Silicones for Personal Care

398 Pages·2007·3.78 MB·English

Silicones for
Personal Care,
2nd Edition
Anthony J. O’Lenick Jr.
Silicones for Personal Care, 2nd Edition
ISBN: 978-1-932633-36-8
Copyright 2008, by Allured Publishing Corporation. All Rights Reserved.
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Disclaimer
The contents of this book are for educational purpose only. Readers should do their own research for new
and updated information, patents, and government regulations.
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is difficult to ensure that all information provided is entirely accurate and up-to-date. Therefore, the author
and the publisher accept no responsibility for any inaccuracies or omissions and specifically disclaim any
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Table of Contents
Preface .......................................................................................................vii
About the Author/Acknowledgement ........................................................ix
1. Introduction .......................................................................11
Silicone .......................................................................................................11
Comparing Silicon with Carbon ...............................................................12
Silicone Compounds .................................................................................14
Silicone from Quartz .................................................................................14
Rochow Process – Chlorosilanes from Silicon .........................................14
Hydrolyzate—Silicone from Chlorosilanes3 .............................................17
Reactions of Chlorosilanes ........................................................................19
Silicones Properties ...................................................................................20
Silicone Backbone Nomenclature ............................................................23

2. Basic Silicone Materials ....................................................35
Cyclomethicone .........................................................................................35
Molecular Weight of Polymeric Silicones.................................................39
Silicone Fluids ...........................................................................................42
Silicone on Substrate .................................................................................47
Cosmetic Usage of Silicone Fluids ...........................................................48
Silanol Compounds ...................................................................................49
3. Silicone Antifoam Compounds .........................................55
Mechanism of Antifoam ............................................................................57
Testing Antifoam Performance .................................................................59
4. Emulsion ............................................................................63
Emulsion Terminology2 .............................................................................66
Emulsion Stability .....................................................................................67
Silicone Emulsions ....................................................................................69
Types of Emulsions....................................................................................70
Deposition of Naturally Derived Hair Color via Reactive
Silicone Emulsions ................................................................................72

5. Silicone Surfactants ...........................................................75
Silicone Molecule Preparation ..................................................................80
Equilibration ..............................................................................................82
Derivitization .............................................................................................90
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SiliconeS for PerSonal care, 2nd edition anthony J. o’lenick, Jr.
6. Dimethicone Copolyol Chemistry ....................................93
Reaction .....................................................................................................94
Dimethicone Copolyol Properties ............................................................94
Structure Function Study..........................................................................99
Water Solubility .......................................................................................105
Water Tolerance ......................................................................................107
Odor .........................................................................................................108
Hydroxypropyl Dimethicone ..................................................................116
7. Silicone Esters .................................................................123
Reaction ...................................................................................................124
Properties .................................................................................................124
Solubility Properties ................................................................................126
Triglyceride-Derived Dimethicone Copolyol Esters .............................126
Dimethicone Copolyol Meadowfoamate ................................................127
Meadowfoam Silicone .............................................................................128
Ester Structure/Function ........................................................................132
Other Esterification Methods .................................................................138
8. Alkyl Dimethicone Copolyol Compounds ......................143
Orientation at the Interface ....................................................................146
Emulsification Properties ........................................................................148
3D Partition Coefficient ..........................................................................155
9. Fluoro Dimethicone ........................................................163
Surface Tension Reduction .....................................................................163
Chemistry .................................................................................................163
Low Fluoro Compounds .........................................................................165
High Fluoro Compounds ........................................................................167
Fluoro Alkyl Silicones..............................................................................167

