Tunable polymer compositions

• US 8,575,245 B2
• Filed: 12/18/2009
• Issued: 11/05/2013
• Est. Priority Date: 12/23/2008
• Status: Active Grant

• Current Assignee: Novomer, Inc (Danimer Scientific, Inc.)
• Original Assignee: Novomer, Inc (Danimer Scientific, Inc.)
• Inventors: LaPointe, Robert E., Allen, Scott D., Conuel, Jeffrey R.
• Primary Examiner(s): USELDING, JOHN E
• Application Number:
  US13/141,532
• Publication Number:
  US 20110257296A1
• Time in Patent Office: 1,418 Days
• Field of Search: 524/238, 524/106, 524/122, 524/177
• US Class Current: 524/106
• CPC Class Codes: C08G 64/0208 saturated
• CPC Class Codes: C08G 64/183 containing polyether sequences
• CPC Class Codes: C08G 64/34 and cyclic ethers
• CPC Class Codes: C08K 5/19 Quaternary ammonium compounds
• CPC Class Codes: C08L 69/00 Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Abstract

The present invention provides polycarbonate compositions having a tunable decomposition temperature. Suitable cationic additives (e.g., phosphonium, phosphazene, quaternary ammonium, guanidinium, pyridinium, arsonium, etc.) are disclosed for lowering the decomposition temperature of polymer compositions. The invention further provides methods of preparing such polymer compositions with tunable decomposition temperatures.

Claims

1. A polymer composition, comprising:

a) a polymer selected from the group consisting of;

2. The polymer composition of claim 1, wherein the polymer contains at least 98 mole percent of the polymer repeat unit:

3. The polymer composition of claim 1, wherein the polymer comprises poly(propylene carbonate).

4. The polymer composition of claim 3, wherein the poly(propylene carbonate) has a molecular weight in the range of about 10,000 to about 400,000 g/mol.

5. The polymer composition of claim 4, wherein the poly(propylene carbonate) has a molecular weight in the range of about 50,000 to about 250,000 g/mol.

6. The polymer composition of claim 3, wherein the poly(propylene carbonate) has a polydispersity index less than 1.5.

7. The polymer composition of claim 3, wherein the poly(propylene carbonate) has a polydispersity index less than 1.2.

8. The polymer composition of claim 2, wherein the polymer comprises a copolymer of carbon dioxide and one or more epoxides selected from the group consisting of:

ethylene oxide, propylene oxide, 1,2-butene oxide, 2,3-butene oxide, butadiene monoepoxide, 1,2-pentene oxide, epichlorohyrin, 1,2-epoxy-2-methylpropane, glycidyl ether, glycidyl ester, 1,2-hexene oxide, C_7-30 alpha olefin epoxide, cyclopentene oxide, cyclohexene oxide, 4-vinyl cyclohexene oxide, 4-ethyl cyclohexene oxide, styrene oxide, limonene oxide, norbornene oxide, cyclooctene oxide, 1,2,5,6-diepoxycyclooctane, and cyclooctadiene monoepoxide.

9. The polymer composition of claim 1, wherein the presence of the additive lowers the decomposition temperature of the polymer composition.

