High glass transition temperature copolycarbonates, methods of manufacture, and uses thereof
View Patent ↗A copolycarbonate of the formula wherein 5 to 75 mole percent of the total number of R 1 groups is derived from a high Tg monomer 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 phenyl, and c is 0 to 4; and 25 to 95 mole percent of the R 1 groups are derived from a dihydroxy compound of formula HO—R 5 —OH, wherein at least 60% of the R 5 groups are aromatic, and the dihydroxy compound of formula (3) is not the same as the high Tg monomer of formula (2), and wherein the copolycarbonate comprises at least 10% fewer carbonate linkages of formula (4) than would be theoretically obtained in a random copolymer made from the same ratio of the high Tg monomer of formula (2) and the dihydroxy compound of formula (3).
1. A copolycarbonate of the formula
wherein
5 to 75 mole percent of the total number of R 1 groups is derived from a high Tg monomer 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, and c is 0 to 4; and
25 to 95 mole percent of the 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 high Tg monomer of formula (2), and wherein
the copolycarbonate comprises at least 10% fewer carbonate linkages of formula (4)
than would be theoretically obtained in a random copolymer made from the same ratio of the high Tg monomer of formula (2) and the dihydroxy compound of formula (3).
2. The copolycarbonate of claim 1 , wherein each c is zero.
3. The copolycarbonate of claim 1 , wherein the HO—R 5 —OH is a dihydroxy compound of 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 3 , wherein each p and q are each zero and X a is 2,2-proplyene.
5. The copolycarbonate of claim 4 , wherein each c is zero.
6. The copolycarbonate of claim 1 , wherein 10 to 70 mole % of the R 1 groups in the copolycarbonate are derived from a high Tg monomer of formula (2), and 30 to 90 mole % of the R 1 units are derived from another dihydroxy compound of formula (3).
7. The copolycarbonate of claim 1 , comprising 10 to 99% fewer carbonate linkages of formula (4) than would theoretically be obtained in a random copolymer made from the same ratio of the high Tg monomer of formula (2) and the dihydroxy compound of formula (3).
8. The copolycarbonate of claim 1 , comprising 15 to 98% fewer carbonate linkages of formula (4) than would theoretically be obtained in a random copolymer made from the same ratio of the high Tg monomer of formula (2) and the dihydroxy compound of formula (3).
9. A method of preparing a copolycarbonate comprising 1 to 75 mole percent of units derived from a high Tg monomer 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, and c is 0 to 4, the method comprising
forming a bischloroformate from a dihydroxy compound of formula (3)
HO—R 5 —OH (3)
wherein at least 60% of the R 5 groups are aromatic, the dihydroxy compound of formula (3) is not the same as the high Tg monomer of formula (2), and the average number of units in the bischloroformate is less than 19; and
reacting the high Tg monomer of formula (2) with the bischloroformate, in a reaction system comprising water, a substantially inert, substantially water-insoluble organic liquid, base, and a phase transfer agent to form the copolycarbonate.
10. The method of claim 9 , wherein reacting the high Tg monomer of formula (2) with the bischloroformate produces a condensate; and further comprising contacting the condensate with an organic base to hydrolyze and condense residual bischloroformates in the condensate.
11. The method of claim 9 , wherein the average number of units in the bischloroformate is 1 to 3.
12. The method of claim 9 , wherein the average number of units in the bischloroformate is 1 to 2.
13. The method of claim 9 , wherein each c is zero.
14. A copolycarbonate prepared by the process of claim 9 .
15. An article comprising the copolycarbonate of claim 1 .
16. An article comprising the copolycarbonate manufactured by the method of claim 9 .