Nonionic Surfactants : Organic Chemistry

title:
Surfactant Science Series ; V. 72
author: Os, Nico M. van.
publisher: CRC Press
isbn10 | asin: 0824799976
print isbn13: 9780824799977
ebook isbn13: 9780585347110
language: English
subject Surface active agents.
publication date: 1998
lcc: TP994.N656 1998eb
ddc: 668/.1
subject: Surface active agents.
Nonionic Surfactants
 SURFACTANT SCIENCE SERIES
CONSULTING EDITOR
MARTIN J. SCHICK
Consultant
New York, New York
1. Nonionic Surfactants, edited by Martin J. Schick (see also
Volumes 19, 23, and 60)
2. Solvent Properties of Surfactant Solutions, edited by Kozo
Shinoda (see Volume 55)
3. Surfactant Biodegradation, R. D. Swisher (see Volume 18)
4. Cationic Surfactants, edited by Eric Jungermann (see also
Volumes 34, 37, and 53)
5. Detergency: Theory and Test Methods (in three parts), edited by
W. G. Cutler and R. C. Davis (see also Volume 20)
6. Emulsions and Emulsion Technology (in three parts), edited by
Kenneth J. Lissant
7. Anionic Surfactants (in two parts), edited by Wamer M. Linfield
(see Volume 56)
8. Anionic Surfactants: Chemical Analysis, edited by John Cross
(out of print)
9. Stabilization of Colloidal Dispersions by Polymer Adsorption,
Tatsuo Sato and Richard Ruch (out of print)
10. Anionic Surfactants: Biochemistry, Toxicology, Dermatology,
edited by Christian Gloxhuber (see Volume 43)
11. Anionic Surfactants: Physical Chemistry of Surfactant Action,
edited by E. H. Lucassen-Reynders (out of print)
12. Amphoteric Surfactants, edited by B. R. Bluestein and Clifford
L Hilton (see Volume 59)
13. Demulsification: Industrial Applications, Kenneth J. Lissant
(out of print)
14. Surfactants in Textile Processing, Arved Datyner
15. Electrical Phenomena at Interfaces: Fundamentals,
Measurements, and Applications, edited by Ayao Kitahara and
Akira Watanabe
16. Surfactants in Cosmetics, edited by Martin M. Rieger (see
Volume 68)
17. Interfacial Phenomena: Equilibrium and Dynamic Effects,
Clarence A. Miller and P. Neogi
18. Surfactant Biodegradation: Second Edition, Revised and
Expanded, R. D. Swisher
19. Nonionic Surfactants: Chemical Analysis, edited by John Cross
20. Detergency: Theory and Technology, edited by W. Gale Cutler
and Erik Kissa
 21. Interfacial Phenomena in Apolar Media, edited by Hans-
Friedrich Eicke and Geoffrey D. Parfitt
22. Surfactant Solutions: New Methods of Investigation, edited by
Raoul Zana
23. Nonionic Surfactants: Physical Chemistry, edited by Martin J.
Schick
24. Microemulsion Systems, edited by Henri L. Rosano and Marc
Clausse
25. Biosurfactants and Biotechnology, edited by Naim Kosaric, W.
L. Caims, and Neil C. C. Gray
26. Surfactants in Emerging Technologies, edited by Milton J.
Rosen
27. Reagents in Mineral Technology, edited by P. Somasundaran
and Brij M. Moudgil
28. Surfactants in Chemical/Process Engineering, edited by Darsh
T. Wasan, Martin E. Ginn, and Dinesh O. Shah
29. Thin Liquid Films, edited by I. B. Ivanov
30. Microemulsions and Related Systems: Formulation, Solvency,
and Physical Properties, edited by Maurice Bourrel and Robert S.
Schechter
31. Crystallization and Polymorphism of Fats and Fatty Acids,
edited by Nissim Garti and Kiyotaka Sato
32. Interfacial Phenomena in Coal Technology, edited by Gregory
D. Botsaris and Yuli M. Glazman
33. Surfactant-Based Separation Processes, edited by John F.
 Scamehom and Jeffrey H. Harwell
34. Cationic Surfactants: Organic Chemistry, edited by James M.
Richmond
35. Alkylene Oxides and Their Polymers, F. E. Bailey, Jr., and
Joseph V. Koleske
36. Interfacial Phenomena in Petroleum Recovery, edited by
Norman R. Morrow
37. Cationic Surfactants: Physical Chemistry, edited by Donn N.
Rubingh and Paul M. Holland
38. Kinetics and Catalysis in Microheterogeneous Systems, edited
by M. Grätzel and K. Kalyanasundaram
39. Interfacial Phenomena in Biological Systems, edited by Max
Bender
40. Analysis of Surfactants, Thomas M. Schmitt
41. Light Scattering by Liquid Surfaces and Complementary
Techniques, edited by Dominique Langevin
42. Polymeric Surfactants, Irja Piirma
43. Anionic Surfactants: Biochemistry, Toxicology, Dermatology.
Second Edition, Revised and Expanded, edited by Christian
Gloxhuber and Klaus Künstler
44. Organized Solutions: Surfactants in Science and Technology,
edited by Stig E. Friberg and Bjöm Lindman
45. Defoaming: Theory and Industrial Applications, edited by P. R.
Garrett
46. Mixed Surfactant Systems, edited by Keizo Ogino and
 Masahiko Abe
47. Coagulation and Flocculation: Theory and Applications, edited
by Bohuslav Dobias *
48. Biosurfactants: Production Properties Applications, edited by
Naim Kosaric
49. Wettability, edited by John C. Berg
50. Fluorinated Surfactants: Synthesis Properties Applications,
Erik Kissa
51. Surface and Colloid Chemistry in Advanced Ceramics
Processing, edited by Robert J. Pugh and Lennart Bergström
52. Technological Applications of Dispersions, edited by Robert B.
McKay
53. Cationic Surfactants: Analytical and Biological Evaluation,
edited by John Cross and Edward J. Singer
54. Surfactants in Agrochemicals, Tharwat F. Tadros
55. Solubilization in Surfactant Aggregates, edited by Sherril D.
Christian and John F. Scamehom
56. Anionic Surfactants: Organic Chemistry, edited by Helmut W.
Stache
57. Foams: Theory, Measurements, and Applications, edited by
Robert K. Prud'-homme and Saad A. Khan
58. The Preparation of Dispersions in Liquids, H. N. Stein
59. Amphoteric Surfactants: Second Edition, edited by Eric G.
Lomax
60. Nonionic Surfactants: Polyoxyalkylene Block Copolymers,
edited by Vaughn M. Nace
61. Emulsions and Emulsion Stability, edited by Johan Sjöblom
62. Vesicles, edited by Morton Rosoff
63. Applied Surface Thermodynamics, edited by A. W. Neumann
and Jan K. Spelt
64. Surfactants in Solution, edited by Arun K. Chattopadhyay and
K. L. Mittal
65. Detergents in the Environment, edited by Milan Johann
Schwuger
66. Industrial Applications of Microemulsions, edited by Conxita
Solans and Hironobu Kunieda
67. Liquid Detergents, edited by Kuo-Yann Lai
68. Surfactants in Cosmetics: Second Edition, Revised and
Expanded, edited by Martin M. Rieger and Linda D. Rhein
69. Enzymes in Detergency, edited by Jan H. van Ee, Onno Misset,
and Erik J. Baas
70. StructurePerformance Relationships in Surfactants, edited by
Kunio Esumi and Minoru Ueno
71. Powdered Detergents, edited by Michael S. Showell
72. Nonionic Surfactants: Organic Chemistry, edited by Nico M.
van Os

ADDITIONAL VOLUMES IN PREPARATION

Anionic Surfactants: Analytical Chemistry, Second Edition,
Revised and Expanded, edited by John Cross
 Page i

Nonionic Surfactants
Organic Chemistry
Edited by
Nico M. van Os
Shell International Chemicals B.V.
Amsterdam, The Netherlands
 Page ii
ISBN: 0-8247-9997-6
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 Page iii

Nico M. van Os (19441996)

 Page v

Foreword
Nonionic surfactants were the subject of the first volume of the
Surfactant Science series published by Marcel Dekker, Inc.
Because this volume was published 30 years ago, a thorough
reappraisal of this class of surfactant, which has attained ever-
increasing importance, has become necessary. An initial step in this
direction was Volume 23 of the series Nonionic Surfactants:
Physical Chemistry, which appeared in 1987. An only slightly
more recent volume was concerned with the analytical chemistry
of nonionic surfactants. The present volume, Nonionic
Surfactants: Organic Chemistry, brings the presentation of this
field up to date.
Through his many years of experience as a research chemist in the
field of surfactant chemistry at the Shell Research and Technology
Center, Amsterdam, Nico van Os had a profound knowledge of
this subject matter. After completing the manuscript for this book,
Nico van Os' untimely death denied him the opportunity to witness
its publication. He had succeeded in recruiting fifteen well-versed
specialists with many years of practical experience in the industrial
sector to present their expert knowledge on synthesis and
application of the various types of nonionic surfactants with the
appropriate conciseness.
The rapid growth in the field of nonionic surfactants continues
unabated today, with new classes of nonionic surfactants being
introduced and new applications being discovered for these
compounds. The area of detergents, cleaning agents, and personal
care products will remain the primary domain for the application
of nonionic surfactants in the future. Other applications for these
compounds must also be taken into account, however. Recent
studies on the phase behavior of functionalized nonionic
surfactants indicate interesting prospects with regard to the
homogeneous catalysis of chemical processes:
 Page vi
nonionic surfactant phosphines control the temperature of a
process that takes place in aqueous solution as "intelligent"
complex ligands, by separating the catalyst complex from the
reaction mixture when a desired temperature identical to the cloud
point of the nonionic phosphine ligands is exceeded. Nonionic
surfactant phosphines are able to play a similarly "intelligent" role
in two-phase catalysis, by transferring the homogeneous catalyst
complex with these surfactant phosphine ligands from the aqueous
phase to the organic substrate phase at the reaction temperature,
where it is able to act like a normal homogeneous catalyst. When
the temperature drops below the cloud point, it returns to the
aqueous phase and is thus separated from the reaction product.
Such examples clearly demonstrate the chemical potential harbored
by the nonionic surfactants and their wide range of potential
applications in areas other than detergents and cleaning agents.
BERNHARD FELL
RHEINISCH-WESTFÄLISCHE TECHNISCHE
HOCHSCHULE
AACHEN, GERMANY
 Page vii

Preface
The main use for nonionic surfactants has been, and in the
foreseeable future will be, in the area of the detergent and personal
care formulations in combination with anionic surfactants.
Nonionic surfactants have also begun to find applications in new
areas such as environmental protection systems, paper processing,
and thin films.
In detergent and personal care formulation, nonionic surfactants
are represented mostly by linear alcohol ethoxylates, with the
alcohols being derived from either petrochemical raw materials or
natural feedstock. Their share of the total use of surfactants has
increased from 4% in 1970 to 35% in the 1990s. The reasons for
this are their excellent detergency properties and favorable
environmental properties such as rapid biodegradability and low
toxicity. In addition, detergent manufacturers use nonionic
surfactants because of their convenience in formulating
concentrated powders and liquids.
Not surprisingly, this increase in market share is also reflected in
the literature on nonionic surfactants. Since the early 1960s, over
50,000 articles, patents, and books have treated the subject of
nonionic surfactants in one way or another. The need for review is
therefore great, and this undoubtedly was the main motive of
Martin Schick in publishing in 1967 his Nonionic Surfactants as
Volume 1 in the Surfactant Science Series. This volume covered
the following disciplines: organic, physical, and analytical
chemistry and biology. The book was well received by the
scientific and technical community, and is a much referenced
introductory text for many scientists in industry and academia who
have since become acquainted with nonionic surfactants
With the passage of time and with the enormous growth in
fundamental and applied research on nonionic surfactants, it was
decided to split the second
 Page viii
edition of Dr. Schick's book into separate volumes. These treat the
chemical analysis of nonionic surfactants, the physical chemistry
of nonionic surfactants, the polyalkylene oxide block copolymers,
the alkylglucosides, the biology of nonionic surfactants, and in the
present volume, organic chemistry.
The polyoxyethylene surfactants, constitute a significant class of
nonionic surfactants and therefore are discussed extensively in the
book. The materials are commercially produced by reaction of
ethylene with an active hydrogen-containing compound RXH
(initiator). A polyoxyethylene surfactant can be represented by the
general formula RX(CH2CH2O)xH, where R can represent H (for
polyethylene glycols) or a hydrophobic group (usually C1C20) and
X represents a hetero atom, such as O (giving polyoxyethylene
alcohols), N (giving polyoxyethylene alkylamines or
polyoxyethylene alkylamides), S (giving polyoxyethylene
mercaptans), or phenol (giving polyoxyethylene alkylphenols).
The number of oxyethylene groups in the product x represents the
average degree of polymerization and is therefore not necessarily
an integer. The product is thus a mixture of polyoxyethylene
surfactants, and properties of the surfactants depend on the details
of this distribution. In Chapter 1, ''Distribution of the Polyethylene
Chain," Edwards discusses the details of the mechanisms of the
reaction of ethylene oxide with various initiators. Of particular
importance is the development of a novel class of catalysts that are
able to produce surfactants with a much narrower distribution than
conventional catalysts.
Over the last 50 years, a substantial portion of the nonionic
surfactant market has been represented by the polyoxyethylene
alkylphenols. In Chapter 2, "Polyoxyethylene Alkylphenols,"
Weinheimer and Varineau discuss the manufacturing of these type
of surfactants. They are used in a wide range of industries from
cleaning systems to paints and coatings to agricultural chemistry.
Because polyoxyethylene alkylphenols are produced by a large
number of different companies and have been on the market for
many years many environmental studies have been performed.
Another important class of nonionic surfactants is the
"Polyoxyethylene Alcohols," which are discussed in Chapter 3 by
Edwards. These materials are produced in an excess of a billion
pounds a year and are used in applications ranging from
household and institutional laundry, textile scouring, pulp and
paper manufacturing, oil field surfactants, and agricultural spray
adjuvants. With an increasing emphasis on environmental issues,
soil remediation could become an important new area for
applications for polyoxyethylene alcohols.
Among the first nonionic surfactants to be commercialized are the
"Polyoxyethylene Esters of Fatty Acids." Kosswig describes
various synthesis methods of these materials in Chapter 4. The
applications of these surfactants are numerous. For example, they
are used as emulsifiers, softeners, antistatic agents, or mold
lubricants. Because polyoxyethylene esters of fatty acids have
 Page ix
in general a low toxicity and irritancy to the skin and mucous
membranes, they are particularly suited for cosmetic and
pharmaceutical applications.
Mercaptans (or thiols) can also be reacted with ethylene oxides to
produce surfactants. In Chapter 5, "Polyoxyethylene Mercaptans,"
Edwards discusses their preparation. Compared to their oxygen or
nitrogen counterparts, there are fewer applications for these
polyoxyethylene mercaptans because of the potential for odor
development from impurities in the product. However, the sulfur
atom does give these surfactants some unique properties, utilizing,
for example, the reactivity of the sulfur atom in the chain, which
results in their use in industrial and institutional applications that
do not have stringent odor requirements.
In Chapter 6, "Polyoxyethylene Alkylamines," Hoey and Gadberry
describe the synthesis of these surfactants. Most of the applications
utilize their affinity for surfaces. For example, polyoxyethylene
alkylamines are used as corrosion inhibitors, to coat films or glass,
or as wettability aids, and as additives in gasoline, drilling fluids,
and plastics. Hoey and Gadberry show that more applications of
these type of surfactants could be foreseen if such problems as the
dark color and the formation of side products during the reactions
could be solved.
Nonionic surfactants containing an amide group are a small part of
the total volume of surfactants. Lif and Hellsten show in Chapter 7,
"Nonionic Surfactants Containing an Amide Group," that because
of their simple manufacturing process combined with their good
chemical stability and their strong surface activity, it is likely that
the importance of these type of surfactants will increase.
The "Polyol Ester Surfactants," discussed in Chapter 8 by Lewis,
are a different class of nonionic surfactants. These materials are
made from reactions of fatty acids with polyols such as glycols,
sorbitol, and sugars. Because these surfactants are made from
natural materials, they are often used as food additives. The
surfactants made from glycols, sorbitol, and sugars are often too
"oily," which limits their value as useful surfactants. To enhance
the hydrophilicity of these materials the residual hydroxyl
functionality in these compounds can be used as the basis for
reaction with ethylene oxide. Recently, there have been interesting
developments in the use of enzyme catalysis to add a degree of
product specificity.
The surfactant properties of nonionic surfactants can be improved
by introducing an ionic group. In Chapter 9, "Nonionics as
Intermediates for Ionic Surfactants," Behler et al. discuss the
synthesis of these type of surfactants. It is shown that (alkyl)
polyoxyethylene alcohols can be used as a feedstock to build up
sulfates, sulfonates, phosphates, and carboxylates. The most
important group is the polyoxyethylene alkyl sulfates, which are
used in dishwashing liquids and cosmetic formulations.
Phosphates and carboxylates are mainly used in technical
applications in the fiber and textile industries.
The nine chapters of this book represented an update of the
organic chemistry described in the first edition of Volume 1. Each
of the chapters contains
 Page x
discussions on laboratory and in particular technical syntheses of
nonionic surfactants. The authors represent a cross-section of
researchers working in industry who are specialists in the
discipline of organic chemistry. Taken together, the chapters of this
book constitute an exhaustive, yet concise view of all aspects of
the organic chemistry of nonionic surfactants. The researcher who
is new to the field will find this volume a valuable introduction; at
the other end of the arc, the specialist in the area will benefit from
the review material contained in the present volume.
NICO M. VAN OS
 Page xi

Contents
Foreword
v
Bernhard Fell
Preface vii
Contributors xiii
1. Distribution of the Polyoxyethylene Chain
1
Charles L. Edwards
2. Polyoxyethylene Alkylphenols
39
Robert M. Weinheimer and Pierre T. Varineau
3. Polyoxyethylene Alcohols
87
Charles L. Edwards
4. Polyoxyethylene Esters of Fatty Acids
123
Kurt Kosswig
5. Polyoxyethylene Mercaptans
147
Charles L. Edwards
6. Polyoxyethylene Alkylamines
163
Michael D. Hoey and James F. Gadberry
7. Nonionic Surfactants Containing an Amide Group
177
Anna Lif and Martin Hellsten
8. Polyol Ester Surfactants
201
Jeremy J. Lewis
 Page xii

9. Nonionics as Intermediates for Ionic Surfactants

Ansgar Behler, Karlheinz Hill, Andreas Kusch, Stefan 241
Podubrin, Hans-Christian Raths, and Günter Uphues
Index 287
 Page xiii

Contributors
Ansgar Behler Henkel KGaA, Düsseldorf, Germany
Charles L. Edwards Westhollow Technology Center, Shell
Chemical Company, Houston, Texas
James F. Gadberry Surfactants America Research and
Development, Akzo Nobel Central Research, Dobbs Ferry, New
York
Martin Hellsten* Central Research and Development, Akzo Nobel
Surface Chemistry AB, Stenungsund, Sweden
Karlheinz Hill Henkel KGaA, Düsseldorf, Germany
Michael D. Hoey Surfactants America Research and Development,
Akzo Nobel Central Research, Dobbs Ferry, New York
Kurt Kosswig* Hüls AG, Marl, Germany
Andreas Kusch** Henkel KGaA, Düsseldorf, Germany
Jeremy J. Lewis Research and Technology, ICI Surfactants,
Everberg, Belgium
* Retired.
**Current affiliation: Boehringer Ingelheim KG, Ingelheim au Rhein,
Germany.
 Page xiv
Anna Lif Central Research and Development, Akzo Nobel Surface
Chemistry AB, Stenungsund, Sweden
Stefan Podubrin Henkel KGaA, Düsseldorf, Germany
Hans-Christian Raths Henkel KGaA, Düsseldorf, Germany
Günter Uphues Henkel KGaA, Düsseldorf, Germany
Pierre T. Varineau Research and Development, Union Carbide
Corporation, South Charleston, West Virginia
Robert M. Weinheimer Research and Development, Union Carbide
Corporation, South Charleston, West Virginia
 Page 1

1
Distribution of the Polyoxyethylene Chain
Charles L. Edwards
Westhollow Technology Center, Shell Chemical Company,
Houston, Texas

I. Introduction 1
II. Chemistry and Handling of Ethylene Oxide 2
A. Structure and Reactivity of Ethylene Oxide 2
B. Handlin, Storage, and Transfer of Ethylene Oxide 3
III. Polyoxyethylene Chain Length Distributions 4
A. Distributions Obtained Using Conventional
4
Homogeneous Catalysts
B. Distributions Obtained Using Narrow-Range
26
Catalysts
References 34

I
Introduction
Nonionic polyoxyethylene surfactants are used extensively in the
chemical industry, e.g., in such areas as detergents, health and
personal care, coatings, and polymers. These materials are
commercially produced by reaction of ethylene oxide with an
active hydrogen-containing compound using a basic catalyst. The
reaction can be represented by the following general equation:

For commercially available surfactants R represents either H (as

for polyethylene glycols) or a hydrophobic group (usually C1 to
C20), and X represents a heteroatom such as O, S, or N. The
number of moles of ethylene oxide reacting with the initiator
(RXH) need not be an integer and represents the number average
degree of polymerization of the ethylene oxide in the product.
However, the
 Page 2
product is a mixture of polyoxyethylene adducts of the initiator
with each adduct having the formula of RX(CH2CH2O)xH with x
being an integer. This product distribution is often referred to as
the ethoxylate distribution (EOD) and is defined by the nature of
R, X, and, importantly, the type of catalyst used in its preparation.
The physical characteristics of the nonionic polyoxyethylene-based
surfactant and its ultimate utility is dependent on the nature of R,
X, the value of x, and the adduct or oligomeric distribution of the
species present in the mixture.
This chapter addresses the mechanism of reaction of ethylene
oxide with various initiators using both conventional
homogeneous catalysts and the recently developed narrow-range
polyoxyethylation catalysts. The latter catalyst systems are capable
of producing surfactants containing much narrower
polyoxyethylene adduct distributions compared with those
produced using conventional catalysts. These materials are
reported to have improved physical and/or performance properties
[1] and will be discussed at the end of this chapter. A discussion of
chain length distribution equations that best fits experimentally
derived product distributions obtained using the various catalyst
systems will follow each discussion of reaction mechanism.
This chapter will only address the reaction of initiators with
ethylene oxide. General information of the chemistry of higher
molecular weight epoxides (i.e., for epoxides containing more than
two carbons) are described in other chapters in this book and
elsewhere [2,3]. Information concerning performance features of
polyoxyethylene alcohols with different values of R, X, and x will
be found in other chapters in this book.
II
Chemistry and Handling of Ethylene Oxide
A
Structure and Reactivity of Ethylene Oxide
Ethylene oxide is the most reactive member of the family of cylic
ethers. It can form adducts with a variety of nucleophiles under the
mildest of conditions. In contrast with larger cyclic ethers, it can
react not only under acidic or basic conditions, but also under
essentially neutral conditions [4]. This marked difference in
reactivity is attributed to the release of the ring strain of the three-
membered compound [5]. This ring strain has been determined
indirectly by several methods [6] with an average value of
approximately 54 kJ/mole. The release of energy during reaction
with initiators accounts for the high heat release (DHf) that occurs
during the polyoxyethylation reaction and that has been reported to
be 92kJ/mole [7]. General physical properties for the molecule can
be found in information concerning the safe handling of ethylene
oxide [8], which is described further in the next section.
The structure of ethylene oxide has been reported [9,10] with
attendant bond lengths and angles. As is the case for cyclopropane
the three-membered ethy-
 Page 3

Fig. 1
Bond lengths and angles for ethylene oxide [8].
lene oxide ring has considerable double-bond character. For
example, the CC bond length as shown in Fig. 1 has been
measured to be 0.146 nm [11], which is midway between a normal
CC single bond (0.154 nm) and C=C double bond (0.135 nm). The
strained ring prevents COC bond rotation and thus the oxygen had
directed lone pairs of electrons, which accounts for the increased
nucleophilicity and basicity of the ether compared with other
ethers, such as diethyl ether. Thus ethylene oxide is a much
stronger ligand for coordination with metallic compounds than
other ethers. It is clear from the reports that the high reactivity of
ethylene oxide is due primarily to the ring strain and double-bond
character of the molecule.
B
Handling, Storage, and Transfer of Ethylene Oxide
Ethylene oxide is a particularly hazardous chemical. When using
this material, care must be taken to minimize personal exposure to
ethylene oxide due to its extreme toxicity and potential for
explosion [8]. Ethylene oxide has been reported to be a carcinogen
[12,13] as well as a fetotoxin [1416]. The current acceptable
Occupational Safety and Health Administration (OSHA) limits of
exposure are <1 ppm per 8-h day (time-weighted average) [17].
When handling, transporting, or transferring ethylene oxide, the
use of respiratory equipment has been recommended by safety
organizations.
Unlike other members of the epoxide family and ethers, ethylene
oxide has an explosion limit of 2.6100% in air [18]. The upper
explosion limit of 100% means that pure ethylene oxide can
decompose even in the absence of air or oxygen. Flammability
limits of ethylene oxide have been reported as mixtures with
various inert gases, such as with H2O [19], N2 [20], CO2 [21], and
CH4 [22]. These reports strongly recommend that ethylene oxide
be stored and used under an inert gas atmosphere (most commonly
N2). Most commercial operations use N2 pressure in the vapor
phase to ensure that the vapor phase ethylene
 Page 4
oxide concentration never reaches the explosion region. Explosion
limit tables should always be consulted prior to use.
III
Polyoxyethylene Chain Length Distributions
The reaction of active hydrogen-containing substrates with
ethylene oxide normally results in an oligomeric distribution of
products even when using less than 1 mole of ethylene oxide per
mole of initiator [23]. Exceptions to this general rule will be
discussed later in this chapter. The mixture of adducts results from
the fact that the inititally formed adduct (RXCH2CH2OH) is also an
active hydrogen-containing species and can compete with the
initiator for reaction with more ethylene oxide. This can be
represented by the following general equations:

The polyoxyethylene product distribution is determined by the

choice of initiator (RXH), the number of moles of ethylene oxide
reacted per mole of initiator (x), and the choice of catalyst used.
Recent work in the area of new polyoxyethylation catalysts has
resulted in the development of catalysts capable of producing
unusually narrow or peaked polyoxyethylene distributions. Prior to
the discovery of these new catalysts, the narrowest distributions
attainable followed a Poisson type of distribution [23]. However,
discovery of these new heterogeneous catalysts allowed
distributions to be attained that permitted the production of
ethoxylates in which the major single adduct approached 25 wt%
of the total product mixture [1].
The polyoxyethylene distributions will be divided into two
sectionsconventional distributions obtained using homogeneous
basic or acidic catalysts and narrow-range distributions obtained
using the new heterogeneous narrow-range ethoxylate (NRE)
catalysts. In each case the proposed mechanism of reaction will be
discussed followed by distribution equations that best describe
each system.
A
Distributions Obtained Using Conventional Homogeneous
Catalysts
Early work involved the use of acidic and basic catalysts for the
ring opening reactions of ethylene oxide [3,2326]. This section will
discuss the effect of the
 Page 5
use of conventional homogeneous catalysts for the reaction of
substrates with ethylene oxide. Conventional distributions fall into
two categoriesbroader distributions obtained using basic catalysts,
and narrower distributions obtained using acidic catalysts.
Although the latter produce narrower ethoxylate distributions, they
are rarely used commercially because they result in significant
production of undesirable side products that would have to be
removed prior to use.
From a mechanistic perspective, the main difference between
conventional base-catalyzed and acid-catalyzed ring opening of
ethylene oxide is which species, RXH or EO, is primarily
associated with the catalyst species. For base-catalyzed reactions
(e.g., when using KOH as catalyst), the metal is primarily
associated with RXH (as RX-), whereas for acid-catalyzed
reactions the catalyst is associated with EO. These differences are a
major factor in determining the polyoxyethylene chain distribution
and will be discussed in each section.
1
Base-Catalyzed Ring Opening of Ethylene Oxide
(a)
Mechanism of Reaction
The vast majority of commercially available polyoxyethylene-
based surfactants are produced using basic catalysts. Although the
most commonly used catalyst is potassium hydroxide, many others
have been reported. These include catalysts derived from alkali
and alkaline earth metal hydroxides, oxides, or alkoxides [27], as
well as amines [28]. Catalyst activity is directly related to the size
of the metallic cation within a specific family in the periodic table,
the larger the ionic radius, the more active the catalyst (e.g., Li <
Na < K < Rb < Cs for group I and Mg < Ca < Sr < Ba for group II
metals). Lanthanide hydroxide or alkoxides have also been
reported to be capable of catalyzing this reaction [29]. The most
commonly employed basic catalyst is potassium hydroxide
conveniently introduced to the reactor by using 50% aqueous
potassium hydroxide solutions. There are several reasons for using
this catalyst system: ease of handling, low cost, high activity, high
selectivity to desired products, and low levels of byproducts.
The mechanism of the ring opening reaction using basic catalysts
can be summarized in the following steps for the case of potassium
hydroxide as catalyst:
 Page 6

In this mechanism the metallic catalyst (in this case potassium

cation) is primarily associated with the RXH or RX(OCH2CH2OH)
and not EO. This significantly controls the polyoxyethylene oxide
chain distribution.
Activation of RXH
The activation step refers to the reaction of RXH with base to
produce the potassium salt of the initiator and water [see Eq. (1)].
This is an equilibrium reaction, and the water must be remove to
achieve high conversion to the potassium salt. The water can be
removed either by N2 sparging or under vacuum during heating of
the mixture. Azeotropic distillation using aromatic hydrocarbons is
also employed under special conditions. Unreacted base or residual
water will produce polyethylene glycol during reaction, so
significant effort must be made to drive the reaction to completion.
While most commercial ethoxylation processes use potassium
hydroxide as catalyst, potassium metal or low molecular weight
potassium alkoxides (such as the ethoxides or t-butoxides) can also
be used. When potassium metal is used, water is not formed and
thus eliminates the need for a drying step. However, when
potassium alkoxides are used as catalyst, the corresponding low
molecular weight alcohol is produced via transalcoholysis, which
must be removed to prevent competitive polyoxyethylation of this
alcohol.
Initiation
The initiation step [Eq. (2)] involves reaction of the deprotonated
initiator (RX-) with ethylene oxide, which falls under the category
of nucleophilic substitution. Because the rate has been shown to be
dependent on both the concentration of deprotonated substrate and
EO that is upon [RX-][C2H4O], it is a second-order reaction
known as an SN2 reaction (30). The actual rate of reaction of RX-
with ethylene oxide for a given metallic catalyst depends on (1) the
nucleophilicity of the X- group [31] and (2) the steric hindrance of
the R group as illustrated below [32]:
(a) RS-> RO-(alkoxide) > RO-(phenoxide) > RCO2-
(b) Primary > secondary >> tertiary
As stated earlier, the order of reactivity of RX- within a series of
metallic catalyst is dependent on the size and valency of the
metallic cation.
 Page 7
Chain Transfer
The chain transfer reaction [Eq. (3)] is the fastest step of the
overall reaction because it involves an acidbase proton transfer.
Because this is an equilibrium reaction, then the concentration of
the active (anionic) species in solution will be determined by the
relative acidities of RXH and RXCH2CH2OH. This dramatically
affects the outcome of the reaction, and this effect will be
discussed under the following three situations:
i. Where the acidity of RXH >> RXCH2CH2OH
ii. Where the acidity of RXH = RXCH2CH2OH
iii. Where the acidity of RXH >> RXCH2CH2OH
(i) Acidity of RXH >> RXCH2CH2OH: conditions for phenols,
mercaptans, and carboxylic acids. When the acidity of RXH is
much greater than RXCH2CH2OH, as for the cases with phenols,
mercaptans, and carboxylic acids, the equilibrium constant for the
proton exchange reaction will be very large.

Under these conditions essentially all of the initiator is converted to

the first polyoxyethylene adduct prior to further reaction of the
monoadduct to higher adducts. Therefore, chain propagation does
not occur even in the presence of excess ethylene oxide until all
RXH has been consumed. Therefore, it is possible to isolate
extremely high yields (in some cases >98 mol%) of RXCH2CH2OH
if equimolar concentrations of RXH and ethylene oxide are reacted
using basic catalysts. This is true for the ethoxylation of phenols
[33], mercaptans [34], and carboxylic acids [35].
An interesting rate effect is observed during the polyoxyethylation
of phenols and carboxylic acids. Because phenolate and
carboxylate anions are less nucleophilic than the polyoxyethylene
anion [31], ethylene oxide adds to the initiator much more slowly
than the ethylene oxide adds to the monoadducts. This results in
the observance of a sharp increase in rate of ethylene oxide
consumption after an equimolar amount of ethylene oxide has
reacted with phenols [33,36] or carboxylic acids [35], as shown in
Figs. 2 and 3.
The reaction between phenols and ethylene oxide has been studied
extensively and the kinetics reported [33,37]. The reaction of
carboxylic acids with ethylene oxide has also been reported [35],
and under the basic reaction conditions, ester interchange occurs
rapidly leading to a mixture of products, including polyethylene
glycol. This leads to products that have a relatively broad
molecular weight distribution relative to that of products obtained
from the polyoxyethylation of phenols.
 Page 8

Fig. 2
Rate of polyoxyethylation of stearic acid and octadecanol at 185°C using
basic catalysts [35].
The reaction of mercaptans with ethylene oxide differs in one
respect from reactions of phenols and carboxylic acids with
ethylene oxide. Mercaptide anions are much more nucleophilic
than either phenolate, carboxylates, or polyoxyethylene anions
[31]. Therefore, the rate of addition of RS- to ethylene oxide
should be much greater than that of RS(CH2CH2O)x- to ethylene
oxide. This is true only if the RS-K+, which is usually insoluble in
the mercaptan, is
 Fig. 3
Rate of addition of ethylene oxide to phenol in excess ethylene oxide
using sodium phenoxide catalyst [33].
 Page 9
solubilized using an additive such as an alcohol or the monoadduct
of the mercaptan to be used [34]. Early reports that mercaptans
were less reactive than alcohols were presumably describing
insoluble anhydrous RS-K+ systems [38]. In this case, the apparent
slow reaction with ethylene oxide would be due to the insolubility
of the catalyst at the beginning of the reaction. Induction periods
would be observed under these circumstances. Using solubilized
catalyst systems (e.g., of molar ratios of RS-K+/RSCH2CH2OH =
1), temperatures as low as 80100°C can be used during the addition
of the first mole of ethylene oxide per mole of mercaptan. The
reaction temperature is then allowed to increase during the addition
of the first mole of ethylene oxide to the initiator to the final
polymerization temperatures (e.g., 140160°C) [34]. As with
phenols and carboxylic acids, mercaptans react with ethylene oxide
to produce the monoethoxylate adduct prior to polymerization
even in using an excess of ethylene oxide. Consequently,
RSCH2CH2OH can be produced in >99 mol% yield.
(ii) Acidity of RXH comparable to RXCH2CH2OH: conditions for
alcohols, amides, and water. When the acidity of RXH and
RXCH2CH2OH is comparable, as for the cases with alcohols,
amides, and water, the equilibrium constant for the proton
exchange reaction will be ~1.

Under these conditions, chain growth (chain propagation) is

competitive with chain initiation. This means that there will be
substantial chain growth prior to complete conversion of initiator
to monoadduct formation. The overall product distribution will be
determined not only by the equilibrium reaction (chain transfer),
but by the relative rates of addition of RX- and RXCH2CH2O- to
ethylene oxide. This will be described in more detail in the chain
propagation section.
The most important class of compounds in this category is fatty
alcohols. These materials are used extensively in the detergents
industry, and consequently much has been published concerning
their reaction with ethylene oxide. The relative acidities of various
alcohols have been studied and compared with that of the
comparable monoethyleneoxy adduct [39,40]. These are illustrated
in Table 1. The rate constants of the reaction of ethylene oxide with
various alcohols have also been reported [41] and are presented in
Table 2. From the pKa values and relative reaction rates, the
distribution equations can be calculated. This will be addressed
later in this chapter.
The reaction rate for polyoxyethylation of alcohols increases with
an increase in the basicity of the catalyst. Despite a report [24] that
Na, NaOCH3, NaOC2H5, and KOH showed comparable activity
for the oxyethylation of tridecanol, close inspection of the data
shows that KOH is actually more active than
 Page 10
Table 1 Relative Acidities of Some Alcohols in Isopropyl
Alcohol Solution
Compound Kea Ref.
Isopropyl alcohol 0.076b 39
t-Butanol c 39
s-Butanol c 39
s-Butanol <0.8 40
n-Propanol ~0.5 39
i-Butanol ~0.5 39
n-Butanol ~0.6 39
n-Butanol 0.8 40
Ethanol 0.95 39
Water 1.2 40
Water 1.2 39
Methanol 4.0 39
Ethylene glycol mono-s-butyl ether 6.3 40
Ethylene glycol mono-n-butyl ether 6.4 40
Ethylene glycol monomethyl ether 8.0 39
Diethylene glycol mono-s-butyl ether 10.5 40
Diethylene glycol mono-n-butyl ether 11 40
Ethylene glycol monophenyl ether 11 39
Ethylene glycol monoethyl ether 12 39
Trimethylene glycol 12 39
Tetramethylene glycol 13 39
Propylene glycol 26 39
Ethylene glycol 43 39
Ethylene glycol 44 40
Diethylene glycol 66 40
aKe = [A-]/[HA][i-PrO-], where HA is the compound
studied.
b This value is fixed by the definition of Ke.
c These acids were too weak to measure; their Ke values
are probably <0.2.

NaOH. This is consistent with the observation that catalyst activity

increases with the size of the metallic cation (i.e, K > Na >> Li).
The catalytic activity of Li+ is quite low and is very seldom used as
an oxyethylation catalyst. Both the hydroxides and alkoxides of the
group I metals have been shown to be useful as catalysts.
Several studies have also shown that the initial reaction rate of
polyoxyethylation of an alcohol decreases as the carbon number of
the alcohol increases and that primary alcohols react more readily
than secondary alcohols, which in turn are more reactive than
tertiary alcohols [42,43]. In fact, successful polyoxyethylation of
secondary and tertiary alcohols can only be achieved using either
acidic catalysts or a two-step procedure initially developed by
Carter [43] using first an acidic catalyst, followed by continued
polyoxyethylation using basic catalysts. These observations may be
explained by a combination of a
 Page 11
TABLE 2 Rate Constants for Addition of Ethylene
Oxide to Various Alcohols at 30°Ca [41]
105k2b
10[NaOR] 105k1b
Alcohol (Liter mol-1
(M) (s-1)
s-1)
CH3OH 2.63 5.63 21.4
C2H5OH 0.68 3.74 55.0
n-C3H7OH 1.25 7.30 58.5
n-C4H9OH 0.97 4.57 47.1
HO(CH2)2OH 1.76 3.71 21.1
HO(CH2)3OH 0.62 3.94 63.6
CH3OC2H4OH 3.54 6.62 18.7
C2H5OC2H4OH 1.17 1.77 15.1
CH3(OC2H4)2OH 2.67 3.15 11.8
C2H5(OC2H4)2OH 2.72 4.51 16.6
C2H5(OC2H4)3OH 2.09 2.36 11.3
a The initial concentrations of ethylene oxide were 12
M. At least a fivefold excess of alcohol, which also
served as the solvent, was present.
bk1 = -d In [C2H4O]/dt; k2 = k1/[NaOR].

decrease in the dielectric constant of the media, a decrease in the

acidity of and an increase in steric bulk of secondary and tertiary
alcohols compared to primary alcohols.
(iii) Acidity of RXH >>RXCH2CH2OH: conditions for amines and
activated hydrocarbons. When the acidity of RXH is much less
than that of RXCH2CH2OH, as for the case of amines or some
activated hydrocarbons, conventional basic catalysts such as KOH
will be ineffective for deprotonation of RXH [44]. Consequently,
there will be little or no reaction of the initiator, RXH,

with ethylene oxide. If this reaction is attempted using KOH as

catalyst, only the catalyst will react with ethylene oxide, leading to
the production of polyethylene glycol. If a very strong base is used
in catalytic concentrations to produce RX-M+, this species will
react stoichiometrically with ethylene oxide with the rest of RXH
acting only as a solvent. This condition can be exploited
synthetically to produce hydroxyethyl derivatives of desired
compounds. Grignard or organolithium reagents can react with
excess ethylene oxide to produce the monoadduct in near-
quantitative yields [45].
 Page 12
Amines are sufficiently nucleophilic to react with ethylene oxide
without the aid of a basic catalyst [4648]. The reaction of primary
amines with ethylene oxide occurs in two step, with the first step
reacting more slowly than the second. Consequently, it is not
possible to isolate the monoethoxylated product in high purity
using this reaction scheme. Water or acids have been shown to
accelerate the uncatalyzed reaction of amines with ethylene oxide
to form diethanolamines either by facilitation of proton transfer or
mild activation of the ethylene oxide via an acid-catalyzed reaction
mixture [47,49].

Polyoxyethylene amines are produced commercially in two

independent stepsby the formation of diethanolamine in an
uncatalyzed reaction, followed by polyoxyethylation using basic
catalysts. Polyoxyethylene amine surfactants will be discussed in
more detail in Chapter 6.
The previous discussion concerning the relative acidities and thus
relative reactivities of various hydrogen-containing initiators is
particularly useful for predicting the results of polyoxyethylation
of initiators containing more than one type of functional group. If
more than one type of active hydrogen-containing functional
group is present in an initiator, the relative acidities and thus
competitive reaction rates will determine which group will react
with the ethylene oxide. Often, both hydroxyl and acid groups or
hydroxyl and amine groups are present in an initiator. In these
cases, the first mole of ethylene oxide might react exclusively with
one group, leaving the less reactive group underivatized. Such is
the case for the reaction of hydroxy acids, such as 12-
hydroxystearic acid, with 1 mole of ethylene oxide per mole of
initiator. For 12-hydroxystearic acid, the ethylene oxide reacts
exclusively with the acid moiety when only 1 mole of ethylene
oxide is added [50,51]. Reaction of 2-hydroxyethylamine with 2
moles of ethylene oxide results in the production of tris(2-
hydroxyethyl) amine. In this case, the primary amine reacts with
the ethylene oxide without any significant reaction of the original
alcohol with ethylene oxide. Therefore, differences in functional
group reactivities can be exploited to prepare more complicated
molecules.
Chain Propagation
The propagation of the polyoxyethylene chain under basic
conditions proceeds by kinetically nearly identical steps, since the
structure of the propagating polyoxyethylene anions are essentially
the same. The acidities of the polyoxyethylene alcohols,
RX(CH2CH2O)xH, are nearly identical when x > 3 [36,40,52] and
therefore independent of chain length. Consequently, proton
exchange between species should not only be fast but should
 Page 13
also occur statistically with no species being favored over another.
At low degrees of polymerization there are small differences
between the nucleophilicity and acidity of the adducts that lead to
small differences in the reaction kinetics. As the degree of
polymerization increases the effect of the initiator on the
polyoxyethylene chain length rapidly diminishes, with the chain
length distribution controlled by a statistical addition of ethylene
oxide to the chain. Consequently, the chain length distribution will
follow the Poisson distribution equation [53,54] at high degrees of
polymerization. The Poison distribution equation will be discussed
in the section on chain distribution equations.

where k1 ~ k2 = k4 ........ = kn
During chain length propagation the dielectric constant of the
medium increases, leading to an increase in the absolute rate of
ethylene oxide consumption. The use of solvents for
polyoxyethylation has been investigated and found to influence the
absolute reaction rate, i.e., the overall rate of ethylene oxide
consumption, presumably by affecting the dissociation of the metal
alkoxide propagating species. In nonpolar solvent media the metal
alkoxide will be less reactive because it exists as a tight ion pair. In
polar solvents the metallic cation is substantially dissociated
producing a free anion pair. Other methods of producing free
anion pairs or solvated anions, such as the use of crown ethers or
polyamines, have been shown to substantially increase the overall
reaction rate (ethylene oxide consumption), but not to significantly
affect the chain length distributions [55,56]. A study has shown
that reaction parameters such as temperature, ethylene oxide
pressure, and catalyst concentration (at relatively low catalyst
concentrations) do not affect the polyoxyethylene chain length
distribution over a 15-fold change in absolute polyoxyethylation
rates [42]. However, as will be discussed later in the section on
distributions obtained
 Page 14
using basic catalyst, use of extremely large catalyst concentrations
(resulting in high concentrations of RX-K+ relative to RXH)
dramatically affects product distributions.
Chain Termination
Chain growth normally continues until all of the ethylene oxide has
been consumed and the basic chains are neutralized with an acid.
Therefore, polyoxyethylation is an example of a living
polymerization. There have been reports that chain termination
occurs at very high degrees of polymerization, which explains the
difficulty in obtaining polyethylene glycols with molecular weights
greater than 1 million [57] using basic catalysts. It is proposed that
the growing chains can undergo chain cleavage either via SN2
reactions [see Eq. 5] or hydrogen abstraction reactions. Special
catalyst systems have been developed that do not suffer from chain
termination via chain transfer in order to obtain extremely high
molecular weight polyethylene glycols (58).
(b)
Distributions Obtained Using Group I Basic Catalysts
Various distribution equations for the base-catalyzed
polymerization of an initiator have been derived from an
understanding of the reaction mechanism. In general, these
equations have been based on various assumptions of the relative
rates of the stepwise addition of ethylene oxide to the deprotonated
species (i.e., RX- or RX(CH2CH2O)x-). Inherent in these
assumptions is the understanding that the concentration of the
various species will be dependent on the relative acidities of the
hydrogen-containing species. Therefore, the equilibrium equations
[see Eq. (3) above] must be considered in any distribution
equation, especially at low orders of polymerization and when
using relatively high catalyst concentrations.
These general polymer distribution equations initially developed
by Flory [53,54], Gold [59], Natta [60], Maget [61], and Weilbull
and Nycander [62] vary in complexity from simple to very
complicated. Some of these early distribution equations have been
modified to improve the agreement between predicted and
experimentally obtained distributions, e.g., the
WeibullNycanderGold [63] and Natta-Mantica [64] distribution
equations. As expected, the simplest model leads to the simplest
equations. The simplest model is one based on the assumption that
all reaction steps are kinetically identical, which can be represented
by the familiar Poisson distribution as given by Flory [53,54]:

In this equation, n is an integer representing each polyoxyethylene

adduct, u is the average molar ratio of ethylene oxide to initiator
used, and o refers to the initial concentration. The product
distribution is completely defined by the term u.
The Poisson equation adequately describes product mixtures
obtained using base under two types of conditions:
1. Reactions where the acidity of RXH is the same as or greater
than RXCH2CH2OH (i.e., for phenols, mecaptans, and carboxylic
acids)
 Page 15
2. For reactions of ethylene oxide with alcohol where base is used
in stoichiometric concentrations (i.e., molar ratio of KOH/ROH =
1).
Under both of these circumstances, the equilibria described in Eq.
(3), do not influence the course of reaction, especially for
condition 2 where there is no free RXH present. Therefore, the
relative reaction rates of each stepwise addition of ethylene oxide
to anionic species is virtually equivalent (i.e., k1» k2» k3 . . . kn).
The second condition is a special case for the reaction of ethylene
oxide with alcohols, with the product mixture being narrow range
[65] as opposed to the normally broad-range distributions obtained
when base is used in catalytic concentrations. For the base-
catalyzed reaction of ethylene oxide with alcohols, equilibrium
considerations [Eq. (3)] have considerable influence, the
differences in nucleophilicity between RO- and RO(CH2CH2O)n-
is significant and thus the rate of reaction for the first few steps
could not be identical (i.e., k1¹ k2¹ k3). Therefore, for the
polyoxyethylation of alcohols using low concentrations of basic
catalyst, other more complicated distribution equations must be
used.
The most complex equation was derived by Natta [58] who made
the assumption that all steps were kinetically different. This leads
to the following equation, the derivation of which is described in
detail elsewhere [23]:
whereRXHis the initiator
EOis ethylene oxide
indicates instantaneous concentration of species
[ ]enclosed; subscript zero is for initial
concentrations
is the second-order rate constant of the initial
ki
reaction
is the second-order rate constant for the further
kp
propagation steps
is the number of oxyethylene units in a polymer
n
molecule
r =is the ratio of the propagation rate constant to the
kp/kiinitiation rate constant
i,jare integral numbers

A less complicated model developed by Weibull and Nycander [62]

is based on a simplification of the Natta equation which assumes
that the chain propagation steps are kinetically identical and differ
only from the chain initiation step (i.e., k1¹ k2 = k3 = k4 . . . etc).
This leads to the WeibullNycander equation, which has been
shown to fit reasonably well with the observed distributions of the
base-catalyzed polyoxyethylation of most initiators.
 Page 16

wheres = r - 1 for r ¹ 1
z=
In[RXH]0/[RXH]

Early work comparing experimentally obtained distributions with

theoretical distributions were complicated due to the difficulty of
accurately separating the oxyethylene adducts. However, advances
made in the analysis of the oxyethylene adducts of most initiators
[42] have led to a high degree of confidence in comparing
experimental data with theoretical curves. One can compare the
product mixture obtained from the reaction of various alcohols
with ethylene oxide using sodium methoxide as catalyst and
ethylene oxide/alcohol molar ratios of 6.0 with the Poisson and
WeibullNycander equations [66]. As seen in Fig. 4, the Poisson
equation does not adequately describe the product distribution,
confirming that the relative reaction rates are indeed not
equivalent. However, the WeibullNycander equation, which
assumes that k1 < k2 = k3 = k4, etc., fits the product distributions
quite well. When the WeibullNycander or WeibullNycanderGold
distribution equations do not adequately predict the product
distributions, the NattaMantica equations [64], which assume that
each addition of ethylene oxide to an activated species is kinetically
different, can be used [67].
A key parameter often used in the WeibullNycander type of
equations is the term r where r = kp/ki, the ratio of the rate
constants of the propagating species to that of the initiator species.
The r value can be taken as a measure of how

Fig. 4
A comparison of the product distribution of an NaOMe-catalyzed reaction of
dodecanol with 6.0 moles of ethylene oxide with a Poisson and
WeibullNycander distribution.
 Page 17
narrow or broad the polyoxyethylene adduct distribution will be
[65]. When r = 1, then each addition step is kinetically identical,
and the Poisson equation will predict the experimental results.
However, the larger the value of r, the broader will be the adduct
distribution. Typical values for primary alcohols have been
reported to be 3, whereas secondary and tertiary alcohols (which
as initiators react much more slowly with ethylene oxide compared
with their polyoxyethylene adducts) have values of ~822 and 3364,
respectively [68]. In these cases, the product mixtures contain
significant amounts of unreacted secondary or tertiary alcohols
even when moderately high ethylene oxide/alcohol molar ratios are
used. Typical values derived for r for various alcohols are shown
in Table 3.
Work continues on the refinement of methods to determine the
best r values or distribution coefficients to use with the
WeibullNycanderGold and NattaMantica distribution equations. In
many studies using homogeneous group I basic catalysts, the
product distribution coefficients, or oligomer reactivity coefficients
(ORCs) as defined by Geissler and Johnson [42], are observed to
change with a change in the degree of polyoxyethylation. This
phenomenon is known as the WeibullTornquist effect [69] and
results in an increase in the reactivity of oligomers with ethylene
oxide up to a maximum, which occurs around the sixth
polyoxyethylene adduct [RO(EO)6-]. This increased reactivity of
the polyoxyethylene adducts from c1 to c6 leads to a broadening of
the product distribution. In one study using sodium hydroxide as
catalyst the distribution coefficients (ci) were determined using the
NattaMantica relationship and found to increase to a maximum at
c6 and then begin to decrease again [67].
The WeibullTornquist effect is explained by the intramolecular
complexation of the cation (e.g., K+) by the polyoxyethylene chain,
which leads to an
TABLE 3 Various r Values for the Base-Catalyzed
Addition of Ethylene Oxide to Alcohols [68]
Ethylene oxide/ROHa molar
Compound rb Rangec
ratio
Methyl alcohol 1.3 0.7 0.60.8
Ethyl alcohol 1.3 2.5 2.22.6
n-Propyl
1.3 2.4 2.22.5
alcohol
i-Propyl
1.3 8.8 7.99.7
alcohol
n-Butyl
1.3 3.3 2.93.5
alcohol
i-Butyl alcohol 1.3 4.7 4.55.1
s-Butyl
1.3 22 1923
alcohol
t-Butyl alcohol 1 33 3136
t-Butyl alcohol 3 64 6465
a Reactions run at 100°, 120°C using 1 wt% sodium
hydroxide catalyst.
br value from the WeibullNycander equation.
c Range of r over four experiments.
 Page 18

Fig. 5
Intramolecular complexation of the
metal cation in base-catalyzed
polyoxyethylation.
increase in oligomer reactivity due to the activation of the metal
alkoxide ion pair; see Fig. 5. Sallay et al. [70] suggested that the
sixth polyoxyethylene adduct represents the highest stability of the
series of oligomers, RO(EO)x-, with stability increasing for x = 16
and decreasing with x > 6. This effect has been seen in studies
involving the use of soluble group I metal hydroxides
[67,42,27,70,71] as well as aliphatic tertiary amines [27,72].
Weibull [71] recently investigated the reaction of ethylene oxide
with 3-phenyl-1-propanol using lithium, sodium, and potassium as
the counterion for the alkoxide. Using modified Natta equations,
Weibull reported in this comprehensive study that the parameters
used in the formulas, often referred to as distribution constants, are
not true constants because they depend on the molar ratio of
ethylene oxide to alcohol used (i.e., the degree of
polyoxyethylation). This dependence was most pronounced for
sodium and potassium but was not observed when using lithium.
Weibull suggests that this phenomenon is caused by the
complexation of the cation by the higher molecular weight
polyoxyethylene adducts. His results were confirmed by
experiments using 18-crown-6 as an effective complexing agent for
the metal cations for polyoxyethylation reactions.
It should be expected that if this complexation between the
polyoxyethylene adduct and the metal cation cannot take place,
then the WeibullTornquist effect would not be observed. Such
seems to be the case as reported in experiments using bridgehead
nitrogen-containing compounds [72] or group II metal hydroxides
(alkoxides) [67] as catalysts for polyoxyethylation reactions. In
each case it has been proposed that the metal cation is effectively
shielded and cannot participate in intramolecular complexation.
Although r values and oligomer distribution coefficients are often
employed to compare various product distributions obtained using
basic catalysts, the effect of the equilibrium reaction [Eq. (3)] on
the resulting product distribution should be emphasized [36]. In
fact, for the case of polyoxyethylation of secondary alcohols, the
equilibrium expression significantly impacts the final
 Page 19

Fig. 6
Products of the reaction of 1-dodecanol and 2-dodecanol with 6 moles
of ethylene oxide using KOH catalyst.
product distribution. As mentioned previously, the acidity of a
secondary alcohol is much less than that of the corresponding
primary alcohol or monoethyleneoxy adduct. This means that the
equilibrium concentration for the secondary alkoxide is much
lower than for primary alkoxides. Therefore, the relative
concentration of RO-/RO(CH2CH2O-) will be much lower for
secondary alcohols than for primary alcohols. Consequently, the
product mixture obtained from using secondary alcohols has
considerably more unreacted alcohol than when using primary
alcohols for a given order of polyoxyethylation. This can be seen
clearly in a comparison of product distributions obtained from the
oxyethylation of 1-dodecanol compared with 2-dodecanol using
basic catalysts (Fig. 6). Application of the WeibullNycander
equation to these systems results in predicted distributions in good
agreement with experimental results.
Commercially, oxyethylation of secondary alcohols must be
conducted using a two-step method to overcome this basic
mechanistic problem. This will be discussed further in the section
on acid-catalyzed oxyethylation.
(c)
Distributions Obtained Using Group II Bases
Product distributions for polyoxyethylene alcohols obtained using
soluble group II metal bases have been shown to be narrower than
those obtained using group I bases such as KOH. The first report
that divalent metal cations were capable of producing different
(and narrower) product distributions was by Yang et al. [73] using
barium oxide as catalyst. Within a few years there were additional
reports based on barium [7478] and new ones based on the other
group II bases, strontium [77,79], calcium [77,78,80,81], and
magnesium [78,8183]. These additional basic divalent metal
catalysts were also shown to be capable of producing
 Page 20

Fig. 7
Product distributions obtained from the reaction of dodecanol with 7 moles of
ethylene oxide using KOH and barium dodecanoate compared with a Poisson
distribution.
narrower product distributions compared with the group I metal
bases. Because the solubility of the group II metal hydroxides is
extremely low in most detergent range alcohols, solubilization
techniques, such as the addition of phenols, ethylene glycol, or low
molecular weight polyether alcohols, had to be used in order to
produce active catalysts. Although the activity of these soluble
group II bases varies (Ba ~ Sr > Ca >> Mg), the product
distributions obtained using these catalyst systems at equivalent
ethylene oxide/alcohol molar ratios are essentially identical. This
suggests that the same mechanism is operating for each system. A
comparison of oligomer distributions obtained using KOH and a
barium dodecanote catalyst system with a typical Poisson
distribution for the same degree of oligomerization is shown in
Fig. 7 [84].
Although less mechanistic and kinetic studies have been conducted
using the group II basic catalysts, two controlling factors have
been proposed in order to explain the narrower distributions
obtained using soluble group II metal bases. One explanation
emphasizes the effect of a change in the relative equilibria
associated with the proton exchange reaction [Eq. (3), discussed
previously], whereas the other addresses factors causing a decrease
in the relative reaction rates of the growing polymer chain. Either
of these factors would, a priori, result in a narrower product
distribution compared with the factors already controlling the
relatively broad distributions obtained using homogeneous group I
basic catalysts.
 Page 21
One study suggests that the narrow distribution is not due to a
kinetic origin but is instead related to the different stabilities of the
polyoxyethylene anion ion pair compared with the alcoholate ion
pair [84]. In this approach different values of the proton exchange
equilibrium [Eq. (3) above] for the first several adducts have been
assumed. For KOH, the same equilibrium constant is assumed for
all polyoxyethylene adducts. For divalent metal catalysts, the
equilibrium constant for the first four adducts is assumed to
decrease from 5.0 to 2.05. Justification for this explanation is given
by assuming a tight ion pair for the monovalent ion pairs. In
contrast, it is suggested that divalent cations can interact with more
ether oxygens in growing chains, thus significantly affecting the
stability and the equilibrium concentration of the growing chains.
The other study has shown in kinetic experiments that only
monovalent catalyst metal ions are subject to the WeibullTornquist
complexation effect described previously, whereas divalent metal
ions are not subject to the effect [67]. Because the divalent cations
are not subjected to the broadening effect of the WeibullTornquist
sequestering complexation, they are capable of producing
narrower product distributions. Distribution coefficients derived
from products obtained using KOH and a calcium-based catalyst
system using a NattaMantica relationship clearly show a decreasing
reactivity of the growing polyoxyethylene anions for the calcium
system compared with the KOH system. It is suggested that the two
polyoxyethylene chains associated with the calcium cation prevent
either chain from entering into an intramolecular coordination,
which is necessary for a WeibullTornquist broadening effect. The
result is a narrower product distribution.
Recognition that the group II metal alkoxide catalysts were capable
of producing narrower product distributions when using alcohol as
an initiator compared with group I metal catalysts led to the
development of additional heterogeneous narrow-range catalyst
systems. Before the advent of this development in catalyst
research, the only method of producing product distributions
narrower than those obtained from KOH was to use acidic catalyst
systems, which are normally undesirable due to the significant
amount of side products that accompany their use. The narrow-
range catalyst systems will be discussed in more detail in a later
section.
In general, the WeibullNycander and modifications of this
distribution equation have predicted the product mixtures obtained
using basic catalysts quite well. Deviations from these predictions
can be explained in most cases by steric hindrance associated with
the initiator. For example, slightly different distributions are
obtained during the ethoxylation of nonylphenol vs.
dinonylphenol. Because the latter substrate has more steric
constraint in the vicinity of the phenolic anion, its conversion to
the monoadduct is slower than that of nonylphenol [85]. These
differences are also known for the ethoxylation of
 Page 22
primary alcohols wherein there exists branching at the alfa carbon
[42]. In such cases, the product mixtures of branched
polyoxyethylene alcohols will always contained more unreacted
alcohol than polyoxyethylene alcohols derived from straight chain
or normal alcohols at equivalent ethylene oxide/alcohol molar
ratios.
2
Acid-Catalyzed Ring Opening of Ethylene Oxide
(a)
Mechanism of Reaction
As stated previously, polyoxyethylene surfactants are not produced
commercially using acidic catalysts due to the formation of
significant concentrations of undesirable side products. In
essentially all cases reported, polyoxyethylene glycol, dioxane, and
2-methyl-1,3-dioxolane are produced during polyoxyethylation
using acidic catalysts [8688]. In many cases the reaction products
are either colored or lead to colored products in subsequent
conversions, such as during sulfation. This is due to the high
concentrations of carbonyls and acetals formed during reaction.
The mechanism of ethylene oxide ring opening under acidic
conditions differs significantly from the base-catalyzed
mechanism. The main difference is that the catalyst species is
primarily associated with ethylene oxide using acidic catalysts. As
discussed previously for base-catalyzed reactions, the basic catalyst
species is primarily associated with the initiator. This difference
has profound effects on the product composition, notably the
almost identical product distributions obtained in the
polyoxyethylation of secondary alcohols compared with primary
alcohols. As noted earlier, using basic catalysts secondary alcohols
are more slow to react with ethylene oxide compared with primary
alcohols, and the product distributions of secondary alcohol
ethoxylates are much broader (with more residual alcohol) than
primary alcohol ethoxylates at equivalent orders of
polyoxyethylation.
The mechanism of reaction using acidic catalysts is dependent on
the strength of the acid catalyst used. The fastest reaction step
using any acidic catalyst is the reaction of the ethylene oxide with
the acid. This is true when using either a Bronsted or a Lewis acid:

where Y = H or metal and x ³ 1

However, at this point the mechanism differs depending on the
strength of the acid. For strong acids (e.g., CF3SO3H) the rate-
determining step is the ring opening of the conjugate acid of
ethylene oxide, followed by reaction with the nucleophile:
 Page 23

With this mechanism the reaction rate is independent of the

structure or concentration of the initiator. Such reaction
mechanisms are known as SN1 reactions [89], wherein the bond
breaking (or ring opening) of ethylene oxide is essentially
complete and in the transition state the bond formation with the
nucleophile is negligible. Sterically hindered initiators, e.g.,
secondary alcohols, will react as rapidly as less sterically
encumbered ones, e.g., primary alcohols, and the product
distribution will be essentially the same.
For weak acids the ring opening of ethylene oxide is either partial
or nonexistent. In this case the involvement of the initiator in the
transition state is considerable, leading to a bimolecular (SN2)
reaction mechanism [30]:

In this case there is discrimination between initiators based on their

relative steric hindrance. For example, secondary alcohols will
react less rapidly than primary alcohols and the product
distributions will be somewhat, but not substantially, different.
Except for the strongest and weakest acids, most catalyst systems
operate somewhere between a pure SN1 and SN2 mechanism. The
factors that influence the type of ring opening and the mechanistic
implications have been reviewed [90]. These include temperature,
solvents, and the steric constraints and electronic features of the
initiator.
There are several plausible mechanisms for the formation of the
major side products that accompany acid-catalyzed ethylene oxide
ring opening. The polyoxyethylene chain is highly subjective to
acid-catalyzed cleavage, potentially leading to the production of
dioxane, 2-methyl-1,3-dioxolane, or polyoxyethylene glycols with
broad molecular weight ranges. However, these side products need
not result from chain degradation only. They could also be formed
from secondary reactions of ethylene oxide. Hydration of ethylene
oxide to form ethylene glycol and isomerization of ethylene oxide
to acetaldehyde could lead
 Page 24
to the formation of polyoxyethylene glycol, dioxane, and 2-methyl-
1,3-dioxolane as shown below.

(b)
Distribution Equations for Acid-Catalyzed Polyoxyethylation
The mechanism of reaction discussed above for the acid-catalyzed
reaction of ethylene oxide with alcohols (or other initiators)
suggests that ethylene oxide should add to all activated hydrogen-
containing species (RXH or RX(CH2CH2O)xH) at essentially the
same rate. Therefore, the ratio of chain initiation to chain
propagation should be unity (kp/ki = 1). In this special case the
Poisson distribution discussed previously should fit well with the
experimental data. This is the simplest distribution equation to use
and requires only one parameter for the calculation, i.e., the mole
ratio of ethylene oxide to active hydrogen-containing compound.
 Page 25

In most cases the Poisson distribution equation fits the experimental

results well, especially for the case of primary alcohols. This is
illustrated in Fig. 8 [105]. However, the fact that the Poisson equation
fits most acid-catalyzed reaction products well, product distributions
obtained using secondary and tertiary alcohols are slightly less peaked
than the Poisson equation would predict. This suggests that kp/ki is
slightly greater than 1. In these cases modification of the
WeibullNycander equation, while more complicated, can be made to
fite the data much more precisely. In these cases the parameter r is
used, which is the ratio of the rate of propagation to the rate of
initiation.

In practice r is an adjustable parameter that is varied to fit the

experimental data. However, the value of r that is determined for a
reaction gives some mechanistic insight into that particular reaction. For
a Poisson distribution r = 1. As previously stated, this indicates that the
rate of chain initiation and propagation are equivalent. However, r
values slightly greater than 1 have been determined for the acid-
catalyzed reaction of secondary and tertiary alcohols, thus indicating
that these alcohols react with ethylene oxide slightly more slowly than
their adducts with ethylene oxide. This can be explained by the
increased steric hindrance of these alcohols and the mechanism being
somewhere between a SN1 and SN2 reaction. A number of r values
have been determined from a study of acid-catalyzed reaction of
ethylene oxide with alcohols [40] with r values ranging from 1.0 for
CH3OH to 2.6 for t-butanol. It should be stated that while
 Fig. 8
A comparison of a product distribution obtained from the reaction of dodecanol with
7 moles of ethylene oxide using an acidic catalyst with a Poisson distribution [105].
 Page 26
some of these r values are higher than 1, each product mixture is
still relatively narrow range in its oligomeric distribution. Using
basic catalysts, the r value of t-butanol is 6465, indicating a very
broad range of polyoxyethylene adducts and considerable
unreacted alcohol in the product mixture at low ethylene
oxide/alcohol molar ratios used [68].
Since polyoxyethylation of secondary and tertiary alcohols using
acidic catalysts tends to produce a narrower range of oligomeric
adducts, these catalysts have been applied to the commercial
preparation of secondary alcohol ethoxylates. However, the side
reactions that accompany the use of acid catalysts to date prevent
these materials from being produced commercially in a single step
using acid catalysts. However, secondary alcohol ethoxylates are
produced commercially by a two-step process initially using an
acid catalyst followed by a basic catalyst. In the first step ~2 moles
of ethylene oxide is added to a secondary alcohol using an acidic
catalyst (usually SnCl4) to produce a low molecular weight ''seed
ethoxylate." This intermediate is washed with water to remove side
products and catalyst residues, residual secondary alcohol is
removed via distillation, and the dried product is further reacted
with ethylene oxide using a basic (KOH) catalyst. The product
obtained has a narrow oligomer distribution, only slightly broader
than a Poisson distribution (e.g., r = 1.2), and is used in the
industrial surfactants market as the Tergitol series produced by
Union Carbide. At this time there have been no reports of a catalyst
system capable of selectively producing a narrow oligomeric
distribution of secondary or tertiary alcohols in one step. This
includes the new narrow-range catalyst systems.
B
Distributions Obtained Using Narrow-Range Catalysts
As mentioned previously, the utility of the polyoxyethylene
alcohols in commercial applications depends not only on the R, X,
and x value of the final product [RX(CH2CH2O)xH], but also on
the chain length distribution. Interest has been shown in obtaining
products with a particularly narrow range of the polyoxyethylene
adducts [1], with low concentrations of free alcohol and higher
molecular weight adducts. For example, some commercial
applications require very low levels of free alcohol in the product
to prevent problems such as volatile emissions (pluming) in spray
tower applications when preparing powdered laundry product.
This need has been filled by using "topped" or "stripped"
commercial products that have been obtained by removal of the
light ends via distillative procedures [91]. In recent years the
capability to produce polyoxyethylene alcohols with extremely low
levels of free alcohol and lower molecular weight adducts has also
been achieved catalytically.
This section will address progress that has been made over the last
couple of decades in the field of new narrow-range catalyst
development. Although
 Page 27
numerous patents have issued describing the preparation and use
of these catalysts [93112], relatively few kinetic studies have been
published discussing the narrow-range catalyst systems [67,84,92].
For convenience, the narrow-range catalysts will be divided into
sections according to structural similarities, e.g., acid-activated
metal alkoxides, metal phosphates, and activated metal oxides.
From experimentally obtained product distributions, some insight
can be gained concerning the reaction mechanism and thus
requirements for adjustment in the WeibullNycander and other
relationships that must exist to properly fit the data.
1
Acid Activation of Metal Alkoxide Catalyst Systems
One of the earliest reports on a nonacidic catalyst system that was
capable of producing adduct distributions narrower than
conventional KOH-based systems was by Yang et al. [73]. This
described how barium salts, mainly the hydroxide or carboxylates,
produced narrower than expected product distributions (see Fig.
7). It was later proposed [84] that group II catalysts were capable
of producing narrower distributions due to the complexation of the
cation by the polyether oxygens in the chain, resulting in a change
in the equilibrium between deprotonated initiator and
polyoxyethylene anion. This, in effect, meant that Keq > 1, which
by the previous discussion described the effect of producing a
narrower distribution.
After the observation that barium was capable of producing
narrower distributions, it followed rapidly that the other group II
bases were found capable of doing this, albeit with different
catalyst activities claimed. Systems based on strontium
[77,79,93,94], calcium [77,78,80,81,94], and magnesium
[78,8183,94] were developed and reported. One interesting aspect
was the observation that each of these systems produced
essentially the same product distributions using a given initiator
and at comparable ethylene oxide/alcohol molar ratios.
Rapidly after this development, several research groups found that
the chain length distribution could be made even narrower if the
group II metal alkoxide were "activated" by partially neutralizing
the group II metal alkoxide [95101]. The reaction mixture was not
completely neutralized because less than stoichiometric amounts of
acid (usually sulfuric or phosphoric) was used to activate the
catalyst. Strong mineral acids were claimed to produce the most
active catalyst systems. In some cases these catalyst systems were
observed to be essentially homogeneous, as catalyst solutions in
the alcohol initiator were optically clear. In many cases, however,
slurries were obtained during catalyst preparation, indicating that
the catalytically active species was indeed heterogeneous.
Although the structure of the catalyst system was not well
characterized, some authors suggested that the catalytically active
species might appear as follows:
 Page 28
Undoubtedly, the actual chemical equilibrium in solution is much
more complicated than that shown above. Nevertheless, some
partially neutralized species must be the active catalyst because
control experiments using inorganic calcium sulfate or calcium
phosphate were shown to be catalytically inactive [95,96].
Complete neutralization of the calcium alkoxide also led to inactive
catalyst systems.
Shortly after these developments, activation of other metal
alkoxides using organic and inorganic acids was reported.
Activation of aluminum alkoxide with both sulfuric acid [102104]
and phosphoric acid [105] was reported to produce very narrow
product distributions. These were mildly acidic catalyst systems
and produce either Poisson or narrow-than-Poisson distributions.
Therefore, the aluminum-based systems could be accurately
described using the Poisson equation.
Further optimization of the acid-activated metal alkoxide systems
led to the first examples of polyoxyethylene adduct distributions
that were significantly narrower than Poisson distributions. Careful
activation of calcium alkoxidebased systems with phosphoric acid
were the first examples of this type of system [95,96]. Adduct
distributions of products prepared using 7 moles of ethylene oxide
per mole of alcohol initiator were obtained that contained as much
as 25 wt% of the product containing one adduct (e.g.,
RO(CH2CH2O)7H) [106]. As shown in Fig. 9 the 7-mole adduct of
a product prepared using a catalyst that has a Poisson distribution
has only 16 wt% of the product.
 Fig. 9
Product distributions obtained from the reaction of dodecanol with 6.5 moles of
ethylene oxide using an activated CaO catalyst system compared with a Poisson
distribution.
 Page 29
2
Heterogeneous Metal Phosphate Catalyst Systems
Activation of the basic group II alkoxides with phosphoric acid led
to heterogeneous catalyst systems that were capable of producing
extremely peaked product distributions. Although the structure of
these catalyst systems was not well understood, it was clear that the
active catalysts were not simple group II inorganic phosphate salts.
Control reactions using calcium phosphate or magnesium
phosphate as catalyst showed these simple phosphate salts to be
inactive. This was somewhat unfortunate because the simple salts
would be much cheaper and simpler to use than the somewhat
complicated recipes [95,96] required to obtain active, peaking
catalysts.
However, activation of basic lanthanum or rare earth alkoxide
catalyst systems [29] led to the development of the first solid,
inorganic metal phosphate catalyst system that was not only active
but also capable of achieving the same extremely narrow product
distribution as that for the calcium-based systems [107,108]. Partial
neutralization of lanthanum alkoxide with phosphoric acid led to
an increase in peak maximum concentration of the main adduct
from 9 wt% for the basic lanthanum alkoxide system to 16 wt% for
the partially neutralized system using ethylene oxide/alcohol molar
ratios of 7.0. However, preparation of inorganic lanthanum
phosphate by one of a number of routes [107] led to a solid, white
powder catalyst capable of achieving a peak maximum of the main
adduct of ~25 wt% at ethylene oxide/alcohol molar ratios of 7.0. A
comparison of product distributions using various lanthanum
catalyst systems is illustrated in Fig. 10. At least for the rare earth
metal phosphates, the active catalyst species is indeed the simple
inorganic phosphate.
It should be pointed out that the unactivated basic lanthanum
alkoxide catalyst system affords product mixtures with the same
oligomer distribution as basic group I metal alkoxide catalysts [29].
This is illustrated in Fig. 11. Thus, this trivalent cation acts more
like a monovalent cation than a divalent (group II) cation in
polyoxyethylation reactions. This could be viewed as unexpected
since divalent cations, such as barium or calcium, were shown
previously to produce narrower oligomer distributions than
monovalent cations. It is possible that complexion of La3+ by the
polyoxyethylene adducts more closely resembles the behavior with
K+ than divalent cationic species, thus leading to broad oligomer
product distributions. Nevertheless, activation of lanthanum
alkoxide with phosphoric acid dramatically changes the catalyst
species to one that produces very narrow oligomer distributions.
Application of the same techniques developed for the rare
earthbased systems led to inorganic barium phosphate narrow-
range catalyst systems [109,110]. While the barium-based systems
produced similar distributions to the activated calcium phosphate
and rare earth or lanthanum phosphatebased systems, catalyst
preparation was somewhat complicated and the catalyst
 Page 30

Fig. 10
A comparison of product distributions obtained by activating lanthanum compounds
with phosphoric acid [29,107].
activity of the barium systems was found to be less than that of the
calcium and lanthanum systems.
3
Heterogeneous Mixed Metal Oxide Catalyst Systems
Recently, heterogeneous mixed metal oxide systems [111118] have
been claimed to produce narrow product distributions. Several of
these systems
 Fig. 11
A comparison of product distributions obtained using KOH and La(OR)3 as
catalysts for the reaction of 7 moles of ethylene oxide per mole of dodecanol.
 Page 31
involve the activation of normally inactive group II metal
phosphates (see above) by solubilization or partial solubilization of
the phosphates with carboxylic acids. These systems are relatively
new and no mechanistic or kinetic work has been published.
The mechanism of reaction using the narrow-range catalyst
systems described above is not well understood. This is
presumably due to the fact that they are for the most part
heterogeneous catalyst systems, which are normally much more
difficult to understand than homogeneous reaction systems.
Nevertheless, basic principles applied to bifunctional acidbase
heterogeneous catalyst systems could be applied to these catalyst
systems. It is possible that the mechanism involves activation of
the active hydrogen containing compound by a basic site on the
catalyst, whereas the ethylene oxide could be activated by a
neighboring acidic site. The structure in Fig. 12 has been proposed
as a possible intermediate with mixed metal oxide catalyst for the
reaction of ethylene oxide with alcohols or methyl esters [119].
The overall reaction could be concerted with deprotonation of the
alcohol assisted by the oxide occurring simultaneously with the
partial ring cleavage activated by the metal cation. This type of
mechanism is often proposed in bifunctional metal oxide catalyst
systems. The same mechanism could be operating in the metal
phosphate catalyst systems. As shown in Fig. 13, the lanthanum
cation could activate the ethylene oxide in concert with the
phosphate anion deprotonating the alcohol species.
Although the above reaction mechanism might describe adequately
each actual ring opening step, the overall mechanism must account
for one important fact. At low orders of polyoxyethylation (e.g., at
ethylene oxide/alcohol molar ratios <2), the product distributions
obtained using heterogeneous narrow-range ethoxylate catalysts
are very similar to those of conventional based-catalyzed products.
However, at ethylene oxide/alcohol molar ratios >2, the
distributions are quite narrow. This can be seen in Fig. 14 for
oligomer distributions obtained using lanthanum phosphate
catalysts compared with conventional catalysts. This strongly
suggests that the relative reaction rate of ethylene oxide addition to
growing chains decreases with an increase in the length of the
polyoxyethylene anion chain. This is in contrast to conventional
homogeneous base-catalyzed reactions wherein the
polyoxyethylene anion chains react at

