Copolymers of polyorganosiloxane, polyisobutylene, and alkyl acrylates or methacrylates

Method of making copolymers of (i) an acrylic or methacrylic-functional polyisobutylene macromonomer, (ii) a polydiorganosiloxane macromonomer, and optionally (iii) a radical polymerizable monomer such as an alkyl acrylate or alkyl methacrylate. The copolymers are prepared by copolymerizing the monomers in a miniemulsion using a free radical initiator at high temperature. In the method, the monomers are mixed with a surfactant(s) and optionally a cosurfactant(s), and subjected to high shear.

BACKGROUND OF THE INVENTION 
This invention is directed to miniemulsion polymerization of (i) an acrylic 
or methacrylic-functional polyisobutylene (PIB) macromonomer, (ii) a 
polydiorganosiloxane macromonomer, and optionally (iii) a radical 
polymerizable monomer such as an alkyl acrylate or alkyl methacrylate. 
Emulsion polymerization is an important industrial method, because it 
produces high molecular weight polymers, and because there is no or 
negligible content of volatile organic compounds (VOC). In a normal 
emulsion polymerization technique, the oil is emulsified in water with a 
conventional surfactant using a mechanical shearing device, to produce 
droplets of 1,000-10,000 nanometers (nm) in diameter. The polymerization 
is achieved with the assistance of a water or oil soluble initiator or 
catalyst. These emulsions are generally opaque, milky, and viscous; but 
they can also be translucent emulsions with particle sizes ranging from 
about 8-80 nm, when a very high surfactant concentration is employed. 
In such conventional emulsion polymerization, the micelles are the primary 
site for polymerization. However, El-Aasser et al in the Journal of 
Applied Polymer Science, Volume 43, Pages 1059-1066, (1991), show that 
nucleation can also occur in monomer droplets if they are very small. They 
termed this phenomenon "miniemulsion polymerization", with particle sizes 
ranging from 50-500 nm. According to El-Aasser et al, the miniemulsions 
are more stable compared to conventional emulsions; they have small 
particle size, i.e., 50-500 nm. High shear devices such as a submicron 
disperser, a MICROFLUIDIZER.RTM., or an ultrasonication unit can be used 
to make the miniemulsion. 
According to their technique, a cosurfactant is employed, which is 
typically a low molecular weight, water insoluble compound, such as cetyl 
alcohol or hexadecane. It is used for the purpose of retarding the 
diffusion of the monomer out of the droplets. They postulate that the 
stability of such acetyl alcohol system can be attributed to the formation 
of intermolecular complexes at the oil/water interface, resulting in lower 
interfacial tension. 
El-Aasser et al do not describe the copolymerization of an acrylic or 
methacrylic-functional polyisobutylene macromonomer, a 
polydiorganosiloxane macromonomer, and optionally an alkyl acrylate or 
alkyl methacrylate. We are not aware of any published report on the 
copolymerization of such monomers. Where there is reference to 
polymerization of macromonomers, the references are focused toward 
copolymerization of non-silicon atom containing macromonomers with 
conventional low molecular weight monomers, i.e., Journal of 
Macromolecular Science, Pure Applied Chemistry, Aniko Takacs & Rudolf 
Faust, A33(2), Pages 117-131, (1996); and Journal of Polymer Science, 
Polymer Chemistry Edition, Joseph P. Kennedy & Misao Hiza, Vol. 21, Pages 
1033-1044, (1983). In particular, these references only relate to the 
preparation of poly(methyl methacrylate-graft-isobutylene) copolymers, 
i.e., PMMA-g-PIB; and neither disclose copolymers of a polyisobutylene 
macromonomer, a polydiorganosiloxane macromonomer, and optionally a 
radical polymerizable monomer such as an alkyl acrylate or alkyl 
methacrylate. In addition, both references use solution polymerization 
rather than a miniemulsion polymerization technique. 
BRIEF SUMMARY OF THE INVENTION 
Our invention relates to a method of making a copolymer in an emulsion by 
heating and shearing a reaction mixture formed by combining (i) water; 
(ii) an anionic surfactant, a cationic surfactant, a nonionic surfactant, 
or a combination thereof; optionally (iii) a cosurfactant which is a 
hydrophobic solvent, or a compound having low water solubility, such as a 
fatty alcohol, an n-alkane, or a halogen substituted n-alkane; (iv) a 
mono-acryloxyalkyl terminated polydiorganosiloxane macromonomer or a 
mono-methacryloxyalkyl terminated polydiorganosiloxane macromonomer; (v) 
an acrylic or methacrylic-functional polyisobutylene macromonomer prepared 
by reacting (A) a polyisobutylene polymer containing at least one 
carbon-bonded silanol group in its molecule with (B) a silane having both 
an acrylic or methacrylic-containing group and a silicon-bonded 
hydrolyzable group in its molecule; optionally (vi) a radical 
polymerizable monomer such as an alkyl acrylate or an alkyl methacrylate; 
and (vii) a free radical initiator. 
