Method for incorporating alkyl ester endgroups to improve the release properties of melt polycarbonate
View Patent ↗Alkyl ester end-capped polycarbonates have improved release properties and may be produced by a method comprising the step of combining a polycarbonate having free terminal OH groups with an end-capping reagent comprising a symmetrical activated carbonate and an alkyl ester, whereby the end-capping reagent reacts with at least some of the free hydroxyl end groups of the polycarbonate to produce an end-capped polycarbonate comprising optionally substituted aliphatic ester end groups.
1. A method for preparing an end-capped polycarbonate, comprising the step of:
combining a polycarbonate having free terminal OH groups with an end-capping reagent comprising a symmetrical activated carbonate and a compound A, wherein compound A has the structure,
wherein R 1 is selected from the group consisting of a branched C 8 –C 40 alkyl and a linear C 8 –C 40 alkyl; and R 2 is selected from the group consisting of hydrogen, a branched C 3 –C 40 alkyl, a linear C 1 –C 40 alkyl, C 6 –C 30 aryl, and C 7 –C 30 , aralkyl group,
or wherein compound A is an esterified polyol having the formula C(COCOR 3 ) 4 wherein R 3 is a C 10 –C 40 alkyl or a C 10 –C 40 alkenyl group,
whereby the end-capping reagent reacts with at least some of the free hydroxyl end groups of the polycarbonate to produce an end-capped polycarbonate comprising optionally substituted aliphatic ester end groups.
2. The method according to claim 1 , wherein the molar ratio of symmetrical activated carbonate to compound A in the end-capping reagent is between 0.5 and 2.0.
3. The method according to claim 2 , wherein the molar ratio of symmetrical activated carbonate to compound A in the end-capping reagent is between 1.1 and 2.0.
4. The method of claim 1 , wherein compound A of the end-capping reagent is selected from the group consisting of lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, the alkyl esters of these acids, and their aryl esters.
5. The method of claim 4 , wherein compound A of the end-capping reagent is stearic acid.
6. The method of claim 1 , wherein compound A is an esterified polyol and is penta erythritol-tetra-stearate (PETS).
7. The method according to claim 1 , wherein the symmetrical activated carbonate of the end-capping reagent has the structure,
wherein R 1 is a C 1 –C 20 alkyl radical, C 4 –C 20 cycloalkyl radical, or C 4 –C 20 aromatic radical; R 2 is a halogen atom, cyano group, nitro group, C 1 –C 20 alkyl radical, C 4 –C 20 cycloalkyl radical, C 4 –C 20 aromatic radical, C 1 –C 20 alkoxy radical, C 4 –C 20 cycloalkoxy radical, C 4 –C 20 aryloxy radical, C 1 –C 20 alkylthio radical, C 4 –C 10 cycloalkylthio radical, C 4 –C 20 arylthio radical, C 1 –C 20 alkylsulfinyl radical, C 4 –C 20 cycloalkylsulfinyl radical, C 4 –C 20 arylsulfinyl radical, C 1 –C 20 alkylsulfonyl radical, C 4 –C 20 cycloalkylsulfonyl radical, C 4 –C 20 arylsulfonyl radical, C 1 –C 20 alkoxycarbonyl radical, C 4 –C 20 cycloalkoxycarbonyl radical, C 4 –C 20 aryloxycarbonyl radical, C 2 –C 60 alkylamino radical, C 6 –C 60 cycloalkylamino radical, C 5 –C 60 arylamino radical, C 1 –C 40 alkylaminocarbonyl radical, C 4 –C 40 cycloalkylaminocarbonyl radical, C 4 –C 40 arylaminocarbonyl radical, or C 1 –C 20 acylamino radical; and b is independently at each occurrence an integer 0–4.
8. The method according to claim 7 , wherein the symmetrical activated carbonate of the end-capping reagent is selected from the group consisting of: bis-methyl salicylate carbonate (BMSC), BPA-bis-methyl salicylate carbonate, bis-ethyl salicylate carbonate, bis-propyl salicylate carbonate, bis-2-benzoylphenyl carbonate, bis-phenyl salicyl carbonate, and bis-benzyl salicyl carbonate.
