Poly(carbonate-co-urea) copolymers and melt transesterification method of preparing these copolymers
View Patent ↗Disclosed herein is a poly(carbonate-co-urea-co-ester) copolymer comprising incorporated urea compound, dihydroxy compound and diacid compound residues. Also disclosed herein is a poly(carbonate-co-urea) copolymer comprising incorporated urea compound and dihydroxy compound residues.
1. A poly(carbonate-co-urea) copolymer comprising incorporated diaryl carbonate, urea compound and dihydroxy compound residues, and internal linkages and end groups,
wherein a portion of the internal linkages have the following structure (d2):
wherein Z is oxygen or nitrogen.
2. The poly(carbonate-co-urea) copolymer of claim 1 , wherein the incorporated urea compound residues have the following structure (b1),
wherein the substituents R 1 and R 2 are independently each a C 1 to C 12 branched or linear alkyl group, a C 6 to C 18 aromatic group, or a C 7 to C 36 aralkyl group.
3. The poly(carbonate-co-urea) copolymer of claim 1 , wherein the incorporated urea compound residues have the following structure (b2),
wherein the substituent R 3 is a C 1 to C 12 branched or linear aliphatic group, a C 6 to C 18 aromatic group, or a C 7 to C 36 aralkyl group.
4. The poly(carbonate-co-urea) copolymer of claim 1 , wherein the incorporated urea compound residues are present in an amount of less than or equal to 50% mole based on the total content of incorporated urea compound and dihydroxy compound residues.
5. The poly(carbonate-co-urea) copolymer of claim 1 , wherein the incorporated urea compound residues are present in an amount of less than or equal to 30% mole based on the total content of incorporated urea compound and dihydroxy compound residues.
6. The poly(carbonate-co-urea) copolymer of claim 1 , wherein the incorporated urea compound residues are present in an amount of less than or equal to 25% mole based on the total content of incorporated urea compound and dihydroxy compound residues.
7. The poly(carbonate-co-urea) copolymer of claim 1 , wherein the incorporated urea compound residue is selected from the group consisting of residues derived from incorporated ethylene urea, hydantoin, 2-benzimidazolinone, propylene urea, uracil, hydrouracil, benzoyleneurea, alloxan, N,N′-dicyclohexyl-urea, and barbituric acid.
8. The poly(carbonate-co-urea) copolymer of claim 1 , wherein the incorporated urea compound residue is derived from the incorporation of ethylene urea, N,N′-dicyclohexyl-urea, or propylene urea.
9. The poly(carbonate-co-urea) copolymer of claim 1 , wherein a portion of the end groups have the following structures (c12) and/or (c13):
wherein Y is an ortho or para electron-withdrawing substituent and Z is oxygen or nitrogen.
10. The poly(carbonate-co-urea) copolymer of claim 9 , wherein the ortho or para electron-withdrawing substituent is selected from the group consisting of alkyl, phenyl or benzyl esters.
11. The poly(carbonate-co-urea) copolymer of claim 9 , wherein the electron-withdrawing substituent is an ortho methyl ester.
12. The poly(carbonate-co-urea) copolymer of claim 1 , wherein the poly(carbonate-co-urea) copolymer contains Fries rearrangement products.
13. The poly(carbonate-co-urea) copolymer of claim 1 , wherein the poly(carbonate-co-urea) copolymer contains a portion of the incorporated urea compound residues as part of an internal dicarbamate-urea linkage (m1)
wherein the substituents R 1 and R 2 are independently each a C 1 to C 12 branched or linear alkyl group, a C 6 to C 18 aromatic group, or a C 7 to C 36 aralkyl group.
14. The poly(carbonate-co-urea) copolymer of claim 1 , wherein the poly(carbonate-co-urea) copolymer contains a portion of the incorporated urea compound residues as part of an internal dicarbamate-urea linkage (m2)
wherein the substituent R 3 is a C 1 to C 12 branched or linear aliphatic group, a C 6 to C 18 aromatic group, or a C 7 to C 36 aralkyl group.
15. The poly(carbonate-co-urea) copolymer of claim 1 , wherein the poly(carbonate-co-urea) copolymer has a number average molecular weight (Mn) measured relative to polystyrene (PS) of between 6,000 g/mol and 150,000 g/mol.