Our invention also relates to the copolymer made according to the method, 
and to the emulsion containing the copolymer. 
These and other features and objects of our invention will become apparent 
from a consideration of the detailed description. 
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING 
Not applicable. 
DETAILED DESCRIPTION OF THE INVENTION 
A macromonomer is a polymer of molecular weight ranging from several 
hundred to tens of thousands, having a functional group at the chain end 
that can further polymerize. The term macromonomer is an abbreviation of 
macromolecular monomer. While the functional group may be any 
polymerizable group, most typically it is a vinyl group, epoxy group, 
dicarboxylic acid group, diol group, diamine group, acryloyl group, or a 
methacryloyl group. 
The PIB-Macromonomer component used to prepare our copolymers is an acrylic 
or methacrylic-functional polyisobutylene macromonomer prepared by 
reacting (A) a polyisobutylene polymer containing at least one 
carbon-bonded silanol group in its molecule with (B) a silane having both 
an acrylic or methacrylic-containing group and a silicon-bonded 
hydrolyzable group in its molecule; or by reacting an alcohol-functional 
PIB and acryloyl chloride or methacryloyl chloride. 
This component and methods of making it are described in detail in a prior 
copending application U.S. Ser. No. 08/708,070, filed Aug. 30, 1996, 
entitled "Polyisobutylene Polymers Having Acrylic Functionality". The 
prior application is assigned to the same assignee as the present 
invention, and is incorporated herein by reference thereto. 
In general, the silanol-functional polyisobutylene polymer (A) is prepared 
by first silylating the corresponding allyl or vinyl-functional 
polyisobutylene polymer with a silane of the formula 
EQU HSiR(.sub.3-x)(Z).sub.x (ii) 
followed by hydrolysis of the resulting hydrolyzable group containing 
functional polymer. In formula (ii), R is a hydrocarbon group with 1-14 
carbon atoms or a halogenated hydrocarbon group with 1-10 carbon atoms, 
excluding groups containing aliphatic unsaturation; Z is a hydrolyzable 
group such as halogen, alkoxy, acyloxy, alkenyloxy, oximo, or aminoxy; and 
x is 1 or 2. Preferably, Z is chlorine. This scheme is illustrated by the 
following two equations, wherein "(Polymer)-" represents the 
polyisobutylene polymer chain residue and Z is chlorine. 
EQU (Polymer)--CH=CH.sub.2 +HSiR.sub.(3-x) (Cl).sub.x 
.fwdarw.(Polymer)--CH.sub.2 --CH.sub.2 --SiR.sub.(3-x) (Cl).sub.x(iii) 
EQU (Polymer)--CH.sub.2 --CH.sub.2 --SiR.sub.(3-x) (Cl).sub.x +H.sub.2 
O.fwdarw.(Polymer)--CH.sub.2 --CH.sub.2 --SiR.sub.(3-x) (OH).sub.x(iv) 
The first of these reactions is typically catalyzed by a hydrosilylation 
catalyst such as platinum on carbon, chloroplatinic acid, or a platinum 
complex. 
The silanol-functional polyisobutylene polymer (A) shown in formula (iv) is 
then reacted with a silane (B) of the formula 
##STR1## 
where R is as defined above; G is a difunctional alkylene oxide group 
having 1-4 carbon atoms, i.e., --(CH.sub.2).sub.n O-- where n is 1-4; and 
L is hydrogen or a methyl radical, corresponding to acryl and methacryl 
functionality, respectively. In formula (v), X is a silicon bonded 
hydrolyzable group capable of condensing with the silanol group of (A) to 
form a siloxane linkage (i.e., .ident.Si--O--Si.ident.), or capable of 
hydrolyzing to form an SiOH group on silane (B), which can then condense 
with the SiOH of silanol-functional polymer (A), to form a siloxane 
linkage. These X groups may be selected from the hydrolyzable Z groups 
previously described in connection with silane (ii) used to prepare the 
silanol-functional polymer (A). Preferably X is again chlorine, and 
preferred silanes (v) are 3-acryloxypropyldimethylchlorosilane H.sub.2 
C=CHCO.sub.2 (CH.sub.2).sub.3 SiCl(CH.sub.3).sub.2 or 
3-methacryloxypropyldimethylchlorosilane H.sub.2 C=C (CH.sub.3)CO.sub.2 
(CH.sub.2).sub.3 SiCl(CH.sub.3).sub.2. The following equation illustrates 
this last reaction for the case where the silanol-functional polymer has 
the formula (iv): 
EQU (Polymer)--CH.sub.2 --CH.sub.2 --SiR.sub.(3-x) (OH).sub.x 
+XSi(R.sub.2)--G--C(O)C(L)=CH.sub.2 .fwdarw.(Polymer)--CH.sub.2 --CH.sub.2 
--SiR.sub.(3-x) (O--Q).sub.x (vi) 
In the above equation, Q is --Si(R.sub.2)--G--C(O)C(L)=CH.sub.2 ; and R, X, 
G, L and x have their previously defined meanings. 