9. The method according to claim 8 , wherein the symmetrical activated carbonate of the end-capping reagent is bis-methyl salicylate carbonate (BMSC).
10. The method of claim 1 , wherein the symmetrical activated carbonate of the end-capping reagent is added in an amount of 0.1 to 2 mole based on 1 mole equivalent of the free terminal —OH groups of the polycarbonate at the time of the addition.
11. The method of claim 1 , wherein the symmetrical activated carbonate of the end-capping reagent is added in an amount of 0.8 to 1.3 mole based on 1 mole equivalent of the free terminal —OH groups of the polycarbonate at the time of the addition.
12. The method of claim 1 , wherein the formed polycarbonate has a content of end-capping reagent of 500 ppm or below.
13. The method of claim 12 , wherein the formed polycarbonate has a content of end-capping reagent of 100 ppm or below.
14. The method according to claim 1 , wherein the formed polycarbonate has a content of terminal 2-(alkoxycarbonyl)phenyl, 2-(phenoxycarbonyl)phenyl, 2-(benzyloxycarbonyl)phenyl, and 2-benzoylphenyl groups of 2,500 ppm or below.
15. The method according to claim 14 , wherein the formed polycarbonate has a content of terminal 2-(alkoxycarbonyl)phenyl, 2-(phenoxycarbonyl)phenyl, 2-(benzyloxycarbonyl)phenyl, and 2-benzoylphenyl groups of 1,000 ppm or below.
16. The method according to claim 1 , wherein the formed polycarbonate has a content of ortho-substituted phenols of 500 ppm or below.
17. The method according to claim 16 , wherein the formed polycarbonate has a content of ortho-substituted phenols of 200 ppm or below.
18. The method according to claim 1 , wherein the polycarbonate to which the end-capping reagent is added has a number average molecular weight M n of at least 2,000 Daltons.
19. The method according to claim 18 , wherein the polycarbonate to which the end-capping reagent is added has a number average molecular weight M n of between 2,000 and 15,000 Daltons.
20. The method according to claim 19 , wherein the polycarbonate to which the end-capping reagent is added has a number average molecular weight M n of between 6,000 and 13,000 Daltons.
21. The method according to claim 20 , wherein the polycarbonate to which the end-capping reagent is added has a number average molecular weight M n of between 7,000 and 12,000 Daltons.
22. The method according to claim 1 , wherein the polycarbonate to which the end-capping reagent is added has a hydroxyl end group content of at least 25%.
23. The method according to claim 22 , wherein the polycarbonate to which the end-capping reagent is added has a hydroxyl end group content of at least 40%.
24. An end-capping reagent comprising a symmetrical activated carbonate and a compound A, wherein compound A has the structure,
wherein R 1 is selected from the group consisting of a branched C 8 –C 40 alkyl and a linear C 8 –C 40 alkyl; and R 2 is selected from the group consisting of hydrogen, a branched C 3 –C 40 alkyl, a linear C 1 –C 40 alkyl C 6 –C 30 aryl, and C 7 –C 30 aralkyl group,
or wherein compound A is an esterified polyol having the formula C(COCOR 3 ) 4 wherein R 3 is a C 10 –C 40 alkyl or a C 10 –C 40 alkenyl group.
25. The end-capping reagent of claim 24 , wherein the molar ratio of symmetrical activated carbonate to compound A in the end-capping reagent is between 0.5 and 2.0.
26. The end-capping reagent of claim 25 , wherein the molar ratio of symmetrical activated carbonate to compound A in the end-capping reagent is between 1.1 and 2.0.
27. The end-capping reagent of claim 24 , wherein compound A of the end-capping reagent is selected from the group consisting of lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, the alkyl esters of these acids, and their aryl esters.
28. The end-capping reagent of claim 27 , wherein compound A of the end-capping reagent is stearic acid.
29. The end-capping reagent of claim 24 , wherein compound A is an esterified polyol and is penta erythritol-tetra-stearate (PETS).
