Degradable polymers from derivatized ring-opened epoxides

• US 6,730,772 B2
• Filed: 06/22/2001
• Issued: 05/04/2004
• Est. Priority Date: 06/22/2001
• Status: Expired due to Fees

• Current Assignee: Venkatram P. Shastri
• Original Assignee: Venkatram P. Shastri
• Inventors: Shastri, Venkatram P.
• Primary Examiner(s): SELLERS, ROBERT E
• Application Number:
  US09/886,394
• Publication Number:
  US 20030050426A1
• Time in Patent Office: 1,047 Days
• Field of Search: 528/354, 528/357, 528/359, 528/409, 528/421, 528/370
• US Class Current: 528/354
• CPC Class Codes: C08G 63/664 derived from hydroxy carboxylic acids
• CPC Class Codes: C08G 65/22 Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
• CPC Class Codes: C08L 2205/05 containing polymer components which can react with one another
• CPC Class Codes: C08L 2666/18 Polyesters or polycarbonates according to C08L67/00 - C08L69/00; Derivatives thereof
• CPC Class Codes: C08L 67/00 Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain of polyester-amides C08L77/12; of polyester-imides C08L79/08; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 71/02 Polyalkylene oxides

Abstract

A polymer of a ring-opened functionalized epoxide is formed by the polymerization of a functionalized epoxide monomer having the structure E-CHR-G wherein E represents an epoxide group, R is hydrogen or an alkyl group, and G is a derivatizable group such as an unsaturated functionality or ester substituent.

Claims

1. A copolymer comprising randomly distributed units of a ring-opened functionalized epoxide and a ring-opened cyclic ester, wherein the functionalized epoxide is an epoxide having the composition E-CH₂—

CHR—

C(O)—

X-G, wherein E=

R is hydrogen or alkyl, X is oxygen or nitrogen, and G comprises a derivatizable group.

2. The copolymer of claim 1 wherein the epoxide is functionalized before ring-opening.

3. The copolymer of claim 1 wherein the epoxide is functionalized after polymerization.

4. The copolymer of claim 1, wherein the derivatizable group G is selected from the group consisting of alkyl groups or chains, esters, ethers, sulfonates, carbonates, amino carbonates, carbamates, amides, imides, anhydrides, peptides, lipids, cationic charge carriers, anionic charge carriers, pluronics, PEG, PEO, PPO, urethanes, fatty acids, fatty alcohols, cholesterol, N,N alkyl amines, sugars, and polysaccharides.

5. The copolymer of claim 1 wherein the epoxide is an epoxide of an ester of 2-methyl-pent-4-enoic acid.

6. The copolymer of claim 5 wherein the ester of 2-methyl-pent-4-enoic acid is ethyl-2-methyl-pent-4-enoate [EMP].

7. The copolymer of claim 5 wherein the ester of 2-methyl-pent-4-enoic acid is monomethyl polyethylene oxide-2-methyl-pent-4-enoate [PEG-MP].

8. The copolymer of claim 5 wherein the ester of 2-methyl-pent-4-enoic acid is (2′

-methacryloyl)ethyl-2-methyl-pent-4-enoate [HEMA-MP].

9. The copolymer of claim 1, wherein the ring-opened cyclic ester is selected from one or more of the group consisting of lactide, glycolide, caprolactone, 1,4-dioxan-2-one, and cyclic carbonates.

10. The copolymer of claim 1 wherein the copolymer is degradable.

31. The polymer as in claims 1, 15, 18, or 25, formed by ring-opening copolymerization of a functionalized epoxide and a cyclic ester.

32. The polymer of claim 31, wherein the functionalized epoxide acts as a solvent for the cyclic ester.

33. The polymer as in claims 1, 15, 18, or 25 wherein the polymers each have a polydispersity (M_w/M_n) of less than about 3.5.

34. The polymer as in claims 1, 15, 18, or 25 wherein the polymers each have a polydispersity (M_w/M_n) of less than about 3.0.

35. The polymer as in claims 1, 15, 18, or 25 wherein the polymers each have a polydispersity (M_w/M_n) of less than about 2.5.

36. The polymer as in claims 1, 15, 18, or 25 wherein the polymers each have a polydispersity (M_w/M_n) of less than about 2.0.

