation but gives low molecular weight
polymer due to chain transfer
Spandex Elastic polyurethane fibers
Spherulites Aggregates of polymer crystallites
Spinneret A metal plate with many small, uniformly sized minute
holes (used in processing of films)
Styrofoam Foamed polystyrene
Suspension polymerisation A polymerisation technique in which monomer contains
the dissolved initiator and is then suspended in water
(also called bead or pearl polymerisation)
Syndiotactic A polymer in which the pendant groups are arranged
alternatively on each side of the polymer backbone e.g.
methyl groups in polypropylene
Tacticity Arrangement of pendant groups in space
,. Appendix D 367
Tanning Cross-linking of leather (protein) with tannic acid

Tensile strength Resistance to pulling stresses
Telomer Low mol. wt. polymer resulting from chain transfer agents.
The additive that causes chain transfer is called talogen
Tenacity Measure of fiber strength
Terylene Polyethylene terephathalate
Thermogravimetric analysis Measurements of change (nomally loss) in weight when
a material is heated
Thermoplasts Polymers which can be softened and moulded on heating
Thermosetts Polymer that can be cured by the application of heat.
These are cross-linked infusible material
Theta solvent A solvent in which a polymer exists as a statistical coil
(i.e. in unperturbed dimensions)
Theta temperature Temperature at which a polymer of infinite mol. wt.
begins precipitating from solution
Thiokol Polysulphide elastomers
Transfer moulding A process in which a preheated briquette is forced through
an orifice into a heated mould cavity
Ultracentrifugation A high speed centrifuge process empolyed for separation
of sub-microscopic particles such as polymer chains and
provides a tool for measuring molecular weight of
polymers
UV stabilizer An additive that retards degradation of polymer by UV
radiation
Vapour phase osmometry A technique that gives average molecular weight of
polymers (usually for low molecular weight range)
Viscoelasticity A property having characteristic features of both solids
and liquids
Viscose process Regeneration of cellulose fibers by precipitation of the
sodium salt of cellulose xanthate in acid
Vulcanisation The process of introducing cross-links in natural rubber
(usually by masticating it with sulphur)
Weight average mol. wt. The second moment of average of a polydispersed polymer
Wet spinning A process of obtaining fibers by precipitation of polymeric
solution
Yield point A point on stress-strain curve below which there is
reversible recovery
Z average mol. wt. The third power average of molecular weight in a
polydispersed polymer (larger than weight average mol.
wt.)
Ziegler-Natta catalyst €.g. TiCl,-R3Al
Zimm plot A method for recording light scattering intensities

measured at different polymer concentrations and different
measured angles on a graph that on double extrapolation
to zero angle and zero concentration gives mol. wt. of
polymers (also gives the radius of gyration on extrapolation
to zero angle and second virial coefficient on extrapolation
to zero angle)
Zone melting Fractionation of a polydispersed polymeric system by
heating over a long period of time
Appendix E
Trade Names for Some Common
Polymers.
Acrilan (Orlon) Polyacrylonitrile based fiber

Araldite, Epan Epoxy Resins
Bakelite Phenol-formaldehyde resin
Balata Same as gutta percha
Cellophane Sheet of regenerated cellulose
Celluloid Plasticized cellulose
Collagen Protein of the connective tissue
Dacron (Terylene) Trade name for polyester fibers
Dextran High molecular weight branched polysaccharide
synthesised from sucrose by bacteria
Dextrin Degraded Starch
Dynel, Vinyon Copolymer of vinyl chloride and acrylonitrile
Ebonite Highly cross-linked rubber with 35% sulphur
Galalith Plastics from moulded casein
Glyptals Alkyd Resins
Gutta percha Natural trans-1, 4 polyisoprene
Humic acid Polymeric aromatic carboxylic acid present in lignin
Hytrel Thermoplastic elastomer
Keratin A fibrillar protein
Kraton Styrene-butadiene-styrene block copolymer
Perspex, Lucite Polymethyl methacrylate
Pluronic Ethylene oxide-propylene oxide block copolymers
Saran Trade name for polymers of vinylidene chloride
Spandex Elastic polyurethane fibre
Styrofoam Foamed polystyrene
Teflon Polytetrafluoroethylene
Thiokol Polysulphide rubbers
Tricel Cellulose triacetate
Vinoflex Copolymer of vinyl chloride and vinyl isobuty! ether
Vinylite Copolymer of vinyl chloride and vinyl acetate
Appendix F
Abbreviated Forms of Some Common
Initiators/Monomers/Polymers/
Additives ete.
AA Acrylic acid
ABR Acrylonitrile-butadiene copolymer
ABS Acrylonitrile-butadiene-styrene copolymer
AIBN Azo bis isobutyronitrile
AM Acrylamide
ASTM American society for testing of materials
BPO Benzoyl] peroxide
CMC Carboxymethyl cellulose
DMT Dimethyl terephthalate
DOP Dioctylphthalate
EO Ethylene oxide
HDPE High density polyethylene
HIPS High impact polystyrene
LDPE Low density polyethylene
LLDPE Linear low density polyethylene
MA Methyl acrylate
MF resins Melamine-formaldehyde resins
MMA Methyl]! methacrylate
NBR Nitrile butadiene rubber
PAN Polyacrylonitrile
PEO Polyethylene oxide
PET Polyethylene terephthalate
PF and UF resins Phenol-formaldehyde and urea-formaldehyde resins
PMMA Polymethy! methacrylate
PO Propylene oxide
PPO Polypropylene oxide
PTA tere-phthalic acid
PTFE Polytetrafluoroethylene
PU Polyurethane
PVA Polyvinyl alcohol
PVAc Polyvinyl acetate
PVC Polyvinyl! chloride
SBR , Styrene butadiene rubber

LER. Tricresyl phosphate
TDI Toluene diisocyanate
TPE Thermoplastic rubber
UHMWPE Ultrahigh molecular weight polyethylene
VA Vinly acetate
Appendix G
Structures of Repeat Units of Some
Common and Specialty Polymers
-— CH,— CH), --CH,—CH} + a =CH— CH,}-
Polyethylene Ce
CH,
CH, Polypropylene 1, 4-Polyisoprene
+$CH)— Int mee a i sherpa
cut, N
O ll
Polyisobutyle CH,
Polyvinyl pyrrolidone 3, 4-Polyisoprene
~- CH; = CH}- Fo
Polybutadiene
Cl
Polyvinyl chloride
Polystyrene rie Cha yfan
CHO
+ CH,—CCl, + a Ss NOH Polyacrolein
Polyvinylideneschloride
2
Polyacrylamide oxime CH,
4C0—cH.
Polyacetaldehyde
CONH 2 Go oarG
Polyacrylamide n oe
S a Polyacrylic anhydride
CH,— CH} COOCH,;
Polymethy] acrylate
7 ~Nn |
2! Cl CN
Polyvinyl pyridine Polychloroprene (Neoprene)
0H C
++ CH,—CH}- sig moran COOCH,
|
OOCCH,CH,CH; CN Poly o-cyanomethacrylate
Polyvinyl butyrate Polyacrylonitrile
ee |
cl gee a gt OCH,
Polyvinyl methyl ether
CH,
Ethylene-propylene elastomer
Polyvinyl] carbazole
CH; $e Gis
| a
OCOCH;
Polyvinyl acetate
CH; CH;
Butyl rubber
-{CH,—CH}
CH; |
OH
|
—{CH,—CH)—CH)—C} Polyviny! alcohol (PVA)
coo?
Ethylene-methacrylic acid copolymers (lonomer) “EC GC ih
CH, a
Cl OOCCH;,
|
$cH:—C4 Polyvinyl chloride-co-vinyl acetate
COOCH;
Polymethy! methacrylate (PMMA)
baat
CH2—CH (CH3)2
Poly 4-methyl-1-pentene
Baia
trans 1,4-polybutadiene
COCH;
Polymethy] vinyl ketone
ea eh
CN
Acrylonitrile-butadiene-styrene terpolymer (ABS)
tba he
-O1-O--f
CH; O
| | CH
CH, CH,
1,2-Polybutadiene
Poly 2,2-propane bis(4-penyl phenylphosphonate)

Appendix G 373
‘ O
O O ||
| | P=0
O-€CH,}-O—C-CH)}-C |
OK*
n n
Polytetramethylene sebacate Potassium polymetaphosphate
O : CH
(CH;)~C—NH
l CH>— GH
|
facta CH
|
n
Poly 11-undecanoamid (Nylon 11) a ee
"
is CHa (CH2)2CH,
CH,— CH CH cs
Polyvinyl butyral
O
SN
n n
Polyvinyl formal Polythiazy]
) O
| |
cl» {C)) Cy —0—C—CH, —CH,—S—CH,—CH,—C—0
Poly p-xylylene thiodipropionate
Lrane gee + naan “ot

Poly 1,4-xylylenyl-2-methylpiperzine Styrene-acrylonitrile copolymer
a ae
Polymethylene bis 4-phenylurea
)
|
NH— id! Set C—NH
7 n
Polymethylene bis 4-phenylurethylene

