principles-of-polymer-science-and-technology-in-cosmetics-and-personal-care.pdf

Principles of PolymerScience and Technology

in Cosmetics andPersonal Care

edited byE. Desmond Goddard

Former Corporate Research FellowUnion Carbide Corporation

Tarrytown, New York

James V. GruberAmerchol Corporation

Edison, New Jersey

M A R C E L

MARCEL DEKKER, INC. NEW YORK BASEL

D E K K E R

Copyright 1999 by Marcel Dekker, Inc. All Rights Reserved.

Library of Congress Cataloging-in-Publication Data

Principles of polymer science and technology in cosmetics and personalcare / edited by E. Desmond Goddard and James V. Gruber.

p. cm.(Cosmetic science and technology : v. 22)Includes bibliographical references and index.ISBN 0-8247-1923-9 (alk. paper)1. Cosmetics. 2. Toilet preparations. 3. Polymers. I. Goddard,

E. D. (Errol Desmond). II. Gruber, James V.III. Series: Cosmetic science and technology series : v. 22.TP983.P8924 1999668 .5dc21 99-17274

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About the Series

The Cosmetic Science and Technology series was conceived to permit discussion of a broad

range of current knowledge and theories of cosmetic science and technology. The series is

composed of both books written by a single author and edited volumes with a number of

contributors. Authorities from industry, academia, and the government participate in writing

these books.

The aim of the series is to cover the many facets of cosmetic science and technology. Topics are

drawn from a wide spectrum of disciplines ranging from chemistry, physics, biochemistry, and

analytical and consumer evaluations to safety, efficacy, toxicity, and regulatory questions.

Organic, inorganic, physical and polymer chemistry, emulsion and lipid technology,

microbiology, dermatology, and toxicology all play important roles in cosmetic science.

There is little commonality in the scientific methods, processes, and formulations required for

the wide variety of cosmetics and toiletries in the market. Products range from preparations for

hair, oral, and skin care to lipsticks, nail polishes and extenders, deodorants, body powders and

aerosols, to quasi-pharmaceutical over-the-counter products such as antiperspirants, dandruff

shampoos, antimicrobial soaps, and acne and sun screen products.

Cosmetics and toiletries represent a highly diversified field involving many subsections of


science and art. Even in these days of high technology, art and intuition continue to play animportant part in the development of formulations, their evaluation, selection of raw materials,

and, perhaps most importantly, the successful marketing of new products. The application of

more sophisticated scientific methodologies that gained steam in the 1980s has increased in such

areas as claim substantiation, safety testing, product testing, and chemical analysis and has led to

a better understanding of the properties of skin and hair. Molecular modeling techniques are

beginning to be applied to data obtained in skin sensory studies.

Emphasis in the Cosmetic Science and Technology series is placed on reporting the current

status of cosmetic technology and science and changing regulatory climates and presenting

historical reviews. The series has now grown to 26 books dealing with the constantly changing

technologies and trends in the cosmetic industry, including globalization. Several of the volumes

have been translated into Japanese and Chinese. Contributions range from highly sophisticated

and scientific treatises to primers and presentations of practical applications. Authors are

encouraged to present their own concepts as well as established theories. Contributors have been

asked not to shy away from fields that are in a state of transition, nor to hesitate to present

detailed discussions of their own work. Altogether, we intend to develop in this series a

collection of critical surveys and ideas covering diverse phases of the cosmetic industry.

The 13 chapters in Multifunctional Cosmetics cover multifunctional products for hair, nail, oral,

and skin care, as well as products with enhanced sunscreen and antimicrobial properties Several

chapters deal with the development of claim support data, the role of packaging, and consumer

research on the perception of multifunctional cosmetic products. The authors keep in mind that

in the case of cosmetics, it is not only the physical effects that can be measured on the skin or

hair, but also the sensory effects that have to be taken into account. Cosmetics can have a

psychological and social impact that cannot be underestimated.

I want to thank all the contributors for participating in this project and particularly the editors,

Perry Romanowski and Randy Schueller, for conceiving, organizing, and coordinating this book.

It is the second book that they have contributed to this series and we appreciate their efforts.

Special thanks are due to Sandra Beberman and Erin Nihill of the editorial and production staff

at Marcel Dekker, Inc. Finally, I would like to thank my wife, Eva, without whose constant

support and editorial help I would not have undertaken this project.

Eric Jungermann, Ph.D.


COSMETIC SCIENCE AND TECHNOLOGY

Series Editor

ERIC JUNGERMANNJungermann Associates, Inc.

Phoenix, Arizona

1. Cosmetic and Drug Preservation: Principles and Practice, edited by Jon J.Kabara

2. The Cosmetic Industry: Scientific and Regulatory Foundations, edited by NormanF. Estrin

3. Cosmetic Product Testing: A Modern Psychophysical Approach, Howard R.Moskowitz

4. Cosmetic Analysis: Selective Methods and Techniques, edited by P. Bor5. Cosmetic Safety: A Primer for Cosmetic Scientists, edited by James H. Whittam6. Oral Hygiene Products and Practice, Morton Pader7. Antiperspirants and Deodorants, edited by Karl Laden and Carl B. Felger8. Clinical Safety and Efficacy Testing of Cosmetics, edited by William C. Waggoner9. Methods for Cutaneous Investigation, edited by Robert L. Rietschel and Thomas

S. Spencer10. Sunscreens: Development, Evaluation, and Regulatory Aspects, edited by

Nicholas J. Lowe and Nadim A. Shaath11. Glycerine: A Key Cosmetic Ingredient, edited by Eric Jungermann and Norman

O. V. Sonntag12. Handbook of Cosmetic Microbiology, Donald S. Orth13. Rheological Properties of Cosmetics and Toiletries, edited by Dennis Laba14. Consumer Testing and Evaluation of Personal Care Products, Howard R. Mos-

kowitz15. Sunscreens: Development, Evaluation, and Regulatory Aspects. Second Edition,

Revised and Expanded, edited by Nicholas J. Lowe, Nadim A. Shaath, andMadhu A. Pathak

16. Preservative-Free and Self-Preserving Cosmetics and Drugs: Principles andPractice, edited by Jon J. Kabara and Donald S. Orth

17. Hair and Hair Care, edited by Dale H. Johnson18. Cosmetic Claims Substantiation, edited by Louise B. Aust19. Novel Cosmetic Delivery Systems, edited by Shlomo Magdassi and Elka Touitou20. Antiperspirants and Deodorants: Second Edition, Revised and Expanded, edited

by Karl Laden21. Conditioning Agents for Hair and Skin, edited by Randy Schueller and Perry

Romanowski22. Principles of Polymer Science and Technology in Cosmetics and Personal Care,

edited by E. Desmond Goddard and James V. Gruber23. Cosmeceuticals: Drugs vs. Cosmetics, edited by Peter Elsner and Howard I.

Maibach24. Cosmetic Lipids and the Skin Barrier, edited by Thomas Frster25. Skin Moisturization, edited by James J. Leyden and Anthony V. Rawlings26. Multifunctional Cosmetics, edited by Randy Schueller and Perry Romanowski

ADDITIONAL VOLUMES IN PREPARATION

Series Introduction

The Cosmetic Science and Technology series was conceived to permit discussion of abroad range of current knowledge and theories of cosmetic science and technology. Theseries is made up of books either written by a single author or edited with a number ofcontributors. Authorities from industry, academia, and the government are participatingin writing these books.

The aim of this series is to cover the many facets of cosmetic science and technology.Topics are drawn from a wide spectrum of disciplines ranging from chemistry, physics,biochemistry, analytical and consumer evaluations to safety, efficacy, toxicity, and regula-tory questions. Organic, inorganic, physical, and polymer chemistry, as well as emulsiontechnology, microbiology, dermatology and toxicology all play a role in cosmetic science.

There is little commonality in the scientific methods, processes, or formulations re-quired for the wide variety of cosmetics and toiletries manufactured. Products range fromhair care, oral care, and skin care preparations to lipsticks, nail polishes and extenders,deodorants, body powders and aerosols, to over-the-counter products, such as antiperspi-rants, dandruff treatments, antimicrobial soaps, and acne and sunscreen products.

Cosmetics and toiletries represent a highly diversified field with many subsections ofscience and art. Indeed, even in these days of high technology, art and intuitioncontinue to play an important part in the development of formulations, their evaluation,and the selection of raw materials. There is a move toward more sophisticated scientificmethodologies in the fields of preservative efficacy testing, claim substantiation, safetytesting, product evaluation, and chemical analyses.

Emphasis in the Cosmetic Science and Technology series is placed on reporting thecurrent status of cosmetic technology and science in addition to historical reviews. Severalof the books have found an international audience and have been translated into Japaneseor Chinese. Contributions range from highly sophisticated and scientific treatises to prim-ers, practical applications, and pragmatic presentations. Authors are encouraged to presenttheir own concepts, as well as established theories. Contributors have been asked not toshy away from fields that are still in a state of transition, or to hesitate to present detaileddiscussions of their own work. Altogether, we intend to develop in this series a collectionof critical surveys and ideas covering diverse phases of the cosmetic industry.


iv Series Introduction

Principles of Polymer Science and Technology in Cosmetics and Personal Care isthe twenty-second volume published in this series. Polymers are important componentsin a broad range of cosmetic and personal care products. They fill a multitude of functionstoo numerous to list. This book covers the many classes of polymers used in almost everytype of cosmetic formulation and their wide range of applications, special properties, andsometimes specialized requirements.

I want to thank the editors, E. Desmond Goddard and James V. Gruber, and all thecontributors for collaborating in the editing and writing of this book. Special recognitionis also due to Sandra Beberman and the editorial staff at Marcel Dekker, Inc. In addition,I would like to thank my wife Eva, without whose constant support and editorial help Iwould never have undertaken this project.

Eric Jungermann, Ph.D.


Preface

Although synthetic polymers first appeared in the last century, it has been the twentiethcentury, especially the second half, which has witnessed an explosive growth in the devel-opment and use of this category of material. Indeed, it is difficult to think of many indus-tries today that do not employ polymers in some form or another. Such employment, ofcourse, includes that by the cosmetic and personal care industry in which the use of poly-meric materials continues to develop rapidly. This trend will continue in the next century.

