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6/19/13 I. BASICS OF ORGANO-MODIFIED SILOXANE POLYMERS : Cosmetic Science and Technology Series, v.21.

1. Conditioning Agents for Hair and Skin, 19

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I. BASICS OF ORGANO-MODIFIED SILOXANE POLYMERS





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A. HIstorial Perspective
English

In general, the term silicone is used to describe organo-
modified siloxanes mentioned by Kipping in 1901 and based
on the generic formula R2SiO-where R is CH3
- (polydimethylsiloxane, PDMS) and R2SiO is referred to as a
!
siloxy group. Two well-known types of silicones are
War Thunder

cyclomethicone and dimethicone. Organic groups attached

to a siloxy group (e.g., alkyl, phenyl, polyether, tri-
,
fluoropropyl, vinyl), in turn create organo-siloxane polymers

which have physi
c al properties of the "inorganic" siloxane

backbone (silicon-oxygen-silicon, Si-O-Si) and the "organic"
group attached to it. These organo-modified silox- ane
polymers have unique properties that make them very useful
in personal care products.

The basic raw material from which silicones are formed is quartz, i.e., silica or silicon dioxide (Si02). In the form of crystals or -

fine grains, quartz is the main constituent of white sand. In 1824, Jons-Jacob Berzelius, a Swedish chemist, was successful
!
in liberating elemental silicon (Si) from quartz by re
d uction of potassium fluorosilicate with potassium. Alkylation of elemental
silicon to prepare alkyl silanes was done initially by Friedel and Crafts (1863)



using zinc compounds, by Kipping (1904) using oigano-magnesium compounds (Grignard reaction), and independently in

the 1930s by Hyde (Coming Glass Works) and Rochow (General Electric) using methyl chloride. These scien
t ists synthesized

the silicon-carbon bondone of the most important steps in the history of organo-siloxane polymer development (1,2).
The silicon-oxy
g en-silicon backbone was synthesized by Ladenburg in 1871 by hydrolyzing diethyldiethoxysilane in the
presence of a dilute acid to form an oil (silicone). Between 1899 and 1944, Kipping published 54 papers on the subject of
silicon chemistry, describing the first systematic study in the field. This work helped Hyde and Rochow develop a commercial

process"the direct process" using elemental silicon and methyl chloride to produce organo-silicon com
p ounds. Current

reviews of the synthesis of organo-siloxane polymers have been written by Colas (3) and Rhone Poulenc (4).
-
!
War Thunder
B. Polymer Manufacturing

The great diversity of functional siloxanes, which can be obtained from a rela
t ively few silicon-containing monomers, may
best be understood by consider
ing the chemistry of these monomers and their many possible combinations. As mentioned
earlier, this process begins with high-grade quartzite rock that is heated with charcoal in an electric furnace to produce
elemental silicon at a purity of 98-99%; with heat, the carbon combines with the oxygen from the silica. Extracted silicon is
ground to a fine powder and induced to react with methyl chloride gas at 250-300C in what is called the direct process
(5), producing several important chlorosilane monomer building blocksmono- chlorotrimethyll silane, di'chlorodimethyl
silane, trichloromethyl silane and tetrachloro silane. These compounds are fractionally distilled as purified chlo- rosilane
monomers.

Organo-modified siloxane polymers are derived from chlorosilane mono


mers via hydrolysis and polymerization and/or
polycondensation. The hy
d rolysis and condensation product of dichlorodimethyl silane is of particular importance
[(Me2SiO)x], as it is the major component of most organo-siloxane polymer fluids and elastomers. When two or more types
!
of functional chlorosilanes are hydrolyzed together, the process is called co-hydrofysis. An example is co-hydrolysis of
monochlorotrimethyl silane and dichlorodimethyl silane to form trimethyl siloxy end-cap polydimethylsiloxane chains. The re
-
sultant polymers from co-hydrolysis may be fluid, gel, crystalline solid, or resin, depending on the average functionality of
the monomer [(CH3)SiO(4^y2jt. If n > 2, the product is a fluid; if n equals 2, the product is a cyclic or linear siloxane
fluid (a gum, if a high-molecular-weight siloxane); and if n < 2, the product is a resin.