: O
+o—cH,—cr,t ||
n fc, —cr,—C—Na
Polyethylene glycol n
Poly B-alanine (nylon 3)
n
CH, {fCHa}- CNA
Polypropylene glycol
— 7 Polycaprolactam (Nylon 6)
O H3;C CH;
| ? if
po—ch—c} oo cen,
n n
Polyglycollic ester Poly 2,3-dimethylbutadiene
O O
| |
0—CH,—CH,—0—c_{())—C
4
—{-cH, —CH,—ssss}-n
n
Polyethylene tetrasulfide
Polyethylene terephthalate
CH,
O O |
| | Si—CH:}-
-L-nn(crt,)-ni—c-er,}-cL | n
n CH;
Poly hexamethyleneadipamide (Nylon 6,6) Polydimethy] silmethylene
O O
I ||
C—HN-{C))—cH, {C))—N—C—0—cH,—CH,—0
n
Polyethylene methylene bis(4-phenylcarbamate)
CH;
O O
N
I
N—C—O—CH,—CH,—O—C
l i
5 aes n
CH; n
Polyethylene N, N’-piperazinedicarboxylate Poly 3,5-dimethyl-1,4-phenylene sulphone
Appendix G 375
ee COOCH, — C,H; (CH};— COOH

|
NHB
Ci CO +t xn—cu—co——}
n
Poly a-L-glutamic acid

Poly y-benzyl-L-glutamate
O-Gy-s=e=9
CH30 OCH; C=c—c=Cc
n
Poly 3,3’ daiendey:-4,4’-biphenylene carbodiimide
Polydiethynylbenzene
0 O
I I 9 CH—O haa
-c-{C)-0—cHt)-0-{C))—c—0 CHCl,
N___ Polydichloroacetaldehyde
Poly 1,3-bis p-carboxyphenoxypropane anhydride
O O
| | {CH} S-
{¢ct:)-0—C—NH-€cHt,}-NH—C—0-}-
n
Polyhexamethylene
Polytetramethylene hexamethylenedicarbamate
4 O we
Lok Qt ozo! LO}

Poly 2,5-dimethylpiperazine terephthalamide Polybutylene terephthalate
Lok Oo-
—Ch{_)—CH,—0 fo—cr,t-
n Polyoxymethylene
Polydihydroxy methylcyclohexy] terephthalate ‘
OG Gio 0
ll | |
+f nn-{en,}-nu—c—c—ce fecu.j-NH—C—Nu
| ~ n
C4Hy Polyhexamethylene urea
Polyhexamethylenedi-n-butylmalonamide
1 mr O.O
ll II
fbuteny.e—Na——CH)—Nu+- —[NH-{CH,},NH——C—C
Polymethyleneadipamide (1,6 Nylon) Polydecamethyleneoxamide
i
o—mc{)—cH—0— Lot}
Poly 1,4-cyclohexanedicarbiny] terephthalate
Pore Polycarbonate
fox]
Polyphenylene oxide
O O O
| | |
—}NH-{CH,},NH—C-{cH,}-C- -{CH, }gNH—C—NH-
n n
Polydecamethylenesebacamide (10,10 polyamide) Polydecamethylene urea
Thiens +o6! C-tcH}C

n
Poly 1,4-phenylene sebacate
Poly N,N’ ee
"1 O
I
mtenszm—os-6 sor} Fo4E)-0- fad
n
n
Poly 1,4-phenylene adipate
Polyhexamethylene m-bezenedisulfonamide
»* Appendix G 377
O O
F-xn-ternj-ni Cen} L
Polyhexamethylenesebacamide (nylon 6,10)
CH; Os
| | fe) O
cC))-0-c—0 T I
| 6-268, ).0—C ;
CH, n n
Poly 2,2-propanebis 4-pheny] carbonate Polytetramethylene isophthalate
—CH,—N— —N—CH,—
OH OH
2
CH, CH,OH Nek | NZ ie Ls, | Nos
Decndbs aHeticeat
CH 5 nee
MAH, jou
CH
CH,OH CH, it ae pe
HC CH,OH N* ~N
— CH,—N Ry ON Cth
OH CH),
Phenol-formaldehyde resins |
Melamine-formaldehyde resins
pth Miele OFM

CH,
|
—NH—CO—N O co
CH, O
n
NH— CONCH, — Poly m-pheny] carboxylate
der
Urea-formaldehyde resins
Oe ‘C—O—CH,—CH—CH,—O—C’ iverinal auporacanod plaxte ts

|| | I| ||
O O O O O oO O
| n
Polyglycery! phthalate
OPO PS Polybenzobenzimidazole Poly2,2’-octamethylene-5,5’-dibenzimidazole
POOF Poly 2,2’-4,4’ oxyphenylene-6,6’-oxydiquinoxaline
O O
CH; CH;
| |
CH2);—N N if i
CH; CH;
O O n
nm Poly p-phenylene bisdimethylsiloxane
Polynonamethylenepyromellitimide
Nxc
n
Poly 2,2’-m-phenylene-5,5’(6,6’-benzimidazole)
Poly 3,5-octamethylene-4-amino-1,2,4-triazole
Appendix H
ASTM Methods
ASTM Type of test or method
wT To measure the thermal conductivity of an insulating plastic

D 149 Measurement of dielectric strength of an insulating polymer material
D 150 Determination of dielectric constant and dissipation factor for a insulating
polymer material
D 265 To measure the relative susceptibility of a standard test thick polymer
specimen to pendulum type impact load (or Izod — Charpy impact test)
D 495 Estimation of arc resistance i.e. ability of plastic material to resist the
action of high voltage arc
D 523 To measure the surface relative shininess on a surface of plastic material
at a specified angle by using gloss meter
D 542 Measurement of refractive index of transparent plastic materials by Abbe
,tefractometer and microscopical methods
D 543 Evaluation of resistance offered by plastics to chemical agents when they
are immersed in the latter (immersion test)
D 568 To evaluate the flammability of flexible plastics
D 570 Determination of water absorption and hygroscopicity of plastic materials
by oven drying and TVI drying test
D 630 To evaluate the flammability of semi flexible or self supporting plastics
D 638 Tensile test for estimation of tensile elongation and tensile modulus for
semi-finished or finished plastic materials
D 648 To monitor the short term effects of temperature on a polymer material
by determining heat deflection temperature (HDT)
D 671 To determine the resistance to deterioration of plastic specimen from
cyclic stress (or flexural fatigue test)
D 695 Determination of compressive properties (i.e. behavior of a plastic material
under applied compressive load) viz. modulus of elasticity, yield stress,
extent of deformation, compressive strain and strength and slender ratio
etc. of polymer plastic materials
D 696 To measure the coefficient of linear thermal expansion of plastic material
D 731 Molding index of thermosetting resin molding powder by cup flow test
Dei3Z To determine the shear strength of a molded plastic or a cut from a
polymer sheet against an applied load
D 746 To measure the temperature at which plastics become rigid and brittle
(brittleness temperature)
ASTM Type of test or method
D 785 Determination of Rockwell hardness of a polymer, plastic material

D 790 To estimate flexural properties viz. flexural modulus or modulus of elasticity
of plastic materials
DPi92 Determination of specific gravity of a plastic material (in the sheet, rod,
tube and moulded forms) and (in the form of moulding powder, flakes
and pellets)
D 794 To monitor the long term heat resistance of polymeric materials
D 864 To measure the coefficient of cubical thermal expansion of plastics
D 1003 To measure the appearance of cloudiness (or haze) in the polymer when
the light is scattered from the bulk or surface of the specimen
D 1044 To test the resistance of transparent plastic materials to abrasion
D 1238 Melt index test for polymers
D 1435 Evaluation of stability of plastic materials to out door exposures such as
climatic changes polluted environment and moisture variation in atmosphere
etc.
D 1499 Determination of resistance offered by plastic materials when they are
exposed to radiation produced by carbon arc lamps
D 1505 Determination of density of plastic materials by density gradient method
D 1525 To monitor the short term effects of temperature on polymer material by
determining vicat softening temperature
D 1692 Measurement of flammability of cellular plastics in a horizontal position
D 1693 Evaluating the widening of a brittle fracture made on the surface of
polyethylene sample in the presence of external crack sensitizing agents
such as detergents, lubricants, sunlight or oil etc. (environmental stress
cracking resistance test)
D 1703 Measurement ofapparent viscosity or melt index of polymer by capillary
rheometer
D 1712 Sulfide staining test for measuring the resistance offered by plastics to
hydrogen sulfide
D 1729 Matching or evaluation of color differences of plastic materials with
reference to a standard by using calorimeter, or spectrophotometer
D 1822 To measure the tensile impact strength of a very thin or flexible polymer
specimen
D 1824 Measurement of viscosity of concentrated polymer solutions, or polymer
melts by Brookfield viscometer based on rotational rheology
D 1895 Determination of apparent (bulk) density, bulk factor and pourability of
plastic material
D 1929 To determine the ignition temperature of a polymer material specimen
D 1939 Estimation of resistance of plastics especially ABS plastics to
(and D 2393) exposure to acetic acid by acetic acid immersion test
D 2152 Estimation of resistance of polyvinyl chloride to acetone by acetone
immersion test
D 2236 To monitor the short term effects on a polymer sample at elevated
temperatures by torsion pendulum test
D 2240 To determine the resistance of a soft plastic material to permanent
deformation, indentation, or scratching by durometer (or Durometer
hardness)
Evaluation of resistance of plastics for the development of stains caused
by staining agents present in food, cosmetic, detergents and pharmaceuticals
ete.
a Appendix H 381
D 2471 Estimation of gel time and peak exothermic temperature of thermosetting