Polymer sciencealready starting from a solid foundation with the early recognitionthat many natural products, including proteins and polysaccharides, are polymerichasgrown apace with these developments. Today some would aver that it has been difficultfor many scientists, including those actually involved in research and development workinvolving polymers, to keep abreast of recent theoretical developments, let alone to retaina working familiarity with what has evolved today as basic polymer science. Be this asit may, a need was identified for a book that could be used not only as a reference sourcefor the polymers currently used in the cosmetics industry, but also as a source of informa-tion on the basic physical chemistry of polymers as it applies to the functions they servein the formulation and use properties of cosmetics. Furthermore, because of both the latterfeatures and the overlapping of technology, it seems that such a text might also be founduseful by investigators in related fields such as detergent formulation, pharmaceuticals,textiles, and even the latex paint industry. Bearing in mind the breadth of the field, weinvited the participation of several other authors, all recognized as experts in their area(s)of polymer science. We believe the result is a comprehensive coverage of the field desig-nated by the title of the book.

The body of the text consists of 12 self-standing chapters comprising a mix of thefundamental science of polymers, their solution and interfacial properties, their interac-tions with surfactants, the intrinsic properties of polymers employed in cosmetic formula-tions, and the properties they confer to treated surfaces. There is also an appendix whichlists and groups the polymers used in cosmetics.

Chapter 1 is an introduction to polymer science, covering its history, fundamentals,and recent developments. The reader is introduced to the different types of polymers, their


vi Preface

classification and synthesis, molecular weight definitions, and properties in the solid andsemisolid state. There follows an overview of the properties of polymers in solution start-ing with their thermodynamics, considerations of molecular size and shape, and finallytheir rheology. It concludes with a list of about 50 definitions used in polymer science,potentially useful to newcomers and seasoned practitioners alike.

Many uses of polymers are concerned with the properties of polymers at interfaces.Chapter 2 presents a summary of theories of polymer adsorption and discusses the proper-ties and state of polymers at interfaces and methods for determining the details of theirstructure, conformations, and so on. The basic theory of colloid-interaction forces in termsof DLVO theory is presented, together with a discussion of the different basic stabilizationmechanisms of colloids.

In Chapter 3, the solution and surface properties of a relatively new class of material,namely, polymeric surfactants, are illustrated in some detail using Flory-Huggins theoryand current polymer-adsorption theory. This is followed by a discussion of the phenome-non of steric stabilization of suspended particles and how it is affected by the detailedstructure of the stabilizing polymeric species. It concludes with a discussion of the stabili-zation of emulsions by interfacial and bulk rheological effects, and presents closing com-ments on multiple emulsions.

When polymers are employed in personal care formulations, in many (if not most)cases they occur as cocomponents with surfactants. Recognizing a widespread tendencyof such components to interact and affect each others properties (sometimes in dramaticways), Chapter 4 outlines a number of methods to investigate and analyze such interactionfor the main types of polymersnonionic, ionic, hydrophobic, and proteinaceous.Chapter 5 presents an illustrative selection of polymer/surfactant interactions in appliedsystems that demonstrates how they can be selected to achieve beneficial performanceeffects.

Realizing that many practicing formulation chemists and research scientists are seek-ing more immediate and nontheoretical discussion of the polymers used so frequently incosmetics and personal care, the next four chapters were written to address, in a more nuts-and-bolts fashion, the most popular and widely used polymers employed in the industry,including synthetic polymers, silicone polymers, polysaccharides, and proteins. However,the intent of the authors of these four chapters was not simply to describe lists of formula-tions, but instead to try and discuss the basic knowledge of these four polymer groupsand to develop insights into 1) how one might better formulate with these materials and2) what behavioral aspects one might expect in using a particular polymer.

Synthetic polymers are ubiquitous in the personal care industry. Chapter 6 strives toaddress this rather broad topic in a straightforward and easily readable fashion. The chapterstarts with a brief discussion of how synthetic polymers are made and the nomenclatureused to describe some of the more basic structural principles of synthetic polymers. Itexpands to address many of the synthetic polymers used in personal care formulationsbased principally on their primary mode of operation, including thickening polymers, fixa-tive polymers, conditioning polymers, and encapsulating polymers, the last subject becom-ing more important as formulators develop more sophisticated topical systems to deliveractive materials.

Chapter 7 discusses the phenomenal range and use of silicone polymers that can befound in nearly every branch of personal care and cosmetic development. The chapterdiscusses how the polymers are made, essentially from sand, and the nomenclature usedto describe the many different types of silicone-based polymers found in the industry.


Preface vii

A lengthy discussion follows, covering how the polymers behave in use, the spreadingcharacteristics, and the many beneficial properties silicone polymers offer when deliveredto keratinous surfaces. The chapter concludes with a thorough discussion of the safetyand environmental impact of silicone-based polymers.

Chapter 8 is a review of the use of polysaccharides, perhaps some of the oldest andmost well-known ingredients used in personal care. Because polysaccharides are derivedfrom natural sources, the nature of the monosaccharides that comprise these sugar-basedpolymers and how nature designs the polysaccharides are addressed first. This discussionis followed by greater details of individual cosmetically important polysaccharides basedprimarily on the ionic nature of the polysaccharide, that is, anionic, cationic, nonionic,or amphoteric, which can be either naturally developed by the polysaccharide source ormanipulated by human intervention and invention. The effects of hydrophobic modifica-tion of polysaccharides are also discussed. The chapter concludes with a brief discussionof certain polysaccharides that appear to have physiological effects on the human bodywhen applied topically.

Chapter 9 addresses the important issues and chemistry surrounding the use of pro-teins in personal care. The chapter begins with a thorough review of the structural proper-ties of proteins, including the basic amino acids of which they are composed, the varioussources (both plant and animal) of the beneficial proteins, and how these amino-acid-based polymers develop secondary, tertiary, and quaternary structures as they form. Thechapter then addresses how proteins behave in formulations and how their functionalitycan be interrupted or changed by formulations or modification of the proteins that affectthese unique protein-folding structures. It concludes with a timely discussion coveringprotein contaminants, particularly bovine spongiphorm encephalopathy (BSE), a humancontagion the nature of which has appeared to grip the industry somewhat emotionally.

Polycationic materials are well known and have long been used as conditioning agentsfor hair and skin. Chapters 10 and 11 discuss methods employed, and results obtained,in measurements of their sorption by these substrates. These model studies show thatuptake of polymer can be substantial, vastly exceeding that required for simple mono-layer coverage. Presumably what is involved is the substantial swelling, and the develop-ment of diffusion channels, in these substrates on immersion in water. Although some ionicsurfactants, that is, anionic, or especially cationic surfactants, can substantially reduce theuptake, they do not eliminate it.

The last chapter (12) is concerned with evaluation methods of polymer-conditionedhair. The first part deals with single-fiber evaluation and includes contact angle, electroki-netic, fluorimetry, friction, and cuticle-cohesion measurements. The second part deals withhair assemblies and includes measurements of combing, body, optical properties, andstatic electrification.

Finally, in the appendix, there is a comprehensive listingan encyclopediaofthe polymers used in the cosmetic industry, together with their INCI designations and abrief description of the polymers. We believe that inclusion of this updated compendiumadds substantially to the general utility of the book.

On a personal note, Dr. Goddard wishes to express his appreciation to Union Carbideand Amerchol Corporation for sustained support of his own research work on many ofthe subjects dealt with in this volume. This work would not have been possible withoutthe cooperation and contributions of many of his former colleagues, including, especially,J. A. Faucher, R. B. Hannan, P. S. Leung, and K. P. Ananthapadmanabhan. In particularhe wishes to thank the last-mentioned (Ananth) for many fruitful discussions during


viii Preface

compilation of Chapter 5. Lastly, he wishes also to express his appreciation to J. V. Gruberwho, as coeditor of this book and author of two chapters and in many other ways, playeda key role in making this undertaking a reality.

Dr. Gruber would like to recognize the friendship and professional relationship whichhas developed with E. D. Goddard as a result of this undertaking, and to express hisappreciation for being invited to become a part of this project. In addition, he wishes torecognize the help that Freida DeBaro provided in completing the chapters he worked on.Her assistance was invaluable. He would also like to thank Frank J. Freiler and the Amer-chol Corporation for giving him the opportunity to work on this volume. Both editorsthank Sandra Beberman for her help in making the project move along quickly and profes-sionally. Dr. Gruber is indebted to Lori Riday for her patience and understanding as thisproject borrowed many weekends of personal quality time. He would like to dedicate hisefforts on this book to his family and especially to his brother Steve Gruber.

