UV curable crosslinking agents useful in copolymerization

• US 5,449,729 A
• Filed: 02/14/1994
• Issued: 09/12/1995
• Est. Priority Date: 11/05/1991
• Status: Expired due to Term

• Current Assignee: Bausch & Lomb Incorporated (Bausch Health Cos., Inc.)
• Original Assignee: Bausch & Lomb Incorporated (Bausch Health Cos., Inc.)
• Inventors: Lai, Yu-Chin
• Primary Examiner(s): CAIN, EDWARD J
• Application Number:
  US08/195,795
• Time in Patent Office: 575 Days
• Field of Search: 526/286, 526/301, 526/302, 526/304, 526/320
• US Class Current: 526/286
• CPC Class Codes: C07C 233/20 having the carbon atom of the carboxamide group bound to a carbon atom of an acyclic unsaturated carbon skeleton
• CPC Class Codes: C07C 271/12 to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
• CPC Class Codes: C07C 271/44 to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
• CPC Class Codes: C07C 275/50 Y being a hydrogen or an acyclic carbon atom
• CPC Class Codes: C07C 327/30 having sulfur atoms of esterified thiocarboxyl groups bound to carbon atoms of hydrocarbon radicals substituted by nitrogen atoms, not being part of nitro or nitroso groups
• CPC Class Codes: C07C 69/96 Esters of carbonic or haloformic acids
• CPC Class Codes: C07F 7/0803 Compounds with Si-C or Si-Si linkages
• 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 246/00 Copolymers in which the nature of only the monomers in minority is defined
• CPC Class Codes: C08F 290/068 Polysiloxanes
• CPC Class Codes: G02B 1/043 Contact lenses

Abstract

A novel class of compounds are disclosed which may be used as novel crosslinking agents for acrylic-containing, vinyl-containing and/or styrene-containing hydrophilic monomers to prepare novel UV-curable hydrophilic copolymers suitable for use as biomedical articles, especially contact lenses.

Claims

1. A composition prepared by polymerizing a monomer mix comprising at least one acrylic-containing monomer, at least one vinyl-containing monomer and a crosslinking agent having the schematic representation:

##STR15## wherein V denotes a vinyl-containing group having the formula;

##STR16## A'"'"' denotes an acrylic-containing group having the formula;

##STR17## S denotes a styrene-containing group having the formula;

##STR18## wherein R₁, is an alkyl radical derived from substituted and unsubstituted hydrocarbons, polyalkylene oxide, poly(perfluoro) alkylene oxide, dialkyl-capped polydimethylsiloxane, dialkyl-capped polydimethylsiloxane modified with fluoroalkyl or fluoroether groups;

R₂,-R₁₀, are independently H, or alkyl of 1 to 5 carbon atoms;

Q is an organic group containing aromatic moieties having 6-30 carbon atoms;

X, Y, and Z are independently O, NH or S;

v'"'"' is 1, or higher; and

a'"'"', s'"'"' are independently greater than or equal to 0, and a'"'"'+s'"'"' is greater than or equal to 1.

4. The composition of claim 1 wherein said acrylic-containing monomer is comprised of at least one (meth) acrylate group.

5. The composition of claim 1 wherein said acrylic-containing monomer is comprised of at least one alkyl (meth) acrylate group.

6. The composition of claim 1 wherein said acrylic-containing monomer is comprised of at least one fluoroalkyl (meth)acrylate group.

7. The composition of claim 1 wherein said acrylic-containing monomer is 2-hydroxyethyl methacrylate.

8. The composition of claim 1 wherein said acrylic-containing monomer is glycerol methacrylate.

9. The composition of claim 1 wherein said acrylic-containing monomer is comprised of at least one (meth)acrylamide group.

10. The composition of claim 9 wherein said (meth)acrylamide is N,N-dimethyl acrylamide.

11. The composition of claim 1 wherein said vinyl-containing monomer is selected from the group consisting of N-vinyl pyrrolidone, alkyl vinyl carbonate, alkylvinyl-carbamate, fluoroalkyl vinyl carbonate, and fluoroalkyl vinylcarbamate.

