Method of preparing polycarbonate
View Patent ↗Polycarbonates incorporating terminal carbonate groups derived from ester-substituted activated carbonates in a transesterification process have unfavorable properties with respect to color, hydrolytic stability and thermal stability, particularly when the polycarbonate containing such end groups is molded. The number of activated carbonate end groups formed during the melt transesterification formation of polycarbonate can be reduced by reacting a dihydroxy compound with an activated diaryl carbonate in the presence of an esterification catalyst to produce a polycarbonate, in the presence of a monohydroxy chainstopper such as para-cumyl phenol in an amount that results in 35 to 65 mol % of the end groups being derived from the monohydroxy chainstopper. Suitably, the reactants are provided such that the molar ratio of activated diaryl carbonate to the total of dihydroxy compound plus ½ the chainstopping reagent that is less than 1.
1. A method for preparing a polycarbonate comprising reacting a dihydroxy reaction component comprising a dihydroxy compound with carbonate reaction component comprising an activated diaryl carbonate in the presence of an esterification catalyst to produce a polycarbonate, wherein the carbonate reaction component and the dihydroxy reaction component are reacted in the presence of a monofunctional chainstopper, said chainstopper being present in an amount effective to yield a polycarbonate in which from 35 to 65% of the total number of end groups are derived from the monofunctional chainstopper.
2. The method of claim 1 , wherein the polycarbonate prepared has end groups derived from the activated diaryl carbonate and from the chainstopper at a combined total level of between 40 and 66 mol % of the total end groups.
3. The method of claim 1 , wherein the carbonate reaction component is reacted in a molar ratio to the total of dihydroxy reaction component plus ½ the chainstopper that is less than 1 when expressed to at least three decimal places.
4. The method of claim 3 , wherein the ratio is between 0.996 or less.
5. The method of claim 3 , wherein the ratio is between 0.962 and 0.996 inclusive.
6. The method of claim 3 , wherein the ratio is between 0.968 and 0.996 inclusive.
7. The method of claim 3 , wherein the ratio is between 0.971 and 0.994 inclusive.
8. The method of claim 1 , wherein the monofunctional chainstopper is a phenolic chainstopper of the formula
where each substituent R is independently selected from the group consisting of alkyl, aryl, and alkaryl having from 1 to 30 carbon units, and hydrogen; and x is an integer between 1 and 5; with the proviso that the substituent R is not an ester or other strongly activating or electron-withdrawing substituent.
9. The method of claim 8 , wherein the polycarbonate prepared has end groups derived from the activated diaryl carbonate and from the monofunctional chainstopper at a combined total level of between 40 and 66 mol % of the total end groups.
10. The method of claim 8 , wherein the carbonate reaction component is reacted in a molar ratio to the total of dihydroxy reaction component plus ½ the monofunctioanl chainstopper that is less than 1 when expressed to at least three decimal places.
11. The method of claim 10 , wherein the ratio is between 0.996 or less.
12. The method of claim 10 , wherein the ratio is between 0.962 and 0.996 inclusive.
13. The method of claim 10 , wherein the ratio is between 0.968 and 0.996 inclusive.
14. The method of claim 10 , wherein the ratio is between 0.971 and 0.994 inclusive.
15. The method of claim 1 , wherein the monofunctional chainstopper is para-cumyl phenol.
16. The method of claim 15 , wherein the polycarbonate prepared has end groups derived from the activated diaryl carbonate and from the monofunctional chainstopper at a combined total level of between 40 and 66 mol % of the total end groups.
17. The method of claim 15 , wherein the carbonate reaction component is reacted in a molar ratio to the total of dihydroxy reaction component plus ½ the monofunctional chainstopper that is less than 1 when expressed to at least three decimal places.
18. The method of claim 17 , wherein the ratio is between 0.996 or less.
19. The method of claim 17 , wherein the ratio is between 0.962 and 0.996 inclusive.
20. The method of claim 17 , wherein the ratio is between 0.968 and 0.996 inclusive.
21. The method of claim 17 , wherein the ratio is between 0.971 and 0.994 inclusive.
22. The method of claim 1 , wherein the dihydroxy compound is an aromatic dihydroxy compound.
23. The method of claim 22 , wherein the activated diaryl carbonate is an ester-substituted diaryl carbonate.
24. The method of claim 23 , wherein the ester-substituted diaryl carbonate is bis(methyl salicyl)carbonate.
25. The method of claim 24 , wherein the polycarbonate prepared has end groups derived from the activated diaryl carbonate and from the monofunctonal chainstopper at a combined total level of between 40 and 66 mol % of the total end groups.
26. The method of claim 24 , wherein the carbonate reaction component is reacted in a molar ratio to the total of dihydroxy reaction component plus ½ the monofunctional chainstopper that is less than 1 when expressed to at least three decimal places.
27. The method of claim 26 , wherein the ratio is between 0.996 or less.
28. The method of claim 26 , wherein the ratio is between 0.962 and 0.996 inclusive.
29. The method of claim 26 , wherein the ratio is between 0.968 and 0.996 inclusive.
30. The method of claim 26 , wherein the ratio is between 0.971 and 0.994 inclusive.
31. The method of claim 26 , wherein the monofunctional chainstopper is para-cumyl phenol.
32. The method of claim 24 , wherein the monofunctional chainstopper is para-cumyl phenol.
33. The method of claim 1 , wherein the dihydroxy reaction component comprises two or more dihydroxy compounds.
34. The method of claim 1 , wherein the polycarbonate is a poly(carbonate-co-ester) and the dihydroxy reaction component comprises a diacid compound.
35. The method of claim 1 , wherein the polycarbonate is a poly(carbonate-co-ester) and the carbonate reaction component comprises a diester compound.
36. The method of claim 1 , wherein the monofunctional chainstopper is a monohydroxy compound.
37. The method of claim 1 , wherein the monofunctional chainstopper is a mono-acid or mono-ester.
38. A polycarbonate having less than 0.5 mole % of terminal alkyl carbonate end groups, less than 1000 ppm of Fries rearrangement products, and free salicylate in the range of from 1 to 500 ppm, said polycarbonate containing free non-salicylate OH groups and carbonate end groups of the formula
wherein X is one or more electron-withdrawing groups in the ortho or para positions, and wherein the free non-salicylate OH groups and carbonate end groups are present in a ratio of at least 0.1, and wherein the polycarbonate comprises end groups that are residues of a monofunctional chainstopper, and wherein the carbonate end groups and the end groups that are residues of the chainstopper are present at a combined total level of between 40 and 66 mol % of the total end groups.
39. The polycarbonate of claim 38 , wherein the polycarbonate has a number average molecular weight measured relative to polystyrene standards, Mn, of from 10,000 to 160,000 g/mol.
40. The polycarbonate of claim 38 , wherein the polycarbonate comprises residues from a dihydroxy compound selected from the group consisting of hydroquinone, resorcinol, methylhydroquinone, butylhydroquinone, phenylhydroquinone, 4-phenylresorcinol and 4-methylresorcinol.
41. The polycarbonate of claim 38 , wherein the free salicylate comprises methyl salicylate.
42. The polycarbonate of claim 38 , wherein the carbonate end groups comprise ends groups of the formula
wherein R is alkyl, phenyl or benzyl.
43. The polycarbonate of claim 38 , wherein the carbonate end groups comprise end groups of the formula
wherein Me is methyl.
44. A molded article molded from the polycarbonate of claim 38 .