Alpha, omega-allyl terminated linear poly(methacrylic acid) macromonomers for end-linked hydrogels and method of preparation

• US 20050113543A1
• Filed: 10/28/2004
• Published: 05/26/2005
• Est. Priority Date: 06/03/2002
• Status: Abandoned Application

• Current Assignee: Trustees Of Columbia University In The City Of New York (Columbia University)
• Original Assignee: Trustees Of Columbia University In The City Of New York (Columbia University)
• Inventors: Turro, Nicholas J., Vojtova, Lucy, Koberstein, Jeffrey T.
• Application Number:
  US10/975,772
• Publication Number:
  US 20050113543A1
• Time in Patent Office: Days
• US Class Current: 526/318
• CPC Class Codes: C08F 120/18 with acrylic or methacrylic acids
• CPC Class Codes: C08F 2438/01 Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
• CPC Class Codes: C08F 290/046 Polymers of unsaturated carboxylic acids or derivatives thereof
• CPC Class Codes: C08F 8/00 Chemical modification by after-treatment graft polymers, block polymers, crosslinking with unsaturated monomers or with polymers C08F251/00 - C08F299/00; of conjugated diene rubbers C08C
• CPC Class Codes: C08F 8/12 Hydrolysis

Abstract

Disclosed is a method for making α,ω-allyl terminated macromonomers comprising a plurality of units of an α,β-unsaturated carboxylic acid. The method comprises forming a first mixture containing an ester of an α,β-unsaturated carboxylic acid, a radical initiator comprising an allyl group and a halogen, and a catalyst comprising a transition metal complex. The ester of the α,β-unsaturated carboxylic acid is an ester capable of reacting with a mixture comprising trifluoroacetic acid (TFA) to form the α,β-unsaturated carboxylic acid. The mixture is stirred to form a second mixture containing an α-allyl, ω-halogen-terminated macromonomer comprising a plurality of units of the ester of the α,β-unsaturated carboxylic acid. A third mixture comprising a compound containing at least one transferable allyl group is then added to the second mixture to form a fourth mixture containing a first α,ω-allyl terminated macromonomer comprising a plurality of units of the ester of the α,β-unsaturated carboxylic acid. The first α,ω-allyl terminated macromonomer is separated from the fourth mixture and is mixed with a mixture containing TFA to form a fifth mixture containing the α,ω-allyl terminated macromonomer comprising a plurality of units of the α,β-unsaturated carboxylic acid. The α,ω-allyl terminated macromonomer comprising a plurality of units of the α,β-unsaturated carboxylic acid is then separated from the fifth mixture. Also enclosed is a related method for making end-linked hydrogels comprising a plurality of units of an α,β-unsaturated carboxylic acid. The method comprises forming a first mixture containing an α,ω-allyl terminated macromonomer comprising a plurality of units of the α,β-unsaturated carboxylic acid and a radical initiator. The first mixture is treated with UV-radiation, visible light, or heat to form a second mixture comprising an end-linked hydrogel comprising a plurality of units of the α,β-unsaturated carboxylic acid.

Claims

1. A method for making an α

,ω

-allyl-terminated macromonomer comprising a plurality of units of an α

,β

-unsaturated carboxylic acid, the method comprising;

(a) forming a first mixture containing an ester of an α

,β

-unsaturated carboxylic acid, a radical initiator comprising an allyl group and a halogen, and a catalyst comprising a transition metal complex, wherein the ester is capable of reacting with a mixture containing trifluoroacetic acid to form the α

,β

-unsaturated carboxylic acid;

(b) stirring the first mixture to form a second mixture containing an α

-allyl,ω

-halogen terminated macromonomer comprising a plurality of units of the ester of the α

,β

-unsaturated carboxylic acid;

(c) adding to the second mixture a third mixture containing a compound having at least one transferable allyl group to form a fourth mixture containing an α