Fig. 12
Proposed bifunctional acidbase
activation of reactant using mixed metal oxide
catalyst; Me = metal, but not Mg.
 Page 32

Fig. 13
Proposed activation of
reactants using metal
phosphate catalyst.
equivalent rates. This could be explained by differences in the rates of
adsorption-desorption on the solid catalyst surface, wherein the higher
molecular weight chains are less able to compete for a catalyst site and
slower to desorb. Thus the overall reaction mechanism might be
explained by a base-catalyzed reaction wherein adduct adsorption-
desorption from the catalyst surface controls the adduct composition.
This would mean that the individual reaction rates would approximate
the following ordering:

Therefore, the individual reaction rates of the initiator and low

molecular weight adducts would increase to a maximum and then
decrease with increasing
 Fig. 14
A comparison of product distributions obtained using KOH and LaPO4 as catalyst
for the reaction of ethylene oxide with a 50:50 mixture of dodecanol and tridecanol
alcohols (x = number of moles of EO/ROH) [28,107].
 Fig. 15
A comparison of Poisson distributions ( ) with NRE catalyst distributions (·
reaction of ethylene oxide with a 50:50 mixture of dodecanol and tetradecanol at EO/ROH
molar ratios varying from 3 to 11 [1].
chain length. A steady decrease in the relative rates would be necessary to
explain why peaking does not significantly decrease with an increase in the
degree of polyoxyethylation. For example, the adduct peak maximum
increases to ~25 wt% of the product mixture using narrow-range catalysts at
ethylene oxide/alcohol molar ratios of 23 and is maintained at that value
even as the average molecular weight of the product increases (to approx.
= 11). In contrast, the peak maximum of products prepared using catalysts
that follow a Poisson distribution, where all reaction rates are identical,
decreases steadily with increasing polyoxyethylation. This is illustrated in
Fig. 15 comparing product distributions obtained using narrow-range and
Poisson-type catalysts over the ethylene oxide/alcohol molar ratio range of
311.
There is some experimental evidence to support this possible mechanism.
For each heterogeneous catalyst system described, the actual overall rate of
ethylene oxide consumption decreases with reaction time. This is the
opposite of the result using homogeneous catalyst systems. This is consistent
with the suggestion that the higher molecular weight adducts react with
ethylene oxide slower than the lower molecular weight species.
Distribution equations describing the product mixtures obtained using these
heterogeneous catalyst systems must therefore contain parameters that
account for different (and decreasing) individual reaction rates for the
individual steps. Therefore, a simple value for r used in the
WeibullNycander equation will not accurately describe these systems. More
complicated equations such as NattaMantica must be used. At this time there
are no definitive reports that describe
 Page 34
these heterogeneous narrow-range catalyst systems with the same
degree of thoroughness as that achieved by Weibull to define the
mechanism of reaction of ethylene oxide with alcohols using
conventional basic group I homogeneous catalyst systems [71].
References
1. K. W. Dillan, J. Am. Oil Chemists Soc. 62:1144 (1985).
2. S. Winstein and R. B. Henderson, Heterocyclic Compounds, Vol
1 (R. C. Elderfield, ed.), Wiley, New York, 1950, p. 1.
3. F. E. Bailey, and J. V. Koleske, Alkylene Oxides and Their
Polymers, Surfactant Science Series, Marcel Dekker, New York,
1991, pp. 3951
4. J. March, in Advanced Organic Chemistry: Reactions,
Mechanisms and Structure, McGraw-Hill, New York, 1968, p. 290.
5. H. Vogel, Angewandte Chemie 72:425 (1960).
6. R. A. Nelson and R. S. Jessup, J. Res. Natl. Bur. Std. 48:206
(1952).
7. L. E. St. Pierre, in Polyethers, Part 1, Polyalkylene Oxides (N.
G. Gaylord, ed.), Wiley-Interscience, New York, 1963, Chap. 3.
8. Ethylene Oxide User's Guide, Shell Chemical Company,
September 1995.
9. G. L. Cunningham, A. W. Boyd, R. J. Myers, W. D. Gwinn, and
W. I. LeVan, J. Chem. Phys. 19:676 (1951).
10. T. E. Turner and J. A. Howe, J. Chem. Phys. 24:924 (1956).
11. C. Hirose, Bull. Chem. Soc. Jpn 47(6):13111318 (1974).
12. Occupational Safety and Health Administration, 25 CFR Ch.
XVII 1910.1047.
13. H. Vaino, D. McGregor, and E. Heseltine, Meeting of the IARC
Working Group on Some Industrial Chemicals, Scand. J. Work
Environ. Health 20:227229.
14. W. M. Generoso, C. T. Cain, L. A. Hughes, G. A. Sega, P. W.
Braden, D. G. Gosslee, and M. D. Shelby, Ethylene oxide dose and
dose-rate effects in the mice dominant lethal test, Environ.
Mutagen. 8:17.
15. W. M. Snellings, R. R. Maranpot, J. P. Zelenak, and C. P.
Laffoon, Teratology study in Fischer 344 rats exposed to ethylene
oxide by inhalation, Toxicol. Appl. Pharmacol. 64:476481.
16. L. Goldberg, Hazard Assessment of Ethylene Oxide, CRC
Press, Boca Raton, FL, 1986.
17. Occupational Safety and Health Administration, 29 CFR
1910.1047.
18. D. Conrad, Bundesgesundheitsblatt 9:139141 (1963).
19. Y. Hashigushi, Tokyo Kogyo Shikensho, 60(3):8591 (1965).
20. J. Osugi, M. Okusima, and M. Hamanoue, Koatsu Gasu
8(4):201206 (1971).
21. L. G. Hess and V. V. Tilton, Ind. Eng. Chem. 42(6):12511258
(1950).
22. B. Pesetsky, Chem. Eng. Prog. Loss. Prev. 13:132141 (1980).
23. N. Shachat and H. L. Greenwald, in Nonionic Surfactants (M.
J. Schick, ed.), Marcel Dekker, New York, 1966, pp. 2831, 37.
24. W. B. Satkowski and C. G. Hsu, Chem. Eng. 49:1875 (1957).
25. J. Falbe, Surfactants in Consumer Products, Springer-Verlag,
Berlin, 1987, p. 88.
26. R. O. Coclough, G. Gee, W. C. E. Higginson, J. B. Jackson,
and M. Litt, J. Polym. Sci. 34:171179 (1959).
 Page 35
27. P. Sallay, L. Farkas, J. Morgos, and I. Rusznak, Period.
Polytech. Chem. Eng. 32(13):169171 (1988).
28. P. Sallay et al., J. Am. Oil Chemists Soc. 62(4):824827 (1985).
29. C. L. Edwards, U.S. Patent 5,059,719 to Shell Oil Co. (1991).
30. J. March, in Advanced Organic Chemistry: Reactions,
Mechanisms and Structure, McGraw-Hill, New York, 1986, p. 251.
31. Ibid. pp. 288289.
32. Ibid. p. 281.
33. F. Patat, E. Cremer, and O. Bobleter, J. Polym. Sci. 12:489
(1954).
34. C. L. Edwards, U.S. Patent 4,575,569 to Shell Oil Co. (1986).
35. A. N. Wrigley, F. D. Smith, and A. J. Stirton, J. Am. Oil
Chemists Soc. 34:39 (1957).
36. E. Santacesaria, M. Di Serio, R. Garaffa, and G. Addino, Ind.
Eng. Chem. Res. 31:24132418 (1992).
37. E. Santacesaria, M. Di Serio, L. Lisi, and D. Gelosa, Ind. Eng.
Chem. Res. 29:719 (1990).
38. N. Shachat and H. L. Greenwald, in Nonionic Surfactants (M.
J. Schick, ed.), Marcel Dekker, New York, 1966, p. 19.
39. J. Hine and M. Hine, J. Am. Chem. Soc. 74:5266 (1952).
40. G. J. Stockburger and J. D. Brandner, J. Am. Oil Chemists Soc.
40:590 (1963).
41. G. Gee, W. C. E. Higginson, P. Levesley, and K. J. Taylor, J.
Chem. Soc. 1338 (1959).
42. P. R. Geissler and Adrain E. Johnson, Jr., J. Am. Oil Chemists
Soc. 67:541546 (1990).
43. C. A. Carter, U.S. Patent 2,870,220 (1959).
44. J. March, in Advanced Organic Chemistry: Reactions,
Mechanisms and Structure, McGraw-Hill, New York, 1968, pp.
220221.
45. R. B. Bening and C. L. Willis, U.S. Patent 5,391,663 to Shell
Oil Co. (1995).
46. Y. Oshiro and S. Komari, Kogyo Kagaku Zasshi 65:1830
(1962).
47. K. Nagase and K. Sakaguchi, Kogyo Kagaku Zasshi 64:1031
(1961).
48. N. N. Lebedev and M. M. Smirnova, Kinetika i Kataliz 2:519
(1961).
49. N. Bortnick, L. S. Luskin, M. D. Hurwitz, W. E. Craig, L. J.
Exner, and J. Mirza, J. Am. Chem. Soc. 78:4039 (1956).
50. A. T. Ballun, J. N. Schumacher, G. E. Kapella, and J. V.
Karabinos, J. Am. Oil Chemists Soc. 31:20 (1954).
51. A. J. O'Lenick, Jr., and J. K. Parkinson, J. Soc. Cosmet. Chem.
44(6):31928. (1993).
52. A. J. Lowe and B. Weibull, J. Polym. Sci. 12:493 (1954).
53. P. J. Flory, J. Am. Chem. Soc. 62:1561 (1940).
54. P. J. Flory, Principles of Polymer Chemistry, Cornell
University Press, Ithaca, NY, 1953, Chap. 10.
55. B. Wesslen, E. Andersson, and K. Holmberg, J. Am. Oil
Chemists Soc. 66(8):11071112 (1989).
56. J. Morgos, P. Sallay, L. Farkas, and I. Rusznak, J. Am. Oil
Chemists Soc. 60(11):19051907 (1983).
57. G. L. Goeke and F. J. Karol, U.S. Patent 4,193,892 to Union
Carbide Corporation (1980).
 Page 36
58. W. T. Reichle, U.S. Patent 4,667,013 to Union Carbide
Corporation (1987).
59. L. Gold, J. Chem. Phys. 20:1651 (1952).
60. G. Natta and M. Simonetta, Rend. 1st Lombardo Sci. Lettere A.
78:307 (1945).
61. H. J. R. Maget, J. Polym. Sci. 57:773 (1962).
62. B. Weibull and B. Nycander, Acta Chem. Scand. 8:847 (1954).
63. L. Gold, J. Chem. Phys. 28:9199 (1958).
64. G. Natta and E. Mantica, J. Am. Chem. Soc. 74:3152 (1952).
65. H. K. Krummel and R. M. Wise, U.S. Patent 4,098,818 to
Procter & Gamble Co. (1978).
66. G. Tischbirek, Proc. of 3rd Int. Congr. Surface Activity,
Cologne, Germany, I, 126 (1960).
67. H. Hreczuch, G. Bekierz, K. Poland, and J. Szymanowski,
Tenside Surf. Det. 32:5560 (1995).
68. Y. Ishii, S. Sekiguchi, and A. Hayakawa, Kogyo Kagaku Zasshi
65:1041 (1962).
69. B. Weibull and J. Tornquist, Chem., Phys. Chem.
Anwendungstech. Grenzflaechenaktiven Stoffe, 6th Ber. Int.
Kongr., 1973.
70. P. Sallay, J. Morgos, L. Farkas, I. Rusznak, G. Veress, and B.
Bartha, Tenside Det. 17:298300 (1980).
71. B. Weibull, Acta Chem. Scand. 49(3):207216 (1995).
72. J. Morgos, P. Sallay, L. Farkas, Laszlo and I. Rusznak, J. Am.
Oil Chemists Soc. 63(9):12091210 (1986).
73. K. Yang, G. L. Nield, and P. H. Washecheck, U.S. Patent
4,210,764 to Conoco Corp. (1980).
74. K. Yang, U.S. Patent 4,239,917 to Conoco Corp. (1980).
75. J. H. McCain, European Patent 115083 to Union Carbide Corp.
(1984).
76. J. H. McCain and L. F. Theilling, European Patent 26544 to
Union Carbide Corp. (1981).
77. D. J. Foster and J. H. McCain, European Patent 26546 and
26547 to Union Carbide Corp. (1981).
78. A. Behler and U. Ploog, Fett Wiss. Techno. 92(3):109114
(1990).
79. K. Yang, G. L. Nield, and P. H. Washecheck, U.S. Patent
4,223,164 to Conoco Corp. (1980).
80. C. L. Edwards, U.S. Patent 4,396,779 to Shell Oil Co. (1983).
81. K. Yang, G. L. Nield, and P. H. Washecheck, European Patent
85167 to Conoco Corp. (1981).
82. C. L. Edwards, U.S. Patent 4,375,564 to Shell Oil Co. (1983).
83. C. L. Edwards, U.S. Patent 4,465,877 to Shell Oil Co. (1984).
84. E. Santacesaria, M. Di Serio, R. Garaffa, and G. Addino, Ind.
Eng. Chem. Res. 31:24192421 (1992).
85. R. C. Mansfield, J. E. Locke, and K. A. Booman, J. Am. Oil
Chemists Soc. 38:289 (1961).
86. H. F. Drew and J. R. Schaeffer, Ind. Eng. Chem. 50:1253
(1958).
87. K. Nagase and K. Sakaguchi, Kogyo Kagaku Zasshi 64:1199
(1961).
88. D. J. Worsfold and A. M. Eastham, J. Am. Chem. Soc.
79:897900 (1957).
89. J. March, in Advanced Organic Chemistry: Reactions,
Mechanisms and Structure, McGraw-Hill, New York, 1968, pp.
256262.
90. R. E. Parker and N. S. Issacs, Chem. Rev. 59:737 (1959).
 Page 37
91. G. Smith, W. M. Sawyer, and R. C. Morris, U.S. Patent
3,682,849 to Shell Oil Co. (1972).
92. J. Zhu and Z. Jin, Riyong Huaxue Gongye 6:281286 (1987).
93. K. Yang, G. L. Nield, and P. H. Washecheck, U.S. Patent
4,306,093 to Conoco Corp. (1981).
94. K. Yang, G. L. Nield, and P. H. Washecheck, U.S. Patent
4,302,613 to Conoco Corp. (1981).
95. J. H. McCain and L. F. Theiling, Jr., U.S. Patent 4,453,022 to
Union Carbide Corp. (1984).
96. J. H. McCain and L. F. Theiling, Jr., U.S. Patent 4,453,023 to
Union Carbide Corp. (1984).
97. L. Cheng, Z. Wu and X. Sun, Riyong Huaxue Gongye 4:185191
(1991).
98. J. H. McCain, S. W. King, R. J. Knogf, C. A. Smith, and C. F.
Hauser, European Patent 361619 A2 to Union Carbide Corp.
(1989).
99. E. C. Y. Nieh, European Patent 347064 A1 to Texaco
Development Corp. (1989).
100. A. Behler, H. Raths, and U. Ploog, German Patent DE
4,225,136 A1 to Henkel (1992).
101. E. L. Brace, M. L. Shannon, and D. L. Wharry, U.S. Patent
4,835,321 to Vista Chem. Co. (1989).
102. C. L. Edwards, U.S. Patent 4,721,816 to Shell Oil Co. (1988).
103. C. L. Edwards, U.S. Patent 4,825,009 to Shell Oil Co. (1989).
104. C. L. Edwards, U.S. Patent 4,931,205 to Shell Oil Co. (1989).
105. C. L. Edwards, U.S. Patent 4,721,817 to Shell Oil Co. (1988).
106. R. J. Knopf and L. F. Theiling, Jr., U.S. Patent 4,886,917 to
Union Carbide Corp. (1989).
107. C. L. Edwards, U.S. Patent 5,057,627 to Shell Oil Co. (1991).
108. C. L. Edwards and R. A. Kemp, U.S. Patent 5,057,628 (1991).
109. R. Wijngaarden, K. Latjes and J. Van Schaik, U.S. Patent
5,175,374 to Shell Oil Co. (1992).
110. B. J. Breukel and E. Gerard, European Patent 665206 A1 to
Shell International Res Mij BV (1995).
111. H. Nakaya, I. Adachi, N. Aoki, and H. Kanao, Japanese Patent
03185095 A2 to Lion Corp. (1989).
112. T. Tsukui, Y. Yanagi, and H. Takeguchi, Japanese Patent
63280036 A2 to Mitsubishi Petrochemical Co. (1987).
113. German Patent Application DE 4325237 A1 to BASF AG
(1995).
114. German Patent Application DE 4010606 to Henkel (1990).
115. German Patent Application DE 4138631 to Henkel (1991).
116. T. Imanaka, J. Kono, H. Nagumo, H. Tamura, and T. Tanaka,
WO9517248-A1 to Kao Corp. (1995).
117. D.H. Champion and G.P. Speranza, U.S. Patent 5,110,991 to
Texaco Chemical Co. (1991).
118. T. S. Sandoval and P. A. Schwab, U.S. Patent 5,220,077 to
Vista Chemical Co. (1993).
119. I. Hama, presented to Am. Oil Chemists Soc. spring meeting,
Anaheim, CA (1993).
 Page 39

2
Polyoxyethylene Alkylphenols
Robert M. Weinheimer and Pierre T. Varineau
Research and Development, Union Carbide Corporation, South
Charleston, West Virginia

I. Introduction 40
II. Alkylphenols 40
A. Nonylphenol 40
B. Octylphenol 42
C. Dodecylphenol 43
D. Properties 43
III. Polyoxyethylene Alkylphenols 44
A. Manufacture 44
B. Product Composition 48
IV. Properties 57
A. Physical Properties 57
B. Solution Properties 59
C. Surface Properties 64
V. Applications 68
A. Detergents 68
 B. Metalworking 70
C. Paints and Coatings 70
D. Agriculture 70
VI. Environmental Issues 71
A. Biodegradation 71
B. Risk Assessment 71
C. Aquatic Exposure/Toxicity 73
D. Mammalian Toxicity 76
E. Other Environmental Issues 78
References 79
 Page 40

I
Introduction
Polyoxyethylene alkylphenols have played a major role in many
markets for over 50 years. Early documentation of the chemistry of
polyoxyethylene alkylphenols appeared in 1937 [1]. Academic
studies of polyoxyethylene octylphenols appeared in the 1940s
[2,3]. The markets for polyoxyethylene alkylphenols have
consistently grown and today represent a substantial portion of the
nonionic surfactant market [4]. Nonylphenol and octylphenol are
the most commonly used hydrophobes with dodecylphenol less
commonly used.
Polyoxyethylation of alkylphenols allows the manufacture of a line
of products with a wide range of solubility and performance
characteristics. Polyoxyethylene alkylphenols, like other classes of
nonionic surfactant, find use in a wide variety of cleaning
products. They are also found in a number of specialty
applications, such as emulsion polymer manufacture, where other
nonionics are not particularly well suited.
Consistent with interest in environmental performance, a
significant body of environmental performance data has been
generated in recent years. Environmental monitoring studies have
demonstrated that the rates of degradation of polyoxyethylene
alkylphenols are sufficiently high to avoid accumulation in the
environment. In addition, studies have demonstrated high removal
rates of poly-oxyethylene alkylphenol from wastewater.
II
Alkylphenols
Polyoxyethylene alkylphenols are made from two major raw
materials, an alkylphenol and ethylene oxide. As ethylene oxide is
a raw material common to many classes of nonionic surfactants,
this chapter will focus on the alkylphenol raw materials. Readers
are referred to an excellent review by Dever et al. for a discussion
of ethylene oxide [5].
Although many alkylphenols are of commercial interest in many
industries, only two are used extensively as surfactant
hydrophobes. Nonylphenol, by far the largest volume surfactant-
related alkylphenol, had a worldwide demand of about 200,000
tons in the early 1990s. Approximately 25,000 tons per year of
octylphenol is produced. A third alkylphenol, dodecylphenol, is of
comparatively lower volume; the volume is difficult to determine
as much of this material is used captively [6].
A
Nonylphenol
Polyoxyethylene nonylphenols are produced from para-substituted
nonylphenol. Although ortho-nonylphenol can be produced by
proper choice of alkylation catalyst, the para isomer is preferred as
it is more readily polyoxyethylated [7].
The nonyl group is a highly branched propylene trimer. Due to
rearrangements arising from proton transfers, this trimer is a
mixture of isomers characterized in Table 1. Branching in the alkyl
chain is further enhanced by proton
 Page 41
TABLE 1 Olefin Types in Propylene
Trimer [104]
Structure Wt%
RCH=CH2 1
RCH=CHR 14
CH2=CR2 8
RCH=CR2 35
R2C=CR2 42

rearrangement during alkylation. Although linear nonyl groups are

often mentioned in relation to these products, none are used
commercially at this time [8]. However, even in reportedly linear
alkylphenols, double bond shifts can result in the formation of a
variety of isomers [9].
While alkylation of phenol can occur in the absence of catalyst, a
judicious catalyst choice produces the desired isomer distribution
and more complete olefin conversion. A review of recent literature
shows a considerable level of effort devoted to catalyst systems for
alkylphenol production. Boron trifluoride has been used as an
effective catalyst and was the catalyst of choice in the past [10].
Acid-activated clays have also been mentioned [11].
Montmorillonite clay acidified by pretreatment with mineral acids
has a high selectivity for palkylphenol [12]. Kiedik et al. describe
the production of nonylphenol with the use of porous or gelling
cationites [13]. Knifton describes the use of heteropolyacids for
adding mixed nonenes to phenol. The catalyst is stable at elevated
temperatures allowing adiabatic reaction [14]. Zeolites as catalyst
for the alkylation of phenols is becoming an area of active interest.
A recent Japanese patent [15] notes that zeolites reduce the need
for reactor anticorrosion protection compared to more acidic
catalysts. Zeolites are effective for the manufacture of alkylphenols
from mixed octenes, mixed nonenes, or mixed dodecenes [16].
Kapustin et al. describe the use of a catalyst consisting of porous
sulfonated copolymers of styrene and divinylbenzene claiming that
yields and purity are increased [17]. It is thought that catalysts of
this type are used in current commercial practice.
In the past, batch processes were used to produce nonylphenol.
These typically were performed in stirred tank reactors with
catalyst suspended in the reaction mixture. Such processes are
becoming obsolete in favor of continuous processes.
The following describes a more modern process [18]:
A mixture of phenol and propene trimer (molar ratio 1.7:1) is preheated
to 70°C and pumped to the top of the first reactor at an hourly rate of
about 30 mass units per 1 mass unit of catalyst. The product leaving the
first reactor with a temperature of 120°C is cooled to 100°C and fed to
the second reactor. The temperature of the reaction product leaving the
second reactor is about
 Page 42
125°C. Product compositions after the first and second step are (in
wt%): propene trimer 28.9 and 3.8; phenol 46.1 and 27.5; nonylphenol
22.4 and 65.8; and dinonylphenol 2.6 and 2.9; respectively. The product
of the second reaction step is purified by distillation. Recovered phenol
and propene trimer, as well as dinonylphenol, are recycled.
As mentioned above, sulfonated polystyrene-polydivinylbenzene
ion exchange resins are commonly used in continuous alkylation
processes as they are highly selective for monoalkylation and can
be readily arranged in fixed beds. They are reported to have long
service lives, important for use in fixed bed reactors. The upper
operating temperature allowable with cation exchangers is about
140°C [19]. The alkylation is quite exothermic resulting in the need
for heat removal. In a continuous process, excess phenol is
commonly used to reduce the temperature rise in the reactor.
Excess phenol also tends to drive the alkylation to the
monoalkylate, the preferred species for polyoxyethylation. Use of
excess phenol also allows operation at or near adiabatic conditions.
As noted in the process description, distillation is frequently
required to purify the product. This is accomplished in a three-
column distillation train. Excess phenol is removed in the first
column. The second column removes light materials such as
unreacted alkene. Heavy byproducts such as dialkylphenols are
removed in the third column in addition to recovering
monoalkylphenol overhead. Because excessive reboiler
temperatures can lead to dealkylation, the distillation is conducted
under vacuum [20].
Finished nonylphenol is stored in heated tanks made of stainless
steel or phenolic lined carbon steel. These tanks are inerted with
nitrogen to limit discoloration caused by product oxidation [21].
Bulk shipments are made in rail cars or tank trucks, likewise made
of stainless steel or phenolic lined carbon steel. As nonylphenol is
a liquid at room temperature, small shipments of nonylphenol are
transported in drums or tote tanks.
B
Octylphenol
Octylphenol used in surfactant production shares many of the
characteristics of nonylphenol. Of greatest importance is that it is
predominantly both para-substituted and highly branched. One
outstanding difference is that the alkyl group is a relatively pure
material, diisobutylene. There are two isomers of diisobutylene,
but alkylation with either isomer results in the same alkyl structure:
 Page 43

The general process description for the manufacture of

nonylphenol applies to octylphenol as well. Detailed process
conditions such as reactant and catalyst ratios and operating
temperatures may be slightly different. The purification steps are
very similar to those for nonylphenol. The materials compatibility
and product quality issues associated with nonylphenol also apply
to octylphenol. Because octylphenol has a high freezing point, it
must be shipped in insulated trucks or rail cars. These vehicles
must be equipped to allow melting of the product should it freeze
in transit. The great difference in freezing points of octylphenol
and nonylphenol provides a quick method for surfactant
manufacturers to confirm the identity of inbound shipments of
alkylphenol.
C
Dodecylphenol
Dodecylphenol is made from propylene tetramer and phenol. This
tetramer is an even more complicated mixture of isomers than the
propylene trimer used in nonylphenol manufacture. The
manufacturing process is similar to that described for octylphenol
and nonylphenol.
D
Properties
In spite of the purification processes employed on alkylphenols,
there is commonly some measurable level of ortho isomer and
dialkylate in the finished product. Typically, alkylphenols contain
at least 90% para isomer, less than 10% ortho isomer, and a trace
of dialkylphenol. Higher purity grades are available [22]. Typical
properties are shown in Table 2. Note that octylphenol, due to the
relative purity of the octyl group, is a solid at room temperature.
Due to the heterogeneity of their alkyl groups, nonylphenol and
dodecylphenol are liquids.
TABLE 2 Physical Properties of Alkylphenols [105]
4-tert- 4- 4-
Property
Octylphenol NonylphenolDodecylphenol
Typical assay
9098 9095 8995
(%)
Molecular weight 206 220 262
Physical form at
Solid Liquid Liquid
25°C
Boiling point
290 310 334
(°C)
Freezing point
81 <20 <20
(°C)
Flash point (°C) 132 146 >100
Molten color
200 100 500
(APHA)
 Page 44
The environmental and toxicologic characteristic of alkylphenols
are discussed in the environmental issues section later in this
chapter.
III
Polyoxyethylene Alkylphenols
Polyoxyethylene alkyphenols are important surfactants as
evidenced by the large number of producers of these products
listed in Table 3. Several companies, including Union Carbide,
Huntsman, and Rhône-Poulenc, have extensive product lines
whereas several others supply only a few products.
A
Manufacture
Polyoxyethylene alkylphenols are produced in a semibatch process
at temperatures ranging from 100°C to 180°C at a reactor pressure
between 5 and 6 bar gauge with alkaline catalyst concentrations of
0.1% to 0.03% by weight. Sodium hydroxide and potassium
hydroxide are most commonly used to catalyze the
polyoxyethylation. Acid catalysts are not often used due to
byproduct formation [23].
The semibatch process is commonly used for production of
polyoxyethylated nonionic surfactants. The reaction vessel is
typically agitated with means for heating and cooling, either
internally by coil or jacket or externally in a circulation loop. The
reactors is inerted with nitrogen to remove oxygen and then
charged with alkylphenol and catalyst. The catalyst can be added as
solid beads, flakes, or aqueous solution. Water is generated during
the catalysis step:
where n is the mole ratio of base to alkylphenol and is typically
0.0050.02. The catalyzed alkylphenol is heated to reaction
temperature and purged with nitrogen to reduce the water level
generally to less than 0.1% by weight. Water removal is important
if polyethylene glycol formation is to be minimized. After drying,
ethylene oxide feed to the reactor is started. The ethylene oxide
may be added via a sparger in the bottom of the reactor, it may be
mixed with the bulk liquid in a external pumped circulating loop;
or it may be added directly to the vapor space of the reactor. It is
important to disperse the ethylene oxide into the bulk liquid
quickly and thoroughly, and different reaction systems accomplish
this in various special sparger designs, reactor agitators, reactor
circulation, spray circulation systems, or eductor mixers. Producers
must avoid a vapor space explosion, and this is done by
eliminating ignition sources or by using
 Page 45
TABLE 3 Polyoxyethylene Alkylphenol Producers [106, 107]
Trademark Supplier Location
Ablunol NP Taiwan Surfactant Corp. Taiwan
Agrimul 70-A Sidobre-Sinnova S.A. France
Agrisol PX Akcros Chemicals England
Akypo OP CHEM-Y GmbH Germany
Akyporox NP, OP CHEM-Y GmbH Germany
Rhône-Poulenc, North
Alkasurf NP, OP USA
American Chem.
Rhône-Poulenc, North
Antarox LF-222 USA
American Chem.
Arkopal N Grades Hoechst AG/Zentrale Werbung Germany
Armul 900
Witco Crop. USA
(series)
Atlas EMJ Atlas Refinery USA
Atlas G-4809,
ICI Surfactants England
5002
Atlox 4898, 4911 ICI Surfactants England
Atlox 775 ICI Surfactants USA
Atsolyn T Atsaun Chemical Corp. India
Basopon LN BASF Corp. USA
Berol (series) Akzo Nobel Surface ChemistryUSA
Berol (series) Berol Nobel AB Sweden
Caloxylate N-9 Pilot Chemical Co. USA
Capcure Henkel Corp./Functional Prod.
USA
Emulsifier 65 Grp.
Carsonon N Lonza Inc. USA
Cedepal CA, CO Stepan Canada Inc. Canada
Cenegen NWA Crompton & Knowles USA
Cenekol FT Supra Crompton & Knowles USA
Chemax NP, OP,
Chemax Inc. USA
DNP
Chimipon NA Auschem S.p.A Italy
Cirrasol AEN-XZ ICI Surfactants England
Corexit CL Exxon Chemical Company USA
Dehydrophen
Pulcra, S.A. Spain
PNP, POP
Delonic NPE,
DeForest Enterprises, Inc. USA
OPE
DeSonic S, N, D Witco Corp. USA
Dowfax 9N Dow Europe SA Switzerland
Eccoscour RC Eastern Color & Chemical Co. USA
Eccoterge EO-100Eastern Color & Chemical Co. USA
Eleminol HA-100, Sanyo Chemical Industries,
Japan
161 Ltd.
Emulan NP, OP,
BASF Aktiengesellschaft Germany
PO
Emulsifier
Ethox Chemicals USA
632/90%
Dai-ichi Kogyo Seiyaku Co.,
Emulsit Japan
Ltd.
Emulsogen A, N-
Hoechst Celanese Corp. USA
600
Emulson AG
Auschem S.p.A Italy
(series)
Ethylan Akcros Chemicals England
Etophen Series Zschimmer & Schwarz Germany
Rhône- Poulenc, North
Geronol AG-821 USA
American Chem.
Gradonic N-95 Graden Chemical USA
Hetoxide NP Heterene, Inc. USA

(table continued on next page)

 Page 46
TABLE 3 (Continued)
Trademark Supplier Location
Hostapal N, CVS Hoechst Celanese Corp. USA
Henkel Corp./Functional
Hyonic NP, OP USA
Prod. Grp.
Iberscour W Conc. A. Harrison & Co. USA
Iberwet W-100 A. Harrison & Co. USA
Iconol NP, OP BASF Corp. USA
Rhône-Poulenc, North
Igepal CA, CO USA
American Chem.
Igepal NP, O, OD, Rhône-Poulenc, Chimie
France
RC (France)
Rhône-Poulenc, North
Igepal SS-837 USA
American Chem.
Lipocol NP-9 USP Lipo Chemicals USA
Liponox NC Lion Corp. Japan
Lutensol AP BASF Aktiengesellchaft Germany
Macol NP OP, DNP PPG Industries USA
Makon 46, 711,
Stepan Europe France
1250
Makon NI 10/NI
Stepan Europe France
20/NI 30
Makon, Makon OP-
Stepan Company USA
9
Marlophen 80, 800 Hüls AG Germany
Marlophen DNP, N,
Hüls AG Germany
P
Marlophen NP, PI Hüls America USA
Marlowet 4900,
Hüls AG Germany
5641
Marlowet BIK,
Hüls AG Germany
ISM, TM
Minemal 320, 325,
330 Nippon Nyukazai Co., Ltd. Japan
Mulsifan RT37, RT
Zschimmer & Schwarz Germany
231
Neutronyx 656 Stepan Company USA
Newcol 500, 600,
Nippon Nyukazai Co., Ltd Japan
700, 800
Nikkol NP, OP Nikko Chemicals Co., Ltd. Japan
Nissan Dispanol N-
NOF Corporation Japan
100
Nissan Nonion HS,
NOF Corporation Japan
NS
Dai-ichi Kogyo Seiyaku Co.,
Noigen EA Japan
Ltd.
Toho Chemical Industry Co.,
Nonal Japan
Ltd.
Nonarox Seppic France
Nonicol 100, 190 Atsaun Chemical Corp. India
Nonionic E Calgene Chemical, Inc. USA
Sanyo Chemical Industries,
Nonipol BX, D-160 Japan
Ltd.
Norfox NP, OP Norman, Fox & Co. USA
NP-55-60, 80, 85,
Hefti Ltd. Switzerland
90
Nutrol 600 (series) Boehme Filatex Canada Inc. Canada
Sanyo Chemical Industries,
Octapol Japan
Ltd.
Polystep OP, F Stepan Company USA
CPB-Companhia
Quimipol ENF Portugal
Petroquimica Do
Remcopal (series) Ceca SA France
Renex 600 ICI Surfactants England
Rioklen Auschem S.p.A Italy
Sabofen AF Sabo S.p.A. Italy
Sermul EN (series) Servo Delden, B.V. Holland
Simulsol NP 575 Seppic France
(table continued on next page)
 Page 47
TABLE 3 (Continued)
Trademark Supplier Location
Sinopol (series) Sino-Japan Chemical Co. Taiwan
Hoechst AG/Zentrale
Solegal W Conc. Germany
Werbung
Rhône-Poulenc, North
Soprophor USA
American Chem.
Rhône-Poulenc Geronazzo
Soprophor 37, 40/D Italy
S.P.A.
Soprophor BSU, CY/8, Rhône-Poulenc, North
USA
S American Chem.
Sterox Monsanto Co. USA
Surflo S Exxon Chemical Company USA
Surfonic N, OP Huntsman Corporation USA
Syn Fac Milliken Chemical USA
Synperonic N, NP,
ICI Surfactants England
NPE1800, OP
Synthrapol N ICI Surfactants USA
Syntopon (series) Witco SA France
T-DET N, O, DD Harcros Organics USA
Tergitol NP (series) Union Carbide Corporation USA
ICI Australia Operations Pty,
Teric (series) Australia
Ltd.
Tex-Wet 1155 Intex Chemical USA
TN Cleaner S Tokai Seiyu Ind. Co., Ltd. Japan
Triton N, X (series) Union Carbide Corporation USA
Henkel Corp./Emery
Trycol 6000 (series) USA
Organic Prod. Grp.
Marubishi Oil Chemical
Value 3608, 3700 Japan
Co., Ltd.
Wettol EM 2 BASF Aktiengesellschaft Germany
Witbreak DRB Witco Corp. USA
nitrogen dilution to limit the ethylene oxide concentration to a
point below its flammable limit at the reactor operating
temperature and pressure. Many producers choose a design and
operating conditions to eliminate both concerns. The ethylene
oxide feed rate is dependent on the heat removal capability and the
reactor design pressure and temperature, plus any constraints
imposed by limiting the ethylene oxide vapor space concentration
to below the flammable limit.
When the alkylphenol has been polyoxyethylated to the desired
extent, the reaction mixture is held at reaction temperature until the
residual ethylene oxide concentration in the liquid product has
been reduced to an acceptable level. Specification tests can then be
conducted to assure product quality. The product is then
neutralized and posttreated as described below [24].
High molecular weight products may require a multistep
manufacturing process. In most cases, a minimum level of
alkylphenol must be charged to the reactor in order to properly
cover the agitator and heat transfer surfaces. This minimum level
of alkylphenol will grow in volume as it is polyoxyethylated; its
volume may equal that of the reactor before the required degree of
poly-
 Page 48
oxyethylation is achieved. In this case, a portion of the reaction
mixture may be removed from the reactor to leave room for
further product growth, and the removed portion may be stored
and used for future production. Alternatively, a lower molecular
weight polyoxyethylene alkylphenol may be used as the starting
alcohol in Eq. (3).
Upon completion of the polyoxyethylation, the reaction mixture
must be neutralized. Commonly used acids include acetic,
phosphoric, propionic, and lactic. If necessary, color may be
reduced by bleaching with hydrogen peroxide. Finally, the product
may be filtered to remove any insoluble salts formed during
neutralization.
B
Product Composition
Due to the high acidity of alkylphenols, the first mole of ethylene
oxide is added with great selectivity. The relative acidity of the
alkylphenol compared to the polyoxyethylene chain results in a
nearly complete conversion of alkylphenol to a polyoxyethylene
(1) before polyoxyethylene (2) alkylphenol forms in appreciable
amounts. The second and subsequent moles of ethylene oxide add
as described by a Poisson distribution.
The general reaction scheme

can be described in two steps if n is >1:

The average degree of ethoxylation represented in Eq. (4), then, is
composed of the individual oligomers

where x is 0, 1, 2, 3, . . ., and the term (x+1)-mer indicates the total

moles of ethylene oxide in the molecule.
The mol% of an individual (x+1)-mer is calculated by
 Page 49
and the wt% by

wheree = 2.71828
m=n+1
x = 1, 2, 3, . . .
Mx+1 = molecular weight of
(x+1)-mer
Mn = molecular weight of
product

Values of molecular weight distributions calculated from these

equations are in Table 4 for polyoxyethylene nonylphenols and in
Table 5 for polyoxyethylene octylphenols. The correlation between
molecular weight distribution calculated from the Poisson
distribution and that determined analytically shows good
agreement as seem in Table 6. ortho-Alkylphenol and
dialkylphenol are always present in the raw materials; therefore
these calculated values are close to but not exactly equal to the
actual composition of the product.
While polyoxyethylene alkylphenols of different molecular weights
can be blended together to yield a product of a known molecular
weight, the molecular weight distribution of the blend may be quite
different from that of a product made by directly polyoxyethylating
the hydrophobe. Table 7 shows the results of blending a
polyoxyethylene (5) nonylphenol with a polyoxyethylene (15)
nonylphenol in proportions leading to a product with the
molecular weight of a polyoxyethylene (10) nonylphenol. Clearly,
the resulting bimodal molecular weight distribution of the blend is
quite different from that of polyoxyethylene nonylphenol (10).
Polyoxyethylene glycols (PEGs) are commonly formed during
surfactant manufacture due to side reactions in the
polyoxyethylation process. In most cleaning applications,
byproduct PEG acts as little more than a diluent. However, if the
polyoxyethylene alkylphenol is to be derivatized by, for example,
sulfation, then the resulting PEG disulfate is not at all surface
active and is undesirable. The presence of PEG in the surfactant
also reduces the solubility of polyoxyethylene alkylphenols in
nonpolar solvents. PEG can also have an effect on
polyoxyethylene alkylphenol product appearance as levels of PEG
>0.5% can lead to the formation of a hazy bottom layer on
extended storage.
Byproduct PEG in a polyoxyethylene alkylphenol can originate
with residual water in the reaction mixture; this water is
polyoxyethylated along with the intended hydrophobe. Small
amounts of water can enter the process as a trace component of the
alkylphenol. A second source of water is the residue from reactor
and line cleaning. Finally, water is formed during the catalysis step
in the polyoxyethylene process. Water from all of these sources is
removed in a
 Page 50
TABLE 4 Poisson Distribution (Wt%) Polyoxethylene Nonylphenol
Mole ratio (n)
x-mer MW 2 3 4 5 6 7 8 9 10 12 15
1 264 31.53 10.15 3.32 1.10 0.37 0.12 0.04 0.01
2 308 36.79 23.68 11.61 5.13 2.14 0.87 0.34 0.13 0.05 0.01
3 352 21.02 27.07 19.91 11.72 6.12 2.97 1.37 0.61 0.27 0.05
4 396 7.88 20.30 22.40 17.5811.48 6.69 3.61 1.84 0.90 0.20 0.02
5 440 2.19 11.28 18.67 19.5415.9511.15 7.02 4.09 2.25 0.60 0.07
6 484 0.48 4.96 12.32 17.1917.5514.7210.81 7.20 4.45 1.45 0.20
7 528 0.09 1.81 6.72 12.5015.9516.0613.7510.47 7.29 2.90 0.52
8 572 0.01 0.56 3.12 7.74 12.3414.9214.9012.9610.15 4.94 1.13
9 616 0.15 1.26 4.17 8.31 12.0514.0413.9612.30 7.31 2.13
10 660 0.04 0.45 1.99 4.95 8.61 11.7013.2913.18 9.58 3.55
11 704 0.01 0.14 0.85 2.64 5.51 8.74 11.3412.6511.24 5.30
12 748 0.04 0.33 1.27 3.19 5.91 8.77 11.0011.94 7.17
13 792 0.01 0.12 0.56 1.69 3.65 6.19 8.73 11.59 8.86
14 836 0.04 0.23 0.82 2.07 4.02 6.38 10.3510.07
15 880 0.01 0.09 0.37 1.09 2.42 4.32 8.56 10.60
16 924 0.00 0.03 0.16 0.53 1.35 2.72 6.59 10.39
17 968 0.01 0.06 0.25 0.71 1.60 4.75 9.52
18 1012 0.02 0.11 0.35 0.89 3.21 8.20
19 1056 0.01 0.04 0.16 0.46 2.05 6.65
20 1110 0.02 0.07 0.23 1.24 5.11
21 1144 0.01 0.03 0.11 0.71 3.72
22 1188 0.01 0.05 0.38 2.57
23 1232 0.02 0.20 1.70
24 1276 0.01 0.10 1.07
25 1320 0.05 0.65
26 1364 0.02 0.37
27 1408Calculated from Eq. (9) 0.01 0.21
28 1452 0.11
29 1496 0.06
30 1540 0.03
31 1584 0.01
31 1584 0.01
32 1628 0.01

(table continued on next page)

 Page 51
(table continued from previous page)
Mole ratio (n) Mole ratio (n)
x-mer MW 20 30 40 x-mer MW 20 30 40
6 484 0.01 38 44 0.01 2.92 5.94
7 528 0.02 39 88 0.01 2.28 6.23
8 572 0.05 40 132 1.73 6.37
9 616 0.13 41 176 1.28 6.35
10 660 0.30 42 220 0.93 6.17
11 704 0.61 43 264 0.65 5.86
12 748 1.11 44 308 0.45 5.42
13 792 1.86 0.01 45 352 0.30 4.90
14 836 2.88 0.02 46 396 0.20 4.33
15 880 4.11 0.05 47 440 0.13 3.75
16 924 5.46 0.10 48 484 0.08 3.17
17 968 6.80 0.19 49 528 0.05 2.62
18 1012 7.94 0.34 50 572 0.03 2.13
19 1056 8.75 0.57 51 616 0.02 1.69
20 1100 9.11 0.91 0.01 52 660 0.01 1.31
21 1144 9.00 1.37 0.02 53 704 0.01 1.00
22 1188 8.46 1.97 0.04 54 748 0.75
23 1232 7.58 2.69 0.06 55 792 0.55
24 1276 6.48 3.52 0.11 56 836 0.40
25 1320 5.31 4.40 0.19 57 880 0.28
26 1364 4.17 5.27 0.31 58 924 0.20
27 1408 3.14 6.07 0.47 59 968 0.13
28 1452 2.28 6.72 0.71 60 1012 0.09
29 1496 1.60 7.18 1.01 61 1056 0.06
30 1540 1.08 7.39 1.41 62 1100 0.04
31 1584 0.70 7.34 1.88 63 1144 0.02
32 1628 0.44 7.06 2.43 64 1118 0.02
33 1672 0.27 6.57 3.04 65 1232 0.01
34 1716 0.16 5.93 3.69 66 1276 0.01
35 1706 0.09 5.19 4.33 66 3124 0.01
36 1804 0.05 4.41 4.95 67 3168 0.00
 Page 52
TABLE 5 Poisson Distribution (Wt%) Polyoxyethylene Octylphenol
Mole ratio (n)
x-mer MW 2 3 4 5 6 7 8 9 10 12 15
1 250 31.28 10.01 3.26 1.07 0.36 0.12 0.04 0.01
2 294 36.79 23.54 11.49 5.05 2.11 0.85 0.34 0.13 0.05 0.01
3 338 21.15 27.07 19.82 11.62 6.06 2.93 1.35 0.60 0.26 0.05
4 382 7.97 20.40 22.40 17.5211.41 6.63 3.57 1.82 0.89 0.19 0.02
5 426 2.22 11.37 18.74 19.5415.9011.09 6.96 4.05 2.22 0.59 0.07
6 470 0.49 5.02 12.41 17.2417.5514.6910.76 7.15 4.42 1.43 0.20
7 514 0.09 1.83 6.78 12.5715.9916.0613.7210.43 7.25 2.88 0.52
8 558 0.01 0.57 3.16 7.80 12.4014.9514.9012.9410.12 4.91 1.12
9 602 0.15 1.28 4.21 8.36 12.0914.0713.9612.28 7.28 2.12
10 646 0.04 0.46 2.01 4.99 8.65 11.7413.3213.18 9.55 3.53
11 690 0.01 0.15 0.86 2.66 5.55 8.78 11.3812.6711.22 5.28
12 734 0.04 0.33 1.29 3.22 5.94 8.80 11.0211.94 7.15
13 778 0.01 0.12 0.57 1.71 3.67 6.22 8.76 11.60 8.84
14 822 0.04 0.23 0.83 2.09 4.04 6.41 10.3710.06
15 866 0.01 0.09 0.38 1.10 2.43 4.34 8.58 10.60
16 910 0.03 0.16 0.54 1.36 2.74 6.62 10.40
17 954 0.01 0.06 0.25 0.72 1.61 4.77 9.54
18 998 0.02 0.11 0.35 0.89 3.23 8.22
19 1042 0.01 0.04 0.16 0.47 2.06 6.67
20 1086 0.02 0.07 0.23 1.24 5.12
21 1130 0.01 0.03 0.11 0.71 3.73
22 1174 0.01 0.05 0.39 2.58
23 1218 0.02 0.20 1.71
24 1262 0.01 0.10 1.08
25 1306 0.05 0.65
26 1350 0.02 0.38
27 1394Calculated from Eq. (9) 0.01 0.21
28 1438 0.11
29 1482 0.06
30 1526 0.03
31 1570 0.01
31 1570 0.01
32 1614 0.01

(table continued on next page)

 Page 53
(table continued from previous page)
Mole ratio (n) Mole ratio (n)
x-mer MW 20 30 40 x-mer MW 20 30 40
6 470 0.01 38 1878 0.01 2.92 5.93
7 514 0.02 39 1922 0.01 2.28 6.23
8 558 0.05 40 1966 1.74 6.37
9 602 0.13 41 2010 1.29 6.35
10 646 0.30 42 2054 0.93 6.18
11 690 0.60 43 2098 0.66 5.86
12 734 1.10 44 2142 0.45 5.42
13 778 1.85 0.01 45 2186 0.30 4.91
14 822 2.86 0.02 46 2230 0.20 4.34
15 866 4.09 0.05 47 2274 0.13 3.75
16 910 5.45 0.10 48 2318 0.08 3.17
17 954 6.78 0.19 49 2362 0.05 2.63
18 998 7.93 0.34 50 2406 0.03 2.13
19 1042 8.74 0.57 51 2450 0.02 1.69
20 1086 9.11 0.91 0.01 52 2494 0.01 1.32
21 1130 9.01 1.37 0.02 53 2538 0.01 1.00
22 1174 8.47 1.97 0.03 54 2582 0.75
23 1218 7.59 2.69 0.06 55 2626 0.55
24 1262 6.49 3.51 0.11 56 2670 0.40
25 1306 5.32 4.39 0.19 57 2714 0.28
26 1350 4.18 5.27 0.31 58 2758 0.20
27 1394 3.15 6.07 0.47 59 2802 0.13
28 1438 2.29 6.72 0.71 60 2846 0.09
29 1482 1.60 7.17 1.01 61 2890 0.06
30 1526 1.08 7.39 1.40 62 2934 0.04
31 1570 0.70 7.35 1.88 63 2978 0.02
32 1614 0.44 7.07 2.43 64 3022 0.02
33 1658 0.27 6.58 3.04 65 3066 0.01
34 1702 0.16 5.93 3.68 66 3110 0.01
35 1746 0.09 5.19 4.34 66 3110 0.01
36 1790 0.05 4.41 4.95 67 3154 0.00
 Page 54
TABLE 6 Comparison of Poisson
Distribution and Measured Molecular
Weight Distribution for Triton X-100
Percent by weight [108]
Oligomer Poisson
Measuredb
number distributiona
1 0.09 0.00
2 0.44 0.9
3 1.4 2.5
4 3.3 4.6
5 6.0 6.9
6 9.2 9.5
7 11.9 11.7
8 13.5 12.7
9 13.5 12.3
10 12.0 11.2
11 9.7 9.1
12 7.2 6.8
13 4.9 4.8
14 3.1 3.1
15 1.8 2.0
16 0.99 1.2
17 0.51 0.7
18 0.25 0.0
19 0.11 0.0
20 0.05 0.0
21 0.02 0.0
22 0.01 0.0
a Calculated from Eq. (9).
b By gas chromatography.

drying step prior to the introduction of ethylene oxide. Enyeart

[25] presents a detailed discussion of the PEG formation process.
For a monofunctional hydrophobe such as an alkylphenol, and
assuming that residual water in the reaction system is the only
source of PEG production, the wt% of PEG in the product, wt%
PEG, can be calculated:

whereH = w% water based on alkylhenol

MWB = molecular weight of alkylphenol
n = degree of polyoxyethylation
MWT = MWB + 44(n), the theoretical molecular
weight of the surfactant
 Page 55
TABLE 7 Effect of Blending Polyoxyethlene
Nonylphenols on Molecular Weight Distribution
Poisson distribution
Mole ratio (n) Blend
Mole ratio Mol. wt. 5 15 10 5/15
1 264 1.10 0.00 0.00 0.37
2 308 5.13 0.00 0.05 1.71
3 352 11.72 0.00 0.27 3.90
4 396 17.58 0.02 0.90 5.87
5 440 19.54 0.07 2.25 6.55
6 484 17.19 0.20 4.45 5.86
7 528 12.50 0.52 7.29 4.51
8 572 7.74 1.13 10.15 3.33
9 616 4.17 2.13 12.30 2.81
10 660 1.99 3.55 13.18 3.03
11 704 0.85 5.30 12.65 3.82
12 748 0.33 7.17 11.00 4.89
13 792 0.12 8.86 8.73 5.95
14 836 0.04 10.07 6.38 6.73
15 880 0.01 10.60 4.32 7.07
16 924 10.39 2.72 6.93
17 968 9.52 1.60 6.35
18 1012 8.20 0.89 5.47
19 1056 6.65 0.46 4.44
20 1100 5.11 0.23 3.41
21 1144 3.72 0.11 2.48
22 1188 2.57 0.05 1.72
23 1232 1.70 0.02 1.13
24 1276 1.07 0.01 0.71
25 1320 0.65 0.43
26 1364 0.37 0.25
27 1408 0.21 0.14
28 1452 0.11 0.07
29 1496 0.06 0.04
30 1540 0.03 0.02
31 1584 0.01 0.01
32 1628 0.01 0.00
Mol. wt. 440 881 660 660
Blend of 33.3% polyoxyethylene (5) nonylphenol and
66.7% polyoxyethylene (15) nonylphenol.
 Page 56
TABLE 8 Theoretical Polyoxyethylene Glycol Content in
Polyoxyethylene Nonylphenola
Initial water content, percent based on nonylphenol
Mole ratio 0.01 0.02 0.05 0.10 0.20 0.50
2 0.08 0.15 0.38 0.75 1.47 3.47
3 0.10 0.19 0.48 0.96 1.87 4.40
4 0.11 0.23 0.56 1.12 2.18 5.12
5 0.13 0.25 0.63 1.24 2.43 5.70
6 0.14 0.27 0.68 1.35 2.63 6.17
7 0.15 0.29 0.73 1.43 2.80 6.56
8 0.15 0.31 0.76 1.51 2.95 6.89
9 0.16 0.32 0.79 1.57 3.07 7.18
10 0.17 0.33 0.82 1.62 3.17 7.43
15 0.19 0.37 0.92 1.81 3.55 8.29
20 0.20 0.39 0.98 1.93 3.77 8.81
30 0.21 0.42 1.04 2.06 4.02 9.41
40 0.22 0.43 1.08 2.13 4.17 9.74
70 0.23 0.46 1.13 2.23 4.36 10.20
a Calculated from Eq. (10).

TABLE 9 Theoretical Polyoxyethylene Glycol Content in

Polyoxyethylene Octylphenola
Initial water content, percent based on octylphenol
Mole ratio 0.01 0.02 0.05 0.10 0.20 0.50
2 0.08 0.15 0.37 0.74 1.45 3.42
3 0.10 0.19 0.47 0.93 1.83 4.32
4 0.11 0.22 0.55 1.08 2.12 5.00
5 0.12 0.25 0.61 1.20 2.36 5.55
6 0.13 0.26 0.66 1.30 2.55 5.99
7 0.14 0.28 0.70 1.38 2.70 6.35
8 0.15 0.29 0.73 1.45 2.84 6.66
9 0.15 0.31 0.76 1.51 2.95 6.93
10 0.16 0.32 0.79 1.56 3.05 7.15
15 0.18 0.35 0.87 1.73 3.38 7.95
20 0.19 0.37 0.93 1.83 3.58 8.42
30 0.20 0.40 0.99 1.95 3.81 8.95
40 0.21 0.41 1.02 2.01 3.94 9.25
70 0.21 0.43 1.06 2.10 4.12 9.66
a Calculated from Eq. (10).
 Page 57
The PEG content of polyoxyethylene nonylphenol and octylphenol
given a variety of initial water levels is shown in Tables 8 and 9.
Clearly, the removal of water from the catalyzed alkylphenol prior
to polyoxyethylation is important if PEG formation is to be
minimized. In commercial practice, the water content of the
catalyzed alkylphenol is reduced to no more than 0.05% prior to
ethoxylation.
In addition to PEG, small amounts of acetaldehyde, formaldehyde,
and 1,4-dioxane are formed. These materials are present at ppm
levels [26]. Mechanisms for formation of these byproducts are
unclear; however, it is well known that ethylene oxide can
isomerize to form acetaldehyde [27] and that acidic catalysis of the
polyoxyethylation reaction is linked to 1,4-dioxane formation [28].
IV
Properties
A
Physical Properties
The physical state of a polyoxyethylene alklyphenol at ambient
conditions depends greatly on its degree of polyoxyethylation. As
seen in Table 10, the pour point of polyoxyethylene nonylphenols
climbs with increasing degree of polyoxyethylation. Products with
more than about 15 moles of polyoxyethylation are solids at room
temperature. It is common practice to make the higher mole
products available for sale as concentrated aqueous solutions.
Adding water to a typical level of 30% in the final product leads to
a lower freezing liquid that is easier to handle.
The pour point of polyoxyethylene octylphenols (Table 11) passes
through a minimum as the degree of ethoxylation increases. Recall
that octylphenol has a freezing point of about 80°C. For low levels
of polyoxyethylation, the polyoxyethylene octylphenol properties
reflect the octylphenol properties and specifically the high pour
point. As the degree of polyoxyethylation increases,
TABLE 10 Typical Physical Properties of Polyoxyethylene
Nonylphenol [109]
Kinematic viscosity
Mole Pour point Specific gravity
Tergitol (mPa·s)
ratio (°C) (20/20°C)
20°C 40°C 60°C
NP-4 4 -40 445 105 8 1.031
NP-6 6 -12 373 99 9 1.035
NP-7 7 -6 338 97 10 1.055
NP-8 8 -3 325 102 11 1.056
NP-9 9 0 318 105 12 1.057
NP-10 10.5 7 327 105 13 1.062
NP-13 13 16 410 125 15 1.071
NP-40 40 48 Solid Solid 48 Solid
 Page 58
TABLE 11 Typical Physical Properties of Polyoxyethylene
Octylphenol [110]
Viscosity
Mole Pour point (mPa·s) Specific gravity
Triton
ratio (°C) 25°C 60°C (25/25°C)
100°C
X-15 1 -9 790 45 8 0.985
X-35 3 -23 370 38 8 1.023
X-45 5 -26 290 36 9 1.040
X-
7.5 -9 260 40 11 1.054
114
X-
9.5 7 240 43 13 1.065
100
X-
12 16 330 50 15 1.071
102

the polyoxyethylene chain plays a greater role in the pour point. As

with polyoxyethylene nonylphenols, the higher oligomers are
solids at room temperature. These products are also available as
aqueous blends.
The liquid polyoxyethylates of both nonylphenol and octylphenol
are colorless to pale yellow and are clear to slightly hazy. Haze can
result from the salt formed while neutralizing the reaction mixture
after concluding the polyoxyethylation step. Sodium phosphate
and potassium phosphate, for example, result from catalyzing the
polyoxyethylation with sodium hydroxide or potassium hydroxide,
then neutralizing with phosphoric acid. These phosphate salts are
not soluble in nonionic surfactants. Present at levels of about
0.05% by weight, they can impart some haze to the product and
with time may settle. This settling has little if any effect on product
performance. As noted earlier, haze can also result from high
levels of PEG.
Another appearance issue is noted with polyoxyethylene
alkylphenols and other classes of nonionic surfactants. Recall that
these products are polydisperse. From Table 4 we can see, for
example, that the polyoxyethylene (9) nonylphenol contains 5% of
the polyoxyethylene (15) and higher oligomers. At temperatures
below ambient but above the pour point some of these higher
oligomers can solidify, then settle. The result can be a hazy layer
on the bottom of the container. Because there may be some
segregation of product in a drum, it is prudent to assure that the
contents are well mixed if the drum has been left to stand for more
than a few days in colder temperatures. Should a drum freeze,
either partially or completely, the entire contents of the drum
should be melted, then mixed well prior to use. Failure to mix the
entire contents of the drum might lead to the use of a
nonrepresentative sample with uncertain results.
Heated circulated storage tanks are recommended for bulk storage
of polyoxyethylene alkylphenols. As these products are subject to
color development caused by oxidation, temperatures should not
exceed 50°C and the tank head space should be inerted with
nitrogen. Concentrated aqueous solutions of poly-
 Page 59
oxyethylene alkylphenols are corrosive; products sold in this form
must be stored in lined steel, glass fiberreinforced plastic, or
stainless steel tanks.
The viscosity of most polyoxyethylene alkylphenols is about
200300 mPa·s at room temperature. Higher ethoxylates at
temperatures close to their pour points may be more viscous.
Lower ethoxylates may also be higher in viscosity. This is a
reflection of the high viscosity of nonylphenol or the physical state
of octylphenol. The viscosity of these products decreases with
increasing temperature (see Tables 10 and 11).
The density or specific gravity increases with increasing degree of
polyoxyethylation. The rate of change is greatest for lower
ethoxylates. These measurements can be used to follow the
polyoxyethylation reaction.
B
Solution Properties
Polyoxyethylene alkylphenols exhibit a number of interesting
properties related to their solution phase behavior. Most obvious
among these properties to users of these products are the cloud
point and aqueous solution viscosity characteristics.
The cloud point is a very useful and important property of
polyoxyethylene alkylphenols. The cloud point is the temperature
above which an aqueous solution of water-soluble nonionic
surfactant becomes turbid. It is widely agreed [2938] that the
micellar molecular weight of a polyoxyethylated nonionic
surfactant increases with temperature due to reduced surfactant
solubility and increased hydrophobicity caused by dehydration of
the polyoxyethylene chain. This increase in micellar molecular
weight becomes very pronounced as the solution temperature
approaches the cloud point. As temperature increases above the
cloud point, the solution may separate into two phasesone
surfactant-rich, the other water-rich.
Polyoxyethylene alkylphenols with 815 moles of polyoxyethylation
exhibit this cloud point phenomena (see Tables 12 and 13). The
cloud point depends
TABLE 12 Cloud Points of Polyoxyethylene
Nonylphenols [111]
Tergitol Mole ratio Cloud point (°C)
NP-4 4 Insoluble
NP-6 6 Insoluble
NP-7 7 20
NP-8 8 43
NP-9 9 54
NP-10 10.5 63
NP-13 13 83
NP-40 40 >100
 Page 60
TABLE 13 Cloud Points of Polyoxyethylene
Octylphenols [112]
Triton Mole ratio Cloud point (°C)
X-15 1 Insoluble
X-35 3 Insoluble
X-45 5 Insoluble
X-114 7.5 22
X-100 9.5 65
X-102 12 88
X-165 16 >100
X-305 30 >100
X-405 40 >100

strongly on the degree of polyoxyethylation and is an excellent

method of assuring product quality during manufacture. Indeed,
cloud point is the principal specification against which water-
soluble polyoxyethylene alkylphenols are sold.
The cloud point is somewhat dependent on the concentration of
the test solution. Sadaghiania and Khan [39] show that the cloud
point of Triton X-100 drops from 69.5°C at a very low surfactant
concentration to 66°C at about 0.2% by weight. The cloud point is
then constant at 66°C through a concentration of 2% by weight.
Above 2% by weight, the cloud point of Triton X-100 gradually
rises to 90°C at a concentration of 60% by weight. For use as a
production specification, it is important to choose a test
concentration whereby cloud point is not a strong function of
concentration. Polyoxyethylene alkylphenols with more than about
15 moles of polyoxyethylation are too water-soluble to exhibit
cloud points; their solutions are clear to the boiling point. They are
usually specified by molecular weight as calculated from hydroxyl
number. Polyoxyethylene alkylphenols with fewer than 8 moles of
polyoxyethylation are not readily water-soluble. Preferably, they
can be specified by molecular weight. Another common but less
reliable method is to measure their cloud point in a polar solvent
such as an alcohol or a glycol ether. If specified by cloud point, the
product is dissolved in a fixed volume of an alcohol such as
isopropanol. Water is then titrated at fixed temperature into the
alcoholic surfactant solution until the alcohol is diluted to the point
that it no longer solubilizes the surfactant. The volume of water
required to bring on insolubility is then reported as the cloud point
[40].
The aqueous cloud point of polyoxyethylene alkylphenol solutions
will be reduced in the presence of many salts. Figure 1 shows the
effects of electrolytes on the cloud point of Tergitol NP-9. Sodium
chloride is sometimes used to make the cloud points of higher
ethoxylates more distinct. One must be careful to properly prepare
the cloud point solution since the salt concentration can strongly
affect the cloud point. Schott et al. [41] show that acids raise the
cloud
 Page 61

Fig. 1
Effect of electrolyte on the cloud point of 1
wt% Tergitol NP-9.
point of Triton X-100. Han et al. [42] show that many urea
derivatives also increase the cloud point of this surfactant.
The aqueous solution viscosity of concentrated polyoxyethylene
alkylphenol solutions can be very interesting. As surfactant
concentration increases, the aqueous viscosity also increases. At
sufficiently high concentrations the mixture may gel due to the
formation of a complex between the surfactant and water. At even
higher surfactant concentrations the mixture is once again a
viscous liquid. Table 14 and 15 illustrate this behavior. Figure 2 is
a phase diagram for Triton X-114 [43] showing a liquid crystalline
region from about 50% by weight to
TABLE 14 Aqueous Solution Viscosities (mPa·s) of
Polyoxyethylene Nonylphenol at 25°C [113]
Active concentration by weight in water
Mole ratio 10% 20% 30% 40% 50% 60% 70% 80% 90%
7 135 137 204 240 3047 38800 95600 338000 330
8 29 224 615 966 1300 9020 43000 364 305
9 9 76 527 13151690 4560 14300 26500 289
10 3 26 312 Gel Gel 2055 19600 602 307
13 2 6 53 Gel Gel Gel 1035 467 303
15 2 8 35 439 Gel Gel Gel 450 315
40 4 28 182 1775 1071 585 Solid
70 10 53 223 718 1172 1790 1258 Solid Solid
 Page 62
TABLE 15 Aqueous Solution Viscosities (mPa·s) of
Polyoxyethylene Octylphenol [114]
Active concentration by weight in
water
Mole Temp.
Triton 10% 30% 50% 70% 90%
ratio (°C)
X-
7.5 25 100 280 500 27000 320
114
X-
9.5 25 2 80 Gel 530 280
100
X-
12 25 3 20 Gel Gel 310
102
X-
9.5 50 3 40 110 100 80
100
X-
12 50 3 9 Gel 110 80
102

about 80% by weight at 25°C. From Table 15 it can be seen that the
viscosity of Triton X-114 is very high in this region. LaMesa et al.
[44] studied the phase behavior of polyoxyethylene (10)
nonylphenol and found, at room temperature, an apparent
hexagonal mesophase from 37% to 55% by weight. They also
found an apparent lamellar mesophase between 63% and 72% by
weight. From Table 14, the hexagonal mesophase coincides with
gelation of the surfactant solution
 Fig. 2
Phase diagram of Triton X-114.
TABLE 16 Solubility of Polyoxyethylene Nonylphenols in Various Solvents [115]
Butyl Butyl Methylene Mineral Propylene
Ethanol
Carbitol Cellosolve chloride spirits
Mole
Tergitol 10% 50% 10% 50% 10%50% 10% 50% 10% 50% 10%
ratio
NP-4 4 M M M M M M M M M M M
NP-6 6 M M M M M M M M TPL TPL M
NP-7 7 M M M M M M M M TPL TPL M
NP-8 8 M M M M M M M M TPL TPL M
NP-9 9 M SH M SH M M M M TPL TPL M
NP-10 10 M M M M M M M M TPL TPL M
NP-13 13 M M M M M M M M TPL TPL M
NP-40 40 TPL S SH S M M M HZ TSPL S SH
All concentrations % v/v, all measurements at 25°C.
HZ, hazy; M, miscible; S, solid; SH, slightly hazy, settling; TPL, two-phase liquid; TPSL, tw
phase liquid/solid.
 Page 64
TABLE 17 Solubility of Polyoxyethylene Octylphenols in
Various Solvents [116]
Polar organic
Mole solvents (alcohols, Aromatic Aliphatic
Triton
ratio glycols, ethers, hydrocarbonshydrocarbons
ketones, etc.)
X-15 1 Miscible Miscible Soluble
X-35 3 Miscible Miscible Solublea
X-45 5 Miscible Miscible Solubleb
X-
7.5 Miscible Miscible Insoluble
114
X-
9.5 Miscible Miscible Insoluble
100
X-
12 Miscible Insoluble Insoluble
102
X-
16 Miscible Insoluble Insoluble
165
X-
30 Miscible Insoluble Insoluble
305
X-
40 Miscible Insoluble Insoluble
405
a Hazy at 1% in isooctane.
b Can be solubilized by the addition of a suitable coupling
agent such as ethylene glycol, butyl alcohol, hexylene
glycol, or oleic acid.

whereas the lamellar mesophase coincides with a region of high

viscosity. The area between these two mesophases is described as a
solution phase, the viscosity of which is much lower. A similar
result was measured by Beyer in the Triton X-100/D2O system.
The hexagonal phase exists below about 30°C whereas the lamellar
phase exists only below about 5°C [45].
On a practical level, this phase behavior can affect surfactant
dissolution rate. As a droplet of surfactant begins to hydrate and
dissolve, a layer of water and surfactant forms around the droplet.
As the local concentration enters this gel range, diffusion of
surfactant and water is greatly inhibited, thus slowing dissolution.
Gelation can be minimized by raising the temperature of
dissolution: note from Table 15 that Triton X-100 does not appear
to gel at 50°C. This gelation phenomenon is not unique to
polyoxyethylene alkylphenols; it is also seen with alcohol
ethoxylates.
Polyoxyethylene alkylphenols are generally soluble in polar
organic solvents and aromatic hydrocarbons. They are generally
not soluble in aliphatic hydrocarbons. Exceptions are
polyoxyethylene alkylphenols with fewer than 5 moles of
ethoxylation that are soluble up to several percent in aliphatic
hydrocarbons. Tables 16 and 17 summarize the solubility of
various polyoxyethylene alkylphenols in a number of different
solvents.
C
Surface Properties
Surface tension reduction and micelle formation are among the key
features of all surfactants including polyoxyethylene alkylphenols.
Polyoxyethylene alkylphenols reduce surface tension very
effectively as shown by typical values for equilibrium surface
tensions of 0.1% solutions in Tables 18 and 19. For poly-
 Page 65
TABLE 18 Surface Tension of Polyoxyethylene
Nonylphenol Solutions [117]
Mole Surface tension (mN/m), 0.1% active
Tergitol
ratio at 25°C
NP-7 7 30
NP-8 8 30
NP-9 9 30
NP-10 10.5 31
NP-13 13 34
NP-40 40 45

oxyethylene nonylphenols and octylphenols, surface tension is at

its lowest when the product is barely soluble. Surface tension rises
steadily as the degree of polyoxyethylation increases.
In recent years, researchers such as Hua and Rosen [46,47] have
described the maximum bubble pressure technique for measuring
dynamic surface tension. The dynamic surface tension of the
polyoxyethylene alkylphenol solutions in Table 20 are not as low
as the equilibrium values in Tables 18 and 19. Unlike equilibrium
surface tension, where the surface tension is measured after an
equilibrium period measured in minutes, dynamic surface tension
measurement allows surface tension determination at a surface age
of a fraction of a second. Joos et al. [48] developed a model that
shows that results such as these can be explained by a surfactant
diffusion-controlled mechanism. It appears that equilibrium
surface tensions may not be adequate predictors of surfactant
performance in cases where rapid wetting is required. For
example, Green and Green [49] report that dynamic surface tension
as measured by the maximum bubble pressure technique correlated
well with the effectiveness of herbicide solutions applied to weeds.
Performance did not correlate with equilibrium surface tension.
TABLE 19 Surface Tension of Polyoxyethylene
Octylphenol Solutions [118]
Mole Surface tension (mN/m), 0.1%
Triton
ratio active at 25°C
X-45 5 28
X-114 7.5 29
X-100 9.5 30
X-405 12 32
X-165 70%
16 35
activea
X-305 70%
30 37
activea
X-405 70%
40 37
activea
X-705 70%
70 39
activea
a Measured at 0.1% active concentration, corrected
for water content in product as sold.
 Page 66
TABLE 20 Dynamic Surface Tension of
Polyoxyethylene Alkylphenols [119]
Dynamic surface tension (mN/m), 0.1%,
25°C
Bubble
Triton N-101a Triton X-100b
frequency
Equilibrium 30 30
2 Hz 36 35
8 Hz 39 37
a Polyoxyethylene (9.5) nonylphenol.
b Polyoxyethylene (9.5) octylphenol.