12. The composition of claim 1 wherein said crosslinking agent is selected from the group consisting of methacryloxyethyl vinyl carbonate, methacryloxyethyl vinyl carbamate, and methacryloxyethyl vinyl urea.

14. The composition of claim 1 wherein said composition comprises methylmethacrylate, N-vinyl pyrrolidone and methacryloxyethyl vinyl carbonate.

15. The composition of claim 1 wherein said composition comprises 2-hydroxyethyl methacrylate, N-vinyl pyrrolidone and methacryloxyethyl vinyl carbonate.

16. The composition of claim 1 wherein said composition is oxygen permeable.

17. The composition of claim 1 wherein said composition is curable by ultraviolet radiation and heat.

18. The composition of claim 1 wherein said composition is curable by ultraviolet radiation.

19. A biomedical device made from the composition of claim 1.

20. A contact lens made from the composition of claim 1.

21. The composition of claim 1 wherein said composition comprises N-vinyl pyrrolidone, said crosslinking agent, and an acrylic-containing monomer further comprised of at least one (meth)acrylate-capped or (meth)acrylamide-capped monomer.

22. The composition of claim 21 wherein said monomer is a poly(organosiloxane) prepolymer represented by the formula:

##STR27## wherein;

A is an activated unsaturated group, selected from an ester or amide of an acrylic or a methacrylic acid;

each R³ -R⁶ is independently selected from the group consisting of a monovalent hydrocarbon radical or a halogen substituted monovalent hydrocarbon radical having 1 to 18 carbon atoms which may have ether linkages between carbon atoms;

R⁷ is a divalent hydrocarbon radical having from 1 to 22 carbon atoms; and

n is 0 or an integer greater than or equal to 1.

23. The composition of claim 21 wherein said monomer is a polyalkylene ether.

24. The composition of claim 21 wherein said monomer is a polyfluorinated ether.

25. The composition of claim 21 wherein said composition further comprises at least one (meth)acrylate or (meth)acrylamide monomer.

26. The composition of claim 25 wherein said (meth)acrylate monomer is an alkyl methacrylate monomer.

27. The composition of claim 25 wherein said (meth)acrylate monomer is a fluoroalkyl methacrylate monomer.

28. The composition of claim 25 wherein said (meth)acrylate monomer is a polysiloxanylalkyl methacrylate monomer.

29. The composition of claim 25 wherein said (meth)acrylamide monomer is N,N-dimethyl acrylamide.

30. The composition of claim 21 wherein said crosslinking agent is selected from the group consisting of methacryloxyethyl vinyl carbonate, methacryloxyethyl vinyl carbamate, methacryloxyethyl vinyl urea, 4-vinylphenyl vinyl carbonate, 4-vinylphenyl vinyl carbamate, and is 4-vinylphenyl vinyl urea.

31. The composition of claim 21 wherein said composition is oxygen permeable.

32. A biomedical device made from the composition of claim 21.

33. A contact lens made from the composition of claim 21.

2. A composition prepared by polymerizing a monomer mix comprising at least one acrylic-containing monomer, at least one vinyl-containing monomer, at least one styrene-containing monomer and a crosslinking agent having the schematic representation:

##STR19## wherein V denotes a vinyl-containing group having the formula;

##STR20## A'"'"' denotes an acrylic-containing group having the formula;

##STR21## S denotes a styrene-containing group having the formula;

##STR22## wherein R₁, is an alkyl radical derived from substituted and unsubstituted hydrocarbons, polyalkylene oxide, poly(perfluoro) alkylene oxide, dialkyl-capped polydimethylsiloxane, dialkyl-capped polydimethylsiloxane modified with fluoroalkyl or fluoroether groups;

R₂,-R₁₀, are independently H, or alkyl of 1 to 5 carbon atoms;

Q is an organic group containing aromatic moieties having 6-30 carbon atoms;

X, Y, and Z are independently O, NH or S;

v'"'"' is 1, or higher; and

a'"'"', s'"'"' are independently greater than or equal to 0, and a'"'"'+s'"'"' is greater than or equal to 1.

