Silcone-containing prepolymers

• US 7,691,917 B2
• Filed: 06/14/2007
• Issued: 04/06/2010
• Est. Priority Date: 06/14/2007
• Status: Expired due to Fees

• Current Assignee: Bausch & Lomb Incorporated (Bausch Health Cos., Inc.)
• Original Assignee: Bausch & Lomb Incorporated (Bausch Health Cos., Inc.)
• Inventors: Quinn, Edmond T., Lai, Yu-Chin, Lang, Weihong
• Primary Examiner(s): Gulakowski; Randy
• Assistant Examiner(s): LOEWE, ROBERT S
• Application Number:
  US11/762,970
• Publication Number:
  US 20080312397A1
• Time in Patent Office: 1,027 Days
• Field of Search: 528/26, 528/27, 528/33, 528/35, 523/106, 523/107
• US Class Current: 523/106
• CPC Class Codes: C07F 7/0838 Compounds with one or more Si-O-Si sequences compounds with a ring containing only alternating Si and O atoms, i.e. cyclosilanes C07F7/21
• CPC Class Codes: C08F 283/12 on to polysiloxanes
• CPC Class Codes: C08F 290/068 Polysiloxanes
• CPC Class Codes: C08G 18/0814 containing ammonium groups or groups forming them
• CPC Class Codes: C08G 18/61 Polysiloxanes
• CPC Class Codes: C08G 18/672 Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
• CPC Class Codes: C08G 2210/00 Compositions for preparing hydrogels
• CPC Class Codes: C08G 77/14 containing silicon bound to oxygen-containing groups C08G77/045 takes precedence
• CPC Class Codes: C08G 77/20 containing silicon bound to unsaturated aliphatic groups C08G77/045 takes precedence
• CPC Class Codes: C08G 77/458 containing polyurethane sequences
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 51/085 on to polysiloxanes
• CPC Class Codes: C08L 53/00 Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 53/005 Modified block copolymers
• CPC Class Codes: C08L 83/10 Block- or graft-copolymers containing polysiloxane sequences obtained by polymerising a compound having a carbon-to-carbon double bond on to a polysiloxane C08L51/08, C08L53/00
• CPC Class Codes: G02B 1/043 Contact lenses

Abstract

Prepolymers comprising at least one block of Formula II and terminated with a polymerizable ethylenically unsaturated radical are useful in hydrogel materials are disclosed:

wherein n, R, R¹, R² and X⁺ are as defined herein.

Claims

1. A prepolymer comprising at least one block of Formula II and terminated with a polymerizable ethylenically unsaturated radical:

2. The prepolymer of claim 1, wherein X⁺ is independently a cationic group comprising an ammonium, phosphonium or sulphonium cationic-containing group.

3. The prepolymer of claim 1, wherein R¹ is a C₁-C₁₂ alkylene group optionally substituted with an ether linkage.

4. The prepolymer of claim 1, wherein R is a C₁-C₆ alkyl group.

5. The prepolymer of claim 1, wherein the prepolymer is terminated at two ends with a polymerizable ethylenically unsaturated radical.

6. The prepolymer of claim 1, wherein the polymerizable ethylenically unsaturated radical is of the formula

7. The prepolymer of claim 1, which is of Formula III:

8. The prepolymer of claim 7, wherein each A is independently a polymerizable ethylenically unsaturated radical of the formula

9. The prepolymer of claim 7, wherein x is from 1 to about 20.

10. A copolymer comprising a polymerization product of a monomeric mixture comprising one or more of the prepolymers of claim 7.

11. The copolymer of claim 10, wherein the monomeric mixture further comprises a hydrophilic monomer, hydrophobic monomer or both.

12. The copolymer of claim 11, wherein the hydrophilic monomer is selected from the group consisting of 2-hydroxyethylmethacrylate, 2-hydroxyethylacrylate, glyceryl methacrylate;

N-vinyl pyrrolidone;

N-vinyl-N-methyl acetamide, N,N-dimethyl methacrylamide, N,N-dimethylacrylamide, acrylic acid, methacrylic acid and mixtures thereof.

13. The copolymer of claim 11, wherein the hydrophobic monomer is a silicone-containing monomer having from 1 to about 20 silicon atoms.

14. The copolymer of claim 13, wherein the silicone monomer is 3-methacryloxypropyl tris(trimethylsiloxy)silane.

15. The copolymer of claim 11, wherein the hydrophobic monomer is an aliphatic ring containing monomer selected from the group consisting of isobornyl acrylate, iosbomyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate and combinations thereof.

16. The copolymer of claim 10, having:

a water content of about 30 weight percent and an oxygen permeability greater than about 80 barrers.

17. The copolymer of claim 10, having:

a water content of about 30 to about 60 weight percent, and an oxygen permeability greater than about 110 barrers.