30. The method according to claim 24 , wherein the symmetrical activated carbonate of the end-capping reagent has the structure,
wherein R 1 is a C 1 –C 20 alkyl radical, C 4 –C 20 cycloalkyl radical, or C 4 –C 20 aromatic radical; R 2 is a halogen atom, cyano group, nitro group, C 1 –C 20 alkyl radical, C 4 –C 20 cycloalkyl radical, C 4 –C 20 aromatic radical, C 1 –C 20 alkoxy radical, C 4 –C 20 cycloalkoxy radical, C 4 –C 20 aryloxy radical, C 1 –C 20 alkylthio radical, C 4 –C 20 cycloalkylthio radical, C 4 –C 20 arylthio radical, C 1 –C 20 alkylsulfinyl radical, C 4 –C 20 cycloalkylsulfinyl radical, C 4 –C 20 arylsulfinyl radical, C 1 –C 20 alkylsulfonyl radical, C 4 –C 20 cycloalkylsulfonyl radical, C 4 –C 20 arylsulfonyl radical, C 1 –C 20 alkoxycarbonyl radical, C 4 –C 20 cycloalkoxycarbonyl radical, C 4 –C 20 aryloxycarbonyl radical, C 2 –C 60 alkylamino radical, C 6 –C 60 cycloalkylamino radical, C 5 –C 60 arylamino radical, C 1 –C 40 alkylaminocarbonyl radical, C 4 –C 40 cycloalkylaminocarbonyl radical, C 4 –C 40 arylaminocarbonyl radical, or C 1 –C 20 acylamino radical; and b is independently at each occurrence an integer 0–4.
31. The end-capping reagent of claim 30 , wherein the symmetrical activated carbonate of the end-capping reagent is selected from the group consisting of: bis-methyl salicylate carbonate (BMSC), BPA-bis-methyl salicylate carbonate, bis-ethyl salicylate carbonate, bis-propyl salicylate carbonate, bis-2-benzoylphenyl carbonate, bis-phenyl salicyl carbonate, and bis-benzyl salicyl carbonate.
32. The end-capping reagent of claim 31 , wherein the symmetrical activated carbonate of the end-capping reagent is bis-methyl salicylate carbonate (BMSC).
33. The end-capping reagent of claim 24 , wherein the symmetrical activated carbonate of the end-capping reagent is bis-methyl salicylate carbonate (BMSC) and compound A is stearic acid.
34. A method for making a molded article comprising the steps of:
(i) combining a polycarbonate having free terminal OH groups with an end-capping reagent comprising a symmetrical activated carbonate and a compound A, wherein compound A has the structure,
wherein R 1 is selected from the group consisting of a branched C 8 –C 40 alkyl and a linear C 8 –C 40 alkyl; and R 2 is selected from the group consisting of hydrogen, a branched C 3 –C 40 alkyl, a linear C 1 –C 40 alkyl, C 6 –C 30 aryl, and C 7 –C 30 aralkyl group,
or wherein compound A is an esterified polyol having the formula C(COCOR 3 ) 4 wherein R 3 is a C 10 –C 40 alkyl or a C 10 –C 40 alkenyl group,
whereby the end-capping reagent reacts with at least some of the free hydroxyl end groups of the polycarbonate to produce an end-capped polycarbonate comprising optionally substituted aliphatic ester end groups, and
(ii) forming a molded article from the end-capped polycarbonate produced in step (i).
35. A molded article produced by the method comprising the steps of:
(i) combining a polycarbonate having free terminal OH groups with an end-capping reagent comprising a symmetrical activated carbonate and a compound A, wherein compound A has the structure,
wherein R 1 is selected from the group consisting of a branched C 8 –C 40 alkyl and a linear C 8 –C 40 alkyl; and R 2 is selected from the group consisting of hydrogen, a branched C 3 –C 40 alkyl, a linear C 1 –C 40 alkyl, C 6 –C 30 aryl, and C 7 –C 30 aralkyl group,
or wherein compound A is an esterified polyol having the formula C(COCOR 3 ) 4 wherein R 3 is a C 10 –C 40 alkyl or a C 10 –C 40 alkenyl group,
whereby the end-capping reagent reacts with at least some of the free hydroxyl end groups of the polycarbonate to produce an end-capped polycarbonate comprising optionally substituted aliphatic ester end groups, and
(ii) forming a molded article from the end-capped polycarbonate produced in step (i).