TABLE 21 Surface Properties of Polyoxyethylene

Nonylphenols at 25°C
Critical micelle Area per
Mole Aggregation
concentration [120], molecule [121],
ratio number [122]
(µmol) (nm2)
5 36 4.8
6 58 5.5
9 70 6.0
10 100
11 82 6.7
15 93 7.4 52
30 169 19

The micellar behavior of polyoxyethylene alkylphenols is

summarized in Tables 21 and 22. Critical micelle concentration
(CMC) increases with the degree of polyoxyethylation.
Polyoxyethylene nonylphenols have lower CMCs than the
polyoxyethylene octylphenols with the same degree of
polyoxyethylation. That the difference in alkyl group size can lead
to such a large difference in CMC has been recognized for some
time [50]. From the Gibbs equation, the area occupied by the
molecule at the airwater interface can be calculated. The
aggregation number of polyoxyethylene nonylphenol micelles
drops with
TABLE 22 Surface Properties of Polyoxyethylene
Octylphenols at 25°C
Area per
Mole Critical micelle concentration
molecule [124],
ratio [123], (µmol)
(nm2)
7 184 5.8
8 247 6.4
9 290 6.6
10 320 8.0
16 430
40 810
 Page 67
TABLE 23 Ross-Miles Foam Heights of Polyoxyethylene
Nonylphenols [125]
Foam height (mm)
Mole ratio Initial 5 min
6 15 10
9.5 80 60
10.5 110 80
15 130 110
20 120 110
30 120 105
40 115 105
50 100 85
100 75 50
Sodium lauryl sulfate [127] 160 140
0.1% Solutions, 25°C

TABLE 24 Ross-Miles Foam Heights of Polyoxyethylene

Octylphenols [126]
Foam height (mm)
Mole ratio Initial 5 min
4.5 20 10
7.5 60 40
9.5 110 100
12 120 100
Sodium lauryl sulfate [127] 160 140
0.1% Solutions, 25°C.

increasing degree of polyoxyethylation. Many researchers have

studied the aggregation number of Triton X-100, polyoxyethylene
(9.5) octylphenol: in water at or near 25°C values range from 100
(measured by Dwiggins et al. [51] by ultracentrifugation) to 111
(measured by Mankowich [52] by light scattering) to 140 (reported
by Kushner and Hubbard [53], again by light scattering).
TABLE 25 Draves Wetting Times for Polyoxyethylene
Nonylphenols [128] at 25°C
Wetting time (s)
Tergitol Mole ratio 0.05% 0.10% 0.20%
NP-8 8 27 8 3
NP-9 9 21 8 3
NP-10 10.5 23 9 2
NP-13 13 26 16 8
 Page 68
TABLE 26 Draves Wetting Times for Polyoxyethylene
Octylphenols [129] at 25°C
Active Ingredient (wt%) for wetting time of
Mole
Triton 10 s 25 s 50 s
ratio
X-35 3 0.36 0.18 0.11
X-45 4.5 0.10 0.055 0.034
X-114 7.5 0.096 0.050 0.031
X-100 9.5 0.092 0.048 0.028
X-102 12 0.123 0.064 0.045
X-165 16 0.780 0.330 0.170

The foaming characteristics of polyoxyethylene alkylphenols are

given in Tables 23 and 24. Initial RossMiles foam heights of
polyoxyethylene nonylphenols pass through a maximum at a mole
ratio of about 10, at all mole ratios foam height drops slightly in 5
min. Polyoxyethylene (6) nonylphenol foams very little as it is
barely soluble in water at 25°C. By comparison, sodium lauryl
sulfate, an anionic, has significantly higher initial and 5-min foam
heights. Similar trends are noted for polyoxyethylene octylphenols.
The wetting performance of polyoxyethylene alkylphenols is given
in Tables 25 and 26. In Table 25, the times required to achieved
wetting in the Draves test are listed for several products at three
concentrations. Wetting occurs most rapidly with products that are
just water-soluble; performance drops rapidly with increasing
degree of polyoxyethylation. Table 26 reports the concentration of
surfactant required to achieve a given wetting time; lower wetting
concentrations are considered to be better. Again, optimum
performance occurs with products that are just soluble in water
under test conditions.
V
Applications
The uses of polyoxyethylene alkylphenols cover a wide a range of
industries from cleaning systems to paints and coatings to
agricultural chemicals. A summary of product uses is given in
Table 27. Specific examples of interesting uses are described
below.
A
Detergents
Cleaning systems can include many things, from cleaning of
clothing to soil remediation. Dry cleaning detergents can use
polyoxyethylene alkylphenols, often in combination with other
surfactants [54]. Liu et al. [55] found polyoxyethylene
nonylphenols and octylphenols with mole ratios of oxyethylene of
912 to the most effective surfactants in their study of the removal
of polycyclic aromatic hydrocarbons from soil. Osberghaus and
Kresse describe powdered dry cleaning systems for carpets using
polyoxyethylene alkylphenols [56].
 Page 69
TABLE 27 Applications of Polyoxyethylene Alkylphenols
[130]
Agriculture Paint
Emulsion polymerization of
Emulsifiers and wetters
latexes
Herbicidal adjuvants Latex stabilization
Pigment wetting and
Fruit washes
dispersion
Cleaners Paper
Household detergents Pulping
Dry cleaning detergents Absorbent papers
Industrial hand cleaners De-inking wastewater
Detergents/sanitizers Wet-felt washing
Solvent degreasers Adhesives
Metal cleaners
Hard surface cleaners Textiles
Commercial laundry
Greige goods scouring
detergents
Bleaching
Dust wetting Carbonizing of wool
Coal mines Scouring agent
Ceramic industries Desizing agent
Foundries Wetting and rewetting agents
Polyethylene softener
emulsifiers
Mineral oil and solvent
Leather
emulsifiers
Hide soaking Fiber lubricant emulsifiers
Degreasing Dye-leveling agents
Fat liquor stabilization Resin bath additives
Tanning and dyeing
Aqueous laundry detergents can also use polyoxyethylene
alkylphenols. Schwarts [57] describes the use of a mixture of
polyoxyethylene dodecylphenol and nonylphenol in a detergent for
the machine washing of delicate cotton articles. Merrill and Wood
[58] describe the use of polyoxyethylene alkylphenols in
combination with an anionic surfactant for use in low-foaming
powdered laundry detergents. Harrison and Weller [59] discuss the
use of polyoxyethylene alkylphenols in liquid laundry detergents
containing anionic and cationic surfactants. These cleaners not
only are good detergents but also have very effective microbiocidal
properties due to the inclusion of the cationic surfactant.
Polyoxyethylene alkylphenols can also clean hard surfaces.
Scardera et al. [60] invented an emulsion cleaner to clean surfaces
contaminated by chemical warfare agents. Polyoxyethylene (6)
alkylphenol is suggested to serve as an emulsifier for solvents that
are used in this emulsion cleaner. Fuggini and Streit [61] invented
a hard surface cleaner that effectively removes dirt and grease,
leaving a protective barrier to repel soil. The preferred
composition includes 2% of polyoxyethylene (9) nonylphenol.
Magyar [62] includes polyoxyethylene nonylphenol and
octylphenol among the possible ingredients in an automotive
 Page 70
cleaner well suited to cleaning whitewall tires, vinyl tops, and
fabric interiors. Another automotive cleaner is described by Smith
[63]; this one can contain polyoxyethylene nonylphenol with 910
moles of polyoxyethylation and is safe for use on clear-coated
alloy wheels and painted surfaces. Polyoxyethylene alkylphenols
are also useful in industrial metal cleaners. Sturwold [64] describes
their use in cleaners to remove grease, oil, dirt, scale, and metal
fines from metals.
It has generally been the experience of the authors that
polyoxyethylene nonylphenols are very effective for the cleaning
of textiles. On the other hand, polyoxyethylene octylphenols are
more widely used for cleaning hard surfaces.
B
Metalworking
Metalworking fluids cool and lubricate in cutting, grinding, and
metal forming operations. Modern fluids include oils containing
surfactants that act as emulsifiers when added to water by the end-
user. Although the predominant emulsifiers are sodium petroleum
sulfonates, polyoxyethylene nonylphenols are also used in hard
water systems or to provide special emulsion characteristics [65].
C
Paints and Coatings
Polyoxyethylene alkylphenols are also found in paints and
coatings. They are frequently used as stabilizers for latex particles;
they are almost always used in conjunction with anionic
surfactants. Polyoxyethylene alkylphenols used for stabilization are
the higher mole ratio products, such as polyoxyethylene (15)
through polyoxyethylene (70), since their physical size contributes
greatly to steric stabilization. Polyoxyethylene alkylphenols are also
used as wetting agents in finished paints. Typical products are
polyoxyethylene (7) through polyoxyethylene (10). It is generally
accepted that polyoxyethylene alkylphenols are much more
effective in this application than polyoxyethylene alcohols. In the
experience of the authors, polyoxyethylene octylphenols are more
generally used than polyoxyethylene nonylphenols in the
manufacture of latexes used in paints and coatings, whereas
polyoxyethylene nonylphenols are more commonly used in the
formulation of finished paints and coatings.
D
Agriculture
Surfactants can serve several purposes in agricultural formulations.
They may serve as emulsifiers or dispersants when a concentrate
of water-insoluble active materials is diluted for use. The wetting
ability of surfactants is used to enhance the leaf wetting
characteristics of spray adjuvants. In a discussion of surfactant use
in herbicide dispersions, Sonntag [66] shows that polyoxyethylene
nonylphenols and octylphenols are very effective at reducing the
surface tension and contact angle of herbicide solutions on plant
leaves.
 Page 71

VI
Environmental Issues
A comprehensive review of the environmental and toxicologic
aspects of alkylphenols and polyoxyethylene alkylphenols is given
in Sylvia Talmage's Environmental and Human Safety of Major
Surfactants [67]. An extensive text on biodegradation of
surfactants was written by Swisher [68].
A
Biodegradation
A vast number of laboratory-based biodegradation studies have
been performed on polyoxyethylene alkylphenols with the degree
of biodegradation ranging from zero [69] to 100% [70], depending
on the test methods used and the duration of the experiments. A
few of the known biodegradation test results for alkylphenols and
the polyoxyethylene alkylphenols are summarized in Table 28.
It is generally accepted that the rates of biodegradation of
polyoxyethylene nonylphenols and polyoxyethylene octylphenols
are slower than those of nonionic surfactants produced with linear
hydrophobes, such as the polyoxyethylene alcohols [71]. However,
studies of environmental levels of alkylphenols as well as the
degree of their removal from wastewater suggest that the
biodegradation rates are sufficient enough to prevent accumulation
in the aquatic environment [72]. Extensive research is underway
internationally, within government (U.S. Environmental Protection
Agency and the European Union), academia, and industry [through
the Chemical Manufacturer's Association (CMA)] with the aim of
understanding the potential risk of alkylphenols and
polyoxyethylene alkylphenols to the environment [73].
Biodegradation of the polyoxyethylene alkylphenols can occur via
either an aerobic or an anaerobic pathway. The aerobic pathway
generates lower moleweight ethoxylates, carboxylic acid
derivatives of both the ethoxylate and hydrophobe chain [74,75],
unspecified intermediate biodegradation products, and ultimate
biodegradation products (water and carbon dioxide). There is no
evidence that alkylphenol is generated during the aerobic
biodegradation process. The anaerobic pathway generates lower
mole-weight ethoxylates, alkylphenol, unspecified intermediate
metabolites, and ultimately, carbon dioxide and methane. It is
presumed that anaerobic digestion of the carboxylic acid
intermediates may also produce alkylphenol in the route to ultimate
biodegradation. The major source of alkylphenol in the
environment is through anaerobic digestion of the parent
surfactant and the subsequent biodegradation intermediates.
B
Risk Assessment
In its simplest form, risk assessment is carried out by comparing
the levels of a compound in the environment (i.e., exposure levels)
with measured toxicity levels (i.e., ''effect" levels). The definition
of "risk" is somewhat contentious,
 Page 72
TABLE 28 Summary of Select Biodegradation Studies
Compound Test Endpoint (analysis) %BiodegradationRef.
28-day closed 28-day BOD as %
NPE-9 45(28 day only) 131
bottle ThOD
28-day
% DOC removal
Screening 61/66/70/72 131
(7/14/21/28)*
(OECD)
28-day
% DOC removal
NPE-13 Screening 66/56/70/72 131
(7/14/21/28)
(OECD)
BOD ad % ThOD
OPE-10 20-day BOD 30/40/49/51 131
5/10/15/20
28-day closed
bottle (OECD) % BOD 11/34/36 11/34/36 131
5/15/28
28-day % DOC removal
58/62/80/90 131
screening, 7/14/21/28
Semi continuous
OPE-8 %DOC removal 40% in 1 day 132
activated sludge
NPE-4 58% in 1 day 132
NPE-9 55% in day 132
Continuous-flow
APE-8 UV spectroscopy >76% 133
activated sludge
River water
OPE-9 Cobalt thiocyanate 68% in 11 days 134
dieaway
NPE-9 91% in 16 days 134
Sludge treated
NP HPLC/UV 80% in 3 weeks 135
soil
NPE-1 135
NPE-2 135
Continuous-flow 98100% in 8
NPE-9 Cobalt thiocyanate 136
activated sludge hours
Foam >95% in 8 hours 136
 Radiolabel3H2O 1042% in 8
production (EO chain hours 136
label)
Radiolabel14-CO2
4759% in 8
production (hydrophobe hours 136
label)
*7/14/21/28 represent the days on which the system was sampled.
NPE-n, polyoxyethylene (n) nonylphenol; OPE-n, polyoxyethylene (n)
octylphenol; APE-n, polyoxythylene (n) alkylphenol; NP, nonylphenol.

but if exposure levels are sufficiently lower than the effect levels,
then the compound is generally not considered to pose an
unacceptable environmental risk. Factors in an assessment of risk
include use patterns, route of entry into the environment, fate of
the material and its metabolites, biodegradation pathways (and
rates), actual levels in the environment, routes of exposure to the
organism, potential exposure levels, potential for uptake (and
elimination) by the organism, and the number of species tested for
"effects."
For risk assessment, the following quantities are commonly used:
NOEC: No Observable Effects Concentration, the level at which
no observable effect is noted for a given species (for a specific
endpoint, such as growth or survival)
 Page 73
LOEC: The Lowest Observable Effects Concentration, the lowest
concentration at which effects are observed
MATC: Maximum Allowable Toxicant Concentration, the
geometric mean of the NOEC and LOEC
Generally, a comparison of the MATC (used predominantly in the
United States) or the NOEC (used predominantly in Europe) with
measured or predicted environmental levels gives an estimate of
the risk. If the environmental levels are sufficiently lower than the
MATC or NOEC, then the risk to the environment is considered
low [76].
C
Aquatic Exposure/Toxicity
1
Environmental Levels of Alkylphenols and Polyoxyethylene
Alkylphenols
Table 29 summarizes levels of alkylphenols and polyoxyethylene
alkylphenols in various aquatic environmental compartments. The
lypophilicity of the alkylphenols and their corresponding 1- and 2-
mole ethoxylates cause the concentrations of these species to be
two to four orders of magnitude higher in the sediment than in the
water column. Actual levels measured in the sediment depend on
the organic carbon content and particle size (i.e., a higher surface
area allows for a higher concentration of alkylphenol adsorption
per kilogram of soil).
Sediment levels of nonylphenol in the United States have ranged
from <2.9µg/kg to 2900 µg/kg (average = 162, with 28% of the
samples having less than the minimum detection limit, or MDL, of
2.9µg/kg) [77]. The corresponding water column concentrations of
nonylphenol ranged from <0.11 to 0.64 (average = 0.12 with 70%
of the samples having less than the MDL of 0.11µg/L).
In Switzerland (Glatt River), sediment concentrations of
nonylphenol have ranged from 190 to 13,100 µg/kg, with
corresponding water column concentrations ranging from <0.3 to
7.9 µg/L (60% of the samples had <2 µg/L) [78]. In Venice, Italy,
the values in the sediments ranged from 5 to 42 µg/kg (with
corresponding water column levels of 0.644.30 µg/L) [79]. It is
important to note that the highest sediment and water column
values observed (Grand Calumet River, United States, and Glatt
River, Switzerland) represent highly polluted areas with little or no
history of secondary treatment; rivers receiving treated discharges
showed substantially lower levels of nonylphenol in both the
sediment and water column.
Bottom-feeding species are potentially exposed to nonylphenol in
the sediment interstitial pore water. Nonylphenol concentrations in
the interstitial pore water are estimated from sediment
concentrations using the following relationship [80]:
 Page 74
TABLE 29 Surface Water Exposure Concentrations of NPEs
Compound Levels(µg/L) Ref.
Italy, several streams NPE 0.644.30 137
<0.08 (n=9) 138
UK estuaries NP
3.1 (n=1) 138
<MDL (n=11) 138
UK rivers NP 0.21.6 (n=12) 138
9.0 (n=1) 138
<MDL (n=1) 138
UK River Aire NP
2453 (n=5) 138
<0.110.64µg/L
(N=98) 139
US, 30 rivers NP
(70% of samples 139
<MDL of 0.11)
NPE-1
<0.060.60 139
NPE-2
<0.071.20 139
NPE-3-
<1.614.9 139
NPE-17
US, subset of 30 riversNPE-1-C <0.072.02µg/L(N=8) 140
<0.075.22 µg/L
NPE-2-C 140
(N=8)
NPE-3-C 140
<0.07µg/L(N=8)
NPE-4-C 140
<0.07µg/L(N=8)
US, New Jersey
drinking water sample NP Not reported 141
(n=1)
NPE-1,
NPE-2
0.1110.113µg/L 141
NPE-3-
0.0620.129µg/L 141
NPE-7
0.164µg/L 141
NPE-2-C
0.0040.016 141
NPE-3-C-
NPE-7-C
Switzerland, Glatt NP <0.37.9 (<N=10) 142,143,144,
River 145,146,147
60% of samples
"
NPE-1 <2µg/L
"
NPE-2 <0.320(n=110)
"
NPE-1-C <0.321 (N=110)
"
NPE-2-C <129 (N=48)
"
2.059 (N=48)
NP, nonylphenol; NPE-n, polyoxyethylene (n) nonylphenol; NPE-n-
C, polyoxyethylene (n) nonylphenol carboxylate.

whereCw = interstitial aqueous concentration of the analyte

Csed = sediment concentration of the analyte
Foc = organic fraction of the sediment
Koc = partition coefficient of nonylphenol between
the sediment and water = 3825
 Page 75
The calculated levels of alkylphenol in interstitial pore waters are
roughly equivalent to the levels measured in the river water above
the sediment. For example, the calculated interstitial water
concentration of nonylphenol was 1.2 µg/L using the sediment
concentration of 2900 µg/L (Grand Calumet River, United States).
The river water concentration of nonylphenol for the Grand
Calumet was measured at 0.64 µg/L.
2
Aquatic Toxicity of Alkylphenols and Polyoxyethylene
Alkylphenols
The aquatic toxicity of the polyoxyethylene alkylphenols and their
breakdown products are inversely proportional to the
hydrophobicity of the product. Generally, alkylphenols are at least
an order of magnitude more toxic to aquatic species than the 10-
mole (and higher) ethoxylates of the alkylphenols. There is a
relatively large database of toxicity data for the alkylphenols and,
in particular, for nonylphenol. A summary of a few key acute and
chronic aquatic toxicity levels is given in Tables 30 and 31.
The lowest MATC for nonylphenol is approximately 5 µg/L (for
the Mysid Shrimp; Table 31). In the United States, the highest level
of nonylphenol (including calculated sediment pore water
concentrations) was 1.2 µg/L. These data came from the "Thirty
Rivers Study," which was designed so that the measured
environmental levels would adequately reflect the river
concentrations of nonylphenol (and the polyoxyethylene
alkylphenols) in the entire United States [81].
Because the highest level of nonylphenol in U.S. water is
significantly lower than the lowest observed MATC, the risk of
nonylphenol to the U.S. environment is considered low.
For the United Kingdom, the highest levels of nonylphenol were
23 to 53 µg/L (River Aire). For all of the other rivers sampled, the
levels of nonylphenol were from 0.02 to 1.6 µg/L. The River Aire,
like the Grand Calumet River (United States), is a highly polluted
area receiving domestic and industrial
TABLE 30 Acute Effects (Aquatic)
No. Level,
Surfactant Test
species (µg/L)
Nonylphenol:
Fish 9 96-h LC50 1303000
24- to 96-h LC-
Invertebrates 9 433000
50
Algae 4 Various 257500
Polyoxyethylene nonylphenol:
24- to 96-h LC-
Fish 10 130018,000
50
24- to 96-h LC-
Invertebrates 17 10050,000
50
Algae 13 Various 210100,000
Compiled from Ref. 148.
 Page 76
TABLE 31 Chronic Effects (Aquatic)
NOEC, LOEC,
Organism Endpoint Compound
(µg/L) (µg/L)
Fish:
Fathead Growth, 28-day NP 23
14
minnow Survival, 33-day NP 7.4
Rainbow
Growth/survival (91-day) NP 6.3 10.3
trout
Invertebrates:
Daphnia
21-day assay NP 24
magna 6.7
Growth, 28-day NP 3.9
Mysid 9.1
Survival, 29-day NP 6.7
shrimp
Ceriodaphnia Reprod., 7-day NP 89 202
dubia Survival, 7-day NP 202 377
Ceriodaphnia Reprod., 7-day NP1.5 285 886
dubia Survival, 7-day NP1.5 285 886
No
35-day fertilization and
Mytilus edulis NP effects at
reproductive effects
>200µg/L
14-day sublethal effects:
NP 39
interstitial water exposure
Chironomus NP 76
dosed water exposure
tentans NP 143
interstitial water dosed
NP 20 mg/kg
sediment
Plants:
Selanastrum
sp. NP 694 1480
Green algae
Lemna
minor NP 901 2080
Duckweed
Data from Refs. 149151.
waste with little or no secondary treatment [82]. In Switzerland the
highest levels of nonylphenol were 7.9 µg/L [83] (60% of the
samples had <2 µg/L nonylphenol).
D
Mammalian Toxicity
In general, alkylphenols are of a low order of acute toxicity (oral
and cutaneous LD50 values >2 g/kg body weight) and subchronic
toxicity (no specific target organ toxicity has been shown at high
doses) [84]. The toxicity of the polyoxyethylene alkylphenols
decreases as the degree of polyoxyethylation increases. The 1- and
2-mole ethoxylates show a similar toxicity to the starting
alkylphenol. Although alkylphenols and the lower mole
polyoxyethylene alkylphenols are generally considered only
minimally toxic to mammals, they can cause severe skin and eye
irritation with possible permanent damage to the cornea.
 Page 77
Alkylphenols and the low-mole polyoxyethylene alkylphenols
have been shown to exhibit very weak estrogenic activity in
screening assays [85,86]. At the time of writing, there is extensive
research and evaluation of a large class of environmental
estrogens, including those derived from natural sources, such as
soybeans [87]. Presently, there is no consensus in the scientific
community on the relevance of chemicals with estrogenic activity
in the environment, particularly those such as nonylphenol which
show a very low estrogenic response in in vivo screening assays.
A rigorous assessment of exposure of alkylphenols and
polyoxyethylene alkylphenols to mammals has not been
performed. Exposure through drinking water that had measured
levels of 0.2 µg/L nonylphenol in one study is not considered a
significant source of alkylphenol from a toxicity standpoint [88].
Polyoxyethylene alkylphenols are commonly applied directly to
agriculture; however, the uptake of alkylphenol into common crop
plants was not detected [89]. Thus, the ingestion of
alkylphenols/polyoxyethylene alkylphenols through agriculture is
minimal. Polyoxyethylene alkylphenols are also used in the
manufacture of plastic food containers; however, the potential for
absorption into food has not been quantified. Finally, it has been
postulated that mammalian exposure may occur through the
consumption of fish, which may concentrate alkylphenol from the
water. Table 32 summarizes the bioconcentration factors of
nonylphenol for fish, invertebrates, and algae. Actual levels of
alkylphenols and polyoxyethylene alkylphenols ingested via fish
consumption have not been determined. However, a single mallard
duck that was captured and sacrificed contained levels of
nonylphenol similar to the fish in the nearby river [90].
TABLE 32 Bioconcentration Factors
Organism BCF Ref.
Invertebrates:
Shrimp 90110 152
Mussels 1.413 153
3430 154
General invertebrates, predicted from
530 155
log Kow = 4.45 and 1.75% lipid
Fish:
Stickleback 1250 156
Fathead minnow 270, 350 157
Salmon 10280 158
General fish, predicted from log Kow 1510 159
and 5% lipid
Microalga 20010,000 160
Aquatic plants 200500 est
BCF = (concentration of test chemical in an
organism)/(freely dissolved water concentration).
 Page 78
E
Other Environmental Issues
It has been demonstrated that activated sludge treatment techniques
remove 9097% of polyoxyethylene alkylphenols from water [91].
However, the efficiency of alkylphenol and polyoxyethylene
alkylphenol removal depends on the treatment conditions, and a
wide range of treatment capabilities have been reported (Table 33)
[92]. Trickling filter waste treatment facilities do not effectively
remove alkylphenols and polyoxyethylene alkylphenols,
presumably because the contact time between the wastewater and
active bacteria is relatively low [93].
Polyoxyethylene alkylphenols are commonly applied directly to the
environment as agricultural adjuvants. Sludge from water
treatment plants (using the activated sludge process), with
measured levels of nonylphenol ranging from 0.01 to 1 g/kg (dry
sludge) is often applied directly to crops as a fertilizer [9496]. Data
on the fate of this nonylphenol are very limited, but one study has
shown that it is reduced to 90% of its original value within 20 days
[97]. Marcomini found that for nonylphenol in sludge applied to
land, >80% of the biodegradation took place within the first month
[98]. Kirchman and Tengsved
TABLE 33 Wastewater Treatment of Polyoxyethylene
Alkylphenols
Location %Removal Ref.
February, average removal of all
Italy, 3 WWTPs 161
APEs = 96.9% (range 93.099.5%)
June, average removal of all APEs
161
= 98.6% (range 98.398.8%)
Overall effluent conc: 0.7412.0
 µg/L NPE 161
Average removal = 97.5% of NP
US, 12 plants (1990s) and NPE combined (range 162
92.599.8%)
Overall NP conc:<0.2015.3 µg/L 162
Overall NPE-1-NPE-17 conc:
162
<5261 µg/L
Canada, 4 plants, 8 NPE range 0.8015.1 µg/L: OP range
163
final effluents 0.120.170 µg/L
UK, 16 sewage
NP dissolved range <0.105.4 µg/L
treatment plants, 8 164
(average = 0.90 µg/L)
rivers
Switzerland, several
NP 77% removal, NPEs 3198%
sites in the Glatt 165
removal
Valley
Hosel (trickling filter) APE 70%
German treatment
removal (March), 75% removal 166
plants
(Sept)
APE, polyoxyethylene alkylphenol; NP, nonylphenol; NPE-n,
polyoxyethylene (n) nonylphenol; OP, octylphenol.
 Page 79
[99] showed that there was little or no uptake of nonylphenol by
agricultural crops.
The aerobic degradation of polyoxyethylene alkylphenols can
result in carboxylic acid intermediates which are not detected using
the normal HPLC/UV analytical techniques for alkylphenol and
polyoxyethylene alkylphenols. Ahel and Giger have monitored
these compounds and have postulated that they represent a major
portion of polyoxyethylene alkylphenols in the environment [100].
Levels (where n = 0.1) ranged from 2 to 116 µg/L in the Glatt
River, in Switzerland. A preliminary examination of these same
compounds in U.S. rivers found much lower levels ranging from
<0.04 to 6 µg/L [101].
The acute toxicity of the ether carboxylates (LC50) (n = 0.1) has
been determined to be approximately six times lower than for
nonylphenol [102]. However, these data are based on one species
of fish (Oryzias latipsekillfish), and no chronic effects have been
measured.
In the United States, the risk of alkylphenols and polyoxyethylene
alkylphenols to the environment is low. Even so, the Chemical
Manufacturer's Association continues to sponsor research to more
fully understand the environmental fate and effects of alkylphenols
and polyoxyethylene alkylphenols. In addition, the U.S.
Environmental Protection Agency, the United Kingdom's
Department of the Environment, the U.S. Interagency Testing
Committee, the World Health Organization through the
International Programme for Chemical Safety, and the European
Union are presently conducting environmental risk assessments of
alkylphenols and their polyoxyethylene derivatives. Recent
information on environmental issues may be obtained from Ref.
103.
Acknowledgments
The authors thank Connie E. Carroll, Kimberly A. Fisher, Mark J.
McGuiness, Albert F. Joseph, Frank H. Kasnick, Jane C. Kimble,
Martin J. Kollmeyer, Thomas A. Maliszewski, Leonard A. Neubert,
Jace D. Patton, Charles A. Smith, Barbara A. Stefl, M. Jane Teta,
John P. Van Miller, James B. White, James B. Williams, Cheryl M.
Wizda (Union Carbide Corporation), Carter G. Naylor (Huntsman
Corporation), and Charles A. Staples (Assessment Technologies,
Inc.) for their help in the preparation of this chapter.
References
1. H. A. Bruson and O. Stein, U.S. Patent 2,075,018, to Rohm and
Haas Co. (1937).
2. A. A. Green and J. W. McBain, J. Phys. Colloid Chem. 51:286
(1947).
 Page 80
3. E. Gonick and J. W. McBain, J. Am. Chem. Soc. 69:334 (1947).
4. A. S. Davidsohn and B. Milwidsky, Synthetic Detergents, 7th
ed., Longman, Essex, England, 1987, pp. 181182.
5. J. P. Dever, K. F. George, W. C. Hoffman, and H. Soo, in Kirk-
Othmer Encyclopedia of Chemical Technology, 4th Ed., Vol. 20
(M. Howe-Grant, ed.), Wiley, New York, 1994, pp. 915959.
6. J. Lorenc, G. Lambeth, and W. Scheffer, in Kirk-Othmer
Encyclopedia of Chemical Technology, 4th Ed., Vol. 2 (M. Howe-
Grant, ed.), Wiley, New York, 1992, pp. 131133.
7. C. R. Enyeart, in Nonionic Surfactants (M. Schick, ed.), Marcel
Dekker, New York, 1967, p. 82.
8. J. Lorenc, G. Lambeth, and W. Scheffer, in Kirk-Othmer
Encyclopedia of Chemical Technology, 4th Ed., Vol. 2 (M. Howe-
Grant, ed.), Wiley, New York, 1992, p. 135.
9. V. Ravendino and P. Sasseti, J. Chromatography 153:181 (1975).
10. H. Fujii, Japanese Patent 48,015,840 to Sugai Chemical Ind.
Co. Ltd. (1973).
11. C. L. Jarreau, Sr., U.S. Patent 4,055,605 to Calumet
Petrochemical (1977).
12. J. F. Knifton and Y. E. Sheu, U.S. Patent 5,171,896 to Texaco
Chemical Co. (1992).
13. J. Klimiec, J. Kolt, and J. Marszycki, Chinese Patent 1,082,530-
A to Inst Ciezkiej Syntezy Orga (1994).
14. J. F. Knifton, U.S. Patent 5,300,703 to Texaco Chemical Co.
(1994).
15. K. Yamauchi, K. Hashimoto, Y. Kera, S. Uemura, and M.
Kajiwara, Japanese Patent 05,329,374 to Nitsusei Kagaku
Kogyosho KK (1993).
16. P. Dai, J. F. Knifton, and Y. E. Sheu, U.S. Patent 5,276,215 to
Texaco Chemical Co. (1994).
17. P. P. Kapustin, P. S. Belov, A. P. Vorozheikin, Y. I. Ryazanov, V.
F. Podtikhov, K. D. Korenev, and V. A. Zavorotnyi, Soviet Union
Patent 1,544,762 to Nizhnekamskneftekhim Industrial Enterprises
and Moscow Institute of the Petrochemical and Gas Industry
(1990).
18. H. Alfs et al., German Patent 2,346,273, to Chemische Werke
Huls AG (1973).
19. H. Fiege, in Ullman's Encyclopedia of Industrial Chemistry,
Vol A19, 5th Ed. (B. Elvers, S. Hawkins, and G. Schulz, eds.),
VCH, New York, 1991, p. 321.
20. J. Lorenc, G. Lambeth, and W. Scheffer, in Kirk-Othmer
Encyclopedia of Chemical Technology, 4th Ed., Vol. 2 (M. Howe-
Grant, ed.), Wiley, New York, 1992, pp. 126127.
21. J. Lorenc, G. Lambeth, and W. Scheffer, in Kirk-Othmer
Encyclopedia of Chemical Technology, 4th Ed., Vol. 2 (M. Howe-
Grant, ed.), Wiley, New York, 1992, p. 128.
22. J. Lorenc, G. Lambeth, and W. Scheffer, in Kirk-Othmer
Encyclopedia of Chemical Technology, 4th Ed., Vol. 2 (M. Howe-
Grant, ed.), Wiley, New York, 1992, pp. 135137.
23. P. Fanelli, 83rd Am. Oil Chemists Soc. Annual Meeting &
Expo, Toronto, 1992.
24. P. Fanelli, 83rd Am. Oil Chemists Soc. Annual Meeting &
Expo, Toronto, 1992.
25. C. R. Enyeart, in Nonionic Surfactants (M. Schick, ed.),
Marcel Dekker, New York, 1967, pp. 6270.
26. Igepal CO-430 Material Safety Data Sheet, Rhone-Poulenc
Surfactants and Specialties (1993).
27. C. R. Enyeart, in Nonionic Surfactants (M. Schick, ed.),
Marcel Dekker, New York, 1697, p. 68.
28. P. Fanelli, 83rd Am. Oil Chemists Soc. Annual Meeting &
Expo, Toronto, 1992.
 Page 81
29. K. Kuriyama, Kolloid Z. 180:55 (1962).
30. K. Kuriyama, Kolloid Z. 181:144 (1962).
31. K. Kuriyama, H. Inoue, and T. Nakagawa, Kolloid Z. 183:68
(1962).
32. R. R. Balmbra, J. S. Clunie, J. M. Corkill, and J. F. Goodman,
Trans. Faraday Soc. 58:1661 (1962).
33. P. H. Elworthy and C. B. Macfarlane, J. Chem. Soc. 1963:907
(1963).
34. R. R. Balmbra, J. S. Clunie, J. M. Corkill, and J. F. Goodman,
Trans. Faraday Soc. 60:979 (1964).
35. C. W. Dwiggins, Jr., and R. J. Bolen, J. Phys. Chem. 65:1787
(1961).
36. M. J. Schick, J. Phys. Chem. 67:1796 (1963).
37. M. E. Ginn, F. B. Kinney, and J. C. Harris, J. Am. Oil Chemists
Soc. 37:183 (1960).
38. J. M. Corkill, J. F. Goodman, and S. P. Harrold, Trans. Faraday
Soc. 60:202 (1964).
39. A. S. Sadaghiania and A. Khan, J. Colloid Interf. Sci. 144:191
(1991).
40. J. Cross, in Nonionic Surfactants Chemical Analysis (J. Cross,
ed.), Marcel Dekker, New York, 1987, p. 381.
41. H. Schott, A. E. Royce, and S. K. Han, J. Colloid Interf. Sci.
98:196 (1984).
42. S. K. Han, S. M. Lee, and H. Schott, J. Colloid Interf. Sci.
126:393 (1988).
43. R. Heusch and F. Kopp, Ber. Bunsenges. Phys. Chem. 24:806
(1987).
44. C. LaMesa, B. Sesta, A. Bonincontro, and C. Cametti, J.
Colloid Interf. Sci. 125:634 (1988).
45. K. Beyer, J. Colloid Interf. Sci. 86:73 (1982).
46. X. Y. Hua and M. J. Rosen, J. Colloid Interf. Sci. 124:652
(1988).
47. X. Y. Hua and M. J. Rosen, J. Colloid Interf. Sci. 141:180
(1991).
48. P. Joos, J. P. Fang, and G. Serrien, J. Colloid Interf. Sci.
151:144 (1992).
49. J. H. Green and J. M. Green, Brighton Crop Prot. Conf.Weeds,
Vol. 1, pp. 323330, 1991.
50. L. Hsia, H. N. Dunning, and P. B. Lorenz, J. Phys. Chem.
60:657 (1956).
51. C. W. Dwiggins, Jr., R. J. Bolen, and H. N. Dunning, J. Phys.
Chem. 64:1175 (1960).
52. A. M. Mankowich, J. Phys. Chem. 58:1027 (1954).
53. L. M. Kushner and W. D. Hubbard, J. Phys. Chem. 58:1163
(1954).
54. M. Wentz, in Detergency Theory and Technology (W. G. Cutler
and E. Kissa, eds.), Marcel Dekker, New York, 1987, pp. 463465.
55. Z. Liu, S. Laha, and R. G. Luthy, Water Sci. Technol. 23:475
(1991).
56. R. Osberghaus and F. Kresse, German Patent 3,444,959, to
Henkel KGaA (1986).
57. L. F. Schwartz, U.S. Patent 4,588,516 (1986).
58. C. L. Merrill and D. L. Wood, U.S. Patent 5,034,158, to Shell
Oil Co. (1991).
59. K. A. Harrison and J. M. Weller, U.S. Patent 4,810,409 to
Sterling Drug, Inc. (1989).
60. M. Scardera, J. Floyd, and F. S. Natoli, U.S. Patent 4,744,917,
to Olin Corp. (1987).
61. C. L. Fuggini and A. L. Streit, U.S. Patent 4,948,531, to Sterling
Drug, Inc. (1990).
62. A. M. Magyar, U.S. Patent 4,670,171, to Pennzoil Co. (1987).
63. R. E. Smith, U.S. Patent 4,895,675, to Pro-Max Performance
(1990).
64. B. J. Sturwold, U.S. Patent 4,675,125, to Cincinnati Vulcan Co.
(1987).
65. J. C. Childers, in Metalworking Fluids (J. P. Byers, ed.),
Marcel Dekker, New York, 1994.
66. N. O. V. Sonntag, in Surfactants in Chemical/Process
Engineering (D. T. Wasan, M. E. Ginn, and D. O. Shah, eds.),
Marcel Dekker, New York, 1988.
 Page 82
67. S. S. Talmage, in Environmental and Human Safety of Major
Surfactants, Alcohol Ethoxylates and Alkylphenol Ethoxylates
(The Soap and Detergent Association), Lewis, Boca Raton, FL,
1994.
68. R. D. Swisher, in Surfactant Biodegradation, Marcel Dekker,
New York, 1987.
69. L. Vaicum, M. Cicei, and L. Stefanescu, Studii Epurarea Apelor
17:27 (1976).
70. H. H. Tabuk and R. L. Bunch, Proceedings of the Purdue
Industrial Waste Conference, Vol. 36, (1981), p. 888.
71. L. Kravetz, J. P. Salanitro, P. B. Dorn, and K. F. Guin, J. Am.
Oil Chemists. Soc. 69:692 (1995).
72. C. G. Naylor, J. P. Mieure, W. J. Adams, J. A. Weeks, F. J.
Castaiki, L. D. Ogle, and R. R. Romano, J. Am. Oil Chemists. Soc.
69:692 (1995).
73. Chemical Manufacturer's Association Panel of Alkyphenol
Ethoxylates, 1300 Wilson Boulevard, Washington, DC 20037.
74. A Corti, S. Frassinetti, G. Vallini, S. D'Antone, C. Fichi, and R.
Solaro, Environ. Pollution 90:83 (1995).
75. M. Ahel, W. Giger, and C. Schaffner, Water Res. 28:1143
(1994).
76. J. A. Weeks, presented at Society for Environmental
Toxicology and Chemistry, Denver, CO, November 1994.
77. C. G. Naylor, J. P. Mieure, W. J. Adams, J. A. Weeks, F. J.
Castalki, L. D. Ogle, and R. R. Romano, J. Am. Oil Chemists Soc.
69:692 (1995).
78. M. Ahel and W. Giger, Water Res. 28:1143 (1994).
79. A. Marcomini, B. Pavoni, A. Sfriso, and A. A. Orio, Marine.
Chem. 29:307 (1990).
80. C. G. Naylor, J. P. Mieure, W. J. Adams, J. A. Weeks, F. J.
Castalki, L. D. Ogle, and R. R. Romano, J. Am. Oil Chemists Soc.
69:692 (1995).
81. G. Naylor, J. P. Mieure, W. J. Adams, J. A. Weeks, F. J.
Castalki, L. D. Ogle, and R. R. Romano, J. Am. Oil Chemists Soc.
69:692 (1995).
82. M. A. Blackburn and M. J. Waldock, Water Res. 29:1623
(1995).
83. M. Ahel, Biogeochemical Behavior of Alkyphenol
Polyethoxylates in the Aquatic Environment, PhD thesis,
University of Zagreb, (1987).
84. S. S. Talmage, in Environmental and Human Safety of Major
Surfactants, Alcohol Ethoxylates and Alkylphenol Ethoxylates
(The Soap and Detergent Association), Lewis, Boca Ratio, FL,
1994.
85. A. M. Soto, H. Justicia, J. W. Wray, and C. Sonnenschein,
Environ. Health Persp. 92:167 (1991).
86. R. White, S. Jobling, S. A. Hoare, J. P. Sumpter, and M. G.
Parker, Endocrinology 135:175 (1994).
87. W. H. Benson and A. C. Nimrod, in a report submitted to the
Chemical Manufacturers Association Panel on Alkylphenol
Ethoxylates, 1995.
88. L. B. Clark, R. T. Rosen, T. G. Hartman, J. G. Louis, I. H.
Suffet, R. L. Lippincott, and J. D. Rosen, Int. J. Environ. Anal.
Chem. 47:167 (1992).
89. H. Kirchmann and A. Tengsved, Swed. J. Agric. Res. 21:115
(1991).
90. M. Ahel, J. Mcevoy, and W. Giger, Environ. Pollut. 79:243
(1993).
91. C. G. Naylor, Textile Chemist and Colorist 27:29 (1995).
92. R. R. Birch and S. G. Hales, Muench. Beitr. Abwasser, Fish.-
Flussbiol. 44:398 (1990).
 Page 83
93. D. Brown, H. de Henau, J. T. Garrigan, P. Gerike, M. Holt, E.
Kunkel, E Matthijs, J. Waters, and R. J. Watkinson, Tenside 24:14
(1987).
94. A. Marcomini, P. D. Capel, W. Giger, and H. Haeni,
Naturwissenschaften 75:460 (1988).
95. P. Diercxsens, M. Wegmann, R. Daniel, H. Haeni, and J.
Tarradellas, Gas, Wasser, Abwasser 66:123 (1987).
96. A. Marcomini, P. D. Capel, T. Lichtensteier, P. H. Brunner, and
W. Giger, J. Environ. Qual. 18:523 (1989).
97. H. Kirchmann, H. Aastroem, and G. Joensaell, Swed. J. Agric.
Res. 21:107 (1991).
98. A. Marcomini, P. D. Capel, T. Lichtensteiger, P. H. Brunner,
and W. Giger, J. Environ. Qual. 18:523 (1989).
99. H. Kirchmann and A. Tengsved, Swed. J. Agric. Res. 21:115
(1991).
100. M. Ahel and W. Giger, Water Res. 28:1143 (1994).
101. J. A. Field and R. L. Reed Environ. Sci. Tech. 30:3544 (1996).
102. K. Yoshimura, J. Am. Oil Chemists Soc. 63:1590 (1986).
103. A comprehensive update on polyoxyethylene alkylphenol
environmental issues, including efforts by the United States
Environmental Protection Agency and members of the European
Community, can be obtained from the Chemical Manufacturer's
Association Panel of Alkylphenol Ethoxylates, 1300 Wilson
Boulevard, Washington, DC 20037.
104. C. R. Enyeart, in Nonionic Surfactants (M. Schick, ed.),
Marcel Decker, New York, 1967, p. 52.
105. J. Lorenc, G. Lambeth, and W. Scheffer, in Kirk-Othmer
Encyclopedia of Chemical Technology, 4th Ed., Vol. 2 (M. Howe-
Grant, ed.), Wiley & Sons, New York, 1992, p 115.
106. McCutcheon's Volume 1: Emulsifiers and Detergents, North
America Edition, MC Publishing, Glen Rock, NJ, 1995.
107. McCutcheon's Volume 1: Emulsifiers and Detergents,
International Edition, MC Publishing, Glen Rock, NJ, 1994.
108. P. T. Varineau, Union Carbide Corp., previously unpublished
data.
109. Union Carbide Corp. Technical Brochure F-48601 A.
110. Union Carbide Corp. Technical Brochure F-80183A ICD.
111. Union Carbide Corp. Technical Brochure F-48601 A.
112. Union Carbide Corp. Technical Brochure F-80183A ICD.
113. G. W. Carr, Union Carbide Corp., previously unpublished
data.
114. Rohm and Haas Company, Triton Surfactants (1960).
115. G. W. Carr, Union Carbide Corp., previously unpublished
data.
116. Union Carbide Corp. Technical Brochure F-80183A ICD.
117. Union Carbide Corp. Technical Brochure F-48601A.
118. Union Carbide Corp. Technical Brochure F-80183A ICD.
119. C. M. Wizda, Union Carbide Corp., previously unpublished
data.
120. R. M. Weinheimer, Union Carbide Corp., previously
unpublished data.
121. R. M. Weinheimer, Union Carbide Corp., previously
unpublished data.
122. P. Becher, J. Colloid Interf. Sci. 16:49 (1961).
123. E. H. Crook, D. B. Fordyce, and G. F. Trebbi, J. Phys. Chem.
67:1987 (1963).
124. E. H. Crook, G. F. Trebbi, and D. B. Fordyce, J. Phys. Chem.
68:3592 (1964).
 Page 84
125. G. M. Gantz, in Nonionic Surfactants, (M. Schick, ed.),
Marcel Dekker, New York, 1967, p. 738.
126. Union Carbide Corp. Triton Tergitol Specialty Surfactant
Reference Chart (1995).
127. G. M. Gantz, in Nonionic Surfactants (M. Schick, ed.), Marcel
Dekker, New York, 1967, p. 738.
128. Union Carbide Corp. Technical Brochure F-48601A.
129. Union Carbide Corp. Technical Brochure F-80183A ICD.
130. Union Carbide Corp. Technical Brochure F-48601A.
131. R. L. Blessing, Union Carbide Corp., unpublished internal
study, 1994.
132. V. W. Saeger, R. G. Kuehnel, C. Linck, and W. E. Gledhill,
Report No. ES-80-SS-46, Monsanto Industrial Chemicals
Company, St Louis, MO, 1980.
133. J. Pudo and E. Erndt, Verh. Int. Verein Limnol. 21:1083
(1981).
134. J. Ruiz Cruz and M. C. Dobarganes, Garcia Grasas Aceites
27:309 (1976).
135. A. Marcomini, P. D. Chapel, T. Lichtensteiger, P. H. Brunner,
and W. Giger, J. Environ. Qual. 18:523 (1989).
136. L. Kravetz, H. Chung, K. F. Guin, W. T. Shebs, and L. S.
Smith, Household Pers. Prod. Ind. 19:46 (1982).
137. C. Crescenzi, A. DiCorcia, R. Samperi, and A. Marcomini,
Anal. Chem. 67:1797 (1995).
138. M. A. Blackburn and M. J. Waldock, Water Res. 29:1623
(1995).
139. C. G. Naylor, J. P. Mieure, W. J. Adams, J. A. Weeks, F. J.
Castalki, L. D. Ogle, and R. R. Romano, J. Am. Oil Chemists Soc.
69:692 (1995).
140. P. T. Varineau, Union Carbide Corp., unpublished results.
This was a study conducted by Prof. J. Field, Oregon State
University.
141. L. B. Clark, R. T. Rosen, T. G. Hartman, J. G. Louis, I. H.
Suffet, R. L. Lippincott, and J. D. Rosen, Int. J. Environ. Anal.
Chem. 47:167 (1992).
142. M. Ahel and W. Giger, Anal. Chem. 57:1577 (1985).
143. M. Agel and W. Giger, Anal. Chem. 57:2584 (1985).
144. M. Ahel and W. Giger, Proc. Seminar on Nonyphenol
Polyethoxylates and Nonylphenol. Swedish Environmental
Protection Agency Report 3907 (1991).
145. M. Ahel and W. Giger. Water Res. 28:1143 (1994).
146. M. Ahel, T. Conrad, and W. Giger, Environ. Sci. Technol.
21:697 (1987).
147. M. Ahel, Biogeochemical Behavior of alkyphenol
polyethoxylates in the aquatic environment, PhD. Thesis,
University of Zagreb, Zagreb (1987).
148. S. S. Talmage, in Environmental and Human Safety of Major
Surfactans, Alcohol Ethoxylates and Alkylphenol Ethoxylates
(The Soap and Detergent Association), Lewis, Boca Raton, FL,
1994.
149. S. S. Talmage, in Environmental and Human Safety of Major
Surfactants, Alcohol Ethoxylates and Alkylphenol Ethoxylates
(The Soap and Detergent Association), Lewis, Boca Raton, FL,
1994.
150. L. T. Brooke, D. Thompson, M. Kahl, D. Cox, R. L. Spehar,
and R. Erickson, Toxicity and Bioaccumulation of Nonylphenol
with Freshwater Organisms, 15th Annual Meeting of the Society of
Environmental Toxicity and Chemistry, Denver, Colorado, 1994.
151. Work commissioned by the Chemical Manufacturer's
Association (ABC Laboratories), Report Numbers 40597, 41756,
and 41766 (19931995).
152. R. Ekelund, A. Bergman, A. Granmo, and M. Berggren,
Environ Pollut. 64:107 (1990).
 Page 85
153. D. W. McLeese, B. B. Sergent, C. D. Metcalfe, V. Zitcko and
L. E. Burridge, Bull. Environ. Contam. Toxicol. 24:575 (1980).
154. R. Ekelund, A. Bergman, A. Granmo, and M. Berggren,
Environ Pollut. 64:107 (1990).
155. F. A. Gobas, Ecol. Model. 69:1 (1993).
156. R. Ekelund, A. Bergman, A. Granmo, and M. Berggren,
Environ Pollut. 64:107 (1990).
157. C. G. Naylor, J. P. Mieure, I. Morici, and R. R. Romano,
presented at Third CESIO International Surfactants Congress,
London, 1992.
158. D. W. McLeese, V. Zitko, D. B. Sergeant, L. Burridge, and C.
D. Metcalfe, Chemosphere 9:79 (1980).
159. F. A. Gobas, Ecol. Model. 69:1 (1993).
160. M. Ahel, J. McEvoy, and W. Giger, Environ. Pollut. 79:243
(1993).
161. C. Crescenzi, A. DiCorcia, R. Samperi, and A. Marcomini,
Anal. Chem. 67:1797 (1995).
162. C. G. Naylor, Textile Chemist and Colorist 27:29 (1995).
163. H. B. Lee and T. E. Peart, Anal. Chem. 67:1976 (1995).
164. M. A. Blackburn and M. J. Waldock, Water Res. 29:1623
(1995).
165. M. Ahel, W. Giger, and M. Koch. Water Res. 28:1131 (1994).
166. D. Brown, H. de Henau, J. T. Garrigan, P. Gerike, M. Holt, E.
Kunkel, E. Matthijs, J. Waters, and R. J. Watkinson, Tenside 24:14
(1987).
167. R. Heusch and F. Kopp, Ber. Bunsenges. Phys. Chem. 24:806
(1987).
 Page 87

3
Polyoxyethylene Alcohols
Charles L. Edwards
Westhollow Technology Center, Shell Chemical Company,
Houston, Texas

I. Introduction 87
II. Synthesis of Hydrophobic Intermediates 88
A. Primary Alcohols 88
B. Secondary Alcohols 97
III. Preparation of Polyoxyethylene Alcohols 100
A. Conventional Polyoxyethylene Alcohols 100
B. Narrow-Range or Peaked Polyoxyethylene
106
Alcohols
IV. Properties of Polyoxyethylene Alcohols 107
A. Alcohol Structure and Surface Properties 107
B. Commercially Available Products 110
V. Applications 116
A. Household Surfactants 116
B. Industrial and Institutional Applications 116
References 117
I
Introduction
The most important class of commercially available nonionic
surfactants is the polyoxyethylene alcohols derived from reaction
of an alcohol with ethylene oxide. These materials are produced in
an excess of a billion pounds a year and are used in such diverse
applications as household and institutional laundry, textile
scouring, pulp and paper manufacturing, oil field surfactants,
agricultural spray adjuvants, and environmental clean-up. The type
of alcohol used as the initiator and the length of the
polyoxyethylene chain define the applications of these versatile
commercial products. A primary driving force for the use of these
surfactants is their ready biodegradability and overall
environmental
 Page 88
acceptability. Current and anticipated environmental pressures
ensure their continued replacement of other surfactant materials.
Conventional polyoxyethylene alcohols are produced
commercially by reaction of an alcohol with ethylene oxide using a
basic catalyst, usually potassium hydroxide. The overall reaction
can be expressed as

In this equation R represents a hydrophobic moiety that can be

either linear or branched, and the alcohol can be in principle
primary, secondary, or tertiary. However, polyoxyethylene alcohols
based on secondary or tertiary alcohols are prepared using a two-
step oxyethylation procedure described in Chapter 1. Whereas
there are limited applications for polyoxyethylene alcohols derived
from secondary alcohols, applications for polyoxyethylene tertiary
alcohols are rare.
The number of moles n of ethylene oxide reacting with 1 mole of
hydrophobe need not be an integral and is the number average
degree of polymerization of ethylene oxide in the product. It is the
structure and molecular weight of the R group as well as the value
of n in the molecule that determines the application of the
surfactant. Further details of the mechanism of this reaction are
given in Chapter 1.
This chapter discusses polyoxyethylene alcohols based on primary
and secondary aliphatic alcohols. Polyoxyethylene alcohols based
on other types of alcohols, such as aromatic alcohols
(alkylphenols), are discussed in detail in Chapter 2. The synthesis
of the hydrophobic intermediates will precede a discussion of the
preparation, properties, and applications of the polyoxyethylene
alcohols.
II
Synthesis of Hydrophobic Intermediates
A
Primary Alcohols
1
Natural Sources
Linear detergent range primary alcohols were first commercially
prepared from naturally occurring fats and oils. The most common
sources were coconut oil, palm kernel oil, sperm oil, castor oil,
and tallow. Coconut oil and tallow are the most commercially
attractive sources because most of the alcohols produced from
these natural products are within the effective detergent range
(C12C18). Coconut oil is particularly attractive as a raw material
because it contains 6570% of C12 and C14 acid derivatives as well
as significant amounts of C8, C10, C16, and C18 acid derivatives.
These natural sources have only even-numbered carbons and are
almost exclusively linear.
The natural fatty alcohols can be produced from coconut oil by
one of several process variations based on the triglycerides
obtained from the crude oil.
 Page 89
Early routes were based on direct hydrogenolysis of the
triglycerides or hydrogenolysis of the fatty acids obtained after
hydrolysis of the triglycerides [110]. However, these routes require
high-pressure and high-temperature operating conditions and are
less selective than current process options. A more selective, low-
pressure hydrogenolysis process [1113] has been demonstrated that
involves the hydrogenolysis of the methyl esters of the fatty acids
obtained by esterification of the fatty acids with methanol. The
products are a mixture of fatty alcohols and glycerol, with the latter
being sold as a valuable side product. Methanol is recycled in the
overall process, which is shown.

The fatty alcohols produced from coconut oil are straight chain,
saturated primary alcohols with even-numbered carbon atoms
from C8 to C18. They are extremely pure, which has allowed their
use in the personal care markets (e.g., cosmetics and shampoos).
However, the cost and availability of linear alcohols based on
natural sources fluctuates significantly, depending on the weather
conditions of the geographic areas producing coconuts and palm
kernels. For this and other strategic reasons, synthetic sources were
developed for the production of aliphatic detergent range alcohols.
2
Synthetic Sources
Synthetic primary alcohols are based on petrochemical raw
materials and are competitive in cost and performance with the
natural fatty alcohols. The hydrocarbon chain of the synthetic
alcohols can be either 100% linear or partially branched (2025 wt%
methyl branching at the 2 position) depending on the
 Page 90
process used. The branching of the hydrophobe has a significant
effect on the end use. The Ziegler alcohol process described in this
section produces 100% linear alcohols with all even carbon
numbers, making them competitive in markets previously
dominated by natural fatty alcohols. The oxo and modified oxo
(Shell hydroformylation) processes described below produce
alcohols with various degrees of branching, making sulfates
obtained from them particularly useful in cold water detergent
applications.
All synthetic alcohols currently produced are based on one of
several ethylene oligomerization process [14]. Originally, the olefin
intermediates used in oxo-type processes were produced from wax
cracking or chlorination-dehydrochlorination of paraffins, but
these processes became less economically attractive with the
advent of the ethylene oligomerization process. Either a- or
internal olefin feedstocks can be used in the oxo or modified oxo
processes, but the Ziegler alcohol process leads to the formation of
100% linear alcohols directly from ethylene without isolation of
the detergent range olefin intermediate. This section describes
processes that are currently used to produce synthetic primary
alcohols.
(a)
Source of Detergent Range Olefin Intermediates
Oxo- and modified oxo-based synthetic alcohol processes use
detergent range olefins (C10C14) as intermediates. These olefins
are almost exclusively linear, but may be either a- or internal
olefins. Because the detergent range olefins are such an important
part of two of the three commercial processes used to produce
synthetic alcohols, this section will address the current commercial
processes to produce detergent olefin intermediates.
Chevron Ethylene Oligomerization Process
Chevron produces high-purity linear a-olefins using a one-step
Ziegler-type oligomerization process that produces a somewhat
broad product mixture that follows the SchulzFlory distribution
[15]. The reaction involves an ethylene growth reaction using a
soluble triethylaluminum (TEA) catalyst. The growth of the alkyl
chain and displacement of the product olefin from the aluminum
catalyst occur simultaneously during reaction. This is illustrated as
follows:
 Page 91
The chain displacement reaction is simplified to show only one
replacement at a time. However, multiple replacements are
occurring during reaction, which leads to the somewhat broad
product distributions predicted by the SchulzFlory equation.

This broad product slate requires that markets be obtained for the
a-olefins produced outside the useful detergent range (i.e., <C10
and >C14) for maximum economic benefit. Balancing the product
slate containing various a-olefins each with different economic
value is always a marketing challenge.
Since the TEA catalyst is used in a relatively low concentration, it
is not economical to attempt to recycle the catalyst after isolation of
the olefins through distillation processes. Instead, it is treated with
aqueous NaOH, which converts the material to sodium aluminate
and is then sent for disposal. Further details of this process can be
found in patents to Chevron and Gulf [1618].
Ethyl's Ethylene Oligomerization-Displacement Process
The Ethyl process also uses a TEA-based ethylene oligomerization
system. However, while the Chevron process is conducted under
high-temperature conditions causing the growth and displacement
reactions to occur simultaneously, the Ethyl process separates the
two steps. This first step involves a low-temperature ethylene
oligomerization reaction under conditions whereby no
displacement occurs. The displacement reaction is conducted in a
second high-temperature reaction. The Ethyl process uses larger
quantities of TEA because the growth step is stoichiometric in
aluminum.

This has two specific consequences. First, the TEA must be

recovered and recycled in order for the process to be economical.
In addition, the linear a-olefin product mixture is much narrower,
following a Poisson distribution as shown below (see Chapter 1
for a complete discussion of the kinetics). This
 Page 92
Table 1 Typical Product
Distributions for the Ethyl Olefin
Process [19]
Carbon number fraction %
C4 13
C6C10 55
C12C18 30
C20+ 2

means that the Ethyl process is somewhat more flexible in its

ability to produce the desired carbon number range for balancing
market demands.

whereis the mole fraction of the chains containing added

X(p)ethylene molecules
pis the number of ethylene units added to a chain
is the average number of moles of ethylene reacted
n
per equivalent of aluminum alkyl bonds

As with all TEA-based ethylene oligomerization reactions (Ziegler-

type), the linear a-olefin products resulting from the Ethyl process
have an even number of carbon atoms. A typical product
distribution resulting from the Ethyl process is shown in Table 1
[19]. The Ziegler-based chemistry has been extensively reported
[2028].
Shell Higher Olefin Process (SHOP)
Shell's higher olefin process (SHOP) is the most complex of the
three commercial processes used to produce linear a-olefins, but it
is also the most flexible. The process is based on a proprietary
homogenous nickel-based catalyst system that produces the same
geometric (SchulzFlory) distribution as the Chevron process.
However, it also includes chemistry to convert the less desirable
lower and higher carbon number compounds to detergent range
linear internal olefins by using a combination isomerization-
disproportionation (metathesis) scheme. The detergent range
internal olefins can be used in Shell's modified oxo process
(described later) as feed for their synthetic alcohol plants. This
combination of the two processes offers unique overall technology
that is used to balance and maximize the profitability of the overall
product slate. A simplified block diagram of the SHOP process is
shown in Fig. 1 [29]. The ethylene oligomerization step is
conducted in a series of reactors using a proprietary
nickel/phosphorus ligand catalyst system in butanediol solvent at
90100°C and at 12001500 psig ethylene pressure. The linear a-
olefin product mixture is then fractionated to produce a C6C20
range and a C20+ range of heavy ends. A majority of the linear a-
olefins in
 Page 93

Fig. 1
Illustrative block diagram for SHOP.
the C6C20 range is further fractionated for sale in the high-value
a-olefins markets, but the remainder along with the C20+ range is
fed to the isomerization-disproportionation system converting the
feedstock to internal olefins in the C11C14 range. These internal
olefins are used for the production if polyoxyethylene alcohols
using the modified oxo process described later in this section.
Typical product distributions (K factors) for the ethylene
oligomerization reaction are shown in Fig. 2.
The isomerization section contains a proprietary isomerization
catalyst operating at 120°C, whereas the disproportionation section
contains a proprietary catalyst system operating at 130°C. The
isomerization and disproportionation reactions are as follows:
Various aspects of the process along with recent process
improvements have been extensively reported in the patent
literature [3041].
 Page 94

Fig. 2
Oligomer product distribution vs. K factor for SHOP [29].
The SHOP process differs from the Chevron and Ethyl processes
in two major respects. First, it is based on a nickel/phosphorus
ligand catalyst system instead of a TEA catalyst system. Second, it
is a far more flexible process, as demonstrated by the fact that the
C11C14 internal olefins produced in the isomerization-
disproportionation section are used almost exclusively in the Shell
hydroformylation (modified oxo) process. Thus, the less
commercially attractive internal olefins are upgraded when used to
produce the synthetic alcohols.
The three commercial processes for producing linear a- and
internal olefins described above can be used to produce olefins for
sale or as intermediates for the production of primary synthetic
alcohols. The next section will address processes for the
production of synthetic primary alcohols.
(b)
The Conventional Oxo (Hydroformylation) Process
The oxo or hydroformylation process is the addition of hydrogen
and carbon monoxide to an olefin using a soluble cobalt metal
catalyst at relatively high temperatures and pressures to produce an
aldehyde containing one carbon more than the starting olefin. The
aldehyde can be isolated for sale but is usually further
hydrogenated in situ to produce the synthetic primary alcohol. The
aldehydes and alcohols produced during hydroformylation are a
mixture of linear and branched products. The reaction can be
illustrated as follows:
 Page 95
A typical conventional oxo- or hydroformylation process is
conducted at 120200°C and 20003000 psig using a soluble cobalt
carbonyl catalyst. The synthesis gas (or H2/CO) ratio is usually 1.0.
The reaction rate is strongly dependent on the structure of the
olefin [42]. The fastest reaction rates are achieved using lower
molecular weight, linear a-olefins. Linear internal olefins react
three to four times more slowly than linear a-olefins. Branching
can reduce reaction rates by an order of magnitude. Several
comprehensive reviews of the kinetics of hydroformylation have
been reported [4348].
Synthetic alcohols prepared using the oxo and modified oxo
processes are significantly different from natural fatty alcohols and
those produced from the Ziegler alcohol process. Synthetic
alcohols derived from the modified oxo process have both odd-
and even-numbered carbon atoms and contain some methyl
branching (2025%) in the 2 position. Natural fatty alcohols and
Ziegler alcohols are 100% linear and are always even-numbered
carbon alcohols. The structural differences lead to differences in
physical properties and thus applications, providing some
differentiation between synthetic alcohols obtained from the two
types of processes.
(c)
Modified Oxo (Shell Hydroformylation) Process
Discoveries made in the 1960s and 1970s by Shell led to ligand-
modified cobalt catalyst systems with distinct advantages over the
conventional oxo process. The conventional oxo process must be
operated at low reaction temperatures with long reaction times and
use linear a-olefin feedstock in order to minimize the production
of the less biodegradable and thus less desirable branched alcohol
isomers. Higher operating pressures are required using the
conventional, unmodified cobalt catalyst system, because it is less
stable than the ligand-modified cobalt catalyst system. Finally, the
oxo catalyst is a poor hydrogenation catalyst, so that the
hydrogenation of the intermediate aldehyde to alcohol must be
accomplished in a second stage or step.
In contrast, the Shell's ligand-modified cobalt catalyst system can
operate at higher reaction temperatures, lower overall operating
pressure, and uses less expensive internal olefins as feedstock.
While use of internal olefins in the conventional oxo process leads
to significant increases in branching (up to 50%) in the alcohol,
improved linearity (7580%) is achieved using the ligand-modified
process. Finally, the Shell catalyst produces alcohol in one step due
to the ability of the catalyst to hydrogenate the intermediate
aldehyde to alcohol. Each of these process improvements results in
a significant economic benefit in capital and variable (catalyst)
costs.
Shell's modified hydroformulation process (SHF) is based on a
proprietary tertiary organophosphine-modified cobalt catalyst
system that operates at 190°C and 1200 psig of H2/CO in a 2:1
molar ratio. The overall chemistry is shown below and is described
in detail in several publications and patents [4954].
 Page 96

(d)
Ziegler Alcohol Process
The Ziegler alcohol process is based on the pioneering
organoaluminum chemistry developed by Karl Ziegler and
coworkers at the Max Planck Institute in Germany. As a result of
this work, 100% linear primary alcohols are commercially
produced by two companies (Vista and Amoco) using a three-step
process. Ethylene is oligomerized in the presence of TEA, followed
by air oxidation to form the aluminum alcoholate, followed by
hydrolysis with dilute sulfuric acid to produce a narrow molecular
weight range of alcohols and aluminum hydroxide.
The Vista (formally Conoco) process involves the oligomerization
of ethylene under conditions (low temperature) that prevent chain
displacement reactions, thus producing hydrophobic chains
following a Poisson distribution as described previously. The
overall reaction is as follows:
 Page 97
This process produces a mixture of alcohols with a significant
amount of alcohols outside the detergent range. This presents a
marketing challenge to Vista because overall economic success is
dependent on the placement of each carbon fraction in a lucrative
market. Modification of the Ziegler alcohol process to produce a
narrower product distribution would be of significant economic
benefit.
The Amoco (formally Ethyl or Albemarle) process produces a
narrower-than-Poisson product distribution by combining the
growth and displacement reactions in the overall process. In this
process the growth reaction product, which has a Poisson product
distribution, is reacted with a C6C10 olefin stream in a
transalkylation scheme as follows:

The product from this reaction contains heavy olefins and an

aluminum alkyl stream (C6C10) that can undergo additional
growth reactions. By the proper combination of growth and
transalkylation reactions, followed by fractionation and recyling of
the appropriate olefin streams, the overall process can be managed
to produce a majority of organoaluminum product in the C12C16
detergent range (85 wt% overall). The concept of combining
various process steps and recyling streams in order to maximize
the desired product slate is similar to the three-step SHOP process
described previously to produce detergent range olefins. The
overall process scheme is summarized in a simplified process
diagram in Fig. 3 and described in patents [55,56].
The alcohols produced by the Ziegler alcohol process are 100%
linear even-carbon-number alcohols. They are essentially the same
as the natural fatty alcohols and can compete in most of the same
markets. The alcohol product mixture follows the Poisson
distribution (as with the Ethyl olefin process) and is subject to
some shifting of the peak by changes in the process parameters.
The alumina produced in the process is quite pure and is sold as a
byproduct of the process. Therefore, the Zeigler alcohol process is
not truly catalytic with respect to TEA, because it is consumed in
the process. Finally, balancing of the alcohol product distribution
is always a challenge, with the overall economics of the process
being dependent on the value of the lower and higher molecular
weight alcohols in their respective markets. The C4C10 alcohol
fraction is used in the solvents and plasticizers markets, whereas
the C16+ fraction find various, but often lower value, markets.
B
Secondary Alcohols
Polyoxyethylene alcohols derived from secondary alcohols are
used primarily in the industrial surfactants markets due to their
increased liquidity and water
 Page 98

Fig. 3
Simplified diagram of the modified ethylene polymerization process [57].
solubility. However, they are reported to have somewhat lower
biodegradability than their primary alcohol counterparts. There are
two major processes reported for the preparation of secondary
alcohols: paraffin oxidation using boric acid as mediator and olefin
hydration using concentrated sulfuric acid. Union Carbide had
commercially produced secondary alcohols by paraffin oxidation
but now imports the secondary alcohol or its derivatives from
Nippon Shokubai.
1
Paraffin Oxidation Using Boric Acid As Modifier
Until recently, Union Carbide produced secondary alcohols as
intermediates for their polyoxyethylene alcohol series of Tergitol S
nonionic and anionic surfactants. They do not market the
secondary alcohols but instead use them captively to make the
polyoxyethylene secondary alcohol surfactant. Union Carbide now
imports the secondary alcohols or polyoxyethylene derivatives
from Nippon Shokubai, who it is believed produces these
secondary alcohols by paraffin oxidation in the presence of boric
acid.
 Page 99
The oxidation of paraffins in the liquid phase without the use of
modifiers or cocatalysts results in the formation of significant
amounts of ketones, aldehydes, peroxides, esters, and acid side
products. However, when the oxidation is conducted in the
presence of boric acid, high yields of the secondary alcohol can be
obtained. The explanation for the increase in selectivity is believed
to be the trapping of the secondary alcohol by the boric acid to
form borate esters, which are known to be quite resistant to further
oxidation. However, water must be removed during the borate
ester formation in order to achieve high selectivities. This process
option has been investigated in detail and more information can be
obtained from the patent literature [5863].

2
Hydration of Olefins
Secondary alcohols can also be obtained using a two-step process
involving reaction of linear olefin with concentrated sulfuric acid
to produce an alkylsulfuric acid (ASA) intermediate, which is
subsequently hydrolyzed to the secondary alcohol in a second step.
The process is conducted in two steps in order to achieve high
overall conversions to secondary alcohol. In the first step,
concentrated sulfuric acid (96100%) is added slowly with cooling
to the olefin in a well-stirred reactor. The reaction goes to
completion virtually instantaneously. The product mixture consists
primarily of the ASA and some dialkyl sulfate. This product
mixture is then hydrolyzed in a second step producing a two-phase
medium consisting of primarily secondary alcohol and dilute
sulfuric acid. The secondary alcohol is isolated by phase
separation, treatment with dilute base, and distillation. The
 Page 100
dilute sulfuric acid is reconstituted to concentrated sulfuric acid
and recycled to the reaction scheme. This process has been studied
periodically since the 1930s [64], and Shell used it in the 1940s to
produce secondary alcohol sulfates (''Teepol") in Europe.
Considerable work has been reported on olefin hydration [65,66].
Secondary alcohols can also be made by direct hydration of
detergent range linear olefins using a strong homogeneous or
heterogeneous (e.g., ion exchange) acid catalyst. This route has the
disadvantage that the equilibrium of the reaction is not favorable
for alcohol formation. Yields are restricted to ~30 mol% per pass
over the catalyst, which means that significant recycling and
separations can make this process uneconomical [6770]. Although
there are several other laboratory methods to prepare secondary
alcohols, none are used commercially.

III
Preparation of Polyoxyethylene Alcohols
Polyoxyethylene alcohols can be produced by a variety of
laboratory routes, but they are produced commercially by reaction
of the alcohol with ethylene oxide using a catalyst. The overall
reaction can be expressed as follows:
In this equation the number of moles n of ethylene oxide reacting
with 1 mole of hydrophobe need not be an integral and is the
number average degree of polymerization of ethylene oxide in the
product. The choice of hydrophobe structure and molecular
weight, the value of n, and the type of catalyst used determines the
physical properties and thus applications of the polyoxyethylene
alcohol produced. The choice of catalyst used in the process is
particularly important, because it controls the distribution of the
polyoxyethylene chain in the product. A more detailed discussion
of the factors controlling the polyoxyethylene chain length
distribution along with kinetics and mechanistic interpretations is
found in Chapter 1. The following section briefly discusses the
two main types of commercial products available to the surfactants
marketconventional, and the new narrow-range or peaked
polyoxyethylene alcohols.
A
Conventional Polyoxyethylene Alcohols
Conventional polyoxyethylene alcohols are produced using a basic
catalyst, typically potassium hydroxide. The products obtained
from this reaction consist
 Page 101

Fig. 4
Product distribution obtained from the reaction of dodecanol with 7 moles of
ethylene oxide using either KOH or barium dodecanoate as catalyst and
compared with a Poisson distribution [71].
of a mixture of polyoxyethylene alcohol oligomers. A typical
product distribution is shown in Fig. 4 using potassium hydroxide
as catalyst and compared with a product with a narrower chain
length distribution obtained using activated catalysts described in
Sec. B.
1
Catalyst
The vast majority of commercially available polyoxyethylene
alcohols are produced using basic catalysts. Although many basic
catalysts have been reported as useful for this reaction (71), the
most commonly used catalyst is potassium hydroxide. Catalyst
activity has been shown to be directly related to the size of the
metallic cation within a specific family in the periodic tablethe
larger the ionic radius, the more active the catalyst (e.g., Li < Na <
K < Rb < Cs for group I and Mg < Ca < Sr < Ba for group II
metals. There are several reasons for using potassium hydroxide as
the catalyst system: ease of handling, low cost, high activity, and
high selectivity to desired products. The catalyst is usually added to
the alcohol as either an aqueous potassium hydroxide solution
(e.g., 50 wt%) or as a solid potassium flake. The catalyst mixture is
activated by converting the potassium hydroxide to the potassium
alkoxide of the alcohol to be reacted. In this manner, water is
removed from the reaction mixture, thus minimizing the amount of
polyethylene glycol produced as a side product.
 Page 102

Fig. 5
Effect of KOH concentration on rate of polyoxyethylation at
135140°C [72]. (Values are moles of KOH per
mole of tridecyl alcohol used.)
As should be expected, an increase in catalyst concentration results
in an increase in reaction rate. However, in a study wherein the
concentration of potassium hydroxide catalyst was progressively
doubled from 1.8 m% to 14.3 m% basis alcohol, the rate of
reaction did not increase each time as expected [72]. The rate
increase was greater when increasing the catalyst concentration at
the lower catalyst concentrations than at the higher concentrations
as shown in Fig. 5.
This can be explained by the fact that the ethylene oxide reacts
with the charge-separated alkoxide ion instead of a covalently
bound metal alkoxide. The degree of ionization is greater at lower
catalyst concentrations than at the higher concentrations [73].
2
Temperature
Normal operating temperatures for the commercial production of
polyoxyethylene alcohols is 140180°C. An increase in reaction
temperature leads to an expected increase in reaction rate using
potassium hydroxide catalyst. However, the rate increase is not
directly proportional to temperature [72,73] as can be seen in Fig.
6. The solubility of ethylene oxide in the catalyzed reaction mixture
is lower at higher reaction temperatures at a given ethylene oxide
partial pressure. Consequently, because the rate expression is
approximately first order with respect to ethylene oxide
concentration, temperature strongly affects the overall reaction rate
due in part to its effect on ethylene oxide solubility.
3
Pressure
Ethylene oxide is an extremely hazardous chemical that is capable
of explosion over a wide range of pressures. A detailed discussion
of the physical properties and safe handling requirements of
ethylene oxide is presented in Chapter 1. It is
 Page 103

Fig. 6
Effect of temperature on rate of polyoxyethylation with NaOH
as catalyst [72].
advisable to conduct polyoxyethylations using an inert gas such as
nitrogen in order to ensure that the ethylene oxide in the vapor
phase does not exceed the explosive limits. In commercial practice,
the gas phase concentration of ethylene oxide is never allowed to
exceed 40 mol%, the reported lower limit of the explosive region.
In fact, it is advisable to conduct these reactions at gas phase
ethylene oxide concentrations significantly below 40 mol%.
Most commercial polyoxyethylation reactors are batch reactors and
operated at a total operating pressure of approximately 75 psia total
reaction pressure (nitrogen + ethylene oxide). The partial pressure
of ethylene oxide used at this total pressure is 1525 psia. Studies
have shown that the rate of reaction increases with a increase in
ethylene oxide partial pressure [71].
4
Alcohol Structure
The structure of the alcohol significantly affects both reaction rate
and the polyoxyethylene chain length distribution in
polyoxyethylation. Linear primary alcohols react more rapidly than
branched primary alcohols, with the position of the branch being
of significantly importance. Primary alcohols, either linear or
branched, react more rapidly than secondary or tertiary alcohols.
Due to the differences in reaction rates, the oligomer distribution
of primary, secondary, and tertiary polyoxyethylene alcohols are
significantly different. For example, a 7-mole polyoxyethylene
adduct of the three types of alcohols would have dramatically
different polyoxyethylene chain length distributions. Since the
secondary and tertiary alcohols are significantly less reactive than
their polyoxyethylene adducts, then the final products contain
substantial amounts of residual secondary or tertiary alcohol with a
very broad polyoxyethylene chain length distribution compared
with primary alcohol products. This is illustrated in Fig. 7 for the
polyoxyethylation of 1-dodecanol and 2-dodecanol using
potassium hydroxide as catalyst and using an ethylene
oxide/alcohol molar ratio of 7.
 Page 104

Fig. 7
Polyoxyethylation of 1-dodecanol and 2-dodecanol with 7 moles of
ethylene oxide using KOH as catalyst [74].
As can be seen in the figure, polyoxyethylene secondary alcohols
produced using potassium hydroxide as catalyst contain much
higher concentrations of residual alcohol (16 wt%) compared with
the primary alcohol materials (8 wt%). For this reason,
polyoxyethylene secondary alcohols must be produced using a
two-step (acidic, then basic catalyst) process as described in
Chapter 1.
5
Commercial Production
Most commercial polyoxyethylation processes are conducted in
batch operations. Traditional stirred tank reactors or the new
Pressindustria SpA horizontal gas phase sparge-type reactors are
used [75]. For maximum efficiency the alcohol/catalyst solution
for the next batch reaction is prepared while the previous batch is
in the process of polyoxyethylation. A typical simplified
commercial reactor system is shown in Fig. 8.
In a typical commercial process, alcohol and 50 wt% aqueous
potassium hydroxide are introduced to the catalyst reactor
(approximately one-fifth the size of the batch reactor). The mixture
is dried at 120130°C under vacuum, usually while the previous
batch is undergoing polyoxyethylation, until a residual water level
of <200 ppm is attained. Then the catalyzed alcohol mixture is
added to the reactor along with additional dried alcohol sufficient
for the desired initial charge. The reaction temperature is increased
to ~145°C at which time all external heating is terminated. Ethylene
oxide and nitrogen are introduced to the reactor, which results in
an exothermic reaction (DH=22 kcal/mole) that increases the
temperature to the desired reaction temperature of ~160180°C.
Ethylene oxide is added at a rate sufficient to maintain reaction
temper-
 Page 105

Fig. 8
Simplified diagram of a typical stirred tank polyoxyethylation reactor.
ature and the heat of reaction is removed by circulating a portion
of the batch reactor contents to a heat exchanger. Safety
procedures require that limits be placed on temperature and
pressure. The gas phase ethylene oxide concentration is continually
monitored by sensors, and if the reaction temperature decreases for
some reason, ethylene oxide feed is immediately terminated to
prevent a buildup of vapor phase ethylene oxide concentration.
After all of the required amount of ethylene oxide is added, the
residual ethylene oxide is consumed by maintaining reaction
temperature until there is no change in the reactor pressure. This
usually requires approximately 3060 min. Because many customers
require that residual ethylene oxide be <5 ppm in the product, a
nitrogen sparge of the product is optionally performed if product
"aging" is insufficient to reduce ethylene oxide concentrations to
the desired levels.
The reaction product is normally neutralized with acetic acid, but
other homogeneous acids can be used on request. In some cases
customers specify that there be no catalyst residues in the product,
which can be accomplished by treating the product with sodium
dihydrogen phosphate powder instead of acetic acid, and filtration
of the product mixture. The potassium is removed by ion exchange
with the inorganic material.
Modern commercial reactors are fully automated with computer-
controlled operations. All current safety features are built into the
control systems with automatic shutdowns set for over temperature
and over pressure, as well as block valves to prevent catalyst
mixtures from becoming backmixed with ethylene oxide supply.
 Page 106
B
Narrow-Range or Peaked Polyoxyethylene Alcohols
Conventional polyoxyethylene alcohols prepared using a basic
catalyst such as potassium hydroxide are a mixture of
polyoxyethylene oligomers with a broad chain length distribution.
Several studies have shown that polyoxyethylene alcohols with a
narrower polyoxyethylene chain length distribution than
conventional are more effective in some detergency tests [76,77].
In these studies, the narrow range ethoxylates were made by
laboratory techniques that were not suitable for commercial
production. However, several synthetic alcohol manufacturers
reported various catalyst systems that were capable of producing a
much narrower polyoxyethylene chain length distribution than
conventional in the 1980s and 1990s. These catalyst systems are
listed and discussed in detail in Chapter 1. A comparison between
the chain length distributions of conventional and narrow range
polyoxyethylene alcohols is shown in Fig. 9.
Although there are not yet large-volume uses for narrow-range
polyoxyethylene alcohols, several detergent manufacturers either
have commercialized or are in the process of commercializing
these materials. Narrow-range products have several inherent
advantages over conventional materials. They usually have lower
viscosity, a higher concentration of surface active oligomers in the
effective detergent range, and lower free alcohol than their
conventional counterparts. The latter is particularly important in
applications wherein residual alcohol is undesirable (e.g., in spray
drying applications).
 Fig. 9
A comparison of the oligomer distribution of conventional and narrow range
polyoxyethylene alcohols [77].
 Page 107
Commercial narrow-range polyoxyethylene alcohol processes are
very similar to the conventional process. Most, if not all, processes
involve the use of a heterogeneous catalyst. A typical narrow-range
polyoxyethylene alcohol process would begin by the preparation
of a slurry of the heterogeneous catalyst in the alcohol to be
polyoxyethylated. At this point the two process would be
conducted in virtually the same manner as described previously. At
the end of the ethylene oxide "aging" or soak-down phase, the
catalyst could either be filtered for removal or left in the product,
depending on customer requirements. The economics of the two
processes would be similar if the heterogeneous catalyst could be
left in the product. Catalyst removal could add 13 cents per pound
to the cost of the process, depending on ease of removal and cost
of disposal. Although 1020 MM lb/year of narrow-range products
is currently being sold, the future demand for these materials is
uncertain.
IV
Properties of Polyoxyethylene Alcohols
The physical properties of polyoxyethelene alcohols define their
use in various applications. The most important physical properties
of these materials are cloud point, pour point, foam profile,
solubility, and wettability. The most common application of these
materials is in emulsification and detergency. This section
discusses various physical properties of surfactants and address
how the structure of the polyoxyethylene alcohol affects these
physical properties and applications.
A
Alcohol Structure and Surface Properties
The properties and applications of polyoxyethylene alcohols are
dependent on the molecular weight and structure of the
hydrophobe R,the number of moles of ethylene oxide (n) per mole
of hydrophobe contained in the chain, and the chain length
distribution (i.e., whether broad or narrow).