C. Polymer Nomenclature

Today's nomenclature system (6) for organo-silicon polymers is based on Sauer's (7) recommendations. These
recommendations were subsequently de
veloped and adopted by the American Chemical Society (8), the Journal of the
Chemical Society (9), and lUPAC (10).

In general, organo-silicon nomenclature is applied to any structure contain


ing at least one silicon atom. Silanes (RtSi) are
silicon-containing compounds with one silicon atom and four directly bonded groups. Silicones, containing alternating silicon
and oxygen atoms, are cyclic, linear, branched, caged, or three-dimensional polymers of the monomeric siloxy group. The
prefix to these siloxane polymers designates the number of silicon atoms in the polymerthat is, disiloxane has two silicon

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atoms, while trisiloxane has three silicon atoms, etc. Siloxanes and silanes are named similarly; the root describes whether it
is a siloxane (Si-O-Si backbone) or silane (only one Si atom), and the organo- functional portion describes the type and
amount of substitution: hexamethyl- disiloxane, decamethylpentacyclosiloxane, Tris(trimethylsiloxy)silane, and
(poly)dimethylsiloxane.

Shown below is a shorthand nomenclature of the four major organo-siloxy chain unitsM, D, T, Q. Each Si-0 bond has
another Si attached through an oxygen linkage. Therefore, the mono-, di-, etc., refers to the number of poly
mer
propagating oxygen bonds on Si.

Me MeSiOt/2

Me M (Mono-) Me3SiOi/2

Me

Oi/iSiOi/a

Me DJW2 MejSiOaa

Me OujSiOj/j 0 T (Tri-)

MeSiOjw

OiflSiOw

Om Q (Quad-) SiO

As an example using this shorthand nomenclature system, (poly)dimethyl- siloxane, containing 10 repeating dimethylsiloxy
groups and terminated with trimethylsiloxy groups, would have a shorthand description of MD10M. Addi
t ionally, the T
structure above represents silsesquioxane (e.g., the simplest form is M3T) and the Q structure represents silicate (e.g., the
simplest form is M4Q).

D. Chemical-Physical Properties

The unique structure of the basic organo-modified Siloxane polymer accounts for the fundamental properties and resulting
benefits to the personal care industry (11a, l1b). A few fundamental chemical properties (12) that make organo-modified
Siloxane polymers versatile are:

1. Si-C bondlow energy (75 kcal/mol) and long length (1.88 A), Si-O bondlow energy (106 kcal/mol) and long
length (1.63 A) (13) means reduced steric interactions.

2. natter Si-O-Si bond angle (130-150") versus C-O-C (105-115) (14).

3. Lower energy of rotation that results from Si-O longer bond length and flatter bond angles.

4. Lower silicon electronegativity (1.8) than carbon (2.5), which leads to a very polarized Si-O bond that is highly
ionic.

5. Low intramolecular and intermolccular (van der Waals) forces.

These chemical properties, in turn, help explain some of the physical prop
e rties (e.g., easy diffusion of organic molecules
through organo-modified silox- ane films, low-tempcraturc stability, water repellency, and low surface ten
sion) of organo-
modified siloxane fluids.

For an understanding of the physical properties of organo-modified silox- ane compounds, one needs to understand the
molecular architecture (15) of silicon-oxygen and silicon-carbon compounds compared to organic carb
o n-carbon and carbon-
oxygen compounds. Low bond energy and low bond rotational energy contribute to a high degree of rotation of a Si-O-Si
back
b one. This freedom of rotation leads to a unique flexibility of a siloxanc mole
c ule . A siloxanc molecule can be compared
to a spring, Slinky, or accordion as its relates to back-and-forth and twisting motion. This bond flexibility is an important
aspect of organo-siloxanc polymers. It is believed that the freedom of rotation of a Si-O-Si backbone allows for an organo-
cloud orientation [see Figure 1 (16)) that facilitates an effective spatial orientation/alignment at the interface of the surface
to which an organo-siloxane polymer is exposed (lines A and B in Figure 1 represent interfaces). This freedom of rotation
allows for maximizing surface activity, aligning the inorganic backbone (high-surface-encrgy Si-O-Si backbone) to high-polarity
surfaces (line B in Figure 1) and organo-groups (low-surfacc-cnergy CH3 groups) to low-polarity surfaces (line A in Figure 1).