polymer resins
D 2565 Determination of resistance offered by plastic material when they are
exposed to light produced by water cooled xenon arc
D 2583 To determine the Barcol hardness of both reinforced or non-reinforced
rigid plastic materials
D 2843 Measurement of density of smoke generated from burning plastics (smoke
burn test) ‘
D 2857 Determination of dilute solution viscosity of polymers
D 3014 Comparison of relative extent, time of burning and loss of weight of rigid
cellular plastics (against a standard), in vertical position
D 3123 Spiral flow of low pressure moulded thermosetting polymer resins
D 3417 Studying of temperature induced phase changes in polymers,
(and D 3418) degree of curing process and thermal degradation of polymers by differential
scanning calorimetry (DSC), thermogravimetry analysis (TGA) and
thermomechanical analysis (TMA)
D 3593 Determinaton of molecular weight distribution (MWD) in polymers by
gel permeation chromatography (GPC)
E 162 To estimate the surface flammability of a plastic material by using a
radiant heat energy source
G21 To estimate the resistance of plastic materials for fungi
GHZ To estimate the resistance of plastic materials to bacteria
Gis Monitoring the deterioration or degradation of polymers by the effects
due to their exposure to fluorescent ultraviolet light and condensation
Appendix I
SI Prefixes
exa E ie atto a
peta P EV eee femto f
tera 40 ie pico p
giga G 10°° nano n
mega M 10° micro L
kilo k ge milli m
hecto h 10° centi c
deca da 10"! deci d
Appendix J
Some Fundamental Physical Constants
Unit Value
Avogadro constant mol! 6.0222 x 1073

Boltzmann constant J-K> 1.3807 x 10°23
Plank constant Js 6.6262 x 107*4
Faraday constant C mol! 9.6485 x 10*
Gas constant J mort Kk" 8.3143
bar cm? mol"! K7! 83.144
atm cm? mol! K7! 82.057
Elementary charge (e 1.6022 x 107!9
Speed of light in vacuum m s~ 1 2.998 x 108
Permittivity of vacuum Fm! 8.8542 x 107)?
Permeability of vacuum Hm! 4x 10-7
Nuclear magneton I igs 5.0509 x 10727
Appendix K
Physical Quantities and SI Units
Physical Unit Symbol Value in SI units

quantity
time minute min 60 seconds

length angstrom A 10°!° m = 0.1 nm
mass unified atomic mass unit U-=ma/('*C)/12 1.6605 x 10°?’ kg
area barn b 10°°8 m?
volume liter L 1073 m3
current ampere I
energy electron volt eV 1.60218 x 1071? J
pressure bar bar 10° Pa
plane angle degree 3 (7/180) rad
temperature celsius temperature 4 (T/K) — 273.15
Appendix L
Important Derived SI Units of Physical
Quantities with their Symbols
Physical quantity Physical unit Unit
Name Symbol Name Symbol Derived Base

frequency i) hertz Hz oe
force F newton N Im! m kg s"!
energy/work/heat et joule J J Nm
power P watt Ww is? m=! kg s~?
pressure, stress p, o pascal Pa N m? may ike, so
electric charge Q coulomb C As
electric potential U volt V EG m? kg s> Av!
electric fe farad F CV! m-? ke! s* A?
capacitance +
resistance/ R ohm Q VAT! m?kg s?A~
impedance
electric G siemens § oF mi ke=te4 A?
conductance
electric ib henry H VA"! s m? kg s? A~
inductance
electric dipole LU debye D 3335x110. . 10; Fr em
moment cm
magnetic flux B tesla T Vs m? kes A"
density
magnetic flux o weber Wb Vs m? kg s? A’!
luminous flux lumen Im cd sr
illuminance lux Ix Im m~.
absorbed D gray Gy Jkg! noe
radiation dose
radiation dose sievert Sv J kg"!
equivalent
radioactivity A becqueral Bq gr
dynamic viscosity n poise oP. 1 mPas mn kes
kinematic viscosity v stokes St Li as
heat capacity C,orCv —clausius — Cl 4.184 JK"!
Appendix M
Other Units and Conversion
1A (1A)=10°"°m
1 light year (1 ly) = 9.461 x 10° m
1 astronomical unit (1 au) = 1.496 x 10'! m
1 inch (1 in) = 2.540 cm = 0.0254 m
1 foot (1 ft) = 30.48 cm = 0.3048 m
Land mile (1 mile) = 1609.344 m = 1.609 km
1 year (1 y) = 3.156 x 10’
1 liter (11) = 1000 cm? = 10° m?
1 pound (1 lb) = 453.592 g = 0.453592 kg
1 calorie (1 cal) = 4.1868 J
1 electron volt (1 eV) = 1.60218 x 10°!° J
1 horsepower (1 hp) = 745.7 W
1 atmosphere (1 atm) = 1.013 x 10° Pa = 0.1013 M Pa
1 mm of mercury (1 mm Hg) = 133.322 Pa = 0.000133 M Pa
degree celsius (1°C) = (T/K) — 273.15
degree fahrenheit (1 °F) = ((T/°C) x 9/5)
British thermal unit (1 BTU) = 1.05579 kJ
dyne (1 dyn) = 1 x 10° N
Appendix N
Definition of the Basic Units
Ampere: The ampere is that constant current which, if maintained in two straight parallel
conductors of infinite length of negligible circular cross section and placed one meter
apart in a vacuum, would produce between these conductors a force equal to 2 x 10’
newton/metre of length.
Candela: The candela is the luminous intensity in the perpendicular direction of a surface
of 1/600 000 square metre of a black body at the temperature of the freezing platinum
under a pressure of 101 325 newton per square metre.
Kelvin: The kelvin unit of thermodynamic temperature is the fraction 1/273.16 of the
thermodymamic temperature of the triple point of water.
Kilogramme: The kilogramme is the unit of mass and is equal to the mass of the
international prototype of the kilogramme (kept in Sevres).’
Mass fraction: It is the mass of a given component divided by total mass of all the i,
components, i.é. m, = m,/>; m;. Mass fraction is also called weight fraction, since same
gravity field is applied every time under normal conditions.
Metre: The metre is the length equal to 1650763.73 wavelengths in vacuum of the
radiation corresponding to the transition between the levels 2p;9 and 5d; of the Krypton—
86 atom.
Mole: The mole is the amount of substance, which contains as many elementary units as
there are atoms in 0.012 kg of C!*. The elementary units must be specified and may be
an atom, a molecule, an ion, an electron, a photon etc. or a given group of such entities.
Mole Fraction: It is the number of moles, n, of a given component divided by total

number of moles of i component, i.e. x; = 1,/%; n;. Mole i.e. unit representing the amount
of substance. The amount of substance equal to one mole is invariably equal to its
molecular weight. In other words mole is defined as weight of substance divided by its
molecular weight.
Radian: The angle subtended at the centre of a circle by an arc of the circle equal in
length to the radius of the circle.
Second: The second is the duration of 9 192 631 770 periods of the radiation corresponding
to the transition between the two hyperfine levels of the ground state of the cestum—133
atom.
Steradian: The solid angle subtended at the centre of a sphere by an area on the surface
of the sphere equal in magnitude to the area of a square having sides equal in length to
the radius of the sphere.
Volume fraction: It is the volume of a given component divided by the sum of volumes
of all the i, components, i.e. @; = V;/¥;V;. The volumes refer to the volume of components
before mixing.
General References
‘
Encyclopedias, Dictionaries and Source Books