E. Desmond GoddardJames V. Gruber


Contents

Series Introduction Eric JungermannPreface E. Desmond Goddard and James V. GruberContributors

1 Elements of Polymer ScienceFrancoise M. Winnik

2 Polymer Adsorption: FundamentalsTimothy M. Obey and Peter C. Griffiths

3 Polymeric Surfactants: Stabilization of Emulsions and DispersionsTh. F. Tadros

4 Polymer/Surfactant Interaction: Manifestations, Methods,and MechanismsE. Desmond Goddard

5 Polymer/Surfactant Interaction in Applied SystemsE. Desmond Goddard

6 Synthetic Polymers in CosmeticsJames V. Gruber

7 Silicones in CosmeticsMarianne D. Berthiaume

8 Polysaccharide-Based Polymers in CosmeticsJames V. Gruber


9 Proteins in CosmeticsAlessandro Teglia and Gianfranco Secchi

10 Measuring and Interpreting Polycation AdsorptionE. Desmond Goddard

11 The Adsorptivity of Charged and Uncharged Cellulose EthersE. Desmond Goddard, R. B. Hannan, and J. A. Faucher

12 Evaluation Methods for Conditioned HairHans-Dietrich Weigmann and Yashavanth Kamath

Appendix: Encyclopedia of Polymers and Thickeners for CosmeticsRobert Y. Lochhead and James V. Gruber


Contributors

Marianne D. Berthiaume, M.Sc. Personal CareWorldwide, Wacker Silicones Corpo-ration, Adrian, Michigan

E. Desmond Goddard, Ph.D. Former Corporate Research Fellow, Union Carbide Cor-poration, Tarrytown, New York

Peter C. Griffiths, Ph.D. Department of Chemistry, Cardiff University, Cardiff, Wales

James V. Gruber, Ph.D. Amerchol Corporation, Edison, New Jersey

Yashavanth Kamath, Ph.D. TRI/Princeton, Princeton, New Jersey

Robert Y. Lochhead, Ph.D. Department of Polymer Science, University of SouthernMississippi, Hattiesburg, Mississippi

Timothy M. Obey, Ph.D. School of Chemistry, University of Bristol, Bristol, England

Gianfranco Secchi Kelisema Italy, Tavernerio, Italy

Th. F. Tadros, Ph.D. Department of Chemical Engineering, Imperial College, London,England

Alessandro Teglia, Ph.D. Kelisema Italy, Tavernerio, Italy

Hans-Dietrich Weigmann, Ph.D. TRI/Princeton, Princeton, New Jersey

Francoise M. Winnik, Ph.D. Department of Chemistry, McMaster University, Hamil-ton, Ontario, Canada


1Elements of Polymer Science

Francoise M. WinnikMcMaster University, Hamilton, Ontario, Canada

I. INTRODUCTIONPolymers are molecules consisting of a large number of identical low molar mass units,named repeat units, that are connected covalently. If -A- is the base unit, then a polymermolecule or macromolecule is represented by:

-A-A-A-A-A-A or (A)n

where n is an integer, called degree of polymerization of this macromolecule. Before1930, polymer molecules were generally considered as physical aggregates of unchangedmonomer molecules (A)n, so-called association colloids. However, already in 1920, Stau-dinger had postulated that these colloidal particles were composed of a single, very longmolecule, a macromolecule. This revolutionary concept paved the way for synthetic or-ganic chemists, in particular Carothers, to start building such macromolecules in a system-atic way from known monomers. Since the 1930s, many thousands of polymers havebeen prepared, but less than 100 of them have reached the phase of large-scale industrialproduction. For accounts of the history of polymer science and technology, see, for exam-ple, Refs. 1 and 1a.

Polymers represent a significant share of raw materials used in the cosmetics industry.They are usually classified according to their use, such as thickening agents, film formers,resinous powders, and humectants. Thickening agents are used to adjust the viscosity ofproducts to make them easy to use and to maintain the product stability. For example,they are used to ensure the stability of milky lotions and liquid foundations by preventingthe separation of emulsified particles and powders. Thickening agents polymers are inwidespread use for this specific purpose. Natural polymers, gums and resins, have beenused in the industry since the early 1940s as water-soluble binders, thickeners, and film-forming agents. In todays products they are added to many cosmetics formulations tofulfill these various functions, but often they are used simply because of the growingconsumer demand for natural products. There are drawbacks, however, to the use ofpolymers isolated from natural sources: they vary in purity and physical appearance, andthey are relatively expensive, compared to common synthetic polymers. Problems securing


2 Winnik

stable supplies coupled with variations in viscosity and microbial contamination led to achange to synthetic or semisynthetic substitutes. Synthetic or semisynthetic polymers,which are chemically modified natural polymers, have been developed to match the prop-erties of gums and resins. Today, the industry is driven by a need of improved formula-tions, attainable through the use of current synthetic methodology and through the under-standing of the molecular interactions between the polymers and the other componentsof a care product.

This chapter covers the chemistry, physical properties, and thermodynamics of poly-mers. First are discussed various methods of macromolecule preparation. Next are dis-cussed the physical properties of polymers in the bulk, with emphasis on the morphologyand rheology of polymeric materials. Finally, several aspects of polymer solutions arediscussed, including their thermodynamics and rheological properties, which will be re-lated to molecular parameters such as chain conformation. Current theories that accountfor the properties of macromolecules in the bulk and in solution are presented briefly. Thereader is encouraged to seek further information in specialized texts (27), dictionaries(8), and encyclopedia (911).

A. Natural and Synthetic Polymers1. BiopolymersProteins, polysaccharides, natural rubber, and gums are all natural polymers. The repeatunits in proteins are amino acids. Nucleic acids are composed of nucleotides and polysac-charides consist of sugar units.

a. Proteins and Polypeptides. Amino acids in proteins are linked by an amidelinkage between the amino group of one molecule and the carboxyl group of another.This amide bond is often called peptide bond (Fig. 1). There are simple proteins composedonly of amino acids, such as albumin, gelatin, casein, collagen, or keratin. Other proteinscontain not only amino acid residues, but also other groups such as carbohydrates in glyco-proteins, or lipids in lipoproteins. Proteins that possess catalytic activity are known asenzymes.

b. Polysaccharides. The repeat units of polysaccharides are simple carbohydrates(sugars) linked to each other by acetal bonds (Fig. 1). Among the important polysaccha-rides are homopolymers of glucose (starch, glycogen, and cellulose), mannose (guar), oramino-sugars, such as chitosan and hyaluronan. Polysaccharides are important materials ofthe cosmetics industry. Their chemistry and physical properties are presented in Chapter 8.

2. Synthetic PolymersCarothers, in 1929, classified synthetic polymers into two classes, according to the methodof their preparation, i.e., condensation polymers and addition polymers. In polycondensa-tion, or step-growth polymerization, polymers are obtained by reaction between two poly-functional molecules and elimination of a small molecule, for example water. Typicalcondensation polymers are shown in Figure 2. Addition (or chain reaction) polymers areformed from unsaturated monomers in a chain reaction. Examples of addition polymersare shown in Figure 2.

We will conform to Carothers classification in the sections devoted to the preparationof synthetic polymers. However, when considering the application of polymers it is moreuseful to consider the following three categories: (1) plastics, which include thermosettingresins, such as urea resins, polyesters, or epoxies, and thermoplastic resins, such as poly-


Elements of Polymer Science 3

Figure 1 Chemical structures of natural polymers.


4 Winnik

Figure 2 Chemical structures of synthetic polymers.

ethylene, polystyrene, or poly(propylene); (2) fibers, which include cellulosics, such asrayon and acetate, and noncellulosic polymers, such as polyester and nylon; and (3) rub-bers, for example styrene-butadiene copolymer.

B. Definitions and NomenclatureHomopolymers are derived from one type of monomer, whereas copolymers require twoor more species of monomers. Copolymers are distinguished according to the sequence



Table 1 Sequence of Monomer Units in Various Copolymers

Copolymer type Schematic composition

Statistical or random

Alternating

Diblock

Triblock

Graft

of the various monomer units. They are subdivided into the major classes listed in Table1. The simplest polymers consist of regular macromolecules, with only one repeat unitin a single sequential arrangement. Examples are poly(acrylic acid), polystyrene, and poly-ethylene (Fig. 2). The constitutional units form a linear chain. Cyclic polymer moleculesresult if the two ends of a linear macromolecule are connected. They are called macro-cycles (12). Small amounts of cyclic molecules are often formed as by-products duringthe synthesis of linear chains. Combinations of linear molecules, of linear molecules withcyclic molecules, and of cyclic macromolecules themselves lead to a great variety ofmolecular architectures (Fig. 3).

Figure 3 Major macromolecular architectures.


6 Winnik

Linear chains may also be arranged at short intervals along a single main chain viatrifunctional branch points. These comb polymers can be synthesized by polymeriza-tion of macromers (a monomer consisting of a polymerizable group linked to a shortpolymer chain) or by grafting (13). Branched polymers contain branch points (junctions)that connect three or four subchains, which may be side chains or parts of a main chain.Polymers are statistically branched if side chains of different lengths are irregularly distrib-uted along the main chain. These polymers resemble trees. In star polymers (14) three ormore branches sprout from a common core. Star polymers with multifunctional ends onthe arms can add additional monomers. The resulting polymers, known as dendrimers(15), can be considered as tree polymers with regular sequences of branches or star poly-mers with subsequent secondary branches.

In cross-linked polymers, all molecules of a sample are interconnected by manybonds, resulting in a single, infinitely large molecule. Networks can be generated byintermolecular covalent bond or by physical junctions, such as ion clusters, crystallites,or microphases. Physical (noncovalently bound) networks can in principle be dissolvedby a solvent, whereas chemical (covalently bound) networks are insoluble in all solvents.The chemical properties of polymer networks depend strongly on the chemical structureof the chemical chain and the type of junction. The mechanical properties are primarilydictated by the cross-link density and by the mobility of the chain segments. Networksmay thus be soft, elastic, brittle, or hard. Two independent networks may interpenetrateto form interpenetrating networks (IPN) (16). Nail enamels are examples of physical net-works formed upon solvent evaporation, with no chemical cross-linking during drying butonly physical interactions among their polymer constituents, primarily nitrocellulose andsynthetic resins.

A classification of polymers especially useful in the case of water-soluble polymersis based on the electric charge born by the macromolecule. Electrically neutral water-soluble polymers include various polysaccharides, mostly cellulose ethers, polyacryl-amides, and certain polyethers, such as poly(ethylene glycols). Polyelectrolytes are water-soluble polymers with many electrically charged groups per molecule. They form polyionson dissociation. These polyions may be polyanions with negative charges as in dissociatedpoly(acrylic acid) [CH2 CH(COO2)]n or polycations as in protonated poly(vinyl-amine), [CH2 CH(NH3)1]n . They may also be polysalts, as in the sodium salt ofpoly(acrylic acid), [CH2 CH(COONa)]n . Polyions should be distinguished frommacroions, which carry only one ionic group, usually at one chain end. Water-insolublepolymers with relatively few ionic groups in the chain are known as ionomers.

II. PREPARATIONS OF MACROMOLECULAR COMPOUNDSSynthetic polymers are prepared by one of two fundamentally different approaches: (a)polymerization of monomer molecules or (b) modification of existent macromoleculesinto macromolecules of different constitution, a process known as polymer analog reaction(1719). Both methods are described briefly in this section, starting with the polymeriza-tion reactions, which can proceed via two different processes, condensation reactions instep-growth polymerizations and addition reactions in chain-growth polymerizations.