The spatial orientation of nonpolar methyl groups (as represented by CH3 in Figure 1), with their low surface energy
measured as lower interface

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Figure 1 Organo-cloud orientation of a (poly)dimcthylsiloxanc molecule.

tensionyields an interface which can be characterized as organic and hydro


c arbon-like. These methyl groups, with low
intermolecular forces and surface energy, are inert and hydrophobic. The flexibility of the Si-O-Si backbone allows for the
maximization of hydrophobicity and surface activity attributes of the methyl groups. Due to the packing of methyl groups at
a surface, the surface tension is very low. The low surface tension of PDMS fluids (PDMS, 20 dynes/cm; cf benzene, 28.9,
and water, 72) permits them to spread easily over surfaces, which, coupled with other properties (e.g., low coefficient of
friction), translates to silky, smooth, nontacky esthetic qualities.

The intra/intermolecular forces are low between siloxane molecule(s), giving rise to low resistance to flow when stressed,
creating the ability to engineer high-molecular-weight polymers with relatively low viscosities. The glass transition
temperature {Tg) of (poly)dimethylsiloxane is low, at 120C (flowable liquid down to the Tg). Polymers with molecular
weight {MN) as high as Vi million are still fluidsa unique distinguishing point com
p ared to similar molecular-weight organic
polymers. At the same time, chang
ing the structure of organo-modified siloxane polymers allows for physical form
differences, e.g., from waterlike-viscosity volatile siloxanes to rubberlike, and even glasslike siloxane resins. The resultant
physical property data on organo-modified siloxane compounds have been referenced in many sources (17).

Siloxane chain entanglement also plays an important role in solvation and flow. Ferry (18) characterized the relationship of
viscosity and molecular weight (M oc Ti). Below 1000 cP viscosity for PDMS, viscosity and molecular weight are more nearly
proportionalthus, viscosity is increasing at a corre
sponding rate to M. Above 1000 cP, viscosity is not proportional to
molecular weight-viscosity increases nearly 3.5% faster than M. This can be explained using the "reptation" model
(molecules are moving through the mass by pull
ing in and out through tunnels). If one thinks of a mass of worms (each
wormstrandis a PDMS molecule), it takes time for the strands to slide in and out. With branching or crosslinking, the
constraint on flow is dramati
c ally slowed and viscoelastic properties play a stronger role. Thus, with crosslinked or high-
molecular-weight PDMS, solvents can swell but not dis
solve the molecules, time and energy being required to solvate and
disentangle the molecules.

E. Classification

The silicone family of products is extensive. The silicon atom has the ability to accept many different substituents, and the
siloxane backbone can take on different structures, which then create the opportunity to change the physical and, as a
result, the performance characteristics of functional silicones from:

Amodimetiiicone

Figure 2 Pictorial of silicone family of products.

Volatile -> range of viscosity -> high-melting-point wax Defoamer -> profoamer -> emulsifier Fluid -> elastomeric -> resinous
powder.

Figure 2 shows a pictorial representation of the silicone family of products dimethyl, alkyl, aromatic, polyethers, amino, and
three-dimensionalthat are commercially available and commonly used in the personal care industry.

What follows is a more in-depth look at some key functional Siloxane prod
uct families.

1. (Poly)dimethylcyclosiloxanes

The most common (poly)dimethylcyclosiloxanes [International Nomenclature Chemical Ingredient (INCI): Cyclomethicones]
possess 6, 8,10,12, or 14 at
o ms in their ring structures (Figure 3) with 3 silo)A bonds (INCI: Ciyclotrisiloxane), 4 siloxy
bonds (INCI: Cyclotetrasiloxane), 5 siloxy bonds (INCI: Cyclopenta- siloxane), 6 siloxy bonds (INCI: Cyclohexasiloxane), and 7
siloxy bonds (INCI:

E-

CH3

S i-0

CH3J,

where n = 3,4,5,6, etc.