Alger, M.S.M., Polymer Science Dictionary, London, Chapman and Hall, 1994.
Ash, M., and I. Ash (eds), Encyclopedia of Plastics, Polymers, and Resins, 4 vols. New
York: Chemical Publishing, 1987.
Brandrup, J., and E.H. Immergut (eds.), Polymer Handbook, 3d ed., New York, Wiley,
1989. -
Carley, J.F. (ed.), Whiltington’s Dictionary of Plastics, 3d ed., Lancester, Pa,: Technomic,
1993.
Chanda, M., and S.K. Roy, Plastics Technology Handbook, New York: Dekker, 1987.
Cheremisinoff, N.P. (ed.), Handbook of Polymer Science and Technology, multivolume,
New York: Dekker, 1994.
Salamone, J.C. (ed.), Polymeric Materials Encyclopedia, Boca Raton: CRC Press, 1996.
Harper, C.A. (ed.), Handbook of Plastics, Elastomers, and Composites, 2nd ed., New
York: McGraw-Hill, 1992.
Heath, R.J., and A.W. Birley, Dictionary of Plastics Technology, New York: Chapman and
Hall, 1993.
Kroschwitz, J.I. (ed.), Polymers, an Encyclopedic Source Book of Engineering Properties,
Mark, H., C. Ovérberger, G. Menges, N.M. Bikales, ets., Encyclopedia of Polymer Science
and Engineering, 2d ed., 18 vols. and 2 supplements, New York: Wiley, 1985.
Rubin, I.I., (ed.), Hand book of Plastic Materials and Technology, New York: Wiley,
1992.
Whelan, T., Polymer Technology Dictionary, London: Chapman and Hall, 1994.
Review Journals
Advances in Polymer Science
Polymer Science and Technology
Research Journals
Angewandte Makromolecular Chemie
British Polymer Journal
Colloid and Polymer Science
Die Makromolecular Chemie
European Polymer Journal
High Performance Polymer
J. Macromolecular Science
J. Polymer Science, Polymer Chemistry, Polymer Physics and Polymer Letters (Eds.)
J. Applied Polymer Science
International Journal of Biological Macromolecules
International Journal of Polymeric Materials
Macromolecules
Polymer
Polymeric Acta
Polymer Bulletin
Polymer Composites
Polymer Journal
Polymer J. USSR
Polymer Materials
Besides these journals a good number of papers on polymers are published in Nature, J.
American Chemical Society, J. Physical Chemistry, Langmuir and J. Organic Chemistry.
Index
Abrasion, 147, 380 Amylose, 238, 239

effect(s), 16 Anionic polymerisation, 28, 29, 30, 31, 32,
resistance, 16, 78, 211, 278 33999, 360942582,°2725'296
ABS Antioxidant(s), 23, 93, 197, 215, 216, 218,
polymer(s), 95, 227, 228, 234 DINE D23) 224
resin(s), 64, 72, 186 Aramide(s), 15, 74, 361
Acetate rayon(s), 9, 207, 212, 238 ASTM, 87, 88, 98, 99, 100, 101, 102, 103,
Acrolein, 73 104, 106, 107, 108, 379
Acrylamide(s), 71, 72, 299, 300 Atacticy 3313; -21,°70/"85;°93 9124," 137,
Acrylic acid(s), 47, 53, 54, 71, 210 149, 154
Acrylic ester(s), 43 Auto-acceleration, 37, 114
Acrylic Autoclave, 47, 247
fiber(s), 71, 206, 208, 210, 212 Average molecular weight
polymer(s), 27, 86, 95, 210, 289 concept, 110
Acrylics, 9, 95, 204, 211, 289 number, 60, 110, 114, 117, 118, 120,
Acrylonitrile, 11, 29, 37, 42, 48, 49, 54, 133, 305
64, 70, 71, 344, 350, 356 viscosity, 110, 121, 122, 132, 306
Activator(s), 226 weight, 110, 112, 117, 124, 133
Active center(s), 27 Azeotropic
Addition polymer(s), 10, 26, 29, 49, 198 copolymer(s), 359
Addition polymerisation, 10, 26, 28, 41, copolymerisation, 53
55981287 Azobisisobutyronitrile, 28, 31, 83
Additive(s), 23, 43, 86, 93, 106, 107, 215,
DUG) 220222 2235224 Batch recator, 46
Adenine, 243, 244 Baekelund, L, 332, 333
Adhesive(s), 43, 49, 66, 67, 68, 203, 204, Bakelite, 14, 15, 24, 75, 76, 350, 351
215, 220, 276, 280, 289 Bending, 89, 90
Aggregate(s), 146, 261, 276, 281 Biosynthesis, 241
Aggregation, 261, 276 Birefringence, 230
AIBN, 28, 31, 39 Bisphenol A, 11, 23, 61, 80, 83
Alkyd resin(s), 14, 15, 73, 82, 206 Blending, 64, 71, 72, 209, 276, 281
Alternating copolymer(s), 5, 24, 53, 141, Blend(s), 147, 161, 276, 282, 283
271 Block copolymer(s), 271, 272, 273, 274,
Amino acid(s); @, 241, 242 361
Amorphous morphology, 273, 274
halo, 137 synthesis, 272, 273
phase(s), 145 Blowing agent(s), 225, 226
polymer(s), 96, 135, 136, 137, 143, 147, Bond(s)
A5ig53, 155516385 218 covalent, 18, 19, 215, 217
Amylopectin, 238, 239 double, 2, 26, 27, 47, 196, 246
392 Index
ionic, 18 Chain growth polymerisation, 26, 41

single, 307 Chain modifier, 38
Bond angle, 22, 90, 164, 199 Chain scission, 158, 197
Bond energy, 47 Chain transfer agent(s) 38, 39, 50, 362
Bond stability, 197 Chain transfer constant(s) 38
BPO, 28, 31 Chain segment, 13, 139, 152, 164, 165, 171
Branched polymers(s), 5, 6, 7, 8,9, 15, 21, Characteristic ratio, 22
33, 61, 97, 123, 164, 165, 241, 288 Chemical potential, 119, 175
Brownian motion, 152 Chitin, 240
Brittleness, 97, 264 Chlorinated rubber, 194
Bulk polymerisation, 37, 43, 70, 114, 362 Chloroprene, 11, 63, 64, 82
Buna N, 9, 72, 82 Cis
Buna S, 9 configuration, 64
Butadiene, 9, 37, 48, 49, 53, 54, 63 isomerism, 13
Butyl lithium, 28, 70 Chloroprene polymerisation, 64
Butyl rubber, 9, 62, 86, 89, 213, 214, 362 Co-catalyst(s), 28, 33, 34
Coil
Calendering, 220, 222, 235 density, 259
Capillary viscometer, 121 perturbed, 182
Caprolactam, &€, 36, 55, 74, 83, 346 unperturbed, 165, 181
Carboxymethy] cellulose, 43, 188, 369 Coefficient of expansion, 102, 103
Carbon black, 104, 216, 217, 219, 276 Cold vulcanisation, 247, 248
Carbon fiber(s), 15, 190, 200, 286 Collagen, 113, 240, 368
Carbowax, 79 Colloid(s), 15, 43, 44, 115, 127, 260, 261,
Carothers, W.H., 333, 334 275, 277, 278, 279, 280, 281
Carother’s equation, 57 Colorant(s), 23, 216, 219, 221, 224
Casting, 45, 46, 70, 220, 221, 222, 223, Comb polymer(s), 265
228, 255, 362 Combinatorial entropy, 282
Catalysis, 14, 63 Comonomer(s), 50, 210
Catalyst(s), 26, 27, 30, 32, 33, 34, 42, 44, Composite(s), 107, 208, 215, 220, 283, 289
57, 61, 62, 64, 66, 70, 76, 77, 81, 114, Compounding, 220, 362
136, 209, 210, 231522),224,.356,.358 Compression moulding, 219, 231, 233
Cationic Polymerisation, 28, 29, 32, 42, 75, Condensation polymerisation, 26, 27, 270
$1, $3,350; 352 Conductor(s), 104, 264, 318, 319
Ceiling temperature, 41, 47, 48, 82, 198, Conformation
200 coilar, 20
Cellophane, 9, 223, 237, 238, 362, 368 helical, 20, 137, 141, 150
Celluloid,9, 14, 15, 217, 368 molecular, 241
Cellulose, 8,9, 19, 139, 188, 189, 200, 206, Constitutional!
207, 216, 236, 237, 238, 239, 290, 345 repeat unit, 1, 8
regenerated, 207 isomer, 13, 25
fiber(s), 15, 207, 236 Contour length, 20, 164, 165, 197
Cellulose acetate, 88, 89, 188, 207, 229, 362 Copolymer(s), def, 5
Cellulose nitrate, 14, 15, 86, 89, 166, 217, alternating, 6, 53, 14
362 block, 6, 11, 21, 29, 32, 49, 82, 147,
Chain(s) LOT 197212, 2755214
branched, 3, 6, 83, 107, 238 graft, 6, 11, 21, 147
linear, 5, 6, 83, 107 random, 6, 147
orientation, 150 azeotropic, 53
Chain flexibility, 136, 139, 163, 199 free radical, 54, 55
Chain folding, 264 Coupling agent, 362
pe Index 393
Crazing, 107, 109, 359 " Density, 61, 78, 86, 89, 93, 122, 127, 136,
Creepr i4ay/2-213. $62 138, 139, 144, 151, 163, 167, 211, 225,
Creeping, 360 226, 259; 273
Critical Deoxyribose, 243, 245
solution temperature, 175, 200 Depolymerisation, 196
stress, 108 Dextran, 239, 368
Critical micelle concentration, 44 Dextrin, 238, 368
Cross-linking reaction, 191, 192, 193, 194, Diblock copolymer(s), 11
195 Die3220; 221, 222, 22349224
Cross-links, examples, 191, 192, 193, 194, Die casting, 220, 221
195, 204, 205 Dielectric, 42, 103, 104, 105, 151, 255
CRU, 1, 263 Dielectric constant, 66, 104, 105, 106, 228,
Cryoscopy, 117, 128 262
Crystal structure, 141, 256 Differential scanning calorimetry, 308
Crystalline polymer(s), 5, 10, 15, 69, 86, Diffraction pattern, 137, 149, 150, 151
136, 137, 147, 152, 153, 154, 163, 200, Diffusion
283, 286 coefficient, 131
Crystallinity, def, 10 in solution(s), 162
degree of, 74, 107, 136, 137, 141, 153, Diisocyanate, 55, 78, 83
207, 237, 285, 345, 348 Dilatometer, 103
Crystallizability, 85, 136, 140 Dilatometry, 103, 137, 363
Crystallization, 136, 140, 142, 150, 155 Dimension(s)
Curing ‘i coil, 164, 165, 166, 180, 198
epoxy resin(s), 80, 81, 162 linear polymers, 165, 227, 288
plastic(s) unperturbed, 22, 165, 180, 181
rubber(s), 194, 195 Diol, 55, 78, 285
thermosett(s), 195, 226 Dispersity, 113, 129
Cyanoacrylate, 71, 215 Disproportionation, 30, 31, 41, 360
Cyclisation, 190, 191, 253 Dissipation factor, 104, 105
Cytosine, 243, 244 Distribution function, 60
Disymmertry, 126
Decomposition, 23, 25, 28, 31, 39, 83, 152, Diviny] benzene, 11, 27, 64
156, 158, 159, 161, 162, 210, 226 DMA, 276
Deformation, 90, 91, 99, 163, 183, 184, DNA, 8, 150, 243, 244, 245, 246
S56 22 Wile 59> 275" 355 Dopant(s), 104, 262, 263
elastic, 163, 183 Double helix, 244, 245
permanent, 184, 275 DP, 1, 28, 38, 39, 40, 42, 57, 58, 59
viscoelastic, 185 Drawing, 136, 187
De Gennes, Pierre, 317, 318, 319 Draining, 66, 178
Degradation Droplet, monomer, 44, 83
biological, 197 Dry spinning, 229
chemical, 160, 197, 215 DSC 15390544155, 1565157561 59551.60)
enzymatic, 197 162, 308
hydrolytic, 197 DTA, 153, 156, 159, 160, 161, 162
photo, 197 Dynamic
thermal, 156, 161, 162, 197 light scattering, 133, 278
ultrasonic, 196 osmometry, 120, 348
Degree of polymerisation, 1, 21, 38, 41,
43, 57, 61, 111, 114, 177, 199, 206, 276, Ebulliometry, 117
303, 307 Elasticity, 10, 20, 23, 64, 183, 184, 185,
Denaturation, 242 206, 208, 212, 214, 247
394 Index
Elastic modulus, 199, 212° Flexural strength, 87, 363

