α,ω-functionalized polyoxyalkylene-siloxane polymers and copolymers made therefrom

A method preparing an α,ω-functionalized polyoxyalkylene-siloxane polymers having the structural Formula (I):

• wherein each R1, R2 and R3 is independently a linear or branched aliphatic group containing from 1 to 20 carbon atoms, a substituted or unsubstituted aryl group containing 6 to 16 carbon atoms, an alicyclic group containing 3 to 16 carbon atoms, a heteronuclear aromatic group containing 3 to 16 carbon atoms, a hydrocarbyl group having from 3 to 16 carbon atoms and containing at least one heteroatom of oxygen, nitrogen or sulfur and/or containing at least one ester, nitrile or halo group, wherein at least one R2 is different from at least one R3;
• R12 is independently hydrogen or methyl;
• A is
• wherein R4 is independently a divalent linear or branched alkylene group having from 2 to 10 carbon atoms, an aralkylene group having from 8 to 12 carbon atoms, an unsubstituted or substituted arylene group having from 8 to 18 carbon atoms, or a hydrocarbylene group having from 2 to 10 carbon atoms and containing at least one oxygen heteroatom, R5 is independently a hydrogen, a halogen, an aliphatic group containing from 1 to 12 carbon atoms, an aromatic group containing from 6 to 12 carbon atoms, an alkoxy group containing form 1 to 12 carbon atoms or an aryloxy group containing from 6 to 12 carbon atoms, R6 is independently a hydroxyl group, an amine group, a carboxylic acid chloride group or a sulfonyl halide group, and p 1;
• wherein m, n, n′, x and y are integers, and wherein m is from 0 to 120, n is from 1 to 120, n′ is from 1 to 10, x is from 1 to 300, and y is from 0 to 100, with the proviso that the sum of n+m is greater than or equal to 2, comprising:
• (a) reacting a hydride terminated siloxane represented by the structural Formula (IV):
• wherein each R1, R2 and R3 is independently a linear or branched aliphatic group containing from 1 to 20 carbon atoms, a substituted or unsubstituted aryl group containing 6 to 16 carbon atoms, an alicyclic group containing 3 to 16 carbon atoms, a heteronuclear aromatic group containing 3 to 16 carbon atoms, a hydrocarbyl group having from 3 to 16 carbon atoms and containing at least one heteroatom of oxygen, nitrogen or sulfur and/or containing at least one ester, nitrile or halo group, wherein at least one R2 is different from at least one R3;
• and x is an integer from 1 to 300 and y is an integer from 0 to 100 with bis-unsaturated polyalkylene containing terminal carbon-carbon double bonds in the presence of a hydrosilylation catalyst to obtain hydride terminated polyoxyalkylene siloxane represented by the structural Formula (V):
• wherein each R1, R2 and R3 is independently a linear or branched aliphatic group containing from 1 to 20 carbon atoms, a substituted or unsubstituted aryl group containing 6 to 16 carbon atoms, an alicyclic group containing 3 to 16 carbon atoms, a heteronuclear aromatic group containing 3 to 16 carbon atoms, a hydrocarbyl group having from 3 to 16 carbon atoms and containing at least one heteroatom of oxygen, nitrogen or sulfur and/or containing at least one ester, nitrile or halo group, wherein R2 and R3 are not the same;
• R12 is independently hydrogen or methyl;
• wherein m, n, n′, x and y are integers, and wherein m is from 0 to 120, n is from 1 to 120, n′ is from 1 to 10, x is from 1 to 300, and y is from 0 to 100, with the proviso that the sum of n+m is greater than or equal to 2;
• and
• (b) reacting the hydride terminated polyoxyalkylene siloxane of step (a) with substituted phenyl containing a carbon-carbon double bond, represented by the Formula (VI):
• wherein R12 is independently hydrogen or methyl;
• R13 is independently a divalent linear or branched alkylene group having from 1 to 8 carbon atoms, an aralkylene group having from 7 to 10 carbon atoms, an unsubstituted or substituted arylene group having from 6 to 16 carbon atoms, a hydrocarbylene group having from 2 to 8 carbon atoms and containing at least one heteroatom of oxygen, R5 is independently a hydrogen, a halogen, an aliphatic group containing from 1 to 12 carbon atoms, an aromatic group containing from 6 to 12 carbon atoms, an alkoxy group containing form 1 to 12 carbon atoms or an aryloxy group containing from 6 to 12 carbon atoms, R6 is independently a hydroxyl group, an amine group, a carboxylic acid chloride group or a sulfonyl halide group, and the subscript q is an integer 0 or 1, to obtain an α,ω-functionalized polyoxyalkylene-siloxane polymer.