10. The polymer composition of claim 9, wherein the organic cation comprises a protonated amine species.

11. The polymer composition of claim 9, wherein the organic cation comprises a quaternary ammonium species.

12. The polymer composition of claim 9, wherein the organic cation is selected from the group consisting of:

13. The polymer composition of claim 12, wherein the additive is of the formula:

14. The polymer composition of claim 13, wherein each occurrence of R⁵¹ is C_1-6 aliphatic.

15. The polymer composition of claim 14, wherein each occurrence of R⁵¹ is butyl.

16. The polymer composition of claim 13, wherein the additive is a tetraalkylammonium carboxylate.

17. The polymer composition of claim 13, wherein the additive is selected from the group consisting of:

tetramethylammonium formate, tetramethylammonium acetate, tetramethylammonium trifluoroacetate, tetramethylammonium propionate, tetramethylammonium butyrate, tetramethylammonium benzoate, tetraethylammonium formate, tetraethylammonium acetate, tetraethylammonium trifluoroacetate, tetraethylammonium propionate, tetraethylammonium butyrate, tetraethylammonium benzoate, tetrapropylammonium formate, tetrapropylammonium acetate, tetrapropylammonium trifluoroacetate, tetrapropylammonium propionate, tetrapropylammonium butyrate, tetrapropylammonium benzoate, tetrabutylammonium formate, tetrabutylammonium acetate, tetrabutylammonium trifluoroacetate, tetrabutylammonium propionate, tetrabutylammonium butyrate, tetrabutylammonium benzoate, benzyltrimethylammonium formate, benzyltrimethylammonium acetate, benzyltrimethylammonium trifluoroacetate, decyltrimethylammonium formate, decyltrimethylammonium acetate, decyltrimethylammonium trifluoroacetate, ethyltrimethylammonium formate, ethyltrimethylammonium acetate, ethyltrimethylammonium trifluoroacetate, tetrahexylammonium formate, tetrahexylammonium acetate, tetrahexylammonium trifluoroacetate, tetrapentylammonium formate, tetrapentylammonium acetate, tetrapentylammonium trifluoroacetate, tetrapropylammonium formate, tetrapropylammonium acetate, tetrapropylammonium trifluoroacetate, tributylmethylammonium formate, tributylmethylammonium acetate, tributylmethylammonium trifluoroacetate trimethylphenylammonium formate, trimethylphenylammonium acetate, and trimethylphenylammonium trifluoroacetate.

18. The polymer composition of claim 1, wherein the additive is present at a concentration in the range of about 100 to 1500 ppm by weight.

19. The polymer composition of claim 18, wherein the additive is present at a concentration in the range of about 500 to 1500 ppm by weight.

20. The polymer composition of claim 1, wherein the onset temperature of the polymer composition is in the range of about 100°

C. to about 220°

C.

21. The polymer composition of claim 20, wherein the onset temperature is in the range of about 120°

C. to about 200°

C.

22. The polymer composition of claim 21, wherein the onset temperature is in the range of about 120°

C. to about 180°

C.

23. The polymer composition of claim 22, wherein the onset temperature is in the range of about 120°

C. to about 160°

C.

24. The polymer composition of claim 23, wherein the onset temperature is in the range of about 130°

C. to about 150°

C.

25. The polymer composition of claim 21, wherein the onset temperature is in the range of about 150°

C. to about 180°

C.

26. The polymer composition of claim 22, wherein the onset temperature is in the range of about 180°

C. to about 200°

C.

27. The polymer composition of claim 1, wherein the polymer composition is substantially free of metals.

28. The polymer composition of claim 1, wherein the polymer composition is substantially free of transition metals.

29. The polymer composition of claim 1, wherein the polymer composition is substantially free of cobalt.

30. The polymer composition of claim 1, wherein the polymer composition comprises cobalt in an amount less than 10 ppm.

39. The polymer composition of claim 30, wherein the polymer composition comprises cobalt in an amount less than 3 ppm.

40. The polymer composition of claim 39, wherein the polymer composition comprises cobalt in an amount less than 1 ppm.

41. The polymer composition of claim 1, wherein the polymer composition comprises transition metals in an amount less than 1 ppm.

42. The polymer composition of claim 13, wherein each occurrence of R⁵¹ is hydrogen.

43. The polymer composition of claim 1, wherein each occurrence of R^b, R^c, and R^d is hydrogen.

44. The polymer composition of claim 43, wherein each occurrence of R^a is optionally substituted C_1-12 aliphatic.

31. A method for modulating the decomposition temperature of a polymer composition, the method comprising:

a) providing a polymer selected from the group consisting of;

32. The method of claim 31, wherein the additive is characterized in that it lowers the decomposition temperature of the resulting polymer composition relative to the polymer composition lacking the additive.

33. The method of claim 31, wherein the polymer composition is substantially free of metal.

34. The method of claim 31, wherein the polymer contains at least 98 mole percent of the polymer repeat unit:

35. The method of claim 31, wherein the additive is present at a concentration in the range of about 100 to 1500 ppm by weight.

36. The method of claim 31, wherein the additive is other than bis(triphenylphosphoranylidene)ammonium chloride.

37. The method of claim 34, wherein the additive is of the formula:

38. The method of claim 37, wherein each occurrence of R⁵¹ is C_1-6 aliphatic.