A. Step-Growth PolymerizationThe term step-growth polymerization refers to the process in which the polymer molecu-lar weight increases in a slow, step-like manner as reaction time increases. This polymeri-



zation depends entirely on individual reactions of the functional groups of monomers.Random reactions of two molecules occur between any combination of a monomer, oligo-mer, or a longer-chain molecule. High-molecular-weight polymers are formed only nearthe end of the polymerization, when most of the monomer has been depleted. Polyesters,polyamides, polyurethanes, and polycarbonates are prepared by step-growth polymeriza-tion (Fig. 4).

The polycondensation technique can also be applied to prepare organic-inorganicpolymers. The most important such polymers are the polysiloxanes, also known as siliconepolymers such as dimethicone, based on the Si O linkage present in glass or sand(see Chapter 7). They are made by polymerization of a low-molecular-weight cyclic ana-log, such as octamethylcyclotetrasiloxane. When this compound is heated above 100 Cwith a trace of an acid or base, it polymerizes to form a highly viscous liquid. Althoughthe dimethylsiloxane structure forms the basis of most silicone polymers, other substituentshave also been introduced as cosubstituents. These include vinyl, ethyl, phenyl, and n-alkyl groups. Polysiloxanes are among the most flexible macromolecules known. Theyalso repel water. Partly because of this property, they are used in protective hand-and-body lotions and creams. They are incorporated also in hair-care formulations to improveluster and sheen.

Condensation polymers can be prepared by several techniques:

The melt technique, where an equimolar mixture of two monomers is heated, possiblyin the presence of a catalyst. It is an equilibrium process in which the polymeris formed by driving the reaction to completion by removal of the by-products,such as water or hydrochloric acid.

The solution condensation, where equimolar amounts of the two monomers are dis-

Figure 4 Synthetic scheme for the preparation of condensation polymers.


8 Winnik

solved in a solvent, which should also be a solvent for the polymer. It is anequilibrium reaction, driven to completion by removal of the by-products, but ithas to be carried out at temperatures lower than melt polycondensations.

The interfacial technique (20), which is a heterophase process where two fast-reactingreactants are dissolved in a pair of immiscible solvents, one of which is usuallywater. The aqueous phase contains a diol or a diamine; the organic phase containsa diacid chloride dissolved in a solvent such as dichloromethane, toluene, ordiethyl ether. Condensation occurs at the water/organic solvent interface oftenin the presence of a phase transfer catalyst.

B. Chain-Growth PolymerizationIn this process, the only chain-extension reaction is that of attachment of a monomer toa growing active chain. The active end group may be a free radical, an anion, or acation. In contrast to step-growth polymerization, some high-molecular-weight polymeris formed in the early stage of the addition polymerization.

1. Free-Radical Polymerization (21)The general scheme for free-radical polymerization can be expressed as follows:

Initiator fi R Initiation

R 1 M fi MR Chain propagation

MR 1 M fi M2 R

MnR 1 Mm R fi Mn1m Chain termination

where M represents the monomer molecule and R a free radical produced in the initialstep. Commonly used initiators are peroxides, such as potassium persulfate (soluble inwater) or benzoyl peroxide (soluble in organic solvents), and aliphatic azo compounds,such as azobisisobutyronitrile (AIBN).

Various experimental techniques may be used to carry out free radical polymeriza-tions. The choice of method is guided on the one hand by the solubility of the monomersand polymers and on the other hand by the preferred isolation method for the polymer.Common techniques are:

1. Bulk polymerization, where the reaction is carried out without solvent.2. Solution polymerization, which is done in an inert liquid that dissolves both the

monomer and the polymer.3. Precipitation polymerization, which takes place in an inert liquid that dissolves

the monomer, but not the polymer. The polymer is isolated by filtration or de-cantation.

4. Suspension polymerization, which is used with water-insoluble monomers sus-pended in water as droplets. Coalescing of the droplets is prevented by use ofsmall amounts of a stabilizer, usually a water-soluble polymer, such as poly(vinylalcohol). The polymer is isolated in the form of discrete particles 101000 nmin diameter.

5. Emulsion polymerization (22), which takes place in a suspension in water of a



water-insoluble monomer in the presence of a surfactant and a water-soluble initi-ator. Unlike suspension polymerization, this technique produces polymer in theform of a latex, or stable dispersion in water of polymer particles ranging in sizefrom 0.05 to 5 nm.

2. Ionic PolymerizationIonic polymerizations are initiated by ionic species. The active chain end is an ion, eithera carbanion, C2, in the case of anionic polymerizations (23,24) or a carbocation, C1, inthe case of cationic polymerizations (25,26). They have to be carried out in organic sol-vents under strictly anhydrous and oxygen-free conditions. Anionic polymerizations areperformed with monomers that contain a double bond substituted with an electron-with-drawing group, such as styrene and various acrylic monomers, and also with oxiranes,such as ethylene oxide, which polymerize by a ring-opening mechanism. Macroanions insolution continue to grow until all initially present monomer molecules are consumed.Addition of new monomer leads to further polymerization. Such polymerizations withoutinternal or external termination reaction are called living polymerizations. They are usefulto synthesize homopolymers with narrow-molecular-weight distribution and star or blockcopolymers.

Cationic polymerizations are started by reaction of electrophilic initiator cations withelectron-donating monomer molecules. Catalysts are Lewis acids and Friedel-Crafts cata-lysts, such as aluminum trichloride (AlCl3), and strong acids, such as sulfuric acid (H2SO4).Monomer molecules able to undergo cationic polymerization include electron-rich olefins,such as vinyl aromatics and vinyl ethers, and ring compounds, such as ethylene oxide andtetrahydrofuran.

Other types of chain-growth polymerizations include: (a) insertion polymerizations,such as the Ziegler-Natta process used in the preparation of polyethylene and metathesispolymerizations (27,28), and (b) group transfer polymerizations, a process in which aninitiator molecule transfers its active group to a monomer molecule under the action ofa catalyst.

C. Polymerization KineticsCondensation reactions follow kinetic schemes similar to those of small molecule reac-tions. They are simple first-order, second-order, etc. reactions. In contrast, the kinetics ofchain reactions, such as free-radical polymerization or ionic polymerization, are muchmore complicated.

1. Condensation Reactions (29)We will discuss the case of polyesterifications, typical condensation reactions that takeplace by reaction of a diol (A, HO R OH) and a diacid (B, HOOC R COOH):

n HO R OH 1 n HOOC R COOH fi H [O R OCO R COO]n2

The experimental rate of polycondensation polymerization is given by the following ex-pression (Eq. 1), where k is the rate constant:

2d[B]dt

5 k[B]2[A] (1)

If [B] 5 [A] 5 c, where c is the monomer concentration at time t, then the rate expressioncan be written as Eq. 2. Upon integration of the rearranged form (Eq. 3), we obtain Eq.


10 Winnik

4, which is conveniently expressed in terms of P, the extent of reaction, defined as thefraction of functional groups that has reacted at time t. The concentration c can be ex-pressed as a function of 1 2 P, the fraction of unreacted A and c0, the initial concentration.Substituting c into Eq. 4, we obtain Eq. 5. A plot 1/(1 2 P)2 versus time should be linear,with a slope of 2c20 k, from which k can be determined.

2dcdt

5 kc3 (2)

2dcc3

5 kdt (3)

2 kt 5 1c2

1 constant (4)

2c20 kt 51

(1 2 P)2 1 constant (5)

The number average degree of polymerization, DPN, for condensation reactions canbe expressed as:

DPN 5number of original moleculesnumber of molecules at time t

5N0N

5c0

c5

c0

c0 (1 2 P)5

11 2 P

(6)

For an essentially quantitative synthesis of polyesters, where P 5 0.9999, the DPN valuecalculated from Eq. 6 is equal to 10,000.

2. Free-Radical polymerizationsFree-radical polymerizations involve the simultaneous generation and disappearance ofinitiator radicals, monomer radicals, and macroradicals. After a few seconds the total con-centration of all radicals becomes constant. This steady state or stationary state is obtainedat very small monomer conversions. In terms of kinetics, the total free-radical concentra-tion becomes stationary when the rate of radical formation equals the rate of radical disap-pearance (Eq. 7).

Rd 52 d[I]

dt5 kd [I ] (7)

Initiators I dissociate with a rate Rd giving two initiator radicals I; therefore, the rateof radical formation Rr is double the rate of initiator decomposition:

Rr 5d[I]dt

5 2kd[I ] 5 2Rd (8)

However, since the initiator molecule dissociates in a cage surrounding monomer andsolvent molecules, some of the newly formed radicals recombine immediately. Due tothis cage effect, only a fraction f of initiator radicals I react with monomer in the startreaction: I 1 M fi IM (st). The rate of radical formation is thus Rr 5 2 f kd [I ]. Monomerradicals are generated with a rate Rst, which is much greater than the rate Rd of initiatordecomposition:

Rst 52 d[I]

dt5 kst[I][M ] (9)



Initiator radicals are consumed as fast as they are generated. The rate-determining step isthus the initiator decomposition. Overall, the instantaneous concentration of initiator radi-cals and the rate of the start reaction are given by Eq. 10 and 11, respectively:

d[I]dt

5 2fkd[I ] 2 kst[I][M ] 5 0 (10)

Rst 5 kst[I][M ] 5 2 fkd [I ] (11)Per initiator radical, only one monomer is consumed in the start of the reaction, but

many hundreds in the subsequent propagation reaction. Monomers are thus practicallyonly consumed by propagation. Their consumption by start, termination, and transfer tomonomer is negligible. For irreversible reactions, the gross rate of polymerization, Rgross,thus approximates Rp (Eq. 12):

Rgross 52d[M ]

dt< Rp 5 kp[P][M ] (12)

The following assumptions underlie the ideal polymerization kinetics:

1. Only initiator decomposition and start, propagation and termination reactions areconsidered.

2. All reactions are irreversible.3. The effective concentration of initiator radicals is steady.4. The concentration of macroradicals is stationary.5. Termination occurs only by mutual deactivation of two macroradicals; hence:

Rgross 7.0Supplier: Rohm and Haas

Acrylic Acid/Acrylonitrogens CopolymerTrade Name: Hypan SA-1OOH, SR-150HFunction in Formula: SA-100H is an emulsifier, viscosifier, and tactile modifier; SR-150H builds

viscosity in presence of electrolytesUse Concentration: 0.05-1% in gels and emulsionsSolubility Characteristics: Hydrogel insoluble in all solvents. Swells in waterFormulating Considerations: Compatible in all aqueous systems. Always added to the water phaseForm Supplied: PowderRegulatory Status: Contains no organic volatiles. OTC drug master file availableSpecial Comments: SA-100H forms continuous film on skin. Produces waterproofing emulsions.

