High glass transition temperature copolycarbonates, methods of manufacture, and uses thereof
View Patent ↗A copolycarbonate is discloses, comprising units of the formula (1) wherein 70 to 99.5 mole percent of the total number of R 1 groups are derived from a dihydroxy compound of formula (2) wherein R 2 and R 3 are each independently a halogen or a C 1-6 alkyl group, R 4 is a methyl or a phenyl group, and c is independently 0 to 4; and 0.5 to 30 mole percent of the total number of R 1 groups are derived from a dihydroxy compound of formula (3) HO—R 5 —OH (3) wherein at least 60% of the R 5 groups are aromatic, and the dihydroxy compound of formula (3) is not the same as the dihydroxy compound of formula (2), and wherein the copolycarbonate has a glass transition temperature of 250° C. or higher.
1. A copolycarbonate, comprising
units of the formula (1)
wherein
70 to 99.5 mole percent of the total number of R 1 groups are derived from a dihydroxy compound of formula (2)
wherein R 2 and R 3 are each independently a halogen or a C 1-6 alkyl group, R 4 is a phenyl group, and each c is independently 0 to 4; and
0.5 to 30 mole percent of the total number of R 1 groups are derived from a dihydroxy compound of formula (3)
HO—R 5 —OH (3)
wherein at least 60% of the R 5 groups are aromatic, and the dihydroxy compound of formula (3) is not the same as the dihydroxy compound of formula (2), and
wherein the copolycarbonate has a glass transition temperature of 250° C. to 285° C., and a molecular weight of 40,000 to 150,000, measured by gel permeation chromatography using polycarbonate standards.
2. The copolycarbonate of claim 1 , wherein each c is 0.
3. The copolycarbonate of claim 1 , wherein the dihydroxy compound of formula (3) has the formula
wherein R a and R b are each independently a halogen atom or a monovalent C 1-6 alkyl group; p and q are each independently integers of 0 to 4; and X a is one of the following groups:
wherein R c and R d are each independently a hydrogen atom or a C 1-29 alkyl group, or R c , C, and R d taken together are a divalent C 3-10 cycloalkyl group that is optionally substituted with one or more C 1-10 alkyl groups, and R e is a divalent hydrocarbon group.
4. The copolycarbonate of claim 1 , wherein each p and q is 0 and X a is 2,2-propylene.
5. The copolycarbonate of claim 1 , wherein 80 to 99 mole % of the R 1 groups in the copolycarbonate are derived from a compound of formula (2), and 1 to 20 mole % of the R 1 groups are derived from the different dihydroxy compound.
6. The copolycarbonate of claim 1 , wherein 90 to 96 mole % of the R 1 groups in the copolycarbonate are derived from a compound of formula (2), and 4 to 10 mole % of the R 1 groups are derived from the different dihydroxy compound.
7. The copolycarbonate of claim 1 having a Tg of 255° C. to 285° C.
8. The copolycarbonate of claim 1 , having a molecular weight of 60,000 to 150,000, measured by gel permeation chromatography using polycarbonate standards.
9. The copolycarbonate of claim 1 , having a transmissivity of greater than 50% measured over wavelengths of 400 to 800 nanometers.
10. The copolycarbonate of claim 1 , having a shrinkage less than 40 ppm after heating at 200° C. for 8 hours.
11. The copolycarbonate of claim 1 , having a CTE of less than 80 ppm/° C. measured over 50-150° C.
12. An article comprising the copolycarbonate of claim 1 .
13. A method of preparing a copolycarbonate, comprising
reacting
a dihydroxy compound of formula (2)
wherein R 2 and R 3 are each independently a halogen or a C 1-6 alkyl group, R 4 is a phenyl group, and each c is independently 0 to 4, and
a dihydroxy compound of formula (3)
HO—R 5 —OH (3)
wherein at least 60% of the R 5 groups are aromatic, and the dihydroxy compound of formula (3) is not the same as the dihydroxy compound of formula (2), and
wherein 70 to 99.5 mole percent of the total number of R 1 groups are derived from the dihydroxy compound of formula (2),
in a reaction system comprising water, a substantially inert, substantially water-insoluble organic liquid, and an alkali or alkaline earth metal base, to produce a bischloroformate;
reacting the bischloroformate with a capping agent in a reaction system comprising water, a substantially inert, substantially water-insoluble organic liquid, and an alkali or alkaline earth metal base, to produce a partially capped bischloroformate composition; and
contacting the partially capped bischloroformate composition with an interfacial polycarbonate formation catalyst and an aqueous alkali metal or alkaline earth metal base to form a copolycarbonate having a glass transition temperature of 250° C. to 285° C. and a weight average molecular weight of 40,000 to 150,000.
14. The method of claim 13 , wherein each c is 0.
15. The method of claim 13 , wherein the capping agent is a phenol compound.
16. The method of claim 13 , wherein the interfacial copolycarbonate formation catalyst is an amine.
17. A copolycarbonate formed by the method of claim 13 , having a weight average molecular weight of 60,000 to 150,000.
18. An film comprising a copolycarbonate manufactured by the method of claim 13 .
19. A method of forming a film comprising a copolycarbonate, comprising
reacting
a dihydroxy compound of formula (2)
wherein R 2 and R 3 are each independently a halogen or a C 1-6 alkyl group, R 4 is a phenyl group, and each c is independently 0 to 4, and
a dihydroxy compound of formula (3)
HO—R 5 —OH (3)
wherein at least 60% of the R 5 groups are aromatic, and the dihydroxy compound of formula (3) is not the same as the dihydroxy compound of formula (2), and
wherein 70 to 99.5 mole percent of the total number of R 1 groups are derived from the dihydroxy compound of formula (2),
in a reaction system comprising water, a substantially inert, substantially water-insoluble organic liquid, and an alkali or alkaline earth metal base, to produce a bischloroformate;
reacting the bischloroformate with a capping agent in a reaction system comprising water, a substantially inert, substantially water-insoluble organic liquid, and an alkali or alkaline earth metal base, to produce a partially capped bischloroformate composition;
contacting the partially capped bischloroformate composition with an interfacial polycarbonate formation catalyst and an aqueous alkali metal or alkaline earth metal base to form a copolycarbonate having a glass transition temperature of 250° C. to 285° C. and a weight average molecular weight of 40,000 to 150,000;
separating the water phase and the substantially inert, substantially water-insoluble organic liquid phase; and
casting the organic phase to form a film.
20. The article of claim 12 , wherein the article is a film.
21. A copolycarbonate, comprising
units of the formula (1)
wherein
70 to 99.5 mole percent of the total number of R 1 groups are derived from a dihydroxy compound of formula (2)
wherein R 2 and R 3 are each independently a halogen or a C 1-6 alkyl group, R 4 is a phenyl group, and each c is independently 0 to 4; and p 1 0.5 to 30 mole percent of the total number of R 1 groups are derived from bisphenol A, and
wherein the copolycarbonate has a glass transition temperature of 250° C. to 285° C., and a molecular weight of 40,000 to 150,000, measured by gel permeation chromatography using polycarbonate standards.