Figure 3 Empirical structure of C-PDMS (cyclomethicone).

Table 1 Heat of Vaporization of Common Personal Care Carriers

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Material

Heat of vaporization (cal/g)

Water Ethanol

Cyclotetrasiloxane Qfclopentasiloxane

539 210 32 32

Cycloheptasiloxane), respectively. Volatile (poly)dimethylcyclosiloxanes are considered non-Volatile Organic Components


(VOC) as regulated by the U.S. federal (19) and state Environmental Protection Agencies (EPA). Cyclometh- icone fluids
have unique physical properties that translate into benefits for personal care applications. These include volatility, low
viscosity, and non- residual transient skin feel. Cyclomethicone fluids have low heat of vaporiza
t ion (Table 1), they are
noncooling (i.e., cooling during evaporation from skin is minimal), and are nonstinginga combination rare for personal care
carriers. Other attributes of cyclomethicone fluids include: colorless, odorless, non- staining, good spreading, detackification,
water sheeting, and transient emol- liency properties. The level of use of cyclomethicone in personal care applica
t ions is
typically from 0.1% to 85%; the low end represents use levels which enhance skin feel in creams (e.g., hand and body
moisturizers), and the high- end use levels are to carry actives to skin and hair (e.g., antiperspirant salts, hair cuticle coat).
Another aspect of cyclomethicone fluids that make them functional in the personal care industry is that they have broad
compatibility with most personal care ingredients, including ethanol, mineral oil, and fatty acid esters.

Another key attribute ot cyclomethicones is their ability to provide appeal


ing sensorial esthetics to personal care products.
Key sensorial esthetics typically associated with (poly)dimethylcyclosiloxanes, of which cyclopenta- siloxane is a good
example, are low residue, low stickiness, low tackiness, low greasiness, and low waxiness. Using a protocol developed by
Dow Corning Corporation (20) in Figure 4 one sees that cyclopentasiloxane has sensory properties normally associated with
silicones. The scale in Figure 4 that is used to rank each attribute is based on 0 to 10, with 10 representing the most and 0
representing the least for the attribute measured. As the ring size of (poly)dimethyl-cyclosiloxane changes, there are minor
changes in sensory effects. Larger-ring-size cyclomethicone fluids are slower to volatilize, and they reside on the skin longer
to give a longer-lasting feel until they totally evaporate.

10

%MM^MMiM WmMr

%5

ft S

Figure 4 Cydotctrasiloxanc sensory profile.

2. Linear (Pofy)dimethylslloxanes (Dimethicone and Dimethiconol)

Linear (poly)dimethylsiloxane (INCI: Dimethicone)see Figure 5having trimcthyl end blocking, can have from two to
thousands of repeating dimethyl- siloxy groups (Figure 5a), with viscosities ranging from 0.65 to > 100,000 ccn- tistokes
(cS) (Table 2). When linear (poly)dimethylsiloxanes are hydroxy ter
minated, they are called dimethiconols (INCI), which
have viscosities as high as 30,000,000 cS (Figure 5b).

HO - S

(J

C H , fS " "1 f H,

-S iO SIO J Si-C H ,

C H , |_C H ,J. t H,

(b)

. rs f .

iO -ISiO -I Si-O II

H LC H J-H

where m it gretter thin 0

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Rgura 5 Empirical structure of (a) linear pofy(dimcthylsiloxane) and (b) dimcthi- conol.