The PDMS-Macromonomer component used to prepare our copolymers can be a 
mono-acryloxyalkyl terminated polydiorganosiloxane macromonomer (I) or a 
mono-methacryloxyalkyl terminated polydiorganosiloxane macromonomer (II) 
having the formula 
##STR2## 
where R in each formula is a divalent hydrocarbon radical with 1-20 carbon 
atoms; R' in each formula is the hydrogen atom, a C.sub.1-8 alkyl radical, 
a haloalkyl radical, or an aryl radical; and z in each formula is 1-1,000. 
These macromonomers can be prepared by methods known in the art, i.e., 
reacting a silanol endblocked polydimethylsiloxane with 
acryloxypropyldimethylchlorosilane or 
methacryloxypropyldimethylchlorosilane, in presence of an acid acceptor 
such as dibutylamine, for example. 
The radical polymerizable monomer used to prepare our copolymers is 
preferably an acrylate monomer such as an alkyl acrylate or an alkyl 
methacrylate containing 1-10 carbon atoms in the alkyl chain. Examples of 
some suitable acrylate monomers are methyl acrylate H.sub.2 C=CHCO.sub.2 
CH.sub.3, ethyl acrylate H.sub.2 C=CHCO.sub.2 C.sub.2 H.sub.5, amyl 
(pentyl) acrylate H.sub.2 C=CHCO.sub.2 C.sub.5 H.sub.11, 2-ethylhexyl 
acrylate H.sub.2 C=CHCO.sub.2 CH.sub.2 CH (C.sub.2 H.sub.5) 
(CH.sub.2).sub.3 CH.sub.3, methyl methacrylate H.sub.2 C=C 
(CH.sub.3)CO.sub.2 CH.sub.3, ethyl methacrylate H.sub.2 
C=C(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5, butyl methacrylate H.sub.2 
C=C(CH.sub.3)CO.sub.2 (CH.sub.2).sub.3 CH.sub.3, hexyl methacrylate 
H.sub.2 C=C(CH.sub.3)CO.sub.2 (CH.sub.2).sub.5 CH.sub.3, and 2-ethylhexyl 
methacrylate H.sub.2 C=C(CH.sub.3)CO.sub.2 CH.sub.2 CH(C.sub.2 H.sub.5) 
(CH.sub.2).sub.3 CH.sub.3. Examples of other radical polymerizable 
monomers that can be used are styrene C.sub.6 H.sub.5 CH=CH.sub.2, 
methylstyrene C.sub.6 H.sub.5 C(CH.sub.3)=CH.sub.2, acrylonitrile H.sub.2 
C=CHCN, and (meth) acrylic acid H.sub.2 C=C(CH.sub.3)CO.sub.2 H. 
The free radical initiator can be an azo initiator conforming generally to 
the formula: 
##STR3## 
where R is an alkyl radical, and Q is a simple carboxylic acid residue or 
derivative thereof such as a nitrile ester. 
The most preferred free radical initiator is 2,2'-azobisisobutyronitrile 
(AIBN) shown below: 
##STR4## 
Similar initiating properties can be obtained using 
4,4'-azo-4-cyanopentanoic acid (ACPA), a compound shown in the previous 
formula where R is --CH.sub.3 and Q is --(CH.sub.2).sub.2 COOH. ACPA is 
soluble in water, unlike AIBN. 
Other classes of free radical initiators can be used including dialkyl 
hyponitrites, diaroyl peroxides, dialkyl peroxydicarbonates, dialkyl 
peroxalates, dialkyl peroxides, alkyl hydroperoxides, and disulfides. 
