Alkylpolyether siloxanes

Abstract: New alkylpolyether siloxanes are prepared by reacting an unsaturated ether with alkylhydrido siloxanes such as (i) comonomers RSi(OSiMe 2 H) 3 , (ii) oligomers (HMe 2 SiO) 2 -Si(R)-O-Si(R)-(OSiMe 2 H) 2 and (iii) higher molecular weight siloxane species RSi[(OSiMe 2 ) x OSiMe 2 H] 3 and [HMe 2 SiO(Me 2 SiO) x ] 2 Si(R)O(R)Si[(OSiMe 2 ) x OSiMe 2 H] 2 . R is a C 2 to C 18 straight-chain or branched-chain alkyl substituent.

Description: A family of new alkylhydrido siloxanes including comonomers of the formula RSi(OSiMe 2 H) 3 , oligomers of the formula (HMe 2 SiO) 2 -Si(R)-O-Si(R)-(OSiMe 2 H) 2 and higher molecular weight siloxanes of the formula RSi[(OSiMe 2 ) x OSiMe 2 H] 3 and [HMe 2 SiO(Me 2 SiO) x ] 2 Si(R)O(R)Si-[(OSiMe 2 ) x OSiMe 2 H] 2 ; in which Me is methyl; R is a C 2 to C 18 straight-chain or branched-chain alkyl substituent; and x has a value of 1-200 is described in US-A 5,446,185. The present claims are an improvement on the prior art in which a new family of alkylpolyether siloxanes are provided by hydrosilylation of the alkylhydrido siloxanes of the prior application. These new alkylpolyether siloxanes are useful as conditioning agents in personal care compositions applied to human skin. This invention is directed to new alkylpolyether siloxanes. The siloxanes are compounds covered by one of the following formulae: RSi(OSiMe 2 Q) 3 , (QMe 2 SiO) 2 -Si(R)-O-Si(R)-(OSiMe 2 Q) 2 , RSi[(OSiMe 2 ) x OSiMe 2 Q] 3 and [QMe 2 SiO(Me 2 SiO) x ] 2 Si(R)O(R)Si[(OSiMe 2 ) x OSiMe 2 Q] 2 . Therein, Me is methyl; R is a C 2 to C 18 straight-chain or branched-chain alkyl substituent; x has a value of 1-200; and Q is a radical containing oxyethylene groups, oxypropylene groups, oxybutylene groups or any combination of oxyethylene groups, oxypropylene groups or oxybutylene groups. A representative Q radical is -(CH 2 ) y (OCH 2 CH 2 ) a (OCH 2 CHCH 3 ) b -[OCH 2 CH(CH 2 CH 3 )] c OR. In the Q radical, R' can be hydrogen atom; an alkyl radical such as methyl, ethyl, propyl or butyl; an aryl radical such as phenyl; an aralkyl radical such as benzyl; or an acyl radical such as acetyl. The integer y is 3-6; a is 0-120; b is 0-50; and c is 0-50; with the proviso that a, b and c, cannot all be zero. In addition, Q can be the same or different. Where Q is different, the compounds covered by the formula RSi(OSiMe 2 Q) 3 can be more conveniently expressed as RSi[(OSiMe 2 Q) z (OSiMe 2 Q') 3-z ] in which z is 1 or 2. Similarly, the compounds covered by the formula RSi[(OSiMe 2 ) x OSiMe 2 Q] 3 can be more conveniently expressed as RSi[(OSiMe 2 ) x (OSiMe 2 Q)] z [(OSiMe 2 ) x (OSiMe 2 Q')] 3-z in which z is 1 or 2. It is an object of the present invention to provide a novel family of alkylpolyether siloxanes as new compositions of matter. Siloxanes according to the invention are prepared by hydrosilylation of alkylhydrido siloxanes with alkenyl ether terminated organic oxyalkylene compounds. Alkylhydrido siloxanes such as RSi(OSiMe 2 H) 3 and (HMe 2 SiO) 2 -Si(R)-O-Si(R)-(OSiMe 2 H) 2 are prepared in high yield by hydrolysis of the corresponding chlorosilanes. Details of the hydrolysis reaction are more fully described in US-A 5,446,185. The reaction is briefly depicted in "Scheme 1". According to "Scheme 1", the amount of RSi(OSiMe 2 H) 3 obtained in the hydrolysis is dependent upon the temperature at which the reaction is conducted. Where R is n-propyl (Pr) and when the temperature is maintained slightly below 15°C., 83% of the product is RSi(OSiMe 2 H) 3 . At 30°C., 79% of the product is RSi(OSiMe 2 H) 3 ; while at 40°C., 47% of the product