Granted Patent B2

US 9,434,820 · App. 14/858,151 · Granted Sep 6, 2016

Abstract

Claims (43)

1. A substituted phenyl-terminated polysiloxane terpolymer comprising the structure:

wherein R, R 1 , R 2 and R 3 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 R 1 , R 2 , and R 3 are not the same group; R 4 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; R 5 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; R 6 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.

2. A composition comprising the substituted phenyl-terminated polysiloxane terpolymer of claim 1 , further comprising at least one polymer selected from the group consisting of: polycarbonate homopolymers, polycarbonate copolymers, polycarbonate-polyesters, polyesters, polysulfones, polyethersulfones, polyetheretherketones, polyimides, polyetherimides, and combinations thereof.

3. An article comprising the composition of claim 2 , wherein the article is one or more of a mobile phone housing, frozen food service equipment, a helmet, an automotive windshield, a motorcycle windshield, an automotive sunroof, a dashboard, a headlamp, or an electric screen.

4. A method of making an article comprising: molding, shaping, or forming the composition of claim 2 to form the article.

5. 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 R 1 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 R 1 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; R 4 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; R 5 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; R 6 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 R 1 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; R 2 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. R 1 and R 2 are not the same; R 4 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; R 5 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; R 6 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 R 1 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; R 2 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. R 1 and R 2 are not the same; R 4 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; R 5 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; R 6 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 R 1 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; R 2 and R 3 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 R 1 , R 2 , and R 3 are not the same; R 4 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; R 5 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; R 6 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.

6. The method of claim 5 , further comprising:

purifying the substituted phenyl-terminated polysiloxane co- or terpolymer.

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

wherein R, R 1 , R 2 and R 3 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 R 1 , R 2 , and R 3 are not the same group; R 4 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; R 5 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; R 6 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.

8. The polysiloxane-thermoplastic resin polymer of claim 7 , further comprising a structural unit having the Formula (VIII):

wherein each R 7 is independently a hydrocarbon group containing from 1 to 60 carbon atoms, a divalent hydrocarbon group, or a group derived from the structural unit of Formula (II):

where R 8 is independently a hydrogen, a halogen, an aliphatic group having from 1 to 6 carbon atoms, an aromatic group having 6 to 8 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, or an aryloxy group; and R 9 is independently a residue of a hydroxyl group, an amine group, an acid chloride group, or a sulfonyl halide group; and X is selected from the group consisting of:

wherein R 10 and R 11 are independently a hydrogen, a 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.

9. The polysiloxane-thermoplastic resin polymer of claim 7 , wherein R 3 is independently a linear alkyl chain from 4 to 15 carbon atoms, a substituted or an unsubstituted aromatic group, or a group derived from vinyl carbazole, allylphenylether, vinylbenzyl chloride, allylmethacrylate, diphenylethylene, vinylbenzocyclobutene, allylphenylsulfide, vinylbenzoate, chlorostyrene, R 9 is hydroxy group and R 10 is alkyl group of 1 to 6 carbon atoms.

10. A composition comprising the polysiloxane-thermoplastic resin polymer of claim 7 and at least one of a polycarbonate homopolymer, a polycarbonate-polyester, a polyester, a polysulfone, a polyethersulfone, a polyetheretherketone, a polyimide, a polyetherimide, a polycarbonate copolymer, or a combination thereof.

11. An article comprising the composition of claim 10 , wherein the article is one or more of a mobile phone housing, frozen food service equipment, a helmet, an automotive windshield, a motorcycle windshield, an automotive sunroof, a dashboard, a headlamp, or an electric screen.

12. A method of making an article comprising: molding, shaping, or forming the composition of claim 10 to obtain the article.

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

wherein R, R 1 , R 2 and R 3 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 R 1 , R 2 , and R 3 are not the same group; R 4 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; R 5 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; R 6 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 R 8 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 R 9 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 R 10 , R 11 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.

14. The method of claim 13 , wherein the carbonate precursor is chosen from phosgene, diphosgene, triphosgene and diarylcarbonates, bis(methylsalicyl)carbonate, or a combination thereof.

15. The method of claim 13 , wherein the polymerizing step is an interfacial polymerization process conducted in the presence of a solvent and optionally one or more catalysts.

16. The method of claim 13 , wherein the polymerizing step is an interfacial polymerization process conducted in the presence of a solvent, a caustic, and optionally one or more catalysts, and wherein the carbonate precursor is chosen from phosgene, diphosgene, triphosgene or diarylcarbonates, bis(methylsalicyl)carbonate, or a combination thereof.

17. The method of claim 13 , wherein the polymerizing step comprises reacting a dihydroxy aromatic compound with triphosgene in a biphasic solvent in the presence of a phase transfer catalyst to form a bischloroformate; and adding the substituted phenyl-terminated polysiloxane co- or terpolymer to form the polysiloxane-thermoplastic resin polymer.

18. The method of claim 17 , wherein a plurality of bischloroformates of the dihydroxy aromatic compound are formed in a tube reactor, and then added into an interfacial polycondensation reactor with a catalyst.

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

wherein R, R 1 and R 3 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; R 2 is a heteronuclear aromatic group containing 3 to 16 carbon atoms, wherein R 1 , R 2 and R 3 are not the same group; R 4 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; R 5 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; R 6 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.

20. A composition comprising the substituted phenyl-terminated polysiloxane co-polymer of claim 19 , further comprising at least one polymer selected from the group consisting of: polycarbonate homopolymers, polycarbonate copolymers, polycarbonate-polyesters, polyesters, polysulfones, polyethersulfones, polyetheretherketones, polyimides, polyetherimides, and combinations thereof.

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

wherein R, R 1 , and R 3 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; R 2 is a heteronuclear aromatic compound, wherein R 1 , R 2 , and R 3 are not the same group; R 4 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; R 5 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; R 6 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.

Assignments (10)