16. The poly(carbonate-co-urea) copolymer of claim 1 , wherein the poly(carbonate-co-urea) copolymer has a number average molecular weight (Mn) measured relative to polystyrene (PS) of between 8,000 g/mol and 150,000 g/mol.
17. The poly(carbonate-co-urea) copolymer of claim 1 , wherein the poly(carbonate-co-urea) copolymer is a random copolymer.
18. A poly(carbonate-co-urea) copolymer comprising incorporated diaryl carbonate, urea compound and dihydroxy compound residues, and internal linkages and end groups, wherein the incorporated urea compound residues have the following structure (b1),
wherein the substituents R 1 and R 2 are independently each a C 1 to C 12 branched or linear alkyl group, a C 6 to C 18 aromatic group, or a C 7 to C 36 aralkyl group, wherein the incorporated urea compound residues are present in an amount of less than or equal to 50 mole % based on the total content of incorporated urea compound and dihydroxy compound residues, and
wherein a portion of the internal linkages have the following structure (d2):
wherein Z is oxygen or nitrogen.
19. The poly(carbonate-co-urea) copolymer of claim 18 , wherein the incorporated urea compound residue is derived from the incorporation of N,N′-dicyclohexyl-urea.
20. The poly(carbonate-co-urea) copolymer of claim 18 , wherein a portion of the end groups have the following structures (c12) and/or (c13):
wherein Y is an ortho or para electron-withdrawing substituent and Z is oxygen or nitrogen.
21. The poly(carbonate-co-urea) copolymer of claim 20 , wherein the ortho or para electron-withdrawing substituent is selected from the group consisting of alkyl, phenyl or benzyl esters.
22. The poly(carbonate-co-urea) copolymer of claim 20 , wherein the electron-withdrawing substituent is an ortho methyl ester.
23. The poly(carbonate-co-urea) copolymer of claim 18 , wherein the poly(carbonate-co-urea) copolymer contains a portion of the incorporated urea compound residues as part of an internal dicarbamate-urea linkage (m1)
wherein the substituents R 1 and R 2 are independently each a C 1 to C 12 branched or linear alkyl group, a C 6 to C 18 aromatic group, or a C 7 to C 36 aralkyl group.
24. The poly(carbonate-co-urea) copolymer of claim 18 , wherein the poly(carbonate-co-urea) copolymer has a number average molecular weight (Mn) measured relative to polystyrene (PS) of between 6,000 g/mol and 150,000 g/mol.
25. The poly(carbonate-co-urea) copolymer of claim 18 , wherein the poly(carbonate-co-urea) copolymer is a random copolymer.
26. A poly(carbonate-co-urea) copolymer comprising incorporated diaryl carbonate, urea compound and dihydroxy compound residues, and internal linkages and end groups,
wherein the incorporated urea compound residues have the following structure (b2),
wherein the substituent R 3 is a C 1 to C 12 branched or linear aliphatic group, a C 6 to C 18 aromatic group, or a C 7 to C 36 aralkyl group, and
wherein a portion of the internal linkages have the following structure (d2):
wherein Z is oxygen or nitrogen.
27. The poly(carbonate-co-urea) copolymer of claim 26 , wherein the incorporated urea compound residues are present in an amount of less than or equal to 50% mole based on the total content of incorporated urea compound and dihydroxy compound residues.
28. The poly(carbonate-co-urea) copolymer of claim 26 , wherein the incorporated urea compound residue is derived from the incorporation of ethylene urea or propylene urea.
29. The poly(carbonate-co-urea) copolymer of claim 26 , wherein a portion of the end groups have the following structures (c12) and/or (c13):
wherein Y is an ortho or para electron-withdrawing substituent and Z is oxygen or nitrogen.
30. The poly(carbonate-co-urea) copolymer of claim 29 , wherein the ortho or para electron-withdrawing substituent is selected from the group consisting of alkyl, phenyl or benzyl esters.
31. The poly(carbonate-co-urea) copolymer of claim 29 , wherein the electron-withdrawing substituent is an ortho methyl ester.