42. The composition of claim 35 2 wherein said polysiloxane-containing monomer further comprises at least one fluoroether-containing group.

3. A composition prepared by polymerizing a monomer mix comprising at least one styrene-containing monomer, at least one vinyl-containing monomer and a crosslinking agent having schematic representation:

##STR23## wherein V denotes a vinyl-containing group having the formula;

##STR24## A'"'"' denotes an acrylic-containing group having the formula;

##STR25## S denotes a styrene-containing group having the formula;

##STR26## wherein R₁, is an alkyl radical derived from substituted and unsubstituted hydrocarbons, polyalkylene oxide, poly(perfluoro) alkylene oxide, dialkyl-capped polydimethylsiloxane, dialkyl-capped polydimethylsiloxane modified with fluoroalkyl or fluoroether groups;

R₂,-R₁₀, are independently H, or alkyl of 1 to 5 carbon atoms;

Q is an organic group containing aromatic moieties having 6-30 carbon atoms;

X, Y, and Z are independently O, NH or S;

v'"'"' is 1, or higher; and

a'"'"', s'"'"' are independently greater than or equal to 0, and a'"'"'+s'"'"' is greater than or equal to 1.

13. The composition of claim 3 wherein said crosslinking agent is selected from the group consisting of 4-vinylphenyl vinyl carbonate, 4-vinylphenyl vinyl carbamate, and 4-vinylphenyl vinyl urea.

34. A composition prepared by polymerizing the monomer mix comprising at least one (meth)acrylate-capped or (meth)acrylamide-capped polysiloxane-containing monomer, at least one vinyl-containing monomer, and at least one crosslinking agent of the schematic representation:

##STR28## wherein V denotes a vinyl-containing group having the formula;

##STR29## A'"'"' denotes an acrylic-containing group having the formula;

##STR30## S denotes a styrene-containing group having the formula;

##STR31## wherein R₁, is an alkyl radical derived from substituted and unsubstituted hydrocarbons, polyalkylene oxide, poly(perfluoro) alkylene oxide, dialkyl-capped polydimethylsiloxane, dialkyl-capped polydimethylsiloxane modified with fluoroalkyl or fluoroether groups;

R₂,-R₁₀, are independently H, or alkyl of 1 to 5 carbon atoms;

Q is an organic group containing aromatic moieties having 6-30 carbon atoms;

X, Y, and Z are independently O, NH or S;

v'"'"' is 1, or higher; and

a'"'"', s'"'"' are independently greater than or equal to 0, and a'"'"'+s'"'"' is greater than or equal to 1.

35. The composition of claim 34 wherein said polysiloxane-containing monomer is a polyurethane siloxane prepolymer.

36. The composition of claim 34 wherein said polyurethane-siloxane is represented by the following schematic representations:

space="preserve" listing-type="equation">E(*D*A"D*G)a*D*A"D*E*;

or

space="preserve" listing-type="equation">E(*D*G*D*A".sub.a *D*G*D*E'"'"';

where

D denotes an alkyl diradical, an alkyl cycloalkyl diradical, a cycloalkyl diradical, an aryl diradical or an alkylaryl diradical having 6 to 30 carbon atoms;

G denotes an alkyl diradical, a cycloalkyl diradical, an alkyl cycloalkyl diradical, an aryl diradical or an alkylaryl diradical having 1 to 40 carbon atoms and which may contain ether, thio or amine linkages in the main chain;

* denotes a urethane or ureido linkage;

a is at least 1;

a" denotes a divalent polymeric radical of formula;

##STR32## wherein;

R^s and R^s'"'"' independently denote an alkyl or fluoro-substituted alkyl group having 1 to 10 carbon atoms which may contain ether linkages between carbon atoms;

m is at least 1; and

p provides a moiety weight of 400 to 10,000;