Table 2 Comparative Molecular Weights for Different Viscosity (Poly)diniethyl- siloxanes

Approximate No. of Example of

Average molecular subunits similar

viscosity (cS)weight (MD.M) viscosity

5 800 9 Water

20 2,000 27 Cooking oil

50 3,800 50

100 6,000 80 Paint

200 9,400 125 Shampoo

350 13,700 185 Mineral oil

500 17,300 230 Ketchup

1,000 28,000 375 Motor oil

5,000 49,300 665 Corn syrup

10,000 62,700 845 Molasses

12,500 67,700 910

30,000 91,700 1,235 Honey

60,000 116,500 1,570 Hot tar

100,000 139,000 1.875

300,000 204,000 2,750

600,000 260,000 3,510 Thick milkshake

4,000,000 400,000 5,400 Petroleum jelly

20,000,000 550,000 7,430 Silly putty

As a class of personal care additives, linear PDMS is considered a good skin emollient and lubricant. Linear PDMS generally
acts as (a) skin-feel mod
ifiers, (b) water barrier protectants, (c) defoamers, (d) desoapers (i.e., eliminators of creamy
whitening of a cosmetic formulation during the initial rubbing onto skin or hair), and (e) providers of conditioning and
emoUiency.

Dimethicone is covered in the "Skin Protectant Monograph" as an over- the-counter drug (21) and is listed in the National
Formulary compendium (22). Because dimethicone can be recognized as a drug, when sold under a compendia name with
skin protectant claims it must meet the requirements as outlined in the compendium, and the substance's name must be
distinguished clearly on the label. The tentative final monograph identifies which active can be used at use levels of 1-30%
as an active ingredient in OTC products with label claims such as "helps prevent and temporarily protects chafed, chapped,

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cracked, or windburned skin and lips."

Linear PDMS is noted for its thermal and oxidative stability over a wide range of temperature. When held in contact with air
at 150C, linear PDMS

is stable for long periods. These compounds oxidize at higher tempertaures, well above those typically associated with
operating temperatures used in the personal care industry. In the absence of oxygen and at temperatures above 250C,
linear PDMS can be broken down to smaller polymers. This breakdown process is known as depolymerization (a
phenomenon similar to the cracking of petroleum). Additionally, the low glass transition temperature (Tga -120C) of PDMS
means that the polymers are flowable liquids down to that Tg.

It is the compatibility (solubility) characteristics of linear PDMS that con


t ributes to its unique esthetics and film-forming
properties. Because linear PDMS has limited compatibility in typical cosmetic ingredients, it tends to migrate to the surface
(away from the skin or hair). The compatibility of linear PDMS varies with its viscosityAwith the low-viscosity fluids having
compati
b ility with more materials than higher-viscosity fluids. Linear PDMS is insol
uble in water, but soluble in aliphatic
hydrocarbons, aromatics, and chlorinate solvents (e.g., hexane, toluene, methylene chloride, and chloroform). Further
-
more, linear PDMS is incompatible in mineral oils and solvents such as iso- propanol; lower-viscosity PDMS has greater
miscibility, especially in mineral oils and solvents such as isopropanol.

Volatility and vapor pressure decrease while viscosity and molecular weight increase for linear PDMS. Hexamethyldisiloxane
(0.65 cS) possesses the high
e st volatility of linear or cyclic (poly)dimethylsiloxane fluidssimilar to etha- nol. PDMS starts to
lose its volatility at about 5 cS (around 800 molecular weight). Volatile PDMSs are classified as non-Volatile Organic
Components (VOC) as regulated by the U.S. Environmental Protection Agency (23) and individual state governments.

When linear PDMS fluids are incorporated with cosmetic ingredients to make a personal care product, sensory attributes
may be slightly different compared to the neat PDMS fluid. The ease of spread and lubricity of a linear PDMS fluid produces
the characteristic velvetlike feel typically associ
ated with silicones. As the molecular weight increases for linear PDMS, an
increase in residue, oiliness, and smoothness can be observed. Figure 6 denotes the sensory attributes for a medium-
viscosity linear PDMS (350 cS)sensorial attributes are evaluated by trained sensory panelists. In Figure

6 one sees an increase in residue, oiliness, greasiness, and waxiness of 350-cS dimethicone, a linear PDMS, compared
to cyclomethicone (reference Figure 4). Dimethicone, 350 cS, shows different attributes than cyclomethicone, be
c ause it
does not volatilize and thus remains on the skin.

