Granted Patent B1

US 9,334,372 · App. 14/631,077 · Granted May 10, 2016

Abstract

Claims (37)

1. A polysiloxane having the general structural formula (I):

wherein each of R 1 , R 2 and R 3 are independently a linear or branched aliphatic group containing up to about 20 carbon atoms, an un-substituted or substituted aryl group containing from 6 to about 18 carbon atoms, optionally containing at least one heteroatom, and an alicyclic group containing up to about 20 carbon atoms; each R 4 is independently a divalent alkyl group of from 1 to about 6 carbon atoms, an un-substituted or substituted aryl group containing up to about 18 carbon atoms, an ester group containing up to about 8 carbon atoms, an ether group containing up to about 8 carbon atoms, or an acetate group containing up to about 8 carbon atoms; each R 5 is independently a hydrogen atom, a halogen atom, a linear or branched aliphatic group containing up to about 20 carbon atoms, an un-substituted or substituted aryl group containing from 6 to about 18 carbon atoms, optionally containing at least one heteroatom, an alkoxy group containing from 1 to about 8 carbon atoms, and an unsubstituted or substituted aryloxy group containing up to about 18 carbon atoms; each R 6 is independently a hydroxyl group, an amine group, an acid chloride group, and a sulfonyl halide group; each Z is independently selected from a divalent linear, branched or cyclic alkyl group containing from 2 to 25 carbon atoms, a divalent linear, branched or cyclic alkenyl group containing from 2 to 25 carbon atoms, and a divalent un-substituted or substituted aryl group of up to about 20 carbon atoms, and the subscript x is an integer of from 1 to 250, the subscript y is from 0 to 40, the subscript n′ is an integer greater than 1, and the subscript m is an integer of from to 1 to 5.

2. A method of preparing the polysiloxane compound (I) of claim 1 , comprising:

hydrosilylating a hydride terminated polysiloxane represented by the general structural formula (II)

wherein each R 1 , R 2 and R 3 are as defined,

with a diene which contains a linear, branched or cyclic alkyl group containing from 2 to 25 carbon atoms or a linear, branched or cyclic alkylene group of from 2 to 25 carbon atoms to obtain a hydride-terminated polysiloxane represented by the structural formula (III):

wherein each of R 1 , R 2 , R 3 , Z, x, y and n′ are as defined,

followed by hydrosilylation of the hydride-terminated polysiloxane of formula (III) with an unsaturated compound of the general formula (IV):

where R 5 and R 6 are as defined, R 4 * is selected from alkenyl group containing from 2 to 6 carbon atoms, allyl acetate group containing up to 8 carbon atoms, a vinyl acetate group containing up to 8 carbon atoms, allyl carbonyloxy group of up to 8 carbon atoms, allyl phenyl group of up to about 18 carbon atoms, vinyl phenyl group of up to 18 carbon atoms, allyl ether group of up to 8 carbon atoms, vinyl ether group of up to 8 carbon atoms, wherein one or more of such R4* groups can optionally contain one or more of a hydroxyl group, an alkoxy group of from 1 to 4 carbon atoms, a hetero atom, and the subscript m is an integer of from 1 to 5, and wherein when the subscript m=1, then the aforementioned groups of R 4 * is a terminal group, and wherein when the subscript m is >1 then R 4 * comprises at least one divalent group and one terminal group.

3. An article comprising the polysiloxane of claim 1 .

4. The article of claim 3 , wherein the article is one or more selected from the group consisting of a mobile phone housing, a frozen food service equipment, a helmet, a helmet shield, an automotive windshield, a motorcycle windshield, an automotive sunroof, a roof, a dashboard, a headlamp, an electric screen a medical article, a medical tube and a medical bag.

5. A copolymer comprising a structural unit represented by the structural formula (V):

wherein each of R 1 , R 2 and R 3 are independently a linear or branched aliphatic group containing up to about 20 carbon atoms, an un-substituted or substituted aryl group containing from 6 to about 18 carbon atoms, optionally containing at least one heteroatom, or an alicyclic group containing up to about 20 carbon atoms; each R 4 is independently, a divalent alkyl group of from 1 to about 6 carbon atoms, an un-substituted or substituted aryl group containing up to about 18 carbon atoms, an ester group containing up to about 8 carbon atoms, an ether group containing up to about 8 carbon atoms, or an acetate group containing up to about 8 carbon atoms; each R 5 is independently a hydrogen atom, a halogen atom, a linear or branched aliphatic group containing up to about 20 carbon atoms, an un-substituted or substituted aryl group containing from 6 to about 18 carbon atoms, optionally containing at least one heteroatom, an alkoxy group containing from 1 to about 8 carbon atoms, or an unsubstituted or substituted aryloxy group containing up to about 18 carbon atoms; each Z is independently a divalent linear, branched or cyclic alkyl group containing from 2 to 25 carbon atoms or a divalent linear, branched or cyclic alkenyl group containing from 2 to 25 carbon atoms; and the subscript x is an integer of from 1 to 250; the subscript y is from 0 to 40; the subscript n′ is an integer greater than 1; and the subscript m is an integer of from to 1 to 5.

6. The copolymer of claim 5 wherein the copolymer further comprises a structural unit of any one or more of a polycarbonate, a polyester, a polyetherketone or a polysulfone.