The hydrophobe R is the oil soluble part of the surfactant. It can

be either a linear or branched hydrocarbon chain obtained from
natural or synthetic petrochemical sources. The hydrophobe is the
basic "building block" of the surfactant molecule. The ethylene
oxide chain is the hydrophile, or water-soluble portion, of the
nonionic. In general, the larger the n value of the molecule, the
more water-soluble is the nonionic.
1
HydrophileLipophile Balance (HLB)
Polyoxyethylene alcohols are often classified according to their
HLB or hydrophilelipophile balance [79,80]. The HLB is an
empirical measure of the emulsifying and solubilizing character of
a nonionic surfactant. It is an
 Page 108
TABLE 2 HLB Ranges and
Applications
EO content
HLB Application
(wt%)
Water in oil
46 2030
emulsion
715 3575 Wetting agent
Oil in water
818 4090
emulsion
1015 5075 Detergent
1018 5090 Solubilizer

expression of the relationship of the size and strength of the polar

(water-soluble) and nonpolar (oil-soluble) groups of a surfactant.
The HLB number for a polyoxyethylene alcohol can be calculated
from the following equation:

where E = the wt% of oxyethylene content in the nonionic

surfactant. For example, the HLB of a C12H25O(CH2CH2O)nH
surfactant where n = 7 is 62 ÷ 5, or 12.4. Oil-soluble surfactants
have low HLBs and water-soluble surfactants have high HLBs.
HLB numbers can be used as a rough guide for selection of a
suitable nonionic surfactant in a specific application, e.g., water
solubility, detergency, or emulsification of oils. Table 2 lists the
suitable HLB ranges for various applications.
2
Cloud Point
The cloud point is a particularly important physical property of a
surfactant because it determines the optimum condition for
detergency and other applications. It is the temperature at which
the nonionic surfactant oils out of solution or becomes insoluble
due to the addition of heat. It is defined technically as that
temperature at which a cloud or haze disappears when the warm,
cloudy surfactant solution is slowly cooled (ASTM D2024 test
method). Generally, nonionic surfactants exhibit optimum
effectiveness when used at temperatures near their cloud points.
As will be seen, the structure of the polyoxyethylene alcohol (i.e.,
both hydrophobe structure and EO content) determines the cloud
point and application of the surfactant.
3
Pour Point
The pour point is a temperature 3°C above the temperature at
which no movement of the product can be observed when cooled
under prescribed conditions (ASTM D97 test method). This can be
particularly important in the industrial applications area, especially
in northern climates in the winter.
4
Solubility and Wettability
Solubility and wettability are particularly important properties
because future projections are that surfactants are going to have to
be more effective (soluble)
 Page 109
at colder water wash temperatures. Wettability is important in
industrial applications because wetting times need to be as short as
possible in order to reduce cycle times.
5
Fundamental Physical Property and Detergency Studies
A number of fundamental detergency studies have been conducted
to explore the effect of alcohol structure and molecular weight on
surfactant properties. Early studies showed that detergency was
strongly dependent on the length of the hydrophobe at a given
polyethyleneoxy chain length [81,82,77]. A particularly interesting
study was conducted comparing the effectiveness of a series of
pure, single polyethylenoxy alcohols (e.g., C12O[CH2CH2O]7H)
with conventional broad-range polyethylenoxy alcohols for oil soil
removal. Specifically, a procedure using radiolabeled oily soils was
used to compare the detergency of a series of pure, narrow-range,
linear dodecanol ethoxylates containing from 3 to 8 moles of
ethylene oxide (EO) and corresponding series of C12C13 alcohol
ethoxylates with normal, broad polyoxyethylene distributions [82].
This study found that the pure, single EO alcohol ethoxylates
significantly enhanced nonpolar soil removal from polyester/cotton
fabrics with an optimum for detergency with the 5-mole EO adduct
of dodecanol. However, there was no difference in detergency
performance between the narrow-range and broad-range
polyoxyethylene alcohols for polar soil (oleic acid) removal. These
results suggest that the broad-range conventional polyoxyethylene
alcohols that contain a significant fraction of the longer EO chain
adducts, which are more water-soluble, are much less effective for
oily soil removal. Thus, narrow-range polyoxyethylene alcohols
contain more of the effective oligomers "concentrated" in the
optimum detergency range compared with broad-range products
for oily soil removal.
Recent studies [83,84] have been conducted addressing the effects
of phase inversion temperature (PIT) and interfacial tension (IFT)
on optimum detergency performance for oily soil removal using
pure, homogeneous dodecyl ethoxylates (e.g., C12E3 and C12E8)
and their blends. Phase inversion temperature is that temperature at
which the transition from oil/water to water/oil phases occurs.
More precisely, the PIT refers to the condition whereby equal
volumes of oil and water are contained in the middle-phase
microemulsion. At the PIT of a system ultralow interfacial tension
occurs thus creating the conditions for maximum detergency.
Detergency results were obtained in a study [83] that established
the effect of temperature and the ethylene oxide content on the soil
removal from polyester/cotton blends. Some of the results from
this study are shown in Fig. 10 and 11. Additional studies [84,85]
involving correlation of PIT to optimum detergency temperatures
were conducted on polar and nonpolar soils using
nonionic/anionic surfactant blends of pure polyoxyethylene
alcohols (e.g., CxEy, where x is the number of carbons in
hydrophobe and y is the number of EO moles per mole of
hydrophobe).
 Page 110

Fig. 10
Effect of temperature on oil soil removal from
polyester/cotton using pure, homogeneous
polyoxyethylene dodoecyl alcohols
(C12E4 = 4 mole ethylene oxide
adduct of dodecanol [83].
B
Commercially Available Products
There are many producers of polyoxyethylene alcohols and a large
variety of products available under a large number of registered
names. A representative but by no means comprehensive list of
current manufacturers is shown in Table 3. A comprehensive
listing can be found in McKutcheon's series of detergent
manufacturers and sources [86]. The important physical and
surface properties of commercially available products are the same
as those discussed for single
 Fig. 11
Effect of ethylene oxide content on detergency using
blends of C12E3/C12E8 [83].
 Page 111
TABLE 3 Major Polyoxyethylene Alcohol
Manufactures
Product Alcohol type Manufacturer
Normal, primary,
Alfonics Vista
Ziegler
Normal, primary,
Alkanol DuPont
natural
Basophor Fatty alcohol BASF
Bio-Soft EA Fatty alcohol Stepan
Brij Normal, primary ICI
Diazopon
Fatty alcohol GAF
AN
Dispersol A Fatty alcohol GAF
EmulphogeneOxo, synthetic Rhone-Poulenc
Genapol Oxo, synthetic Hoecsht-Celanese
Branched
Iconol BASF
decyl/tridecyl
Neodol Oxo, synthetic Shell
Narrow-range
Novel Vista
ethoxylates
Alcolac, Rhone-
Siponic Fatty alcohol
Poulenc
Surfonic Oxo, synthetic Huntsman
Tergitol Secondary alcohol Union Carbide

TABLE 4 Typical Physical Properties of Water-Insoluble Nonionics [80]

Avg. Pour
EO,
Product Company Hydrophobe moles HLB point
(wt%)
EO (°C)
Neodol 91-
Shell C9,C10,C11 2.7 42.3 8.5 -13
2.5
Neodol 1-3 Shell C11 3.0 43.3 8.7 -7
Neodol 1-5 Shell 5.0 56.1 11.2 6
 C11
Neodol 23-1 Shell C12/C13 1.0 18.5 3.7 5
Neodol 23-3 Shell C12/C13 2.9 39.6 7.9 1
Neodol 23-5 Shell C12/C13 5.0 53.3 10.7 7
Neodol 25-3 Shell C12/C13/C14/C15 2.8 37.3 7.5 3
Neodol 45-
Shell C14/C15 2.23 30.8 6.2 15
2.25
Alfonic 610-
Vista C6/C8 /C10 3.1 50 10.0 -7
50R
Alfonic 810-
Vista C8/C10 2.2 40 8.0 -5
40
Alfonic
Vista C10/C12 2.5 39 8.0 -5
1012-40
Alfonic
Vista C12/C14 1.9 30 6.0 7
12146C-30
Alfonic
Vista C12/C14 2.0 40 8.0 4
12146C-40
Alfonic
Vista C14/C12 3.0 40 8.0 8
1412-40
Alfonic
Vista C12/C14/C16 1.3 22 4.4 4
1216-22
Brij30 ICI Lauryl 4 48.5 9.7
Genapol 26- Hoechst-
C12/C14/C16 1.5 25 5.0 10
L-1.6 Celanese
Genapol 26- Hoechst-
C12/C14/C16 3.0 40 8.0 5
L-3 Celanese
Genapol 26- Hoecsh-
C12/C14/C16 5.0 53 10 6
L-5 Celanese
Surfonic
Huntsman C10/C12 3 45 9.0 -15
L12-3
Surfonic
Huntsman C12/C14 2 27 5.3 10
L24-2
Surfonic
Huntsman C12/C14 3 40 8.0 5
L24-3
 Page 112
TABLE 5 Typical Physical Properties of Water-Soluble Nonionics [80]
Avg. Pour
EO,
Product Company Hydrophobe moles HLB point
wt%
EO (°C)
Neodol 91-6 Shell C9,C10,C11 6.0 62.1 12.4 52
Neodol 91-8 Shell C9,C10,C11 8.3 69.7 13.9 80
Neodol 1-7 Shell C11 7.0 64.3 12.9 58
Neodol 1-9 Shell C11 9.0 69.6 13.9 74
Neodol 23-
Shell C12/C13 6.6 60.0 12.0 43
6.5
Neodol 25-7 Shell C12/C13/C14/C157.3 61.3 12.3 50
Neodol 25-9 Shell C12/C13/C14/C158.9 65.6 13.1 74
C12/C13/C14
Neodol 25-12 Shell 11.9 71.8 14.4 78
/C15
Neodol 45-7 Shell C14/C15 7.0 58.2 11.6 45
Neodol 45-13 Shell C14/C15 12.9 71.8 14.4 80
Alfonic 810-
Vista C8/C10 4.8 60 12 38
60
Alfonic 1012-
Vista C10/C12 5.4 60 12 37
60
Alfonic 1412-
Vista C14/C12 7.2 60 12 52
60
Novel 1412-
70a
Vista C14/C12 11 70 14 78
Brij35 ICI Lauryl 23 85 16.9
Genapol 24- Hoechst-
C12/C14 6.3 58 11.6 45
L-45 Celanese
Genapol 24- Hoechst-
C12/C14 7.2 61 12.2 60
L-60 Celanese
Genapol 24- Hoechst-
C12 /C14 8.3 65 12.9 75
L-75 Celanese
Genapol 24- Hoechst-
L-92 Celanese C12/C14 10.6 70 14.0 92
Genapol 24- Hoechst-
C12/C14 7.0 60 12.1 60
L-60Na Celanese
Genapol 24- Hoecsh-
L-98Na Celanese C12/C14 11.3 71 14.2 98
Surfonic L12-
Huntsman C10/C12 6 62 12.4 48
6
Surfonic L24-
Huntsman C12/C14 7 59 11.9 48
7
Surfonic L24-
Huntsman C12/C14 9 65 13.0 73
9
Surfonic L24-
Huntsman C12/C14 12 72 14.4 65
12
Surfonic L46-
Huntsman C14/C16 7 58 11.6 48
7
a Narrow range ethoxylates.

carbon and single polyoxyethylene adducts, namely, foaming,

solubility, wettability, cloud point, and pour point. This section will
deal with information and studies using commercially available
products.
1
Physical Properties
(a)
Cloud Point
Information concerning the physical and chemical properties for a
selection of major commercial nonionic surfactants is given in
Tables 4 and 5 [80]. For convenience, the list is divided into water-
insoluble (oil-soluble) and water-soluble nonionics.
(b)
Viscosity
At room temperature, most nonionic surfactants form a gel with
the addition of water. Table 6 compares the viscosities of selected
commercial polyoxyethylene alcohols with their alkylphenol and
secondary alcohol counterparts at various surfactant concentrations
in water. This information
 Page 113
TABLE 6 Viscosities of Aqueous Ethoxylate Solutions (Centipoise at
22°C)
Product 10 20 30 40 50 60 80
Neodol 91-6 3 13 63 173 187 144 80
Neodol 91-8 2 6 29 138 Gel Gel 120
Neodol 1-5 30 48 58 71 1649 30350 54400
Neodol 1-7 3 14 109 Gel Gel 235 87
Neodol 1-9 2 6 26 245 Gel Gel 104
Neodol 23-5 2824895 Gel Gel Gel Gel 56500
Neodol 23-6.5 27 431 1620Gel Gel 37000a Gel
Neodol 25-7b 960c Gel Gel Gel Gel
Neodol 25-9b 70c Gel Gel Gel Gel
Neodol 25-12b 71c Gel Gel Gel Gel
Neodol 45-7b 2530Gel Gel Gel Gel
Neodol 45-13b 80 Gel Gel Gel Gel
Linear 1012 primary alcohol
160 208176a 37750a 201a
(5.2EO)
Random secondary alcohol (7EO) 88 179205d 1940a 116
Nonylphenol (9EO) 290 Gel Gel 3020 1080a
Octylphenol (9.5EO) 100 Gel Gel 1640 456
aFluid gel, by examination with polarized light.
bMeasured at 25°C.
cCentistokes.
dClear solution.

indicates the problems involved with handling and trying to

formulate aqueous products using various surfactants
(c)
Gel Curves or Phases
As can be seen in Table 6, concentrated solutions of
polyoxyethylene alcohols can often form gels. The gelling
characteristics are depicted in temperature vs. surfactant
concentration plots, called gel curves. To avoid gel formation, the
formulator must add the surfactant to, or dilute neat surfactant
with, water that has been heated above the peak temperature
displayed on the gel curve. A knowledge of gel curves is essential
for the proper handling of these materials. A typical gel curve for
Neodol 1-9 is shown in Fig. 12.
2
Surface Properties
The surface properties of commercially available products can be
obtained from supplier information. The main properties of
interest are wetting, foamability, and detergency.
(a)
Draves Wetting
The Draves wetting test measures the ability of a surfactant to
cause the solution to wet or spread evenly onto surfaces. The
surfactant with the shortest wetting time generally works faster.
Table 7
 Page 114

Fig. 12
Gel curve for Neodol 1-9 ethoxylate [80].
displays the wetting times of some selected commercial surfactants
at room (25°C) and elevated (60°C) temperatures.
(b)
Foam Performance
Polyoxyethylene alcohols have moderate foaming characteristics,
significantly less than their sulfated derivatives. However, foaming
can be both an asset or a liability depending on the desired end
use. Polyoxyethylene alcohols are actually used as foam breakers
when used in formulations above their cloud points, e.g., with
automatic dishwashing prod-
TABLE 7 Draves Wetting Times [79]
Seconds at Seconds at
Product
25°C 60°C
Neodol 91-6 5 4
Neodol 91-8 10 5
Neodol 1-5 5 5
Neodol 1-7 5
Neodol 1-9 9
Neodol 23-5 20 13
Neodol 23-6.5 9 16
Neodol 25-7 11 21
Neodol 25-9 14 6
Neodol 25-12 35 11
Neodol 45-7 17 15
Neodol 45-13 48 11
Linear 1012 primary alcohol
5 5
(5.2EO)
Random secondary alcohol (7EO) 6 9
Nonylphenol (9EO) 11 11
Octylphenol (9.5EO) 10 7
Linear 812 primary alcohol
7 6
EO/PO nonionic
Branched tridecyl alcohol
5 7
ethoxylate
 Page 115
TABLE 8 Dynamic Spray Foam Performance
Dynamic spray foam height, cm
(24°C, 0.1 wt%, distilled water)
Time, min
Product PSIG3 5 10 15 20 25 30
Neodol 91-6 10 33.2 47.0 53.5 >65
Neodol 91-6a 10 29.7 42.5 48.0 51.0
Neodol 91-6 15 0 8.0 30.0 36.0 42.0 52.0 53.0
Neodol 91-8 10 35.8 51.3 >60 >65
Neodol 91-8a 10 34.0 48.0 56.0 >60
Neodol 1-5 10 24.0 36.0 44.0 49.0
Neodol 1-5a 10 26.2 36.8 41.3 43.5
Neodol 1-7 10 32.5 47.0 56.5 >60
Neodol 1-9 10 35.0 52.0 >60 >60
Neodol 23-5 10 24.0 37.0 44.0 47.0 50.0
Neodol 23-6.5 10 33.0 46.0 53.0 58.0 >65
Neodol 25-7 10 19.5 37.5 46.7 50.8
Neodol 25-7a 10 27.2 40.7 46.9 50.3
Neodol 25-9 10 32.0 45.5 53.2 >60
Neodol 25-9 15 0 9.0 3.0 44.0 52.0 53.0 55.0
Neodol 25-12 10 36.5 51.0 >60 >65
Neodol 25-12a 10 32.3 45.8 51.5 56.0
Neodol 45-7 10 28.3 42.7 49.5 53.0
Neodol 45-7 15 0 0 13.0 26.0 37.0 44.0 47.0
Neodol 45-13 10 8.0 22.0 33.0
Nonylphenol (9EO) 10 29.3 42.6 49.0 52.1
Nonylphenol (9EO) 15 0 0 13.0 26.0 37.0 44.0 48.0
Octylphenol (9.5EO) 10 33.0 45.3 52.3 57.0
Secondary alcohol (5EO) 10 28.5 42.1 48.5 51.5
aSolutions containing 2% NaOH.

ucts. Therefore, knowledge of the foam profiles of various

surfactants enables one to choose the correct application.
Foam characteristics are often measured using dynamic spray foam
tests. Table 8 shows the dynamic foam heights for a variety of
commercial ethoxylates determined using the Shell dynamic spray
foam test in distilled water. This test method was designed to
generate foam data under more realistic dynamic conditions. Foam
is generated by injection of the surfactant solution through a spray
nozzle under specific conditions, onto a glass column.
Impingement of the sprayed circulating solution onto the glass
column wall generates foam
 Page 116
continuously and is measured as a function of time. Foam height is
interpreted as a relative measurement.
V
Applications
It is not possible to discuss all the uses of the polyoxyethylene
alcohols in detail. However, the overall use of these products will
be discussed in general terms, with the major areas of applications
being addressed. At the end of this section, future trends for
applications of polyoxyethylene alcohols will be discussed.
A
Household Surfactants
The household market is one of the largest uses for surfactants
with the products being compounded as powders, liquids (or gels),
pastes, or bars. There are a variety of uses that nonionic surfactants
find in the home. Heavy-duty liquids or powders are commonly
used in general home laundry [8793] and light-duty liquids are
used in hand dishwashing [94]. The polyoxyethylene alcohols are
often used in combination with their sulfated derivatives for
maximum efficacy. Such starter formulations can be found in
commercial brochures [94].
Polyoxyethylene alcohols are also a key component as a defoaming
aid for automatic dishwashing applications. Degreasers are also
used both in the house and in the garage to remove oil spills and
stains. Home carpets are often cleaned with the aid of prespotters
that are a combination of surfactants including nonionics. Hard
surface cleaning (e.g., floors, walls, countertops, tiled areas) is a
problem that is facilitated by the use of nonionics such as Shell's
Neodol 1 and Neodol 91 series of surfactants [95,96].
B
Industrial and Institutional Applications
1
Pulp and Paper
The pulp and paper industry uses polyoxyethylene alcohols in
several stages of their manufacturing processes. Wetting agents are
essential for the proper treatment of paper and box board, i.e., for
rapid impregnation of solutions into the fibers. Deinking of
magazines and newsprint requires significant usage of these
alcohols in the need for recycling [97,98]. The deinking process
utilizes surfactants such as polyoxyethylene alcohols for the
dispersion and removal of various inks and coatings. The
surfactants must be sufficiently effective to return the sheet
brightness to essentially that of original newsprint quality paper
[99,100]. An essential characteristic is low foaming for the
deinking process. Often propoxylated polyoxyethylene alcohols
are used for this purpose.
2
Textile and Wool Scouring
Conventional processes for applying chemicals to fabric in textile
finishing mills require 60100% wet pickup from aqueous
solutions. Then the fabric must
 Page 117
be dried to remove the water used in the process. An economic
problem is encountered when large amounts of water must be
handled and long drying times used. These problems can be
minimized using polyoxyethylene alcohols to aid in the wet pickup
process using foams that contain much less water [101].
Another application is the use of the nonionic surfactants to aid in
the dyeing of the fabrics. This is a major application in the area of
textile dyeing [102107] and finishing of cotton textiles. The
surfactants used must be effective in agglomeration of dye particles
into micelles and deposition onto the textile.
3
Agricultural Emulsions and Spray Adjuvants
The polyoxyethylene alcohols are excellent emulsifiers for
agricultural formulations. Most active ingredients for pesticides
and herbicides are hydrocarbonsoluble materials and must be
mixed with water prior to use. Consequently, the solution must be
emulsified using a surfactant [108,109]. Modern liquid fertilizers
also use surfactants to aid in the delivery of the phosphate salt to
the root system. Surfactant are also used in spray adjuvants to
enable the liquid pesticide or herbicide to wet and penetrate the
plant leaves.
4
Enhanced Oil Recovery (EOR)
The recovery of crude oil from oil-producing properties that have
declined in production over the years has been a profitable
industry over the years. The use of surfactants to increase the
production of oil from uneconomic drilling rigs has increased
steadily over the years [110,111]. Interest is always the highest
when the price of crude oil increases. The mechanism of action for
surfactant-assisted recovery of crude oil has also been the subject
of much academic and industrial investigation [112].
5
Future Uses
One attractive potential new application for polyoxyethylene
alcohols and their sulfated derivatives is in the area of soil
remediation and environmental cleanup [113]. Soil has become
contaminated in many parts of the country through a combination
of activities (excessive use of fertilizers, pesticides, chemical
disposal, etc.). One promising new research area is the
development of surfactants and formulations for the removal of
contaminants from soil. With an increasing emphasis on
environmental issues, soil remediation could become a new area
for applications for polyoxyethylene alcohols.
References
1. H. Adkins and R. Conner, J. Am. Chem. Soc. 53:1091 (1931).
2. H. Adkins and K. Folkers, J. Am. Chem. Soc 53:1095 (1931).
3. H. R. Arnold and W. A. Lazier, U.S. Patent 2,116,552 to Dupont
(1938).
4. W. B. Johnston, U.S. Patent 2,347,562 to American Cyanamid
(1994).
5. E. F. Hill, G. R. Wilson, and E. C. Steinle, Ind. Eng. Chem.
46(9):1917 (1954).
 Page 118
6. J. Burgers, Canadian Patent 672,715 to Procter & Gamble
(1960).
7. V. Mills, German Patent 1,008,273 to Procter & Gamble (1957).
8. A. Abbey, British Patent 573,788 to Procter & Gamble (1945).
9. H. Corr, British Patent 921,477 to BASF (1963).
10. K. Negi, French Patent 1,375,472 (1964).
11. G. Harrison, Pet Int. App. 90/8127 to Davy McKee (1990).
12. M. Wilmott, U.S. Patent 5,138,106 to Davy McKee (1992).
13. M. Wilmott, U.S. Patent 5,157,168 to Davy McKee (1992).
14. Linear Alpha Olefins, Report No.12C, Process Economic
Program, SRI International (1990).
15. P. J. Flory, J. Am. Chem. Soc. 62:1561 (1940).
16. H. B. Fernald et al., U.S. Patent 3,482,000 to Gulf (1969).
17. R. T. Armstrong, Canadian Patent 831,550 to Gulf (1970).
18. H. B. Fernald et al., U.S. Patent 3,510,539 to Gulf (1970).
19. G. R. Lappin, et al. (eds.), Alpha Olefins Applications
Handbook, Marcel Dekker, New York, 1989.
20. K. Ziegler, British Patent 944,935 (1963).
21. K. Ziegler, German Patent 1,191,815 (1966).
22. British Patent 1,037,866 (1966).
23. A. E. Harkins, Jr., U.S. Patent 3,655,809 to Ethyl (1972).
24. C. W. Lanier, U.S. Patent 3,789,081, to Ethyl (1974).
25. W. T. Davis, Canadian Patent 834,217, to Ethyl (1970).
26. W. T. Davis, U.S. Patent 3,395,292 to Ethyl (1967).
27. C. W. Lanier, U.S. Patent 3,686,250 to Ethyl (1972).
28. P. Kobetz, U.S. Patent 3,689,584 to Ethyl (1972).
29. Shell Higher Olefins ProcessSHOP, Technical Bulletin SC:335-
84, Shell Chemical Company, 1984.
30. E. F. Magoon et al. U.S. Patent 3,483,269 to Shell Oil (1969).
31. P. W. Glockner, U.S. Patent 3,530,200 to Shell Oil (1970).
32. H. J. Alkema et al., U.S. Patent 3,634,539 to Shell Oil (1972).
33. E. F. Magoon et al., U.S. Patent 3,592,866 to Shell Oil (1971).
34. R. Van Helden et al., U.S. Patent 3,728,414 to Shell Oil (1973).
35. P. A. Verbrugge, U.S. Patent 3,776,975 to Shell Oil (1973).
36. R. F. Mason et al., U.S. Patent 3,758,558 to Shell Oil (1973).
37. E. R. Freitas et al., ''Shell Higher Olefins ProcessSHOP," Paper
No.27a, presented at the American Institute of Chemical Engineers,
85th National Meeting and Chemical Plant Equipment Exposition,
Philadelphia, Pennsylvania, June 48, 1978.
38. A. E. O'Donnell et al., U.S. Patent 4,377,499 to Shell Oil
(1983).
39. D. M. Singleton, U.S. Patent 4,503,280 to Shell Oil (1985).
40. E. F. Lutz, U.S. Patent 4,528,416 to Shell Oil (1985).
41. E. R. Freitas, Chem. Eng. 75(1):73 (1979).
42. I. Wender, S. Metun, S. Ergun, H. W. Sternberg, and H.
Greenfield, J. Am. Chem. Soc. 78:5401 (1956).
43. I. Wender, H W. Sternberg, and M. J. Orchin, J. Am. Chem.
Soc. 75:3041 (1953).
44. H. Lemke, Hydrocarbon Process. Petrol. Refin. 45(2):148
(1966).
45. R. F. Heck and D. S. Breslow, J. Am. Chem. Soc. 83:4023
(1961).
46. L. Marko, G. Bork, G. Almasy, and P. Szabo, Brennstoff-
Chem. 44:184 (1959).
 Page 119
47. L. Kirch and M. Orchin, J. Am. Chem. Soc. 80:4428 (1958).
48. J. Falbe, Carbon Monoxide in Organic Synthesis, Springer-
Verlag, New York, 1967, pp. 175.
49. L. H. Slaugh et al., U.S. Patent 3,239,566 to Shell Oil (1966).
50. L. H. Slaugh et al., U.S. Patent 3,239,569 to Shell Oil (1966).
51. L. H. Slaugh et al., U.S. Patent 3,239,570 to Shell Oil (1966).
52. L. H. Slaugh et al., U.S. Patent 3,239,571 to Shell Oil (1966).
53. C. R. Greene et al., U.S. Patent 3,274,263 to Shell Oil (1966).
54. Robert H. Schwaar and Kenneth E. Lunde, "Linear C12C15
Primary Alcohols," Report No.163, Process Economics Program,
SRI International, 1983.
55. French Patent 1,379,144 to Ethyl (1964).
56. W. T. Davis et al., French Patent 1,433,679 to Ethyl (1964).
57. Robert G. Muller, Linear Higher Alcohols, Report No. 27,
Process Economics Program, SRI International, 1967.
58. T. Hellthaler et al., German Patent 552,886 to A. Riebecksche
Montanwerke, (1934).
59. Japanese Patent 18-157177 to Kao Soap (1943).
60. Technology Newsletter, Chem. Week, p. 59, Jan. 28, 1967.
61. G. H. Twigg, The Mechanism of Liquid-Phase Oxidation,
Special Supplement to Chem. Eng. Sci. 3:5 (1954).
62. V. V. Veselov et al., Oxidation of Liquid Paraffinic
Hydrocarbons to Alcohols in the Presence of Small Amounts of
Boric Acid, Nauch-Issled. Inst. Sintetich, Zhirozamenitelei I
Moyushchikh Sredstv 2:39 (1961).
63. V. V. Veselov et al., The Thermal Stability of Borates of
Secondary High-Molecular-Weight Alcohols, Nauch-Issled. Inst.
Sintetich, Zhirozamenitelei I Moyushchikh Sredstv 2:33 (1961).
64. F. R. Mayo and C. Walling, Chem. Rev. 27:351 (1940).
65. P. J. Garner and H. N. Short, U.S. Patent 2,587,990 to Shell
Development Co. (1952).
66. K. L. Butcher and G. M. Nickson, J. Appl. Chem. (London)
10:65 (1960).
67. R. B. Mosely et al., U.S. Patent 3,299,150 to Shell Oil (1967).
68. A. Mitsutani et al., French Patent 1,457,718 to Kurashiki Rayon
(1966).
69. British Patent 1,049,043 to Kurashiki Rayon (1966).
70. K. C. Rottenberg, U.S. Patent 2,779,803 to Phillips Petroleum
(1957).
71. E. Santacesaria, M. Di Serio, R. Garaffa, and G. Addino, Ind.
Eng. Chem. Res. 31:2419 (1992).
72. W. D. Satkowski and C. G. Hsu, Ind. Eng. Chem. 49:1875
(1957).
73. N. Shachat and H. L. Greenwald, in Nonionic Surfactants (M.
J. Schick, ed.), Marcel Dekker, New York, 1966, p. 22.
74. C. L. Edwards, unpublished results.
75. Michael Arne, Nonionic Surfactants, Process Economic
Program Report No. 168, SRI International, 1984.
76. K. W. Dillan, J. Am. Oil Chem. Soc. 62:1144 (1985).
77. H. L. Benson and Y. C. Chiu, Relationship of Detergency to
Micellar Properties for Narrow Range Alcohol Ethoxylates,
Technical Bulletin SC:443-80, Shell Chemical Company, 1980.
78. C. L. Edwards, U.S. Patent 5,057,627 to Shell Oil Co. (1991).
79. W. C. Griffin, J. Soc. Cosmet. Chemists 1:311 (1949).
 Page 120
80. Neodol Ethoxylates and Competitive Nonionics Properties
Guide, SC:569-94, Shell Chemical Company, 1994.
81. B. M. Finger et al., Detergent Alcohols: The Effect of Alcohol
Structure and Molecular Weight on Surfactant Properties,
Technical Bulletin SC:364-80, Shell Chemical Company, 1980.
82. E. B. M. Finger, G. A. Gillies, G. M. Hartuig, E. R. Ryder, Jr.,
W. M. Sauyer, and H. Stupel, J. Am. Oil Chemists Soc. 44:525
(1967).
83. H. L. Benson and K. H. Raney, The Requirements for Optimum
Detergency, presented at New Horizons 1989 Detergent Industry
Conference, Hershey, PA., October 29November 1, 1989.
84. K. H. Raney and H. L. Benson, J. Am. Oil Chemists Soc.
67:722 (1990).
85. K. H. Raney, J. Am. Oil Chemists Soc. 68:525 (1991).
86. McCutcheon's Volume 1: Emulsifiers and Detergents, North
American Edition, M. C. Publishing, Glen Rock, NJ, 1994.
87. L. Kravetz and D. Scharer, The Formulation and Performance
of Heavy-Duty Liquid Laundry Detergents, Technical Bulletin
SC:180-77, Shell Chemical Company, 1977.
88. D. W. Bisacchi, W. T. Shebs, and H. Stupel, No-Phosphate
Liquid Laundry Detergents, presented at the American Oil
Chemists Society, 47th Annual Fall meeting, September 18, 1973,
Chicago, Illinois.
89. L. Kravetz and M. M. Wald, Detergency and Formulation
Optimization of Unbuilt, Quarter Cup Heavy Duty Laundry
Liquids, Technical Bulletin SC:344-18, Shell Chemical Company,
1981.
90. C. L. Merrill, The Optimization of Heavy Duty Liquids
Containing Fabric Softener, Technical Bulletin SC:839-85, Shell
Chemical Company, 1985.
91. L. Kravetz and K. F. Guinn, Effect of Surfactant Structure on
Stability of Enzymes Formulated into Laundry Liquids, Technical
Bulletin SC:814-91, Shell Chemical Company, 1991.
92. C. L. Merrill, Development of a Nonionic Surfactant-Based
High Density Laundry Powder, Technical Bulletin SC:968-91, Shell
Chemical Company, 1991.
93. L. Kravetz, Effects of Surfactant Structure on Detergency
Performance of Laundry Powders Formulated with Zeolite 4A as
Builder, Technical Bulletin SC:581-94, Shell Chemical Company,
1994.
94. Neodol Product Guide for Alcohols, Ethoxylates and
Derivatives, Technical Bulletin SC:7-94, Shell Chemical Company,
1994.
95. Nonionic Surfactants in Hard Surface Cleaners, Technical
Bulletin SC:441-80, Shell Chemical Company, 1980.
96. B. Lindman, S. Engstroem and J. Baeckstroem, J. Surf. Sci.
Technol 4(1):23 (1988).
97. C. W. Schroeder, U.S. Patent 2,913,356 to Shell Development
Co. (1959).
98. K. J. Lissant, U.S. Patent 3,069,306 to Petrolite Corporation
(1962).
99. J. K. Borchardt and D. L. Wood, Preliminary Studies of the
Deinking of Office Papers, Technical Bulletin SC:1430-92, Shell
Chemical Company, 1992.
100. J. K. Borchardt and D. L. Wood, Surfactants in the Deinking
of Old Newspapers, Technical Bulletin SC:1394-92, Shell
Chemical Company, 1992.
101. NEODOL Ethoxylates in Textile Foam Finishing, Technical
Bulletin SC:541-87, Shell Chemical Company, 1987.
 Page 121
102. H. B. Goldstein and H. W. Smith, Lower Limits of Low Wet
Pickup Finishing, Textile Chemist and Colorist 12:49 (1980).
103. B. L. Richardson, Foam Dyeing of Carpets Hits Its Stride,
Textile World, January 1981, p. 55.
104. D. H. Ashmus, W. W. Rankin, and A. T. Walter, U.S. Patent
4,023,526 (1977).
105. H. Werdenberg, U.S. Patent 3,068,058 to Ciba (1962).
106. K. Knopf and E. Schollmeyer, Tenside Det. 24(2):101 (1987).
107. W. Becker, D. Knittel and E. Schollmeyer, Tenside Det.
24(5):264 (1987).
108. R. L. Sundberg and J. M. Cross, U.S. Patent 2,965,678 to
General Aniline and Film Corp. (1960).
109. J. C. Wiedow, U.S. Patent 2,893,913 to Monsanto (1959).
110. K. Kosswig, Chemie in unserer Zeit 18(3):87 (1984).
111. M. M. da Gama and K. E. Gubbings, Mol. Phys. 59(2):227
(1986).
112. C. C. Mattax, Proc. World Pet. Congr. 11th, 3:205 (1984).
113. C. C. West and J. H. Harwell, Environ. Sci. Technol
26(12):2324 (1992).
 Page 123

4
Polyoxyethylene Esters of Fatty Acids
Kurt Kosswig*
Hüls AG, Marl, Germany

I. Introduction 123
II. Synthesis and Properties of Defined
125
Polyoxyethylene Esters
A. Synthesis of Defined Polyoxyethylene Esters 125
B. Properties of Defined Polyoxyethylene Esters 126
III. Synthesis of Polyoxyethylene Fatty Acid Esters in
Industrial Practice and the Properties of Products 129
Obtained Thereby
A. Oxyethylation of Fatty Acids and of Fats and Oils 129
B. Esterification of Fatty Acids or Transesterification
134
of Fats and Oils with Polyoxyethylene
C. Polyoxyethylene Esters of Ricinoleic Acid and
134
Castor Oil
D. Properties of Commercial Polyoxyethylene Esters
135
of Fatty Acids
E. Oxyethylation of Fatty Acid Methyl Esters 141
IV. Analysis of Polyoxyethylene Fatty Acid Esters 142
 V. Toxicologic Aspects and Biodegradation 142
A. Toxicologic Aspects 142
B. Biological Degradation 142
VI. Synopsis and Future Outlook 142
References 144

I
Introduction
Polyoxyethylene esters of fatty acids were among the first nonionic
surfactants commercialized, when Schöller and Wittwer invented
oxyethylation, i.e., the reaction of ethylene oxide with a proton-
active substrate, in 1930 [1]. The
* Retired.
 Page 124
mono- and diesters of ethylene glycol and oligoethylene glycols
had of course been known before, having been synthesized by
esterification of the corresponding glycols with the acids or by
analogous condensation reactions.*
Goldsmith [2] has given an excellent review on work reported up
to 1942 on the preparation, properties, and uses of polyhydric
alcohol esters of fatty acids, starting with a publication of A. Wurtz
in 1859. In this review six synthesis methods are discussed: (1)
direct esterification of hydroxyl groups with fatty acids or their
anhydrides in the presence or absence of dehydrating agents; (2)
esterification by means of fatty acid halides; (3) transesterification
of triglycerides with polyhydric alcohols; (4) reaction of
hydroxyalkyl halides with fatty acid salts accompanied by the
formation of metal halides; (5) the partial hydrolysis of completely
esterified polyhydric alcohols; and (6) the addition of ethylene
oxide to compounds containing hydroxyl or carboxyl groups. Of
these methods, direct esterification, transesterification, and
addition of ethylene oxide to fatty acids are being carried out today
to synthesize polyoxyethylene esters of fatty acids. While the
esterification and transesterification reactions lead to the
polyoxyethylene diesters in high yields when the appropriate molar
ratios of starting materials are chosen, it is a key feature of these
reactions that they are not suited to selective preparation of the
monoesters, when the molar ratio of polyoxyethylene and acid is
accordingly adjusted. Instead, the reaction product consists of a
mixture of the desired monoesters together with considerable
amounts of diesters and unreacted polyoxyethylene, as long as the
polyoxyethylene is not introduced in great excess. This
composition is explained by equal reactivity of both hydroxyl
groups of the polyoxyethylene (glycol) as well as by the
disproportionation of the polyoxyethylene monoester formed in a
first step by transesterification:

The addition of ethylene oxide to a fatty acid yields a product

mixture similar to that obtained in the esterification reaction of
polyoxyethylene and fatty acid in a molar ratio of (1:1).
The preparation of pure polyoxyethylene monoesters, described
below, is more demanding. At the same time the pure monoesters
by themselves may disproportionate even in the absence of
catalysts [7]. The pure monoesters therefore are of no relevance in
industrial applications, despite the fact that they are, on the
grounds of their chemical structure, the only true surface active
species in the mixtures obtained by esterification or oxyethylation
of fatty acids. Instead, the latter mixtures are produced industrially
and used as such in a variety of applications. Today, quite a few
products are obtained by esterification or oxyethylation of fats and
oils, i.e., triglycerides, instead of the fatty acids originating
therefrom, yielding products with a somewhat different
* See Refs. 16 for historical accounts and general overviews.
 Page 125
composition and containing chemically bound glycerol. Because of
the close relation of these products to the true polyoxyethylene
esters, they are also treated in this chapter.
II
Synthesis and Properties of Defined Polyoxyethylene Esters
A
Synthesis of Defined Polyoxyethylene Esters
The direct esterification of polyoxyethylene with fatty acids in a
molar ratio of 2:1 to yield the diesters is a simple and
straightforward reaction. It is the oldest method recorded [2].
Although the reaction already proceeds at room temperature, it is
too slow to be of practical use. In general, the esterification is
carried out at temperatures between 150 and 250°C. Acidic,
amphoteric, and alkaline catalysts have been suggested for this
reaction [2], sodium or potassium hydroxide or p-toluenesulfonic
acid being preferred. To complete the conversion, water of
reaction must be removed by vacuum or by a current of air or an
inert gas. As the reaction mixture is often heterogenous in the
initial stage, it has to be agitated. To lower the reaction
temperature, carrier solvents such as toluene are often used. At the
end of the reaction, unreacted polyoxyethylene may be removed by
washing with water. Residual fatty acid may be extracted or
precipitated as sodium salt, although some solvent for the diester
such as dichloroethylene or acetone, which subsequently has to be
evaporated, is requisite in this operation.
The formation of the polyoxyethylene monoester is the first step in
the esterification reaction. Fatty acids are more readily miscible
with the monoesters than with polyoxyethylenes and therefore they
react more rapidly with the free hydroxyl group of the monoester
than with one of the two hydroxyl groups of the polyoxyethylene.
This is detrimental for the synthesis of monoesters. Consequently,
high selectivities of monoesters in the esterification reaction can
only be achieved if large excesses of polyoxyethylene over the
fatty acid are employed, with molar ratios of polyoxyethylene to
fatty acid of 612 being quite common [8,9]. After completion of
the reaction, excess polyoxyethylene is washed out with water,
preferably with a concentrated salt solution [2,10]. In this reaction
the methyl esters of the fatty acids may be used instead of the free
acids as starting material, preferably in the presence of an alkaline
catalyst [11].
A more pretentious method of preparing monoesters is the
esterification of fatty acids with polyoxyethylene in which one of
the two terminal hydroxyl groups is protected. Boric acid was
shown to be a good protective agent [12]. Some fatty acid
monoesters of ethylene glycol [12], polyethylene glycol 600 or
dodecaoxyethylene, POE-(12) [13], and monodisperse
polyoxyethylene with 18 ethylene oxide units in the
polyoxyethylene chain [8,14] were prepared. In this method, which
can be accomplished as a one-pot reaction, first poly-
 Page 126
oxyethylene is esterified with boric acid at about 100°C in a molar
ratio of 3:1, which leads to the tris(1-
hydroxypolyoxyethylene)orthoboric acid ester. This in turn is
esterified with fatty acid at 100°C in the presence of p-
toluenesulfonic acid as catalyst. After esterification by removal of
water in vacuo, the boric acid is hydrolyzed by addition of water.
The polyoxyethylene fatty acid monoester can then be extracted,
e.g., with trichloroethylene. Alternatively, the reaction mixture is
washed with brine.

The selective synthesis of polyoxyethylene monoesters or diesters

of fatty acids by the addition of ethylene oxide to fatty acids in an
oxyethylation reaction is not possible:

As will be discussed in Sec. III.A, the ethylene glycol monoesters

initially formed in this reaction quickly transesterify, leading to a
mixture of mono- and diesters and ethylene glycol. The same is
true for the polyoxyethylene esters formed by successive addition
of ethylene oxide to the monoglycol ester formed in the first place.
It is only with certain catalysts, such as amines [15] or amine
oxides [16], that transesterification is suppressed until 1 mole of
ethylene oxide has been added to 1 mole of acid. Beyond that
equilibration occurs again.
The mono- and diesters of polyoxyethylenes can obviously be
isolated from their mixtures by separation techniques. Ethylene
glycol monolaurate and dilaurate for example, as well as diethylene
glycol dilaurate, have been isolated from oxyethylated lauric acid
by distillation [17]. Nevertheless, this method, as well as molecular
distillation [18], is of limited use in the preparation of
polyoxyethylene esters, especially their higher homologs.
B
Properties of Defined Polyoxyethylene Esters
Physical data of pure polyoxyethylene fatty acid mono- and
diesters are scarce and moreover difficult to scrutinize, as
information on the purity of the product and the polydispersity of
the polyoxyethylene chain is lacking in most cases. Unambiguous
data were published by Gerhardt and Holzbauer [14], who reported
the melting points and refractive indices for the first eight
homologous polyoxyethylene monoesters of lauric acid, as shown
in Table 1.
Collected data on melting points of polydisperse polyoxyethylene
esters of fatty acids follow a general pattern. The monoesters melt
at a lower temperature than the diesters with the same
polyoxyethylene chain length. Starting with the ethylene glycol
esters of lauric through stearic acid, the melting points decrease
 Page 127
TABLE 1 Melting Points and Refractive Indicesa
(nD40) of Homologous Polyoxyethylene Monoesters
of Lauric Acid
Melting
C11CO(OCH2CH2)xOH x = nD40
point (°C)
1 2830 1.4405
2 1718.5 1.4431
3 1516.5 1.4449
4 1718 1.4462
5 1921 1.4478
6 2123 1.4495
7 2627.5 1.4515
8 3031 1.4522
a According to Ref. 14.

with increasing number of ethylene oxide units in the

polyoxyethylene chain, with a minimum at an average chain length
of about eight ethylene oxide units, increasing again to the level of
the melting points of the monoethylene glycol esters when an
average chain length of 1220 ethylene oxide units has been
reached. The polyoxyethylene esters of oleic acid have the lowest
melting points and are liquid at room temperature. A comparison
of the melting points of some fatty acid esters of ethylene and
diethylene glycol may be instructive, taking the highest reported in
each case [2]; see Table 2. A study of the phase behavior of the
monomyristate, monopalmitate, and monostearate of ethylene
glycol together with the esters of some other polyhydroxy
compounds has shown that ethylene glycol monostearate is
dimorphic [20].
TABLE 2 Melting Points of Fatty Acid Estersa of Ethylene
and Diethylene Glycol
Ester Melting point (°C)
Ethylene glycol monolaurate 32
dilaurate 54
monomyristate 42
dimyristate 64
monopalmitate 52
dipalmitate 72
monostearate 58
distearate 79
Diethylene glycol monolaurate 18
dilaurate 39
monostearate 42
distearate 58
a According to Ref. 2.
 Page 128
TABLE 3 Surface Tensiona (mN/m) at 25°C of
Polyoxyethylene Monoesters of Fatty Acids at
Three Concentrations
Concentration (wt%)
Fatty acid 0.05 0.1 0.2
Laurate 33.0 32.0 31.1
Myristate 35.3 34.8 34.5
Palmitate 38.5 38.1 37.5
Stearate 41.5 39.8 38.7
Oleate 38.3 36.7 35.6
Ricinoleate 39.4 38.5 38.0
a According to Ref. 13.

The fatty acid monoesters of polyoxyethylene are highly soluble in

water at room temperature if their HLB values are 9 and higher; in
the range of HLB values between 9 and 11 the solutions usually are
cloudy; at higher HLB values they are clear (the lauric acid
monoester of pentaoxyethylene, for example, has an HLB of 10.6).
Data on the surface activity of defined monoesters are scarce. Rao
et al. report values for surface tensions of PEG 600
[polyoxyethylene-(12)] monoesters of some fatty acids at different
concentrations [13], see Table 3.
Critical micelle concentrations (CMCs) cannot be extrapolated
from these values, but one can surmise that these concentrations lie
somewhat above 0.2% or roughly 0.04 mmol/L. Holzbauer and
Gerhardt present a diagram from which CMCs between 0.05 and
1.10 mmol/L can be deduced for the lauric acid monoesters of
ethylene glycol up to octaethylene glycol (octaoxyethylene) [19].
Unfortunately, these values are not very consistent. Aqueous
solutions of polyoxyethylene monoesters are somewhat poor in
foaming. In contrast, the monoesters of at least the lower fatty
acids are good wetting agents. The wetting properties have been
studied in some detail [8]. It was shown that monoesters with HLB
values adjusted to about 10 are excellent wetting agents, comparing
well with the corresponding polyoxyethylene ethers of fatty
alcohols. The monoesters of polyoxyethylenes are good
emulsifiers [13,19]. In practical use, the classical formula of
Griffin for the hydrophilic-hydrophobic balance can be applied:

The colloidal properties of polyoxyethylene monoesters are

impaired by diesters and free polyoxyethylene. A shortcoming is
the fact that they are chemically unstable in the sense that they can
disproportionate or that they can be hydrolyzed in aqueous
medium.
 Page 129

III
Synthesis of Polyoxyethylene Fatty Acid Esters in Industrial
Practice and the Properties of Products Obtained Thereby
A
Oxyethylation of Fatty Acids and of Fats and Oils
The oxyethylation of fatty acids or of fats and oils, i. e., the
addition of ethylene oxide to the mentioned substrates, is carried
out in the presence of alkaline catalysts at temperatures between
120°C and 200°C, preferably 140180°C, and advantageously at
slightly elevated pressures of 15 bar gauge under vigorous stirring
or mixing by circulation, with the usual safety precautions [21]
being taken into account. The oxyethylation of fatty acids, fats, and
oils today is carried out exclusively in a discontinuous batchwise
manner. Continuous oxyethylations of fatty acids, fatty alcohols,
and fatty amines have been described [22] but are not used in
practice.
Catalysts are employed in concentrations from 0.01% to 2.0% by
weight. Usually sodium or potassium hydroxide or carbonate are
used. They are added to the substrate, with the water of reaction
formed thereby being expelled by application of vacuum or by
blowing a current of nitrogen through the mixture at elevated
temperature prior to the successive addition of ethylene oxide. Of
course, the alkali salts of the fatty acids themselves may be
introduced directly as catalyst; furthermore, alkali metals or their
alcoholates may be used to generate the carboxylate ions of the
fatty acids as catalytically active species [23]. Besides these, other
alkaline substances have been proposed, e.g., amines [15] and
amine oxides [16].
The alkali-catalyzed oxyethylation of fatty acids has to be
interpreted as the nucleophilic addition of a carboxylate ion to an
ethylene oxide molecule in the first stage.
Wrigley et al. have elucidated the mechanism of this reaction,
comparing the oxyethylation of fatty acids to that of fatty alcohols
[24]. Some later publications concerning the kinetics of the
reaction of stearic acid with ethylene oxide [25] have only
confirmed the original findings and conclusions. The carboxylate
ion is introduced either as a sodium, potassium, or ammonium salt,
or it is generated in situ from an alkaline moiety and free
carboxylic acid. The carboxylate ion approaches an ethylene oxide
molecule yielding in a rather slow addition reaction an
acyloxyethoxy anion, which in turn exchanges a proton with
unreacted fatty acid in a fast reaction, the anion of the latter being
less basic than the (acyloxy) ethoxy anion:
 Page 130
As long as unreacted acid is available in the reaction medium, the
reaction path described above is the predominant one. Stockburger
and Brandner suggested that the addition of the carboxylate ion to
ethylene oxide might proceed via a loose addition compound of
one molecule of fatty acid to one molecule of ethylene oxide
analogous to an intermediary complex discussed by Woytech and
Patat for the addition of ethylene oxide to phenols [26]. The
acyloxyethanol or ethylene glycol fatty acid monoester formed in
the first reaction step will not react with ethylene oxide present in
the reaction mixture before all fatty acid is consumed because it is
only then that the strongly basic and nucleophilic (acyloxy)ethoxy
anion will not be protonated to an electrically neutral molecule
immediately after it is formed but will nucleophilically attack an
additional ethylene oxide molecule:

It is this reaction that runs into the normal oxyethylation reaction,

yielding an assembly of homologs distributed in a normal way
(Poisson distribution), but which in contrast to the oxyethylates of
fatty alcohols does not contain any unreacted starting material
when the degree of oxyethylation, i.e., the number of moles of
ethylene oxide added to 1 mole of acid, exceeds 1.
The fact that the less nucleophilic and therefore less reactive
carboxylate anion prevails in the reaction mixture in the starting
phase has the peculiar effect that the rate of uptake of ethylene
oxide is slow in this phase, as compared to that of the
oxyethylation of fatty alcohols or as compared to the rate after all
fatty acid in the mixture has been consumed, leaving only species
with alcoholic groups to react. This phenomenon, which is also
encountered in the oxyethylation of phenols, is exemplified in Fig.
1 [24].
As was already mentioned in the introduction to this chapter, the
monoesters of polyoxyethylenes transesterify easily. Conversions
in the oxyethylation of fatty acids therefore are not confined to the
reaction sequence discussed above but also comprise
transesterification, which leads to polyoxyethylene diesters and
free polyoxyethylene in equilibrium with polyoxyethylene
monoesters. Stockburger and Brandner have studied the
oxyethylation of oleic acid in detail, determining the composition
of the reaction product depending on the amount of ethylene oxide
added [26,27]. Their findings are summarized in Fig. 2. This
diagram shows impressively that the equilibrium reaction between
polyoxyethylene monoesters on one side and polyoxyethylene
diesters as well as polyoxyethylene on the other side occurs as
soon as 1 mole of ethylene oxide has been added to 1 mole of acid,
i.e., the point where all fatty acid has been consumed. The molar
ratios of monoesters to diesters to free polyoxyethylene
(polyethylene glycol, which is also called polyol) are found to be
approximately 2:1:1, giving an equilibrium constant of about 4.
 Page 131

Fig. 1
Reaction rate of the oxyethylation of stearic acid
as compared to that of octadecanol. Reaction
conditions: 0.5% KOH, 160°C.
(From Ref. 24, with permission.)

The diagram also shows that diester and free polyol formation
starts at the beginning, yielding substantial amounts of these
species even before all fatty acid has reacted. They originate from
the esterification of ethylene glycol monoester primarily formed
with free fatty acid to the diester and water, with the water reacting
further with ethylene oxide to give polyoxyethylene (polyethylene
glycol). In an uncatalyzed oxyethylation of fatty acids, which
 Page 132

Fig. 2
Product composition in dependence of moles of ethylene oxide reacted with oleic acid.
(From Ref. 27, with permission.)
proceeds very slowly, incidentally water of reaction does not react further
with ethylene oxide [26].
Reactions occurring during the alkali-catalyzed oxyethylation of fatty
acids, which in the end always lead to equilibrium mixtures, can be
summarized as follows:
Initial formation of reactive species:

Starting phase:
Side reactions during the starting phase:
 Page 133
Consecutive phase after all fatty acid has reacted:

and so on, accompanied by proton exchange, which leads to a

normal homolog distribution:

Side reactions during the consecutive phase via anionic

intermediates:

Water present in the reaction mixture, originating either from the

catalyst or from the esterification of acyloxyethylene glycol with
fatty acid in the starting phase, reacts via hydroxylation of ethylene
oxide to ethylene glycol, which in turn reacts to polyethylene
glycol, polyoxyethylene, as the oxyethylation reaction advances.
Although transesterification, which renders polyoxyethylene,
cannot be suppressed, the fraction of polyoxyethylene originating
from the reaction water in the reaction mixture can be avoided if
water is eliminated by distillation in the starting phase [28].
The transesterification of the monoesters of polyoxyethylenes to
the diesters and free polyoxyethylene is hampered when sterically
hindered acids such as neoacids are used instead of linear fatty
acids [29].
Fatty acids most commonly used today are the well-known cuts of
lauric and myristic acids, of palmitic and stearic acids, oleic acids,
ricinoleic acid, and tall oils, which consist of linear fatty acids and
rosin acids. The oxyethylation of brassylic acid has also been
reported [30].
In the industrial production of polyoxyethylene esters of fatty acids
today one can observe a trend to utilize fats and oils instead of the
fatty acids as starting materials for the oxyethylation reaction. Of
course, purified fats and oils, being triglycerides, do not possess a
reactive proton to offer ethylene oxide a reaction site.
Nevertheless, in the presence of an alkaline catalyst and optionally
of water, the triglycerides are partially hydrolyzed, generating
diglycerides, monoglycerides, or even glycerol on the one hand
and salts of the fatty acids on the other [31]. These species may
then be oxyethylated, giving a mixture of polyoxyethylene ethers
of partial glycerides and of polyoxyethylene esters of fatty acids in
a first step, whereas the salts or the polyoxyethylene esters of the
fatty acids can esterify or transesterify in a second step, e.g.:
 Page 134

Depending on the degree of saponification and of oxyethylation,

the final reaction mixtures can contain:
Glycerol, monoglycerides, diglycerides, and triglycerides
Polyoxyethylene ethers of glycerol and of mono- and diglycerides
Esterified polyoxyethylene ethers of glycerol and of mono- and
diglycerides
Polyoxyethylene monoesters and diesters of fatty acids and free
polyoxyethylene
While these mixtures are far away from being well defined
products, they have a wide area of application and are being used
as emulsifying agents in the first place.
B
Esterification of Fatty Acids or Transesterification of Fats and
Oils with Polyoxyethylene
Polyoxyethylene esters of fatty acids can be made by oxyethylation;
industrially they are also produced by esterification or
transesterification of polyoxyethylene (polyethylene glycol or
polyol) with fatty acids or their methyl esters as described above
(Sec. II.A), disregarding the fact that this reaction always yields
mixtures of mono- and diesters of polyoxyethylene insofar as the
fatty acid or its ester are not introduced in excess. This will be the
procedure of choice when the diesters are the desired products.
Transesterification may also be effected with triglycerides, leading
to products similar in composition to products obtained by the
oxyethylation of triglycerides discussed above [32].
It must be pointed out that it is common practice in industry to
term products obtained by the reaction of polyoxyethylene with
fatty acids or their esters in molar ratios around 1 or similar
products manufactured by oxyethylation polyoxyethylene
''monoesters," despite the fact that they are mixtures of monoesters,
diesters, and free polyoxyethylene. This must be borne in mind the
more so as common analytical values used to characterize the
products such as the hydroxyl number or the saponification
numbers will be identical for the pure monoesters and the 2:1:1
molar mixtures of monoesters, diesters, and free polyoxyethylene.
C
Polyoxyethylene Esters of Ricinoleic Acid and Castor Oil
Ricinoleic acid and its triglyceride, castor oil, may also be
converted to the corresponding polyoxyethylene esters by the
above-mentioned methods. Usu-
 Page 135
ally oxyethylation is preferred. The products obtained thereby are
valuable emulsifiers. A special feature of these educts is a
secondary hydroxyl group in allylic position to the double bond in
the unsaturated fatty acid radical. This hydroxyl group can
participate in the oxyethylation and transesterification reactions,
augmenting the number of species in the final reaction product.
The alkali-catalyzed oxyethylation of ricinoleic acid leads to the
expected mixture of monoesters, diesters, and polyoxyethylene. As
side reactions, the dehydration of the ricinoleic acid at the site of
the hydroxyl group and a Claisen condensation of the monoester to
a 2-ricinoloxy-ricinoleic acid ester and polyoxyethylene were
observed [33].
Müller presented a comprehensive study on the composition of
oxyethylated castor oil with 40 moles of ethylene oxide per mole of
triglyceride [34]. He could show that the product contained all of
the species described above for the oxyethylation of triglycerides
(III.A). In addition to these, he could identify higher esters, where
the secondary hydroxyl group or the oxyethylated secondary
hydroxyl group is esterified with ricinoleic acid. The degree of
oxyethylation of the secondary hydroxyl group was found to be
rather low.
D
Properties of Commercial Polyoxyethylene Esters of Fatty Acids
A great number of polyoxyethylene esters of fatty acids are offered
by quite a few companies in the marketplace. These products are
not strictly comparable, even if they have been assigned the same
chemical names. The reasons for this are manifold: the
composition of the starting fatty acid may be somewhat different;
the chain length and the homolog distribution of the
polyoxyethylene in the product, bound and free, may vary within
certain limits; and the composition of the product with respect to
monoesters, diesters, and polyol can differ as a result if specific
reaction conditions of oxyethylation or esterification. While the so-
called monoesters usually are produced by the oxyethylation of
fatty acids, the diesters are synthesized by esterification.
Product characteristics and their performance of course depend
decisively on the type of starting material, fatty acid (alternatively,
its methyl ester in transesterification), or triglyceride.
Polyoxyethylene esters of fatty acids usually are described by their
physical state, their melting or pour points, and their HLB values.
Typical data of some esters are given in Tables 47, taken from the
prospectus of a supplier [35]. In Table 8 data for some
oxyethylated castor oils and hydrogenated castor oils are collected
[36]. Hydrogenated castor oil and its derivatives are preferred for
odor-sensitive applications because hydrogenated castor oil is
practically odorless as compared to castor oil. Polyoxyethylene
esters of fatty acids were studied in some detail in the 1950s. In
this connection the good detergency of these products was an item
of interest [37,38].
 Page 136
TABLE 4 Properties of Industrially Produced Ethylene Glycol and
Diethylene Glycol
Esters [35]
Form Melting point (°C) HLB
Ethylene glycol
monostearate Flake 5660 2.9
distearate Flake 6063 1.5
Diethylene glycol
monostearate Flake 44.547.5 4.3
distearate Flake 4248 2.8
for comparison:
Propylene glycol
stearate Flake 33.538.5 3.4
distearate Flake 3638 2.2

TABLE 5 Properties of Industrially Produced Polyoxyethylenea

Esters of Lauric Acid
[35]
Form Melting point (°C) HLB
Polyoxyethylene (4)
laurate Liquid <5 9.3
dilaurate Liquid <9 5.9
Polyoxyethylene (6)
laurate Liquid <8 11.4
dilaurate Liquid <13 7.9
Polyoxyethylene (8)
laurate Liquid 12 13.0
dilaurate Liquid 18 9.7
Polyoxyethylene (12)
laurate Liquid 23 14.6
dilaurate Soft solid 24 11.7
Polyoxyethylene (20)
laurate Soft solid 40 16.6
dilaurate Soft solid 38 14.2
Polyoxyethylene (32)
laurate Wax 46 17.5
dilaurate Wax 42 15.8
Polyoxyethylene (75)
laurate Wax 55 19.0
dilaurate Wax 52 18.1
Polyoxyethylene (150)
laurate Wax 61 19.3
dilaurate Wax 57 18.7
aNumbers in parentheses indicate number of moles of ethylene
oxide bound per mole of ester.
 Page 137
TABLE 6 Properties of Industrially Produced Polyoxyethylenea
Esters of Stearic
Acid [35]
Form Melting point (°C) HLB
Polyoxyethylene (4)
stearate Solid 31 8.1
distearate Solid 34 4.8
Polyoxyethylene (6)
stearate Solid 28 10.3
distearate Solid 32 6.9
Polyoxyethylene (8)
stearate Solid 32 11.7
distearate Solid 36 8.5
Polyoxyethylene (12)
stearate Solid 37 13.5
distearate Solid 39 10.7
Polyoxyethylene (20)
stearate Solid 41 15.7
distearate Wax 40 13.3
Polyoxyethylene (32)
stearate Wax 47 16.9
distearate Wax 45 14.6
Polyoxyethylene (75)
stearate Wax 56 18.7
distearate Wax 51 17.6
Polyoxyethylene (150)
stearate Wax 61 19.1
distearate Wax 55 18.4
aSee footnote to Table 5.

An excellent review of properties of some polyoxyethylene esters

obtained by the oxyethylation of lauric acid, sperm oil acid, stearic
acid, and hardened fatty (palmitic/stearic) acid was given by Geipel
et al. [39]. Their findings are summarized as follows: The pour
point of the so-called monoesters first decreases with increasing
number of moles of ethylene oxide added to 1 mole of fatty acid,
reaches a minimum, and then increases again. This phenomenon is
demonstrated in Fig. 3. The density of the esters increases with
increasing content of ethylene oxide added. At 50°C the densities
of the pure acids lie between 0.86 and 0.88 g/cm3, increasing with
increasing content of ethylene oxide added and approaching almost
linearly the density of pure polyoxyethylene (1.10 g/cm3). The
refractive indices with increasing content of bound ethylene oxide
also approach the refractive index of pure polyoxyethylene, n50D =
1.462, starting from the corresponding refractive indices of the
pure acids. The cloud points depending on the degree of
oxyethylation or content of
 Page 138
TABLE 7 Properties of Industrially Produced Polyoxyethylene a
Esters of Oleic Acid
[35]
Form Melting point (°C) HLB
Polyoxyethylene (4)
oleate Liquid <-15 8.2
dioleate Liquid <-15 5.0
Polyoxyethylene (6)
oleate Liquid <-5 10.2
dioleate Liquid <-5 6.9
Polyoxyethylene (8)
oleate Liquid <10 11.6
dioleate Liquid <7 8.3
Polyoxyethylene (12)
oleate Liquid 23 13.6
dioleate Liquid 19 10.6
Polyoxyethylene (20)
oleate Soft solid 39 15.9
dioleate Soft solid 37 13.2
Polyoxyethylene (32)
oleate Wax 45 17.0
dioleate Wax 44 14.9
Polyoxyethylene (75)
oleate Wax 55 18.7
dioleate Wax 49 17.7
Polyoxyethylene (150)
oleate Wax 59 19.1
dioleate Wax 56 18.4
aSee footnote to Table 5.

TABLE 8 Properties of Industrially Produced Polyoxyethylenea

Esters of Castor Oil and Hydrogenated Castor Oil [36]

Pour
Form HLB
point (°C)
Polyoxyethylene (14)
hydrogenated castor oil Liquid 7 8.6
Polyoxyethylene (22)
castor oil Liquid 5 10.8
hydrogenated oil Liquid 5 10.8
Polyoxyethylene (26)
castor oil Liquid 9 11.8
Polyoxyethylene (32)
castor oil Liquid 12 12.6
Polyoxyethylene (176)
castor oil Liquid 50 18.1
aSee footnote to Table 5.
 Page 139

Fig. 3
Pour points of some polyoxyethylene esters of
fatty acids in dependence of degree of
oxyethylation. Curve 1: lauric acid; curve 2:
sperm oil acid; curve 3: hardened fatty acid;
curve 4: stearic acid.
(From Ref. 39.)
bound ethylene oxide are shown in Figs. 4 and 5. The viscosities
of the products increase in a typical way with increasing degree of
oxyethylation. A scrutiny of the wetting power of the
polyoxyethylene esters of different fatty acids in aqueous solutions
depending on the degree of oxyethylation shows that the optimum
wetting is reached by the lauric acid esters with 5 moles of ethylene
oxide per mole and by stearic acid esters with 11 moles of ethylene
oxide per mole. The dependency of such properties as cloud point
or wetting power of the polyoxyethylene esters of fatty acids on
their degree of oxyethylation is comparable to those of the
polyoxyethylene ethers of fatty alcohols. This is also true for the
foaming power. Like all surface active polyoxyethylene
derivatives, their monoesters are poor foamers, especially those of
a lower degree of
 Page 140

Fig. 4
Cloud points of polyoxyethylene esters of lauric acid in
dependence of degree of oxyethylation. Concentration:
10%. Curve 1: dist. water; curve 2: 25% aq. solution of
butyl diethylene glycol; curve 3: 10% aq. solution of
sodium chloride.
(From Ref. 39.)