The reaction medium can contain ionic, nonionic, and mixtures of ionic and 
nonionic surfactants to stabilize the copolymer in the emulsion. Ionic 
surfactants can be cationic or anionic including surfactants known in the 
art as useful in emulsion polymerization. 
Suitable anionic surfactants include but are not limited to sulfonic acids 
and their derivatives. Useful anionic surfactants are alkali metal 
sulfosuccinates; sulfonated glyceryl esters of fatty acids such as 
sulfonated monoglycerides of coconut oil acids; salts of sulfonated 
monovalent alcohol esters such as sodium oleyl isothionate; amides of 
amino sulfonic acids such as the sodium salt of oleyl methyl taurate; 
sulfonated products of fatty acid nitriles such as palmitonitrile 
sulfonate; sulfonated aromatic hydrocarbons such as sodium 
alpha-naphthalene monosulfonate; condensation products of naphthalene 
sulfonic acids with formaldehyde; sodium octahydro anthracene sulfonate; 
alkali metal alkyl sulfates; ether sulfates having alkyl groups of eight 
or more carbon atoms; and alkylaryl sulfonates having one or more alkyl 
groups of eight or more carbon atoms. Commercial anionic surfactants 
useful in our invention include dodecylbenzene sulfonic acid (DBSA) sold 
under the tradename BIOSOFT S-100 by Stepan Company, Northfield, Ill.; and 
the sodium salt of dodecylbenzene sulfonic acid sold under the tradename 
SIPONATE DS-10 by Alcolac Inc., Baltimore, Md. 
Useful cationic surfactants are the various fatty acid amines, amides, and 
derivatives, and salts of fatty acid amines and amides. Cationic 
surfactants can be exemplified by aliphatic fatty amines and derivatives 
such as dodecyl amine acetate, octadecyl amine acetate, and acetates of 
amines of tallow fatty acids; homologues of aromatic amines having fatty 
chains such as dodecyl aniline; fatty amides derived from aliphatic 
diamines such as undecyl imidazoline; fatty amides derived from 
di-substituted amines such as oleylamino diethylamine; derivatives of 
ethylene diamine; quaternary ammonium compounds such as tallow 
trimethylammonium chloride, dioctadecyldimethyl ammonium chloride, 
didodecyldimethyl ammonium chloride, and dihexadecyldimethyl ammonium 
chloride; amide derivatives of amino alcohols such as beta-hydroxyethyl 
stearyl amide; amine salts of long chain fatty acids; quaternary ammonium 
bases derived from fatty amides of di-substituted diamines such as 
oleylbenzylamino ethylene diethylamine hydrochloride; quaternary ammonium 
bases of benzimidazolines such as methylheptadecyl benzimidazole 
hydrobromide; basic compounds of pyridinium and derivatives such as 
cetylpyridinium chloride; sulfonium compounds such as octadecyl sulfonium 
methyl sulfate; quaternary ammonium compounds of betaine such as betaine 
compounds of diethylamino acetic acid, and octadecylchloromethyl ether; 
urethanes of ethylene diamine such as condensation products of stearic 
acid and diethylene triamine; polyethylene diamines; and polypropanol 
polyethanol amines. Commercial cationic surfactants include products sold 
under the tradenames ARQUAD T-27W, 16-29, C-33, T-50; and ETHOQUAD T/13 
and T/13 ACETATE; by Akzo Chemicals Inc., Chicago, Ill. The anionic or 
cationic surfactant is present at 0.05-30% by weight of total emulsion, 
preferably 0.5-20%. 
Useful nonionic surfactants have a hydrophilic-lipophilic balance (HLB) of 
10-20. Nonionic surfactants with HLB of less than 10 may be used but hazy 
solutions may result due to limited solubility of the nonionic surfactant 
in water. When using a nonionic surfactant with HLB less than 10, a 
nonionic surfactant with HLB greater than 10 should be added during or 
after polymerization. Commercial nonionic surfactants can be exemplified 
by 2,6,8-trimethyl-4-nonyloxy polyethylene oxyethanols (6EO) and (10EO) 
sold under the trademarks TERGITOL.RTM. TMN-6 and TERGITOL.RTM. TMN-10; 
alkyleneoxy polyethylene oxyethanol (C.sub.11-15 secondary alcohol 
ethoxylates 7EO, 9EO, and 15EO) sold under the trademarks TERGITOL.RTM. 
15-S-7, TERGITOL.RTM. 15-S-9, TERGITOL.RTM. 15-S-15; other C.sub.11-15 
secondary alcohol ethoxylates sold under the trademarks TERGITOL.RTM. 