11. A method of making a copolymer comprising randomly polymerizing a functionalized epoxide and a cyclic ester, wherein the functionalized epoxide is an epoxide having the composition E-CH₂—

CHR—

C(O)—

X-G, wherein E=

R is hydrogen or alkyl, X is oxygen or nitrogen, and G comprises a derivatizable group.

12. The method of claim 11, wherein the derivatizable group G is selected from the group consisting of alkyl groups or chains, esters, ethers, sulfonates, carbonates, amino carbonates, carbamates, amides, imides, anhydrides, peptides, lipids, cationic charge carriers, anionic charge carriers, pluronics, PEG, PEO, PPO, urethanes, fatty acids, fatty alcohols, cholesterol, N,N alkyl amines, sugars, and polysaccharides.

13. The method of claim 11, wherein the cyclic ester is selected from one or more of the group consisting of lactide, glycolide, caprolactone, 1,4-dioxan-2-one, and cyclic carbonates.

14. The method of claim 11 wherein the copolymer is degradable.

15. The copolymer formed by the method of claim 11.

16. The method of claim 11, wherein randomly polymerizing the functionalized epoxide and cyclic ester further comprises using an initiating system that permits polymerization at a temperature of less than about 100°

C.

17. The method of claim wherein the temperature is less than about 90°

C.

18. A degradable polymer comprising a backbone comprised of randomly distributed ether and ester linkages, having the formula:

19. The degradable polymer of claim 18, wherein the derivatizable group G is selected from the group consisting of alkyl groups or chains, esters, ethers, sulfonates, carbonates, amino carbonates, carbamates, amides, imides, anhydrides, peptides, lipids, cationic charge carriers, anionic charge carriers, pluronics, PEG, PEO, PPO, urethanes, fatty acids, fatty alcohols, cholesterol, N,N alkyl amines, sugars, and polysaccharides.

20. The degradable polymer of claim 18, wherein the derivatizable group G comprises unsaturated functionality.

21. The degradable polymer of claim 18, wherein the unsaturated functionality is chemically or photochemically cured.

22. The degradable polymer of claim 18, wherein the derivatizable group G comprises an ester and unsaturated functionality.

23. The degradable polymer of claim 18, wherein the ester linkage, [O—

(CR₁R₂)_a—

C(O)]_x, is derived from one or more of the group consisting of lactide, glycolide, caprolactone, 1,4-dioxan-2-one, and cyclic carbonates.

24. The degradable polymer of claim 18, wherein the ratio of an average ester linkage block length to a theoretical minimum block length, when no two ether linkages are bound to each other, is approximately one.

25. A degradable polymer comprising a backbone of randomly distributed ether and ester linkages, wherein the ether linkages comprise a functionalized ring-opened epoxide, wherein the functionalized epoxide has the composition E-CH₂—

CHR—

C(O)—

X-G, wherein E=

R is hydrogen or alkyl, X is oxygen or nitrogen, and G comprises a derivatizable group and the ester linkages are derived from one or more of the group consisting of lactide, glycolide, caprolactone, 1,4-dioxan-2-one, and cyclic carbonates.

26. The degradable polymer of claim 25, wherein the derivatizable group is selected from the group consisting of alkyl groups or chains, esters, ethers, sulfonates, carbonates, amino carbonates, carbamates, amides, imides, anhydrides, peptides, lipids, cationic charge carriers, anionic charge carriers, pluronics, PEG, PEO, PPO, urethanes, fatty acids, fatty alcohols, cholesterol, N,N alkyl amines, sugars, and polysaccharides.

27. The degradable polymer of claim 25, wherein the derivatizable group comprises unsaturated functionality.

28. The degradable polymer of claim 27, wherein the unsaturated functionality is chemically or photochemically cured.

29. The degradable polymer of claim 25, wherein the derivatizable group comprises an ester and unsaturated functionality.

30. A copolymer comprising randomly distributed units of a ring-opened functionalized epoxide and a ring-opened cyclic ester, wherein the ratio of an average ring-opened cyclic ester unit block length to a theoretical minimum block length, when no two ring-opened functionalized epoxide units are bound to each other, is approximately one.