Elastomer(s), 212, 213, 214, 363 Floor temperature, 82
thermoplastic, 5, 15, 49, 273, 296, 281, Flory, P.J., 314, 315, 316
283 Flory-Huggins interaction parameter, 171,
properties, 8, 62, 64, 66, 137 eS ‘
resistance, 104 Flory-Huggins theory, 171, 172, 173, 199,
Elongation, 183, 184, 186, 204, 205, 208, 363
212213 Flow behaviour, 112, 183, 184
at yield, 186, 187 Foaming agent, 225
at break, 186, 187, 204, 206, 214 Foam(s), 62, 78, 215, 226, 252
Emulsion, 44, 45, 65, 69, 261, 277 Formaldehyde, 14, 75, 76, 77, 205
Emulsion polymerisation, 27, 28, 44, 45, Forces
64, 66, 67, 82, 215, 277, 338 dipole-dipole, 18, 139
End group analysis, 117, 345, 348, 363 intermolecular, 18, 139, 217
End to end distance, def, 22, 165, 363 ionic, 18
unperturbed, 22, 165 valence, 9, 18, 19, 139
Engineering plastic(s), 17, 75, 80 vander waal’s, 18, 19, 139
Entanglement, 123, 135, 283 Fractionation
Enthalpy of polymerisation, 47, 158, 197 by elution, 115
Entropy by precipitation, 115, 128
combinatorial, 282 Fracture, 147, 150, 380
configurational, 171, 280 Free radical
polymerisation, 47 initiator, 28, 49
Enzyme immobilization, 255 polymer, 136, 287
Epoxy resin(s) polymerisation, 28, 31, 41, 54, 64, 68,
curing, 21, 80, 81 70, 80, 82, 83, 136
synthesis, 81, 297 Free rotation, 237
Ethyl cellulose, 99, 188 Free volume, 270
Ethylene Freely jointed chain, 20, 22, 171, 199
monomer, 2, 11, 37, 47, 48, 49, 53, 61, 63 Freely rotating chain, 22
polymerisation, 2, 14, 61, 62, 136 Friction, 64, 66, 178, 215, 230
Ethylene glycol, 2, 3, 11, 15, 56, 61, 72, Frictional coefficient, 289
196, 209 Fringed micelle, 135, 200, 363
Ethylene imine, 210 Functional polymer, 286
Exchange reaction, 269 Functionality, 2, 4, 24, 26, 61, 72, 82, 83
Expansion coefficient, 102, 103 Fusion, 160
Expansion factor, 165, 166, 178, 306
Extenders, 69, 363 Gel effect, 37, 363
Extrusion, 62, 63, 72, 219, 227, 228, 231, Gel filtration, 115
23545255 Gel permeation chromatography, 115, 128
Gel point, 363
Fiber(s), 206, 363 Gelation, 288
spinning, 229, 230 Gelatin, 8, 291
synthetic, 206, 208, 211 Generic name, 73, 95, 261
Filler(s), 23, 106, 107, 108, 216, 221, 225, Geometric isomerism, 1113, 21, 25
276, 283, 287, 363 Gibbs energy, 166, 170, 214, 282
Fineman-Ross method, 51, 52 Glass fiber(s), 74, 228
Flame retardant(s), 15, 16, 24, 215, 216, Glass transition temperature, 137, 151, 153,
218, 363 154, 155, 160, 162, 203, 210, 213, 249,
Flexibility, 49, 61, 72, 77, 135, 139, 140, 253, 261, 364
1525°163, 2996216,.217,.257. GPC, 115, 116, 117, 340, 345, 349, 364, 381
on Index 395
Graft copolymer, 21, 24, 123, 147, 278, 282, cationic, 24, 28
287, 364 decomposition rate, 39
Gutta percha, 7, 8, 14, 20, 246, 364 efficiency, 39
free radical, 28, 39, 51
Hard redox, 28
fiber, 230 Injection blow moulding, 219, 232, 364
rubber(s), 7, 24, 5, 337 Insertion polymerisation, 34
Hardening, 214, 224, 229, 246 ‘ Insulator(s), 104, 105, 106, 161, 208, 262,
Hardness, 10, 72, 88, 138, 200, 217, 228 285
Head-to-head, 11, 21, 339, 359 Integral distribution curve(s), 129
head-to-tail, 11, 21 Interfacial polycondensation, 56, 82, 364
Heat capacity, 151, 161 Interpenetrating network, 283, 284, 285, 364
Heat deflection temperature, 98 Intrinsic viscosity, 122, 123, 131, 177, 178,
Heat distortion temperature, 205 179, 180, 181, 182, 199, 364
Heat stabilizer, 216 Ion exchange resin, 190
Heeger, A.J, 319, 320, 323, 324 Ionomer(s), 10, 49, 261, 262, 269, 364
Helix Isomer
a, 214 constitutional, 13, 25
double, 244, 245 geometric, 11, 13, 21, 25
Hemoglobin, 241 Isoprene, 37, 62, 63, 212, 213, 214, 246,
Heparin, 230, 240, 291 247
Hetero-chain polymers, 5 [sotachtes S293 04S 1532, 62) 471, 83;
Hevea braziliaensis, 247, 364 85, 93, 94, 364
Hexamethylene diamine, 11, 73, 79, 83 IUPAC, 11, 24
High performance plastics, 228
History of polymers, 14 Kevlar, 15, 73, 336
Homochain, 5, 7 Kinetic chain length, 41, 83, 365
Homologous, 140 Kraemer, 122, 123
Homopolymer(s), 5, 24, 49, 53, 61, 62, 82, Kwolek, S, 329, 330
85, 141, 155, 265
Hooke’s equation, 183 Lactam, 34, 72
Huggin’s equation, 123 Ladder polymer, 9, 24, 152, 190, 285, 286
Hydrodynamics, 181 Lamellar, 135, 142, 143, 273, 274
Hydrogen bonding, 18, 19, 87, 136, 138, Laminating, 80
139, 167, 207, 208, 237 Latex, 6, 14, 44, 45, 65, 67, 213, 215, 247,
Hydrogenation, 191, 192 280, 282, 284, 365
LDPE, 6, 10, 15, 17, 60, 61, 86, 136, 140,
Ideal polymerisation, 53 168, 205, 227, 369
Identification of Leather, 70, 257
polymer(s), 85, 87, 88, 90, 95 Leaving group, 291
monomer(s), 90, 95 Lewis acid(s), 28, 32, 36, 55
Immobilization, 255 Lewis-Mayo method, 51
Impact strength, 71, 138, 205, 206, 222, Light scattering, 115, 124, 125, 126, 128
228, 282, 380 angular dependence, 125
Industrial scenario, 16 Light transmission, 146
Industrial polymers, 203 Lignin, 283, 365
Industrial polymerisation, 45 Linear chain, 6, 7, 21, 22, 62, 91, 107, 141,
Inherent viscosity, 122 158
Inhibitor(s), 60, 295, 296, 364 Linear low density polyethylene, 11, 136,
Initiator(s) 369
anionic, 24, 28 Liquid crystalline polymer(s), 15, 286, 287
396 Index
Liquid polymers, 345 Newton, 185