15-S-12, 15-S-20, 15-S-30, 15-S-40; and octylphenoxy polyethoxy ethanol 
(40EO) sold under the trademark TRITON.RTM. X-405. All of these 
surfactants are sold by Union Carbide Corporation, Danbury, Conn. Other 
commercial nonionic surfactants are nonylphenoxy polyethoxy ethanol (10EO) 
sold under the tradename MAKON 10 by Stepan Company, Northfield, Ill. One 
especially useful nonionic surfactant is polyoxyethylene 23 lauryl ether 
(Laureth-23) sold commercially under the tradename BRIJ 35 by ICI 
Surfactants, Wilmington, Del. 
Some commercially available ionic surfactants have characteristics of both 
ionic and nonionic surfactants combined, and can be used. One example is 
methyl polyoxyethylene (15) octadecyl ammonium chloride, sold under the 
tradename ETHOQUAD 18/25 by Akzo Chemicals Inc., Chicago, Ill. 
A cosurfactant is optional, but can be used in the method according to our 
invention. The cosurfactant is preferably a hydrophobic solvent or a 
compound having low water solubility. Representative cosurfactants are, 
for example, fatty alcohols such as cetyl alcohol C.sub.16 H.sub.33 OH; 
and n-alkanes such as n-hexadecane (cetane) C.sub.16 H.sub.34 or the 
halogen substituted derivatives such as 1-chlorodecane (decyl chloride) 
CH.sub.3 (CH.sub.2).sub.9 Cl. The presence of such a low molecular weight 
and relatively water-insoluble compound retards diffusion of monomer out 
of the droplets. 
The reaction mixture is formed by combining 50-80 percent by weight of 
water; 5-15 percent by weight of the surfactant(s); 1-5 percent by weight 
of the cosurfactant(s); 10-50 percent by weight of the macromonomer(s) or 
monomer(s); and 0.5-15 percent by weight of the free radical initiator. It 
is not essential that these ingredients be combined in any given order, 
although one preferred procedure is to combine water, surfactant(s), and 
cosurfactant(s), followed by addition of monomer(s) and initiator. 
However, it is essential to have agitation during and following addition 
of the ingredients, and to have achieved or to heat to the polymerization 
temperature as the ingredients are combined. Where practical, agitation 
and heating should be continued until the monomer(s) is consumed in 
forming the emulsion. 
The process we used for making miniemulsions is similar to the El-Aasser et 
al procedure; although our initiator was not the same as the initiator 
used by El-Aasser et al. 
According to our process, sodium lauryl sulfate, cetyl alcohol, and water, 
were first heated at 65.degree. C. for 2 hours, cooled to 
30.degree.-35.degree. C., and passed through a high shear device to break 
the gel which formed. The high shear device we employed was a high 
pressure impingement emulsifier, sold under the trademark 
MICROFLUIDIZER.RTM., by Microfluidics Corporation, Newton, Mass. 
Such high shear devices are described in detail in, for example, U.S. Pat. 
No. 4,533,254, (Aug. 6, 1985), which is incorporated herein by reference. 
In general, these high shear devices include a high pressure pump (i.e., 
as much as 25,000 psi/172,370 kPa), and an interaction chamber where 
emulsification occurs. A reaction mixture is passed through the emulsifier 
once at a pressure between 5,000-15,000 psi/34,474-103,422 kPa. Multiple 
passes through the high shear device result in smaller average particle 
size, and a narrower range for the particle size distribution. 
The macromonomer(s) and the AIBN initiator were then added to the 
surfactant mixture and stirred at ambient/room temperature 
(20.degree.-25.degree. C./68.degree.-77.degree. F.). The mixture was again 
introduced to the MICROFLUIDIZER.RTM. and passed 10 times at 8,000-14,000 
psi/55,158-96,527 kPa. Particle size was measured with the aid of a NICOMP 
particle size analyzer in dilute solutions. The emulsion was transferred 
to a 3-neck flask, and after bubbling nitrogen, the emulsion was heated at 
60.degree.-65.degree. C. for a period of time. 
After polymerization was completed, the emulsion was broken by adding 
sodium chloride and methanol. The precipitate was separated from the 
mixture by filtration and dried in vacuum. Molecular weight of each 
starting polyisobutylene (PIB) macromonomer and polydimethylsiloxane 
(PDMS) macromonomer was determined by Gel Permeation Chromatography (GPC), 
in toluene or tetrahydrofuran (THF) using standard PIB samples or PDMS 
samples, respectively, for molecular weight calibration, and a Refractive 
Index (RI) detector. The copolymers were further analyzed and 
characterized by GPC, IR, .sup.13 C and .sup.29 Si Nuclear Magnetic 
Resonance (NMR) to confirm molecular structure. 