To effect a perceived sensorial change in a personal care product, one would usually need to use between 0.1 and 5% of
a linear PDMS fluid. Figure

7 shows the minimum threshold levels required for various PDMS polymers before they are judged as perceptibly
different. As the molecular weight of

Organo-Modined Slloxane Potymert

177

Dimethicone (350 cs)

10 8 6 4 2

04

m i ml 1111 11111

Figure 6 Sensory profile of 350 cS linear (poly)dimcthylsiIoxane.

Figure 7 Threshold level of various PDMSs.

linear PDMS increases, a lower weight percent will be needed in formula- tionsthe hypothesis is that a thicker film is
producedto effect perceived sensory change, in particular, residue, oiliness, and smoothness. What can be concluded is
that, to elicit a sensory perception, (a) typically less linear PDMS (dimethicone) is required than cyclomethicone; and (b) as
viscosity (molecular weight) increases, less linear PDMS is required.

3. Other Functional Siloxanes

a. Pofyether Functional (24). Polyether functional siloxanes (SPE, siloxane polyether) are created by replacing some of the
methyl groups on the siloxy backbone with polyether (polyoxyalkylated) substituents (see Figure 9, be- low)Aprimiarily
ethylene oxide and propylene oxide. Substitution of a polyoxyalky substituent for a methyl group on the PDMS backbone
results in a change in the hydrophile/lipophile balance (HLB) of a SPE polymer. Addition of polyether groups allows for
modification of compatibility of SPE polymers in polar and nonpolar solvents. Not only do polyether groups effect solubility,
but also inter- facial tension characteristics of polyether functional siloxanes are different from those of comparable-

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molecular-weight PDMS.

Polyether functional siloxanes can range from water soluble to oleophilic soluble, thus having applications in both water and
oil phases of cosmetic for
mulations. Water and polar solvent solubility increases when the mole percent and molecular
weight of the polyoxyethylene moiety is increased. Complete water solubility occurs when the mass ratio of
polyoxyethylene to dimethyl- siloxy groups is in the range of 2-4. They can be used to detackify water and oil phases of
cosmetic formulations. High-HLB polyether functional siloxanes are used for detackification of water, and low-HLB polyether
functional silox
anes are used for oil phases.

Polyether functional siloxanes are playing an ever-increasing role in the personal care industry as emulsifiers [Silicone
Formulation Aids (25)] for water-in-poly(dimethylcyclosiloxane) and water-in-oil emulsion. Their unique
ness as siloxane
emulsifiers is due to flexibility of the siloxane backbone, which in turn provides for reduction of interfacial tension, more
effective surface coverage, and a thick phase between the water and oil phases without tem
p erature or shear as the
driving force (26). The stability of oil-continuous- phase (water-in-oil) emulsions is the result of a film of high viscoelasticity
at the water-oil phase boundary (27) of the emulsion.

Polyether functional siloxanes provide advantages in producing water-in- poly(dimethylcyclosiloxane) and water-in-oil
emulsions: (1) low levels of emulsifierless than 2%, but usually less than 1%; (2) creation of emulsions that vary in
viscosity from pumpable fluids to extrudable gels to sticks (using phase volume to control viscosity), and from opaque to
crystal clear (using refractive index matching of the water and oil phase)Awithout the need for

( c H ,) i

Figure 8 Empirical structure of phenyl trimethicone.

making significant modifications in phase compositions; and (3) nonirritation or drying of skin. In addition to being efficient
water-in-oil or water-in- (poly)dimethylcyclosiloxane emulsifiers, SPE polymers can enhance percep
t ible skin feel in personal
wash applications [e.g., bar soaps, shower gels (28)], act as good hairspray resin modifiers (29), and mild conditioners for
clear shampoo. Also, it has been reported that certain water-soluble polyether func
t ional siloxanes (30) can reduce eye
irritation in shampoos.

b. Phenyl Functional. Replacement of some methyl groups on a PDMS siloxane backbone with phenol substituents
results in an increase in the refrac
t ive index (imparting shine or sheen), and broadened compatibility in comon personal care
systems. Phenyl groups also enhance thermal stability, oxidative resistance, and nonwhitening and nonresidue attributes
(31). Figure 8 shows the empirical structure of a phenyl functional siloxane, Phenyl Trimethicone (INCI).