Fig. 5
Cloud points of polyoxyethylene esters of
stearic acid in dependence of degree of
oxyethylation. Legend as in Fig. 4.
(From Ref. 39.)
 Page 141
oxyethylation that are insoluble in water. Aqueous solutions of
polyoxyethylene diesters of fatty acids foam even less than the
monoesters.
Almost no information was found in the literature about the
reduction of surface tension by polyoxyethylene fatty acid esters
synthesized by methods put forward in this section. In connection
with adsorption studies of some polyoxyethylene esters on fabrics
and carbon black, curves of surface tensions over concentrations
of polyoxyethylene-(30) and (80) (= PEG 1500 and 4000) stearic
acid esters were published [40]. According to these curves
polyoxyethylene-(80) monostearic and distearic acid esters reduce
the surface tension of water to about 50 mN/m beyond a
concentration of 0.05 mmol/L. The curves have two breaks,
indicating two CMCs. The polyoxyethylene-(30) monostearic acid
ester reduces the surface tension a little further to about 48 mN/m;
this curve also has two breaks. Oxyethylated castor oil reduces the
surface tension of water only slightly [41]. Oxyethylated
hydrogenated castor oil gives vesicle dispersions in water [42].
E
Oxyethylation of Fatty Acid Methyl Esters
Discussing the alkali-catalyzed oxyethylation of triglycerides above
the (Sec. III.A), it was pointed out that ethylene oxide only reacts
with the substrate after a preceding partial hydrolysis of the
triglyceride. A direct insertion of the ethylene oxide molecule into a
ester bond does not take place with alkaline catalysts soluble in the
reaction medium. It was only recently that the direct insertion of
the ethylene oxide molecule into the ester bond was achieved with
bifunctional catalysts, e.g., magnesium oxide modified by a
aluminum oxide [43,44]. These catalysts, introduced into the
reaction medium as fine powders, are not soluble therein and it is
assumed that the reaction between the ethylene oxide and the ester
proceeds on the surface of the solid catalyst. These catalysts have
also been utilized to produce polyoxyethylene ethers of fatty
alcohols with a narrow distribution homologs, the so-called
narrow-range ethoxylates (NREs). In the oxyethylation of fatty acid
methyl esters they yield the monomethyl ethers of polyoxyethylene
monoesters in high yield with a normal distribution of homologs:

It is thus possible to produce true fatty acid monoesters of

polyoxyethylenes, though terminally blocked with a methyl group.
Such esters compare well in surface activity, wetting power,
solubilization capacity, and detergency with the corresponding
polyoxyethylene ethers of fatty alcohols, the fatty alcohol
oxyethylates with a free terminal hydroxyl group. Due to the ester
bond these products are susceptible to hydrolysis, although they
are stable in aqueous solutions in a pH range from 3 to 9.
 Page 142

IV
Analysis of Polyoxyethylene Fatty Acid Esters
The analysis of polyoxyethylene esters of fatty acids is rather
straightforward if the products to be analyzed are of uniform
composition, i.e., monoesters or diesters. These can be hydrolyzed,
the polyoxyethylene and the fatty acids obtained thereby being
identified and quantitatively determined by well-established
methods. But in most cases, products encountered will be
industrial products and will therefore be mixtures of monoesters,
diesters, and free polyoxyethylene. The approved method for
analyzing such mixtures is to separate first the polyoxyethylene
therefrom by extraction with aqueous sodium chloride solution,
leaving behind a mixture of monoesters and diesters free of
polyoxyethylene, the former being characterized by saponification
[45].
Schmitt has collected all relevant methods of analysis of
polyoxyethylene esters of fatty acids [46]: specification (p. 56),
characterization (p. 81), separation by distillation (p. 128), column
adsorption chromatography (p. 150, an elegant method was
overlooked [47]), thin-layer chromatography (p. 262), gas
chromatography (p. 241), high-performance liquid
chromatography (pp. 184, 198), superfluidal chromatography (p.
286), nuclear magnetic resonance spectroscopy (p. 82), and mass
spectroscopy (pp. 319,322).
V
Toxicologic Aspects and Biodegradation
A
Toxicologic Aspects
The polyoxyethylene esters of fatty acids in general have a very
low order of toxicity. They are nonirritant or of low irritancy to the
skin and the mucous membrane. They can be characterized as mild
products. This is especially true of the polyoxyethylene esters of
ricinoleic acid and of castor oil [48].
B
Biological Degradation
A summary on the biodegradation of polyoxyethylene esters of
fatty acids is given by Swisher [49]. The esters with
polyoxyethylene chains as long as 20 ethylene oxide units are
easily biodegraded. The rate of biodegradation is somewhat slow
when the polyoxyethylene chain is as long as 50 ethylene oxide
units. The polyoxyethylene esters of rosin acids seem to be
biodegraded sluggishly.
VI
Synopsis and Future Outlook
With some exceptions the industrially more valuable fatty acid
esters of polyoxyethylene are the monoesters because of their true
amphiphilic character and
 Page 143
the higher surface activity resulting therefrom. However, the
synthesis of products with high contents of monoesters is
cumbersome and questionable after all because the pure
monoesters have a tendency to equilibrate to a mixture of mono-
and diesters and free polyoxyethylene. In industrial practice,
therefore, only such mixtures are used. They are produced by the
esterification of polyoxyethylene (polyethylene glycol) with fatty
acids or by the oxyethylation of these acids. For the use of the
products in established areas of application, a trend can be
observed to take the fats or oils as starting materials, leading to a
somewhat different composition of the products that embody
chemically bound glycerol.
Areas of application for the so-called monoesters, products in
which the molar ratio of polyoxyethylene to fatty acids is
approximately 1:1, are numerous. Their main use is as emulsifiers
in metalworking, mold lubricants, and mold release agents; as
emulsifying or dispersing agents in lubricating oils and dye-
leveling auxiliaries in the textile and leather industries; as softeners
for textiles or as emulsifiers in the preparation of fat liquors and
greases for leather; as antistatic agents in the manufacture of
textiles and plastics; or as emulsifiers in the preparation of plant
protection agents, with the active substance being dissolved in an
emulsified oil.
Because of their toxicologic and dermatologic harmlessness, the
polyoxyethylene esters of fatty acids are particularly suited for use
in cosmetic and pharmaceutic formulations, i.e., as emulsifiers in
creams, lotions, and cleansing milks; as solvents, solubilizers,
emulsifiers, or dispersants for volatile oils, scents, or perfumes; for
colorants or special active ingredients. In this connection the
polyoxyethylene esters of ricinoleic acid and particularly of castor
oil play an important rôle. Besides their wide application in body
care ad cosmetics, they are utilized as solubilizers or emulsifiers of
hydrophobic drugs or vitamins for local or oral application.
In the above-mentioned applications, the (formal) monoesters of
polyoxyethylene usually function as oil-in-water emulsifiers,
which means that the HLB values of the products used are 9 and
higher. The diesters of polyoxyethylene with comparable HLB
values have more or less the same uses as the corresponding
monoesters, although they are not so amply employed for those
purposes. The diesters, on the other hand, have to peculiar
applications in cosmetics and cleaning agents. Thee diesters of the
lower polyoxyethylenes, and in particular the diester of stearic acid
with ethylene glycol, serve as pearlescent agents and opacifiers in
cosmetic creams, lotions, and shampoos. The diesters of the long
chain polyoxyethylenes, e.g., polyoxyethylene-(30) distearate, are
useful as in cosmetic formulations, although the fact that they are
solids that have to be dissolved before application has induced a
search for alternative thickeners [50,51]. The guiding concept in
these attempts was the notion that the two hydrophobic residues on
both ends of the polyoxyethylene chain would
 Page 144
be integrated into two different micelles, thereby building up a
three-dimensional network in the aqueous phase [52]. This
concept is sometimes referred to as associative thickening.
Despite the very useful properties of the polyoxyethylene fatty acid
esters, it must be borne in mind that these esters are in competition
with industrial products of comparable structure, e.g., the esters of
glycerol or polyglycerols and their polyoxyethylene ethers. The
oxyethylated fats and oils treated in this chapter already constitute a
connecting link between the polyoxyethylene esters and
oxyethylated glycerides. Also worth mentioning are the esters of
sorbitol and their polyoxyethylene ethers, allowing for variations
or modifications in the polyoxyethylene chain by introducing, say,
propylene oxide. Last but not least, the polyoxyethylene ethers of
fatty alcohols can replace the esters in some applications.
Acknowledgment
The author thanks the following companies for providing product
information and other literature: BASF, Croda, Henkel, Hüls, ICI
Surfactants, Nikko Chemicals, PPG, Sino-Japan Chemical, Stepan,
Taiwan Surfactants, Th. Goldschmidt, Witco, and Zschimmer &
Schwarz.
References
A
General Overviews
1. K. Lindner, Tenside-Textilhilfsmittel-Waschrohstoffe,
Wissenschaftliche Verlagsgesellschaft, Stuttgart, 1964, pp. 882 ff.
2. H. A. Goldsmith, Chem. Rev. 33:257349 (1943).
3. R. Schneider, Fette Seifen Anstrichmittel 58:549 (1956); 59:876
(1957).
4. W. B. Satkowski, S. K. Huang, and R. L. Liss, in Nonionic
Surfactants (M. J. Schick, ed.), Surfactant Science Series, Marcel
Dekker, New York, 1967, pp. 142174.
5. N. Schönfeld, Surface Active Ethylene Oxide Adducts,
Pergamon Press, Oxford, 1969; Grenzflächenaktive Äthylenoxid-
Addukte, Wissenschaftliche Verlagsanstalt, Stuttgart, 1976, pp.
2528, 4347; Ergänzungsband 1984, pp. 78.
6. R. A. Reck, in Fatty Acids in Industry (R. W. Johnson, ed.),
Marcel Dekker, New York, 1989, pp. 201215.
B
Special References
7. N. Parris and J. K. Weil, J. Am. Oil Chemists Soc. 56:775
(1979).
8. J. K. Weil, R. E. Koos, W. M. Linfield, and N. Parris, J. Am. Oil
Chemists Soc. 56:873 (1979).
9. M. J. Astle, B. Schaeffer, and C. O. Obenland, J. Am. Chem.
Soc. 77:3643 (1959).
 Page 145
10. A. Kotzschmar and H. Metzger, German Patent 1,175,220 to
Farbwerke Hoechst A. G. (1962).
11. R. Celades and C. Paquot, Proceedings 4th International
Congress on Surface Active Substances, CID, Vol. 1 (F. Asinger,
ed.), Brussels, 1964, pp. 249255.
12. L. Hartman, J. Chem. Soc. (London) 1957:1918 (1957).
13. T. C. Rao, Y. S. Ramasastry, R. Subbarao, and G.
Lakshminarayana, J. Am. Oil Chemists Soc. 54:15 (1977).
14. W. Gerhardt and H.-R. Holzbauer, Tenside Surf. Det. 12:313
(1975).
15. E. Sung, W. Umbach, and H. Baumann, Fette Seifen
Anstrichmittel 73:88 (1971).
16. W. Umbach and W. Stein, Tenside Surf. Det. 7:132 (1970).
17. A. N. Wrigley, F. D. Smith, and A. J. Stirton, J. Am. Oil
Chemists Soc. 36:34 (1959).
18. H. Szelag and W. Zwierzykowski, Seifen Öle Fette Wachse
121:444 (1995).
19. H.-R. Holzbauer and W. Gerhardt, Tenside Surf. Det. 19:67
(1982).
20. E. S. Lutton, C. B. Stewart, and A. J. Fehl, J. Am. Oil Chemists
Soc. 47:94 (1970).
21. For example, in Ref. 5 pp. 13.
22. W. Umbach and W. Stein, Fette Seifen Anstrichmittel 71:938
(1969).
23. F. Wolf, G. Geipel, and K. Löffler, Tenside Surf. Det. 5:270
(1968).
24. A. N. Wrigley, F. D. Smith, and A. J. Stirton, J. Am. Oil
Chemists Soc. 34:39 (1957).
25. M. Bares *, M. Bleha, B. Jeneralova, J. Zajíc, and J. Coupek*,
Tenside Surf. Det. 12:162 (1975); M. Bleha, M. Bares, E. Votavová,
J. Zajíc, and J. Coupek, Tenside Surf. Det. 14:123 (1977); M.
Bares, M. Bleha, M. Navratil, E. Votatvová, and J. Zajíc, Tenside
Surf. Det. 16:74 (1979).
26. G. J. Stockburger and J. D. Brandner, J. Am. Oil Chemists Soc.
43:6 (1966).
27. G. J. Stockburger, J. Am. Oil Chemists Soc. 56:774A (1979).
28. H. Grossmann, Tenside Surf. Det. 12:16 (1975).
29. M. Coppersmith and R. C. Maggart, J. Am. Oil Chemists Soc.
46:332 (1969).
30. T. K. Miwa, R. V. Madrigal, W. H. Talent, and I. A. Wolff, J.
Am. Oil Chemists Soc. 45:159 (1968).
31. V. Martin, Seifen Öle Fette Wachse 111:51 (1985).
32. H. Pardun, Seifen Öle Fette Wachse 106:65 (1980).
33. M. Bares, J. Coupek, S. Pkorný. J. Hanzalová, and J. Zajíc,
Tenside Surf. Det. 12:155 (1975).
34. K. Müller, Tenside Surf. Det. 3:37 (1966).
35. Stepan Europe, Voreppe, Stepan Line of Esters in Personal
Care, Leaflet, 1993.
36. PPG Industries, Mapeg Polyethylene Glycol Esters, Gurnee,
Ill., Leaflet, 1994.
37. E. M. Stolz, A. T. Ballun, H. J. Ferlin, and J. V. Karabinos, J.
Am. Oil Chemists Soc. 30:271 (1953); A. T. Ballun, J. N.
Schumacher, G. E. Kapella, and J. V. Karabinos, J. Am. Oil
Chemists Soc. 31:20 (1954).
38. W. B. Satkowski and W. B. Benett, Soap Chem. Specialties
33(7):37 (1957).
39. G. Geipel, F. Wolf, and K. Löffler, Tenside Surf. Det. 5:132
(1968).
40. V. G. Kumar, P. Aravindakshan, I. V. Nagarajan, and A. N.
Bhat, Tenside Surf. Det. 29:195 (1992).
41. C. Drugárin, P. Getia, and M. Vincze, Tenside Surf. Det. 17:17
(1980).
42. M. Tanaka, H. Fukuda, and T. Horiuchi, J. Am. Oil Chemists
Soc. 67:55 (1990).
43. I. Hama, T. Okamoto, and H. Nakamura, J. Am. Oil Chemists
Soc. 72:781 (1995).
44. A. Behler, H.-C Raths, and B. Guckenbiel, Tenside Surf. Det.,
33:64 (1996).
 Page 146
45. J. D. Malkemus and J. D. Swan, J. Am. Oil Chemists Soc.
34:342 (1957).
46. T. M. Schmitt, Analysis of Surfactants, Surfactant Science
Series, Vol. 40, Marcel Dekker, New York, 1992.
47. R. Wickbold, Fette Seifen Anstrichmittel 74:578 (1972).
48. BASF, Ludwigshafen, Cremophor EL, Cremophor RH 40,
technical data sheets, 1987 and 1988.
49. R. D. Swisher, Surfactant Biodegradation, 2nd Ed. Surfactant
Science Series, Vol. 18, Marcel Dekker, New York, 1987, pp. 427,
860862.
50. W. Adam, Seifen Öle Fette Wachse 110:599 (1984).
51. H. Meijer, Seifen Öle Fette Wachse 113:135 (1987).
52. A. Behler, H. Hensen, H.-C. Raths, and H. Tesmann, Seifen Öle
Fette Wachse 116:60 (1990).
 Page 147

5
Polyoxyethylene Mercaptans
Charles L. Edwards
Westhollow Technology Center, Shell Chemical Company,
Houston, Texas

I. Introduction 147
II. Synthesis of Thiol Intermediates 148
A. Aliphatic Primary Mercaptans 148
B. Aliphatic Secondary Mercaptans 149
C. Aliphatic Tertiary Mercaptans 149
D. Aromatic Mercaptans 150
III. Preparation of Polyoxyethylene Mercaptans 150
A. Laboratory Methods for Preparation 150
B. Commercial Processes 151
IV. Properties of Polyoxyethylene Mercaptans 155
A. The ''HLB Problem" 155
B. Solubility and Cloud Points 155
C. Viscosity 155
D. Wetting 156
E. Foam Breaking 157
 F. Detergency 158
V. Applications 159
A. Household 159
B. Industrial and Institutional 159
References 160

I
Introduction
Alkyl and aromatic mercaptans (or thiols) can be reacted with
ethylene oxide in a manner similar to alcohols or amines to
produce surface active products.
 Page 148
However, in the case of mercaptans, there has been very little
interest in polyoxyethylene mercaptans derived from aromatic
sources. Due to the potential for odor development from
impurities in the product, there are significantly fewer applications
for polyoxyethylene mercaptans compared with their oxygen or
nitrogen counterparts. However, the sulfur atom imparts unique
properties to the polyether chain that in many cases show
advantages relative to other non-sulfur-containing surfactants.
Polyoxyethylene mercaptans were first reported by I.G. Farben
[1,2] in the 1930s and they were exclusively primary linear
products. Later, emphasis was placed on using the less expensive
tertiary branched chained hydrocarbons as the hydrophobe source
(3). Over the years the tertiary polyoxyethylene alcohols found
several unique industrial markets and have been commercially
produced by GAF (Emulphogene LM series), Monsanto, and
Rhone-Poulenc (Siponic SK and Alcodet series). This chapter
begins with a discussion of the preparation of these materials and
concludes with information concerning their physical properties
and applications.
II
Synthesis of Thiol Intermediates
The majority of commercially available polyoxyethylene
mercaptans are derived from tertiary branched hydrophobes
leading to tertiary thiol polyoxyethylene derivatives. However,
several recent reports have described the production of secondary
thiol polyoxyethylene derivatives from the catalyzed addition of
H2S to linear a- or internal olefins. This section addresses
laboratory and commercial procedures for the preparation of
primary, secondary, or tertiary alkyl thiols. A brief discussion also
includes the preparation of aromatic thiols. Additional information
can be found in review articles describing the preparation and uses
of thiols [47].
A
Aliphatic Primary Mercaptans
Aliphatic primary mercaptans are relatively easy to prepare using
laboratory methods. However, they are more difficult to prepare
commercially compared with their secondary and tertiary
counterparts. A simple laboratory method for the preparation of
primary mercaptans involves the reaction of sodium hydrosulfide
with a primary halide, such as the bromide [1,2]:

This method produces the primary thiol in good yield but would
be difficult to commercialize. A more recently reported method [8]
that is more amenable to both laboratory and commercial operation
involves the free radical addition of thiolacetic acid to a linear a-
olefin:
 Page 149

In the presence of free radical initiators, H2S and mercaptans add

to double bonds by a free radical mechanism with the orientation
being anti-Markownikoff [911]. This leads to the formation of
primary thiols.
There have been a number of reports indicating that primary thiols
could be prepared by the reaction of H2S with linear a-olefins
using free radical initiators with or without the presence of UV
light [1215]. Another study involved the investigation of the
kinetics of the reaction of a primary alcohol with H2S using an
alkali-modified alumina catalyst [16].
B
Aliphatic Secondary Mercaptans
Secondary mercaptans have been produced using a variety of
acidic catalyst systems. Various alkyl aluminum dichlorides [17],
mixed cobalt/molybdenum oxides [18], ion exchange resins [19],
and zeolite catalyst systems [20] have been reported as useful for
the preparation of secondary mercaptans. Of these catalyst
systems, the zeolite catalyst system [20] appears to be the most
useful with respect to high yields and ease of operation.
C
Aliphatic Tertiary Mercaptans
The preparation of aliphatic tertiary polyoxyethylene mercaptans
has been extensively reported [3,2133]. The most common
hydrophobe used in these preparations is either propylene tetramer
or butylene trimers. Some of the earliest reports involved the use
of silica-alumina catalysts [3] for the preparation of branched
tertiary dodecyl mercaptans. Improvements in these catalyst
systems have been reported more recently [21,20] using both
acidified silica-aluminas as well as zeolites.
One of the most common types of catalyst systems used are the
classical FriedelCrafts catalysts. The most common of these are
boron triflouride [2226] and aluminum trichloride [2733]. These
homogeneous catalysts are quite active for the addition of H2S to
branched olefins. Since the mechanism of reaction involves
carbonium ion intermediates, the addition of the H2S to the olefin
follows Markownikoff's rule:
 Page 150
Therefore, tertiary mercaptans are formed in preference to
secondary mercaptans with little or no primary mercaptans being
formed. Isomerization of the double bond occurs during
hydrosulfurization, so that a mixture of mercaptan products is
always produced even starting with pure olefin feedstock.
One significant problem encountered using any of these strongly
acidic catalyst systems is the propensity for the branched
hydrophobic chain to undergo acid-catalyzed chain degradation.
Considerable cracking occurs in some of these processes resulting
in the formation of low molecular weight olefins that can undergo
further hydrosulfurization. Therefore, the crude product mixtures
often contain significant quantities of low molecular weight thiols.
These byproducts can, however, be stripped from the desired
products and sent for disposal.
D
Aromatic Mercaptans
Aromatic mercaptans are seldom used as initiators for
polyoxyethylation. However, the most common is
alkylbenzenethiol, which is prepared by the acid-catalyzed addition
of alkenes to benzenethiol (34).
III
Preparation of Polyoxyethylene Mercaptans
A
Laboratory Methods for Preparation
The most common laboratory method for the preparation of
polyoxyethylene mercaptans is the reaction of the mercaptan with a
substituted polyoxyethylene compound using stoichiometric
quantities of sodium hydroxide. Monodispersed products can be
obtained using this method as long as the appropriate
polyoxyethylene derivative is used. This general method can be
represented as follows:

The reason that this reaction proceeds in such high yield is that the
mercaptan has a significantly higher acidity (pKa = 12) relative to
the polyoxyethylene alcohol derivative (pKa = 16) [35]. When
conducted at low temperature, the base reacts exclusively with the
mercaptan to form the mercaptide anion, which undergoes an Sn2
reaction with the substituted polyoxyethylene compound. No
significant deprotonation of the alcohol occurs. This method has
been used to prepare a variety of polyoxyethylene mercaptans in
high yield [36,37].
 Page 151
B
Commercial Processes
Polyoxyethylene mercaptans are produced commercially by the
base-catalyzed reaction of mercaptans with ethylene oxide:

This reaction is analogous to the commercial production of

polyoxyethylene alcohols discussed in Chapter 3. However, there
are important differences between the polyoxyethylation of
mercaptans and alcohols that affect the composition of the product
and the process conditions used for their production. These
differences result from the increased acidity, increased
nucleophilicity (reactivity) [35], and reduced catalyst solubility of
the mercaptans compared with the alcohols.
The reaction of mercaptans with ethylene oxide has been
conducted using a variety of catalysts such as sodium methoxide
[38], aqueous sodium hydroxide [39,40], methanolic sodium
hydroxide [41], and the sodium mercaptide of the mercaptan to be
polyoxyethylated [42]. Each of these reports indicates that the
reactivity of the mercaptan with ethylene oxide is considerably
higher than that for a comparable alcohol. This is due to the
increased nucleophilicity of the mercaptide anion compared to the
anionic alkoxide species. Because of this increased nucleophilicity,
the addition of the first mole of ethylene oxide to the mercaptan is
extremely exothermic and must be carefully conducted at lower
temperatures and ethylene oxide partial pressures (e.g., 60°C, 10
psia EO) than those used for alcohol polyoxyethylations (e.g.,
120140°C, 25 psia EO). After the first mole of ethylene oxide has
been added per mole of mercaptan, more conventional
temperatures and pressures can be used to complete the reaction.
The product chain length distributions of polyoxyethylene
mercaptans are also dramatically different from those of
polyoxyethylene alcohols containing the same molar ratio of
ethylene oxide to initiator. The mercaptan products have a much
narrower chain length distribution due to the increased acidity of
the mercaptan relative to the polyoxyethylene adducts. In this
respect, the polyoxyethylene mercaptans are similar to the
polyoxyethylene alkylphenols (see Chapter 2), which also have
narrower chain length distributions than comparable alcohols due
to the increase acidity of the phenols relative to the adducts. A
comparison of polyoxyethylene chain length distributions for a
dodecyl mercaptan ethoxylate and a dodecyl alcohol ethoxylate is
given in Table 1.
Another difference between the polyoxyethylation of the
mercaptans relative to the alcohols is the difference in the
solubilities of the catalytically active species. Although the
potassium alkoxide is soluble in the alcohol to be reacted, the
mercaptide anion is not soluble in the mercaptan initiator. During
the early stages of catalyst drying (e.g., from 25°C to 100°C) the
KOH is soluble in the
 Page 152
TABLE 1 Comparison of Polyoxyethylene Chain
Length Distributions of Polyoxyethylene Mercaptan vs.
Polyoxyethylene Alcohols [43,44]
Product Anadet 912a Neodol 23-9b
EO/RXH (mole/mole) 9.1 9.0
Adduct (wt%)
EO 0 0.1 2
1 0.1 1
2 0.2 2
3 0.8 3
4 2.5 4
5 3.6 5
6 8.3 5
7 10.2 6
8 11.2 7
9 11.4 8
10 11.2 8
11 9.8 8
12 8.6 8
13 6.7 7
14 4.9 6
15 3.4 5
16 2.8 4
17 1.9 3
18 1.6 3
19 0.4 2
20 0.3 2
a Anadet is a trade name for a tertiary dodecyl thiol
ethoxylate.
b Neodol is a trade name for an oxo-type alcohol-
based material.
thiol. Continued heating at 130°C causes the formation of a
heterogeneous mixture and evolution of water:

This could have significant consequences for commercial

production because heterogeneous systems take longer to dry and
also have a propensity to plug catalyst transfer lines.
This problem has been overcome by the observation that the
thiolate hydrate was soluble in the thiol, thus suggesting that a
thiolate alcoholate might also be soluble in the thiol. Addition of
small amounts of an alcohol or a polyoxyethylene alcohol to the
reaction mixture (approximately 1 mole of additive per mole of
catalyst) was shown to produce homogeneous systems throughout
the catalyst
 Page 153
drying process [45]. In the process described the additive used was
the 1-mole ethylene oxide adduct of the mercaptan to be
polyoxyethylated:

In this manner there would be no contamination of the product

with an alternate polyoxyethylene alcohol.
A typical process for the polyoxyethylation of mercaptans is
similar to that of alcohols, except for staged addition of the
ethylene oxide at two different temperatures. The potassium
hydroxide is added to the mercaptan containing the solubilizing
additive. In the case of the example cited previously [45], this
would involve using small amounts of the 1-mole ethylene oxide
adduct of the mercaptan to be reacted (~1 wt% basis the mercaptan
charge). The reaction mixture would be dried by nitrogen sparging
or by vacuum drying for 1 h at 130°C or until a residual water
level of <200 ppm is attained. Then the catalyzed thiol mixture is
added to the reactor along with additional dried thiol sufficient for
the desired initial charge. The reaction temperature is increased to
~80°C at which time all external heating is terminated. Ethylene
oxide and nitrogen are introduced to the reactor, which results in
an exothermic reaction (DH = 22 kcal/mole) increasing the
temperature to the desired final reaction temperature of
~120130°C. Ethylene oxide is added at a rate sufficient to maintain
reaction temperature and the heat of reaction is removed by
circulating a portion of the batch reactor contents to a heat
exchanger. Safety procedures require that limits be placed on
temperature and pressure. The gas phase ethylene oxide
concentration is continually monitored by sensors, and if the
reaction temperature decreases for some reason, ethylene oxide
feed is immediately terminated to prevent a buildup of vapor phase
ethylene oxide concentration.
After all of the required amount of ethylene oxide is added, the
residual ethylene oxide is consumed by maintaining reaction
temperature until there is no change in the reactor pressure. This
usually requires approximately 3060 min. Because many customers
require that residual ethylene oxide be <5 ppm in the product, a
nitrogen sparge of the product is optionally performed if product
"aging" is insufficient to reduce ethylene oxide concentrations to
the desired levels. The reaction product is normally neutralized
with acetic acid, but other homogeneous acids can be used.
Because polyoxyethylene mercaptans often have residual odor due
to the presence of residual mercaptan or sulfur-containing volatile
impurities, the batch reactor product can be stripped under vacuum
at this time to reduce odor.
 Page 154
TABLE 2 Factors Affecting Selectivity in Polyoxyethylation of
Tertiary Dodecyl Mercaptan [45]
wt % wt %
Conditions employed
TTEb PEGc
Drying without
conventional temp.
solubilizera + 88 12
(155°C)
(1 h @ 130°C)
Drying with
conventional temp.
solubilizera + 93 7
(155°C)
(1 h @ 130°C)
Drying with
solubilizera +lower temp. (125°C) 98 2
(1 h @ 130°C)
aOne mole ethylene oxide adduct of dodecyl mercaptan.
bTTE, tertiary dodecyl thiol ethoxylate.
cPEG, polyethylene glycol.

Additional methods to reduce odor have been shown to be

effective, such as steam stripping of the product.
The improved process for the polyoxyethylation of mercaptans
described previously [45] also involves the improvement of
reducing odor and the amount of polyoxyethylene glycol (PEG)
produced during reaction. It has been shown that the odor and
PEG formation is a consequence of using high-temperature
operations and heterogeneous catalyst mixtures due to base-
catalyzed cleavage reactions as follows:

This elimination reaction producing vinyl alkyl sulfide and PEG is

a significant contributor to the production of odorous components
and PEG in commercial
TABLE 3 Comparison of Polyethylene Glycol Impurities in
Commercial Polyoxyethylene Mercaptans
Source Shell GAF Alcolac
Anadet Emulphogene LM- Siponic
Trade name
912 710 SK
EO/RSH
9.1 7.8 8.0
(mole/mole)
Hydrophobe
wt% C10 5.0 a
wt% C11 3.4 28.0 a
wt% C12 96.6 67.0 a
%w PEG in product 2.4 4.4 12.0
Relative odor Acceptable Strong Stronger
aNo analysis available.
 Page 155
polyoxyethylene mercaptans. The effect of temperature and
heterogeneous catalyst mixtures on selectivity, as well as a
comparison of PEG levels in commercial products, is shown in
Tables 2 and 3, respectively. This problem can be minimized
through the use of solubilizers and low reaction temperatures [45].
IV
Properties of Polyoxyethylene Mercaptans
A
The "HLB Problem"
Care must be taken in comparing the physical properties and
detergency of the polyoxyethylene mercaptans with
polyoxyethylene alcohols having the same ethylene oxide/initiator
molar ratio due to the impact of the sulfur atom in the chain. The
effective length of hydrophobes containing sulfur (i.e.,
mercaptans) is greater than that of their alcohol counterparts. One
study has found that polyoxyethylene products obtained from
dodecyl mercaptan are more similar to products obtained from
tetradecyl alcohol. This study has addressed this issue and found
that a sulfur in a chain is equivalent to approximately 1.5 carbon
atoms [46]. This is a result of the less polar sulfur atom "behaving"
more like a carbon than an oxygen. Consequently, the HLB
definition must be modified to take into account this difference. In
general, more ethylene oxide must be added to mercaptans of a
specific carbon number to prepare products more comparable to
the same carbon number alcohol.
B
Solubility and Cloud Points
The solubility of various polyoxyethylene mercaptans has been
reported [47] and compared with their polyoxyethylated alcohol,
amide, and acid counterparts [48]. These materials are soluble in
almost all common organic solvents, e.g., in toluene, ether, carbon
tetrachloride, acetone, ethyl acetate, and ethanol. Products
containing >3 moles of ethylene oxide per mole of mercaptan have
limited solubility in hydrocarbons. The cloud points of a series of
aqueous solutions containing a polyoxyethylene tertiary dodecyl
mercaptan with an average of 7 moles of ethylene oxide per mole
of mercaptan is shown in Table 4. These products were stripped to
various levels (011.38 wt%) to remove lower molecular weight
oligomers (mercaptan and low molecular weight EO adducts) in
order to explore the effect of stripping on cloud point and turbidity
[49]. As can be seen from Table 4, stripping enables the
preparation of clear, one-phase, homogeneous, aqueous
formulations of these polyoxyethylene mercaptans.
C
Viscosity
The polyoxyethylene mercaptans form gels with water over a
relatively wide range of concentrations, as does their alcohol
counterparts. For most
 Page 156
TABLE 4 Cloud Points for Stripped Polyoxyethylated
Tertiary Dodecyl Mercaptan [49]
Turbidity
Samplea % Stripped Cloud point (°C)
(% transmittance)
a 0 15.4 7.7
b 1.67 16.7 8.0
c 2.49 17.8 8.3
d 3.09 18.7 8.4
e 6.69 23.6 76.2
f 7.66 24.5 83.3
g 11.38 28.8 89.2
aag are samples of polyoxyethylated tertiary dodecyl
mercaptans that had been stripped to various levels using a
wiped film evaporator.

commercial mercaptan surfactants, gel formation does not occur

until concentrations as high as 40 wt% in water are reached.
However, their viscosities are generally lower than those of
comparable polyoxyethylene alcohols and alkylphenols. This can
be seen in Fig. 1 for Anadet 912 vs. Igepal CO 630. Additional data
are published in another study [48].
D
Wetting
The polyoxyethylene mercaptans are excellent wetting agents with
tertiary mercaptan hydrophobes showing much superior wetting
compared with primary or normal mercaptans. This is illustrated in
Table 5 [50].
 Fig. 1
A comparison of viscosities of a polyoxyethylene tertiary dodecyl mercaptan
(Anadet 912) and a polyoxyethylene alkylphenol (Igepal CO 630) [37].
 Page 157
TABLE 5 Effect of Alkyl Chain and Ethylene Oxide Ratio on
Wetting Efficiency of Polyoxyethylene Mercaptans [50].
Time to wet in DravesClarkson test, s
conc., %
EO mole
Hydrophobe 0.25 0.125
ratio
5:1 31.3 67.9
n-Dodecyl 10:1 9.1 20.6
15:1 39.1 110.7
5:1 1.9 5.4
t-Dodecyl 10:1 3.6 11.2
15:1 7.9 16.5
5:1
n-
10:1 140 180
Tetradecyl
15:1 160 180
5:1 24.3 67.1
t-Tetradecyl 10:1 4.4 9.6
15:1 13.2 24.9

E
Foam Breaking
A unique property of the polyoxyethylene mercaptans is the
chemical reactivity of the sulfur atom in the chain. The
polyoxyethylene mercaptan can easily be oxidized to the sulfoxide
or sulfone using sodium hypochlorite (bleach) and base. The
former has excellent foaming characteristics, whereas the latter (the
sulfone) has none. This feature has been exploited in breaking
emulsions encountered when using polyoxyethylene mercaptans as
surfactants in wool scouring and pulp and paper processing [51].
Foams in the wastewater streams are a significant problem for
many industrial cleaning operations. The mercaptan surfactants can
be used as excellent emulsifiers for cleaning and then be easily
disposed of by converting them to nonfoaming sulfones using
bleach and base. This is a significant physical property and
application advantage that the mercaptan derivatives have
compared to polyoxyethylene alcohols or alkylphenols.
 Page 158

Fig. 2
A comparison of the effectiveness of soil removal using a polyoxyethylene tertiary
dodecyl mercaptan (EO/RSH = 7) (Anadet 712) vs. a polyoxyethylene alkylphenol
(EO/ROH = 7) (Igepal CO 630) in a hard surface cleaning test program [37].
F
Detergency
Polyoxyethylene mercaptans have been shown to be excellent
detergents in a wide variety of applications [45, 49, 5154]. They are
particularly useful in hard surface cleaning and removing triolein fat
in wool scouring. Results from tests in these areas are shown in Figs.
2 and 3 [37].
 Fig. 3
Effect of nonionic surfactant structures on removal of triolein fat from wool at
35°C. The N91-6 is a C9C11 alcohol reacted with
an average of 6 moles of ethylene oxide per mole of alcohol [37].
 Page 159

V
Applications
A
Household
The polyoxyethylene mercaptans have found limited use in the
household markets due to the concern for odor development in the
formulations. The main household application is in shampoos,
because the mercaptan-based products have excellent foaming,
rinsability, and resistance to hard water [5557]. A recent patent
claims that their polyoxyethylene mercaptans have substantially
reduced odor and when used with other materials produce a
superior permanent wave lotion formulation [58]. Additional hair
waving formulations containing polyoxyethylene mercaptans are
claimed to have much improved performance [59].
B
Industrial and Institutional
There are quite a few industrial applications for the
polyoxyethylene mercaptans, most of which do not have strict
odor requirements. The main applications are found in metal
cleaning, textile cleaning (wool scouring), pulp and paper, hard
surface cleaning, agricultural chemical spray adjuvants, and
emulsion stabilizers and polymerizations.
1
Metal Cleaning
Mercaptan-based surfactants are excellent for oil and grease
removal from metal surfaces and materials [60]. The mercaptan
derivatives are also effective as foam breakers in these
formulations [61]. Improvements have been made in reducing any
odor that may be associated with these products in the metal
cleaning area [62]. Water-soluble lubricating additives for water-
based metal working fluids have been developed with a key
component being polyoxyethylene mercaptans [63].
2
Pulp and Paper
As mentioned previously the polyoxyethylene mercaptans are
easily oxidized to the sulfone or sulfoxide using bleach, which
makes them valuable surfactants for the breaking of emulsions that
occur in the flotation de-linking process. The mercaptan products
are particularly good at ink removal and dispersion, thus aiding in
the recycling of newspaper and magazines.
3
Wool Scouring
As shown in Fig. 3, the polyoxyethylene mercaptans show superior
removal of oil and grease from wool. Several studies have shown
additional grease removal properties from various wool blends
under a variety of conditions [35,64,65].
 Page 160
4
Miscellaneous Applications
The polyoxyethylene mercaptans have been shown to be useful for
hard surface cleaning applications (see Fig. 2), agricultural spray
adjuvants [66], and as emulsion stabilizers and in emulsion
polymerization [67,68].
References
1. H. Schuette and C. Schoeller, U.S. Patent 2,129,709 to I.G.
Farbenindustrie A. G. (1938).
2. H. Schuette, C. Schoeller, and M. Wittwer, U.S. Patent 2,205,021
to I. G. Farbenindustrie A. G. (1938).
3. W. A. Schulze, J. P. Lyon, and G. H. Short, Ind. Eng. Chem.
40:2308 (1948).
4. C. M. Raynor, Contemp. Org. Synth. 1(3):191203 (1994).
5. L. Field, Sulfur Rep. 13(2):197277 (1993).
6. Y. Labat, Phosphorus Sulfur Silicon Rel. Elem. 74(14):17394
(1993).
7. C. Forquy and E. Arretz, Stud. Surf. Sci. Catal. 41 (1988).
8. H. E. Fried, Shell Chemical Co., unpublished results.
9. F. W. Stacey and J. F. Harris Jr., Org. Reactions 13:150376
(1963).
10. G. Sosnovsky, Free Radical Reactions in Preparative Organic
Chemistry, Macmillan, New York, 1964.
11. C. Walling, Free Radicals in Solution, John Wiley and Sons,
New York, 1957.
12. Jap. Patent 55009087 to Pennwalt Corp. (1980).
13. Fr. Patent 1582488 to United Kingdom Atomic Energy
Authority. (1970).
14. Shiro Ishida and Tokiyuki Yoshida, Japan Oils and Fats Co,
Ltd. (1969).
15. G. F. Kite, U.S. Patent 3,397,243 to Gulf Research and
Development Co. (1968).
16. L. I. Kiseleva, L. N. Khairulina, and A. V. Mashkina, Reaction
Kinet. Catal. Lett. 53(1):7378 (1994).
17. G. A. Tolstikov, F. Y. Kanzafarov, Y. A. Sangalov, and U. M.
Dzhemilev, Neftekhimiya 19(3):425429 (1979).
18. J. S. Roberts, Eur. Patent 354460 to Phillips Petroleum Co.
(1990).
19. Emmanuel Arretz, Eur. Patent 329520 to Societe Nationale Elf
Aquitane (1990).
20. H. E. Fried, Eur. Patent 122654 to Shell Internationale Research
Maatschappij B. V., Neth. (1985).
21. P. F. Warner, U.S. Patent 3,534,106 to Phillips Petroleum Co.
(1971).
22. R. T. Bell, U.S. Patent 2,531,602 to the Pure Oil Co. (1950).
23. J. F. Olin, U.S. Patent 2,434,510 to Sharples Chemicals, Inc.
(1948).
24. J. L. Eaton and J. B. Fenn, U.S. Patent 2,468,739 to Sharples
Chemicals, Inc. (1949).
25. Monsanto Chemical Company Has Developed a Simplified
Process for Synthesizing Dodecyl Mercaptan, Petrol Management
35(13):212 (1963).
26. J. Y. Lee, U.S. Patent 4,612,398 to Ethyl Corporation (1986).
27. C. H. Gross, A. V. Belea, and R. Marcu, Romanian Patent
95629 to Institutul de Cercetari pentru Produse Auxiliare Organice,
Medias, Rom. (1990).
28. W. Cleve, R. Lindenhahn, H. Martin, and R. Scheibe, Ger.
Patent 160,222 to VEB Chemische Werke Buna (1983).
 Page 161
29. E. Pajda, C. Przybyl, Z. Kubica, and S. Chybowski, Pol. Patent
102,838 to Instytut Ciezkiej Syntezy Organicznej ''Blachownia"
(1980).
30. V. E. Mazaev and M. A. Korshunov, Organ. Soedineniya Sery.
1:328333 (1976).
31. M. A. Korshunov, V. E. Mazaev, and R. N. Kudinova, Prom.
Sin. Kauch.- Tekh. Sb. 910:35 (1969).
32. S. Regula and E. Kardos, Chem. Prum. 20(11):519521 (1971).
33. H. D. Steinleitner and W. Cleve, Ger. Patent 1,274,122 to VEB
Chemische Werke Buna (1968).
34. E. A. Bartkus, E. B. Hotelliing, and N. B. Neuworth, J. Org.
Chem. 25:232 (1960).
35. J. March, in Advanced Organic Chemistry: Reactions,
Mechanisms and Structure, McGraw-Hill, New York, 1968, pp.
220, 288.
36. B. R. Schwartz, U.S. Patent 2,588,771 to Hart Product
Corporation (1952).
37. Shell Chemical Company, unpublished data (19831986).
38. J. F. Olin, U.S. Patent 2,565,986 to Sharples Chemicals, Inc.
(1951).
39. L. T. Eby, U.S. Patent 2,570,050 to Standard Oil Development
Co. (1951).
40. P. H. Schlosser and K. R. Gray, U.S. Patent 2,392,103 to
Rayonier, Inc., (1946).
41. W. W. Crouch and R. P. Louthan, U.S. Patent 2,720,543 to
Phillips Petroleum Co. (1955).
42. Br. Patent 693,966 to Standard Oil Development (1953).
43. Shell Chemical Company, unpublished data (19861988).
44. Neodol Product Guide for Alcohols, Ethoxylates and their
Derivatives, Shell Chemical Co. Technical Bulletin SC:794 (1994).
45. C. L. Edwards, U.S. Patent 4,575,569 to Shell Oil Company
(1986).
46. A. Sokolowski, Comun. Jorn. Com. Esp. Deterg. 21:259272
(1990).
47. R. A. Greff and P. W. Flanagan, J. Am. Oil Chemists Soc.
40:118 (1963).
48. T. M. Kassem, Tenside Det. 21(3):144146 (1984).
49. C. L. Edwards, H. E. Fried, and W. Lilienthal, U.S. Patent
4,931,205 to Shell Oil Company (1990).
50. British Patent 675,993 to Monsanto Chemical Company (1952).
51. D. L. Wood and H. E. Fried, U.S. Patent 4,618,400 to Shell Oil
Company (1986).
52. L. J. Mathias and J. B. Canterberry, Polym. Sci. Technol.
24:359370 (1984).
53. E. Schmitt and M. Quaedvlieg, Br. Patent 1,205,721 to
Farbenfabriken Bayer A. G. (1968).
54. W. K. Griesinger, J. A. Nevison, and G. A. Gallagher, J. Am.
Oil Chemists Soc. 26:241 (1949).
55. O. Albrecht and E. Matter, U.S. Patent 2,992,994 to Ciba, Ltd.
(1961).
56. R. L. Mayhew and J. M. Cloney, Am. Perfumer, 72(4):83, 86,
88 (1958).
57. G. Kalopissis, P. Roussopoulos and C. Zviak, U.S. Patent
3,768,490 to Oreal S. A. (1965).
58. A. Savaides and L. Salce, U.S. Patent 5,350,572 to Shiseido
Co., Ltd Japan (1993).
59. S. Naito and K. Ohshima, Eur. Patent 235783 to Kao Corp.
Japan (1987).
60. Br. Patent 993,226 to Cowles Chemical Co. (1965).
61. S. A. Bolkan, G. Byrnes, S. Dunn, A. Vinci, and A. E. Winston,
WO Patent 9,609,366 to Church and Dwight Co, Inc. (1995).
62. S. Dunn and A. E. Winston, WO Patent 9,609,368 to Church
and Dwight Co., Inc. (1995).
 Page 162
63. A. D. Schuettenberg, M. R. Lindstrom, B. R. Bonazza, H. F.
Efner, R. L. Bobsein, and M. D. Herd, Eur. Patent 249,783 to
Phillips Petroleum Co. (1987).
64. J. C. Harris, U.S. Patent 2,572,805 to Monsanto Chemical
Company (1951).
65. Technical Data Sheet I-169, Monsanto Chemical Company, St.
Louis, Missouri.
66. Br. Patent 705,117 to Monsanto Chemical Company, (1954).
67. A. B. Goel, U.S. Patent 4,696,992 to Ashland Oil Company
(1986).
68. F. Vidal, J. Guillot, and A. Guyot, Polym. Adv. Technol.
6(7):473479 (1995).
 Page 163

6
Polyoxyethylene Alkylamines
Michael D. Hoey and James F. Gadberry
Surfactants America Research and Development, Akzo Nobel
Central Research, Dobbs Ferry, New York

I. Introduction 163
II. Synthesis 164
III. Reactions of Polyoxyethylene Alkylamines 167
IV. Properties 167
A. Physical 167
B. Conductivity and CMC 167
C. Toxicity 168
D. Biodegradation 168
V. Applications 168
VI. Problems to Be Solved 169
Appendix: Trade Names Used for Ethoxylated
169
Alkylamines
References 170

I
Introduction
Strictly speaking, polyoxyethylene alkylamines should be
considered as cationic surfactants. Indeed, in some references
polyoxyethylene alkylamines are reviewed as cationic surfactants
[1]. This notwithstanding, polyoxyethylene alkylamines made by
reaction of >6 moles of ethylene oxide per mole of primary amine
do exhibit solubility characteristics, e.g., high-temperature cloud
point, of classical nonionic surfactants. Although adducts from
propylene oxide and mixed adducts of ethylene oxide and
propylene oxide are beginning to become more available, they will
not be discussed. In this review we shall address only those
surfactants that have attained significant commercial importance.
Any omissions are a matter of the perspectives of the authors.
 Page 164
For ease of discussion we employ a nomenclature based on listings
given in [2] wherein, for example, an adduct of tallowamine with
10 moles of ethylene oxide is called PEG-10 tallowamine.
Nomenclature used by Chemical Abstract Services is too complex
and unwieldy for our purposes, e.g., PEG-XX oleylamine, CAS
Registry Number 26635-93-8, is listed as poly(oxy-1, 2-ethandiyl),
a,a'-[9-octadecenylimino)di-2, 1-ethandiyl]bis[w-hydroxy-, (Z)-,
in the 9th Collective Index. This causes PEG-15 oleylamine and
PEG-25 oleylamine, for example, to be indistinguishable under
Chemical Abstracts nomenclature. As much as possible we tried to
avoid reference to commercial trade names, however, some of the
major trade names, along with their respective manufacturer, can
be found in the Appendix.
II
Synthesis
The traditional synthesis of polyoxyalkylene amines may be
separated into two reactions [3,4]. In the first, an epoxide, such as
ethylene oxide, is reacted with an amine to generate an amino
alcohol (Scheme 1). The second reaction is growth of the
polyoxyethylene chain through reaction of more epoxide with the
hydroxyl group of the aminoethyl alcohol (Scheme 2). The most
commercially common surfactants prepared this way are the
ethoxylated fatty amines. Although any epoxide may be used in
preparing a polyalkoxylated amine, the most important are made
from ethylene oxide.
Alkoxylation of the amine proceeds through the nucleophilic attack
of the amine upon the epoxide to produce the hydroxyethylamine
(Scheme 3). This reaction continues until all of the primary and
secondary amine has been consumed. Further alkoxylation of the
product beyond this point usually requires a catalyst. Historically,
sodium hydroxide and potassium hydroxide have been the
catalysts of choice [3,4]. These bases will generate an alkoxide
anion at the terminal hydroxyl on the growing polyoxyethylene
chain, which then lengthens through addition of further
oxyethylene groups. This type of chain growth might be expected
to give an approximately symmetrical distribution of oxyethylene
units if all of the hydroxyls present in the system are of equal
nucleophilicity and have an equal chance to react with the base to
generate an alkoxylate anion [5,6]. The distribution that is obtained
typically does not agree with this assumption. Because of this a
considerable amount of recent

Scheme 1
 Page 165

Scheme 2
research activity has seized on this discrepancy to develop catalysts
that will provide a narrower distribution than the one obtained
with sodium and potassium hydroxides [710]. Much of this work
is based on the theory that the growing polyoxyethylene chains can
chelate with the sodium and potassium catalyst cation(s) (Scheme
4). These chelated cations would be able to stabilize an alkoxylate,
thus giving the polyoxyethylene-cation-chelate-alkoxylate-anion a
greater probability of reacting with more ethylene oxide and
growing this polyoxyethylene chain. This would give a broad
distribution with the longer, more reacted chain, tending to react
more at the expense of the other alcohols in the reaction. Thus this
difference in probability of reaction would skew the product
distribution formed. By using a catalyst that contains different
cations and thus will not chelate with the polyoxyethylene as
sodium and potassium do, many of the new catalyst patents are
expected to produce a product with a narrower distribution of
chain length/mole equivalents of ethylene oxide reacted. Calcium
[1122], barium [2330], strontium [12,22,25,26,2831], aluminum
[3236], magnesium [3739], and zirconium [4042] have all been
used as well as rare earth cations [4348], bimetallic [4954] and
heterogeneous catalysts [46,5561]. The new catalysts do generate a
different distribution(s), but they also provide different costs to the
producers who use them. Therefore one must balance the added
costs with the real benefits that the new product distributions
provide to the customer.
A complication that is observed with this synthesis of
polyoxyethylene amines is the additional catalysis of the ethylene
oxide polymerization by the tertiary amines [3,62]. This catalytic
pathway involves the reaction of the tertiary amine with ethylene
(or propylene) oxide to form a quaternary

Scheme 3
 Page 166

Scheme 4
ammonium salt. These quaternary ammonium salts then can
catalyze this polymerization of ethylene oxide with an alcohol. The
quaternary ammonium alkoxylate salt formed in situ can then
catalyze other alcohols to react, or continue to react, at the anion
formed from the quaternization. The quaternary ammonium salt
may decompose during the reaction because the temperature of the
ethoxylation is above the decomposition temperature of many
quaternary ammonium salts. These decomposition products may
be ethylene oxide and a tertiary amine, or they may be a
polyoxyethylene glycol and a tertiary amine. Dioxane and other
ring glycols may also be formed. Dioxane and polyoxyethylene
glycols may also be formed by the reaction of water with the
ethylene oxide. Unsaturated alkyl products may be formed via a
Hoffman degradation. Many of these byproducts may continue to
react/degrade and complicate the final product mix.
Another type of polyoxyethylene amine is typified by the
Jeffamine series from Huntsman and the Tectronic series from
BASF. The Jeffamine products are made by alkoxylating a short
chain alcohol, or glycol, to obtain a polyalkoxylated alcohol. This
alcohol is then aminated to generate an amine [63,64]. These
products may be primary, secondary, or tertiary amines. This
method has been described for a number of different
reduction/amination catalysts [6368]. The primary and secondary
amines can also be alkoxylated by further reaction with an
epoxide. This reaction may take place in the presence of water
(515%) without forming undue amounts of glycols [69,70]. The
Tectronic products are made by alkoxylating a small diamine, such
as ethylene diamine. These products are all tertiary amines, and
may be made of mixtures of ethylene oxide and propylene oxide.
Some other syntheses have been described in the patent literature.
One such patent describes the reaction of a long chain epoxide,
made from a long chain a-olefin, with an amine or ammonia [71].
Although this is a similar reaction to the traditional method
described above, the size of the alkyl group on the epoxide will
greatly affect the rate of this alkoxylation reaction as well as the
solubility of the product amine.
Monoethoxylated amines have been prepared by reaction of an
imine and an alkylene oxide to produce an oxazolidine [72]. This
can then be cleaved with water to produce the monoethoxylated
fatty amine.
 Page 167

III
Reactions of Polyoxyethylene Alkylamines
Polyxyethylene alkylamines react as typical tertiary amines. These
reactions include quaternization, oxidation, and formation of salts
with inorganic and organic acids. Quaternization magnifies the
cationic properties to such an extent that the products can no
longer be considered nonionic. Oxidation is generally unknown
except for the lower adducts, e.g., PEG-2 cocoamine. Amine
oxides of higher adducts have not yet been exploited to any great
extent.
The presence of terminal hydroxyl groups on polyoxyethylene
alkylamines allows formation of esters with carboxylic acids.
Though these products should have greater lipophilicity that the
parent poloyoxyethylene amines, they have not been yet achieved
significant commercial success.
IV
Properties
A
Physical
The best sources of information regarding the physical properties
of polyoxyethylene alkylamines are the product bulletins and
brochures from commercial suppliers. This is especially important
as small but important differences may exist for similar products
from different suppliers. Solubility data and formulations may also
be available. A good general source of information on products
and suppliers is the Handbook of Industrial Surfactants [2].
Depending on fatty alkyl chain length and degree of ethoxylation,
polyoxyethylene alkylamines can vary from free-flowing liquids to
pastes or solids. Generally, long saturated alkyl chains and high
moles of ethoxylation give pastes to solids. The color of
polyoxyethylene alkylamines varies from golden to dark brown
depending on reaction catalyst, temperature, degree of
ethoxylation, etc.
B
Conductivity and CMC
In a study of the conductivities of ethoxylated laurylamines and
ethoxylated stearylamines, Riva and Ribe [73] found that lauryl
derivatives have higher conductivities than the stearyl products at
equivalent ethoxylation. Furthermore, conductivity of the
ethoxylated laurylamines increases with increasing ethoxylation;
increased ethoxylation was reported to little affect the conductivity
of the stearyl derivatives. These results suggest that chain length of
the hydrophobe plays an important role in the aggregation
properties of these surfactants. This study also reports that critical
micelle concentrations (CMCs) range from 0.4 to 1.0 mmol/L.
 Page 168

Scheme 5
C
Toxicity
Polyoxyethylene alkylamines are organic bases and therefore
should be considered corrosive to skin if the adduct number of
moles of ethylene oxide is <10. Nevertheless, adducts with >10
moles of ethylene oxide should be handled with care. All
polyoxyethylene alkylamines should be considered as severely
irritating and corrosive to eyes.
D
Biodegradation
Biodegradation of ethoxylated fatty amines has been studied by
van Ginkel et al. [74] using a "prolonged" closed bottle test. The
researchers propose that degradation of the polyoxyethylene
alkylamines proceeds via initial oxidative cleavage of the fatty
alkyl chain to form an easily degraded fatty residue and a less
easily degraded polyoxyethylene secondary amine (Scheme 5). The
polyoxyethylene secondary amines are not considered toxic to
aquatic organisms. This is understandable because the
polyoxyethylene secondary amines will have minimal surfactant
properties.
V
Applications
There is a wide range of applications for these polyoxyalkylene
amines. For the purposes of this chapter, we will limit this
discussion to polyoxyalkylene amines possessing an alkyl chain of
more than six carbons. Also, due to the large number of patents in
this area, we are limiting this discussion to U.S. patents. The list of
patents is not exhaustive but rather is designed to be an overview.
Many of the applications described below owe their use to the
polyoxyalkylene amine's affinity for surfaces. The use of these
products to coat films or glass [7577], to coat wool or cloth
[78,79], to coat yarns [8083], or as wettability aids [84] comes
from the propensity for these amines to adsorb to surfaces from a
solution. They are also used as solubilizers and emulsifiers in
formulations [8596], to stabilize dispersions [97], and as antistat
additives [98110]. They have been used as anticaking aids [111],
dyeing auxiliaries [112116], and, with borated derivatives, as
friction-modifying additives [117124]. They are included in
herbicide formulations [125131] and are used to degrease, or dye,
leather surfaces [132134]. They are included in many cleaning and
deter-
 Page 169
gent formulations for contributing antistatic behavior,
antideposition properties, and dispersing abilities [135144]. They
have been used as additives in gasoline [145], drilling fluids
[146151], corrosion inhibitors [152159], and plastics [160165]. The
great variety of uses seems to stem from the their ability to interact
well with other surfactant types, and their surface absortivity. It is
this effect that is used most often in the patents described herein.
VI
Problems to Be Solved
Two major problems yet unsolved for polyoxyethylene
alkylamines are dark color and formation of dioxane. Higher mole
ethylene oxide adducts are typically brown to dark brown liquids.
The exact nature of the color bodies is unknown but may be
speculated to arise from the presence or formation of acetaldehyde,
which may result in chromophoric condensation products.
Improvement of the color of polyoxyethylene alkylamines should
lead to an increased number of use possibilities, e.g., in personal
care applications. Distillation of polyoxyethylene alkylamines is
not practical.
Formation of dioxane, a suspected carcinogen, is becoming
increasingly problematic as consumers of polyoxyethylene
alkylamines impose more stringent requirements on suppliers.
Removal of dioxane can add significantly to productions cycle
times thereby increasing production costs. No published sources
have addressed this problem in a meaningful manner.
Another similar issue that may or may not be important for some
applications is the formation of PEGs simultaneously during
preparation of polyoxyethylene alkylamines. Water (or hydroxide)
must be present in order for PEGs to form. Therefore, sufficient
drying of both the PEG-2 alkylamine and ethylene oxide should
minimize PEG contamination.
Appendix:
Trade Names Used for Ethoxylated Alkylamines
Trade name Manufacturer
Accomeen Karlsham
Alkaminox Rhone-Poulenc
Chemeen Chemax
Ethomeen Akzo Nobel
Genamine Hoechst
Hetoxamine Hetere
Katapol Rhone-Poulenc
Mazeen PPG
Protox Protameen
Teric ICI
Trymeen BASF
Varionic Witco
 Page 170

References
1. H. L. Sanders, J. B. Braunwarth, R. B. McConnell, and R. A.
Swenson, J. Am. Oil Chemist Soc. 46:167 (1969).
2. C. Schoeller and M. Wittwer, U. S. Patent 1,970,578 to I. G.
Farbenindustrie (1934).
3. E. Santacesaria, M. Diserio, R. Garaffa, and G. Addino, Ind.
Eng. Chem. Res. 31:2413 (1992).
4. B. Bartha, L. Farkas, J. Morgos, P. Sallay, I. Rusznak, and G.
Veress, J. Am. Oil Chemist Soc. 58:650 (1981).
5. J. Morgos, P. Sallay, L. Farkas, and I. Rusznak, J. Am. Oil
Chemists Soc. 60:1905 (1983).
6. W. Hreczuch and J. Szymanowski, J. Am. Oil Chemists Soc.
73:73 (1996).
7. K. L. Matheson, T. P. Matson, and K. Yang, J. Am. Oil Chemists
Soc. 63:365 (1986).
8. K. W. Dillan, G. C. Johnson, and P. A. Siracusa,
Soap/Cosmetics/Chemical Specialties 34 (March 1986).
9. C. L. Edwards, U.S. Patent 4,396,779 to Shell Oil Company
(1983).
10. J. H. McCain, and L. F. Theiling, Jr., U.S. Patent 4,453,022 to
Union Carbide Corporation (1984).
11. R. J. Knopf and L. F. Theiling, Jr., U.S. Patent 4,754,075 to
Union Carbide Corporation (1988).
12. R. J. Knopf and L. F. Theiling, Jr., U.S. Patent 4,820,673 to
UOP (1989).
13. B. E. Leach, M. L. Shannon, and D. L. Wharry, U.S. Patent
4,835,321 to Vista Chemical Company (1989).
14. R. J. Knopf and L. F. Theiling, Jr., U.S. Patent 4,886,917 to
Union Carbide Chemicals and Plastics Company (1989).
15. S. W. King and R. J. Knopf. U.S. Patent 4,902,658 to Union
Carbide Chemicals and Plastics Company (1990).
16. C. F. Hauser, U.S. Patent 4,946,984 to Union Carbide
Chemicals and Plastics Company (1990).
17. S. W. King and R. J. Knopf, U.S. Patent 5,104,575 to Union
Carbide Chemicals and Plastic Company (1992).
18. S. W. King, U.S. Patent 5,114,900 to Union Carbide Chemicals
and Plastics Company (1992).
19. S. W. King, U.S. Patent 5,120,697 to Union Carbide Chemicals
and Plastics Company (1992).
20. T. S. Sandoval and P. A. Schwab, U.S. Patent 5,220,077 to
Vista Chemical Company (1993).
21. K. Yang, G. L. Nield, and P. H. Washecheck, U.S. Patent
4,210,764 to Conoco, Inc. (1980).
22. K. Yang, G. L. Nield, and P. H. Washecheck, U.S. Patent
4,302,613 to Conoco, Inc. (1981).
23. K. Yang, U.S. Patent 4,239,917 to Conoco, Inc. (1980).
24. K. Yang, G. L. Nield, and P. H. Washecheck, U.S. Patent
4,376,868 to Conoco, Inc. (1983).
25. J. H. McCain and L. F. Theiling, Jr., U.S. Patent 4,453,023 to
Union Carbide Corporation (1984).
26. A. J. Heuvelsland, U.S. Patent 5,010,187 to Dow Chemical
Company (1991).
27. A. J. Heuvelsland, U.S. Patent 5,114,619 to Dow Chemical
Company (1992).
 Page 171
28. R. A. Reck, in Cationic Surfactants, Organic Chemistry (J. M.
Richmond, ed.), Marcel Dekker, New York, 1990, pp. 180182.
29. M. Ash and I. Ash, in Handbook of Industrial Surfactants,
Gower, London 1993.
30. D. E. Laylock and R. A. Sewell. U.S. Patent 5,374,705 to Dow
Chemical Company (1994).
31. K. Yang, G. L. Nield, and P. H. Washecheck, U.S. Patent
4,223,164 to Conoco, Inc. (1980).
32. C. L. Edwards, U.S. Patent 4,721,816 to Shell Oil Company
(1988).
33. C. L. Edwards, U.S. Patent 4,721,817 to Shell Oil Company
(1988).
34. B. E. Leach, M. L. Shannon, and D. L. Wharry, U.S. Patent
4,775,653 to Vista Chemical Company (1988).
35. C. L. Edwards, U.S. Patent 4,825,009 to Shell Oil Company
(1989).
36. C. L. Edwards, U.S. Patent 4,933,502 to Shell Oil Company
(1990).
37. C. L. Edwards, U.S. Patent 4,375,564 to Shell Oil Company
(1983).
38. C. L. Edwards, U.S. Patent 4,465,877 to Shell Oil Company
(1984).
39. H. Nakamura, Y. Nakamoto, and Y. Fujimori, U.S. Patent
5,012,012 to Lion Corporation (1991).
40. S. W. King, U.S. Patent 4,727,199 to Union Carbide
Corporation (1988).
41. S. W. King, U.S. Patent 4,873,017 to Union Carbide
Corporation (1989).
42. S. W. King, U.S. Patent 5,025,094 to Union Carbide
Corporation (1991).
43. C. L. Edwards, U.S. Patent 5,057,627 to Shell Oil Company
(1991).
44. C. L. Edwards and R. A. Kemp, U.S. Patent 5,057,628 to Shell
Oil Company (1991).
45. C. L. Edwards, U.S. Patent 5,059,719 to Shell Oil Company
(1991).
46. R. A. Kemp, U.S. Patent 5,118,870 to Shell Oil Company
(1992).
47. R. A. Kemp, U.S. Patent 5,208,199 to Shell Oil Company
(1993).
48. R. A. Kemp and P. R. Weider, U.S. Patent 5,210,325 to Shell
Oil Company (1993).
49. C. L. Edwards, U.S. Patent 4,665,236 to Shell Oil Company
(1987).
50. C. L. Edwards, U.S. Patent 4,689,435 to Shell Oil Company
(1987).
51. S. W. King, U.S. Patent 5,104,987 to Union Carbide
Corporation (1992).
52. S. W. King, U.S. Patent 5,112,788 to Union Carbide
Corporation (1992).
53. C. F. Hauser, S. W. King, R. J. Knopf, J. H. McCain, and C. A.
Smith, U.S. Patent 5,112,789 to Union Carbide Corporation (1992).
54. S. W. King, U.S. Patent 5,118,650 to Union Carbide
Corporation (1992).
55. S. W. King, U.S. Patent 4,873,017 to Union Carbide
Corporation (1989).
56. S. W. King and R. J. Knopf, U.S. Patent 4,902,658 to Union
Carbide Corporation (1990).
57. S. W. King, U.S. Patent 5,025,094 to Union Carbide
Corporation (1991).
58. S. W. King, U.S. Patent 5,104,987 to Union Carbide
Corporation (1992).
59. D. H. Champion and G. P. Speranza, U.S. Patent 5,110,991 to
Texaco Chemical Company (1992).
60. S. W. King, U.S. Patent 5,136,106 to Union Carbide
Corporation (1992).
61. M. Cuscurida, J. F. Knifton, and P. E. Dai, U.S. Patent
5,256,828 to Texaco Chemical Company (1993).
62. B. Bartha, L. Farkas, J. Morgos, P. Sallay, I. Rusznak, and G.
Veress, J. Am. Oil Chemists. Soc. 62:824 (1985).
63. M. Cuscurida and E. L. Yeakey, U.S. Patent 5,103,062 to
Texaco Chemical Company (1992).
64. J. F. Knifton and C. G. Naylor, U.S. Patent 5,344,984 to Texaco
Chemical Company (1994).
 Page 172
65. J. M. Larkin and G. P. Speramza. U.S. Patent 4,827,038 to
Texaco Chemical Company (1989).
66. J. M. Larkin and G. P. Speramza. U.S. Patent 4,847,417 to
Texaco Chemical Company (1989).
67. K. R. Smith, U.S. Patent 4,888,447 to Ethyl Corporation (1989).
68. K. R. Smith, U.S. Patent 4,967,005 to Ethyl Corporation (1990).
69. M. Cuscurida and H. P. Klein, U.S. Patent 4,465,858 to Texaco
Chemical Company (1984).
70. M. Cuscurida and W. P. Krause, U.S. Patent 4,479,010 to
Texaco Chemical Company (1984).
71. R. Hoefer, U.S. Patent 4,689,366 to Henkel
Komanditgesellschaft auf Aktien (1987).
72. H. Cho and D. Frank, U.S. Patent 4,677,208 to Akzona
Incorporated (1987).
73. A. Riva and J. Ribe, Bol. Inst. Invest. Text. Coop. Ind. (Univ.
Politec. Barcelona) 81:31 (1982).
74. C. G. van Ginkel, C. A. Stroo, and A. G. M. Kroon, Tenside
Surf. Det. 30:213 (1993)
75. C. A. Johnson, U.S. Patent 4,039,716 to Owens-Corning
Fiberglas Corporation (1977).
76. S. Razac and P. E. Eckler, U.S. Patent 5,409,574 to Rhone
Poulenc Inc. (1995).
77. D. M. Regan, U.S. Patent 5,472,493 to Cabot Corporation
(1995).
78 H. Abel, H. Hostettler, and R. Topfl, U.S. Patent 3,944,385 to
Ciba-Geigy Corporation (1976).
79. H. U. von der Eltz, H. Maier, and K. Rostermundt, U.S. Patent
4,701,182 (1987).
80. K. C. Dardoufas and R. M. Marshall, U.S. Patent 4,103,068 to
Allied Chemical Corporation (1978).
81. K. C. Dardoufas and R. M. Marshall, U.S. Patent 4,105,568 to
Allied Chemical Corporation (1978).
82. K. C. Dardoufas and R. M. Marshall, U.S. Patent 4,210,700 to
Allied Chemical Corporation (1980).
83. H. Dumm, G. Koener, M. Krakenberg, H. Rott, and G.
Schmidt, U.S. Patent 4,434,008 to Th. Goldschmidt AG (1984).
84. R. E. Beetschen, B. P. Lynch, and A. A. Short, U.S. Patent
4,170,682 to Kellwood Company (1979).
85. B. J. Bishop and A. J. Moon, U.S. Patent 4,106,901 to Star
Chemical, Inc. (1978).
86. T. Wershofen, U.S. Patent 4,803,012 to Henkel
Komanditgesellschaft auf Aktien (1989).
87. H. M. Muijs and J. V. Schaik, U.S. Patent 5,061,386 to Shell Oil
Company (1991).
88. I. Rivenaes, U.S. Patent 5,075.040 to Denbar, Ltd. (1991).
89. M. P. Breton, M. D. Croucher, K. M. Henseleit, B. Helbrecht,
and F. M. Pontes, U.S. Patent 5,129,948 to Xerox Corporation
(1992).
90. T. Wershofen, U.S. Patent 5,145,608 to Ecolab Inc.(1992).
91. D. W. Reichgott, U.S. Patent 5,282,992 to Betz Laboratories,
Inc. (1994).
92. L. J. Barker, M. N. O'Connor, and R. G. Ryles, U.S. Patent
5,298,555 to American Cyanamid Company (1994).
93. R. M. Blanch and M. J. Kaszubski, U.S. Patent 5,310,772 to
Allied Signal Inc. (1994).
94. L. J. Barker, M. N. O'Connor, and R. G. Ryles, U.S. Patent
5,376,713 to Cytec Technology Corp (1994).
 Page 173
95. S. O. Aston and J.R. Provost, U.S. Patent 5,403,358 to Imperial
Chemical Industries PLC (1995).
96. R. M. Holdar, U.S. Patent 5,460,753 to NCH Corporation
(1995).
97. M. J. Wisotsky, U.S. Patent 4,505,829 to Exxon Research and
Engineering Co. (1985).
98. A. J. Castro and J. W. Stoll, U.S. Patent 4,147,742 to Akzona
Incorporated (1979).
99. A. J. Castro and J. W. Stoll, U.S. Patent 4,210,556 to Akzona
Incorporated (1980).
100. R. P. Pardee, U.S. Patent 4,232,072 to Ball Corporation
(1980).
101. B. N. Hendy, U.S. Patent 4,268,583 to Imperial Chemical
Industries Limited (1981).
102. A. J. Castro and J. W. Stoll, U.S. Patent 4,314,040 to Akzona
Incorporated (1982).
103. W. Lybrand, U.S. Patent 4,391,952 to Bengal, Inc. (1983).
104. W. Lybrand, U.S. Patent 4,393,159 to Bengal, Inc. (1983).
105. W. Lybrand, U.S. Patent 4,393,176 to Bengal, Inc. (1983).
106. J. P. Duffy, U.S. Patent 4,417,999 to Witco Chemical
Corporation (1983).
107. S. E. Gloyer, U.S. Patent 4,764,428 to Witco Chemical
Corporation (1988).
108. B. D. Stevens, U.S. Patent 5,132,060 to the Dow Chemical
Company (1992).
109. S. R. Seshadri, U.S. Patent 5,219,493 to Henkel Corporation
(1993).
110. M. J. Incorvia, U.S. Patent 5,478,486 to Henkel Corporation
(1995).
111. J. H. Finley, C. W. Lutz, and M. L. Pinsky, U.S. Patent
4,316,879 to FMC Corporation (1982).
112. T. Sato and S. Nagao, U.S. Patent 4,215,992 to Kao Soap Co.,
Ltd. (1980).
113. A. S. Canale and R. D. Canale, U.S. Patent 4,234,443 to
Michael A. Canale (1980).
114. R. Fricker and R. Gross, U.S. Patent 4,362,530 to Sandoz Ltd.
(1982).
115. U. Buchel and P. Muther, U.S. Patent 4,523,923 to Ciba-Geigy
Corporation (1985).
116. A. Fredj, J. P. Johnston, and C. A. J. Theon, U.S. Patent
5,470,507 to the Procter and Gamble Co. (1995).
117. B. D. Busch and D. J. Yeavello, U.S. Patent 4,261,842 to
Fremont Industries, Inc. (1981).
118. A. G. Horodysky, U.S. Patent 4,382,006 to Mobil Oil
Corporation (1983).
119. A. G. Horodysky and J. M. Kaminisky, U.S. Patent 4,406,802
to Mobil Oil Corporation (1983).
120. A. G. Horodysky and J. M. Kaminisky, U.S. Patent 4,478,732
to Mobil Oil Corporation (1984).
121. A. G. Horodysky and J. M. Kaminisky, U.S. Patent 4,568,472
to Mobil Oil Corporation (1986).
122. A. G. Horodysky and J. M. Kaminisky, U.S. Patent 4,594,171
to Mobil Oil Corporation (1986).
123. W. T. Brannen, G. D. Burt, and R. A. McDonald, U.S. Patent
4,965,002 to Elco Corporation (1990).
124. K. P. Kammann, Jr., and W. R. Garrett, U.S. Patent 5,080,813
to Ferro Corporation (1992).
125. M. Grunert, and H. Tesman, U.S. Patent 4,356,020 to Henkel
Komanditgesellschaft auf Aktien (1982).
126. J. L. Ahle, U.S. Patent 4,528,023 to Starrier Chemical
Company (1985).
127. P. M. Ronning and G. A. Vandesteeg, U.S. Patent 4,556,410 to
Minnesota Mining and Manufacturing Company (1985).
128. P. M. Ronning and G. A. Vandesteeg, U.S. Patent 4,557,751 to
Minnesota Mining and Manufacturing Company (1985).
 Page 174
129. W. T. Hulshof, U.S. Patent 5,226,943 to Akzo N. V. (1993).
130. J. P. Bell, U.S. Patent 5,426,121 to Akzo Nobel N. V. (1995).
131. R. H. McIntosh and D. E. Triestram, U.S. Patent 5,474,739 to
Interface, Inc. (1995).
132. F. Feichtmayr, D. Lach, and R. Streicher, U.S. Patent
4,272,243 to BASF Aktiengesellschaft (1981).
133. F. Landbeck, R. Leberfinger, H. Matschkal, and P. Rathfelder,
U.S. Patent 4,470,825 to Schill and Seilacher GmbH and Co.
(1984).
134. B. Danner, U.S. Patent 4,572,721 to Sandoz Ltd. (1986).
135. E. Daubach, H. Saukel, and L. Von Rambach, U.S. Patent
3,960,486 to BASF Aktiengesellschaft (1976).
136. J. T. Inamorato, U.S. Patent 3,959,157 to Colgate-Palmolive
Company (1976).
137. R. M. Butterworth, J. R. Martin, and E. Willis, U.S. Patent
4,622,154 to Lever Brothers Company (1986).
138. R. M. Butterworth, J. R. Martin, and E. Willis, U.S. Patent
4,627,925 to Lever Brothers Company (1986).
139. E. P. Gosselink and Y. S. Oh, U.S. Patent 4,664,848 to the
Proctor and Gamble Company (1987).
140. H. Andree, M. Berg, and W. Seiter, U.S. Patent 4,675,124 to
Henkel Komanditgesellschaft auf Aktien (1987).
141. D. H. Leifheit, U.S. Patent 4,743,395 to the Drackett Company
(1988).
142. R. P. Adams, U.S. Patent 4,741,842 to Colgate-Palmolive
Company (1988).
143. G. Bosserhoff, H. Buchler, R. Puchta, and H. Wilsberg, U.S.
Patent 4,931,063 to Henkel Komanditgesellschaft auf Aktien
(1990).
144. S. Q. Lin, L. V. Salas, and L. S. Tsaur, U.S. Patent 5,429,754
to Lever Brothers Company, Division of Conopco, Inc. (1995).
145. M. Vataru, U.S. Patent 4,797,134 to Wynn Oil Company
(1989).
146. J. J. Rayborn, U.S. Patent 4,645,608 to Sun Drilling Products
Corp. (1987).
147. C. J. Davidson, U.S. Patent 4,828,724 to Shell Oil Company
(1989).
148. K. A. Knitter and J. L. Villa, U.S. Patent 4,363,637 to
Diamond Shamrock Corporation (1982).
149. M. J. Schick and E. L. Kelley, U.S. Patent 4,492,590 to
Diamond Shamrock Chemicals Company (1985).
150. L. R. Norman and T. R. Gardner, U.S. Patent 4,324,669 to
Halliburton Company (1982).
151. R. W. Jahnke, U.S. Patent 4,061,580 to The Lubrizol
Corporation (1977).
152. F. W. Valone, U.S. Patent 4,420,414 to Texaco Inc. (1983).
153. B. Mosier, U.S. Patent 4,470,918 to Global Marine, Inc.
(1984).
154. H. Haugen, U.S. Patent 4,224,170 to Texaco Inc. (1980).
155. R. N. Buggs, R. K. Gabel, and A. R. Syrinek, U.S. Patent
5,009,799 to Nalco Chemical Company (1991).
156. J. M. Brown, R. D. McBride, and J. R. Ohlsen, U.S. Patent
5,415,805 to Betz Laboratories, Inc. (1995).
157. J. M. Brown, J. J. Herrold, and H. A. Roberts, U.S. Patent
5,425,914 to Betz Laboratories, Inc. (1995).
158. R. Bohm, M. Hille, and R. Kupfer, U.S. Patent 5,421,993 to
Hoechst AG (1995).
159. J. M. Brown, G. F. Brock, V. K. Mandlay, and J. R. Ohlsen,
U.S. Patent 5,459,125 to BJ Services Company (1995).
160. H. K. Ficker and F. M. Teskin, U.S. Patent 4,684,683 to El
Paso Products Company (1987).
 Page 175
161. H. K. Ficker and F. M. Teskin, U.S. Patent 4,692,489 to El
Paso Products Company (1987).
162. K. G. McDaniel, U.S. Patent 4,760,100 to Arco Chemical
Company (1988).
163. C. Bath and J. Trotoir, U.S. Patent 4,829,114 to Imperial
Chemical Industries PLC (1989).
164. C. Breuer, U. Gelderie, and G. Holzer, U.S. Patent 5,030,686 to
Isover Saint-Gobain (1991).
165. D. Augustin, C. Collette, and R. Parsy, U.S. Patent 5,089,546
to Atochem (1992).
 Page 177

7
Nonionic Surfactants Containing an Amide Group
Anna Lif and Martin Hellsten*
Central Research and Development, Akzo Nobel Surface
Chemistry AB, Stenungsund, Sweden

I. Introduction 177
II. Synthesis and Production 178
A. Glycol Ethers of Fatty Acid Amides 178
B. Ethoxylation of Alkanolamides 179
C. Derivatives of Ethoxylated Amides 180
D. Nonionic Surfactants Containing Both an Amide
181
and a Carbohydrate Group
III. Commercial Products 183
IV. Physical and Amphiphilic Properties 184
A. Polyoxyethylated Alkylamides 184
B. N-acyl, N-alkyl Sugar Amides 186
C. Dialkyl Disugar Amides 187
V. Functions and Applications 188
A. Polyoxyethylated Amides 188
B. Glucamides 191
 VI. Environmental Properties 193
References 194

I
Introduction
Nonionic surfactants containing an amide group are still a
relatively small part of the total volume of nonionic surfactants,
but they will probably be growing part. Their main advantage in
comparison to other nonionic surfactants depends on the strong
attraction between the amide groups, which leads to a dense
packing at interfaces and thus an increased technical effect. Other
advantages
* Retired.
 Page 178
with the amide group are a good chemical stability combined with
fast biodegradation and somewhat simple manufacturing
processes.
The carbohydrate-based amides are also wholly based on
renewable raw materials, an advantage which they share with other
carbohydrate-based surfactants, e.g. the alkylglucosides.
Two groups of amide-containing nonionic surfactants dominate,
namely the (poly)glycol ether amides and the carbohydrate amides
of fatty acids.
The mono- and diethanolamides of fatty acids were well treated in
[1] and since then a few significant developments have taken
place. We will thus only take up work regarding the
polyoxyethylated fatty acid amides, which are also called
polyglycol ether amides (of fatty acid).
The carbohydrate amides of fatty acids are often made via reaction
of fatty acid esters with glucamine leading to a N-acyl, N-
methylglucamide. In biochemical journals the acronym MEGA-n is
common. Another common denomination for this type of
compound is fatty acid polyhydroxyamide.
II
Synthesis and Production
An excellent review of the various synthesis routes for
polyoxyethylene alkylamides is given by E. Jungermann et al. [1]
which covers the literature up to 1967. Only publications that
appeared later than 1967 and that represent significant advance in
technology will be covered in this chapter.
A
Glycol Ethers of Fatty Acid Amides
The most common route for the production of glycol ethers of
fatty acid amides is by reaction of fatty acid esters or fatty acids
with ethanolamine or diethanolamine. In the latter case only esters
will be used. The fatty acid ethanolamides thus produced may then
be ethoxylated and/or propoxylated to achieve the desired nonionic
surfactant. For both of these process steps significant progress has
been made.
The use of fatty acid methyl esters or triglycerides for the
production of fatty acid mono- and dialkanolamides has long since
been established [2,3] and will permit a much lower reaction
temperature and thus less discoloration of the amides, which is
particularly important when unsaturated fatty acids are present. A
variation of this ester route to amides is given by [4] whereby the
fatty acids are alkoxylated and then reacted with alkanolamine. In
this reaction the glycol ethers formed are left in the product and
lower its melting point due to its solvent properties.
For the production of diethanolamides directly from triglycerides it
has been proposed that one use 1.4 mmoles of ZnO as catalyst to 1
mole triglyceride and 3 moles of diethanolamine and a reaction
temperature of 200°C [11]. The process is said to give a high yield
of the diethanolamide.
 Page 179
For the preparation of every pure alkanolamides a large molecular
excess of alkanolamine, e.g., 10 times, may be used [3].
In [5] a method is described for the production of
monoethanolamides with a purity of more than 95% from either
fatty acids or the corresponding methyl esters by first reacting this
acid or ester with 5060% of the calculated amount of
monoethanolamine at 100150°C, whereby mainly the esteramide,
RCOOC2H4NHOCR, will be formed. When this reaction is
completed the residual amount of monoethanolamine is added and
the reaction continued at 140150°C for 6 h.
B
Ethoxylation of Alkanolamides
Some interesting work on the ethoxylation of alkanolamides has
been reported [3], from which Table 1 was compiled. This table
gives the product composition after ethoxylation of a pure lauric
acid monoethanolamide to which various amounts of esteramide
RCOOC2H4NHOCR had been added. It is seen that the only
important change of the product composition when the
monoethanolamide is contaminated by esteramide is a decrease in
the content of alkanolamines and a corresponding increase of the
polyglycol ethers.
The formation of byproducts depends on a transamidation reaction
at the ethoxylation temperature whereby 2 moles of
monoethanolamide are in equilibrium with 1 mole of esteramide
and 1 mole of monoethanolamine and this mixture is in turn in
equilibrium with 2 moles of esteramine (RCOOC2H2NH2):
The different components will then be ethoxylated at various rates.
TABLE 1 Product Composition Following Ethoxylation of
Lauric Acid Monoethanolamide
Monoethanolamide (%) 100 95 90 85 0
Esteramide (%) 0 5 10 15 100
Reaction products
RCONH(C2H4O)xH
84.0 83.8 85.4 84.4 69.8
RCOO(C2H4O)yH
RCOOC2H4N(C2H4O)zH 2.3 2.0 4.1 4.2 10.3
N(C2H4O)uH (alkanolamines) 11.2 7.0 5.9 5.1 3.4
HO(C2H4O)vH (polyglycol ether) 1.8 6.6 6.0 5.6 16.0
RCOO-M+ (soap) 0.8 0.6 0.6 0.7 0.5
 Page 180
In order to avoid the transamidation reaction as much as possible,
Sandberg [6] was able to carry out the ethoxylation process at a
significantly lower temperature than normal by using a tertiary or
quaternary amine as catalyst. The reaction temperature can then be
lowered from 140150°C to 7580°C. With this process light-colored
amide ethoxylates may be produced, containing <0.5% esteramide.
Another way of eliminating esteramides from the ethoxylated
products is given by Kado et al. [7] who treat the amide
ethoxylates with monoethanolamine or monoaminoglycol ethers,
thereby causing the reverse reaction, from III to I, in the reaction
scheme given above.
Ethoxylated amides with a light color may also be produced at high
ethoxylation temperature and alkali as catalyst if 0.010.5% (w/w)
NaBH4 is added to the fatty acid alkanolamide [21].
Instead of ethoxylating a fatty acid alkanolamide, it has been
suggested [22] that an alkyl polyglycol ether amine be produced
and reacted with a fatty acid ester according to the following:

where RCOOH is a fatty acid and R1OH an alcohol containing one

to four atoms.
Low-foaming surfactants, e.g., for machine dishwashing, may be
produced according to this method.
C
Derivatives of Ethoxylated Amides
The ethoxylated fatty acid amides can be derivatized to anionic
surfactants in the same manner as ethoxylated fatty alcohols. The
only important difference consists of the numerous byproducts in
the amides, e.g., the esteramides which may be completely or
partly hydrolyzed during the reactions.
A process for the production of carboxymethyl acids of
ethoxylated fatty acid alkanolamides is described in [8] whereby
the alkanolamide is reacted first with ethylene oxide and then with
a haloacetic acid in the presence of solid alkali. The haloacetic acid
is used in less than stoichiometric amounts. The resulting
surfactant mixture is claimed to have good foaming properties and
mildness to the skin and is useful for the formulation of
shampoos, skin cleansers, and dishwashing detergents.
A phosphate ester of ethoxylated alkanolamide may be prepared
according to [9] by first treating an ethoxylated monoethanolamide
based on coconut fatty acids with ethanol during 1 h at 80°C in
order to eliminate the contents of
 Page 181
esteramide and then to treat the product with POCl3 and neutralize.
The surfactants formed are suitable for the formulation of low-
temperature liquid detergents and have a good foaming ability.
By using chlorosulfonic acid instead of POCl3 in the process
outlined above, sulfates of the ethoxylated ethanolamides may be
produced [10]. The resulting surfactants are also claimed to be
useful for low-temperature detergents and to have a good foaming
ability.
D
Nonionic Surfactants Containing Both an Amide and a
Carbohydrate Group
During the last 10 years much work has been done on the
combination of a carbohydrate and a fatty acid via an amide group.
Two different routes have become dominant:
1. A reducing sugar is reacted with a lower alkylamine and this
product is then hydrogenated to the corresponding sugar amine. A
fatty ester is then amidated with this amine to the N-acyl, N-alkyl
sugar amide. So far glucose has been the most common reducing
sugar used for this reaction and consequently the whole group of
surfactants is often called N-alkylglucamides or just glucamides.
2. A reducing sugar is oxidized to the corresponding carboxylic
acid and this acid is then amidated with a primary (or secondary)
amine. The products are usually named after the sugar used, e.g.,
lactose is oxidized to lactobionic acid and then amidated to
lactobionamide.
1
N-Alkyl Sugar Amines
A straightforward process for N-alkylglucamine is described in
[12] and comprises the following steps: Glucose is reacted with a
slight excess of CH3NH2 at 3060°C with methanol as a solvent.
After completion of this reaction the solvent is evaporated until no
methylamine is present in the solution. The hydrogenation is then
carried out at 5090°C and a pressure of 250 psi using a supported
nickel catalyst.
2
N-Alkyl Sugar Amides
An example of a possible process for the amidation of a fatty acid
ester with N-methylglucamine is given in [13]: A mixture of
methyllaurate and methanol + Na-methylate was treated at 80°C
with a solution of N-methylglucamine in propylene glycol and the
methanol was continuously evaporated from the reaction mixture
resulting in a waxy N-lauryl, N-methylglucamide having a bright
color.
A variation of this process is given in [14] whereby Na2CO3 or
K2CO3 in an amount of 0.550% of the reactants (mol%) is used as
a catalyst and 220% (w/w) of a preformed glucamide surfactant is
used as a phase transfer agent. The
 Page 182
advantage of this process is supposedly a very short reaction time
(0.510 min) at the highest reaction temperature (160180°C).
Another variation of the basic process is given in [15] whereby
M3PO4, M4P2O7, M5P3O10, M3-Citrate, M2-tartrate, and Mn-basic
aluminosilicates are mentioned as catalysts in an amount of 1095%
(w/w) based on the sum of the reactants. The resulting product
seems to be aimed as an ingredient for a laundry detergent.
The possibility of balancing higher fatty acids by mixing the
glucose with reducing di- or polysaccharides at the production of
surfactants of the glucamide type has been observed in [16] where
it is pointed out that the amidation should be carried out at 5080°C
to avoid cyclization and that the N-alkyl sugar amine should be
derived from a glucose maltose mixture in ratio of 4:1 to 99:1
(w/w).
N-Alkylglucamides aimed for liquid hand dishwashing
formulations should have a low content of fatty acid soaps and
esters. Otherwise they will have a detrimental effect on foam
stability, particularly in hard-water areas. The glucamides may be
improved in this respect according to [17] by treating the final
product with an amine, particularly an ethanolamine, thereby
transforming the soaps and esters to alkanolamides, which
normally will have a foam-stabilizing effect.
A continuous process for the amidation of fatty acid ester is
described in [18] where the apparatus consists of a cascade of two
stirred reactors. To the first reactor equimolar amounts on N-
methylglucamine and C1214-fatty acid methyl ester were fed
continuously together with 5 mol% of Na-methylate and 50 mol%
of propylene glycol. The temperature was kept at 95°C and the
mean reaction time was 1.9 h. The conversion in this first reactor
was 82%. The effluent from this reactor was fed to a second one,
which was kept at 90°C and a pressure of 22 mbar. The mean
reaction time was 2.1 h and the overall conversion 94% based on
the N-methylglucamine.
3
Formulation of N-Alkylamides
Due to the high melting point of the N-alkylglucamides they are
normally delivered as solutions. As solvents have been suggested
water, lower alcohols, and propylene glycol containing various
amounts of water. In [19] the solubilizing effect of certain
carboxylates, particularly Na-citrate, is pointed out. In an example,
a 40% solution of C1214-akyl-N-methylglucamide is first dissolved
in water at 60°C and then 2% of citric acid is added and neutralized
to pH 79 with NaOH. The resulting solution has a viscosity of 1200
cPs at 31°C and remains stable at this temperature for at least 7
weeks.
A dry, flowable powder can be produced by treating a solution of
N-lauroyl, N-methylglucamide, to which sodium chloride and silica
has been added, with superheated steam [20]. The powder has no
disagreeable odor or taste and may be used as an ingredient in
toothpastes.
 Page 183