E and E'"'"' independently denote a polymerizable unsaturated organic radical represented by formula;

##STR33## wherein;

R¹⁴ denotes a divalent alkylene radical having 1 to 10 carbon atoms;

R¹² denotes H or CH₃ ;

R¹³ denotes H, a (C₁ -C₆) alkyl radical or a --CO--Y--R¹⁵ group wherein Y is --O--, --S-- or --NH-- and R¹⁵ is a alkyl radical having 1 to 12 carbon atoms;

X is --CO-- or --OCO--;

Z is --O-- or --NH--;

Ar denotes an aromatic radical having 6 to 30 carbon atoms;

w is 0 to 6;

x is 0 or 1;

y is 0 or 1; and

z is 0 or 1.

37. The composition of claim 36 wherein said polyurethane-siloxane prepolymer is m methacrylate-based urethane prepolymer represented by the formula:

##STR34## wherein;

R¹⁶ is a diradical of a diisocyanate after removal of the isocyanate group, and is most preferably the diradical of isophorone diisocyanate, and m, p and a are the same as previously defined.

38. The composition of claim 34 wherein said vinyl-containing monomer is N-vinylpyrrolidone.

39. The composition of claim 38 wherein said composition may further comprise a (meth)acrylate- or (meth)acrylamide-capped wetting monomer.

40. The composition of claim 39 wherein said (meth)acrylate-containing monomer is selected from the group consisting of derivatives of alkyl methacrylate, 2-hydroxyethyl methacrylate, glycerol methacrylate, polysiloxanylalkyl methacrylate and fluoroalkyl methacrylate.

41. The composition of claim 35 wherein said polysiloxane-containing monomer further comprises at least one fluoroalkyl-containing group.

43. The composition of claim 35 wherein said polysiloxane-containing monomer further comprises at least one alcohol-containing group.

44. The composition of claim 39 wherein said (meth) acrylamide-capped wetting monomer is N ,N-dimethyl acrylamide or its derivative.

45. The composition of claim 39 wherein said (meth)acrylate-capped wetting monomer is methacrylic acid.

46. The composition of claim 35 wherein said polysiloxane-containing monomer is a bulky polysiloxanylalkyl (meth)acrylic monomer represented by the formula:

##STR35## wherein;

X is O or NR;

each R is independently hydrogen or methyl; and

each R¹ is independently a lower alkyl or phenyl group; and

f is 1 or 3 to 10.

47. The composition of claim 46 wherein said bulky polysiloxanylalkyl (meth)acrylate monomer is selected from the group consisting of methacryloxypropyl tris(trimethylsiloxy)silane, pentamethyldisiloxanylmethylmethacrylate, tris(trimethylsiloxy)methacryloxy propylsilane, phenyltetramethyldisiloxanylethyl acetate, and methyldi(trimethylsiloxy)methacryloxymethyl silane.

48. The composition of claim 34 wherein said vinyl-containing monomer is 2-vinyl-4,4-dimethyl-2-oxazolin-5-one.

49. The composition of claim 34 wherein said vinyl-containing monomer is selected from the group consisting of polysiloxanylalkylvinyl carbonates, polysiloxanylalkylvinyl carbamates, polysiloxanylalkylvinyl ureas, carboxylic acid-containing vinyl carbonates, carboxylic acid-containing vinyl carbamates, and carboxylic acid-containing vinyl ureas.

50. The composition of claim 34 wherein said vinyl-containing monomer is a vinyl-containing polysiloxane prepolymer.

51. The composition of claim 50 wherein said vinyl-containing polysiloxane prepolymer is a silicone-containing vinyl carbonate or vinyl carbamate monomer represented by the formula:

##STR36## wherein;

Y'"'"' denotes --O--, --S-- or --NH--;

R^Si denotes a silicone-containing organic radical having the formula;

##STR37## wherein;

R¹⁰ denotes ##STR38## wherein p'"'"' is 1 to 6;

R¹¹ denotes an alkyl radical or a fluoroalkyl radical with 1 to 6 carbon atoms;

e is 1 to 200;

n'"'"' is 1, 2, 3 or 4;

m'"'"' is 0, 1, 2, 3, 4 or 5;

R⁸ denotes hydrogen or methyl;

d is 1, 2, 3 or 4; and

q is 0 or 1.