,ω

-allyl terminated macromonomer comprising a plurality of units of the ester of the α

,β

-unsaturated carboxylic acid;

(d) separating the α

,ω

-allyl terminated macromonomer formed in step (c) from the fourth mixture;

(e) mixing the α

,ω

-allyl terminated macromonomer formed in step (c) with a mixture containing trifluoroacetic acid to form a fifth mixture containing an α

,ω

-allyl terminated macromonomer comprising a plurality of units of the α

,β

-unsaturated carboxylic acid; and

(f) separating the α

,ω

-allyl terminated macromonomer formed in step (e) from the fifth mixture.

2. The method of claim 1, wherein the α

,ω

-allyl terminated macromonomer formed in step (e) has a molecular weight between about 1,000 and about 10,000.

3. The method of claim 1, wherein the α

,β

-unsaturated carboxylic acid is an α

,β

-unsaturated carboxylic acid having a C_β

═

C_α

double bond which is polymerizable.

4. The method of claim 3, wherein the α

,β

-unsaturated carboxylic acid is selected from the group consisting of acrylic acid and methacrylic acid.

5. The method of claim 4, wherein the α

,β

-unsaturated carboxylic acid is methacrylic acid.

6. The method of claim 1, wherein the ester of the α

,β

-unsaturated carboxylic acid comprises the group having the formula III

7. The method of claim 6, wherein the ester of the α

,β

-unsaturated carboxylic acid is selected from the group consisting of t-butyl methacrylate and phenylmethyl methacrylate.

8. The method of claim 7, wherein the radical initiator is allyl-2-bromoisobutyrate.

9. The method of claim 1, wherein the transition metal complex is a complex of a transition metal selected from the group consisting of molybdenum, chromium, rhenium, ruthenium, iron, rhodium, nickel, palladium and copper.

10. The method of claim 1, wherein the transition metal complex comprises a ligand selected from the group consisting of amines, phosphines, arenes, and monovalent anions.

11. The method of claim 10, wherein the ligand is selected from the group consisting of C₆H₄(CH₂NMe₂)₂, 2,6-bis[(dimethylamino)methyl]pyridine, N(nBu)₃, phenanthroline, substituted or unsubstituted picolylamine, N,N,N′

,N′

,N″

,N″

-hexamethyltriethylenetetraamine, P(nBu)₃, triphenylphosphine, isopropyltoluene, indenyl, cyclopentadienyl, chloride, bromide, and iodide.

12. The method of claim 1, wherein the transition metal complex is selected from copper bromide and a complex of copper bromide and N,N,N′

,N′

,N″

,N″

-hexamethyltriethylenetetraamine in a 1;

1 molar ratio.

13. The method of claim 1, wherein the compound containing at least one transferable allyl group is an allylmetal.

14. The method of claim 13, wherein the allylmetal is allyltributyltin.

15. The method of claim 1, wherein the first mixture contains an organic solvent.

16. The method of claim 15, wherein the organic solvent is selected from the group consisting of acetone, benzene and tetrahydrofuran.

17. The method of claim 16, wherein the organic solvent is selected from one of tetrahydrofuran and benzene, and the stirring in step (b) is carried out at a temperature of about 60°

C.

18. The method of claim 16, wherein the organic solvent is acetone and the stirring in step (b) is carried out at a temperature of about 50°

C.

19. The method of claim 15, wherein the ester of the α

,β

-unsaturated carboxylic acid and the organic solvent are present in the first mixture in a ratio of about 2;

1 by volume.

20. The method of claim 1, wherein the first mixture does not contain a solvent.

21. The method of claim 1, wherein the ester of the α

,β

-unsaturated carboxylic acid, the radical initiator, and the catalyst comprising a transition metal complex are in a molar concentration ratio of 50;

1;

0.5.

22. The method of claim 21, wherein stirring in step (b) is carried out at a temperature ranging from about 50 °

C. to about 60°

C.