is RSi(OSiMe 2 H) 3 . At higher temperatures, larger amounts of (HMe 2 SiO) 2 -Si(R)-O-Si(R)-(OSiMe 2 H) 2 and higher molecular weight siloxane species are formed. The products RSi(OSiMe 2 H) 3 and (HMe 2 SiO) 2 Si(R)O(R)Si(OSiMe 2 H) 2 from the hydrolysis in "Scheme 1", can be used in the preparation of higher molecular weight siloxane species. The higher molecular weight materials are prepared by an acid catalyzed ring opening of cyclic siloxanes such as a dimethylcyclosiloxane, followed by insertion into RSi(OSiMe 2 H) 3 and (HMe 2 SiO) 2 Si(R)O(R)Si(OSiMe 2 H) 2 . Such a process is also described in US-A 5,446,185 and is briefly depicted in "Scheme 2". The acid catalyst in "Scheme 2" can be hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid, acetic acid, trichloroacetic acid or trifluoromethane sulfonic acid. The method in "Scheme 2" is carried out by creating a mixture of the cyclic siloxane (Me 2 SiO) a , RSi(OSiMe 2 H) 3 or (HMe 2 SiO) 2 Si(R)O(R)Si(OSiMe 2 H) 2 and the acid catalyst. The mixture is heated with agitation at a polymerization reaction temperature, until essentially all of the cyclic siloxane is reacted. The time required will vary depending on the reactants and the reaction conditions. The polymerization reaction in "Scheme 2" is stopped at the desired level of conversion of cyclic siloxane, by using methods known in the art such as neutralization of the catalyst by the addition of an equal or slightly greater stoichiometric amount of base. A weak base may also be used to neutralize the reaction. The siloxanes depicted in "Scheme 1" and "Scheme 2" include comonomers, oligomers and higher molecular weight siloxane species and are used as intermediates in the preparation of the alkylpolyether siloxanes of this invention. The R group in "Scheme 1" and "Scheme 2" is a C 2 to C 18 straight-chain (unbranched) or branched-chain alkyl substituent. Suitable R substituents are ethyl; n-propyl; isopropyl; butyl; 2-methylpropyl; pentyl; 2-methylbutyl; 2,2-dimethylpropyl; hexyl; 2-methylpentyl; 3-methylpentyl; 2,2-dimethylbutyl; 2,3-dimethylbutyl; heptyl; 2-methylhexyl; 3-methylhexyl; 2,2-dimethylpentyl; 2,3-dimethylpentyl; 2,4-dimethylpentyl; 3,3-dimethylpentyl; 3-ethylpentyl; 2,2,3-trimethylbutyl; octyl; nonyl; decyl; undecyl; dodecyl; tridecyl; tetradecyl; pentadecyl; hexadecyl; heptadecyl and octadecyl. The cyclic siloxanes most suitable for "Scheme 2" are (i) hexamethylcyclotrisiloxane with a boiling point of 133°C. and the formula [(Me 2 )SiO] 3 ; (ii) octamethylcyclotetrasiloxane with a boiling point of 171°C. and the formula [(Me 2 )SiO] 4 ; (iii) decamethylcyclopentasiloxane with a boiling point of 205°C. and the formula [(Me 2 )SiO] 5 ; and (iv) dodecamethylcyclohexasiloxane with a boiling point of 245°C. and the formula [(Me 2 )SiO] 6 . In preparing the alkylpolyether siloxanes of the invention, one or more unsaturated ethers are reacted with one of the above described alkylhydrido siloxanes containing the ≡SiH group. Suitable alkenyl-ether terminated organic oxyalkylene compounds which can be employed contain at least three to ten carbon atoms in the alkenyl group. Examples of such groups are allyl, isopropenyl, 2-butenyl, 3-butenyl or hexenyl. Allyl is the most preferred alkenyl group and representative allyl-ether terminated organic oxyalkylene compounds are: H 2 C=CH-CH 2 -O-(CH 2 -CH 2 O) m -R''; H 2 C=CH-CH 2 -O-[CH 2 -CH(CH 3 )O] n -R''; and H 2 C=CH-CH 2 -O-(CH 2 -CH 2 O) m -[CH 2 -CH(CH 3 )O] n -R". In those formulae, m is 1-120; n is 1-50; and R'' is hydrogen atom; an alkyl radical such as methyl, ethyl, propyl or butyl; an aryl