III
Commercial Products
Table 2 lists some of the presently available fatty acid alkanolamide
ethoxylates. The commercial fatty acid mono- and dialkanolamides
are not included. The mean number of ethylene oxide units given
includes the hydroxyethyl group(s) emanating from the
alkanolamine. The hydrophilelipophile balance (HLB) values are
according to Griffin and the cloud points are valid for 1% of
product in water unless other conditions are stated.
TABLE 2 Fatty Acid Amide Ethoxylates: Market Products and
Producers
EO Cloud Active
Trade name Producer HLB Remarks
units point (°C) matter (%)
A. Products derived from lauric acid CAS 26635-75-6
Amidox L-2 Stepan 3 100
Amidox L-5 Stepan 5 100
Based on
Mazamide L-5 PPG 6 100
DEA
Unamide L-2 Lonza 3 100
Unnamide L-5 Lonza 6 100
B. Products based on coconut or palm kernel oil acids, CAS 61791-
08-0
Rhone
Alkamide C2 100
Poulenc
Amadol CMA
Akzo Nobel 3 7.7 80
2 (80%)
CMA 5 Akzo Nobel 6 11 80* 100 * At pH 3
Albright &
Empilan LP2 100
Wilson
Albright &
Empilan LP10 100
Wilson
 Albright &
Empilan MAA 6 9.6 100
Wilson
Ethylan CH Harcros UK 80 100
Ethylan CRS Harcros UK 100
Ethylan LM2 Harcros UK 100
Eumulgin PC2 Pulcra SA 2 5.8 100
Eumulgin PC4 Pulcra SA 4.5 8.8 100
Eumulgin PC
Pulcra SA 10 14 100
10/85
Eumulgin C4 Henkel 5 8.5 100
Mazamide C5 PPG 6 100
C. Products based on oleic acid, CAS 31799-71-0 or 26027-37-2
Amadol OMA
Akzo Nobel 3 6.4 100
2
OMA 3 Akzo Nobel 4 100
OMA 4 Akzo Nobel 5 8.8 70* 100 * At pH 3

(table continued on next page)

 Page 184
TABLE 2 Continued
EO Cloud point Active
Trade name Producer HLB Remarks
units (°C) matter (%)
C. Products based on oleic acid, CAS 31799-71-0 or 26027-37-2
(continued)
* In 25%
Dionil OC Hüls 3 67* 100
BDG
Dionil SH
Hüls 6 100
100
* In 10%
Dionil W 100 Hüls 14 60* 100
NaOH
Akzo
Ethomid 0/15 5 8.8 80 100
Nobel
Akzo
Ethomid 0/17 7 100
Nobel
Lutensol FSA
BASF 12 80 100
10
Rewopal 08 Rewo 9 10 100
Rewopal 015 Rewo 15 100
D. Products based on hydrogenated tallow fatty acids, CAS 68155-
24-8
Ethomid Akzo
5 8.8 100
HT/15 Nobel
Ethomid Akzo
13 13 5577 100
HT/23 Nobel
Ethomid Akzo
50 18 100
HT/60 Nobel
Schercomid
Scher 50 100
HT/60
E. Product based on rapeseed oil fatty acids, CAS 85536-23-8
Aminol Tec N Chem-Y 4 7.7 92
IV
Physical and Amphiphilic Properties
In table 3 are given the foaming properties, wetting power, and
HLB values for some of the commercial amide ethoxylates
mentioned in Table 2. From the table it seems obvious that good
foaming and foam stability characterizes the ethoxylated amides
based on lauric and myristic acids and that these products also
have a good wetting power independent of the polyglycol ether
chain length in the range of 36 ethylene oxide units.
A
Polyoxyethylated Alkylamides
Heusch [36] studied the lyotropic phases of oleic amide
heptaethylene glycol ether in water and interpreted the results
depending on the formation of various hydrates with very different
solubilities (Fig. 1).
Khan et al. [37] investigated a similar compound, an oleic amide
nonaethylene glycol ether, with viscosity measurements, nuclear
magnetic resonance, and direct imaging by the cryo-TEM
technique and conclude that small, spherical micelles coexist with
large spheroidal and thread-like micelles in dilute solutions. The
solution has a high viscosity, which increases rapidly with the
concentration to a maximum at 20% and then decreases again.
 Page 185
TABLE 3 Properties of Some Commercial Amide Ethoxylates
Foam
Wetting power
Product name height HLB Fatty acids
(s)
(mm)
Amadol CMA 2 113/108 22 7.7 Lauric/myristic
Cocodiethanolamide 90/85 27 8.5 Lauric/myristic
Empilan MAA 107/95 44 9.6 Lauric/myristic
CMA 5 125/122 20 11.1Lauric/myristic
Ethomid 36/31 600 8.8 Oleic
OMA 4 20/18 280 8.8 Oleic
Lutensol FSA 10 95/90 110 12.1Oleic
Ethomid HT/15 39/33 220 8.8 Stearic
Ethomid HT/60 84/32 600 17.7Stearic
Aminol Tec N 16/13 500 7.7 Oleic/erucic
Foam height: Ross-Miles, 50°C, 0.05%, immediately and after 5
min. Wetting power: Draves, 20°C, 1 g/L. HLB: Griffin.
 Fig. 1
Lyotropic phases of oleic amide heptaethylene glycol ether.
 Page 186
B
N-Acyl, N-Alkyl Sugar Amides
Pfannemüller et al. [2328] conducted a comprehensive study to
characterize the structures in water solution and the crystal
structures of sugar amides synthesized from aldonic acid lactones
of glucose and maltose and alkylamines or the similar compounds
made from N-(2-aminoethyl)aldonamine and alkanoic acids where
the acyl groups have been varied from C6 to C20.
Highly ordered aggregates are formed in water due to the strong
hydrogen bonding between the amide and carbohydrate groups.
This leads to the formation of stable monolayers suitable for the
preparation of technical membranes (C1220-acyl groups).
With C610-acyl chains, gels consisting of a loose network of
regularly twisted helical strands are formed from dilute solutions.
Lyotropic liquid crystalline phases are formed from more
concentrated solutions, particularly for N-methylated samples with
a C10-acyl chain.
Fuhrhop et al. [29] made the very interesting observation that
dihelical fibers, several micrometers in length, are formed in water
solutions of octyl L-or D-glucamides, but not from the racemate.
The single strands have the thickness of a bimolecular layer.
Since Hildreth in 1982 reported [30] that acyl-N-methylglucamides
are useful for solubilization of membrane proteins from animal
cells, other research groups have investigated the amphiphilic
properties of these surfactants [3134]. In Table 4 are given the
CMCs for C89-and C10-acyl-N-methylglucamides, which in the
biochemistry literature often are called MEGA-8, MEGA-9, etc.
The CMC decreases only slightly with increasing temperature for
MEGA-9 and MEGA-10 according to [32], whereas the CMC for
MEGA-8 is practically independent of the temperature in the range
540°C.
It has long been known that carbohydrate surfactants can form
thermotropic lamellar phases, but their lyotropic phases were
recently investigated by Hall et al. [35] from whom the schematic
phase diagram in Fig. 2 emanates. The diagram is somewhat rich in
mesophases, whereas the corresponding diagram for MEGA-8 will
show only a hexagonal phase existing between 0 and 39°C. The
oleic acid N-methylglucamide, on the other hand, will show only a
lamellar
TABLE 4 Critical Micelle
Concentrations (CMCs) for Three N-
Acyl, N-Sugar Amides
CMC (mmol/L)
Ref. 31, T = Ref. 32, T =
Surfactant
20°C 25°C
MEGA-8 51
MEGA-9 25 16
MEGA-
7 4.8
10
 Page 187

Fig. 2
Schematic phase diagram for MEGA-9.
(From Ref. 35.)
phase. The phase behavior of N-acyl, N-methylglucamides is thus
highly dependent on the size and structure of the hydrophobic
group.
C
Dialkyl Disugar Amides
The concept of ''gemini surfactants," i.e., surfactants containing
two hydrophobic and two hydrophilic groups, has received much
attention in recent years. Eastoe et al. recently published two
papers [173,174] regarding the amphiphilic properties of dichain
glucamides with the following structure:
As an acronym for the long names of these gemini surfactants, di-
(Cn-Glu) has been introduced.
In Table 5 the CMCs for the investigated four members of this
series are given at 35°C. This type of dichain glucamide is claimed
to lower the interfacial tension between oil and water even more
than the monochain compounds and thus be suitable as detergent
ingredients [175].
 Page 188
TABLE 5 Critical Micelle
Concentrations for Four
Dealkyl Sugar Amides
Surfactant CMC (mmol/L)
di-(C5-Glu) 10.5
di-(C6-Glu) 1.35
di-(C7-Glu) 0.16
di-(C8-Glu) 0.04

V
Functions and Applications
A
Polyoxyethylated Amides
Polyoxyethylated amides are used in broad range of applications,
but nonetheless the total volume is limited. One reason could
possibly be that the alkanolamides were introduced earlier and can
be used in most of the same applications as the polyoxyethylated
amides. However, for environmental and human toxicity reasons,
the use of polyoxyethylated amides should be preferred, due to the
very low amount of nitrosamines (see Sec. VI, "Environmental
Properties") as well as the absence of diethanolamides in the
products. The surfactant as a class has been known for a long time
and many of the surfactant manufacturers can offer one or more
polyoxyethylated amides. The alkanolamides will not be covered
in this chapter.
1
Functions
The functions of polyoxyethylated amides are used in a wide range
of different applications. Table 6 lists some functions and the
corresponding applications. It can be seen in the table that the main
functions of the polyoxyethylated amides are foam stabilization,
thickening, and dispersion.
TABLE 6 Functions and Applications of Polyoxyethoxylated
Amides
Function as: Applications
Liquid detergents, hard surface cleaners, general-
Foam
purpose cleaners, hand cleaning gels, personal
stabilizer
care products
Cutting fluids, lubricants, rust inhibitors, plant
Emulsifier
protection agents, emulsifier for solvents and fuels
Suspending Industrial degreasers, cleaning formulations,
agent detergents
Antistatic
Polymers, fabric softeners
agent
Solubilizer
coupling Personal care products, detergents
agent
Fulling
agent
Textile-processing agents
scouring
agent
Wetting
Low-temperature detergents, hand cleaners
agent
 Page 189
For the low-oxyethylated amides thickening and foaming are the
most important functions. An example of foaming is an alkaline
foam cleaner composition reported to contain polyoxyethylated
coconut fatty acid monoethanolamide giving copious stable foam
[38]. Another example is a detergent composition with
polyoxyethylated amide as a suds-boosting agent [39]. Concerning
the polyoxyethylated amide as thickener, the thickening properties
of polyoxyethylated rapeseed monoethanolamides with a
maximum of 3 moles of ethylene oxide have been studied in
different surfactant mixtures [40].
For the more highly oxyethylated amides suspending and
emulsifying are very important functions. Examples are
polyoxyethylated linseed oil fatty acid monoethanolamides with
718 moles of ethylene oxide that are used in different paint
applications [41,42].
Concerning the other functions, an example is given of an
antistatic effect when at polyoxyethylated (16-EO) oleic acid amide
is used as a fabric softener [43].
2
Applications
(a)
Personal Care
The use of different polyoxyethylated amides is not only restricted
to shampoo and soap formulations, where the foaming and
thickening properties are utilized. It can also be used in special
applications such as lipstick [44] or in medicated face washing
compositions in combination with Na selenite [45]. In the different
compositions used as shampoo, soap, and other personal care
products, the polyoxyethylated amides are used together with other
surfactants and additives [46,47] and give varying properties to the
compositions [48,49].
(b)
Cleaning
In the cleaning area the polyoxyethylated amides are found in
compositions both for hard surface and textile cleaning as well as
in different fabric softener compositions.
The household hard surface cleaning agents cover dishwashing
liquids and all-purpose kitchen liquid detergents [50]. The
polyoxyethylated amides are used as suds-boosting agents [39], in
combinations of anionic and nonionic surfactants [51], and in
alkaline compositions [52]. The type of fatty acids used as a base
for the amides differs between the various applications. A mixture
of fatty acid carbon chain lengths and unsaturation in the
polyoxyethylated amide, i.e., lauric, oleic, linoleic, and linolenic, is
found to give superior detergency and a low melting point [53].
In laundry detergent composition the polyoxyethylated amides are
used in combinations with soap [54], with Na-lauryl or cetyl
sulfate [55], and with polyoxyethylated fatty C1018-alcohol [56].
The fatty acids contain both shorter (C1012) and longer (C18)
chains. In [55] both polyoxyethylated fatty acid monoethanolamide
and diethanolamide can be used. The polyoxyethylated amides are
also found in combination with an anionic surfactant and the
enzyme lipase [57]. In a special application the detergent
composition contains layered
 Page 190
silicate in combination with the polyoxyethylated amide for
improved washing power in the area of cosmetic staining, e.g.,
make-up, lipstick, and eyelash finish [58]. Also reported is a
nonfoaming laundry detergent with superior laundering properties
containing a polyoxyethylated rapeseed oil monoethanolamide
with 57 moles of ethylene oxide [59].
The polyoxyethylated amide, based on C10-fatty acid and up to 7
alkylene oxide units, are used in different fabric softener
compositions in combination with cationic surfactants [6062]. The
polyoxyethylene (1418 moles) oleic acid ethanolamide can be used
as a textile softener [43]. Also in a combination of a cationic and
nonionic softener the polyoxyalkylated (115 moles) C822-fatty acid
amide may be used [63]. Further, polyoxyethylated C1016-fatty
acid amides are used in antistatic detergent compositions where
cleaning and softening properties are combined in the same
composition [6466]. Polyoxyethylated oleic acid amide is also
found in compositions with both detergent and softening
properties (softergent) [67].
(c)
Industrial Cleaning
Industrial cleaning and degreasing compositions are used in
various applications, e.g., degreasing of metallic surfaces prior to
painting or coating [6871], degreasing to reduce corrosion [72],
removal of deposits [73] or hydrocarbon oil [74] from metallic
surfaces. Polyoxyethylated amides are also used in a composition
with glycol t-butyl ether for cleaning of hard glass and ceramic
surfaces [75].
The polyoxyethylated amides can also be used in cleaning and
disinfecting compositions. For example, in combination with
quaternary ammonium compounds (e.g., alkyltrimethylammonium
chloride) for use in, say, the dairy industry [76,77]. In a
disinfectant-cleaning composition polyoxyethylated coconut oil
diethanolamide is added as a component that will reduce eye
irritation [78].
A surfactant mixture of alkylglucoside and polyoxyethylated amide
is used in washing and cleaning composition for wool, dishes, and
so forth. The mixture can also be used as a flotation aid or in bore-
flushing fluids [79].
Polyoxyethylated fatty acid amides with a short hydrophobic end
group are useful in a wide range of washing and cleaning
products, where low foaming is needed, and as emulsifiers [80].
(d)
Miscellaneous
A very special application for polyoxyethylated amide is as a drag-
reducing agent in cold water distribution systems [8184]. The
polyoxyethylated amide forms thread-like micelles that will
stabilize the laminar flow also at high flow rates and thus reduce
the pump work. Heating of the cold water by the pumps will also
be reduced.
Alkyd emulsions, in which the alkyd oil is emulsified in water and
stabilized by surfactants, are interesting from an environmental
point of view due to the lower need for organic solvents in the
paint. The surfactants used are biodegrad-
 Page 191
able polyoxyethylated amides, preferably based on linseed oil fatty
acid and with 718 moles of ethylene oxide [41,42].
Compositions for the textile industry, concerning dyeing and
finishing, are described in [8588]. The compositions are low
foaming and give good wetting.
Various special applications have also been found. For example,
the polyoxyethylene amides are used as dye penetrants for
detecting flaws in articles [89]. A coating for kaolin powderbased
on polyoxyethylene amide has been effective [90]. Addition of
polyoxyethylene amide to a lubricant for cold drawing of metals
results in several improvements [91]. Polyethylene film for soil
mulching in agriculture contains polyoxyethylated amide as an
antistatic compound [92].
B
Glucamides
The use of glucamides has become strongly focused on cleaning
formulations during the last 5 years. But there are also a lot of
industrial and medical applications for glucamides, which have
been patented since 1960.
1
Functions
The most important functions of the glucamides are foaming,
thickening, and emulsifying.
A fatty acid polyhydroxyamide is said to give more foam than a
conventional foam booster, e.g., amine oxide [93]. Also a mixture
between a short chain (C810) and long chain (C1216) fatty acid N-
methylglucamide gives enhanced foaming [94]. A C622-fatty acid
N-methylglucamide should give excellent foam for toothpaste
compositions [95].
The fatty acid (C218) N-methyl glucamides are used as thickeners
for aqueous surfactant solutions [96]. The coconut oilbased
glucamides are especially useful for thickening cosmetic and
detergent compositions. They are said to be more effective in such
compositions than fatty acid diethanolamides and alkoxylated fatty
acids.
2
Applications
(a)
Personal Care
Glucamides can be used in various personal care products, e.g.,
shampoos and other hair care formulations, soaps, and
toothpastes.
There are a number of patents whereby glucamides are used in
shampoos and other hair care formulations. A shampoo
composition with glucamide is said to give rich foam properties
and to be mild to the eyes [97]. A soap bar composition containing
glucamide can give good lathering and a decreased tendency to
crack [98]. A personal care or cosmetic detergent composition
containing glucamide and vegetable oil adducts has been reported
[99]. Addition of silicones to shampoos, hair rinses, etc.,
containing C1214-fatty acid alkyl-N-
 Page 192
methylglucamide improves their foaming capacity [100]. A
personal cleansing composition comprising C1218-fatty acid
polyhydroxyamide is very mild and has good conditioning
benefits, stability, lathering, and rinsability [101]. The C1214-fatty
acidbased glucamides are also used in combinations with cationic
polymers giving excellent foaming, cleansing, and hair brightening
[102]. Lauric acid N-methylglucamide is used in combination with
monomeric cationic surfactants in a hair conditioner [103].
In toothpastes the glucamides are used as the sole surfactant [95]
or in a mixture with sodium dodecyl sulfate [104]. The surfactants
used show high mucosal compatibility, high foaming capacity, and
improved flavor quality [105].
(b)
Cleaning
Glucamides are also found in compositions for both hard surface
and textile cleaning. There are also multipurpose compositions
covering dishwashing and laundry cleaning (106108) and, in some
cases, personal care products [109112]. The glucamides are
combined with other nonionic or anionic surfactantsin one case
with silicon added as foam control [107] and in another case with
oxygen bleach [111].
The cleaning agents for hard surfaces in households cover chiefly
dishwashing liquids. The different compositions have different
benefits, such as enhanced foaming and wetting [94], removal of
greasy deposits and tarnish [113], and high detergency and
gentleness to skin [114]. There exist a wide range of patents
concerning the advantages of dishwashing liquids. There are
compositions with good cleaning and foaming properties that are
mild to the skin [115120]. There are also compositions that are low
foaming [121,122] and high foaming [93,123], both types with
good soil release performance. The addition of amine oxides to the
glucamides improves the ease and rate of soil removal [124], and
the addition of alkyl ether carboxylate provides good cleaning and
grease removal [125,126].
The use of different detergent compositions comprises a broad
variety of applications in the laundry cleaning area. There are
compositions especially for removing oil and grease [127], with
the help of lipase [128] or in combination with a polymeric
dispersing agent for enhanced particulate clay soil removal,
together with the grease and oil cleaning [129]. Low-foaming or
controlled foaming detergent compositions are an advantage in
automatic washing machines [130136]. There are also
compositions that are free of phosphate builders and
alkylbenzenesulfonates [137,138], laundry compositions for
handwash [139], compositions for color maintenance [140],
compositions with enhanced soil release properties [141],
compositions with bleaching agents [142], and compositions with
added detergent enzymes [143].
Different types of builders are used, i.e., zeolite or layered silicate
[144146] or polycarboxylates [147]. To the detergent compositions
with builder is also
 Page 193
added brightener [148]. The production method for granular
laundry detergent is also patented [149151].
Glucamides can be used in compositions together with softening
clay [152,153]. Other types of rinsing or after-treatment
compositions for laundry have also been reported [154,155].
The aldobionamides when used in detergent compositions for
washing fabrics in combination with anionic surfactants show
good detergency [156,157].
(c)
Industrial Cleaning
The use of glucamides in the industrial cleaning area is limited.
Only a few examples are found. Compositions containing mixtures
of polyoxyethylene-polyoxypropylene ether and fatty acid N-
alkylpolyhydroxyamide can be useful as hard surface cleaners, dye
dispersants, flotation aids, etc. [158]. Fatty acid N-
alkylpolyhydroxyamides are used in rinsing agents for mechanical
cleaning of hard surfaces [159].
A biodegradable C1618-fatty acid N-alkoxypolyhydroxyamide can
be used in a composition for cleaning hard surfaces [160]. A
combination of N-alkylpolyhydroxyfatty acid amide and the C1618-
fatty acid N-alkoxypolyhydroxyamide can be used as emulsifier
for, say, paints, fabric softener, agricultural chemicals, cosmetics,
and so forth.
(d)
Miscellaneous
A C12-fatty acid N-methylglucamide is used in a biodegradable
softener system for treating tissue paper [161]. Also C1214-fatty
acid N-methylglucamide can be used in such systems [162].
The fatty acid polyhydroxyamides can be used as dispersants or
wetting agents in pesticide formulations [163]. The amides can also
be used in dispersant composition for dyes and pigments [164].
Furthermore, glucamides based on saturated fatty acids can be
useful as accelerating emulsifiers in emulsion polymerization of
vinyl chloride [165].
The remediation of chlorocarbon-contaminated aquifers is
performed by microemulsification of the chlorocarbons. The
surfactants used are glucamides [166,167]. A mixture of
alkylglucoside and glucamide, used as environmentally friendly
synthetic leather or hide-greasing agents, is used instead of
chlorinated hydrocarbons [168].
The N-alkylaimide of lactobionic acid is used in a corrosion
inhibitor for use in metal working media [169].
VI
Environmental Properties
The renewable raw materials in polyhydroxy fatty acid amides
(glucamides) and part of the polyoxyethylated fatty acid amides,
and the fact that they are readily biodegradable, makes those two
types of surfactants very attractive.
 Page 194
The biodegradability of a polyoxyethylated fatty acid amine has
been reported [170]. A proposed route for biodegradation is given.
The polyoxyethylated amides OMA 4, CMA 5, Amadol OMA 2,
and Amadol CMA 21 are all readily biodegradable. The OMA
amides are based on C18-fatty acids and the CMA amides are based
on C1214-fatty acids, and the numbers refer to the amount of
ethylene oxide added.
The biodegradation of glucamides has been reported as well. An
activated sludge study [171] and field studies [172] show that the
concentration of glucamides is considerably reduced. In [173] the
reduction is more than 99.6%. The reduction is assumed to be
caused by biodegradation.
The nitrosamine content has been analyzed in Amadol OMA 2,
Amadol CMA 2, and diethanolamide. The "total" nitrosamine
content (as NO) was determined to 1020 ppb in the Amadols and
100 ppb in diethanolamide. The former amount of nitrosamines is
concerned low and the latter is considered high. High amounts of
nitrosamines in the diethanolamides make them questionable for
use in personal care products and light-duty detergents.
References
1. E. Jungermann and D. Tabor, Polyoxyethylene Alkylamides, in
Nonionic Surfactants, Surfactant Science Series Vol. 1, Marcel
Dekker, New York, 1967, pp. 208246.
2. H. Grossmann, Fette Seifen Anstrichm. 74(1):5863 (1972).
3. S. H. Fairheller, R. G. Bistline, A. Bilyk, R. L. Dudley, M. F.
Kozempel, and M. J. Haas, J. Am. Oil Chemists Soc. 71(1):863866
(1994).
4. R. B. McConnell and D. W. Keuer, U.S. Patent 4085126 to
Ashland Oil Co. (1978).
5. H. Grossmann, BRD Patent 2129425 to Chem. Werke Hüls AG
(1972).
6. E. Sandberg, WO Patent 9208690 to Akzo Nobel Surface Chem.
AB (1992).
7. K. Kado, K. Matsushita, T. Fujii, and K. Usuba, Jap. Patent
07102292 to Kawaken Fine Chemicals Co.
8. H. Terasaki, A. Fujiu, K. Isobe, T. Azuma, H. Nishikawa, and T.
Imamura, Eur. Patent Appl. 960044 A2 to Kao Co., Japan (1996).
9. T. Fujii, H. Sekido, and K. Usuba, Jap. Patent 07197078 A2 to
Kawaken Fine Chemicals Co. (1995).
10. T. Fujii and K. Usuba, Jap. Patent 07194958 A2 to Kawaken
Fine Chemicals Co. (1995).
11. A. M. Naser, M. A. El-Azmirly, and A. Z. Gomaa, J. Oil Colour
Chem. Assoc. 60(1):1822(1977).
12. J. J. Scheibel, D. S. Connor, R. E. Shumate, and J. StLaurent,
WO 9206984 to Procter and Gamble Co. (1990).
13. B. Strecker, H. Wolf, A. Oftring, H. H. Bechtolsheimerand, and
D. Hertel, Ger. Pat. 4235783 Al to BASF AG (1994).
14. D. S. Connor, J. Kao, J. J. Scheibel, and J. N. Kao, WO
9206071 A to Procter and Gamble Co. (1990).
1 Trademarks by Akzo Nobel.
 Page 195
15. D. S. Connor, J. Kao, J. J. Scheibel, and J. N. Kao, WO
9206070 A to Procter and Gamble Co. (1990).
16. D. S. Connor, J. J. Scheibel, and R. G. Severson, WO 9206073
A (1990).
17. D. S. Connor, J. J. Scheibel, B. P. Murch, P. Bruce, M. N. Mao,
E. P. Gosselink, and R. G. Severson, Jr., U.S. Patent 5188769 to
Procter and Gamble Co. (1993).
18. R. Aigner, A. Fruth, H. Keck, U. Meyer, H. Seitz, J. Strauss, H.
Stühler, M. Vervuert, G. Koch, and R. Vybiral, EP 63244 A2 to
Höchst AG (1995).
19. Y. Fu, P. R. Foley, J. A. Dyet, P. G. Mather, R. Mermelsten, and
B. J. Roselle, WO 9319146 Al to Procter and Gamble Co. (1993).
20. W. Raehse, K. Paatz, W. Breitzke, W. Seispel, and H. Tesmann,
DE 4340015 Al to Henkel KgaA (1995).
21. S. Stüring and L. Kuhnen, BRD Patent Appl. 1806010 to
Chem. Werke Hüls AG (1970).
22. B. Strecker, G. Oetter, A. Oftring, J. Perner, R. Baur, V.
Schwendenmann, M. Kahmen, and W. Reif, BRD Patent Appl. DE
4336247 Al to BASF AG (1995).
23. B. Pfannemüller and W. Welte, Chem. Phys. Lipids 37:227240
(1985).
24. V. Zabel, A Müller-Farnow, R. Hilgenfeld, W. Saenger, B.
Pfannemüller, V. Enkelmann, and W. Welte, Chem. Phys. Lipids
39:313327 (1986).
25. B. Pfannemüller and I. Kühn, Makromol. Chem. 189:24332442
(1988).
26. A. Müller-Farnow, R. Hilgenfeld, H. Hesse, and W. Saenger,
Carbohydrate Res. 176:165174 (1988).
27. B. Pfannemüller, Starch/Stärke 40:(12):476486 (1988).
28. F. R. Taravel and B. Pfannemüller, Makromol. Chem.
197:30973106 (1990).
29. J.-H. Fuhrhrop, P. Schnieder, J. Rosenberg, and E. Boekema, J.
Am. Chem. Soc. 109:33873390 (1987).
30. J. E. K. Hildreth, Biochem. J. 207:363366 (1982).
31. M. Hanatani, K. Nishifuji, M. Futai, and T. Tsuchiya, J.
Biochem. 95:13491353 (1984).
32. A. Walter, S. E. Suchy, and P. K. Vinson, Biochim. Biophys.
Acta 1029:6774 (1990).
33. M. Shigeyoshi, K. Hirotaka, I. Yuuhichi, and Tsuyoshi, Bull.
Chem. Soc. Jpn. 67(9):23982402 (1994).
34. H. Shigeharu and S. Hideko, Langmuir 10(11):40734076
(1994).
35. C. Hall, G. J. T. Tiddy, and B. Pfannemüller, Liquid Crystals
9(4):527537 (1991).
36. R. Heusch, Tenside Det. 21(6):298303 (1984).
37. A. Khan, A. Kaplun, Y. Talmon, and M. Hellsten, J. Coll.
Interf. Sci. 181:191199 (1996).
38. U.S. Patent 3,639,283 to Grace & Co W R (1972).
39. G. J. Jakubicki, C. Schwarz, and A. J. Uray, EP Patent 487,170
to Colgate Palmolive (1992).
40. J. K. Smid and R. H. Van der Veen, EP Patent 386,826 to Kao
Corp (1990).
41. G. Östberg, B. Bergenståhl, and M. Huldén. J. Coat. Technol.
66:37 (1994).
42. G. Östberg, B. Bergenståhl, and M. Huldén. Colloids and
Surfaces A 94:161 (1995).
43. R. Brueckmann and T. Simenc, EP Patent 415,279 to BASF AG
(1991).
44. DE patent 1,930,954 to Yardley of London Inc. (1969).
45. V. A. Yushchenko, E. A. Melnik and V. A. Drashchink, SU
Patent 1,046,280 to Chem Ind Res Des and Biotech Res Inst
(1983).
46. DE Patent 4,409,189 to Chem-Y Chem. Fab. GmbH (1995).
 Page 196
47. JP Patent 8,041,489 to Ajinomoto KK (1994).
48. DE Patent 2,846,639 to P. Jurgensen (1980).
49. A. R. Naik, EP Patent 552,032 to Unilever (1993).
50. G. Toninelli and G. Osti, EP Patent 109,022 to Mira Lanza Spa
(1984).
51. JP Patent 59,078,297 to Asahi Denka Kogyo and Cope Clean
KK (1984).
52. US Patent 3,644,210 to Chemed Corp. (1972).
53. JP Patent 59,210,998 to Sanyo Chem. Ind. Ltd. (1984).
54. JP Patent 56,038,399 to Asahi Denka Kogyo and Cope Clean
KK (1981).
55. JP Patent 60,060,196 to Kanebo KK (1985).
56. B. K. Daurov, Z. H. E. Golovina, and L. K. Dzhelmach, SU
Patent 1,011,682 to Chem Ind Res Des (1983).
57. J. Klugkist, EP Patent 341,999 to Unilever (1989).
58. H. Upadek, DE Patent 3,632,107 to Henkel KGaA (1988).
59. J. Przondo, Z. Kot, and Z. Kossinski, Pollena: Tluszcze, Srodki
Piorace, Kosmet. 26:6 (1982).
60. R. M. Butterwort, J. R. Martin, and E. Willis, EP Patent 159,918
to Unilever (1985).
61. R. M. Butterwort, J. R. Martin, and E. Willis, EP Patent 159,919
to Unilever (1985).
62. R. M. Butterwort, J. R. Martin, and E. Willis, EP Patent 159,922
to Unilever (1985).
63. S. Billenstei, A. May, and H. W. Buecking, EP Patent 43,547 to
Hoechst AG (1982).
64. A. G. Nikitenko, N. I. Golyatovsk, and B. I. Lesman, SU Patent
834,117 to Chem Ind Res Des (1981).
65. A. G. Nikitenko, N. I. Golyatovsk, and V. A. Yushchenko, SU
Patent 883,168 to Chem Ind Res Des (1981).
66. A. G. Nikitenko, N. N. Lysova, and E. K. Ivanauskas, SU
Patent 639,925 to Chem Ind Res Plan (1978).
67. JP Patent 60,096,695 to Sanyo Chem Ind Ltd. (1985).
68. A. Y. A. Nagina, A. I. Mikhalska, and E. I. Nechesova, SU
Patent 732,370 to Atom Eng Reactor (1980).
69. A. Y. A. Nagina, A. I. Mikhalska, and E. I. Nechesova, SU
Patent 785,350 to Atom Eng Reactor (1980).
70. M. P. Shemelyuk, M. M. Oleinik, and L. A. Gnutenko, SU
Patent 745,925 to Car Ind Cons Techn (1980).
71. M. M. Oleinik, V. T. Protsishin, and A. V. Galkin, SU Patent
749,888 to Auto Ind Tech Inst (1980).
72. I. K. Getmanskii, M. M. Bebko, and V. D. Yakovlev, SU Patent
662,578 to I. K. Getmanskii (1979).
73. R. Baur, H. H. Goertz, H. W. Neumann, D. Stoeckigt, and N.
Wagner, EP Patent 340,704 to BASF AG (1989).
74. M. Blezard and W. H. McAllister, EP Patent 84,411 to Albright
and Wilson Ltd. (1983).
75. R. Osberghaus, K. H. Rogmann, and B. Frohlich, EP Patent
288,856 to Henkel KGaA (1988).
76. C. A. Beronio, B. T. G. Graubart, E. J. Sachs, and A. L. Streit,
EP Patent 621,335 to Eastman Kodak Co and Reckitt & Colman
Inc. (1994).
77. R. G. Alagezyan, B. V. Andriasyan, and A. G. Nikitenko, SU
Patent 735,630 to Erev Zool Veter Ins. (1980).
78. B. M. Like, D. Smialowicz, and E. Brandli, U.S. Patent
4,336,151 to American Cyanamid Co. (1982).
 Page 197
79. B. Giesen, DE Patent 4,023,334 to Henkel KgaA (1992).
80. R. Baur, M. Kahmen, G. Oetter, A. Oftring, J. Perner, W. Reif,
V. Schwendemann, and B. Strecker, DE Patent 4,336,247 to BASF
AG (1995).
81. I. Harwigsson, A. Khan, and M. Hellsten, Tenside Surf., Det.
30:174 (1993).
82. I. Harwigsson and M. Hellsten, J Assoc Off Chemists Soc
73:921 (1996).
83. I. Harwigsson, Thesis ''Surfactant aggregation and its
application to drag reduction," Lunds University, 1995.
84. Y. Hu and E. F. Matthys, Submitted to J. Rheol.
85. A. Blum, H. Schwab, and Oppenlaend, DE Patent 2,643,804 to
BASF AG (1978).
86. R. Brueckmann, A. Hohmann, and T Simenc, DE Patent
4,133,852 to BASF AG (1992).
87. E. Beckmann, R. Brueckmann, J. P. Dix, P. Freyberg, and E.
Kromm, DE Patent 4,216,316, to BASF AG (1993).
88. L. V. Basova, I. N. Kokoreva, and E. N. Anishchuk, SU Patent
713,891 to L. V. Basova (1980).
89. G. B. Patent 1,265,476 to Ardrox Ltd. (1972).
90. U.S. Patent 3,301,812 to Philipp Minerals and Chem. Corp.
(1967).
91. A. I. Soshko, O. M. Dzikovskii, and I. M. Shapoval, SU Patent
709,666 to Lvov Poly and Elektrostal Electrometal (1980).
92. V. I. Kuznetsov, I. V. Konoval, and R. G. Markovich, SU Patent
711,064 to V. I. Kusnetsov (1980).
93. J. M. Clarke, P. R. Foley, Y. Fu, and P. K. Vinson, WO Patent
95 20026 to Procter and Gamble (1995).
94. B. Fabry, DE Patent 4,400,632 to Henkel KGaA (1995).
95. B. Fabry, DE Patent 4,406,745 to Henkel KGaA (1995).
96. H. Kelkenberg, K. Engel, and W. Ruback, EP Patent 285,768 to
Huels AG (1988).
97. E. D. Brock and A. L. Larrabee, WO Patent 92 05764 to Procter
and Gamble (1992).
98. J. E. Kaleta and F. A. Pichardo, WO patent 92 13059 to Procter
and Gamble (1992).
99. M. J. Giret, A. Langlois, R. P. Duke, and E. Jedla, WO Patent
93 21293 to Procter and Gamble (1993).
100. B. Fabry, DE Patent 4,435,383 to Henkel KGaA (1995).
101. C. M. Bellemain, M. J. M. Giret, and W. V. J. Richardson, WO
Patent 96 03974 to Procter and Gamble (1996).
102. B. Fabry, DE Patent 4,422,404 to Henkel KGaA (1996).
103. H. Hensen, H. Tesmann, J. Kahre, R. Mueller, and W. Scholz,
DE Patent 4,309,568 to Henkel KGaA (1994).
104. W. Breitzke and K.-H. Gantke, DE Patent 4,406,746 to Henkel
KGaA (1995).
105. W. Breitzke and A. Behler, DE Patent 4,406,748 to Henkel
KGaA (1995).
106. J. H. Collins and B. P. Murch, WO Patent 92 06160 to Procter
and Gamble.
107. A. A. Fisk and A. Surutzidis, EP Patent 593,841 to Procter and
Gamble.
108. D. S. Connor, B. P. Murch, and J. J. Scheibel, WO Patent 95
07341 to Procter and Gamble (1995).
109. B. Fabry and J. Kahre, DE Patent 4,430,085 to Henkel KGaA
(1996).
110. M. Biermann, B. Fabry, U. Hees, and M. Weuthen, DE Patent
4,439,091 to Henkel KGaA (1996).
111. B. J. Roselle and D. T. Speckman, WO Patent 93 14183 to
Procter and Gamble (1996).
 Page 198
112. D. S. Connor, Y. Fu, and J. J. Scheibel, WO Patent 95 07340
to Procter and Gamble (1995).
113. B. Burg, J. Haerer, K. Hill, and P. Jeschke, DE Patent
4,401,103 to Henkel KGaA (1995).
114. Y. Abe, T. Yasumasu, and T. Sakatani, JP Patent 7,053,988 to
Lion Corp. (1995).
115. T. R. Rolfes and R. T. Richard, WO Patent 92 06156 to
Procter and Gamble (1992).
116. Y. Fu and J. J. Scheibel, WO Patent 92 06157 to Procter and
Gamble (1992).
117. M. H. K. Mao, WO Patent 92 06161 to Procter and Gamble
(1992).
118. J. A. Dyet and P. R. Foley, WO Patent 92 06171 to Procter and
Gamble (1992).
119. P. R. Foley, K. Ofusu-Asante, and K. W. Willman, WO Patent
93 05132 to Procter and Gamble (1993).
120. J. M. Clarke, P. R. Foley, D. L. Strauss, J. M. Van der Meer,
and K. W. Willman, WO Patent 95 20024 to Procter and Gamble
(1995).
121. K. Ofosu-Asante, WO Patent 95 20025 to Procter and Gamble
(1995).
122. K. Ofosu-Asante, WO Patent 95 20028 to Procter and Gamble
(1995).
123. D. S. Connor, Y. Fu, and J. J. Scheibel, WO Patent 95 07337
to Procter and Gamble (1995).
124. J. M. Clarke, P. R. Foley, D. L. Strauss, J. M Vander Meer, and
K. W. Willman, GB Patent 2,292,562 to Procter and Gamble
(1996).
125. K. Ofosu-Asante, WO Patent 94 05755 to Procter and Gamble
(1994).
126. K. Ofosu-Asante, WO Patent 95 06106 to Procter and Gamble
(1995).
127. G. M. Bailley and S. Powell, WO Patent 92 22629 to Procter
and Gamble (1992).
128. M. S. Showell and A. M. Wolff, WO Patent 93 23516 to
Procter and Gamble (1993).
129. B. P. Murch, WO Patent 92 06153 to Procter and Gamble
(1992).
130. J. Boutique, A. Surutzidis, R. J. Jones, and A. A. Fisk, EP
Patent 709,450 to Procter and Gamble (1996).
131. R. J. Jones and P. J. M. Baets, EP Patent 709,451 to Procter
and Gamble (1996).
132. A. C. Huber and R. K. Panandiker, U.S. Patent 5,288,431 to
Procter and Gamble (1994).
133. J. Boutique, D. S. Connor, Y. Fu, B. P. Murch, J. J. Scheibel,
and A. Surutzidis, U.S. Patent 5,318,728 to Procter and Gamble
(1994).
134. G. M. Baillely and T. E. Cook, WO Patent 92 06150 to Procter
and Gamble (1992).
135. B. P. Murch, S. W. Morrall, and M. H. K. Mao, WO Patent 92
06162 to Procter and Gamble (1992).
136. J. P. Morelli, D. Lappas, S. L. Randall, R. K. Panadiker, J.
Boutique, and C. E. Housmekerides, WO Patent 96 12000 to
Procter and Gamble (1996).
137. M. H. K. Mao and B. P. Murch, WO Patent 92 06159 to
Procter and Gamble (1992).
138. J. Boutique and Y. Fu, WO Patent 94 24246 to Procter and
Gamble (1994).
139. F. Figueroa and R. Jarrin, WO Patent 96 01306 to Procter and
Gamble (1996).
140. S. G. Cauwberghs and I. M. A. J. Herbots, EP Patent 576,778
to Procter and Gamble (1994).
141. E. P. Gosselink and R. Y. L Pan, WO Patent 92 06152 to
Procter and Gamble (1992).
142. F. E. Hardy and B. P. Murch, WO Patent 92 06155 to Procter
and Gamble (1992).
 Page 199
143. T. E. Cook, M. H. K. Mao, R. K. Panandiker, and A. M.
Wolff, WO Patent 92 06154 to Procter and Gamble (1992).
144. S. W. Morrall and B. P. Murch, WO Patent 92 06151 to
Procter and Gamble (1992).
145. M. C. Addison and M. A. J. Moss, WO Patent 94 03554 to
Procter and Gamble (1994).
146. G. M. Baillely, S. C. Ersolmaz, M. A. J. Moss, and G. A.
Sorrie, WO Patent 94 03572 to Procter and Gamble (1994).
147. S. L. Honsa and M. H. K. Mao, WO Patent 92 06164 to
Procter and Gamble (1992).
148. S. L. Honsa, WO Patent 92 06172 to Procter and Gamble
(1992).
149. A. L. Chisholm and K. M. A. Schamp, EP Patent 694,608 to
Procter and Gamble (1996).
150. P. France, S. Ongena and C. Wilkinson, EP Patent 709,449 to
Procter and Gamble (1996).
151. R. L. Tadsen and G. W. Bufler, WO Patent 92 06170 to Procter
and Gamble (1992).
152. A. C. Convents, A. Busch, and A. C. Baeck, AU Patent
9,211,048 to Procter and Gamble (1993).
153. A. Convents, A. Busch, and J. A. Pretty, EP Patent 522,206 to
Procter and Gamble (1993).
154. Fr. Patent 1,586,913 to Henkel and Cie GmbH (1969).
155. Fr. Patent 1,550,144 to Henkel and Cie GmbH (1968).
156. V. Au, U.S. Patent 5,516,460 to Lever Bros Co (1996).
157. V. Au, WO Patent 95 27770 to Unilever PLC (1995).
158. B. Fabry and I. Wegener, DE Patent 4,327,327 to Henkel KgaA
(1995).
159. B. Burg, B. Fabry, J. Haerer, U. Hees, P. Jeschke, and M.
Nejtek, DE Patent 4,323,253 to Henkel KGaA (1995).
160. D. S. Connor, Y. Fu, and J. J. Scheibel, WO Patent 95 07256
Procter and Gamble (1995).
161. L. N. Mackey, S. Ferershtekhou and J. J. Scheibel, U.S. Patent
5,354,425 to Procter and Gamble (1994).
162. A. V. Warner, L. N. Mackey, A. Wong, J. J. Franxman, B. A.
Goldslager, T. J. Klofta, and D. V. Phan, WO Patent 95 16824 to
Procter and Gamble (1995).
163. R. H. Garst, WO Patent 96 16540 to Henkel Corp. (1996).
164. C. Ullrich, I. Wegener, and B. Fabry, DE Patent 4,229,442 to
Henkel KGaA (1994).
165. A. Fischer and R. Vybiral, DE Patent 4,237,434 to Hoechst AG
(1994).
166. E. Arenas, J. R. Baran, Jr., G. A. Pope, W. H. Wade, and V.
Weerasooriya. Langmuir 12:588 (1996).
167. J. R. Baran Jr., G. A. Pope, W. H. Wade, and V. Weerasooriya.
Environ. Sci. Technol. 30:2143 (1996).
168. B. Fabry, J. Kahre, and I. Wegener, DE Patent 19,504,643 to
Henkel KGaA (1996).
169. K. Gerling, H. Rau, P. Schwarz, K. Uhlig, and K. Wendler, EP
Patent 726,335 to Solvay Deut GmbH (1996).
170. C. G. van Ginkel, C. A. Stroo, and A. G. M. Kroon. Tenside
Surf. Det. 30:3 (1993).
171. M. Stahlmans, E. Matthijs, E. Weeg, and S. Morris, SÖFW J.
13:794 (1993).
 Page 200
172. E. Matthijs, G. Debaere, N. Itrich, P. Masscheleyn, A. Rottiers,
M. Stahlmans, and T. Federle, Water Sci. Technol. 31:321 (1995).
173. J. Eastoe and P. Rogueda, Langmuir 10 44294433 (1994).
174. J. Eastoe and P. Rogueda, Langmuir 12 27012705 (1996).
175. D. S. Connor, Y. Fu, and J. J. Sceibel, WO Patent 9519953 to
Procter and Gamble (1995).
 Page 201

8
Polyol Ester Surfactants
Jeremy J. Lewis
Research and Technology, ICI Surfactants, Everberg, Belgium

I. Introduction 202
A. Structural Considerations 202
B. Fatty Acids 204
C. Polyol Esterification 206
D. Major Polyol Ester Surfactant Families 207
E. Introductory Guidelines 208
II. Glycol Esters 209
A. Oxyethylation Process 210
B. Esterification Process 211
III. Glycerol Esters 212
A. Esterification of Glycerol 212
B. Glycerolysis of Fats and Oils 213
IV. Polyglycerol Esters 216
V. Sorbitan Esters 219
VI. Sucrose Esters 223
VII. Polyoxyalkylene Polyol Esters 226
VIII. Enzyme-Catalyzed Esterification 228
A. Glycerol Esterification Using Enzymes 230
B. Other Carbohydrate Esterification Using Enzymes 234
IX. Summary 236
References 237
 Page 202

I
Introduction
The purpose of this chapter is to give a practical insight into the
chemical synthesis, processing methods, and composition of
polyol fatty acid ester surfactants. These materials are among the
most common surfactant types because esterification is one of the
easiest chemical reactions to carry out. The ready availability of
polyols such as glycerol, sorbitol, sugars, and ethoxylated
feedstocks, in addition to a wide variety of fatty acid materials,
ensures that a multiplicity of products can be tailored for many
application needs. However, control over processing conditions,
and hence over the final product composition, can give rise to very
subtle variations in performance. In addition, as all commercially
available materials are mixtures and exact processing pathways can
be difficult to interpolate, precise structureactivity relationships for
any particular application must be treated with a great deal of
caution. Following an overview of current products and processes,
a short survey of the emerging technology of enzyme esterification
is also given.
This introduction outlines some of the basic ideas behind the
concept of a fatty acid polyol ester. These include what type of
structure is required for surfactancy effects, the composition of
commercially available fatty acids, the complex nature of products
arising from simple polyol esterification methods, and major
families of materials currently being manufactured. Lastly, this
introduction is summarized in a series of guidelines that provide
the basic rules for this area of chemistry prior to consideration of
the individual variations displayed by each individual family of
product.
A
Structural Considerations
The simplistic view of these surfactant types can be readily
understood. Fatty acids are used as the building blocks for many
oleo chemical products, of which the commonest are the
appropriate alkali metal salts, or soaps (Fig. 1). In these materials,
a simple paraffinic chain 1020 carbons long is functionalized on
one end as a carboxylic acid group. If the carboxylic end is
neutralized with, for example, sodium hydroxide, the acid is
converted to its sodium salt.

Fig. 1
Soap as a model surfactant system.
 Page 203
Soaps of this type have a good balance between water solubility
(the salt of the carboxylic acid) and water insolubility (the oily
hydrocarbon chain). The water solubility of a surfactant is known
as its hydrophilicity, whereas its water insolubility is known as
hydrophobicity. This balance leads to the collection of these
molecules at an interface (e.g., between oil and water), such that
both solubility properties can be satisfied at the same time. For oil
and water, the hydrocarbon part is soluble in the oil, whereas the
carboxylic acid salt portion is soluble in the water. As the water-
soluble portion is usually smaller in size than the hydrocarbon
chain, it is usually referred to as the headgroup. However, this
tendency to collect at, and to alter the physical properties of, the
interface between two different phases leads directly to numerous
surfactancy effects. A more detailed introduction to surfactancy
can be found elsewhere [1]. However, the key requirement in
surfactancy applications is the balance between the water and oil
solubility (the hydrophilelipophile balance, or HLB requirement)
for the system under study.
The HLB system was proposed as a way in which the relative
water or oil solubility of nonionic surfactants could be gauged on a
scale from 1 to 20. Figures toward the low end at the scale (15)
indicated relatively oil-soluble materials, useful as water-in-oil
emulsifiers. Figures toward the high end of the scale (1420)
indicated water-soluble materials, useful as oil-in-water
emulsifiers. Materials with associated intermediate values could be
used as wetters and detergents. Detergency remains the major
outlet in tonnage terms for surfactant use.
This balance of HLB properties for soaps is easy to understand. If
the soap has a hydrocarbon chain, or alkyl group, of less than 10
carbons long, the molecule is likely to be too water-soluble to
allow it to collect at an interface and hence to perform effectively.
Alternatively, if the alkyl chain is too long (more than 20 carbons),
the material may become too water-insoluble and may
preferentially collect in the oil phase rather than at the interface.
It is not a large step to view the replacement of the alkali salt part
of a soap with another hydrophilic headgroup, joined through an
ester linkage to the carboxylic group, to create molecules that are
ester surfactants. As an example, ethylene glycol can be reacted
with fatty acids in such a way as to provide a monoester product,
with a hydrophilic headgroup containing a hydroxyl group, and a
polar ester function (Fig. 2). Such a headgroup is likely to be much
less hydrophilic than the salt of the carboxylic group due to the
lack of strong ionic charges of the latter. Nevertheless it has the
ability to form a hydration sphere in water due to hydrogen
bonding with the terminal hydroxyl. Similarly, soap is used in its
strongly ionic alkali metal salt form, rather than as the neutral
carboxylic acid, as the latter is relatively oil-soluble.
The chemistry of commercially available ester surfactants is
therefore the product of two main elementsa particular fatty acid,
and a compound with a
 Page 204

Fig. 2
An idealized fatty acid ester surfactant derived from
ethylene glycol.
number of hydroxyl groups, a polyol. Some general points
regarding the composition of feedstocks and the esterification
reaction are worth considering prior to some more detailed
discussion of individual products based on common polyol
feedstocks.
B
Fatty Acids
Figure 2 depicts a reaction between pure lauric acid and ethylene
glycol. While this can indeed be carried out, it is highly unlikely
that any commercial product is based on such a fatty acid
feedstock. Fatty acids are sourced from naturally occurring fats
and oils, which not only contain a mixture of carbon chain lengths
but also be fully saturated (no double bonds), or which can occur
with various degrees of unsaturation (up to three double bonds in
the chain). These naturally sourced acids also display another
interesting feature in that they are normally mixtures of only even-
numbered carbon atom chains. Other sources of fatty acids are
available, e.g., from the oxidation of paraffin feedstocks, but these
remain much less widespread in their occurrence.
Returning to lauric fatty acid, this is sourced by the hydrolysis of
coconut oil. However, in addition to this material, significant
quantities of caprylic, caproic, myristic, palmitic, stearic, and oleic
acids are also found in the crude acid feedstock. Lauric acid
material derived from simple hydrolysis of coconut oil is therefore
usually a broad mixture of homologs and, although grossly
impure, can be referred to commercially as lauric acid. The use of
such broad mixtures can be seen as resulting from two
complementary factors. First, it does make better commercial sense
to use all of the raw material readily available, instead of
discarding some and consequently increasing the price of the
remainder. Second, most surfactancy effects appear to work better
with a mixed alkyl chain, rather than with a single pure carbon
chain homolog (a fortunate coincidence!). A list of typical
commercially available fatty acids, together with their chemical
compositions, is given in Table 1.
This table illustrates a number of important points. Commercial
lauric acid can be seen as the hydrolysis product of coconut oil and
indeed sometimes is referred to as coconut oil fatty acid (COFA).
Tallow fat shows a wide range of saturated and unsaturated
species, but by the use of common processing methods, these two
types of fatty acid can be economically separated [2]. This gives
rise to commercial stearic and oleic acid compositions, marked as
derived from
TABLE 1 Typical Alkyl Chain Distributions for Commercially Available Fatty Acids
Single isomer fatty acids Fatty acid isomers (%)
Lauric
Carbon CoconutTallow Palm Stearic
Systematic name Trivial (coconut
numbers oil fat oil (tallow)
oil)
C8 Octanoic Caprylic 7 7
C10 Decanoic Capric 6 6
C12 Dodecanoic Lauric 48 48
C14 Tetradecanoic Myristic 18 2 1 18
C16 Hexadecanoic Palmitic 9 25 43 9
C18 Octadecanoic Stearic 3 19 5 3
C16:1 9c-Hexadecenoic Palmitoleic 3
C18:1 9c-Octadecenoic Oleic 7 44 41 8
9c, 12c-
C18:2 Linoleic 2 6 11 1
Octadecadienoic
9c, 12c, 15c-
C18:3 Linolenic 1
Octadecatrienoic
 Page 206
"tallow." Again, commercial grades can either be rich in their
nominal isomer (oleic), or much less pure than might be
anticipated by their name (stearic). Finally, once separation of
saturated and unsaturated material has been achieved, fractional
distillation can give rise to fairly pure cuts of fatty acids (compare
the commercial grade of palmitic acid with the alkyl chain
distribution of the palm oil from which it was derived).
While the above description of common ester fatty acid feedstocks
means that care must be exercised when considering the exact
nature of the product resulting from it, it is worth remembering
that to a large degree an alkyl chain of carbon length C10C20,
whether saturated or not, will produce essentially the same
hydrophobic characteristics necessary for surfactant performance.
The lower alkyl chain lengths, such as those found in COFA, and
unsaturated alkyl chains will tend to confer liquidity on ester
products at room temperature, whereas long and fully saturated
chains tend to give a more solid, waxy character.
C
Polyol Esterification
Fatty acid esterification of a material containing a number of
hydroxyl groups (a polyol) may at first sight be a simple way of
converting two readily available feedstocks (such as lauric acid
and ethylene glycol) to a product that should have utility as a
surfactant. As shown in Fig. 2, the reaction product appears to
have the right type of molecular structure (hydrophobic tail and
hydrophilic head), and variation of the fatty acid and polyol type
could be used to fine-tune application performance.
However, this simple view of the chemistry must be tempered by
an appreciation of the complexities that such an apparently simple
chemical conversion may generate. Two examples will be used to
illustrate this idea furtherethylene and propylene glycol esters.
1
Esterification of Ethylene Glycol
Esterification of an acid with an alcohol is an equilibrium reaction
in which the final product ester is reacting with the byproduct
water at the same rate at which the raw materials are being
converted to the product materials:

The equilibrium constant for this reaction is given by the following

equation, which is known as the law of mass action [3]:

Thus, in order to force the equilibrium to give the greatest amount

of product, esterification reactions are usually carried out such that
water is removed from the reaction medium. However, this is not
sufficient to yield only the desired
 Page 207

Fig. 3
The common product mixture derived from simple reaction of equimolar quantities
of a fatty acid and a polyol.
monoester. Reaction of 1 mole of ethylene glycol with 1 mole of fatty
acid results in a mixed product composed of monoester, diester, and
free ethylene glycol, as either of the two hydroxyl groups on the
glycol is as statistically likely to react to give the ester function (Fig.
3). The molar ratio of product is therefore about 50:25:25,
respectively. Only the monoester part of this mixture fits into the
simplified description of a surfactant outlined above, and it is only
this which is likely to be useful. The free ethylene glycol will be too
water-soluble and the diester will be too oil-soluble to be of use.
Simple esterification with equimolar amounts of starting materials is
therefore an inefficient way to produce polyol ester surfactants,
particularly the monoester materials, which are those of primary
surfactant interest.
2
Esterification of Propylene Glycol
An added complication to the above consideration of statistical
likelihood of polyol esterification is that if the polyol contains both
primary and secondary hydroxyls, a further bias in the ratio of esters
formed will occur. The esterifiability of a primary hydroxyl is
approximately three times that of a secondary hydroxyl [4]. Thus,
when propylene glycol is esterified with a molar equivalent of fatty
acid, the final product composition consists of free glycol, 1-
monoester, 2-monoester, and diester. However, the majority of the
monoester is found at the 1 position (Fig. 4). When considering the
final product composition of a fatty acid polyol ester, therefore,
awareness must be given to the nominal ratio of fatty acid to polyol
being described and to the ratio of primary to secondary hydroxyl
groups in the polyol structure.
D
Major Polyol Ester Surfactant Families
The major families of the polyol ester surfactants are given in Table 2.
This table gives a simple overview of ester manufacture in the United
States for 1990 [5]. It is included to illustrate the point that more than
80% of the needs in this area are accounted for by only a relatively
few product types and that this forms the basis for the rest of the
chapter. While many other ester types have been
 Page 208

Fig. 4
Extension of esterification product complexity is due to the disproportionate
reactivity of primary and secondary hydroxyl groups.
produced and commercialized over the years, this short overview
seeks to illustrate the main industrial processes, limitations, and
product compositions as a practical guide to the area.
The chemistry of sucrose esters is also discussed, although the
volume of product manufactured and sold is very small. However,
it remains an area in which the superficial appeal of a renewable
resource surfactant is heavily outweighed by the reality of
processing and product shortcomings.
For more details about individual product materials, available
ranges, and manufacturing suppliers, the reader is referred to some
standard reference works [6,7].
E
Introductory Guidelines
This introduction provides the basis for the discussion of the
complex polyol ester chemistry that follows. However, the main
reason for the above remarks has been to present the remainder of
the chapter within the context of a few simple observations.
TABLE 2 Major Families of Polyol Fatty Acid Ester
Surfactantsa
Family %
Glycerol 29
Glycol or polyethylene 20
Ethoxylated fats and oils 16
Anhydrosorbitol 11
Ethoxylated anhydrosorbitol (polysorbates) 9
Others 15
a(U.S., by production, from Ref. 5.)
 Page 209
1. Fatty acid feedstocks used for the production of commercial
surfactant polyol esters are always mixtures of homologs with
varying degrees of unsaturation.
2. Esterification of a polyol will almost inevitably lead to a mixed
product when the number of moles of fatty acid used is less than
the total number of hydroxyls on the polyol.
3. If the polyol contains both primary and secondary hydroxyls,
esterification will predominantly occur with the former.
4. Polyol monoesters tend to be the most desired forms of product
sought, as they give the best balance of hydrophobic and
hydrophilic properties.
Bearing these ideas in mind, the rest of this chapter will seek to
clarify how the final surfactant ester composition is affected by the
structure of the polyol considered and the stoichiometry of its
reaction with a fatty acid. Although there are many chemical ways
to produce much more well-defined, single-isomer species of great
purity, it should be remembered that such species are really only of
academic interest, as commercial competition and application
utility over many years has established the performance baseline as
gross mixtures, or materials that have undergone some simple
processing modification. Introduction of innovative techniques to
overcome the inelegant established processes can only be
acceptable in the marketplace if the cost of the innovation does not
lead to the newer products becoming noncompetitive.
II
Glycol Esters
Simple ethylene and propylene glycol esters have been mentioned
in the introduction, but they are only specific examples of the
much broader classes of glycols made from two common
industrially important raw materialsethylene oxide and propylene
oxide. These feedstocks both feature the highly strained oxirane
(epoxide) ring structure and can easily be polymerized under basic
conditions to form either homo- or copolymers. The sodium
hydroxide catalysis of this oxyethylation or oxypropylation leads to
the polymer structure (Fig. 5). This is more fully covered in
Chapter five, but is mentioned here in order to contrast the two
ways in which a fatty acid glycol ester may be prepared. This can
be done either by alkoxylation of a fatty acid by reaction with
ethylene or propylene oxide, or by the esterification of a
preformed glycol.
Before continuing this synthetic appraisal, it is worth remembering
that what is ideally sought from this chemistry is the
polyoxyalkylene monoester, in order to give the best surfactancy
effect in the product. Unreacted polyoxyalkylene chains, or the
diester compounds, are much less efficient at delivering these
effects.
The reaction conditions for the two synthetic approaches to glycol
esters can take place under very different catalysis. Alkoxylation is
usually base-
 Page 210

Fig. 5
Oxyethylation and oxypropylation polymerization.
catalyzed, whereas esterification can be base-, acid-, or
amphoterically catalyzed. However, the two different approaches
lead to essentially the same general product mixture. This will be
exemplified for polyoxyethylene glycol esters rather than for
polyoxypropylene materials, which are far less common. This is
due to the polyoxyethylene moieties adding hydrophilicity to the
hydrophobic fatty acid feedstock, giving rise to surfactancy effects,
whereas polyoxypropylene addition would only add a
hydrophobic effect to a hydrophobic feedstock, thereby rendering
it more oleaginous.
A
Oxyethylation Process
Oxyethylation of a fatty acid is carried out using a catalytic amount
of base and proceeds by the addition of ethylene oxide to the anion
of the fatty acid [Eq. (1), Fig. 6]. Once all of the carboxylate has
been turned into an oxyethylated compound, further addition of
ethylene oxide may occur [Eq. (2), Fig. 6 n > 1). This process
represents a simple way to control the balance of hydrophilic and
hydrophobic properties, as the hydrophilicity can be controlled by
the degree of oxyethylation, and the hydrophobicity by the
selection of the desired fatty acid feedstock. It should be noted that
the basicity of the product monooxyethylate anion in Eq. (1) is
higher than that for the carboxylate anion and that this results in all
of the carboxylic acid being converted to a monooxyethylene
derivative before any further reaction takes place. However, as the
oxyalkylation reaction proceeds, there is an additional reaction
taking place [Eq. (3), Fig. 6]. The
 Page 211

Fig. 6
Sequential oxyethylation and then interesterification of fatty acids.
oxyalkylate anion end of the polyoxyethylene chain may react with
another ester function to give a transesterification reaction. As this
is a ready reaction, and also reversible, the product from fatty acid
oxyethylation is a typical mixture of free glycol, mono- and
diesters.
B
Esterification Process
Esterification of polyoxyethylene glycol can be carried out under a
variety of typical conditions, such as by using p-toluenesulfonic
acid at 140°C under a reduced pressure of about 3050 mm Hg [8].
The reduced pressure allows the water of reaction to be stripped
out of the product, and so helps to displace the equilibrium in
favor of the desired ester product. Although water could be
removed simply by increasing the temperature to drive it off more
quickly, this will generally result in an inferior color and odor of
product. Other techniques have also been used to aid water
removal, including the addition of an azeotroping solvent such as
toluene, but the occurrence of low levels of organic solvents in the
final product is undesirable for most end-use applications.
Once again, due to the nonselectivity of the esterification reaction,
whereby the ester can form with equal likelihood on either end of
the glycol, the product consists of a mixture of free glycol, mono-
and diesters. To some degree, the composition can be biased
toward a greater monoester content by using an excess of glycol in
the reaction mixture. Reaction of 3 moles of ethylene glycol with 1
mole of palmitic acid leads to a product containing almost 70% by
weight of monoester [9]. A further increase in starting glycol
content can drive the monoester content close to 100%. For a
monostearate ester of propylene glycol, a molar ratio of 10:1 for
the glycol to stearic acid has been reported as optimum conditions,
using an ion exchange resin at 100110°C. The practical drawback
to these monoester-biased reaction strategies is whether such a
crude product composition (rich in monoester, but containing a lot
of free glycol) is either commercially or end-use effective. This
must be balanced against materials in which extra processing is
done to remove the excess polyol, if possible, or
 Page 212
in which the simple mixed glycol, mono-and diester product (the
cheapest option) remains cost and end-use competitive.
Glycol esters can also be synthesized using materials such as fatty
acid chlorides, by carrying out the reaction in solvents such as
pyridine [10]. However, although such a strategy is simple to carry
out on a laboratory scale, where materials may be prepared for
further experimentation and study, this approach is far too
expensive to be used on a commercial scale. In addition, toxic
solvents such as pyridine are generally unacceptable to most
potential application uses, and quite involved purification of the
final product is normally required.
III
Glycerol Esters
Glycerol esters are the largest volume group of fatty acid partial
esters of commercial significance. This should not be surprising, as
the hydrolysis of fats and oils with water to give fatty acid
feedstocks results in glycerol as the byproduct. That is to say, most
fats and oil are simply particular mixtures of triesters of glycerol
(triglycerides). As both the fatty acids and glycerol have major uses
outside the surfactants area [11], the hydrolysis of triglycerides is
an industrially important process in itself (Fig. 7). To form the
required monoester compounds, which have the greatest utility as
surfactants, there are two possible synthetic routes. These are
illustrated in Fig. 8.
A
Esterification of Glycerol
Esterification of glycerol with fatty acids is normally carried out at
temperatures of 200250°C, with a sparge of inert gas such as
nitrogen through the mixture to aid the removal of water [12]. The
catalysts normally used are either basic (sodium, potassium, or
calcium hydroxide; or potassium carbonate) or acidic (such as p-
toluene sulfonic acid). By the use of alkali metal salts of fatty
acids, the resultant soap helps the emulsification of glycerol and
the fatty acids. The esterification reaction allows the manufacturer
to exercise some control over the final product properties by
controlling the distribution of fatty acids homologs in the
feedstock. As described in Sec. I, this can be as wide or as narrow
as desired, and is essentially dictated by the cost of the uniqueness
of the homolog blend versus the value of the product to the end
user.

Fig. 7
Simple hydrolysis of triglyceride compounds.
 Page 213

Fig. 8
Reaction products derived from glycerolysis of oils and fats, or by the
esterification of glycerol.
B
Glycerolysis of Fats and Oils
Instead of the hydrolysis of fats and oils with water, reaction with
glycerol (an interesterification known as glycerolysis) can also give
a product that is similar to that obtained by direct esterification.
This processing technology has been well reviewed by Sonntag
[13]. The method has the advantage that no mass is lost during the
reaction stage (water does not need to be liberated), but it has the
disadvantage that account has to be taken of the distributions of
fatty acid alkyl chain homologs in the product, which are dictated
by the nature of the triglyceride used. Catalysts and temperatures
are as for the simple esterification method. In practice, this method
of glycerol ester synthesis is much more common than that of
direct esterification.
Overall, however, if the distributions of the fatty alkyl chain
homologs are comparable, then the product arising from either
method will be comparablea mixture of free glycerol, mono-, di-,
and triester. If a base catalyst is used, then residual soap will also
be present. The simple reaction of stoichiometric quantities of fatty
acid and glycerol will therefore give a very impure product, with a
typical monoester content of about 4248%. This type of product
has found many application outlets due to the economical way in
which it is made.
In addition, it is possible to push up the amount of monoester in
the product by again using an excess of the polyol feedstock,
glycerol. If 10 moles of
 Page 214
glycerol is used, the monoester content can approach 100%. Again,
the trade-off for the operation of such a process becomes the
acceptability of the excess polyol in the product, or the extra cost
associated with the separation of the excess from the desired ester,
with the consequently decreased utilization of the reactor volume.
One final aspect of these esterification procedures is also worth
noting. This is the low solubility of glycerol in either the starting
fatty acids or the resultant glyceride esters. At room temperature,
the solubility is only around 5%, whereas at 250°C it is closer to
50%. Obviously, the higher temperatures not only make the
esterification reaction proceed faster but also allow a greater degree
of contact to take place between the glycerol and the fatty acid or
triglyceride. The drawback to this is that as the reaction mixture
cools, glycerol may split out of the ester layer. This physical loss of
polyol from the ester layer means that the equilibrium set up
between the forward-and-backward reaction of the esterification
results in a disproportionation of the monoester content back into
free glycerol and triglyceride. For this reason, after the
esterification reaction has been carried out, the catalyst usually is
neutralized. When the product is then cooled, the reversion to free
glycerol and triglyceride is minimized.
Although the basic chemistry leads to gross mixtures of ester
products, there remains a commercial demand for higher purity
grades of glycerol fatty acid monoesters. This need is met by the
use of a technique known as ''molecular distillation" [14]. The
crude reaction mixture from the esterification reaction is fed into a
short path distillation still, and given that the different degrees of
esterification give rise to a stepwise change in molecular weight
(depending on how many fatty acid groups are attached to the
glycerol moiety), fractions of relatively high purity can be
obtained. Monoesters of approximately 95% purity are made in this
way. In addition, the byproducts of this treatment (free glycerol
and the di- and triglycerides) can be recycled back to the reaction
stage. Typical compositions for the two main types of
commercially available glyceride monoesters are given in Table 3.
It should also be noted that the diester compounds, although very
hydrophobic, still retain some useful surfactancy characteristics.
There remains, however, one further compositional detail which
adds to the complexity of glycerol ester understanding. Glycerol
has two dissimilar hydroxyl environments, and the variation in the
proportions of the ester groups at these two different positions
may be sufficient to give some subtle end-use variation. Current
nomenclature is to describe monoesters as being joined to glycerol
at the 1 or 2 position, on the primary or secondary hydroxyl,
respectively. Earlier descriptors that have been used (and can still
be found) are the a or b positions (Fig. 9). Once again, if
consideration is given to how a glycerol ester may act as a
surfactant, with a water-soluble headgroup and an oil-soluble tail,
it is clear that the two positional isomers give rise to two different
shapes of
 Page 215
TABLE 3 Composition (%) of Standard and Molecularly Distilled
Monoglycerides
Glycerol monostearate
Feature Standard grade Molecularly distilled
Monoglyceride content 46 92
Diglyceride content 40 5
Free glycerol 1 1

headgroup (Fig. 10). If small changes in surfactant packing at an

interface are critical to a particular application, then this effect may
well be important. However, for most end uses this effect is not
vital. As Sonntag has pointed out, use of monoglycerides for the
baking of bread is done at a temperature that probably establishes
an equilibrium between the two forms in any case!
In addition, as there is an equilibrium between the formation of an
ester at either the 1 or 2 position, and this is temperature-
dependent, then there is a difference in the composition of a
product at reaction temperature when compared to that at ambient.
However, before the hot product is cooled down, the catalyst is
neutralized, and so the achievement of equilibrium between the 1
and 2 isomers is very slow at normal temperatures. This, coupled
with the fact that many of the useful monoglyceride products are
solids melting at 5060°C, means that nonequilibrium mixtures of
isomers may be frozen into the commercial grades.
The above description of the basic methodologies for the
production of glycerol esters commonly sold is supplemented in
the open literature [15] by a number of synthetic strategies that
result in different reaction or product characteristics. Should
specific well-defined products be required in order to gain a better
understanding of structure-activity phenomena at a molecular
level, or in preparation for further synthetic transformation, then
such methodologies should be carried out. Effects of solvents, use
of fatty acid chlorides, and protection followed by deprotection
have all been studied extensively and their consequences for ester
ratio and product composition reported. However, for the vast
majority of industrial operations the financial penalty involved
usually precludes their use.

Fig. 9
Positional naming for the different glycerol hydroxyl
environments.
 Page 216

Fig. 10
Different shapes of headgroup arising from
the different esterification sites of glycerol.