Our invention is illustrated in more detail in the following examples. All 
reactions were carried out in an atmosphere of nitrogen. GPC analyses were 
performed on a WATERS 150C Chromatograph, using a flow rate of 1.2 
ml/minute and an injection volume of 200 .mu.l. IR spectra were measured 
on neat liquids in KBr plates on a Perkin Elmer Spectrophotometer. 
Particle size measurements were made with a NICOMP 370 particle size 
analyzer. All parts and percentages in these examples are on a weight 
basis, and all measurements were obtained at 25.degree. C. unless 
indicated to the contrary. Averages of molecular weight such as the 
number-average molecular weight M.sub.n, and the weight-average molecular 
weight M.sub.w, are used to describe the general shape of the molecular 
weight distribution.

EXAMPLE 1 
Preparation of PIB-Macromonomer 
Glissopal.RTM. 1000 was hydrosilylated with dimethylchlorosilane 
(CH.sub.3).sub.2 HSiCl as follows. Glissopal.RTM. 1000 is described as a 
polyisobutylene having a high proportion of terminal double bonds, and 
having a number average molecular weight of about 1,180. It is a product 
and trademark of BASF AG, Ludwigshafen, Germany. Glissopal.RTM. 1000 (400 
gm) was charged to a three-neck flask fitted with a magnetic stirring bar, 
condenser, and dropping funnel. A reaction product of chloroplatinic acid 
and 1,3-divinyltetramethyldisiloxane H.sub.2 C=CH(CH.sub.3).sub.2 
SiOSi(CH.sub.3).sub.2 CH=CH.sub.2 (200 .mu.l of catalyst prepared 
according to U.S. Pat. No. 3,419,593 to Willing) was added, and the 
solution was heated to 70.degree. C. under an atmosphere of nitrogen. 
Dimethylchlorosilane was added dropwise. The addition rate of silane was 
then controlled so as to maintain a reaction temperature of 
65.degree.-70.degree. C. (total silane added was 76 g). The solution was 
stirred overnight at 70.degree.-75.degree. C. and the solvent and excess 
silane were stripped off in a rotary evaporator at 85.degree.-90.degree. 
C./2-5 torr/3 hours. A pale yellow polymer was obtained. NMR analysis 
confirmed a PIB polymer wherein the vinyl functionality was quantitatively 
converted to end groups of the formula --Si(Me.sub.2)Cl, in which Me 
hereinafter represents a methyl radical. 
The resulting hydrosilylated product (105 g) was dissolved in 225 g of THF. 
Sodium bicarbonate solution (10% in water, 100 g) was slowly added. The 
mixture was shaken vigorously for 2-3 minutes. The water and organic 
layers were separated, and the organic layer was dried over Na.sub.2 
SO.sub.4 for 10 minutes. The salt byproduct was filtered through a 
pressure filter, and the solvent was removed by vacuum distillation. A 
pale yellow polymeric material was obtained. IR and .sup.29 Si NMR showed 
the presence of SiOH groups, but showed little of the 
.ident.Si--O--Si.ident. structure. M.sub.w at this point was 2,180 and 
M.sub.n was 1,500. 
The above described SiOH-functional PIB (97 g, 0.08 mole) was dissolved in 
tetrahydrofuran (125 g), and this solution was charged to a 500 ml 3-neck 
flask equipped with a magnetic stirring bar and a nitrogen purge. 
Triethylamine (12.24 g, 0.12 mole) was added under an atmosphere of 
nitrogen. 3-Methacryloxypropyldimethylchlorosilane (18 g, 0.08 mole) was 
slowly added, and the mixture was stirred overnight at room temperature. 
This product was filtered through a pressure filter, and the solvent and 
excess reactants were removed by vacuum distillation. A pale yellow 
polymeric material was obtained which had a M.sub.w of 2,070 and M.sub.n 
of 1,540. It had a structure consistent with the formula 
EQU (PIB)--Si(Me.sub.2)OSi(Me.sub.2)--CH.sub.2 CH.sub.2 CH.sub.2 
--OC(O)C(Me)=CH.sub.2 
wherein PIB represents the residue of the polyisobutylene chain. This 
PIB-Macromonomer was used in Examples 4 and 5. 