10. Alkyl Dimethicone ...........................................................171
Typical Physical Properties .....................................................................177
Alkyl Dimethicone Orientation on Surfaces ..........................................177
Structure/Function Properties ................................................................180
Alteration of Functionalization ...............................................................180
Melt Point ................................................................................................180
Alteration of Construction ......................................................................181
Physical Properties ..................................................................................183
Alteration of Properties ...........................................................................185
SPF Enhancement ..................................................................................188
11. Cationic Silicone Compounds .........................................193
Silanol Groups .........................................................................................198
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anthony J. o’lenick, Jr. SiliconeS for PerSonal care, 2nd edition
Amino Groups .........................................................................................198
D Units.....................................................................................................199
Dimethicone Copolyol Amine ................................................................200
Polymerization Process ...........................................................................201
Applications Evaluation...........................................................................201
12. Carboxy Silicone Complexes ...........................................209
Energetics of Complex Formation .........................................................211
Mild Conditioning Products ...................................................................212
Fatty Quaternary Ammonium Compounds ...........................................212
Chemistry .................................................................................................215
Desirable Properties of Cationic Silicone Complexes ...........................216
Silicone/Silicone Complexes ...................................................................223
13. Silicone Phosphate Esters ...............................................227
Emulsifiers ...............................................................................................231
Water Soluble Emollients .......................................................................231
Foaming Agents .......................................................................................232
Irritation Reduction of Sodium Lauryl Sulfate ......................................235
Irritation Reduction of Alpha Hydroxy Acids (AHA) ............................235
14. Silicone Resins .................................................................243
Chemistry .................................................................................................252
Applications .............................................................................................254
Future Developments .............................................................................260
15. Silicone Phospholipids .....................................................261
Phosphobetaines ......................................................................................261
Phospholipids ...........................................................................................263
Complexation with Anionic Surfactants .................................................264
Silicone Products .....................................................................................265
Chemistry .................................................................................................266
16. HLB ..................................................................................271
HLB System ............................................................................................271
Applicability of the HLB System to Surfactant Types ...........................273
Three-Dimensional HLB ........................................................................275
Testing the 3-D HLB System .................................................................279
17. Applying the Three-Dimensional HLB System .............283
The 3-D HLB System .............................................................................283
Compounds ..............................................................................................284
Testing ......................................................................................................288
Discussion ................................................................................................290
Emulsifier Kits .........................................................................................293
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SiliconeS for PerSonal care, 2nd edition anthony J. o’lenick, Jr.
18. Silicone Quats ..................................................................297
Structure ..................................................................................................299
Properties .................................................................................................301
Softness ....................................................................................................303
19. Silicone Ester Amido Quaternary Compounds ..............309
Formulating .............................................................................................313
Applications Data – Foam .......................................................................313
Wet Comb Test ........................................................................................314
20. Silicones for Coating Pigments .......................................325
Definitions ...............................................................................................325
Historical Perspective..............................................................................325
Silicone Coatings for Pigments ...............................................................326
Pigment Reactive Binding Mechanisms .................................................326
Silicone Structure ....................................................................................328
Chemistry. ................................................................................................328
Other Functional Groups ........................................................................330
21. Silicone Surface Tension in Formulation .......................341
Silicone in Mixed Systems .......................................................................341
Simple Surfactant Systems ......................................................................343
Test Methodology ....................................................................................348
22. Properties of Silicone Compounds .................................351
Refractive Index ......................................................................................351
Surface Tension .......................................................................................353
Foam ........................................................................................................355
23. Reactive Silicone Compounds .........................................361