c. Alkyl Functional (32). Substituting alkyl groups (six or more carbons) for some methyl groups on a PDMS siloxane
backbone results in an alkyl func
t ional siloxane (more specifically, alkyl methyl siloxanes or AMS). Alfcyl func
t ionality of these
siloxanes improves occlusivity (33) (decrease in water per
meability) and compatibility in common personal care systems. AMS
polymers have product forms ranging from fluids to very-high-melting-point waxes (above WC). Alkyl substitution results in
the modification of sensory characteristics of a PDMS siloxane, providing esthetics approaching both hydrocarbons and
siliconesthat is, a waxier and greasier feel during rub-out and a "silicone" smooth after-feel. AMS waxes have been
reported (34) to provide bodying and cushioning to all types of emulsions, with moisturization comparable to petrolatum.

d. Amino Functional. The addition of aminoalkyl groups to a PDMS siloxane backbone increases substantivity (35,36)
of silicones. The most widely used amine group is based on the ethylene diamine structure. Amine functional siloxanes can
be trimethyl siloxy or dimethyl hydroxyl siloxy end-

Vf n ) w n j t nj

c h ,(si)o - c sf i o 10 )r-(iio ),.si(c h ,) d h ( ft

ch

ch

ch

dh

whet* R - i Ik o x y It it (EO o r E R ' m ethyl or *lkyl

Figure 9 Empirical formula of siloxane polyether.

blocked. Typical INCI names assigned to this class of materials are Amodi- methicone, Amodimethiconol, and
Trimethylsilylamodimethicone (see Fig
ure 9). Amine functional siloxanes can differ in length of siloxane backbone, linear
versus branching of the siloxane backbone, substitution amount and type of amino groups on the backbone, and the

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linking group on the amino moiety. The addition of an amine group to a siloxane backbone allows for excellent hair
conditioning for both leave-in and wash-off conditioners. Amino- functional PDMS polymers can potentially cause skin
irritation; therefore, caution is required when using them as skin conditioners.

e. Crosslinked Poly(dimethylsiloxanes). This group of PDMS polymers is based on crosslinking of siloxane backbones. INCI
names are Silicates ("Q" structures), Silsesquioxane ("T" structure), Crosspolymer, and Copoly- mer. Changing the degree of
crosslinking of the PDMS backbone results in a change in the physical form from a soft gel to a glasslike solids. Recent
patents have been issued outlining the ability to modify rheology of functional silox
anes with crosslinked PDMS polymers
(37-40). These patents show how to improve appearance, bodying, cushioning of cosmetic products, and set reten
-
tion/styling of hair. Also, it has been speculated that crosslinking of the PDMS backbone could improve substantivity without
adding heaviness to resultant films.

/ Beyond Classical PDMS. How functional siloxanes are delivered to skin and hair is as critical as the structure/properties of
the specific functional silox
ane. As an example, functional siloxanes can be added directly to a formula
t ion and delivered to
specific skin or hair sites as a solution or dispersion of the formularequiring transport through the formula matrix to reach
the de
sired location. Functional siloxanes can be predispersed as colloidal systems (e.g., emulsions and microemulsions) for
ease of incorporation. Engineering the PDMS colloidal systemsparticle size distribution, polymer rheology, and surfactant
typecan affect how other functional conditioners are delivered to hair and skin. Further, blending of functional siloxanes
can provide the oppor
t unity for synergistic enhancement of performance.

The above functional siloxane classifications and benefits for skin and hair conditioning are based on a simplistic view of the
organo-modified siloxane backbone. One can visualize the potential for significant changes in properties and the resultant
benefits when the backbone is further modified (e.g., com
b ination of functionality on the backbone, or reaction product of
active sites on the functional attached moiety to the PDMS backbone. New, evolving mul
t ifunctional siloxanes are covered
by O'Lenick in Chapter 9 in this book.

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