Detacktifies other polymers. SR-150H tolerates high electrolytes concentrationsSupplier: Lipo


610 Lochhead and Gruber

Acrylic/Acrylate CopolymerR' CH3

r- i n r i-CH2-CCH2-C ~1

c=oIOR

c=oIO(CH2CH20)n-(CH2)17-CH3

where R = alkyl; n has average value of 20R' = H or CH,

Chemical Description: Copolymer of acrylic acid and a monomer consisting of methacrylic acidor a simple ester of acrylic acid or methacrylic acid

Trade Name: Carboset 514, 515, 525, XL-19, XL-19X2, XL-40;526Function in Formula: Film former, waterproofing agentUse Concentration: 1-25% in waterproof sunscreens; 1-10% in waterproof mascaraSolubility Characteristics: Soluble in ethanol, isopropanol ethyl acetate. Soluble at 10% solids in

ammonia water, pH 7-8.5Form Supplied: 515syrup; 525, 526flake; 514, XL-19, XL-28, XL-4030-40% dispersions

in ammonia waterMicrohial Considerations: Preservation required in contact with water. 515, 525, 526 stable as

supplied. XL-19X2, XL-28 are preserved with Dowicil 200. XL-40 is preserved with methylpara-ben plus propylparaben

Supplier: BF Goodrich

Acrylic Esters and Methacryfics Esters CopolymerR1

-CH2-CH CH2-C

C=OI

OR

C=OIOR"

R = H or lower alkvl

Trade Name: Diahold EX-55Function in Formula: Anionic hair fixative resinSolubility Characteristics: Soluble in water and alcoholFormulating Considerations: Compatible with most propellants and additivesForm Supplied: 55% SD-alcohol solutionSupplier: Mitsubishi Yuka


Encyclopedia of Polymers and Thickeners 611

Adipic Acid/Dimethylaminohydroxypropyl DiethylenetriamineCopolymer

r.NH(CH2)2NH

CH2

HO-CH Ch3

H2C

HO CH3

N+CHzCCHzN*CK,I l |

H CH2

HCOHI

.c(CH2)4CNH-(CH2)2N(CHzfc NH

2nd'

Trade Names: Cartaretin F-4 Liquid, Cartaretin F-23 LiquidFunction in Formula: Hair conditioner and bodifierUse Concentration: 1-3% in shampoos; 3-10% in hair conditioners, rinses; 3-20% in hair-setting

lotions, gels, spraysSolubility Characteristics: Miscible in water, ethanolFormulating Considerations: Compatible with cationics and most anionics, can be compatibilized

with strongly anionic surfactantsForm Supplied: 30% active liquid in H2O (F-4); 23% active liquid (F-23)Microbial Considerations: No microbial problems experiencedRegulatory Status: No known hazardous components, nonirritant, not CIR reviewedSupplier: Sandoz

Aluminum Starch Octenyl SuccinateChemical Description: Aluminum salt of the reaction product of octenylsuccinic anhydride with

starchTrade Name: Dry FloFunction in Formula: Active ingredient in powders and lotionsUse Concentration: 1-5% in powders; 1-20% in gels; 1-10% in lotionsSolubility Characteristics: Insoluble in water and alcoholsFormulating Considerations: Free-flowing, not wetted by liquid waterForm Supplied: Fine, white powderMicrobial Considerations: A starch derivative, will support growth of bacteria, etc.Supplier: National Starch

Ammonium Acrylates/Acrylonitrogens CopolymerTrade Name: Hypan SS-201Function in Formula: Detackifier, thickenerUse Concentration: 0.05-1% in gels and emulsionsSolubility Characteristics: Hydrogel-insoluble in all solvents. Swellable in waterFormulating Considerations: Compatible in all aqueous systems. Always added to water phase



Form Supplied: PowderRegulatory Status: Contains no organic volatiles. OTC drug master file availableSupplier: Lipo

Amodimethicone

HO- -SiO-

m

-SiO

(CH2)3

NH (CH2)2 NH2

Chemical Description: Silicone polymer end-blocked with amino functional groupsTrade Name: 929 Cationic EmulsionFunction in Formula: Hair conditioning agent. Especially effective for damaged hair to give dura-

bility without buildupUse Concentration: 2% in hair conditionersFormulating Considerations: Excellent compatibility with cationic surfactants, glycol ethers, non-

ionic surfactants and anionic surfactants, at low concentrations. Amodimethicone emulsion shouldbe added to anionic surfactants with continuous stirring to minimize chances of precipitation

Form Supplied: Water-thin emulsionSpecial Comments: During formulation and processing, like other cationic emulsions, this product

should be kept away from the face and eyesSupplier: Dow Coming

AMP-Acrylated CopolymerR R

CH2-C CH2-C

C = 0

O"NH3+"

H3C-C-CH2-OH

CH,

c=oIOR'

m

= H o r C H

Chemical Description: Copolymer of methacrylic acid and methacrylate neutralized with 2-amino-2-methylpropanol

Trade Name: Diahold A-503Function in Formula: Fixative and film formerUse Concentration: 4-7% in hair sprays (actives basis); 4% in setting lotion (actives basis)Solubility Characteristics: Water-soluble as suppliedFormulating Considerations: Supplied preneutralized with AMP. Good propellant compatibilityForm Supplied: 40% actives in ethanolSupplier: Sandoz


Encyclopedia of Polymers and Thickeners

Behenoxy Dimethicone

CH3

H3C(CH2)XOSiO-

CH3

CH3 CH3

-SiO?jO-

CH3 CH3

x = 21

613

CH3

-SiO(CH2)X-CH3

CH3

Chemical Name: Dialkoxy dimethyl polysiloxaneTrade Name: Abil Wax 2440Function in Formula: Emollient, pigment disperser, moisture barrier properties, lubricantUse Concentration: 1-5% in deodorant roll-onsSolubility Characteristics: Soluble in oilsFormulating Considerations: Add to oil phase, melting point 30-35C. Warm to liquify before

grinding pigmentsForm Supplied: Solid wax, 100% activeSupplier: Goldschmidt

C24.28Methicone

CH,

H,CSiO

CH,

CH3

Si O

R

CH3

CH3n

= C24,24-28

Chemical Name: Polymethylalkyl siloxaneTrade Name: Abil Wax 9810Function in Formula: Emollient and barrier properties, nonionicUse Concentration: 2-8% in eye makeup removersSolubility Characteristics: Soluble in mineral oil, emollients, and estersFormulating Considerations: Add with oil or wax phase. Melting point is 70CForm Supplied: Solid waxSpecial Comments: Reduces greasiness or oils, soft emollient afterfeel, gels mineral oilRegulatory Status: NonhazardousSupplier: Goldschmidt

Carbomer

CH2-CH

C=O

OHn


614 Loch head and Gruber

Chemical Description: Poly (acrylic acid) cross-linked with ally] ethers of pentaerythritol or ally!ethers of sucrose

Trade Names: Carbopol resins: 907, 910, 934, 934-P, 940, 941, 954, 980, 981, 2984, and 5984(BF Goodrich); Acritamer 934, 934-P, 940, and 941 (R. I. T. A.); Synthalen K, Synthalen M,Synthalen N (3-V)

Function in Formula: Thickening/gelling agent. Suspension and emulsion stabilizerUse Concentration: 0.3-1% in gels; 0.2-0.6% in creams; 0.0-0.5% in lotionsSolubility Characteristics: Very hydrophilic; highly swellable in water, alcohol, and polar solventsFormulating Considerations: Highly efficient thickener needs care in dispersing in liquid. Swells

rapidly in water upon neutralization with suitable base (no heat required). Effective thickenersin pH range 5-10. Thickening efficiency is reduced in presence of electrolytes. Incompatible withsome cationic surfactants and some cationic polymers

Form Supplied: White, fine amorphous powderMicrobial Considerations: Resists bacterial attack and does not support mold growth. Preservation

required for other components in the final formulation and for dispersions that will be stored forseveral weeks

Regulatory Status: Ultrapure and benzene-free grades are available. Carbomers 954, 980, 981,2984, and 5984 are not synthesized in benzene. CIR Final Safety Assessment has been published.These materials have been determined to be safe. Carbomer resin are approved by the JapaneseMHW

Special Comments: Carbomers 940 and 980 give highest clarity for gels. Carbomers 934, 941,954, 981, 2984, and 5984 preferred for emulsion stabilization

Suppliers: BF Goodrich; 3-V; R. 1. T. A

Carbomer

CH2-CH

C=0

O"Na+' X

Chemical Description: Sodium salt of cross-linked poly(acrylic acid)Trade Names: PNC 430. PNC 410, PNC 400Function in Formula: To provide viscosity, stabilization, and rheologyUse Concentration: 0.1-1%- in water-based gels; 0.1-0.3% in emulsionsSolubility Characteristics: Soluble in waterFormulating Considerations: Requires no neutralization. Should be added after all water-soluble

materials are homogeneous, or dispersed in the oil phase prior to emulsificationForm Supplied: Fine white powderMicrobial Considerations: Does not support microbial growth and not does not prevent the growth

of microorganismsRegulatory Status: Benzene-freeSpecial Comments: Easy to use, offers all of the attributes of traditional carbomersSuppliers: 3-V