Living polymer(s), 29 Modifier, 38, 42, 44
Living polymerisation, 30, 83 Modulus of elasticity, 10, 184, 199. 212
Long range order, 152 Molecular architecture, 266, 268, 271
Lubricant(s), 109, 177, 215, 240, 249, 252, Molecular weight, 1, 3, 14, 21, 27, 34, 35,
380 38, 41, 43, 45, 50, 54, 59, 60, 61, 85,
O7*-109, 1105 11S 12; is itagtis,
MacDiarmid, A.G, 322, 323 116, 117, 118, 119, 120, 121, 128, 131,
Macroanion, 29 132; 1357913 7913851395 203, 2109239;
Macrocation, 32, 42 249, 252, 256, 259, 264, 270, 274, 276,
Macromoleule, 2, 7, 8, 14, 15, 19, 20, 21, 281, 285, 286, 288, 290
47, 145, 166, 182, 236, 237, 241, 243, Molecular weight distribution, 35, 47, 50,
249, 259, 289, 290 85, 109, 110, 113, 114
Mark-Houwink equation, 112, 123, 132, Molecular weight average, 110, 112, 113,
179, 365 117, 120; 1312-180
Mark-Houwink-Sakurada equation, 123, 182 Monodisperse, 5, 110, 241, 337, 344, 345
Mark H.F, 325, 326, 327, 328, 329 Monomer, def, 1, 365
Mass fraction, 131, 144 Monomeric unit, 5, 237, 239
Mayo equation, 38 Monomer feed ratio, 51
Mechanical Mould, 216, 219, 220, 222, 224, 227, 228
property, 7, 59, 74, 87, 99, 107, 137, Moulding
138, 142, 145, 146, 151, 183, 203, Blow, 219, 224, 233
209, 225, 228, 252, 265, 266, 282 Compression, 231
behaviour, 274 Extrusion, 234
Melamine-formaldehyde resin, 77, 78, 82, Injection, 64, 232
DF 2057215 transfer, 232
Melamine resin(s), 14, 15, 24, 77, 106 Multimer, def, 193
Melt, 5, 27, 56, 57, 138, 141, 143, 144, Myoglobin, 241
152, 154, 209
Melt spinning, 211, 230, 365 Name(s)
Melt viscosity, 59, 138, 177, 203, 211, 219, generic, 73, 95, 261
261, 365 IUPAC, 11, 24
Melting temperature, 86, 99, 151, 155, 164, trivial, 11, 77
302, 308 Natta, Guilio, 15, 24, 33, 312, 313
Membrane osmometry, 118, 119, 182, 199 Natural
Merrifield, B, 316, 317 fiber(s), 9, 147, 206, 207, 208, 220, 228,
Merrified synthesis, 242, 291 230
Methyl methacrylate, 37, 48, 53, 54, 70, resin, 9, 206
95; 499, 256, 301, 369 rubber, 6, 8, 14, 15, 20, 64, 137, 140,
Methyl styrene, 24, 48, 54 143, 166, 191, 194, 212, 213, 246,
Micelle(s), 44, 45, 83, 252, 273, 275, 276, 247, 248, 337, 344, 348
288 Neoprene, 14, 15, 24, 213, 214
Microscope Network
electron, 146, 147 interpenetrating, 283, 284, 285, 365
polarising, 142 Newton’s law, 184
Mobile phase, 95 Newtonian viscosity, 183, 184
Mobility Nitrile rubber, 86, 214, 282
segmental, 188, 204 Nitrocellulose, 188
Model NMR, 88, 93, 94
Hooke’s, 184, 185 Nobel prize, 310, 312, 313, 314, 316, 319,
Maxwell, 185 329
yp Index 397
Non-solvent, 180, 181, 182, 229 - Polyacetylene, 262, 263, 264

Novolac, 76, 82, 365 Polyacrylic acid, 10, 11, 29, 140, 183, 189,
Nuclear magnetic resonance, 88, 93, 94 259, 260
Nucleic acid, 8, 14, 243, 259, 289 Polyacrylonitrile, 24, 29, 43, 71, 152, 154,
Number average, def., 110 166, 190, 191, 205, 210, 212, 286, 289,
Number fraction, 60, 110, 111 292, 335
Nylon, 10, 14, 15, 16, 17, 18, 19, 20, 21, Polyaddition, 47, 57
24, 25, 30, 36, 55, 73, 81, 86, 87, 88, Polyamic acid, 75
89, 97, 100, 124, 134, 136, 139, 140, Polyamide(s)
154, 167, 184, 200, 206, 209, 210, 212, aromatic, 74, 197, 286
216, 220, 227, 336, 340, 343 fiber(s), 209, 211
Nylon salt, 73 Polyanion, 290, 291
Polyacrylate, 70, 204, 21
Olefin(s), polymer, 2, 32, 46, 67 Polyblend(s), 16, 63, 220, 281, 282
Oligomer, 55, 361 Polybutadiene, 9, 11, 16, 17, 29, 49, 63,
Optical properties, 146, 225, 264 64, 89, 139, 151, 154, 274, 276, 281,
Orthorhombic, 141, 274 282
Osmometry, 118, 119, 121, 182, 199, 340, Polycarbonate, 15, 24, 27, 30, 80, 86, 89,
343, 348, 350 96, 102, 156, 197, 228, 234, 282
Osmotic pressure, 117, 118, 120, 132, 173, Polychloroprene, 9
174, 182 Polycondensation
Ostwald viscometer, 121 degree of, 54, 55, 57
kinetics, 56
Palit#S:RS, 331; 332 interfacial, 56, 82, 364
PAN, 15, 25, 71, 158, 292, 341, 352, 369 molecular weight distribution, 58
Paper, 19, 23, 66, 216, 219, 220, 227, 236, Polycyanoacrylate, 355
237 Polydimethy]! siloxane, 121, 154
Pearl polymerisation, 43 Polydisperse, 5, 110, 114, 115, 119, 131,
Pectin, 241 163
Peptide likage, 241 Polydispersity, 82, 114, 272, 274
Perturbed coil, 182 Polyelectrolyte, 10, 176, 188, 199, 259, 260,
PET, 1557/2787, (88> 1675 2115/3525 269 261, 278, 366
Phase separation, 168, 170, 174 Polyester
Phenol-formaldehyde resin, 14, 75, 76, 97, fiber, 16717, 18% 308209521155 212
158, 162, 176, 205, 219, 227, 369 unsaturated, 9, 15, 73, 196, 205, 206,
Phenolic resin(s), 17, 68, 76, 206, 215, 223, 21532239226
227, 302 Polyetheretherketone, 15, 81
Photo initiators, 39 Polyethylene
Photo polymerisation, 83 branching, 20, 139, 241
Pigment(s), 108, 215, 216, 219, 283, 287 crystal structure, 21, 139, 141
Plasticity, 17 high density, 6, 61, 86, 136
Plasticization, 14, 155, 200, 335, 341, 354, low density, 6, 61, 86, 136
359 linear low density, 10, 136, 364
Plastic(s), def, 204 Polyethylene oxide, 12, 35, 79, 86, 116,
compounding, 220, 341 124, 197, 199, 264, 266, 268
disposal, 220 Polyethylene terephthalate, 24, 72, 82, 209,
foamed, 225, 226 220, 284
processing, 220, 224 Polyformaldehyde, 36, 75
reinforced, 73, 220, 222, 228 Polyimide, 74, 83
PMMA, 24, 86, 87, 88, 93, 94, 121, 167, Polyisobutylene, 29, 62, 83, 136, 151, 166,
183, 199, 205, 215, 289, 369 186, 197, 204, 337
398 Index
Polylactic acid, 290 termination, anionic, 26, 32, 349