EXAMPLE 2 
Preparation of PIB-Macromonomer 
The procedure of Example 1 was used to prepare another PIB-Macromonomer. In 
this example, the SiOH-functional PIB (8 g) was dissolved in 
tetrahydrofuran (15 g), and this solution was charged to a 100 ml 3-neck 
flask equipped with a magnetic stirring bar and a nitrogen purge. 
Triethylamine (1 g) was added under an atmosphere of nitrogen. 
3-Methacryloxypropyldimethylchlorosilane (2 g) was slowly added, and the 
mixture was stirred overnight at room temperature. This product was 
filtered through a pressure filter, and the solvent and excess reactants 
were removed by vacuum distillation. A pale yellow polymeric material was 
obtained which had a M.sub.w of 2,277 and M.sub.n of 1,630. It had a 
structure consistent with the formula 
EQU (PIB)--Si(Me.sub.2)OSi(Me.sub.2)--CH.sub.2 CH.sub.2 CH.sub.2 
--OC(O)C(Me)=CH.sub.2 
wherein PIB represents the residue of the polyisobutylene chain. This 
PIB-Macromonomer was used in Example 6. 
EXAMPLE 3 
Preparation of PDMS-Macromonomer 
A mono-SiOH-functional polydimethylsiloxane (PDMS) (500 g) was charged to a 
one liter 3-neck flask equipped with a magnetic stirring bar and a 
nitrogen purge. Dibutylamine (10.5 g) was added under an atmosphere of 
nitrogen. 
3-Methacryloxypropyldimethylchlorosilane (13.25 g) was slowly added, and 
the mixture was stirred overnight at room temperature. This product was 
filtered through a pressure filter, and the solvent and excess reactants 
were removed by vacuum distillation. An off white polymeric material was 
obtained which had a M.sub.w of 13,530 and M.sub.n of 12,650. It had a 
structure consistent with the formula 
EQU (PDMS)--Si(Me.sub.2)OSi(Me.sub.2)--CH.sub.2 CH.sub.2 CH.sub.2 
--OC(O)C(Me)=CH.sub.2 
wherein PDMS represents the residue of the polydimethylsiloxane chain. This 
PDMS-Macromonomer is used in Examples 4 and 5. 
EXAMPLE 4 
Preparation of Copolymer of PIB-Macromonomer and PDMS-Macromonomer 
Deionized water (160 gm) was taken in a 250 ml beaker provided with a 
magnetic stirrer. Sodium laurel sulfate (0.2 gm) and cetyl alcohol (0.8 
gm) were added to the water, and the contents were heated to 
65.degree.-67.degree. C. for 2 hours. The contents were allowed to cool to 
30.degree.-35.degree. C. and a white gel-like material was obtained. The 
gel-like material was introduced to a MICROFLUIDIZER.RTM. and the contents 
were circulated at 5,000-6,000 psi/34,474-41,369 kPa. The 
PDMS-Macromonomer (20 gm) prepared in Example 3, and the PIB-Macromonomer 
(20 gm) prepared in Example 1, were added and the contents stirred for 30 
minutes with a magnetic stirrer. At this point, AIBN 
(2,2'-azobisisobutyronitrile, 0.45 gm) was added. The mixture was again 
introduced to the MICROFLUIDIZER.RTM. and cycled at least 10 times at 
8,000 psi/55,158 kPa. The average particle size was 303 nm. The emulsion 
was transferred to a 3-neck flask fitted with a nitrogen inlet, condenser, 
and thermometer. Nitrogen was bubbled through the solution. The emulsion 
was heated at 65.degree. C. for 24 hours. More AIBN was added (0.2 g) 
after 24 and 48 hours, and the heating was continued for a total of 72 
hours. Some whitish gray precipitate appeared which was filtered. The 
precipitate was insoluble in toluene. The emulsion was broken by pouring 
it into methanol (600 gm) and a solution of NaCl in water (5 gm in 25 ml). 
The mixture was shaken vigorously and filtered. A white precipitate was 
obtained which was dissolved in hexane and dried over MgSO.sub.4. It was 
filtered and the solvent was removed. An off white highly viscous polymer 
was obtained. GPC: in THF; Mn=50050, Mw=147700. 