Cetyl Dimethicone

H3CSiO

615

(

S O

CH2]X

CH3

CH3

CH3

rCH3

n

m

x=15

Chemical Name'. Polysiloxane polyalkylene copolymerTrade Name: Abil Wax 9801DFunction in Formula: EmollientUse Concentration: 1.5% in creams and lotions; deodorant sticks, roll-ons; skin care emulsions;

lipsticks, pressed powdersSolubility Characteristics: Soluble in oils, insoluble in waterFormulating Considerations: Add in oil phase of emulsions, disperse into oils/waxes in pigmented

products and antiperspirantsForm Supplied: LiquidSpecial Comments: Improves the application of solid antiperspirants, improves the color of decora-

tive cosmeticsSuppliers: Goldschmidt

Cetyl Dimethicone Copolyol

H3C-

CH3

CH3

(:H3

[CH2]16X

CH3

Si O

CH2CH3y

CH3

Si O

CH3

CH3

CH3z

O (C3HB0)4

Chemical Name: Polysiloxane polyalkyl polyether copolymerTrade Name: Abil EM 90Function in Formula: Emulsifier, emollientUse Concentration: 2% w/o in creams and lotions; 0.05% in conditioning shampoos for gloss,

body, and combabilitySolubility Characteristics: Soluble in oils, insoluble in waterForm Supplied: 100% active liquidSpecial Comments: Provides emolliency in personal care productsSuppliers: Goldschmidt


616

Cyclomethicone

,O

H3C'Si

c>

H3C\Si

Lochhead and Gruber

O

-Si' -CH3

>iO CH3C^\

CH3

Chemical Name: OctamethylcyclotetrasiloxaneTrade Name: Abil K4Function in Formula: Gives smoothness and silky sheen to hairUse Concentration: 1-10% in hair sprays; 1-10% in skin care emulsions; up to 50% in deodorantsSolubility Characteristics: Soluble in ethanol and cosmetic oilsSuppliers: Goldschmidt

H3CV ,CH3-Si.

H,C o- -o

H,C'

\ /Si

\/Si

CH-,

CH,

O\

O

Ch3

CH, H,C

Chemical Name: DecamethycyclopentasiloxaneTrade Name: Abil B 8839Function in Formula: Gives smoothness and silky sheen to hairUse Concentration: 1-10% in hairsprays; 1-10% in skin care emulsions; up to 50% in deodorants,

antiperspirantsSuppliers: Goldschmidt

rCH3SiCH3

where n averages between 3 and 6



Chemical Name: Cyclic poly(dimethylsiloxane)Trade Names: Silicone Fluids 244, 245, 344, 345 (Dow Corning); Silicone Fluids VS-79207, VS-

7349, VS-7158 (Union Carbide)Function in Formula: Reduces tackiness, conditions hair, lubricates, dry feel, aids gloss, emollient,

carrier for activesSolubility Characteristics: Soluble in ethanol, cetyl alcohol, aliphatic solvents, isopropyl myristateForm Supplied: LiquidSpecial Comments: Volatile emollient, wide range of solubility, nonstaining, low heat of vaporiza-

tionSuppliers: Union Carbide, Dow Corning

Diglycol/Cyclohexanedimethanol/lsophthalates/Sulfoisophthalates

SO3H'Na+

Chemical Description: Copolyester of diethylene glycol, 1,4-cyclohexanedimethanol, dimethylisophthalate, and dimethyl sodiosulfoisophthalate

Trade Name: AQ 55S PolymerFunction in Formula: Film former, dispersantSolubility Characteristics: Disperses in hot waterFormulating Considerations: Not compatible with cationics. Generally compatible with nonionics

and anionics. Disperse in water first.Form Supplied: Solid pelletsMicrobial Considerations: Microbicide needed to stabilize aqueous dispersionsRegulatory Status: Included in TSCA inventorySupplier: Eastman



Diglycol/lsophthalates/Sulfoisophthalates Copolymer

-OCH2CH2OCH2CH2O-

Chemical Description: Copolyester of diethylene glycol, dimethyl isophthalate, and dimethyl sodi-osulfo isophthalate

Trade Name: AQ 29S PolymerFunction in Formula: Film former, dispersantSolubility Characteristics: Disperses in hot waterFormulating Considerations: Not compatible with cationics. Generally compatible with nonionics

and anionics. Disperse in water first or separatelyForm Supplied: Solid pelletsMicrobial Considerations: Microbicide needed to stabilize aqueous dispersionsRegulatory Status: Included in TSCA inventorySupplier: Eastman

Dimethicone

-Si- -SiO-

CH3

-SiCH,

Trade Names: Abil 10-10 000 (Goldschmidt); Silicone Fluid SWS-101 (SWS Silicones); DimethylSilicone Fluids L-45, 200, 225 (Union Carbide); Silicone Fluids 200, 225 (Dow Corning); SE-30, Viscasil, SF-96 (GE)

Function in Formula: Elimination of ' 'whitening effect." Emollient, lubricant, and water repellentfor hair and skin care products



Use Concentration: 0.5-5% in skin care emulsions. SE-30: 8-10% in hair cuticle laminate, 8-10% in skin preparations, 0.5-1% in shampoo/conditioner. Viscasil: 1-4% in shampoo/condi-tioner and soaps. SF-96: 0.5-7% in skin care. 5-10% in AP

Solubility Characteristics: Insoluble in polar mediaFormulating Considerations: Solubilize first in cyclomethicone; for shampoo, use low-viscosity

dimethiconeForm Supplied: Liquid/gum. Fluids range in viscosity from 0.65 to 60,000 centistokesSupplier: Goldschmidt; Dow Corning; Wacker; GE Silicones

Dimethicone (and) TrimethylsiloxysilicateTrade Name: SS-4267Function in Formula: 3-5% in sunscreen formulations, 1-5% in hand lotionsSolubility Characteristics: Disperses in hot waterFormulating Considerations: Best used with anionic emulsifiers, avoid common organic estersForm Supplied: FluidsMicrobial Considerations: Microbicide needed to stabilize aqueous dispersionsSupplier: GE Silicones

Dimethicone Copolyol

H3CSiO

( s

(C

;HS- O

^H2)x 1 m

CH3

Si O

CH3I 1

(

(

3H3

:H3n

O

(CH2CH2O)y(CH2CHO)ZRCH3

Chemical Name: Polysiloxane polyether copolymerTrade Names: Abil B 8843D, B 8851D (Goldschmidt); Silwet L- Series (Union Carbide); SF-

1188 (GE); Silicone Fluids 190, 193, Q2-5520 (Dow Corning)Function in Formula: Refatting agents, smoothness, softness, shine hair products. Wetting, foam-

ing, lubricantUse Concentration: 0.5-3% in hair care; 0.5-3% in creams and lotions; 0.5-3% in antiperspirants;

0.2-1% in shaving foams; 0.2-1% in aftershaves/facial cleansers, shampoos, hair rinses, hairgels; 2-4% in conditioning shampoos; 1-3% in shaving cream; 0.1-0.5% in styling products

Solubility Characteristics: Water, lower alcohols, propylene glycol solubleFormulating Considerations: Add to water phaseForm Supplied: 100% liquidRegulatory Status: NonhazardousSpecial Comments: Contributes to gloss, sheen and combability. Contributes to skin feelSupplier: Goldschmidt; Union Carbide; GE Silicones, Dow Corning



Dimethicone Copolyol Phosphate

CH3

-SiO-

CH3'm

CH3

H3C SiO-

CH3

-SiO-

CH3

-SiCH3

CH3

OH-x

HOP=O

OH

Trade Name: PECOSIL PS-100Function in Formula: Emulsifier/gloss/substantivityUse Concentration: 3% in body cream, 5% in sunscreen, 3% in conditionerSolubility Characteristics: Soluble in waterForm Supplied: LiquidRegulatory Status: Benzene-freeSupplier: Phoenix

Dimethicone/Disodium PG-Propyldimethicone Thiosulfate Copolyol

me- -SiO- -SiO-

CH3

-SiO-ICH2

-SiCH3

mICH2

HCOH

H2CS2O3"Na+

Chemical Name: Polysiloxane polyorgano thiosulfateTrade Name: Abil S 255Function in Formula: Conditioning agentUse Concentration: 5-15% in permanent waves; 0.2-1% in hair conditioners; approx. 0.2% in

hairspraysSolubility Characteristics: Soluble in waterForm Supplied: LiquidSupplier: Goldschmidt



Dimethicone Propyl PG-BetaineCH3

H3CSiO-

CH3L- -Iml-,

ClI

621

( S

(

-'113

0

-


Dimethiconol (and) Cyclomethicone (and) Dimethicone

HO -Si O-

CH3

-SiOH

CH3

Trade Names: Abil OSW 12, Abil OSW 13Function in Formula: Film formerUse Concentration: 100% as hair treatment fluidForm Supplied: LiquidSupplier: Goldschmidt

Ethylene/Acrylate CopolymerR1

m

c=oIOR"

Chemical Description: Copolymer of ethyiene and a monomer consisting of acrylic acid, metha-crylic acid, or one of their simple esters