A copolymer comprising a structural unit of Formula (II):

• wherein each R1, R2 and R3 is independently a linear or branched aliphatic group containing from 1 to 20 carbon atoms, a substituted or unsubstituted aryl group containing 6 to 16 carbon atoms, an alicyclic group containing 3 to 16 carbon atoms, a heteronuclear aromatic group containing 3 to 16 carbon atoms, a hydrocarbyl group having from 3 to 16 carbon atoms and containing at least one heteroatom of oxygen, nitrogen or sulfur and/or containing at least one ester, nitrile or halo group, wherein at least one R2 is different from at least one R3;
• R12 is independently hydrogen or methyl;
• A1 is
• wherein R4 is independently a divalent linear or branched alkylene group having from 2 to 10 carbon atoms, an aralkylene group having from 8 to 12 carbon atoms, an unsubstituted or substituted arylene group having from 8 to 18 carbon atoms, or a hydrocarbylene group having from 2 to 10 carbon atoms and containing at least one oxygen heteroatom, R5 is independently a hydrogen, a halogen, an aliphatic group containing from 1 to 12 carbon atoms, an aromatic group containing from 6 to 12 carbon atoms, an alkoxy group containing form 1 to 12 carbon atoms or an aryloxy group containing from 6 to 12 carbon atoms, W is independently a divalent group selected from the group consisting of −O—, —NR—, —C(═O)O— and —S(═O)2O—, and the subscript p is 1;
• wherein m, n, n′, x and y are integers, wherein m is from 0 to 120, n is from 1 to 120, n′ is from 1 to 10, x is from 1 to 300, and y is from 0 to 100, with the proviso that the sum of n+m is greater than or equal to 2.

A method of preparing a copolymer comprising polymerizing α,ω-functionalized polyoxyalkylene-siloxane polymer is a polymer having the structural Formula (I):

• wherein each R1, R2 and R3 is independently a linear or branched aliphatic group containing from 1 to 20 carbon atoms, a substituted or unsubstituted aryl group containing 6 to 16 carbon atoms, an alicyclic group containing 3 to 16 carbon atoms, a heteronuclear aromatic group containing 3 to 16 carbon atoms, a hydrocarbyl group having from 3 to 16 carbon atoms and containing at least one heteroatom of oxygen, nitrogen or sulfur and/or containing at least one ester, nitrile or halo group, wherein at least one R2 is different from at least one R3;
• R12 is independently hydrogen or methyl;
• A is
• wherein R4 is independently a divalent linear or branched alkylene group having from 2 to 10 carbon atoms, an aralkylene group having from 8 to 12 carbon atoms, an unsubstituted or substituted arylene group having from 8 to 18 carbon atoms, or a hydrocarbylene group having from 2 to 10 carbon atoms and containing at least one oxygen heteroatom, R5 is independently a hydrogen, a halogen, an aliphatic group containing from 1 to 12 carbon atoms, an aromatic group containing from 6 to 12 carbon atoms, an alkoxy group containing form 1 to 12 carbon atoms or an aryloxy group containing from 6 to 12 carbon atoms, R6 is independently a hydroxyl group, an amine group, a carboxylic acid chloride group or a sulfonyl halide group, and the subscript p is 1;
• wherein m, n, n′, x and y are integers, and wherein m is from 0 to 120, n is from 1 to 120, n′ is from 1 to 10, x is from 1 to 300, and y is from 0 to 100, with the proviso that the sum of n+m is greater than or equal to 2,
• with a compound of Formula (III):
• where R8 is independently a hydrogen, a halogen, an aliphatic group having from 1 to 6 carbon atoms, an aromatic group having from 6 to 8 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, or an aryloxy group;
• and R9 is independently a hydroxyl group, an amine group, an acid chloride group, or a sulfonyl halide group;
• and X is a compound represented by a structural formula selected from the group consisting of:
• wherein R10, R11 are independently a hydrogen, halogen, an alkyl group having from 1 to 18 carbon atoms, an aryl group having from 3 to 14 carbon atoms, an aryloxy group having from 6 to 10 carbon atoms, an aralkyl group having from 7 to 20 carbon atoms, an alkoxy group having from 1 to 10 carbon atoms, a cycloalkyl group having from 6 to 20 carbon atoms, a cycloalkoxy group having from 6 to 20 carbon atoms, an alkenyl group having from 2 to 10 carbon atoms, an aralkyloxy group, a nitro group, an aldehyde group, a cyano group, or a carboxyl group in the presence of a carbonate precursor.