EXAMPLE 5 
Preparation of Copolymer of PIB-Macromonomer, PDMS-Macromonomer, and 
Acrylate Monomer 
Deionized water (160 gm) was taken in a 250 ml beaker equipped with a 
magnetic stirrer. Sodium laurel sulfate (0.2 gm) and cetyl alcohol (0.8 
gm) were added to the water, and the contents were heated to 
65.degree.-67.degree. C. for 2 hours. The contents were allowed to cool to 
30.degree.-35.degree. C. and a white gel-like material was obtained. The 
gel-like material was introduced to the MICROFLUIDIZER.RTM., and the 
contents were circulated at least 5 times at 10,000 psi/68,948 kPa. The 
PDMS-Macromonomer (10 gm) prepared in Example 3, methyl methacrylate (20 
gm), and the PIB-Macromonomer (10 gm) prepared in Example 1, were added 
and the contents stirred for 30 minutes with a magnetic stirrer. At this 
point, AIBN (0.6 gm) was added. The mixture was again introduced to the 
MICROFLUIDIZER.RTM.and cycled at least 10 times at 12,000 psi/82,738 kPa. 
The average particle size was 395 nm. The emulsion was transferred to a 
3-neck flask fitted with a nitrogen inlet, condenser, and thermometer. 
Nitrogen was bubbled through the solution. The emulsion was heated at 
65.degree. C. for 24 hours. More AIBN was added (0.2 g) after 24 and 48 
hours, and the heating was continued for a total of 72 hours. The emulsion 
was broken by pouring it into methanol (800 gm) and a solution of NaCl in 
water (5 gm in 25 ml). The mixture was shaken vigorously and filtered. A 
white solid was obtained which was dried in vacuum. GPC: in Toluene; 
Mn=71030, Mw=127100.13.sup.C NMR data showed that the product was a 
copolymer of the PIB-Macromonomer, the PDMS-Macromonomer, and methyl 
methacrylate. 
EXAMPLE 6 
Preparation of Copolymer of PIB-Macromonomer, PDMS-Macromonomer, and 
Acrylate Monomer 
Deionized water (150 gm) was taken in a 250 ml beaker equipped with a 
magnetic stirrer. Sodium laurel sulfate (0.2 gm) and cetyl alcohol (0.8 
gm) were added to the water, and the contents were heated to 
65.degree.-67.degree. C. for 2 hours. The contents were allowed to cool to 
30.degree.-35.degree. C. and a white gel-like material was obtained. The 
gel-like material was introduced to the MICROFLUIDIZER.RTM., and the 
contents were circulated at least 5 times at 10,000 psi/68,948 kPa. The 
PDMS-Macromonomer (5 gm) prepared in Example 3, methyl methacrylate (40 
gm), and the PIB-Macromonomer (5 gm) prepared in Example 2, were added and 
the contents stirred for 30 minutes with a magnetic stirrer. At this 
point, AIBN (0.42 gm) was added. The mixture was again introduced to the 
MICROFLUIDIZER.RTM., and cycled at least 10 times at 14,000 psi/96,527 
kPa. The particle size was 171 nm. The emulsion was transferred to a 
3-neck flask fitted with a nitrogen inlet, condenser, and thermometer. 
Nitrogen was bubbled through the solution. The emulsion was heated at 
65.degree. C. for 45 hours. The average particle size was 192 nm. The 
emulsion was broken by pouring it into methanol (400 gm) and a solution of 
NaCl in water (5 gm in 25 ml). The mixture was shaken vigorously. A white 
solid was obtained which was filtered and dried in vacuum. GPC: in THF; 
Mn=137900, Mw=505300.13.sup.C NMR data showed that the product was a 
copolymer of the PIB-Macromonomer, the PDMS-Macromonomer, and methyl 
methacrylate. 
The preparation of copolymers of (i) an acrylic or methacrylic-functional 
polyisobutylene macromonomer, (ii) a polydiorganosiloxane macromonomer, 
and optionally (iii) a radical polymerizable monomer such as an alkyl 
acrylate or alkyl methacrylate, in emulsion form provides many advantages 
and benefits. For example, the miniemulsion polymerization process herein 
provides a technique where monomers can be polymerized to high molecular 
weight copolymers, and yet the emulsions are very stable. The resulting 
water-based emulsions provide low content of volatile organic compound 
(VOC), and allow for ease of handling of the copolymers. 
These copolymers have applications in the personal care arena, i.e. in 
cosmetics; as well as in ink, paint, and coating industries. Typically, 
the emulsions are used without first extracting the copolymer; and this is 
convenient for use in water-based products, especially in personal care. 
The result is a significant savings in cost of production. 
Other variations may be made in compounds, compositions, and methods 
described herein without departing from the essential features of our 
invention. The forms of our invention are exemplary only and not intended 
as limitations on its scope as defined in the appended claims.