radical such as phenyl; an aralkyl radical such as benzyl; or an acyl radical such as acetyl. It is preferred to conduct the hydrosilylation reaction with an allyl to ≡SiH ratio of 1.0 to 1.2, although other ratios may be employed. The alkylpolyether siloxane products of the hydrosilylation reaction are best made by reacting the allyl ether of the desired oxyalkylene compound with the corresponding siloxane containing ≡SiH groups. This reaction is best carried out by heating a mixture of the reactants in the presence of a platinum catalyst, such as platinum dispersed on an inert carrier or a compound of platinum such as chloroplatinic acid, at temperatures from 30-100°C. Representative hydrosilylation reactions of our invention are depicted in Schemes 3 and 4 as follows: In Scheme 4, Q is -(CH 2 ) 3 (OCH 2 CH 2 ) 20 OH; Q' is -(CH 2 ) 3 (OCH 2 CH 2 ) 40 OH; and the two groups Q and Q' are randomly arranged on the siloxane in a ratio approaching 50:50. Hydrosilylation catalysts are well known in the art and the following patents provide detailed descriptions regarding their preparation and use: U.S. Patent 2,823,218; U.S. Patent 3,419,359; U.S. Patent 3,445,420; U.S. Patent 3,697,473; U.S Patent 3,814,731; U.S. Patent 3,890,359 and U.S. Patent 4,123,604. Many of the catalysts known in the art require that the reactants be heated for reaction to occur. When such catalysts are employed, this additional requirement must be taken into consideration. The concentration of the catalyst may be determined by routine experimentation. Typically, however, the effective amount of catalyst should be in a range to provide from 1-1,000 parts per million (ppm) of platinum by weight in the compositions of the present invention. This invention is illustrated in more detail in the following examples. EXAMPLE I - Preparation of PrSi(OSiMe 2 H) 3 n-propyltris-(dimethylsiloxy)silane. A mixture of PrSiCl 3 (59.92 g, 0.338 moles) and Me 2 HSiCl (95.90 g, 1.014 moles) was added drop-wise to a 3-necked round bottom flask containing ice water (166.0 g, 9.22 moles). The flask was fitted with a thermometer, a mechanical stirrer and a pressure equalizing addition funnel. The chlorosilanes were added drop-wise through the addition funnel at a rate to maintain a temperature in the flask slightly below 15°C. The solution was vigorously mixed throughout this addition. The solution was stirred for 30 minutes after completion of the chlorosilane addition. An aqueous layer was drawn off, followed by several NaHCO 3 washes and several water washes until neutral to pH paper. The siloxane was dried over MgSO 4 overnight and filtered under N 2 pressure, yielding a clear, colorless liquid. The final product contained 83% of PrSi(OSiMe 2 H) 3 ; 9% of (HMe 2 SiO) 2 Si(Pr)-OSi(Pr)(OSiMe 2 H) 2 and 8% of other siloxane impurities. Characterization included Si-29 Nuclear Magnetic Resonance (NMR), Gas Chromatography/Mass Spectrometry (GC/MS) and Gas Chromatography/Flame Ionization Detection (GC/FID). EXAMPLE II Example I was repeated, except that room temperature water was used instead of ice water and the temperature was allowed to rise to 30°C. The final product contained 79% of PrSi(OSiMe 2 H) 3 , 12% of (HMe 2 SiO) 2 Si(Pr)OSi(Pr)(OSiMe 2 H) 2 and 9% of other siloxane impurities. EXAMPLE III Example I was again repeated, except that room temperature water was used instead of ice water and the temperature was allowed to rise to 40°C. The final product contained 47% of PrSi(OSiMe 2 H) 3 , 30% of (HMe 2 SiO) 2 Si(Pr)OSi(Pr)(OSiMe 2 H) 2 and 23% of other siloxane impurities. EXAMPLE IV - Preparation of PrSi[(OSiMe 2 ) 3.5 OSiMe 2 H] 3 A solution of n-propyltris(dimethylsiloxy)silane PrSi(OSiMe 2 H) 3 (18.94 g, 0.064 moles) prepared in Example I, (Me 2 SiO) 4 cyclosiloxane (49.82 g, 0.672 moles) and 41 microliters of trifluoromethane sulfonic acid, was heated to 70°C. The flask was fitted with a water cooled condensing column, a magnetic stirrer and a thermometer. The flask was flushed with N 2 prior to heating, followed by N 2 positive pressure through the top of the condenser. After heating, the flask at 70°C. for four hours, the solution was cooled to room temperature, followed by the addition of NaHCO 3 (1.0 g) and diatomaceous earth (Celite™) (1.0 g). The mixture was stirred for 4 hours, followed by filtration under N 2 pressure and yielded a clear, colorless liquid. The final average structure determined by Si-29 NMR was (PrSi) 1.0 [(OSiMe 2 ) 3.5 OSiMe 2 H] 3 . In that structure, the value "1.0" was plus or minus 0.2; the value "3.5" was plus or minus 0.5; and the value "3.0" was plus or minus 0.2. Dimethylcyclicsiloxanes were also present in the product. EXAMPLE V - Preparation of PrSi(OSiMe 2 Q) 3 where Q was -CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 20 H. Allyloxy-initiated ethylene-oxide homopolymer (208.51 g, 0.218 moles) of the formula H 2 C=CH-CH 2 -O-(CH 2 CH 2 O) 20 H and isopropyl alcohol (60.0 g) were weighed into a three necked round bottom flask equipped with a thermometer, mechanical stirrer and a Claisen adapter fitted with a water cooled condenser and a pressure equalizing addition funnel. Homogeneous platinum catalyst (10 ppm as Pt) was added to the 40°C. solution. Dropwise addition of PrSi(OSiMe 2 H) 3 (18.69 g, 0.0631 moles) was adjusted to maintain the temperature near 65°C. throughout the addition. The temperature was increased to 90°C. until no SiH was observed in the infraRed spectrum. Removal of isopropyl alcohol under reduced pressure yielded the product, a waxy solid at room temperature. EXAMPLE VI - Preparation of PrSi(OSiMe 2 Q) 3 where Q was -CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 40 H. Allyloxy-initiated ethylene-oxide homopolymer (187.84 g, 0.136 moles) of the formula H 2 C=CH-CH 2 -O-(CH 2 CH 2 O) 40 H, PrSi(OSiMe 2 H) 3 (12.16 g, 0.0411 moles) and isopropyl alcohol (40.0 g) were weighed into a three-necked, round-bottom flask equipped with a thermometer, mechanical stirrer and a water cooled condenser. Homogeneous platinum catalyst (9.2 ppm as Pt) was added to the 80°C. solution. The temperature was maintained at 90°C. until the SiH level was below 5 ppm. Removal of isopropyl alcohol under reduced pressure yielded the product, a waxy solid at room temperature. EXAMPLE VII - Preparation of PrSi[(OSiMe 2 Q) 3-x (OSiMe 2 Q')x] where x = 0-3, Q was -CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 7 H and Q' was -CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 18 (CH 2 CHCH 3 O) 18 H. Allyloxy-initiated, ethylene-oxide homopolymer (26.72 g, 0.073 moles) of the formula H 2 C=CH-CH 2 -O-(CH 2 CH 2 O) 7 H, allyloxy-initiated, ethylene-oxide/propylene oxide copolymer (69.14 g, 0.0365 moles) of the formula H 2 C=CH-CH 2 -O-(CH 2 CH 2 O) 18 (CH 2 CHCH 3 O) 18 H, PrSi(OSiMe 2 H) 3 (10.13 g, 0.0342 moles) and isopropyl alcohol (26.0 g) were weighed into a three-necked, round-bottom flask equipped with a thermometer, mechanical stirrer and a water cooled condenser. Homogeneous platinum catalyst (10 ppm as Pt) was added to the 75°C. solution. The temperature was maintained at 90°C. until the SiH level was below 5 ppm. Removal of isopropyl alcohol under reduced pressure yielded the product, a straw-colored liquid.