IV
Polyglycerol Esters
Polyglycerol fatty acid esters are normally produced by a two-step
procedure [16]. The first step involves the controlled reaction of
glycerol into a polymeric form, and then this polymer is reacted
with the appropriate amount of fatty acid to achieve a balance of
hydrophobic and hydrophilic properties.
The simplest way of carrying out the polymerization step is to react
glycerol at about 260270°C in the presence of an alkali catalyst,
such as 1% sodium hydroxide. Studies have been carried out for
the optimization of this process [17] and acid-catalyzed procedures
are also known [18]. The condensation of two glycerol molecules
is illustrated in Fig. 11, with the dominant reaction being the
formation of an ether linkage at the expense of two primary
hydroxyl groups, and the concomitant formation of 1 mole of
water.
Although the diglycerol compound is shown in Fig. 11, the
presence of two primary hydroxyl groups at either end of this
molecule allows further reaction to continue. Products formed
from the condensation of up to 30 glycerol units are known,
although most commercially available materials feature 210 units
[7]. Traces of air must be excluded from the process during
reaction, as oxygen will cause acrolein to form, giving rise to high
colors and odors. The polymerization itself can be followed by the
viscosity, refractive index, or hydroxyl value of the reaction
mixture. Viscosity does rise markedly during polymer formation,
as each additional glycerol unit adds an additional hydroxyl group
to the final polymer in addition to the increase in molecular size.
Hydrogen bonding between the multitude of hydroxyls in the final
product can therefore lead to a very viscous product.
Esters of polyglycerol can be made at temperatures above 200°C,
with or without the addition of further catalyst. The easiest process
is simply not to neutralize the sodium hydroxide present from the
polymerization reaction and

Fig. 11
Polymerization of glycerol.
 Page 217
then to add the desired fatty acid. Treatment of the reaction mass
after esterification is dependent on the degree to which ester
formation has been carried out. If less than one third of the total
number of hydroxyl groups has been reacted, the mixture may split
into two layers when cooled. The lower free polyol layer may then
be separated out and recycled for further reaction. If more than
one third has been reacted, no settling may be required, and the
products can be bleached and deodorized using methods normally
used for fats and oils.
The addition of one more hydroxyl group with each additional
glycerol unit means that a large range of polyglycerol esters can be
made, and the potential range of HLB that can be spanned is quite
large. For decaglycerol, the HLB range for various esters can be
range of 316 for fatty acids with a carbon chain length of 1018.
The ideal polyglycerol structure therefore appears to be quite
simple. It would seem to be a linear glycerol polymer, usually 210
units long, with a variable amount of fatty acid attached as esters.
Three potential problems with this idealized picture can be
predicted from the preceding discussion, namely, that all fatty acids
used will be mixtures of homologs, that there will be an
equilibrium between species such as free polyglycerol, mono-, di-,
and higher esters, and the location of the acyl groups distributed
over all the hydroxyls on the polymer backbone. The additional
complication that arises is from the polymerization reaction itself,
as the polymer formed is not entirely linear.
The polymerization of glycerol is seen as proceding through the
condensation of two primary hydroxyl groups. However,
condensation of a primary hydroxyl with a secondary hydroxyl is
possible, although the condensation of two secondary hydroxyls is
very unlikely. The structures resulting from these three
condensations is given in Fig. 12. The dominant nonlinear isomer
is the 1,2'-diglycerol, which can be present in amounts of up to
15%. The presence of this 1,2' isomer is usually inferred, as the
molecule readily undergoes a facile internal condensation to give a
substituted dioxane structure. Although such a cyclic
polymerization product has been detected in early attempts to
analyze polyglycerol [19], it is only comparatively recently that
Indian workers [20] have not only quantified this species but
demonstrated how the amount is affected by the temperature at
which the reaction is carried out.
Again, the essential finding is that the polymerization reaction
mainly takes place through the primary hydroxyl groups. In
addition, the cyclic dimeric species only tend to appear when the
reaction temperature is 260°C or more. However, as the
polymerization reaction itself is fairly slow below 250°C or less,
cyclic dimer is a usual consequence of most commercial processes,
although not to any major extent.
Some exploration of more highly reactive monomeric species
(epichlorhydrin [21] or glycidol [22]) as potentially more selective
ways of generating much better defined glycerol polymers has
been carried out. These have not
 Fig. 12
Possible isomers of diglycerol resulting from reaction at either the primary or secondary hy
 Page 219
resulted in commercially viable products, however, as these
starting materials or newer processes have been more inherently
expensive to realize than the established routes. Even the use of
polyglycerol esters over polyoxyethylene esters (Sec. II) suffers
from this problem.
V
Sorbitan Esters
The reaction of fatty acids with sorbitol results in a group of
products known as sorbitan esters. Commercial quantities of the
sorbitol feedstock are derived from the hydrogenation of glucose,
and the material is classified as a sugar alcohol. Both sorbitol and
its stereoisomer mannitol (Fig. 13) are used for the production of
surfactants, although sorbitol has the much higher volume usage.
From the structures shown in the figure, the initial impression
might be that the ester chemistry of these materials should
resemble a more complex version of the glycerol ester theme. That
is, although both feature primary and secondary hydroxyls, the
presence of six hydroxyl functions on these sugar alcohols would
add a degree of complexity above that for glycerol. However, the
further degree of complication is not this feature but rather is due
to the property that sorbitol exhibits of undergoing internal
dehydration during normal esterification reactions. This internal
dehydration (or anhydrization) leads to the formation of
substituted furan ring systems. It is also possible for such single-
furan-ring systems to anhydrize further to give a fused bicyclic
structure. The single anhydrization product is known as a sorbitan
and the dual-ring system as isosorbide.
The ability of sorbitol to cyclize first to 1,4-sorbitan and then to
isosorbide was originally demonstrated by the isolation and
characterization of both of these compounds. However, more
recent studies by Bock and coworkers [23] have shown that
isomers of sorbitan other than the 1,4 material were also possible.
These are shown in Fig. 14. The more usual anhydrisation pathway
appears to be through the 1,4- or 3,6-sorbitans, which can both
give rise to isosorbide.

Fig. 13
Fischer projection drawings of sorbitol and mannitol.
 Page 220

Fig. 14
Anhydrosorbitol (sorbitan) isomers arising from the dehydration of sorbitol.
However, a certain quantity of the 2,5 and 5,2 isomers can also be
formed, both of which cannot be anhydrized further. The
dominance of the 1,4- and 3,6-isomer pathways has been put down
to the preference for secondary hydroxyl groups to displace
primary hydroxyls during the anhydrization step [24]. Beyond this,
steric arguments have been advanced to rationalize the fact that the
1,4 isomer can easily be isolated as a crystallizable solid, whereas
the 3,6 isomer is difficult to detect. Effectively, the argument is
used to explain that while cyclization to the 1,4 isomer is relatively
quick, the onward reaction to isosorbide is slow [25,26]. For the
3,6 isomer, formation of the sorbitan is slow, but the onward
reaction is quick. The intermediate is therefore only ever present in
very low quantities (Fig. 15).
 Fig. 15
Formation of 1,43,6-dianhydrosorbitan (isosorbide) via either 1,4- or 3,6-
sorbitan.
 Page 221
The practical outcome of the above is that commercially available
sorbitan esters do not contain sorbitol as the central polyol but
rather mixtures of sorbitol that has been anhydrized to various
degrees. This probably includes most of the above species
illustrated in Fig. 14, but also possibly others in small percentages.
However, given the long history of use of these products and their
good toxicological profiles, they may be considered to be very
useful and safe materials whatever their exact composition.
The compexity of the underlying chemical and compositional
considerations can be contrasted with the essential simplicity of the
processing conditions. Sorbitol and the appropriate fatty acid are
reacted together at temperatures between 200°C and 280°C, in the
presence of either acid or base catalysis [27]. Hydroxyl and acid
values of the product are monitored until they fall into the required
specification range, and then the reaction mixture is cooled.
Recently, Ropuszinski and Sczesna reported work relating to the
effect of various catalytic regimes on both the esterification and
anhydrization reactions [28]. The systems they studied include p-
toluenesulfonic acid, phosphoric acid, and sodium hydroxide. The
acid catalysts appear to promote anhydrization over esterification,
whereas the basic conditions give the opposite precedence. In
addition, combinations of caustic catalysis (to initially promote
esterification), followed by acidification of the reaction mixture (to
promote anhydrization), as well as acid followed by base, were
studied. The work implies that it may be possible to control the
sorbitan ester reaction by controlling the two distinct chemical
steps more exactly. As an extension of this work, it was later
reported [29] that the rate of sorbitol anhydrization was dependent
on the particular sodium phosphate species used as catalyst. At
230°C, trisodium phosphate had no catalytic effect. Disodium
phosphate was moderately catalytic, but the monosodium salt was
faster still.
The amount of academic study of these products has been
relatively limited due to two main factors. First, the products
resulting from these reactions are extremely complex mixtures, and
hence the effect of process changes on the final product
composition is likely to remain poorly understood. Analysis of
these mixtures, even by recent high-performance liquid
chromatography (HPLC) or supercritical fluid chromatography
(SFC) methodologies, has still proved to be a difficult task [30,31].
Structureactivity relationships therefore may prove very difficult to
determine. Second, the raw materials are relatively cheap, and the
methods for their processing to sorbitan esters have been known
for 50 years. The possibility of further optimization may be
unnecessary, as formulators know how to optimize around the
standard commercial materials.
An economic process for the production of sorbitol monoesters,
on the other hand, does remain a research target. While the simple
processing of sorbitol into fatty acid esters is accompanied by
anhydrization and this internal etherification results in the loss of
hydroxyl functionality, the hydrophobicity of these
 Page 222
materials will remain high. If a sorbitol monoester could easily be
made, this material would have a much greater water affinity and
could be a much more versatile surfactant compound.
The reaction of equimolar amounts of fatty acid chloride and
sorbitol in pyridine has been known for many years. However, the
starting acid chloride is relatively expensive, and running the
reaction in a toxic solvent such as pyridine also adds to the costs
by requiring a scrupulous cleanup of the product. More recently, a
process has been disclosed that involves running a simple sorbitan
ester process featuring very quick heat-up and cool-down phases
of the reaction [32]. Although some anhydrization takes place, the
final product does retain much of the hydroxyl functionality of the
sorbitol. A mixed sorbitol-glycerol-polyglycerol ester product has
also been produced by the reaction of a triglyceride with sorbitol in
the presence of 410% of various polyglycerols [33].
More highly substituted sorbitol esters do seem easier to produce
with little anhydrization. For example, sorbitol tetraoleate can be
made by the reaction of sorbitol with methyl oleate in the presence
of a basic catalyst at temperatures of 120155°C at various reduced
pressures [34]. However, these types of product have very little
surfactant activity. The proposed use for these compounds is as
low-calorie butter or margarine substitutes, which is based on the
idea that the greater the degree of ester functionality, the more
difficult it is for the polyester fat to be broken down in the human
gut.
In contrast to the highly complex picture of sorbitan/sorbitol
chemistry, there has been some interest in the esterification of pure
isosorbide. This diol can be prepared in moderate yields by driving
the anhydrization of sorbitol through the sorbitan stage until the
cyclization reactions are complete. A yield above 70% has been
reported when using sulfuric acid at 135°C, or 66% when using
hydrochloric acid [35]. This cyclization of optically active sorbitol
produces a molecule featuring a cis-fused junction, and a V-shaped
molecule with one hydroxyl inside (exo) and one outside (endo;
Fig. 16).
While at first sight it might be expected on steric grounds that
esterification of isosorbide should preferentially take place at the 2-
exo hydroxyl, it has been

Fig. 16
Possible hydrogen bonding may explain
the different reactivity of the 5-endo
and 2-exo hydroxyls of isosorbide.
 Page 223
found that the 5-endo hydroxyl function is usually favored under
kinetic conditions. Stoss and coworkers [36] found that the
acylation with acetic anhydride at room temperature in the
presence of lead oxide could give yields of up to 7085% of the 5-
endo acyloxy group. In contrast, if the same reaction is carried out
and is followed by equilibration of the mixture with potassium
hydroxide, then the 2-exo group is found in the product in yields
of 5090%. This migration of the acyl group shows that the ester at
the 2-exo position as the thermodynamically favored outcome.
One explanation put forward for this behavior is that the 5-endo
hydroxyl can be seen as hydrogen-bonded to the ether oxygen of
the adjacent ring, which enhances the reactivity to esterification
[37].
The production of esters from mannitol has followed along the
lines of those from sorbitol. Original work on these fatty acid
esters was conducted at about the same time as that for sorbitol
[38], but as mannitol is a more expensive feedstock for these types
of products, these materials have a much smaller use in the
marketplace. Studies into the cyclization of mannitol to give
mannitan and isomannide have been carried out alongside the key
work that has been conducted for sorbitol anhydrization [23,25].
VI
Sucrose Esters
Sucrose would appear to be a very interesting feedstock for the
production of polyol esters. It is a disaccharide with eight hydroxyl
groups, and an additional three ether linkages, making it a very
attractive hydrophilic group (Fig. 17). It is produced worldwide in
million tonne quantities, and is therefore very cheap and abundant.
Unfortunately, the highly polar nature of sucrose results in several
problematic attributes. It is a high-melting solid (melting point
160180°C) and has a tendency to caramelize rather than melt.
Given these physical constraints, the usual processing method for
the manufacture of sucrose derivatives is to use a solvent for the
reaction. This leads to a further constraint. There are only a few
solvents that can dissolve this compound effectively. These include
water as well as such highly polar aprotic solvents as
dimethylsulfoxide (DMSO) and dimethyl formamide (DMF).

Fig. 17
Structure of sucrose.
 Page 224
The attraction of surfactant monoesters derived from sucrose is the
higher water solubility of these compounds when compared with
glycerol or sorbitan esters, due to the greater abundance of
hydrophilic groups. This should result in a wider applicability of
this type of material, given the cheapness of the raw materials, and
the ready biodegradability and low toxicity.
The physical processing restrictions remain the main problem.
Early work in surfactant ester preparation was carried out by
reacting fatty acid methyl esters with sucrose in pyridine as the
preferred solvent [39]. The reaction temperature was 100°C and
sodium methoxide was used as the catalyst. Removal of methanol
from the reaction vessel drives the preparation to the desired
product, and this was complete in about 4 h. Purification of the
desired product from the toxic and flammable solvent is an
obvious drawback, as the production of a sucrose ester would
appear to be ideal for use in applications such as food
emulsification. Heterocyclic amines, DMF, and DMSO have also
been reported as solvents for the reaction but suffer from the same
drawback [40]. The usual catalysts for the reaction include alkali
metal hydroxides and carbonates. Yields of up to 50% of sucrose
ester are disclosed.
Osipow overcame the need for a highly polar but undesirable
solvent by using a method whereby reaction took place in a
transparent emulsion [41]. By bringing two immiscible liquids
together in a very fine emulsion, it was shown that reaction
between the two phases was possible, as if they were dissolved in
a solvent. In order to achieve the intimate contact required, the
droplet size needed to be about one-quarter of the wavelength of
light, rendering the emulsion transparent. A suitable emulsifying
agent was also required. For one specific example, an emulsion of
sucrose, sodium oleate, and propylene glycol was formed after
heating to 130°C. The propylene glycol was then removed by
distillation over 5 h, and after an extractive workup, more than
50% of the desired ester had been formed.
This approach was later modified to use water as the solvent
instead of propylene glycol [42]. The emulsifying agent was a
combination of soap and previously prepared product at a level of
1040%. The product mass contained approximately equal
quantities of sucrose mono- and higher esters. Again, separation of
the desired products from the rest of the reaction mass remains a
potentially laborious process. This is particularly necessary when
soap is used as one of the emulsifiers, as the surfactant properties
of this anionic compound could radically interfere with those of
the true sucrose derivatives. In addition, the taste of soap is
certainly undesirable for emulsifiers used for food applications,
currently a key outlet for these materials.
In 1973, Tate and Lyle published a patent that exemplified the
transesterification of a triglyceride with sucrose, in a process that
did not employ a solvent [43]. Reaction was carried out at
110140°C in the presence of a basic catalyst such as potassium
carbonate. An emulsifier, present in 510% by weight of the
 Page 225
reaction mass, was also preferred. One of the advantages of this
method is that the triglyceride ester is used as the acyl group source
for transfer to sucrose. The byproducts of the reaction (di- and
monoglycerides) also confer useful surfactant properties to the
final mixture. Two of the disadvantages of this method are the
longer reaction times required (up to 16 h) and the necessary
restriction on the use of these products into applications where
impure sucrose esters can be useful. These were exemplified as
cosmetics, agricultural chemicals, and detergent powders.
Another interesting method disclosed for overcoming the physical
incompatibility problems of the reactants is by use of a high-
temperature worm shaft reactor [44]. This describes the use of a
single-screw extruder with a fatty acid methyl ester, sucrose, and
soap at 170180°C. The soap catalyst was used at levels of 1020%.
This stage of the reaction provided only about 10% conversion to
products, and the extruded product was then reacted further in a
conventional reactor at 150°C under reduced pressure. The
effectiveness of this technique was not explicitly demonstrated,
however, as disappearance of the methyl ester was monitored, but
the appearance of the required ester products was not.
Use of molten soap to provide a reaction medium into which both
methyl ester and sucrose could be added has also been described.
In this way, the overwhelming presence of soap as a solvent and
reaction catalyst allows the buildup of product to happen gradually,
and so helps facilitate the main reaction [45].
Preparation of sucrose polyesters has tended to be a much easier
reaction to carry out than the production of the more interesting
monoesters. Procter and Gamble have introduced a sucrose
polyester (more than five fatty acid ester groups per molecule of
sucrose) as a low-calorie alternative to butter and margarine [46].
The high degree of esterification allows the compound to pass
through the human intestine unchanged. However, once the
polyester has been formed, further reaction with sucrose can give a
product that has a much lower degree of substitution. Polyesters
with three to eight ester groups have been reacted to give products
with about half the total number of esters per sucrose. Again,
extractive purification adds to the complexity of the workup
procedure.
The main production and use of fairly pure sucrose esters takes
place in Japan. This is usually carried out utilizing a highly polar
aprotic solvent for the synthesis step, followed by extensive
product cleanup. Methods for the economic purification of sucrose
esters continue to appear in the patent literature. Recently, an
aqueous extractive method has been reported by Dai-Ichi, which is
carried out after a conventional ester preparation in DMSO [47].
The reaction mixture is neutralized and a sediment precipitated out
of solution. The sediment is triturated with acidified water, and
fatty acid is added to the aqueous washings. The fatty acid forms
micelles with the very water-soluble esters. About 8595% of these
esters can be recovered in this way. The resultant
 Page 226
solid is neutralized, redissolved in water, and spray-dried to give a
highly purified version of the sucrose monoester.
The Japanese market has been estimated at about 2600 tonnes per
annum in total, which illustrates that for all potential that the basic
elements of feedstock costs, desirability of the product, low
toxicity, and excellent biodegradability represent, the fundamental
physical processing or product cleanup costs continue to make this
type of product very expensive in comparison with simple
ethoxylated products. This results in the low volume of product
sold and the high-value application areas (such as food) into which
they go.
Less pure products are still finding uses in some market sectors.
Mixed sucrose/glyceride ester materials have been claimed as
having attractive properties for plant protection and for detergent
formulations [48].
VII
Polyoxyalkylene Polyol Esters
The preceding sections have described some of the chemistry
associated with a number of different polyol moieties. These have
included glycerol, polyglycerol, sorbitan, and sucrose materials. In
the main, reaction of these materials with fatty acids results in
relatively oily (low HLB) esters being produced, which does limit
their value as useful surfactants. However, residual hydroxyl
functionality in these compounds can be used as the basis for
reaction with ethylene oxide to form much more hydrophilic
polyoxyethylene chains.
This can be most readily exemplified by considering the
polyoxyalkylene derivatives of sorbitan esters, commonly known
as polysorbates. For the basic sorbitan ester products themselves,
there is a limited range of HLB variation. By varying the length and
number of fatty acid chains, the HLB of the ester can be altered
from 8.6 (sorbitan monolaurate) to 4.3 (sorbitan monooleate) to
1.8 (sorbitan trioleate). This range of values (1.88.6) is still
confined to the low end of the HLB scale (120). Addition of
ethylene oxide, however, can raise the HLB of the resultant ester
products to regions that greatly increase their utility. Oxyethylation
of sorbitan monolaurate with 4 moles of ethylene oxide raises the
HLB of the product from 8.3 to 13.3, and a reaction with a total of
20 moles increases this to 16.7. The common ranges of sorbitan
and polysorbate esters and their HLBs are given in Table 4.
It should be mentioned at this stage that continual adjustment of
oxyethylene content in order to generate a multitude of products is
not really required, as it is possible to combine materials of
different HLB values in a straightforward linear mathematical
relationship to achieve intermediate HLB values. In fact, the HLB
scale was devised on the basis of using sorbitan and polysorbate
esters as nonionic emulsifiers in a number of different
applications. Perhaps following from this original generation of a
spectrum of surfactant emulsifiers capability, now combined with a
long history of application utility, sorbitan and poly-
 Page 227
TABLE 4 HLB Values of Commercially Available Sorbitan Esters
and Their Derived Polysorbates
Polysorbate products degree of
ethoxylation
Sorbitan
45 EO 20 EO
esters
Monoesters Laurate 8.6 13.3 16.7
Palmitate6.7 15.6
Stearate 4.7 9.6 14.9
Oleate 2.1 10.0 15.0
Triesters Stearate 4.3 10.5
Oleate 1.8 11.0

sorbate ester materials continue to be a common starting point for

many new applications.
Oxyethylation of sorbitan esters is generally carried out using
procedures that could be equally applied to most other feedstocks
(see Chapter 5). Reaction under base-catalyzed conditions (sodium
or potassium hydroxide, or the alkali metal salt of the appropriate
fatty acid) at temperatures of 130170°C results in the smooth
addition of ethylene oxide. However, just as ester interchange has
been previously described as a common feature of base-catalysed
processes, so this is probably taking place in these oxyethylation
reactions. Although fatty acid groups may originally be attached to
the sorbitan ring systems in the feedstock ester, these can easily
rearrange to join onto the end of any growing oxyethylene chain
[49]. The net effect of this ester interchange would appear to be as
if the ethylene oxide inserts itself between the sorbitan ring and the
fatty acid moiety. In this way, the overall shape of the final ester is
not as simple as the earlier idealized version of a surfactant, i.e.,
with hydrophilic headgroup and oleophilic tail. It is closer to a
core sorbitan ring, with radiating oxyethylene chains, which are
capped to a lesser or greater extent by the fatty acid ester functions.
By analogy with the polysorbate ester reaction, similar surfactant
ester feedstocks that feature free hydroxyl functions can also
undergo oxyethylation reactions to give materials of higher HLB.
These include glycerol, polyglycerol, and sucrose esters. In
addition, many naturally occurring fats and oils are also similarly
reacted to raise their water solubility.
Although many other oxyethylated materials have been studied,
such as those derived from reaction of sucrose, sorbitol, or
methylglucoside first with ethylene oxide and second with fatty
acids, the major commercial ranges of polyoxyalkylene polyol
esters are limited. Materials derived from anhydrosorbitol, glycerol
(fats and oils), and simply polyoxyethylene make up about 90% of
the volume of such products. More specialized esters can be easily
tailored,
 Page 228
but for the majority of needs, a blend of low- and high-HLB esters,
such as the sorbitan and polysorbate materials, will perform
efficiently.
VIII
Enzyme-Catalyzed Esterification
The above discussion has focused on the relatively nonspecific
ways in which commercially available products are made.
Although it is possible to synthesize a wide range of chemically
pure entities if these species need to be studied, such syntheses
tend to be too expensive to operate on a large manufacturing scale
for industrial applications. More recently, interest has turned to the
possible use of enzyme catalysis to add a degree of product
specificity not previously available. This technology is still
emerging, and what will be presented here are simply some of the
trends that are currently emerging in this field.
Enzymes are natural catalysts that mediate biological processes. For
example, various yeasts are able to turn sugars into alcohol, a very
well-studied process! However, since the early 1960s, when
commercialization of enzymes in detergent formulations was first
achieved, interest in their potential organic synthetic ability has
expanded rapidly. Although the original commercialization was for
relatively impure and expensive actives, development of the
technology has led to the production of purer and less costly
enzymes. At present, several thousand enzymes have been isolated
and characterized, and several hundred are commercially available.
Enzymes themselves are produced by living systems in order
catalyze biological processes [50,51]. They are protein-based and
are typically polymers of about 250400 amino acid units.
Frequently they contain about 215% by weight of sugar residues,
but the function of these residues is not absolutely clear.
As the amide functions of the protein chains are very polar, and as
each amino acid residue has its own substitution pattern and shape,
is it possible for these molecules to fold up and hydrogen-bond in
very intricate ways (something like a ball of string). However, most
will fold up into one particular shape or primary structure. Once
this has formed, the enzymes will possess a small area on the outer
surface that will catalyze particular reactions. This is known as the
active site, and this area has a degree of flexibility that allows
reactant molecules to be accommodated and for product molecules
to be released.
However, as the primary structure of any enzyme is dependent on
only the relatively weak hydrogen bonding of the amide functions,
these materials are not stable to high temperatures. Most cannot be
heated above 50°C, although some may continue to operate up to
70°C. Above the appropriate critical temperature, the enzyme
structure will unravel (denature), and all catalytic effect is lost. A
very slow decrease in temperature may result in the reformation of
the original shape, but the phenomenon of denaturation does
impose a
 Page 229
definite operating limit on any temperatures of organic reactions
for which these proteins are used.
There is a great range of potential catalysis that enzymes can offer
to synthetic chemists. As they operate at relatively low
temperatures and cover a wide range of stereo- and regioselective
reactions, this makes them very attractive to use in the synthesis of
natural products or pharmaceutical actives, where a high number
of selective transformations may be required to define a useful
synthetic pathway. This attractive ability for the efficient
conversion of raw materials to a desired product is currently offset
by the general high cost of these products. The isolation and
stabilization of sufficient quantities of enzymes from natural
sources remains an expensive activity. However, as these high-
value activities, particularly in the pharmaceutical field, continue to
stimulate the technology around the production of enzymes, the
possible application of these catalysts to moderate-value processes
is becoming more realistic.
Enzymes are classified into six main groupings, depending on their
mode of action (Table 5). This section concentrates on the
chemistry that derives from only one of these, lipases, which are
catalysts built by living systems in order to hydrolyze fats and oils.
For mammals, such lipases are made and released from the
pancreas. The pancreatic lipase is released into the small intestine,
where it attacks emulsified triglycerides in preference to those that
occur in the walls of the pancreas itself. This has led to the
hypothesis that the lipase works best at an oilwater interface.
Because of this, most lipases would appear to need a mixture of oil
and water to perform at their best. Lipases are also produced by
microorganisms such as bacteria as a mechanism for the cleavage
of triglycerides. Again, the cleavage reaction is a mechanism for
the organism to gain a source of carbon for growth.
Although lipases are used by biological systems in an aqueous
environment to promote hydrolysis of esters, it should be
remembered that they are essentially performing the function of
any other catalystthey are promoting the
TABLE 5 Enzyme Classifications and Functions
Enzyme
Function
classification
Catalyze the hydrolytic cleavage of CO, CN,
Hydrolases and CC bonds. This category includes lipases,
proteases, esterases, and glycosidases.
Catalyze molecular isomerizations, and
Isomerases
includes racemases and isomerases.
Catalyze the formation of a covalent bond
Ligases
between two molecules.
Catalyze the cleavage of C-O, C-N, and C-C
Lyases
by elimination.
OxidoreductasesCatalyze all redox reactions.
Transferases Catalyze the transfer of a specific group.
 Page 230
speed at which an equilibrium is attained between reactants turning
into products. The same basic mass action law discussed above
(Sec. 2) still holds. Similarly, in a water-poor environment, lipases
will act to esterify an alcohol and an acid, i.e., the mass action law
can still be driven in the direction required.
A
Glycerol Esterification Using Enzymes
Of course, given that enzymes have a natural capability for reacting
with triglycerides, it follows that esters of glycerol have received
much study. Linfield looked at the hydrolysis of tallow, coconut,
and olive oils by Candida rugosa [52]. He found that the reaction
approximated to a first-order kinetics model and was not affected
by a temperature change over the range 2646°C. To hydrolyze all
three substrates, however, required above 72 h of reaction time.
Lipase from Aspergillus niger and Rhizopus arrhizus were also
studied, with the latter giving a considerably slower reaction rate.
Esterification was also studied by stirring a mixture of the
appropriate enzyme, glycerol, and an excess of fatty acid for at
least 24 h, prior to distilling some water out of the mixture via
reduced pressure. No external heat was applied. The mixture was
again stirred at ambient temperature and water stripped out at
regular intervals. In this way, an almost 80% conversion to product
was achieved over a 6-week reaction time. Thin-layer
chromatography at this stage showed that the product consisted of
1.4% monoglycerides, 19.8% diglycerides, 43.6% triglycerides, and
35.3% free fatty acid. Aspergillus niger and C. rugosa produced
comparable results. Attempts to esterify other polyols using this
technique proved difficult, with sorbitol not reacting with oleic
acid, and ethylene and diethylene glycol reacting only very slowly.
An interesting observation made during this work was that if
vacuum dehydration was too severe, the enzyme would stop
working. It could then be reactivated if a small amount of water
was added back into the mixture. This observation supports the
need for a lipase to have an oilwater interface to operate correctly.
The possibility of converting such a method for glyceride synthesis
into a practical process was outlined by Yamane [53]. He reported
that use of a microporous membrane reactor could be used to give
continuous production of glycerides from separate glycerol and
fatty acid streams. On one side of the membrane in the reactor, he
recycled a mixture of lipase (Chromobacterium viscosum) in
glycerol. This circulating loop featured a dehydration chamber, for
the removal of the byproduct water, and a fresh glycerol source.
On the other side of the membrane, fatty acid was fed in, and
glyceride products were produced.
The two most effective methods used for the dehydration section
were either molecular sieves or a vacuum dehydrator operating at a
pressure of 5 mm Hg. The best conversion (90%) occurred when
the glycerol solution contained about
 Page 231
34% water. The reaction produced mainly mono- and diglycerides
in almost equimolar amounts.
More recently, a full review of immobilized lipase reactors for
effecting hydrolysis, esterification, and transesterification was
published [54].
As mentioned above, the most desirable glyceride product is
normally the monoester. Alcoholysis of an oil or fat to achieve
high yields of this material without the need for molecular
distillation is technically attractive and should consume much less
energy than the conventional process.
Holmberg has shown that it is possible to obtain monoglycerides in
yields of up to 80% by simple hydrolysis of a triglyceride with a
lipase that was specifically active at the 1,3 positions of glycerol
[55]. The byproduct of this reaction was 2 moles of fatty acid. The
process was carried out by the formation of an oil-rich
microemulsion with isooctane as the hydrocarbon component, and
an aqueous phase buffered to pH 7. Use of the 1,3-specific lipase
Rhizopus delemar to carry out such a specific reaction does have a
practical limitation, as the migration of an acyl group from the 2
position to the more thermodynamically stable 1 or 3 position will
eventually result in total glyceride hydrolysis. Optimal reaction
time for this system was found to be 3 h at 35°C.
This work was extended to show that glycerolysis of palm oil
could be carried out in the presence of 2 moles of glycerol to give
an impure monoester product [56]. The need to maintain an
emulsified system, together with a certain concentration of water to
allow the lipase to function, led to a mixture of desired
monoglyceride and free fatty acids. This product was obtained in
spite of the use of four different enzyme types. It should be noted
that although 1,3-specific and positionally nonspecific lipases are
known, there has so far been no report of an enzyme that operates
only at the 2 position. This has been described as a way of
determining the difference between enzymically and chemically
catalyzed interesterifications [57] and has also been used to
produce 2-monoesters by selective hydrolysis [58].
Yamane reported [59] that the glycerolysis of beef tallow in the
solid phase using an enzyme can increase the yield of
monoglyceride (up to 70%) over that obtained at temperatures
above the melting point of the fat. This has been explained by the
observation that monoglycerides have higher melting points than
the corresponding triglycerides, and this lower solubility results in
the preferential precipitation of the desired product. This effective
removal of this product from the reaction medium provides a
mechanism for driving the equilibrium away from the typical
proportion of monoester that would be achieved for a simple
homogeneous reaction mixture. The highest yields obtained with
commercially available lipases were given by Pseudomonas
fluorescens or Chromobacterium viscosum. Using the best
conditions (temperature 44°C, water content 2%, 2 moles of
glycerol per mole of fat),
 Page 232
approximately 60% of monoester was formed within 5 h, slowly
rising to 70% after a total of 25 h reaction time.
The work was extended by further screening of commercially
available lipases, both singly and in combination, together with a
stepped reaction temperature profile [60]. Lipases from
Pseudomonas sp. were highly active, as previously reported.
Geotrichum candidum was virtually inactive to the fats studied, an
observation that was explained away by the known preference of
this enzyme for unsaturated fatty acids. Penicillum camembertii
was also inactive, as this enzyme is most active toward mono- and
diglycerides, rather than triglycerides. Combinations of various
lipases did not give an increased yield of monoesters above 70%,
which may simply be a limiting value for this particular
methodology. A product containing 90% monoester was obtained,
however, using Pseudomonas and olive oil at the relatively low
temperature of 10°C. This may be due to more monoglyceride
precipitating from the cooler reaction mixture. Mucor meihei also
showed this effect but gave a slightly lower yield (80%). While this
level of monoester is approaching that of a molecularly distilled
product, the major hindrance to the use of this technology is the
time required to achieve the desired monoester type. An 80%
monoester may require 24 h, whereas 90% may require up to 5
days of reaction time.
In contrast, the use of a thermostable lipase and a solvent can
considerably hasten reaction time. Lion Corporation reported some
studies on 17 different lipases, which showed that Candida
antarctica and M. meihei were among the most thermally stable
(withstanding 70°C for 30 min) and active (at 50°C) for the
synthesis of glycerol esters [61]. A typical procedure employed
immobilized C. antarctica catalyzing the reaction between oleic
acid and glycerol at 50°C in tertiary butyl alcohol over molecular
sieves as a drying agent. After 6 h, the reaction product contained
87% monoester and 9% diester. The molar ratio of oleic acid to
glycerol, however, was 1:3. The excess glycerol does speed the
reaction to products, but again complicates vessel utilization and
process operability for full-scale manufacture.
The Lion patent [61] exemplified reactions using either fatty acids
or their lower alkyl esters, and demonstrates that polyglycerols or
polypropylene glycol can be similarly converted to high-monoester
product. The work was extended to ester interchange reactions,
where glycerolysis of oils and fats was carried out. Conversion to
products containing mono- and diester content of 8090% and
1015% respectively, was obtained for numerous triglycerides.
Finally, continuous use of the enzyme over many reaction cycles
was demonstrated with a reaction between glycerol and olive oil
over C. antarctica. The monoester content of the product was
shown to remain at about 85% monoester, even after 1500 h of use
at 50°C. This continuous use of the enzyme remains a very
desirable feature, as recycling over many reaction periods brings
down the high cost of enzyme use per unit of product made to a
much commercially competitive level.
 Page 233
Schneider and coworkers also looked at the possibility of
producing monoesters of glycerol [62,63]. Due to the inherent
mismatch of polarities of glycerol and fatty acids or derivatives, a
method was developed whereby preadsorption of glycerol on a
silica support was used. Reaction in an aprotic solvent over
Chromobacterium viscosum, Rhizopus delemar, or Rhizomucor
meihei was then carried out. However, this methodology did not
give rise to exceptionally high yields of monoester, and so a
separate purification step was devised. By using a combination of
diethyl ether and hexane as solvent, and by cooling the mixture
down to between -2 and 10°C, 8091% yields of monoester could
be obtained. All other byproducts were simply returned to the
reaction stage, from which the immobilized enzyme and silica
support had been filtered. This initial methodology was followed
up by work showing its wider applicability. Reaction times
unfortunately remained relatively long, at between 24 and 96 h.
In addition to the development processes around monoglyceride
synthesis using enzymes, several other facets of this glycerol ester
chemistry have been studied. Simple hydrolysis of fats and oils has
been reviewed by Sonntag [64], who pointed out that the
economic equation for making enzymic fat splitting a favorable
alternative to current methods requires that the overall cost be
lower than the cost of the heat and electrical energy normally
utilized. It should also be remembered that heat recovery is usually
designed in many modern plants, making the equation even more
difficult to satisfy. In addition, as most lipases interact best at the 1
and 3 positions of glycerol, the critical factor influencing
triglyceride hydrolysis is the rate at which the ester at the 2 position
moves to the end hydroxyls. Although enzyme hydrolysis can be
effective at 4060°C, temperatures of 100°C may be required to
promote this rearrangement at a sufficient speed to allow a fully
competitive process to be reached. The existence of an enzyme
process capable of operating at such a temperature has yet to be
proven.
Lipases have also demonstrated a selectivity for promoting
reactions of some fatty acid or ester moieties over others. A review
by Macrea [51] concluded that most microbial lipases show little
specificity, although that from Geotrichum candidum can show a
difference in the rate of hydrolysis of fatty acid methyl esters of up
to 100 times. Oleate or linoleate alkyl chains are much faster than
myristate or stearate. A possible theory to rationalize this effect is
that the active site contains a functionality that allows some
interaction with p-bond orbitals, or perhaps olefinic bonds.
Alternatively, Jones postulated that the shape of the active site is
why some substrates fit in easily, and converted more quickly, than
those that do not fit as well [65]. More recently, Mukherjee [66]
reported that selective esterification of a hydroxyl-containing
substrate is possible such that specific enrichment of the free fatty
acid or ester products can be achieved. For the two lipases studied,
from either seedlings of rape (Brassica napus cv Ceres) or from
Mucor meihei, g-linoleic acid is converted very slowly through to
ester and so builds up in the
 Page 234
free fatty acid portion of the product mixture. When starring from
fatty acids derived from evening primrose oil, containing 9.5% of
g-linoleic acid, enrichment of up to 85% has been achieved by
converting other acids to their butyl ester. Although this method
presents an opportunity to make enriched, unsaturated feedstocks
for the production of pharmaceutically interesting materials, it also
demonstrates that awareness of this phenomenon is necessary
when trying to make esters of fatty acid materials with both
saturated and unsaturated components.
In contrast to the work of Mukherjee, Ward [67] has shown that
for polyunsaturated fatty acids such as eicosapentaenoic and
docosahexaenoic acid, Mucor meihei and Pseudomonas sp are
actually the best enzymes for achieving glycerides from glycerol in
a waterhexane mixture at 30°C. Clearly, much more
characterization work is needed before fatty acid selectivity and
reactivity can be fully defined.
B
Other Carbohydrate Esterification Using Enzymes
Following the interest and extensive reporting on the enzyme-
catalyzed synthesis of glycerol esters, other carbohydrate
feedstocks have be investigated. These include materials such as
sorbitol, glucose, sucrose, and simple glucosides.
Heino published some work in 1984, aimed at using enzymes with
this type of raw material [68]. Due to the low temperatures at
which these reactions could be carried out, the implication was that
much cleaner and purer versions of the chemically catalyzed
products could be obtained, as much less decomposition of the
feedstock would take place. The reaction procedure consisted of
mixing the enzymes studied with fatty acids and sucrose, fructose,
sorbitol, and glucose at 40°C in an aqueous buffered solution for
2495 h. From the eight enzymes studied, Candida cylindracea was
the most active. A semioptimized process showed that the best
reaction conditions occurred when the concentrations of sucrose
and oleic acid were 0.05 mol/L and 0.2 mol/L, respectively, after 72
h. Conversion to ester was more than 60% for sucrose, fructose,
and sorbitol, but for glucose it was only about 28%.
Klibanov published a number of papers investigating the
esterification of similar carbohydrate hydrophiles. Instead of an
aqueous environment, he concentrated on the use of dry, aprotic
solvents such as pyridine and DMF. However, while these solvents
are ideal for the carbohydrate reactant, not many lipases are active
in such an anhydrous environment, or with di- or
oligosaccharides. In 1988, he reported work with proteases,
specially Bacillus subtilis [69]. He also utilized a highly activated
form (a 2,2,2-trichloroethanol ester) of the fatty acids he studied in
order to drive the reaction to completion. Although the
conversions to the desired esters were fairly successful (up to 96%
based on gas chromatographic disappearance of the carbohydrate),
reaction times were
 Page 235
still of the order of 27 days at 45°C. The acyl group of the ester
was predominantly found on one of the primary hydroxyl groups
of the carbohydrate substrate. Reactions with salicin, riboflavin,
adenosine, and uridine were also studied.
While this work has shown that the esterification reaction is not
confined to lipases alone, it is evident that the major problems that
need to be dealt with still involve elimination of the use of a toxic
solvent and a speed of reaction that makes such a synthetic
pathway worthwhile. Klibanov has also studied some
transesterification reactions at about the same time [70]. He studied
model reactions between triolein (glycerol trioleate) and sorbitol in
pyridine. Only porcine pancreatic lipase and, to a lesser extent,
Chromobacterium viscosum were active. In a typical reaction,
sorbitol was reacted with a slight molar excess of triolein in dry
pyridine at 25°C. After 3 days, the enzyme was filtered off and the
product purified by column chromatography. The pancreatic
enzyme gave a monoester compound, as an almost equimolar
mixture of the 1 and 6 derivative. The overall yield was very poor,
however. The work was extended to natural triglycerides, which
demonstrated the generality of the reaction. Surfactant properties
of the derived materials were then examined and shown to be quite
different from those derived by more conventional chemical
means. However, these comparisons were being done between a
sorbitan ester (and its relatively few free hydroxyl groups) and a
sorbitol ester (where many more hydroxyls are giving rise to a
greater water solubility).
Lion Corporation disclosed some details of work on saccharide
fatty acid monoesters in a 1990 patent [71]. The process involved
use of a fatty acyl donor (acid, lower ester, or triglyceride) with a
saccharide or disaccharide compound in a secondary or tertiary
alcohol solvent in the presence of a thermostable lipase. As for the
glyceride work mentioned above, Candida antarctica again
featured as the most thermally stable and active enzyme found. The
fatty acyl groups included both saturated and unsaturated materials;
the saccharides included glucose, fructose, sucrose, and various
short chain glucosides (methyl to butyl); and typical solvents
included tertiary butanol and diacetone alcohol. Although most of
the reactions featured an excess of one of the reactants in order to
force the reaction to completion, the reactions with the glucosides
appeared to be the easiest to catalyze. This may be due to the extra
solubility of these materials in the relatively low-polarity solvent.
The reaction temperature was 5060°C, and the time of reaction
varied between 8 and 24 h. The purity of the monoesters
produced, however, was claimed as high as 98%.
This work was extended in a further patent, which explored
different solvent systems. These included acetylacetone, ethylene,
and propylene carbonate, g-butyrolactone, and various substituted
pyridine derivatives [72]. The reaction times were subsequently
reduced from 24 to about 10 h, with a conversion that remains
high, at about 90%. In addition, byproduct formation of the diester
 Page 236
compounds is suppressed. Candida antarctica and Mucor meihei
were the favored lipases used. Reactions with most of the
saccharide compounds studied still featured a large excess (usually
4, but up to 20 times) of the acyl-donating material, which again
complicates the overall industrial utility of the method. Most of the
reactions employed methylglucoside as the saccharide substrate,
although the wider applicability of the method was also
exemplified.
Some further work [73] on saccharide esters was also patented by
Novo, a company that is heavily involved in the production and
immobilization of enzymes for commercial sales. Methylglucoside
esters were prepared from methy glucose and the appropriate acyl
donor material without the need for solvent using Candida
antarctica at 80°C under reduced pressure (0.01 bar). Reaction
time varied between 17 and 36 h, and greater than 90% conversion
to ester could be achieved, although these products did sometimes
contain significant amounts of diester (up to 15%).
The work was extended in a later patent to other saccharides [74].
Candida antarctica was again employed as the appropriate
catalyst, and reaction times were relatively long (up to 24 h for
high product yields). Although no solvent was used, an emulsifier
(normally soap, at up to 20% by weight of the reaction mixture)
was required to allow the saccharide and acyl donor to mix
effectively. Saccharide substrates studied included ethylglucoside,
xylitol, sorbitol, and mannose.
As can be seen from this brief glimpse of practical work that is
currently being done in this area, the fundamental problem of
physical incompatibility of the feedstock materials remains a large
barrier to efficient exploitation of enzyme esterification. In
addition, the limited temperatures that commercially available
enzymes can withstand may make for more selective reactions, but
at the expense of reaction rate. This, coupled with the expense of
the enzymes themselves, makes the possibility of industrial
utilization of limited attractiveness at present.
IX
Summary
The purpose of this chapter has been to highlight the chemistry,
product composition, and technology limits of polyol fatty acid
ester surfactants. Although the creation of surfactant products from
readily available polyol and fatty acid feedstocks can be easily
carried out, this ease of reaction gives rise to little structural
discrimination. A fundamental problem is therefore inherent in the
chemistry. While an idealized ester surfactant structure may be for
a polyol with only one fatty acid group attached, reaction of 1 mole
of polyol with 1 mole of fatty acid will not give 1 mole of
monoester. It will ordinarily give a mixture of a free polyol, mono-
and polyesters. It should also be remembered that the fatty acids
usually employed are also mixtures and not single-isomer
feedstocks.
 Page 237
In addition to the fundamental random nature of the reaction
described above, further complicating factors are evident for the
families of surfactants described in the previous sections.
1. Glycerol features both primary and secondary hydroxyl groups,
and esterification of the former is much greater than the latter. This
difference in esterification ability holds true for all polyol
substrates with a mixture of such hydroxyls.
2. Polymerization of glycerol to give the polyglycerol polyol does
not proceed in an entirely linear manner, and some cyclic species
are evident. The polyol again features primary and secondary
hydroxyls.
3. Sorbitan esters feature a wide variety of ester types, based on a
number of internally dehydrated sorbitol structures. Full
characterization has so far proved very difficult.
4. The conversion of sucrose into fatty acid esters remains an area
that has promised much, but delivered little to date, due to physical
processing problems.
In contrast to the existing technologies described above, the
possibility of using enzyme catalysts to form much more well-
defined ester structures does offer an interesting field of study.
Although so far processing has remained time consuming,
difficult, and costly, it will become progressively cheaper and more
commercially attractive to carry out over time However, given the
cost competitiveness of the established polyol ester surfactants
ranges, this newer technology may only prove to be of utility in
specialist application areas. Overcoming some of the inherent
physical processing problems for some substrates has also not
been completely achieved.
It should be remembered that the commercial ranges of product,
although perhaps multicomponent mixtures, are nevertheless made
in well-controlled ways in order to give reproducible application
results. The lack of simple structural discrimination in the ester
surfactant chemistry should not be seen as negating either the usual
good standard of manufacture, or the proven value in use of these
materials.
In essence, the major commercial ranges of polyol fatty acid ester
surfactants are still those based on glycerol and sorbitol. Their
limiting low HLB values easily be overcome by the addition of
ethylene oxide. These ranges therefore remain the backbone of this
area of surfactant chemistry. Although newer technology and
product ranges may be developed over time, they will need to be
competitive with this well-established and cost-effective baseline.
References
1. J. J. Lewis, in Preservation of Surfactant Formulations (F. F.
Morpeth, ed.), Blackie, Glasgow, 1995, Chapter 4.
 Page 238
2. E. Fritz, in Fatty Acids in Industry (R. W. Johnson and E. Fritz,
eds.), Marcel Dekker, New York, 1989, Chapter 3.
3. M. Aslam, G. D. Torrence, and E. G. Zey, in Kirk-Othmer
Encyclopedia of Chemical Technology, Vol. 9,4th ed. Wiley, New
York, 1994, pp 758759. 1994.
4. J. D. Brandner and R. L. Birkmeier J. Am Oil Chemists Soc.
41:367(1964).
5. K. D. Tau, V. Elango, and J. A. McDonough, Kirk-Othmer
Encyclopedia of Chemical Technology, Vol 9, 4th ed. Wiley, New
York, 1994, pp 798799.
6. A. Cahn and J. L. Lynn, in Kirk-Othmer Encyclopedia of
Chemical Technology, Vol 22, 3rd ed. Wiley, New York, 1983, pp
367373, 1983.
7. M. Ash and I. Ash, Condensed Encyclopedia of Surfactants,
Chemical Publishing Co., USA, 1989.
8. Ref. 3, pp. 760761.
9. T. P. Hilditch and J. G. Rigg, J. Chem. Soc. 1774 (1935).
10. H. Saudinger and H. Schwalenstoecker, Chem. Ber. 68:727
(1935).
11. D. Stern (ed.), Bailey's Industrial Oil and Fat Products, Vol.
2, 4th ed. Wiley, New York, 1982, pp. 97113.
12. Ref. 11, pp. 113127.
13. N. O. V. Sonntag, J. Am. Oil Chemists Soc. 59:795A (1982).
14. N. H. Kuhrt, E. A. Welch, and F. J. Kovarik, J. Am. Oil
Chemists Soc. 310 (1950).
15. F. R. Benson, in Nonionic Surfactants (M. J. Schick, ed.),
Surfactant Science Series, Vol. 1, Marcel Dekker, New York, 1967,
Chapter 9.
16. R. T. McIntyre, J. Am. Oil Chemists Soc. 56:835A (1979).
17. N. Garti, A. Aserin and B. Zaidman, J. Am. Oil Chemists Soc.
58:878 (1981).
18. P. Seiden and J. B. Martin, U.S. Patent 3,968, 169 to the Procter
and Gamble Company (1975).
19. M. R. Sahasrabudhe, J. Am. Oil Chemists Soc. 44:376 (1967).
20. T. N. Kumar, Y. S. R. Sastry, and G. Lakshminarayana, J.
Chromatogr. 298:360 (1984).
21. H. Sebag, GB Patent 2, 168, 348 to L'Oreal (1984).
22. K. S. Dobson, K. D. Williams, and C. J. Boriack, J. Am. Oil
Chemists Soc. 70: 1089 (1993).
23. K. Bock, C. Pederen and H. Thogersen, Acta Chem. Scand.
B35:441 (1981).
24. P. F. Vlad and N. D. Ungur, Synthesis 217 (1983).
25. Z. Cekovic, J. Serb. Chemists Soc. 51:205 (1986).
26. R. Barker, J. Org. Chem. 35:461 (1970).
27. K. R. Brown, U. S. Patent 2,322,820 to Atlas Powder Company
(1939).
28. S. Ropuszynski and E. Sczesna, Tenside Surf. Det. 22:190
(1985).
29. S. Ropuszynski and E. Sczesna, Tenside Surf. Det. 27:350
(1990).
30. Z. Wang and M. Fingas, J. High Resolut. Chromatogr. 17:15
(1994).
31. Z. Wang and M. Fingas, J. High Resolut. Chromatogr. 17:85
(1994).
32. H. Stuehler, Ger. patent DE 3,240,892 to Hoechst (1982).
33. P. Bickert, Ger. patent DE 3,623,371 to Huels (1986).
34. G. D. Gruetzmacher, J. Raggan, and B. Wlodecki, WO Patent
93/00016 to Pfizer (1992).
35. G. Fleche and M. Huchette, Starch 38:26 (1986).
36. P. Stoss, P. Merrath, and G. Schlueter, Synthesis 174 (1987).
37. R. U. Lemieux and A. G. Mclnnes, Can J. Chem. 88:136 (160).
 Page 239
38. W. N. Haworth and L. F. Wiggins, GB Patent 600, 870 to
Edgbaston University (1946).
39. J. B. Martin, U.S. Patent 2,831,855 to Procter and Gamble
(1958).
40. N. B. Tucker, U.S. Patent 2,831,856 to Procter and Gamble
(1958).
41. L. I. Osipow and W. Rosenblatt, U.S. Patent 3,480,616 to
University of Nebraska (1969).
42. L. I. Osipow and W. Rosenblatt, U.S. Patent 3,644,333 to
University of Nebraska (1972).
43. K. J. Parker, R. A. Khan, and K. S. Muffi, GB Patent 1,399,053
to Tate and Lyle (1973).
44. H. J. W. Nieuwenhuis and G. M. Viomen, EPA 190, 779 to
Cooperatieve Vereniging Suiker Unie(1986).
45. UK Patent 1,332,190 to Dai-Ichi Kogyo Seiyaku (1970).
46. F. H. Mattson and R. A. Volpenheim, U.S. Patent 3,600,186 to
Procter and Gamble (1971).
47. S. Matsumoto, Y. Hatakawa and A. Nakajima, U.S. Patent
5,144,022 to Dai-Ichi Kogyo Seiyaku (1990).
48. R. Khan and H. F. Jones, in Chemistry and Processing of
Sugarbeet and Sugarcane (M. A. Clarke and M. A. Godshall,
eds.), Elsevier, Amsterdam, 1988, Chapter 23.
49. Ref. 15, p 270.
50. A. R. Macrae, in Microbial Enzymes and Biotechnology (W. N.
Fogarty, ed.), Applied Science, Ann Arbor, 1983, Chapter 5.
51. P. H. Nielsen, H. Malmos, Ture Damhus, B. Diderichsen, H. K.
Nielsen, M. Simonsen, H. E. Schiff, A. Oestergaard, H. S. Olsen, P.
Eigtved, and T. K. Nielsen, in Kirk-Othmer Encyclopedia of
Chemical Technology, Vol. 9, 4th ed., Wiley, New York, 1994 pp.
567620.
52. W. M. Linfield, R. A. Barauskas, L. Silvieri, S. Serota, and R.
W. Stevenson, J. Am. Oil Chemists Soc. 61: 191 (1984).
53. M. M. Hoq, T. Yamane, and S. Shimizu, J. Am. Oil Chemists
Soc. 61:776 (1984).
54. F. X. Malcata, H. R. Reyes, H. S. Garcia, C. G. Hill, and C. H.
Amundsen, J. Am. Oil Chemists Soc. 67:890 (1990).
55. K. Holmberg and E. Osterberg, J. Am. Oil Chemists Soc.
65:1544 (1988).
56. K. Holmberg, B. Lasser, and M.-B Stark, J. Am. Oil Chemists
Soc. 66:1796 (1989).
57. S. S. Roy and D. K. Bhattacharyya, J. Am. Oil Chemists Soc.
70:1293 (1993).
58. A. Zaks and A. T. Gross, U.S. Patent 5,316,927 to Opta Food
Ingredients (1992).
59. G. P. McNeil, S. Shimizu, and T. Yamane, J. Am. Oil Chemists
Soc. 67:779 (1990).
60. G. P. McNeil, and T. Yamane, J. Am. Oil Chemists Soc. 68:6
(1991).
61. K. Kitano, R. Iwasaki, N. Mori, H. Sasamoto, and T.
Akamatsu, EPA 407, 959 to Lion Corporation (1989).
62. M. Berger, K. Laumen, and M. P. Schneider, J. Am. Oil
Chemists Soc. 69:955 (1992).
63. M. Berger, and M. P. Schneider, J. Am. Oil Chemists Soc.
69:961 (1992).
64. N. O. V. Sonntag, in Fatty Acids in Industry (R. W. Johnson
and E. Fritz, eds.), Marcel Dekker, New York, 1989, Chapter 2.
65. J. B. Jones, Aldrichemica Acta 26:105 (1993).
66. M. J. Hills, I. Kiewitt, and K. D. Mukherjee, J. Am. Oil
Chemists Soc. 67:561 (1990).
 Page 240
67. Z-Y Li and O. P. Ward, J. Am. Oil Chemists Soc. 70:745
(1993).
68. H. Heino, T. Uchibori, T. Nishitani, and S. Inamasu, J. Am. Oil
Chemists Soc. 61:1761 (1984).
69. S. Riva, J. Chopineau, A. P. G. Kieboom, and A. M. Klibanov,
J. Am. Oil Chem. Soc. 110:584 (1988).
70. J. Chopineau, F. D. McLafferty, M. Therisod, and A. M.
Klibanov, Biotechnol Bioeng 31:208 (1988).
71. H. Miyake, M. Kurahashi, H. Toda, K. Kitano, and T. Mori,
EPA 413, 307 to Lion Corporation (1990).
72. H. Andoh, M. Tamiya, and R. Iwasaki, EPA 507, 323 to Lion
Corporation (1992).
73. O. Kirk, F. Bjorkling, and S. Godtfredsen, WO 90/09451 to
Novo-Nordisk (1989).
74. M. Barfoed and J. P. Skagerlind, WO 94/12651 to Novo-
Nordisk (1992).
 Page 241

9
Nonionics As Intermediates for Ionic Surfactants
Ansgar Behler, Karlheinz Hill, Andreas Kusch,*
Stefan Podubrin, Hans-Christian Raths, and
Günter Uphues
Henkel KGaA, Düsseldorf, Germany

I. Introduction 242
II. Sulfates 243
A. Sulfated Alkyl Polyoxyethylene Alcohols (Alkyl
243
Ether Sulfates)
B. Sulfated Fatty Acid Monoglycerides 249
C. Sulfated Alkanolamides 252
D. Miscellaneous 253
III. Sulfonates 255
A. Sulfosuccinates 255
B. Sulfonated Polyoxyethylene Alkenols 257
IV. Phosphates 259
A. Structures and Preparation Methods 259
B. Analytical Methods 263
C. Properties and Applications 264
V. Carboxylates 266
A. Preparation 266
B. Analytical Methods 269
C. Properties and Applications 270
D. Environmental and Toxicologic Aspects 272
VI. Quaternary Ammonium Compounds 273
Appendix: Trade Names and Suppliers 279
References 281

*Current affiliation: Boehringer Ingelheim KG, Ingelheim au Rhein,

Germany
 Page 242

I
Introduction
The surfactant properties of nonionic surfactants (see previous
chapters) are modified or further improved with regard to certain
applications by introduction of an ionic group. This derivatization
is usually carried out by reaction at the terminal hydroxyl group of
the nonionic surfactant, typically being a polyoxyethylene or a
glycerol derivative, to build up sulfates, phosphates, and
carboxylates as the anionic products [Eq. (1)] [1,2]. The most
important feedstocks for these reactions are the polyoxyethylene
alcohols or alkyl polyoxyethylene alcohols. It is estimated that the
annual growth rate of polyoxyethylene alcohols as the typical
nonionic surfactant is 4% [3]. The major reason is the gradual
substitution of the polyoxyethylene alkylphenols, which are still
used in certain regions of the world. This development, of course,
affects the use of the corresponding ionic derivatives as well.

In the case of sulfated products, nowadays the polyoxyethylene

alkyl sulfates are by far the most important group of nonionic
derivatives. They are mainly used in dishwashing liquids and
cosmetics formulations, such as shampoos and shower baths, in
combination with other mild surfactants. On the other hand, the
sulfated polyoxyethylene alkylphenols lost their important role of
20 years ago, mainly because of less favorable ecological and
toxilogic properties compared to the sulfated products based on
nonaromatic straight alkyl chains [2]. Phosphates and carboxylates
as nonionic derivatives are produced on the basis of
polyoxyethylene alcohols as well. They are mainly used in
technical applications, such as the textile and fiber industries.
Another method of producing an anionic surfactant is the sulfation
of unsaturated nonionic species. Under certain conditions, the
sulfating agent reacts with the double bond in the alkyl chain of the
starting molecule to form sulfonates as the final products.
Examples are sulfonated polyoxyethylene alcohols and
sulfosuccinates.
Cationic surfactants or quaternaries based on nonionics are formed
by a quaternization reaction of a polyoxyethylene amine with a
quaternization reagent R3X [(Eq. 2)]; however, further
modifications of this reaction are known and are discussed in the
following in detail. Depending on their structure, these products
cover a broad range of applications, mainly in the textile, fiber, and
cosmetic industries [4].

Derivatives from nonionic surfactants based on carbohydrates,

such as sorbitane esters, alkyl polyglycosides, and fatty acid
glucamides are not part of the following review.
 Page 243
A list of some of the major trade names and their respective
manufacturers/suppliers is included in the Appendix. It must be
emphasized that this list is not complete and that the reader is
encouraged to consult the literature for more complete summaries.
II
Sulfates
A
Sulfated Alkyl Polyoxyethylene Alcohols (Alkyl Ether Sulfates)
1
Introduction
Through conversion of alkyl polyoxyethylene alcohols with
sulfation agents, alcohol ether sulfates are obtained, presumably
the most significant derivatives of the alkyl polyoxyethylene
alcohols. Approximately 34% of alkyl polyoxyethylene alcohols
are processed into alcohol ether sulfates. The estimated annual
world production of alcohol ether sulfates (AES) in 1993 was
about 750,000 t [5].
This product group has been known since the 1930s and was
intensively used by the former IG Farben, which, however, mainly
utilized alkylphenol or alkylnaphthol as the alcohol. The
importance of these phenol-based products for applications in
detergents has sharply declined due to increasing ecological
awareness and is only dealt with marginally in this chapter.
Emphasis is placed on products that are based on aliphatic
alcohols.
2
Sulfur Trioxide As Sulfation Agent
On a large technical scale ether sulfates are mainly produced in a
continuous process through mild conversation with sulfur trioxide
in a multitube falling film reactor [6]. Usually sulfur trioxide (SO3)
is obtained by controlled combustion of sulfur to sulfur dioxide
(SO2) and subsequent conversion into SO3 at the vanadium
pentoxide or cesium oxide contact. An alternative that can be used
in small pilot plants is the evaporation of SO3 from oleum, where
sulfuric acid results as a residue, or even from liquid SO3. Sulfur
trioxide is highly reactive, so that conversion with SO3/air takes
place in a dilution of 35 vol%. The air should be well dried (dew
point <-60°C) in order to avoid the formation of sulfuric acid. The
reaction with SO3 primarily leads to a pyrosulfate:

The primarily obtained pyrosulfate is metastable and decomposes

very rapidly in the presence of further alcohol into the desired
sulfuric acid half-ester:

With DH = -150 kJ/mole the reaction enthalpy is very high. Usually

in the following step the sulfuric acid half-ester RO(C2H4O)xSO3H
is converted with
 Page 244
an aqueous solution of the respective base, e.g., NaOH, KOH,
NH4OH, or with an organic amine into the desired salt:

The process is continuous and the short residence time between

formation of the sulfuric acid half-ester and neutralization
contributes to the high conversion rate up to 98%. Since sulfur
trioxide is oxidative, under unfavorable conditions and with
qualitatively inadequate raw materials discolorations (yellow and
brown) of the product may occur; they can be eliminated in a
bleaching step (preferably with H2O2) after neutralization.
Ether sulfates are stable in the alkaline range but are hydrolyzed in
an acid medium (autocatalytic reaction). Often phosphate or citrate
buffers are added to the finished products for pH stabilization.
Further additives used in technical products are EDTA for
complexing of traces of iron; preservation with formaldehyde and
adjustment of the viscosity through electrolyte, polyethylene
glycols, or alcohols.
The increasing consumer awareness with regard to product safety
and ecological compatibility leads to a continuous optimization of
the product qualities, e.g., reduction of unwanted byproducts [7].
One byproduct during sulfation of alkyl polyoxyethylene alcohols
is dioxane; in 1986, the known carcinogenic effect was discussed
heatedly. The dioxane quantity can be reduced to <10 ppm,
referring to 100% product, by means of technical measures such as
conscientious process optimization and aftertreatment. These
residual concentrations do not involve any health risk for the
consumer [8].
Ether sulfates are usually obtained as aqueous pastes with
concentrations of approximately 30 wt% or approximately 70 wt%.
This is due to the viscosity behavior of the aqueous products,
which is represented in Fig. 1 dependent on the concentration [9].
Processing is in principle possible below 30 wt% and in the
lamellar liquidcrystal range around 70 wt%. The viscosity
maximum in the hexagonal-liquid crystalline range is
approximately at 4050 wt%, so that such products are solid at room
temperature. This phase behavior can be explained as follows:
ether sulfates form spherical micelles at low concentrations; from
>2030 wt% they change into rod-like micelles then aggregate into
compact hexagonal phases. At higher concentrations
(approximately 70 wt%) a lamellar structure develops and the
viscosity decreases.
3
Other Sulfating Agents
In addition to sulfur trioxide sulfuric acid (H2SO4), chlorosulfonic
acid (ClSO3H), and amidosulfonic acid (H2NSO3H, mainly for
alkylphenol ether sulfates) can also be used on a technical scale.
On a smaller scale (mainly in the laboratory) complexes of the SO3
with bases are used; here the reactivity of the
 Page 245

Fig. 1
Viscosities of aqueous solutions of dodecyl/tetradecyl polyoxyethylene [2]
sodium sulfate.
SO3 is reduced. For example, complexes with pyridine,
trimethylamine, dimethylformamide, or dioxane can be utilized. In
this context chlorosulfonic acid is probably the most important
reagent. During the reaction hydrochloric acid (HCl) is produced
and removed from the reaction mixture efficiently by degassing:

The advantage of chlorosulfonic acid sulfation is that the technical

apparatus needed is relatively simple. Disadvantages are the high
corrosiveness of the resulting HCl gas and the content of chloride
in the neutralized product, which can have an influence on the
viscosity. Chlorosulfonic acid is particularly suitable for sample
preparation in the laboratory. In the case of high-melting products
or for conversion under very mild conditions, inert solvents such
as chloroform, melthylene chloride, tetrachloroethylene,
dichloroethane, and, providing they are soluble, aliphatic
hydrocarbons may also be used.
4
Properties
The sulfation of polyoxyethylene alcohols results in increased
hydrophilicity of these products, which corresponds to an
additional six or seven oxyethylene (EO) units in the starting
molecule. The products show a characteristic anionic character,
i.e., their foaming behavior is better, they are highly soluble in hot
water, the electrolyte content has a strong influence on the phase
behavior, and the processability in powder products is improved.
 Page 246
The most commonly used ether sulfates are based on C12/C14 or
C12/C18 primary native fatty alcohols or on similar synthetic
alcohols (Ziegler or oxosynthesis). The properties of these
products are not dependent on the raw material source
(oleochemical or petrochemical) [10]. Alkyl ether sulfates in this
range of carbon chain length with degrees of ethoxylation of 14
display an especially distinct foaming power. Unlikely many other
anionic surfactants, these products are clearly insensitive to water
hardness. The foam characteristics of these products can be
influenced favorably by addition of alkanolamides, alkylbetaines,
and alkylamidobetaines.
From the dermatologic point of view the skin compatibility of
alkyl ether sulfates is better than that of the alkyl sulfates, the
optimum skin compatibility being approximately 4 EO. Most
technical products have EO degrees between 2 and 3 due to a
compromise between foam performance, solubility, and
thickening, on the one hand, and optimum skin compatibility, on
the other hand.
The counterion also influences the skin compatibility; the skin
compatibility of ammonium salts and salts with other amines is
more favorable. Magnesium salts additionally show advantages
with regard to cleaning performance and foam [11,12].
The interfacial activity of the alkyl ether sulfates can be controlled
through variation of the carbon chain length and the degree of
ethoxylation. The CMC (critical micelle formation concentration)
decreases with an increasing EO degree and with an increase in the
alkyl chain length. The solubility is improved by introduction of an
additional EO group. Usually the solubility of the ether sulfates is
characterized by the Krafft temperature which, according to the
International Organization of Standardization (ISO), is the
temperature at which the solubility of an ionic surfactant suddenly
increases. At this temperature the solubility reaches the CMC. The
consistency of the aqueous products can be adjusted through
addition of an electrolyte. Sodium chloride, for instance, is more
efficient than sodium sulfate. The temperature dependence of the
viscosity is highly characteristic.
5
Fields of Application
On account of their good foaming power alkyl ether sulfates are
preferentially used in foam baths, shampoos, and manual
dishwashing detergents; in particular, in combination with
sulfosuccinates, amphoteric surfactants, and amine oxides, they
have synergistic effects with regard to skin compatibility.
Products with alkyl chain lengths of C12C18 and one to four EO
units are emulsifiers for oils and fragrances. Apart from the
excellent foaming power of these low-ethoxylated products, they
are highly efficient in the reduction of surface tension; their
thickening behavior and the cleaning performance is good [13].
The combination with fatty acid monoalkanolamides has a foam
stabilizing effect.
 Page 247
Through addition of fatty acid diethanolamide and sodium
chloride the viscosity of a diluted ether sulfate solution can be
increased. Alternatively, fatty alkyl polyoxyethylene alcohols with
narrow-range homolog distribution (NRE) can be utilized (e.g.,
C12/C14 + 2.5EO NRE) [14]. The viscosity of alkyl ether sulfates
can also be increased by addition of protein hydrolyzates [15].
Ether sulfates based on alkyl polyoxyethylene alcohols with
narrow-range homolog distribution show a lower content of alkyl
sulfate and have advantages with regard to their thickening ability
[1619]. The improved skin compatibility, which can be expected
because of the lower alkyl sulfate content, has so far not been
detected.
Further areas of application are light-duty and liquid detergents
and foam cleaners.
Short chain products can be used as hydrotropes, in particular in
alkaline cleaners. Products with branched alkyl chains are
sometimes advantageous with regard to wetting and washing
properties; however, their biodegradability is poor.
6
Alkylphenol Ether Sulfates
Products on the basis of nonylphenyl and dodecylphenyl
polyoxyethylene (4, 6) alcohols are of particular technical
importance in this context. Preparation is in principle also possible
with sulfur trioxide and chlorosulfonic acid [20]; however, usually
amidosulfonic acid is used in order to avoid sulfonation of the
aromatic ring [Eq. (7)]:
Sulfation with sulfuric acid also takes place without formation of
ring sulfonates [21,22]. Typical areas of application are light-duty
detergents and dishwashing detergents. However, they are
increasingly losing importance on account of their relatively weak
biodegradibility.
7
Analysis of Alkyl Ether Sulfates
The combination of oxyethylene and sulfate groups in one
molecule makes the complete analysis of these products more
complex than, say, the analysis of alcohol sulfates. With regard to
the proportion of oxyethylated alcohol, the analysis after acid
hydrolysis of the sulfate groups established for alkyl
polyoxyethylene alcohols is feasible. If the hydrolysis is carried out
with hydrogen iodide (HI), the polyoxyethylene chain can be
degraded into diiodoethane, which is thermally unstable and splits
off iodine; the iodine can be back-titrated with sodium thiosulfate
and provides information about the number of EO units. This is a
standard method for the determination of the EO content of
nonionic surfactants [23]. Anionic active matter, unsulfated matter,
sulfate, and chloride content as well as the water content are the
typical specifications of alcohol ether sulfates.
 Page 248
Dioxane traces can be determined via GC head space. The
complete analysis of this product class is described in standard
methods of the ISO [24] or the Standard Methoden der Deutschen
Gesellschaft für Fettwissenschaft e.V. (German Society for Fat
Science DGF) [25].
The most important method is that for the determination of the
anionic active matter, which will be described in detail. This
method was developed by and named after Epton [26]. The Epton
titration is also known as two-phase titration in which the anionic
surfactant in diluted sulfuric acid solution is titrated with
cetylpyridinium bromide, a cationic surfactant, in the presence of
an indicator, e.g., methylene blue. The principle is based on the ion
pair formation between the anion and the cationic surfactant,
which is soluble in an organic medium such as chloroform. The
anionic surfactant and methylene blue form a blue complex that is
perceived visually as a coloring of the organic phase. In the course
of titration methylene blue is displaced by the cationic surfactant
and leads to a coloring of the aqueous phase. When the endpoint is
reached, both the aqueous and the organic phases show the same
blue color.
This standard method has been subjected to many modifications
because there are a large variety of cationic surfactants, dyes, and
solvents. Often hyamine is used as a cationic surfactant and a
mixed system of disulfine blue and dimidium bromide [(DGF-H-
III 10 (1992), standard method of the DGF)] is the indicator [27].
In particular because of solvents such as chloroform there is a
strong tendency in this area to develop new methods, e.g.,
potentiometric titration in combination with ion-selective
electrodes [2830] or polarographic methods.
Thin-layer chromatography (TLC) and high-pressure liquid
chromatography (HPLC) in combination with ion exchanger
columns [31] and ion pair chromatography are also frequently
used [32,33]. The determination of the unsulfated matter via
simple extraction of the unsulfated proportion from an acid
solution with one organic solvent usually fails in the case of ether
sulfates because of the high hydrophilicity of the unsulfated alkyl
polyoxyethylene alcohols.
1,4-Dioxane, resulting as a byproduct, is usually detected by means
of GC head space analysis [34]. Instrumental analysis such as
nuclear magnetic resonance (NMR) or infrared spectroscopy is
only used in very specific cases.
8
Environmental Aspects
(a)
Biodegradability
Linear alkyl ether sulfates are surfactants with good degradability,
under both aerobic and anaerobic conditions [35,36]. Although the
structure of ether sulfates resembles that of primary alkyl sulfates,
ether sulfates are not cracked by sulfatases. The first catabolic step
is ether hydrolysis [37,38]. Starting from the unsulfated end, the
hydrophilic fractions are shortened successively under separation
of glycolic acid molecules until finally the sulfate is released.
 Page 249
One distinguishes primary degradation with a loss of surfactant
properties and total decomposition, i.e., final mineralization. The
loss of surfactant properties can be determined via the
decomposition of the methylene blue active substance (MBAS; see
Epton titration); the ether sulfates in the above mentioned range,
which is especially interesting for application, achieve values of
>96%. For final degradation there are individual screening tests,
e.g., determination of the biological oxygen demand (BOD) and
also sum parameter analysis methods such as the coupled units
test, where ether sulfates reach >60% for final degradation, usually
even >70%. Typically, branching in the alkyl chain leads to slower
degradability rates compared to the linear molecules.
(b)
Toxicity
With LD50- values of 400010,000 mg/kg the toxicity for mammals
is low. The toxicity declines with an increasing EO degree.
The aquatic toxicity also decreases with an increasing EO degree,
with LC50 = 1.420 mg/L for fish and EC50 = 150 mg/L for
daphniae [39].
B
Sulfated Fatty Acid Monoglycerides
In view of a growing environmental awareness of the consumer,
the development of surfactants on the basis of renewable raw
materials is constantly gaining in importance. Monoglyceride
sulfates (Fig. 2) are anionic surfactants that, in terms of their
organic backbone, can be obtained exclusively on the basis of
oleochemical raw materials. A large variety of processes are
available for the preparation of monoglyceride sulfates. As early as
1935 Colgate Palmolive Peet Co. patented a manufacturing process
for monoglyceride sulfate [40]. In the same year, Colgate launched
a soap-free shampoo formulation under the brand name ''Halo"
making use of monoglyceride sulfates as a surfactant component.
Accordingly, monoglyceride sulfates are among the first synthetic
surfactants used in cosmetics. In 1954 Colgate-Palmolive claimed a
continuous process for the preparation of monoglyceride sulfates
[41]. In this case, in a first reaction step glycerol is converted with
oleum to the corresponding acid glycerol sulfuric acid half-ester.
This intermediate product is then transesterified with a triglyceride,
usually coconut oil, thus leading to monoglyceride

Fig.2
Molecular formula of
monoglyceride sulfate
sodium salt (R = alkyl).
 Page 250

Fig. 3
Reaction pathway to fatty acid monoglyceride sulfates.
sulfate (the mechanism of this conversion is described below). The
resulting products were, for example, applied in the household
cleaner "Vel," which was marketed by Colgate in the 1950s and
1960s. The industrial production process is a multistep process that
uses 20% oleum as a sulfation agent. In the first reaction step,
glycerol is converted with oleum in such a way that all three
hydroxyl groups of the glycerol are sulfated, thus forming a
glycerol trisulfuric acid halfester (Fig. 3). In a second reaction step
this glycerol trisulfuric acid half-ester is converted with a
triglyceride, usually hardened coconut oil (molar ratio 2:1).
Similar to a transesterification reaction, sulfuric acid half-ester
functions are now exchanged for a fatty acid residue, so that from
two molecules of glycerol trisulfuric acid half-ester and one
triglyceride molecule three molecules of monoglyceride-disulfuric
acid half-esters are obtained. According to Colgate the sulfuric acid
half-ester function in the b-position with the fatty acid ester
function is unstable. Therefore, after neutralization, e.g., with
ammonia or caustic soda solution, a 1,3-fatty acid monoglyceride
sulfate is obtained in a highly selective process. Due to the high
oleum excess during sulfation of the glycerol, large quantities of
sodium sulfate are formed in the neutralization step. The unwanted
salts are removed from the monoglyceride sulfate by means of
extraction process as follows: By adding alcohol with a low boiling
point, e.g.,
 Page 251
ethanol, to the aqueous, neutralized surfactant solution, two liquid
phases are formeda heavier aqueous phase that is saturated with
sodium sulfate and an alcohol phase that contains the
monoglyceride sulfate. The salt-containing aqueous phase is
separated and the surfactant is obtained by evaporation of the
ethanol. The resulting product yields the desired monoglyceride
sulfate in a purity of approximately 80%; byproducts are partial
glycerides and fatty acid.
Patent literature describes further manufacturing processes for
monoglyceride sulfates: Monsanto claims a process for the
sulfation of glycerol monolaurate with sulfur trioxide (SO3) in
liquid sulfur dioxide (SO2) [42]. Colgate also describes a further
development of the original manufacturing process; according to
the new process, glycerol is initially sulfated with 2 moles SO3 and
subsequently converted with oleum to obtain the glycerol
trisulfuric acid halfester. This mixture is then transesterified with
coconut oil and neutralized [43]. The literature [44] provides an
overview of the state of the art for the preparation of
monoglyceride sulfates until the beginning of the 1970s. In more
recent times, attempts were also made to further develop the
process originally invented by Colgate. As an example, Wako Pure
Chemical Ind. in Japan claimed a process in 1975 for the
preparation of pure monoglyceride sulfates via oleum sulfation
with monoglyceride and subsequent extraction with isobutanol
[45]. In 1978 Riken Vitamin Oil claimed the conversion of glycerol
with chlorosulfonic acid and subsequent transesterification with
triglycerides [46]. In EP 0267518 Hoechst describes a process for
the sulfation of monoglycerides with SO3 in triethylamine as a
solvent [47]. In 1988 Colgate described a new process for the
preparation of monoglyceride sulfates via the sulfation of glycerol
with chlorosulfonic acid in chloroform as a solvent and
subsequent transesterification with fatty acid or fatty acid ester
[48]. In the early 1990s, Henkel developed a continuous process
for the preparation of monoglyceride sulfates [49]. In this process,
technical grade monoglycerides are converted into the
corresponding monoglyceride sulfates with gaseous SO3 in a
continuous falling film reactor.
Monoglyceride sulfates, in particular those based on coconut oil,
are soluble, high-foaming anionic surfactants. They are
distinguished by an excellent skin compatibility, which is
comparable to mild anionic surfactants such as sulfosuccinate or
ether sulfate [50]. On account of these properties, coconut
monoglyceride sulfate was used in a hair shampoo as early as
1935, as mentioned above. In the 1950s and 1960s, the coconut-
based monoglyceride sulfates, which Colgate produced on an
industrial scale for sale under the brand names Arctic Syntex L and
M, and Monad G, were applied in many household products, e.g.,
a household cleaner with abrasive additives [51] or in the
household cleaner Vel. In the United States monoglyceride sulfates
are still used as mild surfactants in syndet soaps [52]. In addition
to lauryl sulfate, monoglyceride sulfates are described as
surfactants for toothpastes/dental care products in combination
with specific active substances [5358]. The excellent skin
compatibility of
 Page 252
monoglyceride sulfates predestines these products for application
in personal care products. A large variety of combinations of
monoglyceride sulfates with other mild surfactants has been
described for this field of application; e.g., combination of
monoglyceride sulfate with phosphoric acid esters [59], with
succinic acid [60], with an aminophosphate surfactant [61] for
skin-cleansing agents and with combinations with amino acids and
amphoteric surfactants for hair shampoos [62].
Detergent mixtures of alkyl polyglycosides with monoglyceride
sulfates show synergistic effects with regard to the washing,
rinsing, foaming, and cleaning power as well as its skin
compatibility [63]. In this combination, highperformance and
especially mild shaving preparations [64] or toothpastes [65] can
be obtained.
C
Sulfated Alkanolamides
1
Preparation
The synthesis of sulfated alkanolamides has been reviewed in a
previous volume of this series [66] comprising literature up to the
early 1970s. Concerning the basic preparation steps for sulfated
alkanolamides, the reference is still up to date [67], so that recent
developments focus on the fields of application and new starting
materials.
To produce amide ether sulfates, alkanolamides may be sulfated
directly or first oxyalkylated and then sulfated, yielding amide
sulfates (1) or amide polyoxyethylene sulfates (2) after subsequent
neutralization with a base as shown in Fig.4.
The most common alkanolamine basis for sulfated alkanolamides
is definitely monoethanolamine [68], although N-alkyl-substituted
as well as branched alkanolamines such as isopropanolamine have
also been used [69]. Apart from