7. The copolymer of claim 5 , further comprising a structural unit having the general formula (VI):

wherein each R 7 is a divalent hydrocarbon group containing from 1 to 60 carbon atoms, a group derived from a structural unit having the general formula (VII):

where each R 8 is independently selected from hydrogen, halogen, an aliphatic group containing from 1 to 6 carbon atoms, an aromatic group containing from 6 to 8 carbon atoms, an alkoxy group containing from 1 to 6 carbon atoms, or an aryloxy group containing from 6 to 18 carbon atoms; and each R 9 is independently chosen from 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 each R 10 and each R 11 are independently chosen from hydrogen, halogen, an alkyl group containing from 1 to 18 carbon atoms, an aryl group containing from 3 to 14 carbon atoms, an aryloxy group containing from 6 to 18 carbon atoms, an aralkyl group containing from 7 to 20 carbon atoms, an alkoxy group containing from 1 to 10 carbon atoms, a cycloalkyl group containing from 6 to 20 carbon atoms, a cycloalkoxy group containing from 6 to 20 carbon atoms, an alkenyl group containing from 2 to 10 carbon atoms, an aralkyloxy group containing from 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, or a carboxyl group.

8. The copolymer of claim 7 wherein R 9 is a hydroxy group and R 10 is an alkyl group of from 1 to 6 carbon atoms.

9. A composition comprising the copolymer of claim 7 , and at least one of a polycarbonate homopolymer, a different polycarbonate copolymer, a polycarbonate-polyester, a polyester, a polysulfone, a polyethersulfone, a polyetheretherketone, a polyimide or a polyetherimide.

10. An article comprising the composition of claim 9 .

11. The article of claim 10 , wherein the article is one or more selected from the group consisting of a mobile phone housing, a frozen food service equipment, a helmet, a helmet shield, an automotive windshield, a motorcycle windshield, an automotive sunroof, a roof, a dashboard, a headlamp, an electric screen a medical article, a medical tube, a medical bag.

12. A method of making an article comprising: molding, shaping, or forming the composition of claim 9 to obtain the article.

13. An article comprising the copolymer of claim 5 .

14. The article of claim 13 , wherein the article is one or more selected from the group consisting of a mobile phone housing, a frozen food service equipment, a helmet, a helmet shield, an automotive windshield, a motorcycle windshield, an automotive sunroof, a roof, a dashboard, a headlamp, or electric screen a medical article, a medical tube and a medical bag.

15. A method of preparing a polycarbonate-polysiloxane copolymer, comprising:

polymerizing a polysiloxane represented by the general formula (I):

wherein each of R 1 , R 2 and R 3 are independently a linear or branched aliphatic group containing up to about 20 carbon atoms, an un-substituted or substituted aryl group containing from 6 to about 18 carbon atoms, optionally containing at least one heteroatom, or an alicyclic group containing up to about 20 carbon atoms; each R 4 is independently, a divalent alkyl group of from 1 to about 6 carbon atoms, an un-substituted or substituted aryl group containing up to about 18 carbon atoms, an ester group containing up to about 8 carbon atoms, an ether group containing up to about 8 carbon atoms, or an acetate group containing up to about 8 carbon atoms; each R 5 is independently a hydrogen atom, a halogen atom, a linear or branched aliphatic group containing up to about 20 carbon atoms, an un-substituted or substituted aryl group containing from 6 to about 18 carbon atoms, optionally containing at least one heteroatom, an alkoxy group containing from 1 to about 8 carbon atoms, or an unsubstituted or substituted aryloxy group containing up to about 18 carbon atoms; each R 6 is independently a hydroxyl group, an amine group, an acid chloride group, or a sulfonyl halide group; each Z is independently a divalent linear, branched or cyclic alkyl group containing from 2 to 25 carbon atoms or a divalent linear, branched or cyclic alkenyl group containing from 2 to 25 carbon atoms, and the subscript x is an integer of from 1 to 250, the subscript y is from 0 to 40, the subscript n′ is an integer greater than 1, and the subscript m is an integer of from to 1 to 5,

with a compound of the general formula (IV):

wherein each R 8 is independently selected from hydrogen, halogen, an aliphatic group containing from 1 to 6 carbon atoms, an aromatic group containing from 6 to 8 carbon atoms, an alkoxy group containing from 1 to 6 carbon atoms, or an aryloxy group containing from 6 to 18 carbon atoms; and each R 9 is independently chosen from 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 each R 10 and each R 11 are independently chosen from hydrogen, halogen, an alkyl group containing from 1 to 18 carbon atoms, an aryl group containing from 3 to 14 carbon atoms, an aryloxy group containing from 6 to 10 carbon atoms, an aralkyl group containing from 7 to 20 carbon atoms, an alkoxy group containing from 1 to 10 carbon atoms, a cycloalkyl group containing from 6 to 20 carbon atoms, a cycloalkoxy group containing from 6 to 20 carbon atoms, an alkenyl group containing from 2 to 10 carbon atoms, an aralkyloxy group containing from 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, or a carboxyl group, and in the presence of a carbonate precursor, to provide a polycarbonate-polysiloxane copolymer.

16. The method of claim 15 , wherein the carbonate precursor is at least one selected from the group consisting of phosgene, diphosgene, triphosgene, diarylcarbonates, bis(methylsalicyl)carbonate and combinations thereof.

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

18. The method of claim 15 , wherein the polymerizing step comprises reacting bisphenol A with triphosgene in a biphasic solvent in the presence of a phase transfer catalyst to form a bischloroformate; and adding a hydroxy-terminated silicone of formula (1) to form the polycarbonate-polysiloxane copolymer.

19. The method of claim 18 , wherein the chloroformates of the hydroxy-terminated silicone are formed in a tube reactor, and added into an interfacial polycondensation reactor with catalyst.

20. A polycarbonate-polysiloxane copolymer made by the method of claim 15 .

21. An article comprising the polycarbonate-polysiloxane copolymer of claim 20 .

Assignments (10)