23. An α

,ω

-allyl terminated macromonomer comprising a plurality of units of an α

,β

-unsaturated carboxylic acid.

24. The macromonomer of claim 23, wherein the macromonomer has a molecular weight between about 1,000 and about 10,000.

25. A method for making a macromonomer comprising a plurality of units of an α

,β

-unsaturated carboxylic acid, the method comprising

(a) mixing a macromonomer comprising a plurality of units of an ester of the α

,β

-unsaturated carboxylic acid with a first mixture comprising trifluoroacetic acid to form a second mixture comprising the macromonomer comprising a plurality of units of the α

,β

-unsaturated carboxylic acid; and

(b) separating the macromonomer comprising a plurality of units of the α

,β

-unsaturated carboxylic acid from the second mixture.

26. The method of claim 25, wherein the macromonomer has a molecular weight between about 1,000 and about 10,000.

27. A method for making end-linked hydrogels comprising a plurality of units of an α

,β

-unsaturated carboxylic acid, the method comprising;

(a) forming a first mixture containing an α

,ω

-allyl terminated macromonomer comprising a plurality of units of the α

,β

-unsaturated carboxylic acid and a radical initiator; and

(b) treating the first mixture with at least one of UV-radiation, visible light, and heat to form a second mixture containing the end-linked hydrogel comprising a plurality of units of the α

,β

-unsaturated carboxylic acid.

28. The method of claim 27, wherein the first mixture does not contain water.

29. The method of claim 28, wherein the first mixture does not contain a solvent.

30. The method of claim 27, wherein the hydrogel comprises a plurality of crosslinked sites which define segments comprising a plurality of units of the α

,β

-unsaturated carboxylic acid.

31. The method of claim 30, wherein each segment has a molecular weight between about 1,000 and about 10,000.

32. The method of claim 27, wherein the α

,β

-unsaturated carboxylic acid is an α

,β

-unsaturated carboxylic acid having a C_β

═

C_α

double bond which is polymerizable.

33. The method of claim 32, wherein the α

,β

-unsaturated carboxylic acid is selected from the group consisting of acrylic acid and methacrylic acid.

34. The method of claim 27, wherein the first mixture is heated to a temperature of maintained at about 60°

C., and the radical initiator is 2,2′

-azobis(2-methyl-propionitrile).

35. The method of claim 27, wherein the first mixture is treated with ultraviolet radiation having a wavelength between 356 nm and 514 nm and the radical initiator is 2,2-dimethoxy-2-phenyl acetophenone.

36. The method of claim 27, wherein the first mixture is treated with visible light, and the radical initiator is selected from the group consisting of ethyl eosin and eosin Y, and wherein the first mixture further comprises a nitrogen based compound.

37. An end-linked hydrogel comprising a plurality of units of an α

,β

-unsaturated carboxylic acid, prepared by the method comprising;

(a) forming a first mixture comprising an α

,ω

-allyl terminated macromonomer comprising a plurality of units of the α

,β

-unsaturated carboxylic acid and a radical initiator; and

(b) treating the first mixture with at least one of UV-radiation, visible light, and heat to form a second mixture containing the end-linked hydrogel comprising a plurality of units of the α

,β

-unsaturated carboxylic acid.

38. The method of claim 37, wherein the first mixture further comprises a solvent selected from one of an organic solvent and water.

39. The method of claim 37, wherein the hydrogel comprises a plurality of crosslinked sites which define segments comprising a plurality of units of the α

,β

-unsaturated carboxylic acid.