Fig. 4
Reaction paths to amide sulfates and amide polyoxyethylene sulfate.
 Page 253
these monoalkanolamides, polyhydroxyalkanolamides such as
diethanolamides or 2,3-hydroxypropylamides have been prepared
too [70].
The corresponding alkanolamides are derived from (saturated or
unsaturated) C2- to C22-carboxylic acids or hydroxycarboxylic
acids [71], mainly from coconut- or tallow-based feedstocks. A
main drawback of the sulfation process of alkanolamides is the
high viscosity of the sulfation mixture, which may be overcome by
means of a cosulfation with lower molecular weight alcohols [72],
alkanolamines [73], fatty alcohols [74], or oxyethylated fatty
alcohols [75]. Due to a lower sulfation temperature the products
obtained by this route have an improved color. The choice of
cations comprises ammonium (including alkyl-and
alkanolammonium), alkali, and earth alkali metals.
2
Properties and Application
Sulfated alkanolamides are excellent foaming surfactants with
good detergency [76]. Their hydrolytic stability as well as
physicochemical data have been compiled elsewhere [66]. Sulfated
alkanolamides are used almost exclusively as cosurfactants
together with anionic, nonionic, and sometimes cationic
components.
Cosmetics (body, hair, and baby care) is the main field of
application according to numerous patents (during the last 5 years
predominantly Japanese companies have dealt with this issue)
because of the low skin irritancy of alkanolamide sulfates [77a],
which had already been noticed during the late 1960s [77b]. The
same reason applies for an increasing use of alkanolamide sulfates
in manual dishwashing formulations [78].
Alkanolamide sulfates are good lime soap dispersants and have
thus been used in detergent compositions suitable for hard water
applications [79].
Technical applications concerning emulsion polymerization of
ethylenically unsaturated monomers [80] or leather preparation
[81] relate to the favorable emulsifying properties of sulfated
alkanolamides. Sulfated alkanolamides have also been used as
mold release [82] or antiadhesive reagents for rubber [83].
Together with cationic surfactants alkanolamide sulfates may serve
as dehydration promotion for the production of granular slag [84].
D
Miscellaneous
1
Hydroxyalkyl Polyoxyethylene Sulfates
Alkyl polyoxyethylene-2-hydroxyalkyl ethers (2), which
themselves present an interesting class of low-foaming nonionics,
are raw materials for the corresponding alkyl polyoxyethylene-2-
hydroxyalkyl ether sulfates (hydroxyether sulfates) (3) (Fig. 5).
These products are available by acid- or base-catalyzed ring
opening of an a-epoxide (1) with an oxyethylated alcohol. The
resulting secondary alcohol (2) can subsequently be sulfated in the
usual manner to ether sulfate (3). These products show a good
biodegradability and can be adjusted
 Page 254

Fig. 5
Reaction scheme for the synthesis of alkyl polyoxyethylene-2-hydroxyalkyl
ether sulfates.

concerning their application profile by variation of the starting a-

epoxide or the polyoxyethylene alcohol in a broad range. No
commercial application is known so far [8587].
2
Glycerol Ether Sulfates
Glycerol, which is mainly obtained as a "coupled" product in the
conversion of fats and oils into fatty acid methyl esters, can be
converted to glycerol ethers by
 Fig. 6
Telomerization reaction of glycerol with butadiene.
 Page 255

Fig. 7
Sulfation of glycerol octyl ether.
telomerization with butadiene in the presence of a
palladium/triphenylphosphine complex as catalyst [88], yielding a
mixture of glycerol mono-, di-, and trioctadienyl ethers (Fig. 6).
The saturated ethers are available by hydrogenating the resulting
mixture or the purified mono- and diethers in presence of
palladium-supported charcoal (Pd/C) as catalyst [89].
The glycerol monoether is structurally similar to a monoglyceride,
which is an interesting nonionic emulsifiers and also a raw material
for sulfation (Sec II.B). The glycerol mono- and dioctyl can be
converted to the corresponding glycerol octyl ether sulfates by
sulfation with SO3/air (Fig. 7).
An alternative route to prepare glycerol ether sulfates starts with
the reaction of fatty alcohol or fatty alcohol ethoxylate with
epichlorohydrin, followed by sulfation [90]. Glycerol ether sulfates
are described as high foaming and good biodegradable surface
active materials. They are not yet produced on a commercial scale.
III
Sulfonates
A
Sulfosuccinates
Sulfosuccinates (Sulfosuccinic acid esters) are anionic surfactants
that are accessible on the basis of maleic anhydride. One
distinguishes mono- and dialkyl esters of the sulfosuccinic acid
(Fig. 8). Both mono- and diesters are

Fig. 8
Structure of sulfosuccinic acid esters.
R1, R2 = H, alkyl, POE-alkyl.
 Page 256

Fig. 9
Reaction scheme for the synthesis of maleic acid mono- and dialkyl esters.
R = alkyl, POE-alkyl.
obtained in a two-step process. In the first reaction step, maleic
acid anhydride is esterified with compounds containing hydroxyl
groups to the mono- or diester (Fig. 9). While diesters are mainly
produced with alcohols, many different raw materials with
hydroxyl groups are used in the case of monoesters. Fatty alcohols,
fatty acid alkanolamides and its oxethylates are most commonly
used [91]. Usual esterification catalysts such as p-toluenesulfonic
acid are suitable as catalysts for diester production.
In the second reaction step, the maleic acid ester is sulfated with an
aqueous sodium sulfite solution to obtain the corresponding
sulfosuccinate (Fig. 10). In the case of the sulfosuccinic acid
monoester, two regioisomeric sulfosuccinates are possible (Fig.
11). It was detected by 1H NMR analysis that the b position is
preferred during sulfation. The ratio b/a is approximately 4:1 [92].
Sulfosuccinates are used in many different fields of application.
Comprehensive overviews are given in [91, 9395]. Sulfosuccinic
acid dialkyl esters are weakly foaming surfactants with good
wetting power. In particular, products on the basis of octanol or 2-
ethyl hexanol are distinguished by their outstanding wetting
properties. Even at low concentration they can cause a
considerable reduction in the surface tension of aqueous solutions
[94]. Sulfosuccinic acid dialkyl esters on the basis of alcohols with
fewer than nine carbon atoms are water-soluble. Branched alkyl
groups increase the solubility [96]. Because of their good wetting
properties, sulfosuccinic acid dialkyl esters are applied as "rapid
wetting agents" in the textile industries [97]. In fiber technology
these products are used in spinning oils for nylon production.
Furthermore, they are used in agriculture for pesticides as well as
in paint formulations and in the leather industry. With regard to
household products the application of sulfosuc-

Fig. 10
Reaction scheme to sulfosuccinates. R1, R2 = H, alkyl, POE-alkyl.
 Page 257

Fig. 11
Regiomeric isomers of
sulfosuccinic acid monoalkyl
ester. R = alkyl.
cinic acid dialkyl esters is restricted to specific glass cleaners, e.g.,
for spectacle lenses or windscreens as well as carpet shampoos.
In contrast to sulfosuccinic acid dialkyl esters, sulfosuccinic acid
monoalkyl esters are good-foaming surfactants. Especially
products on the basis of oxethylated fatty alcohols, e.g.,
lauryl/myristyl polyoxyethylene (3) alcohol, exhibit an outstanding
skin compatibility [98]. Due to their mildness to skin, large
quantities of sulfosuccinic acid monoalkyl esters are used in
personal care products such as shower gels, shampoos, and skin-
cleaning agents. In particular, they are utilized in mild products
such as baby shampoos or shampoos for sensitive skin. Their
compatibility is very good, not only with regard to sensitive skin
but even on diseased skin [99]. In combinations with anionic
surfactants, e.g., lauryl sulfate or lauryl ether sulfate, sulfosuccinic
acid monoalkyl esters reduce the skin-irritating effect of these
anionic surfactants while maintaining the foaming power [95].
Sulfosuccinic acid monoalkyl esters are very soluble in water and
have a good hard water resistance with a low tendency to form
calcium soaps. They exhibit a high detergency that is
synergistically enhanced in combinations with other surfactants
[100]. On account of the hydrolysissensitive ester bond their
application is limited to a pH range of 68. In the industrial sector
sulfosuccinic acid monoalkyl esters are, for example, used as
emulsifiers for emulsion polymerization. Both the mono-and the
dialkyl esters are readily biodegradable and show low toxicity [91].
B
Sulfonated Polyoxyethylene Alkenols
1
Oleyl Polyoxyethylene Alcohol Sulfonates
In the sulfation of unsaturated polyoxyethylated fatty alcohol,
reaction occurs mainly at the terminal free hydroxyl group under
formation of the corresponding ether sulfate. Internal sulfonates,
which form if the reaction takes place on the CC double bond, are
only obtained subordinately. This compound class of internal ether
sulfonates is accessible by introducing a protective group.
The corresponding oxethylated fatty alcohol acetic acid esters (1)
are formed by esterification of oxyethylated fatty alcohols with
acetic acid and/or acetic anhydride as shown in Fig. 12. If
oxyethylated unsaturated alcohols, such as oleyl alcohol, are used,
the internal CC double bond can be sulfonated with
 Page 258

Fig. 12
Reaction scheme to oleyl ether sulfonates.
gaseous SO3. This leads to oxyethylated oleyl alcohol acetates with
an internal sulfonate group (2). The required internal oleyl ether
sulfonates (3) are obtained by alkaline saponification.
These products combine the features of anionic and nonionic
surfactants. In particular, at higher degrees of oxethylation, the
products have a good foaming

Fig. 13
Reaction scheme for the sulfation of alkenyl polyoxyethylene alkyl ethers.
 Page 259
power and detergency. They are readily biodegradable and show a
good skin compatibility. However, no commercial use is known so
far [101].
2
Alkenyl Polyoxyethylene Ether Sulfonates
Alkyl polyoxyethylene alkyl ethers (4) are accessible by conversion
of alkyl polyoxyethylene alcohol with alkyl halides according to
Williamson (Fig. 13) [102]. If unsaturated polyoxyethylene
alcohols on the basis of oleyl alcohol are used, the products can be
sulfonated with gaseous SO3. In this case, products with an
internal sulfonate group result, i.e., alkene sulfonates (5) and
hydroxyalkanesulfonates (6). Through variation of the alkyl group
and the degree of ethoxylation, products with different property
profile are accessible [102, 103].
IV
Phosphates
A
Structures and Preparation Methods
Phosphates deriving from nonionic surfactants have long been
known. First references trace back to Schöller and Wittwer [104]
as well as Steindorff et al. [105]. The classical methods for
preparing phosphoric acid esters, i.e., by using phosphorus
pentoxide [106], polyphosphoric acid [107], or phosphorus
oxychloride, were applied to the phosphatation of polyoxalkylated
alcohols. Contrary to the half-sulfuric esters the nonionic-based
phosphates are more complex product mixtures, composed mainly
of mono- and diesters and triesters as minor components (Fig. 14).
In the figure, R denotes residues of alcohols, alkylphenols, and
others. In addition, the phosphatation of oxyethylated fatty acids is
also known [108]. It was Nüsslein [109] who reported early on the
wide range of

Fig. 14
Structures of phosphoric acid esters.
 Page 260
TABLE 1 Various Examples of Phosphate Ester Compounds
[109]
Primary, secondary, or tertiary
esters; same alcohol or mixed-
chain-length alcohols
Esters with polyvalent alcohols
made by forming the fatty acid
ester last

Polyesterification

variations for phosphoric acid esters using the different synthesis

methods. They are summarized in Table 1.
The large variety of synthesis procedures have been expressed by a
huge number of publications and patents. Accordingly, only the
fundamental reaction types using the above-mentioned
phosphorylating agents are referred to. For technical and economic
reasons phosphorus oxychloride is used in nearly all cases for the
preparation of triesters [Eq. 8]. In order to prevent the formation
of alkyl chlorides [110], the generated hydrochloric gas must be
removed from the reaction mixture immediately. Tertiary amines
are used preferentially as absorbents [111]; amine salts formed
must be removed by filtration. Phosphorus oxychloride (POCl3)
has also been suggested for the preparation of monoesters
[112,113]. The reaction only succeeds in the presence of large
quantities of nonpolar solvents at low temperatures. The
production of diesters is described by a patent of Kao Corporation
[114], according to which the alcohol component can be reacted
with POCl3 using substoichiometric amounts. To destroy the
mono- and triesters the resulted mixture is treated with alkali
hydroxide. The diesters remain stable.

In industrial and laboratory practice, phosphatation by means of

phosphorus pentoxide is the most important route. The highly
purified reagent exists as a cyclic structure having the sum formula
P4O10. The phosphatation reaction is very complex and may occur
according to Eq. (9). As suggested by König and Langley [115],
pure phosphorus pentoxide reacts spontaneously with 3 moles of
 Page 261
alcohol by forming the triester of a tetrameric phosphoric acid in
the first step. In general, it is recommended to work at a
temperature of 50°C and with efficient agitation because of the
strong exothermic reaction. The remaining POP anhydride bonds
are then split off successively by reacting with an additional 3
moles of alcohol in subsequent reaction steps.

In practice it is not possible to obtain a molar ratio of 1:1 between

mono- and diester as it is impossible to get 100% pure phosphorus
pentoxide and to charge it unchanged into the reaction vessel.
Traces of water in the alcohol and the air cause an undesirable
splitting of the ring system into tetrameric phosphoric acid, so that
the content of monoesters is larger than the quantity of diesters.
Additionally, technical phosphorus pentoxide mostly contains
polymers [116], which also influences the molar ester ratio. In case
the reaction has not been carried out under optimum conditions
pyrophosphate esters may be formed as byproducts, which may
change the properties of the desired product.
Furthermore, phosphoric acid esters can be synthesized by reacting
nonionic surfactants with polyphosphoric acid [108,117,118]. The
concentration of the commercial quality is typically 84 % on the
basis of phosphorus pentoxide. According to Clark and Lions
[119], polyphosphoric acid has the composition shown in Table 2.
Polyphosphoric acid can also be made in situ by mixing o-
phosphoric acid, water, and phosphorus pentoxide. The
composition then depends on the mixing ratio of the single
components [120,121]. The
 Page 262

alcoholysis of the POP anhydride bonds and formation of the final

product occur in subsequent steps as shown in Eq. (10).

Tetrameric phosphoric acid is reacted with a maximum of 3 moles

of alcohol. During this procedure only monoesters are formed
along with free phosphoric acid. It should be pointed out that the
alcoholysis reaction is relatively slow and requires elevated
temperatures of 80100°C. In case of the direct esterification of o-
phosphoric acid, olefins may be produced [122]; consequently, its
use as a phosphorylating agent was not considered for a long time.
By adding small quantities of basic substances, especially tertiary
amines, the formation of olefins can be prevented virtually
completely [123]. According to the procedure of azeotropic
dehydration at >160°C mixtures of mono-, di-, and triesters are
obtained. The final composition is determined by the molar ratio
of the educts.
In addition to the aforementioned possibilities of synthesizing
phosphoric acid esters of oxyalkylated alcohols, the literature
offers certain more specific procedures. Two interesting routes are
described in the following paragraphs.
As mentioned before, a successful production of triester can only
be guaranteed by the phosphatation with phosphorus oxychloride.
For a series of special
 Page 263
applications it has been suggested that the ester mixtures, resulting
from the reaction with phosphorus pentoxide, be reacted with
oxyalkylenes (EO;PO) in order to obtain triesters [Eq. (11)].

Another very interesting synthesis route is the preparation of

highly concentrated diesters [124], starting with triesters and
phosphorus pentoxide [Eq. (12)]. Reaction conditions are given as
an example: Within 1 h 0.5 mole of P4O10 is added at 80°C to 2
moles of triphosphate by stirring for further 2 h. Two moles of
alcohol is then added and kept at a temperature of 100°C for 5 h.
The tetraalkyl diphosphate having been prepared in addition to the
2 moles of diester will also be hydrolyzed to diester with 1 mole of
water at 85°C within 3 h. The final product should contain more
than 85 mol% of the diester. Additionally, this route makes it
possible to synthesize mixed esters.

B
Analytical Methods
Finding reliable methods regarding the quantitative detection and
characterization of all potential components, above all alkyl
polyoxyalkylene phosphates, was problematic in the past. A simple
potentiometrical titration procedure has been known for some
time. Its use, however, is limited to specific applications, especially
when quantitative results are needed [125]. A solution of the
sample in ethanol in the presence of small amounts of sodium
chloride and water is titrated with 0.1 or 0.5 M sodium hydroxide
solution. As soon as a second inflection point appears, 10 mL of a
10% aqueous calcium chloride solution is added. Titration is
continued until a third inflection point is indicated as shown in Fig.
15. The first inflection point comprises one proton of the
monoester and
 Page 264

Fig. 15
Titration of phosphate esters.
the free phosphoric acid as well as the proton of the diester. The
second inflection point indicates the second proton whereas the
third inflection point stands for the third proton of the free
phosphoric acid. The composition of the ester mixture is calculated
according to the equations indicated in Fig. 15. For ester mixtures
not containing any pyrophosphates the results are extremely
accurate. In the presence of POP anhydride bonds the method can
provide qualitative data, i.e., more than three inflection points or a
molar mono-/diester quotient below 1 indicates the presence of
pyrophosphates. Quantitative data in this case are obtained by
means of 31P NMR analysis [126].
C
Properties and Applications
Regarding their properties phosphoric acid esters based on
nonionics differ distinctly from the classical phosphates.
Depending on the length of the polyoxyethylene chain the stability
to hard water is increased considerably. Furthermore, the
dissolution in highly alkaline media is improved. The antistatic
effectivity is made possible by the polyether chain. The
compatibility in hydrophilic systems is based on the same fact. As
expected, there is a loss of compatibility in hydrophobic systems.
The surface active properties such as foaming, wetting power,
depression of the surface tension, and emulsifying ability depend
on the kind of alkyl residues, the mono-/diester ratio, the polyether
chain, as well as on the degree of neutralization (pH value). The
distinct stability to hydrolysis reac-
 Page 265
tions over a wide range of pH values is comparable with the
classical phosphates. The ester bonds are cleaved only under
extremely acid or alkaline conditions, most of all caused by
increased temperatures. The high-temperature resistance of the
esters is also remarkable. The improved solubility in water
accelerates the biological degradability.
The nonionic-based phosphates are used according to their wide-
ranging properties. Various applications are described in the
literature, mainly in patents. Especially in the cosmetic sector alkyl
polyoxyethylene ether phosphates are of high value because of
their mildness to hair and skin in a number of detergent
compositions [127]. They have even been recommended for use in
toothpastes [128]. Triesters of oxethylated fatty alcohols (e.g.,
Hostaphat, Hoechst AG) are excellent emulsifiers for ointments,
creams, and lotions [129]. Shampoos containing mono-
/diphosphates based on lauryl polyoxyethylene (3) alcohol make
hair easily combable, shiny, and antistatic [130]. Transparent
perfume gels can be obtained by combining with suitable
nonionics, paraffin, and perfume oils [131]. The nonfading
properties of antibacteriologic soaps are improved by the addition
of partial ether phosphates [132].
In the metal industry, there are also a large number of patent
applications. Generally speaking, partial esters of phosphoric acid
are used in lubricants as extreme pressure (EP) and antiwear
additives with corrosion inhibiting effects [133]. They are also
used in acid [134] and alkaline [135] cleaners for aluminum. In
metal flotation polyoxyalkylene phosphates are used for the
separation of fluorides [136].
In the plastics industry, phosphates of oxalkylated polysiloxanes
can be used as lubricants and antistats [137]. Alkyl
polyoxyethylene phosphates act as polymerization emulsifiers for
olefins. The dispersions remain homogeneous and stable [138]
while also having a better light stability [139].
For textile fiber applications, alkyl polyoxyethylene phosphates are
distinguished regarding their multifunctional properties.
Depending on their composition they can be used as wetting agents
or emulsifiers, in view of their thermal stability as antistats [140],
spinning aids [141], or lubricants. EO/PO block C9/C13 alkyl
phosphates that were prepared by reaction with polyphosphoric
acid are used as wetting agents for the textile pretreatment in
alkaline media [117]. Several proposals exist for the use of alkyl
polyoxyethylene phosphate detergent compositions for washing
and cleaning agents [118,142,143]. Large quantities of special
phosphates are delivered to the agricultural industry as emulsifiers
for pesticides. Last but not least, it is noteworthy that alkyl
polyoxyethylene phosphates included in phospholipids are
described as having pharmaceutical effects, i.e., inhibitory
activities against HIV-1 and HIV-2 [144], malate dehydrogenase
activation analogous to Mycobacterium smegmatis [145], or
antileukemic effects [146].
 Page 266

V
Carboxylates
In recent years, alkyl polyoxyethylene carboxylic acid or
alkyl(poly-l-oxapropen)oxaalkene carboxylic acid, also known as
ether carboxylic acids, have gained in importance. The
combination of advantageous ecological and toxicologic
properties, outstanding dermatologic behavior, and excellent
emulsifying, wetting, and cleaning properties implies that this class
of surfactants has a broad field of application. Ether carboxylic
acids are valuable components in cosmetic formulations, washing
and cleansing agents, as well as auxiliaries in the textile, printing,
paper, plastics, and metalworking industries. Due to their structure,
the physicochemical properties of ether carboxylic acids can be
adjusted to the application requirements by modification of the
hydrophobic alkyl or alkylaryl chain, the number of ethylene oxide
units, and the degree of carboxylation.
A
Preparation
The conventional methods of preparation of ether carboxylic acids
start with fatty alcohols, which are then primarily ethoxylated
[147,148]. Conversion to ether carboxylic acid may be afforded, in
principle, by several routes (Fig. 16).
 Fig. 16
Synthesis of ether carboxylic acids.
 Page 267
The alkyl polyoxyethylene alcohols can be carboxymethylated by
reaction with monochloroacetic acid in the presence of sodium
hydroxide or through terminal oxidation of the fatty alcohol
ethoxylate. The ether carboxylic acid can also be synthesized by the
addition of a vinylic system, i.e., acrylonitrile, to an oxyethylated
fatty alcohol and subsequent hydrolysis.
In analogy to Williamson's ether synthesis, conversion of the alkyl
polyoxyethylene alcohols with sodium chloroacetate and sodium
hydroxide into the sodium salt of the ether carboxylic acid is
accomplished. In the first reaction step, the alcoholate is formed
[Eq. (13)]. This reacts subsequently with sodium chloroacetate,
resulting in the ether carboxylate [Eq. (14)]:

The inductive effect of the oxygen atoms in the polyglycol ether

chain has an acidifying effect on the terminal hydroxyl group.
Therefore, the reactivity of the alkyl polyoxyethylene alcohol
increases with an increasing degree of ethoxylation [149,150], as
does the dissociation constant of the resulting ether carboxylic
acid. Thus, in a partial carboxymethylation, the homologous
distribution of the ether carboxylic acid will be shifted to products
with a higher degree of ethoxylation, whereas the nonconverted
alkyl polyoxyethylene alcohol contains more low-oxyethylated
fractions. Furthermore, the reactivity and the realizable conversion
level also depends on the structure of the alkyl component. In the
case of ethylene oxide- and propylene oxide-containing ether
carboxylic acids, the proportion of propylene glycol in the
polyglycol chain is also important.
Residual, nonreacted alkyl polyoxyethylene alcohol, glycolic acid,
water, and sodium chloride result as byproducts. The free ether
carboxylic acids can be isolated by adding sulfuric acid to the
product mixture and separating the resulting phases. Using this
method, salt contents in ether carboxylic acids of <10 ppm can be
achieved without any problem. The disadvantage, however, is the
high wastewater load due to the process-related salt formation.
High degrees of carboxymethylation and product purity can be
achieved by use of bromoethyl acetate and subsequent
saponification of the resulting ester [151]. It is also possible to
carboxymethylate polyhydroxy compounds, polyalkylene oxides
[152], acetylene derivatives, and amino- or amidooxyethylates with
this method.
The Michael addition of primary or secondary alcohols to
acrylonitrile allows the synthesis of cyanoethyl ethers [153] [Eq.
(15)]. These can be hydrolyzed to form the corresponding ether
carboxylic acids [154] [Eq. (16)]. The cyanoethylation of aliphatic
alcohols conveniently takes place at room temperature when strong
bases such as sodium, sodium hydroxide, or ion exchange resins
[155] are employed as catalysts:
 Page 268

This method can also be applied to convert diols and polyols to

cyanoethyl ether. Other functionalities, such as dialkylamino,
halogen, or olefin groups, do not affect the reaction. Cycloaliphatic
alcohols, (poly)glycols, even high molecular weight hydroxy
compounds and polyvinyl alcohol, can easily be converted with
acrylonitrile. However, in the case of phenols, higher temperatures
are required.
After cyanoethylation, the alkaline catalyst must be neutralized;
otherwise the dissociation of the product into the initial alcohol
and polymerization of the acrylonitrile will take place. At a pH of
46, however, the ether nitriles are stable and storable. Nevertheless,
polyacrylonitrile was sometimes found as a byproduct in this
reaction. These nitriles are important as intermediates for plastics,
synthetic fibers, pharmaceutical products and insecticides, but
rarely for surfactants.
An advantage of this synthesis is the fact that the entire conversion
of the fatty alcohol to the ether carboxylic acid can be carried out
as a one-pot reaction. In most cases, the catalyst used for the
oxyethylation of alcohol is also sufficient for the catalysis of the
Michael addition. The subsequent hydrolysis can be undertaken
with alkali, but often concentrated hydrochloric acid is used.
Ammonium chloride is formed as a byproduct.
An elegant process for the preparation of ether carboxylic acids is
the catalytic oxidation of the terminal hydroxyl groups of an alkyl
polyoxyethylene alcohol [156]. Although alcohol ethylene oxide
adducts can be oxidized with inorganic oxidizing agents such as
chromic acid, potassium permanganate, or peroxides, the oxidation
with oxygen in the presence of metal catalysts is more selective
[Eq. (17)]. This reaction is carried out with a mixture of the alkyl
polyoxyethylene alcohol in an aqueous solution of sodium
hydroxide with palladium/charcoal in an autoclave at 6090°C.
Bismuth, lead, cadmium, and cobalt also serve as cocatalysts or
catalyst activators. For technical reasons the oxidation takes place
in a dilute, approximately 1020% solution of the alkyl
polyoxyethylene alcohol in water. Although the catalytic oxidation
proceeds with high selectivity and yield and is also advantageous
from an ecological point of view, it has not gained importance on a
technical production scale. Difficulties in connection with the
workup of the reaction mixture and the low concentration of the
ether carboxylate in the solution inhibit large-scale production.
 Page 269
B
Analytical Methods
For the qualitative and quantitative determination of ether
carboxylic acids, a variety of analytical methods are suitable [157].
The qualitative evaluation of the reaction products and reaction
monitoring is done by thin-layer chromatography [158,159]. The
separation is carried out according to functionality and not to
polymer size. The eluent system chloroform/methanol 20:80 has
proven to be particularly suitable. Reverse phase HPLC allows
identification of the ether carboxylates in the form of
tetramethylammonium salts [160]. In this way, the
tetramethylammonium salts of the ether carboxylic acids can be
separated from other anionic or nonionic surfactants.
Ether carboxylic acids can be separated by gas chromatography
into the individual polymer homologs and subsequently
determined with the aid of mass spectroscopy. In the case of
nonylphenyl polyether carboxylates it is indeed possible to
distinguish the ortho and para isomers [157].
Infrared spectroscopy is very helpful for reaction control in the
preparation of ether carboxylic acids according to the nitrile route
[Eq. (15)]. The characteristic absorptions for the oxyethylates
[v(OH) 3400 cm-1], ether nitriles [v(CN) 2250 cm-1], and ether
carboxylic acids [v(CO) 1710 cm-1] enable the identification of the
individual components of a reaction mixture [161].
The quantitative evaluation of ether carboxylic acids is also
achievable through potentiometric titration. In this case, the
determination of free ether carboxylic acids is carried out by
titration of the ether carboxylic acid with sodium hydroxide. The
salts of ether carboxylic acid are titrated against hydrochloric acid.
Solubility problems and insufficiently defined potential steps can
be avoided by using a 95% solution of the ether carboxylic acid in
methanol. For technical products, the quantitative content of ether
carboxylic acid is calculated on the basis of the mean molecular
weights of the corresponding ethoxylates. The pKa values of ether
carboxylic acids of the type R-(EO)x-COOH are between pKa = 4.1
(x = 12) and pKa = 5.6 (x = 3). The acidity increases with an
increasing degree of oxyethylation [4]. Two-phase titration, which
is established as a standard method [26] for quantitative
determination of anionic surfactants, shows difficulties in the
determination of ether carboxylic acids depending on the structure
and composition of the product. The titration of ether carboxylates
with other cationics is also described in the literature [162].
For fast or routine analysis of technical products, where usually
both polymer distribution and nonconverted educt and byproducts
prove to be problematic, NMR spectroscopy is not
recommendable. On account of the overlap of resonances of the
polyethylene oxide unit with the signal of the methylene protons
adjacent to the carboxyl group, 1H NMR spectroscopy allows
conclusions only in optimal conditions because the resonances of
these protons depend strongly on the concentration and pH value
of the solution. For the estimation of the
 Page 270
yield or degree of conversion, 13C NMR spectroscopy is more
suitable because the resonance of the carboxyl carbon atom is
sufficiently shifted to low fields [163].
The literature also discusses ion exchange chromatography [157],
oleochemical indices, and elemental analysis as methods for
characterization of ether carboxylic acids.
C
Properties and Applications
The physicochemical properties of ether carboxylic acids are
particularly determined by the hydrophobic alkyl chain, the degree
of ethoxylation, and the degree of carboxymethylation, as well as
the type of neutralization and the pH of the solution. Ether
carboxylic acids are temperature-stable and resistant to alkali and
hydrolysis, even under strongly acidic or alkaline conditions.
Through variation of the length and structure of the hydrophobic
carbon chain, above all the wetting and foaming behavior of the
ether carboxylic acids can be influenced. The foam volume
increases with an increasing chain length. Unlike many nonionic
surfactants, which are only low foaming at the cloud point, short
chain ether carboxylic acids keep their low foaming properties
over a wide temperature and pH range [164].
On account of its complexing capacity for cations, the hydrophilic
polyglycol group is responsible for the hard water stability and the
lime soap dispersing power of the ether carboxylic acids [165].
Both properties improve with increased ethoxylation. Therefore,
ether carboxylic acids are outstandingly suitable for surfactant
applications in hard water. And especially, as stated above, the
foaming properties of the ether carboxylic acids can be controlled
by the degree of ethoxylation.
The carboxyl group enables the ether carboxylic acids to perform a
double function as nonionic and anionic surfactant. In an acidic
medium, ether carboxylic acids act as nonionic surfactants,
whereas in an alkaline medium they gain the properties of an
anionic surfactant. In aqueous solutions the ether carboxylic acids,
as weakly dissociating acids, are present in nonionic form. In
aqueuos solutions, the formation of micelles starts at the same
concentration as in the case of the corresponding nonionic
surfactant [164]. The salts of ether carboxylic acids form micelles
at higher concentrations; therefore the surface tension is reduced at
low pH values.
The carboxymethylation level of the ether carboxylic acids also
influences the properties of technical ether carboxylic acids
because, even in an optimized reaction, in practice there will
always remain a certain proportion of alkyl polyoxyethylene
alcohol that is not carboxymethylized. This combination of ether
carboxylic acid and alkyl polyoxyethylene alcohol, for example,
has a positive effect on the emulsifying capacity. Synergistic effects
can also be observed with
 Page 271
regard to wetting power and foaming behavior. The oxidation and
alkali stability of the ether carboxylic acids is increased with a
higher conversion level.
The pH influences the viscosity of an ether carboxylic acid
solution. Generally, a reduction of the pH lowers the viscosity of
the ether carboxylic acid solution.
On account of their advantageous ecological, toxicologic, and
physicochemical properties and the good compatibility with
representatives of all surfactant classes, ether carboxylic acids can
be applied effectively in many fields. Ether carboxylic acids, for
example, are used in washing and cleaning agents as well as
cosmetics. They are utilized as emulsifying and auxiliary agents in
the textile, printing, paper, plastics, metalworking, and
pharmaceutical industries [166].
The salts of ether carboxylic acids with high degree of ethoxylation
are considered to be very mild and skin-compatible surfactants.
Therefore, they are particularly suitable for applications in
cosmetics [77a]. The good dermatologic and ecotoxicologic
properties such as low defatting effect, nontoxicity, easy
biodegradability, as well as outstanding cleaning and emulsifying
effect are exploited in numerous cosmetic formulations. In
particular, for medical cleansing agents, the disinfecting effect of
salts of the ether carboxylic acids with rare earths is important.
Because ether carboxylic acids show very good hard water stability
and lime soap dispersing power, they are interesting as surfactants
for phosphate-free washing agents and dishwashing detergents.
Furthermore, they are distinguished by low-foaming behavior and
high redeposition-inhibiting capacity. Through the variation of the
hydrophobic carbon chain and hydrophilic polyglycol chain as
well as the degree of carboxymethylation, the detergency of ether
carboxylic acids can be optimized [167]. Ether carboxylic acids are
also used for manual dishwashing detergents, carpet cleaners, and
other household products [168].
Due to their good wetting properties and their outstanding alkali
and oxidation resistance, ether carboxylic acids are predestined for
applications in formulations based on sodium hypochlorite or
hydrogen peroxide. They are frequently used in textile-bleaching
agents, toilet cleaners, and high-pressure bottle and metal cleaners.
Thanks to their beneficial properties, members of this surfactant
group are applied in the pretreatment of wool and cotton, as
dyeing and printing auxiliaries, as additives for paints and inks,
and for the de-inking of paper. In the plastics industry ether
carboxylic acids are employed as auxiliary agents for emulsion
polymerization and as antistatics.
Because they exert a good corrosion inhibiting effect, ether
carboxylic acids are also used as emulsifiers in drilling, rolling, and
cutting oil emulsions and cooling lubricants [169]. Ether
carboxylates show a high long-term stability, even under extreme
chemical and thermal conditions. As they are compatible with
brine and crude oil, they are also effective surfactants for
recovering oil by
 Page 272
micellar polymer flooding from reservoirs of high salinity [170].
Based on their structure, alkyl ether carboxylates can be tailored to
the needs of the particular reservoir.
Due to their high alkali and electrolyte stability, ether carboxylic
acids can also be utilized as hydrotropes. They allow formulation
of stable products even under high salt or alkaline conditions.
Apart from this, synergistic effects regarding foaming properties,
detergency, wetting, and cleaning power are frequently observed
when ether carboxylic acids are combined with other surfactants.
Conversion products of ether carboxylic acids with
monoethanolamide can serve as thickeners for surfactant solutions
[171].
D
Environmental and Toxicologic Aspects
Alkyl ether carboxylic acids are considered to be a toxicologically
safe surfactant class. The acute toxicity as well as skin and mucous
membrane compatibility were examined. With an LD50 of over
2000 mg/kg (C12/C144.5EO-carboxylate) alkyl ether carboxylates
are assessed as nontoxic [164]. The Zein test, which allows
statements about the skin compatibility of anionic surfactants and
tests on rabbit skin and rabbit eye mucous membranes, identify
alkyl ether carboxylic acids as a skin-compatible substance class.
The skin mildness of ether carboxylic acids increases with a higher
degree of ethoxylation.
The biodegradability of ether carboxylic acids was proven in the
OECD test [164]. Above all, ether carboxylic acids based on linear
fatty alcohols were proven to be easily biodegradable in the OECD
confirmatory test with a degradation rate of 95% [167]. The
degradation of fatty alkyl polyoxyethylene alcohols, and therefore
indirectly that of ether carboxylic acids, was examined on the
system Pseudomonas. It showed that both etherases and alcohol
and aldehyde dehydrogenases are involved in the degradation
process [172]. Ether carboxylic acids, which correspond to
terminally oxidized fatty alkyl polyoxyethylene alcohols, were
found as metabolites. The degradation products, as alcohol,
aldehyde, and carboxyl group-containing metabolites, were
detected, but none accumulated under the test conditions. The
structure of the hydrophobic alkyl chain has a great influence on
the biodegradability of ether carboxylic acids.
Tests on fish toxicity show that the aquatic toxicity depends on the
degree of carboxymethylation. With a increasing
carboxymethylation level, the fish toxicity of the ether carboxylic
acid and alcohol ethoxylate mixture decreases [167]. As compared
to other, conventional anionic and nonionic surfactants, certain
alkyl ether carboxylic acids have been shown to be less toxic.
However, in the ecologic evaluation of a substance the
biodegradability is more important than the aquatic toxicity
because surfactants usually lose their aquatoxic activity during the
degradation process.
 Page 273

VI
Quaternary Ammonium Compounds
The practically used quaternary surfactants are based exclusively
on a tetra-coordinated nitrogen atom. Tetraalkylammonium salts
containing at least one longer alkyl chain represent the group of
cationic surfactants. Often the analogous amine salts are described
as quaternaries as well. But contrary to the true quaternary
surfactants, they are formed by neutralization with acids. Therefore
they consist of protonated amines and should be named as
pseudocationics (Fig. 17). The substantial difference between both
classes of cationics is that the pseudocationics only show
surfactant properties at a pH value lower than 7. In this section
''true quaternaries" based on nonionics will be discussed.
Polyoxyethylene ether quaternaries represent an extremely complex
class of substances that allow a large number of tailor-made
products due to the high potential of variations. On the other hand,
the chemical diversity makes a systematic classification regarding
only a few main types more difficult. The structure differences in
this section could be very useful. The examination of the
comprehensive literature allows the classification of nonionic
surfactant based quaternaries into the following groups:
1. Substances prepared by quaternization of polyoxyalkylene
amines
2. Substances in which the polyether chain is not directly bound to
the nitrogen atom
3. Substances containing a polyether chain that is introduced by the
quaternization agent
A fourth group which, strictly speaking, does not correspond to
the main title "nonionic intermediates" should also be presented:

Fig. 17
Structures of tetra-coordinated
ammonium salts.
 Page 274
4. Substances in which the polyoxyalkylene moiety is introduced
during or after the quaternization step
On the basis of characteristic examples an introduction into the
chemistry of the individual groups is given. In group 1,
oxyalkylated, mostly oxyethylated amines serve as raw materials.
In a simple manner the oxyethylated fatty amines will be
quaternized analogous to the ordinary tertiary amines by means of
methyl chloride, dimethyl sulfate, benzyl chloride, etc., as
alkylation agents [173] [Eq.(18)].

Sometimes the addition of potassium iodide is recommended as a

catalyst. Nevertheless it is difficult to reach a conversion to
quaternaries of more than 90%. Probably a steric hindrance is
responsible. By increasing the polyether chain length the reactivity
drops continuously. Quaternaries based on partial fatty amides of
polyvalent amines [174], as described in Eq. (19), have shown to
be of practical use as less hydrophobic textile softeners.
Very interesting is the synthesis shown in Eq. (20), where in the
first reaction step oxyalkylated triethanolamine is reacted with
long-chain epoxides followed by a quaternization reaction [175].
 Page 275

In a completely different route the quaternization can also be done

with alkylene oxide in the presence of water [176,177] as
demonstrated in Eq. (21).

Primary and secondary amines can also be used in this reaction

and form quaternaries if the amount of epoxide is appropriate.
Additional hydroxyl functions will be formed [178] that can react
further with the alkylene oxide (see group 4 products). The
thermal instability of the formed quaternary ammonium bases is
real disadvantage for the procedure. As a consequence, the
resulting dealkylation reaction decreases the yield of quaternaries.
But fortunately, the neutralization of the amine before the addition
of alkylene oxide seems to be a successful alternative [179].
However, for the dissociation of the amine salt the presence of
water is necessary and glycols will be formed as byproducts. Table
3 shows results of the quaternization reaction with ethylene oxide
depending on the presence of acid. The respective reaction
temperature was adjusted to 80°C. The concentration of water in
the final product was 50% [180].
Polyoxyethylated amines can also be quaternized in such a manner
that, as shown in Eq. (22), unusual acid compounds, i.e., partial
phosphates, form the anion [178,181]:
TABLE 3 Quaternization with Ethylene Oxide
Analytical results
(%)
EO- Quaternization in
Degree of
Amines Acid supply the presence of Glycols
quaternization
[mole] acid
Tallow
H3PO4 5 No 22 8.6
amine
Tallow
H3PO4 5 Yes 91 3.1
amine
Tallow
H3PO4 5 No 40 11.1
amine·5EO
Tallow
H3PO4 5 Yes 91 6.5
amine·5EO
Tallow Lactic
5 Yes 98 13.7
amine·5EOacid
 Page 276
Following Eq. (23), the preparation of polyquaternary cationics is
possible, with so-called polyester tertiary amines being produced
by polycondensation reaction of polyoxyethylated fatty amines
with dicarboxylic acids like adipic acid [182] as well will be
quaternized with ethylene oxide [183].

Basically, other epoxides are also applicable, i.e., propylene or

butylene oxide. Even long chain oxiranes are mentioned in the
literature [184]. It should also be mentioned that the use of strong
acids during the quaternization reaction with ethylene oxide
generates dioxane.
The references for product types of group 2, the polyoxy alkylene
chain of which is bonded to basic nitrogen atoms by a spacer, are
less numerous. Methods to obtain such substances have been
published by R. J. Stenberg [185] and E. I. Carpenter [186] who
added acrylonitrile to oxyethylated alcohols. The resulting
propionitriles were converted to primary amines by hydrogenation
followed by an alkylation reaction before a quaternization could be
applied. The reaction sequences are shown in Eq. (24).
Another, simpler route [180] is represented in Eq. (25) according
to which polyether fatty carboxylic acids are reacted with
dimethylaminopropylamine to
 Page 277
amidoamines, which can easily be quaternized leading to the
cationic product in high yields.

At this point it is interesting to mention that amphoteric surfactants

such as betaines, which also contain a tetra-coordinated nitrogen
atom, can be synthesized by reaction of the aforementioned
amidoamines with chloroacetic acid salts [Eq. (26)]:

Quaternaries of group 3, where the polyether chain is introduced

by the quaternization agent, are represented by numerous examples
in the literature. Here, typical syntheses are described. Often the
use of chloroacetic acid esters of polyoxyethylated alcohols is
proposed for the quaternization of tertiary fatty amines [187,188],
as follows:
The product from Eq. (27), the so-called betaine ester, can be
hydrolyzed easily to betaines [Eq. (28)]:

In order to obtain cationic surfactants that are stable toward

hydrolysis, the quaternization reaction is carried out with
chlorohydrin ethers of nonionic surfactants.
Polyquaternary products are obtained by reaction of
bischlorohydrin ethers with tetramethyldiaminoethane as shown in
Eq. (29) [180]:
 Page 278

Bisquaternary ammonium bromides with polyoxyethylene ether

chains [189] were synthesized in analogy to Eq. (30) and the
physical-chemical properties were studied.

While the last synthesis route only has academic interest,

chloroacetic acid esters and chlorohydrin ethers act as simply
available quaternization agents with highly variable possibilities.
Cationic ammonium salts that were obtained by quaternization
with alkylene oxide (see group 1) and by a further oxyalkylation
reaction are mentioned here as examples for group 4 products
[178].
The oxyalkylation of hydroxy groups containing quaternaries in a
separate reaction step fails as the high reaction temperature causes
a dealkylation reaction of the quaternary nitrogen atom. Finally the
cationic modification of nonionics with
glycidyltrimethylammonium chloride as suggested by the
manufacturers (i.e., Degussa, Shell) is mentioned [Eq. (31)]:
 Page 279
The above-described quaternary ammonium compounds based on
nonionic surfactants possess the general characteristics of classical
quats. Most of all, the affinity to anionic surfaces may be the
significant property. Depending on length and kind of the
polyoxyalkylene chains, however, additional effects will be
obtained. For example, the water solubility will be improved as
well as the compatibility with anionic surfactants or the wetting
power.
Typical applications are given in the textile and fiber industry
where they act as softening, antistatic, fixing, or emulsifying agents
[175,190193]. It was also suggested that they be used as spin
finishing for fibers and yarns including lubricating effects.
Accordingly, their compatibility with anionic surfactants make
them applicable for hair care and hair rinse products in which they
impart antistatic properties and an improved combability [194196].
Cationics that are prepared by quaternization with propylene oxide
find application as demulsifiers for mineral oilcontaminated
wastewater [197].
Appendix
Trade Names and Suppliers
Alkylether sulfates Supplier
Perlankrol Harcros Chemicals
Elfan NS Akzo Nobel
Empicol Albright & Wilson
Cosmopon, Rolpon Auschem Cesalpinia
Chemsalan Chem-Y
DAC International
Daclor, Dacpon
Surfactants
Laural Elf Atochem
Caflon Ellis & Everad
Disponil, Euperlan, Standapol,
Henkel KGaA
Texapon
Manro, Tensagex Hickson Manro
Genapol, Geropon Hoechst AG
Marlinat Hüls
Emal, Sapanol Kao Corp.
Maprofix Millchem
Nikkol Nikko Chemicals
Rhodapex Rhone-Poulenc
Montelane, Oronal Seppic
Dobanol Shell
Polystep, Steol Stepan Europe
Surfac Surfachem
Neopon, Rewopol, Witcolate Witco

(table continued on next page)

 Page 280
(table continued from previous page)
Sulfated fatty acid monoglycerides Supplier
Plantapon CMGS Henkel KGaA
Nikkol SGC-80 N Nikko
POEM-LS-90 Riken Vitamin Oil
Sulfated alkanolamides
Genapol AMS Hoechst AG
Genapol AMG Hoechst AG
Phosphates
Alkaphos Alcaril Chem.
Crodafos Croda Chem.
Gafac GAF Chem.
Crafol AP, Forlanit, Standapol, Nopcostat Henkel KGaA
Hostaphat Hoechst AG
Marlophor Hüls
Alkawet Lonza Chem.
Monafac Mona Ind.
Pecosil Phoenix Chem.
Triton Röhm & Haas
Servoxyl Servo
Rewophat, Ultraphos Witco Chem.
Carboxylates
Alkypo R-Types Kao Corp.
Akypo-Soft-Types Kao Corp.
Akypofoam-Types Kao Corp.
Marlowet Hüls
Rewopol C-Types Rewo
Sandopan Sandoz
Velsan Sandoz
Quarternary ammonium compounds
Rewoquat Witco Chem.
Mirataine Rhone Poulenc
 Page 281

References
1. H. Stache, Anionic Surfactants, Surfactant Science Series, Vol.
56, Marcel Dekker, New York, 1965.
2. J. Falbe, Surfactants in Consumer Products: Theory,
Technology and Application, Springer-Verlag, Berlin, 1987.
3. P. Hövelmann and B. Brackmann, 21st World Congress and
Exhibition of the International Society for Fat Research (ISF), The
Hague, 1995.
4. B. R. Bluestein and C. L. Hilton (eds.), Amphoteric Surfactants,
Surfactant Science Series, Vol. 12, Marcel Dekker, New York,
1982.
5. M. F. Cox, 3rd World Conference and Exhibition on Detergents,
Montreux, Sept. 1993.
6. W. H. deGroot, Sulfonation Technology in the Detergent
Industry, Kluwer Academic, Dordrecht, 1991.
7. W. Skrypzak and O. Szappan, in Kozmet (Sec. Issue), pp. 5966
(1994).
8. Study of the German "Industrieverband Körperpflege und
Waschmittel e.V.," Frankfurt/M., Nov. 1986.
9. T. Förster, H. Hensen, R. Hofmann and B. Salka, Cosmet.
Toiletries 110:29 (1994).
10. B. D. Condon, K. L. Matheson, J. Am. Oil Chemists Soc.
71(1):5359(1994).
11. H. Plate, Parfüm. Kosmet. 76:28(1995).
12. M. E. Spiess, Parfums. Cosmet., Aromes 109:65 (1993).
13. M. F. Cox, J. Am. Oil Chem. Soc. 66:1637 (1989).
14. A. Behler, H. Hensen, H.-C. Raths, and H. Tesmann, Seifen Öle
Fette Wachse 116(2):60 (1990).
15. H. P. Welzel, H. P. Neumann, and K. Haage, Tenside Surf., Det.
31(5):286.
16. H. Hensen, H.-C. Raths, and W. Seipel, Seifen Öle Fette
Wachse 117:592 (1991).
17. G. Crass, Seifen Öle Fette Wachse 118:921 (1992).
18. M. F. Cox, J. Am. Oil Chemists Soc. 67(9):599 (1990).
19. D. L. Smith, J. Am. Oil Chemists Soc. 68(8):629 (1991).
20. Wu Guozhong, Zhang Zhicheng, Huaxue Shiji 16(1):58 (1994).
21. V. P. Gordnov, V. V. Sorokin, A. A. Petrow, Khim. Tekhnol.
Topl. Masel 4:23 (1974).
22. R. T. Savel'yanova, N. N. Evsees, V. P. Savel'yanov, T. A.
Shashkova Zh. Org. Khim. 2253 (1984).
23. J. Cross, in Nonionic Surfactants (J. Cross, ed.), Surfactant
Science Series, Vol. 19, Marcel Dekker, New York, 1987, pp.
137224.
24. Methods of Analysis, International Organization for
Standardization (ISO),1, rue de Varembeè. Case postale 56, CH-
1211 Geneve 20.
25. German Standard Methods, Abteilung H-Tenside, Deutsche
Gesellschaft für Fettwissenschaft e.V., Münster, Wissenschaftliche
Verlagsgesellschaft mbH, Stuttgart 1992.
26. S. R. Epton, Trans. Faraday Soc. 44:226 (1948).
27. V. W. Reid, G. F. Longman, and E. Heinerth, Tenside 4(2):292
(1967).
28. S. Alegret, J. Alonso, J. Bartroli, J. Baro-Roma, J. Sanchez,
and M. de Valle Analyst 119(11): (1994).
29. R. Schulz, R. Gerhards, Tenside Surf. Det. 32(1):6 (1995).
30. H. J. Buschmann, U. Denter, and K.-F. Elgert, Melliand
Textilberichte, 951, No. 12 (1995).
 Page 282
31. G. Krusche, Tenside Surf. Det. 27(2):122 (1990).
32. M. Y. Ye, R. G. Walkup, and K. D. Hill, J. Liq. Chromatogr.
17(19):4087 (1994).
33. A. Stemp, V. A. Boriraj, P. Walling, and P. Neill, J. Am. Oil
Chemists Soc. 72(1):17 (1995).
34. S. Scalia, and G. Frisina, Proc. Chromatogr. Soc. Int. Symp.
(D. Stevenson and I. D. Wilson, eds.), Plenum Press, New York,
1991, pp. 219226.
35. P. Schoeberl, Munch. Beitr. Abwasser-, Fisch-, Flussbiol.
44:367 (1990).
36. J. Steber and H. Berger, in Biodegradability of Surfactants (D.
R. Karsa and M. R. Porter, eds.), Blackie, London, 1995
37. S. G. Hales et al., Environ. Microbiol. 44:790 (1982).
38. B. Ziolkowsky, Seifen Öle Fette Wachse 116:450 (1990).
39. P. Schöberl, K. J. Bock, and L. Huber, Tenside Surf., Det.
25:86 (1988).
40. B. R. Harris, U.S. Patent 2,023,387 to Colgate-Palmolive-Peet
Company (1932).
41. J. Ross, U.S. Patent 2,693,479 to Colgate-Palmolive Company
(1950).
42. J. K. Fincke, U.S. Patent 2,634,287 to Monsanto (1948).
43. F. W. Grag, U.S. Patent 2,979,521 to Colgate-Palmolive
Company (1958).
44. (a) G. Gawalek in Tenside, Akademie- Verlag, Berlin, 1975, p.
171; (b) M. Linfield (ed.), Anionic Surfactants, Surfactant Science
Series, Vol. 7, Marcel Dekker, New York, 1976, pp. 219.
45. K. Yamashita et al., JP 50/70322 to Wako Pure Chemical Ind.
(1975).
46. M. Shinohara, JP 78/77014 to Riken Vitamin Oil (1975).
47. H. Stühler, EP 267,518 to Hoechst AG (1987).
48. F. Ahmed et al., DE 3,831,446, to Colgate-Palmolive Company
(1988).
49. A. Behler et al., DE 4,038,477, to Henkel KGaA (1990).
50. U. Zeidler, J. Soc. Cosmet. Chem. Japan 20:17 (1986).
51. A. Straw et at., GB 2031455, to Colgate-Palmolive Company
(1978).
52. F. Ahmed, EP 318729 to Colgate-Palmolive Company (1989).
53. H. Raaf et al., DE 2440802 to Blendax Werke Schneider (1974).
54. W. J. King et al., U.S. Patent 3956478 to Colgate-Palmolive Co.
(1975).
55. R. Zimmerer and R. Berg, EP 18019 to Procter + Gamble Co.
(1979).
56. A. Takahashi et al., JP 84/040940 to Lion Corp. (1984).
57. Y. Yamazaki, JP 85/161920 to Lion Corp. (1990).
58. I. D. Hill, U.S. Patent 4942034-A to Hill ID (1990).
59. S. Mitsyama, JP 03,153,796 to Tamanohada Soap Co., Ltd.
(1991).
60. H. Takahashi et al., JP 85/269,578 to Sanyo Chem. Ind. Ltd.
(1987).
61. K. Tsubone, JP 90/28099, to Kanebo KKK (1990).
62. J. Shiomi, JP 93/95493 to Mandamu KK (1994).
63. A. Behler et al., WO 95/06702 to Henkel KGaA (1993).
64. W. Breitzke and A. Behler, DE 4328355 to Henkel KGaA
(1993).
65. W. Breitzke and A. Behler, DE 44067488 to Henkel KGaA
(1994).
66. J. K. Weil and A.J. Stirton, in Anionic Surfactants (W.M.
Linfield, ed.), Surfactant Science Series, Vol.7, Marcel Dekker,
New York, 1976, pp. 224230.
67. R. G. Bistline, Jr., in Anionic Surfactants (H. Stache, ed.),
Surfactant Science Series, Vol. 56, Marcel Dekker, New York,
1995, pp. 633634.
68. A. K. Reng, Parf. u. Kosmet. 61:87 (1980).
69. a) J. K. Weil, N. Parris, and A. J. Stirton, J. Am. Oil Chemists
Soc. 47:91(1970).
b) M. Fukuda and T. Tamura, JP 62001448 to Lion Corp (1987).
70. A. Fujio et al., JP 7070047 to Kao Corp. (1995).
 Page 283
71. A. El-Sawy, S.A. Essawy, M.M. El-Sukkary, and A.M.F. Eissa,
Hung. J. Ind. Chem. 20:25 (1992).
72. R. G. Bistline, Jr., W. R. Noble, F.D. Smith, W. M. Linfield, J.
Am. Oil Chemists Soc. 54:371 (1977).
73. M. Yoshio, S. Etsuo, and H. Yasushi, JP 55149243 to Nippon
Oils and Fats (1980).
74. M. A. Podustov et al., SU 1051068 to Kharkov Polytechnic
Institute (1983).
75. M. A. Podustov et al., SU 1544769 to Kharkov Polytechnic
Institute (1990).
76. A. K. Reng and J. M. Quack, Seifen Öle Fette Wachse 102:307
(1976).
77. (a) A. Turowski, W. Skrypzak, A.K. Reng, and P. Jürges,
Parfüm. Kosmet 76:16 (1995); (b) J. Bohunek, G. Täuber, H.
Berghausen, DE 1815657 to Farbwerke Hoechst AG (1968).
78. G. Crass, Tenside Surf., Det. 30:408(1993).
79. (a) T. Konekiyo et al., JP 1016898 to Mitsubishi Petrochemical
Co. (1989); (b) P. Goffinet, R. Canaguier, EP 189687 to Union
Generale de Savonnerie (1986).
80. F. Hironobu, K. Fumitaka, and M. Yoshio, JP 58015501 to
Nippon Oils and Fats (1983).
81. H. H. Friese, U. Ploog, and F. Pieper, DE 3419405 to Henkel
KGaA (1985).
82. R. Prather, U.S. Patent 4376088 to Upjohn Co.(1983).
83. G. D. Kudinova et al., SU 1151470 to Belorussian
Technological Institute (1985).
84. A. Yamamoto, Y. Arimoto, and M. Konno, BE 902736 to
Chemical Works Co. (1985).
85. R. Piorr, R. Höfer, H. J. Schlüssler, and K. Schmid, Fette
Seifen, Anstrichm. (1987).
86. M. J. Schwuger and R. Piorr, Tenside 24:70 (1987).
87. H. Baumann, Fat Sci. Technol. 92:4956 (1990).
88. A. Behr, in Aspects of Homogeneous Catalysis Vol. 5 (R. Ugo,
ed.) Reidel, Dordrecht, 1984 pp. 573.
89. B. Gruber, B. Fabry, B. Giesen, R. Müller, and F. Wangemann,
Tenside Surf. Det. 30:422(1993).
90. B. D. Condon, J. Am. Oil Chemists Soc. 71:739 (1994) and
71(7):743 (1994).
91. A. Domsch and B. Irrgang, in Anionic Surfactants (H.W.
Stache, ed.), Surfactant Science Series, Vol. 56, Marcel Dekker,
New York, 1995, p. 501.
92. Henkel KGaA, unpublished results.
93. J. A. Milm, R. Soc. Chem. (Ind. Appl. Surf.) 77:76(1990).
94. A. J. O'Lenick, Jr., and W.C. Smith, Soap Cosmet. Chem.
Spec. 64:36 (1988).
95. T. Schoenberg, Cosmet. Toiletries 105:105(1989).
96. J. Falbe (ed.), Surfactants in consumer products, Springer-
Verlag, Berlin, 1987, p. 83.
97. K. Lindner, in Tenside Textilhilfsmittel Waschrohstoffe, Vol. 1,
Wissenschaftliche Verlagsgesellschaft, Stuttgart, 1964, p. 747.
98. W. Kästner and P. J. Frosch, Fette Seifen Anstrichm. 83:33
(1981).
99. J. Valeé, Parfum. Cosmet. Savons 4:205 (1961).
100. G. Gawalek, in Tenside, Akademie Verlag, Berlin, 1975, p.
232.
101. B. Fabry, Tenside Surf. Det. 29:320 (1992).
102. R. Piorr and A. Meffert, 40th DGF lecture meeting,
Regensburg, 1984.
103. R. Piorr and A. Meffert, DE 3331513 to Henkel KGaA (1983).
104. C. Schoeller and M. Wittwer, U.S. Patent 1,970,578 to IG
Farbenindustrie A. G. (1934).
 Page 284
105. A. Steindorff, G. Balle, K. Horst, and R. Michel, U.S. Patent
2,213,477 to General Aniline and Film Corp. (1940).
106. F. Vögeli, Ann. Chem. 69:180 (1849).
107. A. Lassaigne, Ann. Chim. 3:294 (1820).
108. DE 2,658,862 to Hoechst AG (1976).
109. J. Nüsslein, Parfum. Cosmet. Savons 2:554 (1959); CA
54,7074 f(1960).
110. T. Kurosaki and A. Manbu, DE 3,047,378 to Kao Soap Co.
(1979).
111. K. Sasse, in Methoden der Organischen Chemie (E. Müller,
ed.), Thieme, Stuttgart, 1964, Bd. 12/2, p. 311.
112. G. Imokawa et al., J. Am. Oil Chemists Soc. 55:839 (1978).
113. H. Schlecht and H. Distler, DE 2,350,851 to BASF (1973).
114. T. Kurosaki and N. Nishikawa, DE 3,325,337 to Kao Soap Co.
(1982).
115. S. König and J. Langley, Henkel Corp., private information.
116. T. Fay, G. P. Sheridan, and D. R. Karsa, presented by Comite
Espanol de la Detergentes, XII. Jornado (1981).
117. A. Wiedemann, DE 3,735,049 to Sandoz (1986).
118. S. C Williamson, U.S. Patent 4,493,782 to Amchem Products
(1983).
119. F. B. Clarke and J. W. Lyons, J. Am. Chemists Soc. 88(19):
4401 (1966).
120. T. Kurosaki and A. Manba, DE 3,047,378 to Kao Soap Co.
(1979).
121. T. Kurosaki, J. Wakasuki, H. Furugaki, and K. Kojima, DE
3,520,053 to Kao Soap Co. (1984).
122. K. Sasse, in Methoden der Organischen Chemie (E. Müller,
ed.), Thieme, Stuttgart, 1940, Bd. 12/2, p. 143.
123. G. Uphues and U. Ploog, EP Patent 0,272,568 to Henkel KGaA
(1987).
124. O. Marten, Henkel do Brasil, private information.
125. U. Ploog and G. Uphues, Henkel Ref. 26:63 (1990).
126. G. Jaumann, E. Keck, M. Köhler, G. Uphues, A. Wilsch-
Irrgang, and W. Winkle, Fat Sci. Technol. 92:389 (1990).
127. H. Hirota, H. Ogino, H. Ishido, Y. Shibata, S. Igarashi, and C.
Fukami, U.S. Patent 4,758,376 to Kao Soap Co. (1985).
128. D. H. Birtwistle, P. Carter, and D. A. Rosser, EP 0,371,801EP
Patent 0,371,804 to Unilever (1988).
129. W. Skrypzak, A. K. Reng, and J. M. Quack, Parfüm.
Kosmet.60:317 (1979).
130. I. Homma, DE 2,927,278 to Kao Soap Co. (1980).
131. H. Hoffmann, F.-J. Gohlke, and B. Krönert, FR 2,011,893 to
Hoechst AG (1968).
132. H. Watanabe, M. Arisawa, and M. Koike, GB Patent 2,025,451
to Kao Soap Co. (1980).
133. J. P. G. Beiswanger, and A. Nassry, U.S. Patent 3,933,658 to
GAF Corp.(1970).
134. J. Kandler, K. Merkenich, G. K. Koehler, and H. Peters, DE
2,249,639 to Knapsack AG (1972).
135. L. Westermann, G. Sorbe, H.-D. Wasel-Nielen, and W. Klose,
EP 0,078,918 to Hoechst AG (1981).
136. H. Schranz, DE 1,142,803 to Klöckner-Humboldt-Deutz AG
(1957).
137. A. J. O'Lenick, Jr., U.S. Patent 5,070,171 to Siltech Inc.
(1991).
138. C. H. Hwa, S. F. Gelman, and P. Kraft, DE 2,035,792 to
Stauffer Chemical Co. (1970).
139. D. H. Lorenz and E. P. Williams, DE 2,533,043 to GAF Corp
(1974).
140. R. L. Hawkins, U.S. Patent 4,294,883 to Hoechst AG (1979).
 Page 285
141. R. Veitenhansl, and H. Thiel, in Schriftenreihe Deutsches
Wollforschungsinstitut, Aachen (1984).
142. J. Kamegai, Y. Kajihara, and M. Arisawa, EP 0,324,575 to Kao
Soap Co. (1988).
143. J. Kamegai and M. Arisawa, EP 0,324,451 to Kao Soap Co.
(1988).
144. T. Calageropoulou, M. Koufaki, A. Tsotinis, J. Balzerini, E.
De Clrecq, and A. Makriyannis, Antiviral Chem. Chemother.
6(1):43 (1995).
145. T. Imai and T. Murata, Biochem. Int. 19(16):1277 (1989).
146. Y. Homma et al., Cancer. Chemother. Pharmacol. 11(2):73
(1983).
147. J. G. Aalbers, Ph.D. thesis, Amsterdam, 1964.
148. W. Gerhardt et al., Tenside Surf. Det. 29:169 (1992).
149. J. G. Aalbers, Fette Seifen Anstrichm. 70:174 (1968).
150. S. Ebel and W Parzefall, Experimentelle Einführung in die
Potentiometrie, Verlag Chemie, Weinheim, 1975, p 150.
151. A. F. Bückmann et al., Makromol. Chem. 182:1379 (1981).
152. M. Leonard et al., Tetrahedron 40:1581 (1984).
153. H. A. Bruson, Org. Reactions 5:79 (1949).
154. R. V. Christian and R. M. Hixon, J. Am. Chem. Soc. 70:1333
(1948).
155. C. S. Hsia Chen, Org. Chem. 27:1920 (1962).
156. K. Heyns and L. Blasejewicz, Tetrahedron 9:67 (1960); K.
Heyns and H. Paulsen, Angew. Chem. 69:600 (1957); K. Fiege and
Wedemeyer, Angew. Chem. 93:812 (1981).
157. W. Gerhardt et al., Tenside Surf. Det. 29:285 (1992).
158. E. Kunkel, Tenside Surf. Det. 17:10 (1980).
159. E. T. Griffiths et al., Biotechnol. Appl. Biochem. 9:217 (1987).
160. H. König and Strobel, Fresenius Z. Anal. Chem. 728 (1990).
161. P. S. Klose and D. Menz, Erdöl-Erdgas-Z. 97:167 (1981).
162. J. A. Brenkmann, Chem. Weekbl. 63:73 (1967).
163. M. Matsuda et al., Kiyo-Suzuka Kogyo Koto Senmon Gakko
20:51 (1987).
164. N. A. I. van Paassen, Seifen Öle Fette Wachse 109:353
(1983).
165. E. Stroink, Seifen Öle Fette Wachse 115:235 (1989).
166. G. Czichocki et al., Fat Sci. Technol. 94:66 (1992).
167. K. Schulze, Seifen Öle Fette Wachse 101:37 (1975).
168. L. Leusink, C. Broer, Seifen Öle Fette Wachse 119:810 (1993).
169. H. Meijer, Chem. Ind. 58 (1988).
170. D. Balzer, Erdöl-Erdgas-Z. 36:514 (1983).
171. H. Meier, Seifen Öle Fette Wachse 114:159 (1988).
172. E. T. Griffiths et al, Biotechnol. Appl. Biochem. 9:217 (1987).
173. M. E. Chiddix and R. L. Sundberg, U.S. Patent 2,759,975 to
General Aniline and Film Corp. (1956).
174. C. Schoeller and E. Ploetz, U.S. Patent 2,214,352 to General
Aniline and Film Corp. (1940).
175. H. Rutzen, DE 2,844,451 to Henkel KGaA (1978).
176. E. Ploetz and H. Ulrich, U.S. Patent 2,127,476 to I. G.
Farbenindustrie A. G. (1938).
177. E. Ploetz and H. Ulrich, U.S. Patent 2,173,069 to I. G.
Farbenindustrie A. G. (1939).
178. G. Demmering, DE 2,052,321 to Henkel KGaA (1970).
 Page 286
179. J. Kolbe, W. Kortmann, and J. Pfeiffer, EP 0,075,770 to Bayer
A. G. (1982).
180. G. Uphues, unpublished results.
181. G. Uphues, U. Ploog, W. Becker, and I. Goebel, DE 3,807,069
to Henkel KGaA (1988).
182. U. Ploog and M. Petzold, DE 3,032,216 to Henkel KGaA
(1980).
183. M. Hofinger, A.K. Reng, and J. M. Quack, DE 3,345,156 to
Hoechst A. G. (1983).
184. H. Rutzen, Fette Seifen Anstrichm. 84:87 (1982).
185. R. J. Stenberg, U.S. Patent 2,983,738 to Archer-Daniels-
Midland Co. (1961).
186. E. L. Carpenter, U.S. Patent 2,372,624 to American
Cyanamide Co. (1945).
187. O. Manzke, DE 1,618,026 to Wella A. G. (1967).
188. J. R. Wechsler and M. Lane, U.S. Patent 4,370,272 to Stepan
Chemical Comp. (1981).
189. H. C. Parreira, E. R. Lukenbach, and M. K. O. Lindemann, J.
Am. Oil Chemists, Soc. 86:1015 (1979).
190. M. Saiki, Y. Imai, and M. Takagi, EP 0,240,622 to Takemoto
Yushi Kabushiki Kaisha (1986).
191. M. Hofinger, R. Kleber, and L. Jäckel, DE 3,325,228 to
Hoechst A. G. (1983).
192. M. Tsumadori, K. Shimizu, J. Inokoshi, and M. Murata, EP
0,299,176 to Kao Corp. (1988).
193. W. Wagemann, A. May, and H.-W. Bücking, DE 2,926,772 to
Hoechst A. G. (1979).
194. S. Nakamura, H. Kurokowa, and J. Mitamara, DE 3,642,009
to Lion Corp. (1985).
195. J. Faucher, EP 0,153,435 to Union Carbide Corp. (1984).
196. M. E. Spiess, Parfum. Kosmet. 72: 370 (1991).
197. C.-P. Herold, U. Ploog, G. Uphues, B. Spei, and V. Wehle, DE
4,002,472 to Henkel KGaA (1990).
 Page 287

Index
A
Acid-catalyzed ring opening, 22
N-Acyl, N-alkyl sugar amides, 186
N-Acyl, N-sugar amides, (CMCs), 186
Alkanolamides (sulfated), 252
application, 253
preparation, 252
properties, 253
Alkenyl polyoxyethylene ether sulfonates, 259
N-Alkyl amides, formulation, 182
Alkyl ether sulfates, 243, 247
application, 246
environmental aspects, 248
properties, 245
Alkyl polyoxyethylene alcohols (sulfated), 243
application, 246
properties, 245
Alkylamines, 167
 applications, 168
biodegradation, 168
CMC, 167
conductivity, 167
physical, 167
properties, 167
toxicity, 168
trade names, 169
Alkylphenols, 40
physical properties, 43
N-Alkyl sugar amides, 181
Amide ethoxylates, 183
physical properties, 184
producers, 183
products, 183
B
Base-catalyzed ring opening, 5
C
Carbohydrate esterification using enzymes, 234
Carboxylates, 266
applications, 270
 environmental aspects, 272
preparation, 266
properties, 270
toxicologic aspects, 272
Chevron ethylene oligomerization process, 90
 Page 288

D
Dialkyl disugar amides, 187
CMC, 188
Diethylene glycol esters, properties, 136
Dodecylphenol, 43
E
Enhanced oil recovery, 117
Enzyme-catalyzed esterification, 228
Esterification of fatty acids, 134
Ethoxylate solutions, viscosities, 113
Ethoxylated alkylamines, trade names, 169
Ethoxylated amides, derivatives, 180
Ethoxylation of alkanolamides, 179
Ethyl's ethylene oligomerization-displacement process, 91
Ethylene glycol esters, properties, 136
Ethylene glycol, esterification, 206
Ethylene oxide, 2, 40, 88, 130, 147, 153, 163, 180
F
Fatty acid amide ethoxylates, 183
physical properties, 184
 producers, 183
products, 183
Fatty acid monoglycerides (sulfated), 249
G
Gemini surfactants, 187
Glucamides, applications, 191
Glycerol ether sulfates, 254
Glycerol, esterification, 212
using enzymes, 230
Glycerolysis of fats and oils, 213
Glycol esters, 209
Glycol esters, esterification process, 211
homo- or copolymers, 209
oxyethylation process, 210
Glycol ethers of fatty acid amides, 178
H
Hydration of olefins, 99
Hydroformylation process, 94
Hydroxyalkyl polyoxyethylene sulfates, 253
L
Lauric fatty acid, 204
Liquid crystalline phases, 186
M
Mercaptans, 148
aliphatic primary, 148
aliphatic secondary, 149
aliphatic tertiary, 149
applications, 159
aromatic, 150
detergency, 158
foam breaking, 157
HLB, 155
properties, 155
solubility and cloud points, 155
viscosity, 155
wetting, 156
Metal alkoxide catalysts, 27
Metal phosphate catalysts, 29
Mixed metal oxide catalysts, 30
N
Natta equation, 15
Nonionics, physical properties of water-insoluble, 111
Nonylphenol, 40
Nonylphenols (polyoxyethylene)
cloud points, 59
foam heights, 67
physical properties, 57
Poisson distribution, 50
solubility, 63
surface properties, 66
surface tension, 65
viscosities, 61
wetting times, 67
O
Octylphenol, 42
 Page 289
Octylphenols (polyoxyethylene)
cloud points, 60
foam heights, 67
physical properties, 58
solubility, 64
surface properties, 66
surface tension, 65
viscosities, 62
wetting times, 68
Oleyl polyoxyethylene alcohol sulfonates, 257
Oxyethylation of fatty acid methyl esters, 141
P
Paraffin oxidation, 98
Phosphates, 259
applications, 264
preparation, 259
properties, 264
Poisson distribution, 14, 25, 48, 101
Polyglycerol esters, 216
Polyol ester surfactant families, 207
Polyol fatty acid ester, 202
Polyoxyalkylene amines, synthesis, 164
Polyoxyalkylene polyol esters, 226
Polyoxyethylated alkylamides, 184
Polyoxyethylated amides, applications, 188
Polyoxyethylene alcohols, 87
applications, industrial and institutional, 116
catalyst, 101
Chevron ethylene oligomerization process, 90
cloud point, 108
commercial production, 104
conventional, 100
detergency studies, 109
enhanced oil recovery, 117
ethyl's ethylene oligomerization-displacement process, 91
foaming, 114
household surfactants, 116
hydration of olefins, 99
hydroformylation process, 94
hydrophile-lipophile balance, 107
manufacturers, 111
 narrow range, 106
paraffin oxidation, 98
physical property, 109
Poisson distribution, 101
pour point, 108
preparation, 100
primary alcohols, 88
properties, 107
secondary alcohols, 97
Shell higher olefin process (SHOP), 92
Shell hydroformylation process, 95
solubility and wettability, 108
surface properties, 107
synthesis of hydrophobic intermediates, 88
wetting, 113
Ziegler alcohol process, 96
Polyoxyethylene alkenols (sulfonated), 257
Polyoxyethylene alkylamides, 178
Polyoxyethylene alkylamines, 163
applications, 168
biodegradation, 168
 CMC, 167
conductivity, 167
physical, 167
properties, 167
toxicity, 168
Polyoxyethylene alkylphenols, 44
applications, 68, 69
aquatic exposure/toxicity, 73
biodegradation, 71
mammalian toxicity, 76
 Page 290
[Polyoxethylene alkylphenols]
manufacture, 44
physical properties, 57
Poisson distribution, 48
producers, 45
product composition, 48
solution properties, 59
surface properties, 64
wastewater treatment, 78
Polyoxyethylene esters of castor oil, 134
properties, 138
Polyoxyethylene esters of fatty acids, 123
properties, 135
Polyoxyethylene esters of hydrogenated castor oil, properties, 138
Polyoxyethylene esters of lauric acid, properties, 136
Polyoxyethylene esters of oleic acid, properties, 138
Polyoxyethylene esters of ricinoleic acid, 134
Polyoxyethylene esters of stearic acid, properties, 137
Polyoxyethylene esters
biological degradation, 142
 industrial applications, 129
properties, 126
synthesis, 125
toxicologic aspects, 142
Polyoxyethylene fatty acid esters, analysis, 142
Polyoxyethylene mercaptans, 148
aliphatic primary, 148
aliphatic secondary, 149
aliphatic tertiary, 149
applications, 159
aromatic, 150
detergency, 158
foam breaking, 157
HLB, 155
properties, 155
solubility and cloud points, 155
viscosity, 155
wetting, 156
Polyoxyethylene monoesters
of fatty acids, surface tension, 128
of lauric acid, melting points, 127
Polyoxyethylene nonylphenols
cloud points, 59
foam heights, 67
physical properties, 57
Poisson distribution, 50
solubility, 63
surface properties, 66
surface tension, 65
viscosities, 61
wetting times, 67
Polyoxyethylene octylphenols
cloud points, 60
foam heights, 67
physical properties, 58
solubility, 64
surface properties, 66
surface tension, 65
viscosities, 62
wetting times, 68
Primary alcohols
natural sources, 88
 synthetic sources, 89
Propylene glycol, esterification, 207
Q
Quaternary ammonium compounds, 273
S
Secondary alcohols, 97
Shell higher olefin process (SHOP), 92
Shell hydroformylation process, 95
Sorbitan esters, 219
HLB, 227