Polymer blend(s), 147, 161, 162, 283 termination, cationic, 26, 32, 349
Polymer composite(s), 15, 283 Ziegler-Natta, 14, 30, 35, 82
Polymer crystal(s), 141, 149, 150 Polymerisation enthalpy, 47, 158, 197
Polymer(s) Polymerisation entropy, 47, 171
branched, 5, 6, 7, 8, 9; 15;221,,33-61, Polymerisation free energy, 47, 168, 169
97, 123, 164, 165, 335, 350, 358 Polymerisation reactor(s), 45, 46, 211
constitution, 1, 9, 113, 158 Polymerisation temperature, 47, 256
cross-linking, 4, 5, 6, 8, 27, 68, 79, 85, Polymerisation technique(s)
86, 97, 191, 192, 193, 194, 195, 204, bulk, 37, 43, 70
205,/215,, 252, 255,268 p28 e285, emulsion, 27, 28, 44, 45, 64, 66, 67, 82,
284, 285, 288, 291, 335, 342 338, 363
crystalline, 10, 39, 86, 136, 137, 147, industrial, 45
152,953; 154516352001 2567 283; solution, 27, 43, 70, 82, 366
286, 362 suspension, 27, 43, 70, 82, 366
deformation(s), 91, 99, 163, 183, 184, Polymethy!] methacrylate
185 synthesis, 70, 301
dimension(s), 22, 145, 164, 165, 166, nmr, 94
177, 180 Polyoxyethylene, 81, 290, 342
functionality, 2, 4, 24, 60, 72, 82, 196 Poly p-phenylene, 263, 272
history, 14, 15 Polypeptide, 21, 24, 207, 208, 241, 242,
hydrodynamics, 181 366
inorganic, 5, 7, 8, 24, 82, 249, 251, 252, Poly p-phenylene vinylene, 79, 271, 272
255 Polypropylene
nomenclature, 10 nmr, 93, 94
size, 22, 141, 145, 164, 165, 176, 178, tacticity, 34, 154
279, 280 Polysaccharide(s), 8, 14, 20, 21, 236, 237,
solid state property, 4, 10, 82, 200 238, 239, 280, 288, 342, 346, 349, 352
solution(s), 16, 21, 86, 112, 115, 119, Polystyrene, 29, 49, 62, 64
120; 121, '122;° 1245125) 127),138, Polysulfide, 9, 82, 214, 223
162, 163, 164, 165, 171, 172, 173, Polytetrafluoroethylene, 9, 14, 27, 66, 86,
175, 176, 177, 178, 182, 184, 229, 95, 140, 158, 220, 269, 289, 368
260, 264, 275, 279 Polyurethane(s),
solution viscosity, 110, 121, 128, 163, elsatomer(s), 213
176, 177, 179, 229 foam(s), 76, 226
swelling, 97, 107, 162, 163, 167, 180, synthesis, 78
346, 353 Polyvinyl acetate, 9, 24, 29, 67, 83, 86, 92,
water soluble, 8, 10, 15, 68 124, 154, 168, 188, 190, 204, 302
Polymeric sulfur, 8, 249, 250 Polyvinyl alcohol, 9, 11, 13, 24, 29, 43, 67,
Polymerisation 86, 92, 154, 188, 190, 200, 204, 302,
anionic, 26, 28, 33, 36, 82, 211, 272 338
cationic, 26, 28, 32, 42, 73, 82, 83, 362 Polyvinyl butyral, 24, 67, 190, 204
desree*of, 1, 21, 3784194315761, Polyvinyl chloride, 1,9, 11, 16, 19, 21, 29,
111, 114, 177, 199, 206, 270, 347 49, 64, 65, 91, 96, 102, 124, 136, 151,
free radical, 28, 31, 41, 54, 64, 68, 70, 152, 154, 156, 158, 161, 197, 204, 227,
80, 82, 83, 114, 136, 222, 344, 345 369
industrial, 45 Polyvinyl crown ether, 8, 258
kinetics, 16, 36, 39, 40, 41, 42 Polyviny] fluoride, 65, 95, 205
propagation, 26, 30, 31, 32, 33, 34, 35, Polyvinyl pyrrolidone, 9, 29, 68, 86, 124,
37, 38, 49, 50, 54 290
rate(s), 36, 39, 40, 42 Polyvinylidene chloride, 64, 140, 350
fe?
Index 399
Polyvinylidene fluoride, 66, 102 “ Ring opening polymerisation, 34, 36, 37,
Precipitation polymerisation, 43, 83 79, 82
Prepolymer(s), 73, 81, 196 RNA, 8, 243, 246, 289
Process technique(s) Rod(s), 99, 126, 140, 143, 182, 270, 222, 286
blow moulding, 219, 231, 233, 234 Rubber
calendering, 219, 221, 222, 235 Buna N, 9, 72, 82, 344
compression moulding, 219, 231 Buna S, 9
die casting, 221, 222 ‘ butyl, 9, 62, 213, 214, 345, 350, 352
extrusion moulding, 231, 234 chlorinated, 194
fiber spinning, 209, 211, 229, 230 cold, 64, 247, 248
foaming, 225 natural, 6, 8, 14, 15, 20, 64, 86, 89, 124,
injection moulding, 219, 228, 231, 232, 137, 140, 143, 166, 191, 212, 213,
364 246, 247, 248, 282, 337, 341
thermoforming, 224, 225, 227 nitrile, 86, 214, 282
vacuum forming, 224 processing, 193
properties, 137, 213
Q-e scheme, 52, 53, 82 silicone, 9, 214, 289
Quasi elastic light scattering, 344 styrene-butadiene(SBR), 9, 16, 21, 49,
82, 86, 88, 124, 140, 214, 370
Radius of gyration, 22, 125, 164, 178, 198, synthetic, 9, 63
366 types, 9, 13
Random coil, 164 vulcanisation, 7, 14, 15, 193, 194, 200,
Random copolymer, b, 5, 24, 123, 141, 213, 214, 247, 248, 281, 367
366 Rubber elasticity, 20, 23, 64, 212, 213
Rayleigh ratio, 125, 127
Rayon, 9, 206, 207, 212, 227, 229, 366 Saran, 24, 49, 368
Reactivity ratio, 50, 51, 53, 54, 61, 82, 343, Scaling concepts, 318
349 Scattering methods, 124, 125, 126
Reactor(s), 45, 46 Second virial coefficient, 120, 125, 126, 133,
Reclaimed, 231 173, 174, 182, 198
Recombination, 270 Sedimentation
Recyclic, 23 coefficient, 127, 128
Redox system(s), 28, 31, 44, 64, 82 equilibrium, 112, 127, 128
Reduced viscosity, 122, 179, 180 rate, 127
Refractive index increment, 125, 133 velocity, 127, 350
Regenerated fiber Semi-synthetic
cellulose, 15, 207, 237, 238 fiber(s), 207
Reinforced plastic(s), 73, 220, 222, 228 polymer, 9
Relative viscosity, 122, 132 Shear modulus, 99, 100
Repeat(ing) unit, 1, 9, 10, 24, 60, 82, 89, Shear rate, 177, 185
90, 91, 107, 161, 198, 199, 237, 240, Shear stress, 185
249, 259, 264, 265, 266 Shear thinning, 184
Resin(s) Shear thickening, 184
polymeric, 77, 228 Shellac, 24, 206, 366
epoxy, 9, 21, 24, 30, 80, 81, 89, 97, 162, Shirakawa, H, 321, 322
205, 206, 285 Silicon, 7, 9, 24, 81, 206, 215, 223, 228,
Retention volume, 95, 116 251, 252, 289
Rheology, 183, 201 Silk fiber, 9, 206, 208
Ribonucleic acid, 243, 246 Size exclusion chromatography, 115, 128
Ribose, 243 Solubility parameter, 86, 87, 133, 167, 199,
Rigidity, 16, 222, 247, 256, 265, 285 216, 336, 343
400 Index
Solution(s) Styrene-butadiene, 11, 49, 82, 140, 191, 213,

association, 341 214, 274, 370
concentrated, 142, 165, 184, 229, 286 Styrene copolymer, 11, 72, 140, 190, 191,
Flory theory, 171, 172, 173, 174 200, 228
viscosity, 110, 121, 128, 163, 176, 177, Substitution, 158, 253, 254
179, 200 Surface
Solution temperature, 175, 200 resistivity, 104
Solvent tension, 221, 252
good, 86, 120, 133, 165, 166, 179, 180, Surfactant(s), 43, 44, 45, 252, 273, 276,
181, 199, 276, 278, 280, 342, 343 277, 280, 288, 338, 342
poor, 120, 166, 180, 181, 182, 199, 278 Suspension, 27, 223, 261, 277
non, 115, 180, 181, 182, 229 Suspension polymerisation, 27, 43, 44, 45,
Spandex fiber, 15, 273, 360, 366 82, 366
Specialty polymer(s), 259 Svedberg equation, 128, 348, 359
Specific viscosity, 122, 178 Swelling, 97, 107, 162, 163, 167, 180, 207,
Sphere(s); 126, 143551715 AL82.2229273, 213, 214
286 Syndiotactic, 5, 13, 21, 25, 29, 32, 34, 70,
Spherulite(s), 135, 141, 142, 143, 144, 343, 137, 246, 366
349, 366 Synthetic
Spinning, 209, 211, 229, 255 fiber(s), 9, 147, 206, 208, 209, 210, 211,
Spiro polymer(s), 285, 286 212, 228
Stablizer(s), 43, 107, 209, 215, 216, 217, rubber(s), 9, 63
223, 276, 282, 288
Star polymer, 8, 15, 350 Tacticity, 11, 21, 174, 366
Starch, 8, 9,.19, 200, 215, 236, 238, 239, Technology
344, 345, 249 plastic, 235
Statistical thermodynamics, 170 rubber, 202
Staudinger. H, 2, 14, 24, 310, 311 Teflon, 9, 14, 15, 21, 24, 86, 89, 197, 204,
Steady state, 40, 42, 50, 100 339, 341, 344, 349, 368
Step growth polymerisation, 26, 47 Tensile strength, 10, 23, 61, 69, 87, 136,
Stereo isomerism, 13, 348 138, 212, 213, 214, 228, 246, 367
Stereo regularity, 29, 34, 337 Termination
Stereo regular polymer(s), 15, 140, 353 by chain transfer, 31, 37
Steric factor, 339 by coupling, 30, 31, 40, 41
Steric hindrance, 152 by disproportionation, 30, 31, 41
Steric parameter, 22 in anionic polymerisation, 26, 32
Stoke’s law, 128 in cationic polymerisation, 26, 32
Strain, 48, 107, 183, 184, 185, 186, 187, in coordination polymerisation, 33, 82
200, 355 in free radical polymerisation, 28, 30,
Strength, 10, 16, 17, 20, 23, 62, 70, 71, 72, 31, 39
87, 88, 104, 108, 135, 136, 137, 138, Terylene, 10, 15, 24, 26, 30, 59, 72, 154,
139, 186, 187,205,207, 2089211 212; 336, 344, 345
214, 216, 221, 227, 228, 246, 265, 281, Testing of polymer(s)
283, 379 chemical, 86, 106
Stress electrical, 103
cracking, 62, 107, 108, 109 physical, 86
crazing, 360 thermal, 97
critical, 108, 109 Thermodynamics
Stress-strain curve(s), 184, 186, 187, 200 of polymerisation, 47, 82
Stretching, 89, 90, 91, 109, 136, 137, 207, solution, 168, 169, 170, 171, 173, 200
210, 213, 225, 230 statisical, 170
4 Index 401
Thermoforming, 224, 225 Vinyl fluoride, 66