Trade Names: A.C. Copolymer 540, 540AFunction in Formula: To gel solvent, especially mineral oil in lipstick gloss, stick products, cleans-

ing creams, hand creams; film former in waterproof sunscreenUse Concentration: 5-10% in solvent phase; 1% in finished product; 1-2% in waterproof sun-

screenSolubility Characteristics: Insoluble in water, insoluble in alcohol. Insoluble at room temperature

in all solvents, flocculated dispersion when heated above the cloud point and allowed to coolForm Supplied: Powder or prillMicrobial Considerations: Formulation needs to be preserved. The polymer itself is biologically

inertRegulatory Status: CIR reviewed and deemed safeSupplier: Allied-Signal

Ethylene/Vinyl Acrylate Copolymer

r~ ~i r ~i

m

O

c=o_CH3



Chemical Name: Poly (ethylene-co-vinyl acetate)Trade Names: A.C. Copolymer 400, 430Function in Formula: Gellant for antiperspirants and gelsUse Concentration: 5-10% in solventSolubility Characteristics: Insoluble in water, insoluble in alcohol. Insoluble at room temperature

in all solvents. Forms flocculated dispersion when heated above the cloud point and allowed to coolForm Supplied: Powder or prillMicrobial Considerations: Formulation requires preservation. The polymer itself is biologically

inertRegulatory Status: CIR reviewedSupplier: Allied-Signal

Glycerin and Diglycol/Cyclohexanedimethanol/lsophthalated/Sulfoisophthalates CopolymerTrade Name: Lipo PE Base G-55Function in Formula: Thickening, waterproofingUse Concentration: 30-55% in emulsions, gels, and makeupSolubility Characteristics: Water-soluble, insoluble in organic solventsFormulating Considerations: Used as a film former. Leaves a tack-free, flexible, water-resistant

film that can be removed with soap and waterForm Supplied: Viscous liquidSupplier: Lipo

Graft-copoly(dimethylsiloxane/t-butyl methacrylate)CH3

-SiO--SiO-

m(CH2)3

>--CH2CH-

0=C

I ?"'CH2CH

CH3

Chemical Name: Poly(dimethylsiloxane)-g-poly(isobutylmethacrylate)Trade Names: 3M Brand Silicones "Plus" VS-70-IBMFunction in Formula: Lubricating, water-resistant, durable film former with good bioadhesionUse Concentration: 1-5% in cosmetically acceptable solvents, e.g., Finsolv cyclomethicones, etc.Solubility Characteristics: Soluble in alcohol, ketones, esters, glycol ethers, etc.Formulating Considerations: Polymer solution can be mixed or diluted with other organic fluids

or be converted into other solvents by standard solvent exchange processesForm Supplied: Polymer solution in Finsolv (25% solids)



Special Comments: One part graft polymer combines silicone and acrylic benefits in cosmeticsand toiletries

Suppliers: Encapsulated Products, 3M

Graft-copoly(IBMA; MeFOSEA/PDMS)(

""CM C

C

'H3 CH3

N ' 1 J-VI 1 .^1 1 1 ' /-M I ^ 1

:=o

O

(H3C C

;H2

;H_ H3C

n

C=01

O1CH2

CH2

H3C N

C8F17O2S

m

C=0

O

Cn3 Cri3

H3C Si (0-Si)x-0 si CH3CH3 CH3 ci_|3

' P

Chemical Name: [Poly(isobutylmethacrylate-co-methylFOSEA)]-g-poly(dimethylsiloxane) (70:5:25 mass%)

Trade Names: 3M Brand Silicones "Plus" SA-70-5-IBMMFFunction in Formula: Lubricating, water-resistant, durable film former with good bioadhesionUse Concentration: 1-5% in cosmetically acceptable solvents, e.g., Finsolv cycomethicones, etc.Formulating Considerations: Polymer solution can be mixed or diluted with other organic fluids

or be converted into other solvents by standard solvent exchange processesForm Supplied: Polymer solution in Finsolv (25% solids)Special Comments: One part graft polymer combines silicone and acrylic benefits in cosmetics

and toiletriesSupplier: Encapsulated Products, 3M

Hydrogenated Polyisobutenes

1%Cri2~C "CH3

CH,

n

Trade Name: Panalane L-14EFunction in Formula: OilSolubility Characteristics: HydrophobicForm Supplied: Liquid polymerRegulatory Status: Nontoxic meets PDA Title 21 CFR 178.3740Supplier: Amoco



Hydrolyzed Soy Protein/Dimethicone Phosphocopolyol CopolymerChemical Description: Polymer hydrolysate of soy protein reacted with dimethicone copolyol

phosphate via an alkyl chloride bridge to form a copolymerTrade Name: PECOSIL SSPFunction in Formula: Conditioner/film formerUse Concentrations: 5% in hair styling gels, hair conditioners and shampoosSolubility Characteristics: Soluble in waterForm Supplied: 35-38% in aqueous solutionRegulatory Status: Benzene-freeSupplier: Phoenix

Hydrolyzed Wheat Protein/Dimethicone PhosphocopolyolCopolymerChemical Description: Hydrolysate of wheat protein reacted with dimethicone copolyol phosphate

polymer form a copolymerTrade Name: PECOSIL SWP-83Function in Formula: Conditioner/film formerUse Concentration: 5% in hair styling gels, hair conditioners and shampoosSolubility Characteristics: Soluble in waterForm Supplied: 35-38% in aqueous solutionRegulatory Status: Benzene-freeSupplier: Phoenix

Methacryloyl Ethyl Betaine/Methacrylates CopolymerCH3 CH3

-! CH2-C CH2-C 'Ic=oIOR

I CH

C=O V 3

OCH2CH2N+CH3

CH2CO2' m

where R = C, - C,8 alkyl group

Chemical Description: Betaine-type methacrylate polymerTrade Name: Z-W, A-301, Z-AT, Z-400, Z-A, Z-5MFunction in Formula: Fixative resins and film former. Z-W is a conditioning polymerUse Concentration: 0.5-1% (actives) in shampoos; 1-3% (actives) in conditioners and rinses; 1-

5% in gels; 4-7% (actives) in hairsprays; 2-4% (actives) in mousses; 4-5% (actives) in settinglotions

Solubility Characteristics: Z-W soluble in water, Z-310 is compatible with carbomer gels; Z-AT,Z-400, Z-A, and Z-SM are soluble in ethanol and hydroalcoholic solutions

Formulating Considerations: Compatible with commonly used propellants and most additives, atboth acidic and basic pH ranges. Water-soluble grades are easily added to the formulation. Nopredispersion is required

Form Supplied: Z-W as 30% actives in water/8% ethanol solution. Z-301 as 30% actives in etha-nol. Z-AT, Z-400, Z-A, and Z-SM do not require neutralization, they have good propellant com-



patibility, and they may be used in formulations containing up to 90% water. They are suppliedin solution and do not need to be predispersed

Microbial Considerations: Free of bacterial contaminationsRegulatory Status: TSCA registeredSpecial Comments: Z-W has substantivity to hair and provides excellent antistatic properties in

the formulationSupplier: Sandoz

N-Dodecylamidopropyl-N', N'-dimethyl-N"-dimethiconeCopolyolphospho-2 Propanol Ammonium Chloride

O CH.C,- O

H25C12C N (CH2)3-N* CH2-CH-CH2-0-pDCCH3 OH ^

DC = dimethicone copolyol copolymer

Trade Name: PECOSIL CAP-1240Function in Formula: ConditionerUse Concentration: 5% in hair conditioner, shampoo, and hand lotionSolubility Characteristics: Soluble in waterForm Supplied: LiquidRegulatory Status: Benzene-freeSupplier: Phoenix

Octyldodecyl Dimethicone Copolyol Citrateo

H2CcO(CH2)17 CH3OII

OHCCDCOII

H2CCDC

DC = dimethicone copolyol copolymer

Trade Name: PECOSIL CAS -55Function in Formula: Pigment wetter and dispersant, emollientUse Concentration: 3-5% in makeup products, lipsticks, creams, and lotionsSolubility Characteristics: Oil-solubleForm Supplied: LiquidRegulatory Status: Benzene-freeSupplier: Phoenix



Octylacrylamide/Acrylates CopolymerR1

627

Chemical Description: Copolymer of octylacrylamide and two or more monomers consisting ofacrylic acid, methacrylic acid, or any of their simple esters

Trade Name: Versacryl-40Function in Formula: Binder/hair fixativeUse Concentration: 1-8% in ethanol for hairspraySolubility Characteristics: Soluble in ethanol and isopropanolFormulating Considerations: For optimum properties, suggest 90-95% neutralization with potas-

sium hydroxideForm Supplied: Fine white powderSupplier: National Starch

Octylacrylamide/Acrylates/ButylaminoethylmethacrylateCopolymer

CH3 CH, CH3n_r_. 1 nI

c=o

OR1^~" m

|c=o1OH

""" n

On2~^n |C=01NHi1 P

|C=O

OR" _l q

CsHi7

Ic=o1o1(CH2)2NH

C H

\c=o1OR

' m

|C=O1

OH n

|C=O1NH1

H3C C CH3CH2

H3C C CH3|CH3

CH3 CH3' f"LJ f^ f^> ' ^

1C=0

1OR"

q

|C=01O1(CH2)2NH1

H3C C CH31 1 '

CH3n



Chemical Description: Copolymer of octylacrylamide, f-butylaminoethyl methacrylate, and twoor more monomers consisting of acrylic acid, methacrylic acid, or any of their simple esters

Trade Name: Amphomer 28-4910, Amphomer LV-71Function in Formula: Binder/hair fixativeUse Concentration: 3-5% in hairspray; 5% in styling lotionsSolubility Characteristics: Soluble in ethanol and isopropanolFormulating Considerations: Must be neutralized when formulated. Aminomethylpropanol

(AMP) is most commonly used neutralizes Normally 90% with AMP for use in hairspray. Be-comes water-soluble when 100% neutralized

Form Supplied: Fine white powderRegulatory Status: Benzene-freeSpecial Comments: 28-4910 acidity = 2.05 mEq/g; LV-71 acidity = 2.45 mEq/gSupplier: National Starch

Oxidized PolyethyleneChemical Name: Poly(ethylene)Trade Name: A.C. Polyethylene 629, 680Function in Formula: Gellant for anhydrous esters and oils. Emulsifiable polyethylene for creams

and lotionsUse Concentration: 8-10% in solventSolubility Characteristics: Insoluble in water and short-chain alcoholsFormulating Considerations: Can be emulsified with anionic, cationic, or nonionic emulsifiers,

soluble hot in fatty acids, fatty alcohols, fatty esters, petrolatum, mineral oil. Forms a flocculateddispersion upon cooling. Stable gels or dispersions form at 6-15%

