Polycarbonate-polysiloxane copolymers, methods for the preparation thereof, and articles derived therefrom
A polycarbonate-polysiloxane copolymer comprising structural units of the formula: wherein each R 1 , R 2 , and R 3 is independently the same or different monovalent C 1-12 should this be C1-C13 like in the document? hydrocarbon group, G comprises a monovalent C 6-1000 poly(oxyalkyl) group, each R 4 and R 5 taken together is independently the same or different divalent C 3-30 hydrocarbon linking group wherein R 4 is a C 1-28 hydrocarbon and R 5 is a C 2-29 aliphatic group, a is 0 or greater, and b is one or greater; and structural units of the formula: wherein each R is independently the same or different C 6-60 divalent hydrocarbon group, and at least 60% of the R groups comprise aromatic moieties.
1. A polycarbonate-polysiloxane copolymer comprising
structural units of the formula
wherein each R l , R 2 , and R 3 is independently the same or different monovalent C 1-13 hydrocarbon group, G comprises a monovalent C 6-1000 poly(oxyalkyl) group attached to the silicon atom via a divalent C 2-20 hydrocarbon linking group, each R 4 and R 5 taken together is independently the same or different divalent C 3-30 hydrocarbon linking group wherein R 4 is a C 1-28 hydrocarbon and R 5 is a C 2-29 aliphatic group, a is 0 or greater, and b is one or greater; and
structural units of the formula
wherein each R is independently the same or different C 1-60 divalent hydrocarbon group, and at least 60% of the R groups comprise an aromatic moiety.
2. The copolymer of claim 1 , wherein G is of the formula
wherein each R 6 , R 7 , and R 8 are independently the same or different hydrogen atom or a monovalent C 1-8 hydrocarbon group, R l0 is a monovalent C 1-10 hydrocarbon group, W is a divalent C 1-18 hydrocarbon group, A is a divalent C 1-6 alkyl, c is 1, and d is 1 to 100.
3. The copolymer of claim 1 , wherein G is of the formula
wherein R 10 is a hydrogen atom or a C 1-8 monovalent hydrocarbon group, m is 0 to 20, n is 0 to 20, and o is 0 to 20, provided that m+n+o is 1 to 20.
4. The copolymer of claim 3 , wherein m is 2 to 20, n is zero, o is zero, and R 10 is a C 1-4 alkyl group.
5. The copolymer of claim 1 , wherein a is 5 to 200, and b is 1 to 100.
6. The copolymer of claim 1 , wherein a is 22 to 45, and b is 3 to 15.
7. The copolymer of claim 1 , wherein each R 4 is independently the same or different substituted or unsubstituted C 6-28 aromatic group, and each R 5 is independently the same or different substituted or unsubstituted C 2-29 aliphatic group.
8. The copolymer of claim 7 , wherein each R 4 and R 5 taken together are the same, and are a group of the formula
wherein R 11 is a hydrogen atom or a C 1-6 alkoxy group.
9. The copolymer of claim 8 , wherein each R 4 and R 5 taken together is the same, and is a group of the formula
10. The copolymer of claim 1 , wherein R is derived from an aromatic dihydroxy compound of the formula:
wherein R a and R b each represent a halogen or C 1-12 alkyl group and can be the same or different, p and q are each independently integers of 0 to 4, and X a represents a bridging group, wherein the bridging group and the hydroxy substituent of each aromatic are disposed ortho, meta, or para to each other, and X a is single bond, —O—, —S—, —S(O)—, —S(O) 2 —, —C(O)—, or a divalent C 1-18 hydrocarbon group.
11. The copolymer of claim 10 , wherein p and q are each zero, and X a is isopropylidene.
12. The copolymer of claim 1 , having a transparency of at least 50% when measured on a sample 3.2 mm thick in accordance with ASTM D1003-00.
13. A composition comprising the copolymer of claim 1 and a polycarbonate homopolymer, a polycarbonate copolymer different from the copolymer of claim 1 , a polycarbonate-polyester, a polyester, or a combination comprising at least one of the foregoing polymers.
14. The composition of claim 13 , comprising, based on the total weight of the polymers in the composition, 0.5 to 99.5 weight percent of a polycarbonate bisphenol A homopolymer.
15. An article comprising the polycarbonate-polysiloxane copolymer of claim 1 .
16. The article of claim 15 , further comprising, based on the total weight of the polymers in the composition, 0.5 to 99.5 weight percent of a polycarbonate bisphenol A homopolymer.
17. The article of claim 15 , in the form of a medical device.
18. A method of making an article comprising molding, shaping, or forming a composition comprising the polycarbonate-polysiloxane copolymer of claim 1 to form the article.
19. The method of claim 18 , comprising molding the composition.
20. The method of claim 19 , wherein the composition further comprises, based on the total weight of the polymers in the composition, 0.5 to 99.5 weight percent of a polycarbonate bisphenol A homopolymer.
21. A method of preparing a polycarbonate-polysiloxane copolymer, comprising polymerizing
a dihydroxy silicone the formula
wherein each R 1 , R 2 , and R 3 is independently the same or different monovalent C 1-13 hydrocarbon group, G comprises a monovalent C 6-1000 poly(oxyalkyl) group attached to the silicon atom via a divalent C 2-20 hydrocarbon linking group, each R 4 and R 5 taken together is independently the same or different divalent C 1-30 hydrocarbon linking group wherein R 4 is a C 1-28 hydrocarbon and R 5 is a C 2-29 aliphatic group, a is 0 or greater, and b is one or greater, with
a compound of the formula
HO—R—OH
wherein each R is independently the same or different C 6-60 divalent hydrocarbon group, and at least 60% of the R groups comprise aromatic moieties, in the presence of a carbonate precursor, to provide the polycarbonate-polysiloxane copolymer of claim 1 .
22. The method of claim 21 , wherein the polymerizing is a melt process, using diphenyl carbonate, bis(methylsalicyl)carbonate, or a combination comprising at least one of the foregoing carbonate as the carbonate precursor.
23. The method of claim 21 , wherein the polymerizing 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 phosgene.
24. The method of claim 23 , wherein polymerizing comprises reacting bisphenol A with phosgene in a biphasic solvent in the presence of a phase transfer catalyst to form a bischloroformate; and adding the dihydroxy silicone to form the copolymer.
25. The method of claim 23 , wherein the chloroformates of the dihydroxy silicone are formed in a tube reactor, and then added into an interfacial polycondensation reactor with catalyst.
26. A polycarbonate-polysiloxane copolymer comprising
structural units of the formula
wherein each R 1 , R 2 , and R 3 is independently the same or different monovalent C 1-13 hydrocarbon group, each R 4 and R 5 taken together is independently the same or different divalent C 3-30 hydrocarbon linking group wherein R 4 is a C 1-28 hydrocarbon and R 5 is a C 2-29 aliphatic group, a is 0 or greater, and b is one or greater, and wherein G is of the formula
wherein R 10 is a hydrogen atom or a C 1-8 monovalent hydrocarbon group, m is 0 to 20, n is 0 to 20, and o is 0 to 20, provided that m+n+o is 1 to 20; and
structural units of the formula
wherein each R is independently the same or different C 1-60 divalent hydrocarbon group,
and at least 60% of the R groups comprise an aromatic moiety.