Claims: Alkyl polyether siloxane compounds selected from the formulae of RSi(OSiMe 2 Q) 3 or (QMe 2 SiO) 2 -Si(R)-O-Si(R)-(OSiMe 2 Q) 2 , wherein Me is methyl; R is a C 2 to C 18 straight-chain or branched-chain alkyl substituent and Q is a radical containing oxyethylene groups, oxypropylene groups, oxybutylene groups or combinations of oxyethylene groups, oxypropylene groups and oxybutylene groups. Alkyl polyether siloxane compounds selected from the formulae of RSi[(OSiMe 2 Q) z (OSiMe 2 Q') 3-z ] or (QMe 2 SiO) 2 -Si(R)-O-Si(R)-(OSiMe 2 Q') 2 , wherein Me is methyl; R is a C 2 to C 18 straight-chain or branched-chain alkyl substituent; z is 1 or 2; Q and Q' are the same or different radicals containing oxyethylene groups, oxypropylene groups, oxybutylene groups or combinations of oxyethylene groups, oxypropylene groups and oxybutylene groups; and Q and Q' are randomly arranged on the siloxane. Alkylpolyether siloxane compounds selected from the formulae of RSi[(OSiMe 2 ) x OSiMe 2 Q] 3 or [QMe 2 SiO(Me 2 SiO) x ] 2 Si(R)O(R)Si[(OSiMe 2 ) x OSiMe 2 Q] 2 wherein Me is methyl; R is a C 2 to C 18 straight-chain or branched-chain alkyl substituent; x has a value of 1-200; and Q consists only of an oxyethylene group or an oxybutylene group. Siloxane compounds according to any of claims 1 - 3 in which R is selected from the group consisting of ethyl; n-propyl; isopropyl; butyl; 2-methylpropyl; pentyl; 2-methylbutyl; 2,2-dimethylpropyl; hexyl; 2-methylpentyl; 3-methylpentyl; 2,2-dimethylbutyl; 2,3-dimethylbutyl; heptyl; 2-methylhexyl; 3-methylhexyl; 2,2-dimethylpentyl; 2,3-dimethylpentyl; 2,4-dimethylpentyl; 2,4-dimethylpentyl; 3,3-dimethylpentyl; 3-ethylpentyl; 2,2,3-trimethylbutyl; octyl; nonyl; decyl; undecyl; dodecyl; tridecyl; tetradecyl; pentadecyl; hexadecyl; heptadecyl and octadecyl. Siloxane compounds according to claim 4 in which the Q or Q' radicals are -(CH 2 ) y (OCH 2 CH 2 ) a (OCH 2 CHCH 3 ) b [OCH 2 CH(CH 2 CH 3 )] c OR' wherein R' is hydrogen, an alkyl radical, an aryl radical, an aralkyl radical or an acyl radical; y is 3-6; a is 0-120; b is 0-50; and c is 0-50; with the proviso that a, b and c, cannot all be zero. Siloxane compounds according to claim 5 in which Q or Q' are randomly arranged on the siloxane in a ratio approaching 50:50. Silioxane compounds according to claim 6 in which R is n-propyl. The use of a siloxane compound as defined in any of claims 1 - 7 as a skin conditioning agent.

Inventors: COBB VICKY SUE, GUTEK BETH IRENE, LEGROW GARY EDWARD, COBB, VICKY SUE, GUTEK, BETH IRENE, LEGROW, GARY EDWARD
Applicants: DOW CORNING, DOW CORNING CORPORATION
Application year: 1996
Main classification: C08G77
IPC codes: A61K8, C08G77, C08L83, A61Q19, A61Q5, C07F7