24. Methods in Silicone Chemistry .......................................371
Instrumental Methods .............................................................................371
Wetting Test Methodology ......................................................................377
Additional Silicone Information..............................................................381
Optimization of Emulsion .......................................................................384
25. Future Trends ..................................................................387
Technology ...............................................................................................387
Appendix A .............................................................................391
Index .......................................................................................399
Preface
First Edition
The intention of this book is to provide a source of information to the cosmetic
chemist on the basic chemistry and properties of silicone polymers used in the
cosmetics industry. Over the years, these silicone polymers have become more
and more important in advanced cosmetic formulations. As these materials have a
tendency to be more expensive compared to traditional fatty materials, the benefit
that silicones provide to formulations needs to be either more effective at lower
concentrations or must provide benefits not attainable with other traditional prod-
ucts. While silicone compounds can do both, it is critically important to properly
select the right silicone compound, and therefore, understanding the structure of
these materials is crucial to successful selection.
The book stresses the various steps on the synthesis of silicone compounds: con-
struction, functionalization and derivitization. As you will see, each has a profound
impact on the performance and each needs to be understood. Many suppliers of
these materials do not provide such critical information, which makes using their
products in cosmetic formulations much like throwing darts in the dark—you may
hit the bull’s-eye, but the odds are highly unlikely.
The topic of silicone polymers for personal care is broad in scope and cannot be
contained within a single work. It is also a topic in which many new developments
are being made, any of which could revolutionize the industry. Each new invention
builds upon the work of the previous inventor and the science as a whole advances.
It is incredible that, in 1946, the silicone pioneer Rochow, looking at the very im-
pressive body of work that he had done, wondered if there was any commercial
utility to these products. The commercial reality of silicone technology requires a
different skill set—that of the chemist and the engineer. It is the combination of
the two contributions that keeps product development moving forward.
Second Edition
The years have passed rapidly since the first edition. I am most grateful to update
this work for a second edition. What is most interesting to me is the rate of growth
of the use of silicone compounds in our industry and the collective creativity of the
raw material manufacturer, finished product formulator and the consumer product
marketer. The raw materials, finished products and substantiated claims that have
been developed in the last five years have been truly magnificent. Table P.1 shows
the dramatic growth in patents that include the terms “silicone” and “cosmetic.”
One US patent was issued in the five-year period 1976–1980. In the last two years,
there have been an incredible 6,034 US patents located by the same search.
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SiliconeS for PerSonal care, 2nd edition anthony J. o’lenick, Jr.
Both the number of patents and products based upon silicone have grown
immensely. It is the goal of this book to provide information that will allow the re-
searcher to develop and commercialize new products that meet consumer needs.

Table P.1. US Patents Containing Words “Silicone” and “Cosmetic”
Period Patents % Issued
1976–1980 1 0.01
1981–1985 11 0.1
1986–1990 28 0.3
1991–1995 69 0.9
1995–1999 131 1.3
2000–2004 3,282 34.3
2004–2006 6,034 63.1
Total 9,556 100.0
The Author
Anthony J. O’Lenick Jr.
Anthony J. O’Lenick Jr. is president of Siltech LLC, a company he founded in 1989,
specializing in organo-functional silicones and specialty chemicals. He has more
than 250 patents and 30 years of experience in innovative personal care ingredients.
He has held technical and executive positions at Alkaril Chemicals, Henkel Corp.
and Mona Industries.
Tony has four published books: Patent Peace of Mind (Allured Publishing Corp.,
2008); Surfactants—Strategic Personal Care Ingredients (Allured Publishing Corp.,
2005); Silicones for Personal Care (Allured Publishing Corp., 2003) and Primary
Ingredients (Zenitech, 1998). He has written more than 40 technical articles in
scientific and industry journals, including Cosmetics & Toiletries magazine and
HAPPI. Additionally, he has authored two book chapters and co-edited Chemistry
of Colored Cosmetics (Marcel Dekker). His next books, being published by Al-
lured Publishing Corp., include Oils of Nature and Silicones for Personal Care,
2nd Edition. Tony also writes the Comparatively Speaking column for Cosmetics
& Toiletries magazine.
Tony is the recipient of numerous awards for his research on silicone-based
surfactants, including awards from the Soap and Detergents Association and the
American Oil Chemists’ Society. His work in developing a three-dimensional HLB
system (oil-water-silicone) and its use in formulating emulsions was recognized
by the Advanced Technology Group. In 2006, Tony was elected as a fellow of the
Society of Cosmetic Chemists (SCC), having served the society as a member of its
Committee on Scientific Affairs and Education. He teaches a course for the SCC
on silicones and on patents. Additionally, Tony has been an invited speaker at a
symposia organized by the Cosmetics Toiletry and Fragrance Association (CTFA),
Allured Publishing and HBA. Tony and his wife reside outside of Atlanta. They
have three sons (Kevin, Thomas and Andrew), two daughters-in-law (Nicole and
Courtney) and two grandsons (Ty and Jackson).
Acknowledgements
The author gratefully acknowledges his wife, Alice, who has provided him with
encouragement during the various phases of his work and throughout the last 30
years. He also acknowledges the contribution of Kevin O’Lenick, for reading the
manuscript and making helpful suggestions.
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