55. The composition of claim 50 wherein said polysiloxane prepolymer comprises at least one fluoroether-containing group.

56. The composition of claim 50 wherein said polysiloxane prepolymer comprises at least one alcohol-containing group.

57. The composition of claim 34 wherein said crosslinking agent is selected from the group consisting of methacryloxyethyl vinyl carbonate, methacryloxyethyl vinyl carbamate, methacryloxyethyl vinyl urea, 4-vinylphenyl vinyl carbonate, 4-vinylphenyl vinyl carbamate, and 4-vinylphenyl vinyl urea.

58. The composition of claim 34 wherein said composition is comprised of methacrylate-capped polysiloxane, a polysiloxanylalkyl methacrylate, N-vinyl pyrrolidone and said crosslinking agent.

59. The composition of claim 34 wherein said composition further comprises N,N-dimethyl acrylamide.

60. The composition of claim 34 wherein said composition further comprises 2-vinyl-4,4-dimethyl-2-oxazolin-5-one.

61. The composition of claim 34 wherein said composition comprises a fluoroalkyl modified methacrylate-capped polysiloxane prepolymer, a fluoroalkyl methacrylate-containing group, N-vinyl pyrrolidone and said crosslinking agent.

62. The composition of claim 61 wherein said composition further comprises 2-vinyl-4,4-dimethyl-2-oxazolin-5-one.

63. The composition of claim 34 wherein said composition comprises at least one methacrylate-capped fluoroether-modified polysiloxane, at least one (meth) acrylate- or (meth) acrylamide-containing monomer, N-vinyl pyrrolidone and said crosslinking agent.

64. The composition of claim 63 wherein said (meth)acrylamide-containing monomer is N,N-dimethyl acrylamide.

65. The composition of claim 34 wherein said composition comprises at least one vinyl carbonate- or vinyl carbamate-capped polysiloxane prepolymer, at least one polysiloxanylalkyl vinyl carbonate or carbamate monomer, N-vinyl pyrrolidone, at least one acrylic-containing monomer and said crosslinking agent.

66. The composition of claim 65 wherein said polysiloxane prepolymer further comprises at least one fluoroalkyl-containing group.

67. The composition of claim 65 wherein said polysiloxane prepolymer further comprises at least one fluoroether-containing group.

68. The composition of claim 65 wherein said polysiloxane prepolymer further comprises at least one alcohol-containing group.

69. The composition of claim 65 wherein said acrylic-containing monomer is selected from the group consisting of N,N-dimethyl acrylamide and glycerol methacrylate,

70. The composition of claim 65 wherein said composition is oxygen permeable.

71. The composition of claim 65 wherein said composition is curable by ultraviolet radiation and heat.

72. The composition of claim 65 wherein said composition is curable by ultraviolet radiation.

73. A biomedical device made from the composition of claim 34.

74. A contact lens made from the composition of claim 34.

54. The composition of claim 54 wherein said polysiloxane prepolymer comprises at least one fluoroalkyl-containing group.

52. The composition of claim 54 wherein said vinyl-containing polysiloxane prepolymer is a silicone-containing vinyl carbonate or vinyl carbamate monomer selected from the group consisting of 1,3-bis[4-vinyloxycarbonyloxy)but-1-yl]tetramethyl-disiloxane;

3-(trimethylsilyl)propyl vinyl carbonate;

3-(vinyloxycarbonylthio)propyl -[tris(trimethylsiloxy)silane];

3-[tris(trimethylsiloxy)silyl]propyl vinyl carbamate;

3-[tris(trimethylsiloxy)silyl]propyl allyl carbamate;

3-[tris(trimethylsiloxy)silyl]propyl vinyl carbonate;

t-butyldimethylsiloxyethyl vinyl carbonate;

trimethylsilylethyl vinyl carbonate;

trimethylsilylmethyl vinyl carbonate; and

"V₂ D₂₅ ", represented by the following formula;

##STR39##

53. The composition of claim 54 wherein said vinyl-containing polysiloxane-containing prepolymer comprises urethane, urea, ester or carbonate linkages.