Form Supplied: Prill or fine powderSupplier: Allied-Signal

Oxy(methyl-1-1,2-ethanediyl) a-Hydro-w-hydroxy polymer with1,1 '-methylenabis(4-isocyanatocyclohexane)

r n _/~\ AA i r~iHO(HCCH2-0)12jC HH-< }CH2( }NH-C(0CH2CH)12-0-pH

r rs r~\ _/~\ \ r~\HO(HCCH20)50-jCNH-( JCH2-/ JNH-C (0CH2CH)5o-Oy-H

I... ^^... in. I,./ \_ __-* I

Trade Name: Polyolprepolymer-2Function in Formula: Skin conditioning agent, delivery and deposition of active ingredientUse Concentration: 0.5-2% in personal care formulationsSolubility Characteristics: Insoluble in water, soluble in alcohol



Formulating Considerations: Compatible with most personal care formulation ingredientsForm Supplied: Viscous liquidMicrobial Considerations: Does not support microbial growthRegulatory Status: Cosmetic and pharmaceutical excipientSupplier: Barnet

PEG-N where N = 4, 6, 8, 12, 20, 32, 75, 100, and 150HO(CH2CH2O)nH

n = 4-150

Chemical Name: Polyethylene glycol 200, 300, 400, 600, 1000, 1450, 3350, 4600, and 8000Trade Name: Carbowax Polyethylene GlycolsFunction in Formula: Solvent, carrier, humectant, lubricant, binder, base, coupling agent, solventUse Concentration: 5-30% in toothpaste, dentifrices; 5-15% in bar soap; 1-10% in shampooSolubility Characteristics: Water-soluble, soluble in ethanolFormulating Considerations: Add directly to formulation; dissolve in water and add to formula-

tion; compatible with cosmetic ingredients. Water-soluble but will precipitate near 100CForm Supplied: Liquid (200-600), soft solid (1000-1450), flake or powder (3750-8000)Microbial Considerations: Does not support microbial growthRegulatory Status: PEG-6 to PEG-150 are USP/NF/FCC; listed in the Handbook of Pharmaceuti-

cal Excipients and in the Handbook of Food, Drug, and Cosmetic Excipients', not reviewed byCIR

Special Comments: Low volatility; wide range of viscosity and melting pointSupplier: Union Carbide

PEG-2M, PEG-5M, PEG-7M, PEG-14M, PEG-9M,GEG-20M, PEG-23M, PEG-45M, PEG-90M

HO(CH2CH2O)nH

Chemical Description: High-molecular-weight polymer of polyethylene oxide)Trade Name: Polyox Water Soluble ResinsFunction in Formula: Depending upon the concentration and grade, can provide lubricity or tack

to a formulationUse Concentration: 0.5-1% in shave cream/gel; 0.1-0.5% in shampoo; 0.1-0.3% in liquid/bar

soap systemsSolubility Characteristics: Soluble in waterFormulating Considerations: Nonionic polymer, which ensures wide compatibility with most per-

sonal care ingredientsForm Supplied: White powderMicrobial Considerations: Does not contain an antimicrobial as sold. Normal precautions need

to be followed to include a preservative in a formulation containing PolyoxRegulatory Status: Three grades have been approved for use and sale by MHW in Japan (PEG-

9M. PEG-14M, PEG-90M). All grades have been shown to be safe and are sold in the othermajor markets, including North America and Europe

Special Comments: Impart a great deal of lubricity to a solution. They are extremely mild and areexcellent film formers. At high concentrations, Polyox resins can add adhesive properties to aproduct

Supplier: Amerchol



PEG-N-Methyl Ether where N - 6.10, 16.40, or 100H,CO(CH,CH;O)nH

n = 6-100

Chemical Names: Methoxy polyethylene glycols 350, 550, 750, 2000, and 5000Trade Name: Carbowax Methoxy Polyethylene GlycolsFunction in Formula: Solvent, carrier, lubricantUse Concentration: 5-15% in nail polish remover; 5-10% in hand cleaner; 5-15% in bar soapSolubility Characteristics: Soluble in water, soluble in ethanolFormulating Considerations: Dissolve ingredients in MPEG, add to formulation; dissolve in water

and add to formulationForm Supplied: Liquid (350-550), soft solid (770), flake or powder (2000-5000)Microbial Considerations: Resists microbial growthSpecial Comments: Low volatility, wide range of viscosity and melting pointSupplier: Union Carbide

PEI

H,N*

Chemical Name: PolyethylenimineTrade name: PolyminFunction in Formula: Carrier for active, tie coat, solubilizerSolubility Characteristics: Water-solubleFormulating Considerations: Order of addition important to control ionic reactionsForm Supplied: Aqueous and liquidSpecial Comments: High cationic density, high substantive to skin, hair, and nailsSupplier; BASF

Perfluoropolymethylisopropyl Ether

rF3C (OCFCF2)n-(OCF2)m-pOCF3

I Jp

n/m = 20/40Avg. MW = 1500-6250



Chemical Name: PerfluoropolyetherTrade Name: Fomblin HC (grades: HC/04, HC/25, and HC/R)Function in Formula: Skin protectant, emollient, coemulsifierUse Concentration: 1-3% in barrier creams and lotions; 0.2-1.0% in moisturizing creams and

lotions; 0.05-0.3% in emulsion stabilizerSolubility Characteristics: Completely insoluble in any cosmetic ingredientFormulating Considerations: Fomblin HC can be pre-emulsified with glycerin; Fomblin HC can

be added either to water or oil phase before emulsificationForm Supplied: 100% pure liquid materialMicrobial Considerations: Absolutely inert from the biological point of viewRegulatory Status: Approved in Japan (up to 5%) by the MHWSupplier: Ausimont (Brooks Industries, U.S.)

Phenyl Dimethicone

CH3

H3CSiO

CH3

Chemical Name: Phenylmethyl polysiloxaneTrade Name: Abil AV8853Function in Formula: Improves spreadability of emulsions; solubilizerUse Concentration: 2-20% in deodorantsSolubility Characteristics: Soluble in ethanol and cosmetic oils. Chemically stable compounds

that are not attacked by reagents. Excellent surface binding and very good spreading propertiesForm Supplied: Clear odorless and tasteless liquids. Noncorrosive. Inert in the presence of metals

and plasticsSupplier: Goldschmidt

Phenyl Trimethicone

-SiO- -SiO

m

'P

Trade Names: Abil AV 20, Abil AV 1000 (Goldschmidt); Phenyltrimethicone (Dow Corning)Function in Formula: Improvement of spreadability; film-forming propertiesUse Concentration: 0.5-5% in skin care and skin-protecting emulsions; 0.5-5% in deodorants,

antiperspirants; 0.5-5% in decorative cosmeticsSolubility Characteristics: Soluble in ethanol as well as in cosmetic oils



Form Supplied'. LiquidSuppliers: Goldschmidt; Dow Corning

Poloxamer 407CH,

HO[CH;CH,O]S[CH2CHO], [CH:CH,O]SH

Chemical Name: Polyethylene glycol/polypropylene glycol block copolymerTrade Name: Pluronic F-127Function in Formula: Thickener, gelling agent for aqueous systemsUse Concentration: Use up to 20% in waterSolubility Characteristics: Soluble in waterFormulating Considerations: Should be added to cold water, mixed thoroughly, and then allowed

to warm to room temperature for best resultsForm Supplied: PrillSuppliers: BASF

Polyacrylamidomethylpropane Sulfonic AcidChemical Name: Poiysulfonic acid polymerTrade Name: Kraft Polymer 80-11Function in Formula: Thickener, lubricity, friction reducer, emollientForm Supplied: Clear, viscous liquid (17-18% active in water)Special Comments: An anionic polymer supplied in 17% active solution in water. Special "smooth

feel" agent for creams, lotions, liquids and bars, shaving creams, etc. Provides a pleasant slipduring application and leaves a talc-like feel. Neutralization of this polymer has no effect on therheology of the product

Supplier: Kraft Chemical

Poly(acrylic acid)

Trade Name: Carbopol 400 series (BF Goodrich); Aquatreat (Alco)Function in Formula: Thickener, pigment disperser, calcium soap disperserUse Concentration: 0.1-2.0% in pigment dispersions, soapsSolubility Characteristics: Soluble in waterForm Supplied: Aqueous and isopropanol solution, flake, powderSuppliers: BF Goodrich; 3-V

Polydecene/Polybutene CopolymerTrade Name: Poly fix 106Function in Formula: Film former, water resistance



Use Concentration: 4% in creams and lotions, 6% in foundations, 4% in silicone-based hair prod-ucts

Solubility Characteristics: Oil-solubleFormulating Considerations: Miscible with volatile silicones, mineral oil, most vegetable oils,

esters, and sunscreens. Not miscible with water, alcohol, glycerin, or propylene glycol. Can beemulsified

Form Supplied: 100% active moderately viscous clear liquidMicrobial considerations: Does not support microbial growthRegulatory Status: No known constraints under TSCA, SARA, OSHA, RCRASupplier: Collaborative Laboratories

Polyethylene

-j-CH2-CH2^n

Chemical Name: Poly(ethylene)Trade Name: A. C. Polyethylene 6A, 617A, 9A, 316AFunction in Formula: Abrasive in acne scrub and hand scrub productsSolubility Characteristics: InsolubleForm Supplied: PowderMicrobial Considerations: Microbiologically inertSupplier: Allied-Signal

Trade Name: A. C. Polyethylene 617, 6, 7, 8, 9Function in Formula: Gellant for anhydrous hydrocarbon oil and fatty esters in eye shadow, medi-

cated gels and ointments, pomades. Binder for pressed powders, eye shadowUse Concentration: 5-10% in solventSolubility Characteristics: Insoluble in short-chain alcohols and waterFormulating Consideration: Soluble in hot petrolatum, mineral oil, fatty acids, fatty alcohols, fatty

esters. Forms a flocculated dispersion on coolingForm Supplied: Pellets, prills, or fine powderMicrobial Considerations: Microbiologically inertSupplier: Allied-Signal

Trade Name: A. C. Polyethylene-9FFunction in Formula: Gellant in denture adhesiveForm Supplied: Prills or fine powderMicrobial Considerations: Microbiologically inertSupplier: Allied-Signal

Trade Name: Ac

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