Thermogravimetry, 157, 367 Vinyl pyridine, 53, 217, 285
Thermoplastic elastomer(s), 15, 49, 273, Vinyl pyrrolidone, 37, 69, 72
276, 281, 283 Vinylidene chloride, 49, 65
Thermoplastics, def, Vinyon, 49, 54
Thermosett resin(s), 5, 17, 228, 379 Virial coefficient
Thermosett(s), 5, 86, 88, 97, 367 light scattering, 125, 126
Theta solvent(s), 121, 165, 179, 180% 367 osmometry, 120, 173, 174, 182
THF, 124, 199, 255 Viscoelastic liquid, 186, 275
Thickener(s), 68 Viscometer(s)
Thiokol Viscosity, 121, 122
resin, 15 concentration dependence, 179, 180, 181
rubber, 14, 79, 82, 213, 214 Newtonian, 183, 184
Thixotropy, 199, 223 reduced, 122, 179, 180, 260
Toughness, 10, 16, 72, 80, 88, 200, 208, relative, 122, 131
226, 282 specific, 122, 178
Tracking, 106 Viscosity average molecular weight, 110,
Trans,, 14, 20, 34, 63, 140, 246 {PAN IP, LIBYA Shey
configuration, 6, 14 Viscosity-Molecular weight relationship,
isomerism, 14, 292 176-182
Triblock copolymer;-11, 274, 276 Volume, def, 145
elution, 116
Ubbelohde viscometer, 121, 122 fraction, 167, 174, 178, 283, 388
Utracentrifugation, 127, 367 Vulcanisation, 7, 14, 15, 193, 194, 195, 200,
Ultracentrifuge, 127, 128 213, 214, 247, 248, 281, 367
Unit Vulcanised rubber, 19, 89, 213, 214, 247
constitutional, 9
monomer, 5, 14, 164, 224, 237, 239 Wet spinning, 229, 367
repeat(ing), 1, 9, 10, 24, 60, 82, 89, 90, Wool fiber, 9, 207, 208
915, 107, 2161, 198; 199) 237, 238,
240, 249, 259, 264, 265, 266 X-ray diffraction, 135, 137, 147, 148, 149,
Unperturbed dimension, 22, 165, 180, 181 150, 230, 245
Unsaturated polyester,9, 15, 196, 205, 206, X-ray scattering, 150
2153-223, 226
Upper critical solution temperature, 175 Yield
Urea-formaldehyde resin, 14, 17, 77, 97, 205 point, 108, 186, 187, 367
Uracil, 243 strength, 186
Urethane(s), 222, 284 stress, 187, 379
UV absorbers, 217 Young modulus, 249, 261
UV spectroscopy, 88, 93
Ziegler-Natta catalyst(s), 33, 34, 136, 211,
Valence force(s), 9, 18, 19, 139 367
Vegetable fiber, 207 Zimm method, 126
Vinyl acetate, 43, 48, 49, 53, 54, 67, 70, 210 Zimm plot, 127, 367
Vinyl chloride, 1, 23, 43, 49, 54, 64, 65, Z-average, 367
83, 217 Zinc oxide, 247
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01850 OUbIO4G 3
QD 381 .B345 2002
Bahadur, P.
Principles of polymer
science
DATE DUE
in USA
HIGHSMITH #45230
PSSa all
> YMERSCIE
POL
rinciples of
|
P. Bahadur
South Gujarat University
Surat, Gujarat, India
N.V. Sastry
Sardar Patel University
Vallabh Vidyanagar, Gujarat, India
Principles of Polymer Science deals with several aspects covering

synthesis, characterization, behavior and processing of polymers from
an introductory level to a bit advanced coverage. A discussion on natural,
inorganic and speciality polymers has been made in separate chapters.
Additional and useful supplementary material such as common
: laboratory experiments, multiple choice and conceptual based Si
questions with answers, brief sketches of polymer pioneers and a

glossary of technical polymer words has been appended.Itcovers
all aspects of polymer science in great depth familiarizing readers to
the fascinating world of polymers.
The main features are:
¢ Neatand simplified illustrations and understandable tables
e Several problems including numerical problems, multiple choice
and concept based problems with their answers
¢ Laboratory experiments on synthesis of common polymers and
theiridentification and characterization
¢ Glossary
_ This book is written for undergraduate and graduate students in
chemistry, chemical engineering and material science, along with
chemists and chemical engineers working in industries who often desire
a ready reference book>-

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In 2022 with funding from

Analytical Chemistry of Macrocyclic and Supramolecular

Organic Spectroscopy (81-7319-295-2)

Library of Congress Cataloging-in-Publication Data:

Exclusive distribution in North America only by CRC Press LLC

Copyright © 2002 Narosa Publishing House, New Delhi-110 002, India

No claim to original U.S. Government works

3. Polymer Analysis and Characterisation 85

3.1.1 Physical Testing 86

4. Behaviour of Polymers 135

5. Polymer Technology 203

6. Natural Polymers 236

7. Inorganic Polymers 249

8. Specialty Polymers 259

é —t hae . Sol anili2.

Td} VTE, erin aint ib YoneinietO ee

(i) Monomer : Vinyl chloride

l (ii) DP: 1000

(iii) Molecular weight of polymer

(iv) CRU CH) — CH

H,C=CH, -(CH,— CH2};

HO—CH, —CH,— OH (CH) CH, —0>-

Let us consider following examples to show that bi-functionality in a monomer

For a reaction between two compounds one possessing a monofunctional

Thus if n moles of a bifunctional species such as malonic acid is reacted with

Mono and Bifunctional Molecules:

Bifunctional Molecules: Small Molecule

Bifunctional Molecules in presence of some Trifunctional Molecules:

Cross linked or Polymeric Network

Fig. 1.2 Reactions between molecules with different functionality

1.2 Classification of Polymers

Natural and synthetic polymers

Organic and inorganic polymers

c Homopolymers and copolymers

Isotactic, syndiotactic and atactic polymers

Table 1(a) Comparison between thermoplastics and thermosetts

the joining of units of two different monomers). Copolymers can also be of

(1) Homopolymers: www AAAAAAAAAAAAA

(a) Alternating: Www ABABABABABABABwwv

(b) Random: ww» ABBABAAAABAABAwww

(c) Block (two block): wwww+§ AAA AAAABBBBBBBwww

(three block): Www A AAAABBBBBAAAAWw

(3) Terpolymers:) wwwABAACBAACCAABwww

Fig. 1.4 Molecular architecture of homo-, co- and terplymers

Polymers can be classified as linear, branched or cross-linked polymers. High

Lineat polymers) =< > 7

Cross linked polymers:

Fig. 1.5 Schematic representation of linear, branched and cross-linked polymers

In heterochain polymers, the main chain consists of linkages between different

Polymers are also classified as organic, elementoorganic and inorganic polymers.

Fig. 1.6 Some common inorganic polymers

Form Type Polymeric material

Fibers Natural Cotton, wool, silk and asbestos

Plastics, fibers and elastomers possess different physical properties. While

Table 1(c) Physical characteristics of polymers

Polymers Modulus, dyne cem~? Elongation, %

Elastomers 105-10" 1000

Polymers may be charged or uncharged. Charged polymers have some free

}~_——__——_——- Toont —__—_+|

(ii) Fe +H,O, ——» Fe+ + OH* + OH™

Initiation: CH )= CH) + R —» *CH)—CH)—R