Polysiloxane co- or terpolymers and polymers made therefrom

A method of preparing a substituted phenyl-terminated polysiloxane co- or terpolymer, comprising:

• (a) reacting a cyclic siloxane with disiloxane hydride in presence of acidic and/or basic catalyst to provide for a hydride-terminated polysiloxane having the structure represented by the structural Formula (III):
• wherein R and R1 are 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;
• x is an integer from 1 to 300;
• (b) hydrosilylating the hydride terminated polysiloxane of step (a) with a substituted phenyl compound having and carbon-carbon double bond and at least one functional group selected from the group consisting of hydroxyl group, an amine group, a carboxylic acid chloride group and a sulfonyl halide group to obtain a substituted phenylalkyl-terminated polysiloxane;
• (c) equilibrating the phenylalkyl-terminated polysiloxane of step (b) with a hydride substituted polysiloxane and/or cyclic siloxane to make a substituted phenylalkyl-terminated polysiloxane containing at least one Si—H (silicon hydride) group and is represented by the structural Formula (IV):
• wherein R and R1 are 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;
• R4 is independently a divalent linear or branched alkylene group having from 1 to 10 carbon atoms, an aralkylene group having from 6 to 12 carbon atoms, an unsubstituted or substituted arylene group having from 6 to 18 carbon atoms, hydrocarbylene group having from 2 to 10 carbon atoms and containing at least one heteroatom of oxygen to form an ether or a covalent single bond;
• 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;
• x is an integer from 1 to 300;
• y is an integer from 1 to 100;
• (d) hydrosilylating the substituted phenylalkyl-terminated polysiloxane containing at least one Si—H (silicon hydride) group with a compound containing a carbon-carbon double bond and a linear or branched aliphatic group containing from 1 to 18 carbon atoms, a substituted or unsubstituted aryl group containing 6 to 14 carbon atoms, an alicyclic group containing 3 to 14 carbon atoms, a heteronuclear aromatic group containing 3 to 14 carbon atoms, a hydrocarbyl group having from 3 to 14 carbon atoms and containing at least one heteroatom of oxygen, nitrogen or sulfur and/or containing at least one ester, nitrile or halo group to obtain a substituted phenylalkyl-terminated polysiloxane copolymer having the structural Formula (V):
• wherein R and R1 are independently an 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;
• R2 is aliphatic group containing from 2 to 20 carbon atoms, a substituted or unsubstituted aryl group containing 8 to 16 carbon atoms, an alicyclic group containing 5 to 16 carbon atoms, a heteronuclear aromatic group containing 5 to 16 carbon atoms, a hydrocarbyl group having from 5 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. R1 and R2 are not the same;
• R4 is independently a divalent linear or branched alkylene group having from 1 to 10 carbon atoms, an aralkylene group having from 6 to 12 carbon atoms, an unsubstituted or substituted arylene group having from 6 to 18 carbon atoms, hydrocarbylene group having from 2 to 10 carbon atoms and containing at least one heteroatom of oxygen or a covalent single bond;
• 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;
• x is from 1 to 300;
• y is from 1 to 100;
• (e) equilibrating the substituted phenylalkyl-terminated polysiloxane copolymer of step (d) with a hydride substituted polysiloxane and/or cyclic siloxane to provide for a substituted phenylalkyl-terminated polysiloxane terpolymer containing at least one Si—H (silicon hydride) group and having the structural Formula (VI):
• wherein R and R1 are independently an 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;
• R2 is aliphatic group containing from 2 to 20 carbon atoms, a substituted or unsubstituted aryl group containing 8 to 16 carbon atoms, an alicyclic group containing 5 to 16 carbon atoms, a heteronuclear aromatic group containing 5 to 16 carbon atoms, a hydrocarbyl group having from 5 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. R1 and R2 are not the same;
• R4 is independently a divalent linear or branched alkylene group having from 1 to 10 carbon atoms, an aralkylene group having from 6 to 12 carbon atoms, an unsubstituted or substituted arylene group having from 6 to 18 carbon atoms, hydrocarbylene group having from 2 to 10 carbon atoms and containing at least one heteroatom of oxygen or a covalent single bond;
• 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;
• x is from 1 to 300;
• y is from 1 to 100 and z is 1 to 50;
• and
• (f) hydrosilylating the substituted phenylalkyl-terminated polysiloxane terpolymer containing at least one Si—H (silicon hydride) group of step (e) with a compound containing a carbon-carbon double bond and a linear or branched aliphatic group containing from 1 to 18 carbon atoms, a substituted or unsubstituted aryl group containing 6 to 14 carbon atoms, an alicyclic group containing 3 to 14 carbon atoms, a heteronuclear aromatic group containing 3 to 14 carbon atoms, a hydrocarbyl group having from 3 to 14 carbon atoms and containing at least one heteroatom of oxygen, nitrogen or sulfur and/or containing at least one ester, nitrile or halo group to obtain a substituted phenylalkyl-terminated polysiloxane terpolymer having the structural Formula (VII):
• wherein R and R1 are 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 and/or sulfur or containing at least one ester, nitrile or halo group;
• R2 and R3 are independently a linear or branched aliphatic group containing from 2 to 20 carbon atoms, a substituted or unsubstituted aryl group containing 8 to 16 carbon atoms, an alicyclic group containing 5 to 16 carbon atoms, a heteronuclear aromatic group containing 5 to 16 carbon atoms, a hydrocarbyl group having from 5 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 R1, R2, and R3 are not the same;
• R4 is independently a divalent linear or branched alkylene group having from 1 to 10 carbon atoms, an aralkylene group having from 6 to 12 carbon atoms, an unsubstituted or substituted arylene group having from 6 to 18 carbon atoms, hydrocarbylene group having from 2 to 10 carbon atoms and containing at least one heteroatom of oxygen or a covalent single bond;
• 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;
• x is from 1 to 300;
• y is from 1 to 100;
• z is from 1 to 50.