18. A biomedical device comprising a copolymer of claim 10.

19. An ophthalmic lens comprising a copolymer of claim 10.

20. A contact lens comprising a copolymer of claim 10.

21. A hydrogel comprising a hydrated polymerization product of a monomeric mixture comprising one or more of the prepolymers of claim 7.

22. The hydrogel of claim 21, wherein the monomeric mixture further comprises a comonomer.

23. The hydrogel of claim 21, wherein the monomeric mixture further comprises at least one hydrophilic comonomer selected from the group consisting of an unsaturated carboxylic acid, (meth)acrylic substituted alcohol, vinyl lactam, (meth)acrylamide and combinations thereof.

24. A copolymer comprising a polymerization product of a monomeric mixture comprising one or more of the prepolymers of claim 1.

25. The copolymer of claim 24, wherein the monomeric mixture further comprises a hydrophilic monomer, hydrophobic monomer or both.

26. The copolymer of claim 25, wherein the hydrophilic monomer is selected from the group consisting of 2-hydroxyethylmethacrylate, 2-hydroxyethylacrylate, glyceryl methacrylate;

N-vinyl pyrrolidone;

N-vinyl-N-methyl acetamide, N,N-dimethyl methacrylamide, N,N-dimethylacrylamide, acrylic acid, methacrylic acid and combinations thereof.

27. The copolymer of claim 25, wherein the hydrophobic monomer is a silicone-containing monomer having from 1 to about 20 silicon atoms.

28. The copolymer of claim 27, wherein the silicone monomer is 3-methacryloxypropyl tris(trimethylsiloxy)silane.

29. The copolymer of claim 25, wherein the hydrophobic monomer is an aliphatic ring containing monomer selected from the group consisting of isobornyl acrylate, isobornyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate and combinations thereof.

30. The copolymer of claim 24, having:

a water content of about 30 weight percent and an oxygen permeability greater than about 80 barrers.

31. The copolymer of claim 24, having:

a water content of about 30 to about 60 weight percent, and an oxygen permeability greater than about 110 barrers.

32. A biomedical device comprising a copolymer of claim 24.

33. An ophthalmic lens comprising a copolymer of claim 24.

34. A contact lens comprising a copolymer of claim 24.

35. A hydrogel comprising a hydrated polymerization product of a monomeric mixture comprising one or more of the prepolymers of claim 1.

36. The hydrogel of claim 35, wherein the monomeric mixture further comprises a comonomer.

37. The hydrogel of claim 35, wherein the monomeric mixture further comprises at least one hydrophilic comonomer selected from the group consisting of an unsaturated carboxylic acid, (meth)acrylic substituted alcohol, vinyl lactam, (meth)acrylamide and combinations thereof.

38. A prepolymer of Formula IV:

39. The prepolymer of claim 38, wherein X⁺ is independently a cationic group comprising an ammonium, phosphonium or sulphonium cationic group.

40. The prepolymer of claim 38, wherein each A′

is an isocyanate ethyl methacrylate-containing radical.

41. A copolymer comprising a polymerization product of a monomeric mixture comprising one or more of the prepolymers of claim 38.

42. A biomedical device comprising a copolymer of claim 41.

43. An ophthalmic lens comprising a copolymer of claim 41.

44. A contact lens comprising a copolymer of claim 41.

45. The copolymer of claim 41, wherein the monomeric mixture further comprises a hydrophilic monomer, hydrophobic monomer or both.

46. The copolymer of claim 45, wherein the hydrophilic monomer is selected from the group consisting of 2-hydroxyethylmethacrylate, 2-hydroxyethylacrylate, glyceryl methacrylate;

N-vinyl pyrrolidone;

N-vinyl-N-methyl acetamide, N,N-dimethyl methacrylamide, N,N-dimethylacrylamide, acrylic acid, methacrylic acid and combinations thereof.

47. The copolymer of claim 45, wherein the hydrophobic monomer is a silicone-containing monomer having from 1 to about 20 silicon atoms.

48. The copolymer of claim 47, wherein the silicone monomer is 3-methacryloxypropyl tris(trimethylsiloxy)silane.

49. The copolymer of claim 45, wherein the hydrophobic monomer is an aliphatic ring containing monomer selected from the group consisting of isobornyl acrylate, isobornyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate and combinations thereof.

50. A hydrogel comprising a hydrated polymerization product of a monomeric mixture comprising one or more of the prepolymers of claim 38.

51. The hydrogel of claim 50, wherein the monomeric mixture further comprises a comonomer.

52. The hydrogel of claim 50, wherein the monomeric mixture further comprises at least one hydrophilic comonomer selected from the group consisting of an unsaturated carboxylic acid, (meth)acrylic substituted alcohol, vinyl lactam, (meth)acrylamide and combinations thereof.