32. The poly(carbonate-co-urea) copolymer of claim 26 , wherein the poly(carbonate-co-urea) copolymer contains Fries rearrangement products.
33. The poly(carbonate-co-urea) copolymer of claim 26 , wherein the poly(carbonate-co-urea) copolymer contains a portion of the incorporated urea compound residues as part of an internal dicarbamate-urea linkage (m2)
wherein the substituent R 3 is a C 1 to C 12 branched or linear aliphatic group, a C 6 to C 18 aromatic group, or a C 7 to C 36 aralkyl group.
34. The poly(carbonate-co-urea) copolymer of claim 26 , wherein the poly(carbonate-co-urea) copolymer has a number average molecular weight (Mn) measured relative to polystyrene (PS) of between 6,000 g/mol and 150,000 g/mol.
35. The poly(carbonate-co-urea) copolymer of claim 26 , wherein the poly(carbonate-co-urea) copolymer is a random copolymer.
36. A poly(carbonate-co-urea-co-ester) copolymer comprising incorporated diaryl carbonate, urea compound, dihydroxy compound and diacid compound residues, and internal linkages and end groups, wherein a portion of the internal linkages have the following structure (d2):
wherein Z is oxygen or nitrogen.
37. The poly(carbonate-co-urea-co-ester) copolymer of claim 36 , wherein the incorporated urea compound residues are present in an amount of less than or equal to 50 mole % based on the total content of incorporated urea compound, dihydroxy compound, and diacid compound residues.
38. The poly(carbonate-co-urea-co-ester) copolymer of claim 36 , wherein the diacid compound residue is selected from the group consisting of residues derived from incorporated terephthalic acid, isophthalic acid, adipic acid, succinic acid, 1,7-cyclododecanedioic acid, 1,4-cyclohexanedicarboxylic acid, hexanedioic acid, octanedioic acid, decanedioic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, cis 9-octenedioic acid, alpha-nonyldecanedioic acid, alpha-octylundecanedioic acid, and hydrogenated dimer acid.
39. A poly(carbonate-co-urea) copolymer comprising incorporated urea compound and dihydroxy compound residues and internal linkages, and
wherein a portion of the internal linkages have the following structure (d2):
wherein Z is oxygen or nitrogen.
40. A poly(carbonate-co-urea) copolymer comprising incorporated diaryl carbonate, urea compound and dihydroxy compound residues, wherein the incorporated urea compound residues have the following structure (b1),
wherein the substituents R 1 and R 2 are independently each a C 1 to C 12 branched or linear alkyl group, a C 6 to C 18 aromatic group, or a C 7 to C 36 aralkyl group, and wherein the incorporated urea compound residues are present in an amount of less than or equal to 50 mole % based on the total content of incorporated urea compound and dihydroxy compound residues, and
having internal linkages, and
wherein a portion of the internal linkages have the following structure (d2):
wherein Z is oxygen or nitrogen.
41. A poly(carbonate-co-urea) copolymer comprising incorporated diaryl carbonate, urea compound and dihydroxy compound residues, wherein the incorporated urea compound residues have the following structure (b2),
wherein the substituent R 3 is a C 1 to C 12 branched or linear aliphatic group, a C 6 to C 18 aromatic group, or a C 7 to C 36 aralkyl group, and wherein the incorporated urea compound residues are present in an amount of less than or equal to 50 mole % based on the total content of incorporated urea compound and dihydroxy compound residues, and
having internal linkages, and
wherein a portion of the internal linkages have the following structure (d2):
wherein Z is oxygen or nitrogen.
42. A poly(carbonate-co-urea-co-ester) copolymer comprising incorporated urea compound, dihydroxy compound and diacid compound residues, and
having internal linkages, and
wherein a portion of the internal linkages have the following structure (d2):
wherein Z is oxygen or nitrogen.
43. The poly(carbonate-co-urea-co-ester) copolymer of claim 42 , wherein the poly(carbonate-co-urea-co ester) copolymer is a random copolymer.
44. The poly(carbonate-co-urea-co-ester) copolymer of claim 42 , wherein the incorporated urea compound residues are present in an amount of less than or equal to 50 mole % based on the total content of incorporated urea compound, dihydroxy compound, and diacid compound residues.