A polysiloxane-thermoplastic polymer comprising a structural unit represented by the structural formula:

• wherein R, R1, R2 and R3 are 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 R1, R2, and R3 are not the same group;
• R4 is independently a divalent linear or branched alkylene group having from 1 to 10 carbon atoms, an aralkylene group having from 6 to 12 carbon atoms, an unsubstituted or substituted arylene group having from 6 to 18 carbon atoms, hydrocarbylene group having from 2 to 10 carbon atoms and containing at least one heteroatom of oxygen or a covalent single bond;
• 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 residue of hydroxyl group, an amine group, a carboxylic acid chloride group or a sulfonyl halide group;
• x is an integer from 1 to 300;
• y is an integer from 1 to 100;
• z is an integer from 1 to 50.

A method of preparing a polycarbonate-polysiloxane copolymer, said method comprising polymerizing a substituted phenyl terminated polysiloxane terpolymer of the Formula (I):

• wherein R, R1, R2 and R3 are 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 R1, R2, and R3 are not the same group;
• R4 is independently a divalent linear or branched alkylene group having from 1 to 10 carbon atoms, an aralkylene group having from 6 to 12 carbon atoms, an unsubstituted or substituted arylene group having from 6 to 18 carbon atoms, hydrocarbylene group having from 2 to 10 carbon atoms and containing at least one heteroatom of oxygen or a covalent single bond;
• 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;
• x is an integer from 1 to 300;
• y is an integer from 1 to 100;
• z is an integer from 1 to 50, with a compound of Formula (II):
• 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 residue of a hydroxyl group, an amino group, a carboxylic chloride group, or a sulfonyl halide group;
• and X is 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 at least one carbonate precursor.

A substituted phenyl-terminated polysiloxane co-polymer comprising the structure:

• wherein R, R1 and R3 are independently a linear or branched aliphatic group containing from 1 to 20 carbon atoms, a substituted or unsubsstituted 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;
• R2 is a heteronuclear aromatic group containing 3 to 16 carbon atoms, wherein R1, R2 and R3 are not the same group;
• R4 is independently a divalent linear or branched alkylene group having from 1 to 10 carbon atoms, an aralkylene group having from 6 to 12 carbon atoms, an unsubstituted or substituted arylene group having from 6 to 18 carbon atoms, hydrocarbylene group having from 2 to 10 carbon atoms and containing at least one heteroatom of oxygen or a covalent single bond;
• 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;
• x is an integer from 1 to 300;
• y is an integer from 1 to 100;
• z is 0.

A polysiloxane-thermoplastic polymer comprising a structural unit represented by the structural formula:

• wherein R, R1, and R3 are 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;
• R2 is a heteronuclear aromatic compound, wherein R1, R2, and R3 are not the same group;
• R4 is independently a divalent linear or branched alkylene group having from 1 to 10 carbon atoms, an aralkylene group having from 6 to 12 carbon atoms, an unsubstituted or substituted arylene group having from 6 to 18 carbon atoms, hydrocarbylene group having from 2 to 10 carbon atoms and containing at least one heteroatom of oxygen or a covalent single bond;
• 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 residue of a hydroxyl group, an amine group, a carboxylic acid chloride group or a sulfonyl halide group;
• x is an integer from 1 to 300;
• y is an integer from 1 to 100;
• z is 0.