40. The method of claim 39, wherein each segment has a molecular weight between about 1,000 and about 10,000.

41. A method for making end-linked hydrogels comprising a plurality of units of an α

,β

-unsaturated carboxylic acid, the method comprising;

(a) forming a first mixture containing an α

,ω

-allyl terminated macromonomer comprising a plurality of units of an ester of the α

,β

-unsaturated carboxylic acid and a radical initiator, wherein the ester is capable of reacting with a mixture comprising trifluoroacetic acid to form the α

,β

-unsaturated carboxylic acid;

(b) treating the first mixture with at least one of UT-radiation, visible light, and heat to form a second mixture containing an end-linked gel comprising a plurality of units of the ester of the α

,β

-unsaturated carboxylic acid;

(c) mixing the end-linked gel with a mixture comprising trifluoroacetic acid to form a third mixture containing the hydrogel comprising a plurality of units of the α

,β

-unsaturated carboxylic acid; and

(d) separating the end-linked hydrogel formed in step (c) from the third mixture.

42. The method of claim 41, wherein the first mixture further contains a solvent selected from an one of an organic solvent and water.

43. The method of claim 41, wherein the hydrogel formed in step (c) comprises a plurality of crosslinked sites which define segments comprising a plurality of units of the α

,β

-unsaturated carboxylic acid.

44. The method of claim 43, wherein each segment has a molecular weight between about 1,000 and about 10,000.

45. A method for coating a surface with a hydrogel comprising a plurality of units of an α

,β

-unsaturated carboxylic acid, comprising;

(a) coating the surface with a first mixture containing an α

,ω

-allyl terminated macromonomer comprising a plurality of units of the;

α

,β

-unsaturated carboxylic acid and a radical initiator; and

(b) treating the coating of the first mixture on the surface with one of UV-radiation, visible light, and heat to form a coating comprising the end-linked hydrogel having a plurality of units of the α

,β

-unsaturated carboxylic acid.

46. A surface coated with an end-linked hydrogel comprising a plurality of units of an α

,β

-unsaturated carboxylic acid, wherein the surface is prepared by the method comprising;

(a) coating the surface with a first mixture containing an α

,ω

-allyl terminated macromonomer comprising a plurality of units of the α

,β

-unsaturated carboxylic acid and a radical initiator; and

(b) treating the coating of the first mixture on the surface with one of UV-radiation, visible light, and heat to form a coating comprising the end-linked hydrogel having a plurality of units of the α

,β

-unsaturated carboxylic acid.

47. A method for coating a surface with a hydrogel comprising a plurality of units of an α

,β

-unsaturated carboxylic acid, comprising;

(a) coating the surface with a first mixture containing an α

,ω

-allyl terminated macromonomer comprising a plurality of units of an ester of the α

,β

-unsaturated carboxylic acid and a radical initiator, wherein the ester is capable of reacting with a mixture comprising trifluoroacetic acid to form the α

,β

-unsaturated carboxylic acid;

(b) treating the coating of the first mixture with at least one of UV-radiation, visible light, and heat to form a coating containing an end-linked gel comprising a plurality of units of the ester of the α

,β

-unsaturated carboxylic acid; and

(c) treating the coating containing the end-linked gel with a mixture comprising trifluoroacetic acid to form a coating containing the hydrogel comprising a plurality of units of the α

,β

-unsaturated carboxylic acid.

48. A surface coated with an end-linked hydrogel comprising a plurality of units of an α

,β

-unsaturated carboxylic acid, wherein the surface is prepared by the method comprising;

(a) coating the surface with a first mixture containing an α

,ω

-allyl terminated macromonomer comprising a plurality of units of an ester of the α

,β

-unsaturated carboxylic acid and a radical initiator, wherein the ester is capable of reacting with a mixture comprising trifluoroacetic acid to form the α

,β

-unsaturated carboxylic acid;

(b) treating the coating of the first mixture with at least one of UV-radiation, visible light, and heat to form a coating containing an end-linked gel comprising a plurality of units of the ester of the α

,β

-unsaturated carboxylic acid; and

(c) treating the coating containing the end-linked gel with a mixture comprising trifluoroacetic acid to form a coating containing the hydrogel comprising a plurality of units of the α

,β

-unsaturated carboxylic acid.