75. A hydrogel prepared by polymerizing a monomer mix comprising methacryloxyethyl vinyl carbonate, N-vinyl pyrrolidone, and 2-hydroxyethyl methacrylate.

76. A contact lens made from the hydrogel of claim 75.

77. A hydrogel prepared by polymerizing a monomer mix comprising N-vinyl pyrrolidone, 2-vinyl-4,4-dimethyl-2-oxazoline-5-one, N,N-dimethyl acrylamide, and methacryloxyethyl vinyl carbonate.

78. A contact lens made from the hydrogel of claim 77.

79. A hydrogel prepared by polymerizing a monomer mix comprising a UV curable hydrogel composition further comprising α

,ω

-Bis(methacryloxyalkyl) polysiloxane, 3-methacryloxypropyl tris(trimethylsiloxy)silane, N-vinyl pyrrolidone, and methacrlyoxyethyl vinyl carbonate.

80. The contact lens made from the hydrogel of claim 79.

81. A method of making a hydrogel comprising the steps of

a) forming a monomer mix combining at least one acrylic-containing monomer and at least one vinyl-containing monomer and a crosslinking agent having the schematic representation:

##STR40## wherein V denotes a vinyl-containing group having the formula;

##STR41## A'"'"' denotes an acrylic-containing group having the formula;

##STR42## S denotes a styrene-containing group having the formula;

##STR43## wherein R₁, is an alkyl radical derived from substituted and unsubstituted hydrocarbons, polyalkylene oxide, poly(perfluoro) alkylene oxide, dialkyl-capped polydimethylsiloxane, dialkyl-capped polydimethylsiloxane modified with fluoroalkyl or fluoroether groups;

R₂,-R₁₀, are independently H, or alkyl of 1 to 5 carbon atoms;

Q is an organic group containing aromatic moieties having 6-30 carbon atoms;

X, Y, and Z are independently O, NH or S;

v'"'"' is 1, or higher; and

a'"'"', s'"'"' are independently greater than or equal to 0, and a'"'"'+s'"'"' is greater than or equal to 1;

b) curing the mix of step a) to form a polymer; and

c)hydrating the polymer produced in b) to form a hydrogel.

82. The method of claim 81 wherein said hydrogel is UV curable.

83. The method of claim 81 wherein said crosslinking agent is methacryloxyethylvinyl carbonate.

84. A method of making a hydrogel composition comprising the steps of

a) forming a monomer mix combining at least one acrylic-containing, at least one vinyl-containing, at least one styrene-containing monomer and a crosslinking agent having the schematic representation:

##STR44## wherein V denotes a vinyl-containing group having the formula;

##STR45## A'"'"' denotes an acrylic-containing group having the formula;

##STR46## S denotes a styrene-containing group having the formula;

##STR47## wherein R₁, is an alkyl radical derived from substituted and unsubstituted hydrocarbons, polyalkylene oxide, poly(perfluoro) alkylene oxide, dialkyl-capped polydimethylsiloxane, dialkyl-capped polydimethylsiloxane modified with fluoroalkyl or fluoroether groups;

R₂,-R₁₀, are independently H, or alkyl of 1 to 5 carbon atoms;

Q is an organic group containing aromatic moieties having 6-30 carbon atoms;

X, Y, and Z are independently O, NH or S;

v'"'"' is 1, or higher; and

a'"'"', s'"'"' are independently greater than or equal to 0, and a'"'"'+s'"'"' is greater than or equal to 1;

b) curing the mix of step a) to form a polymer; and

c) hydrating the polymer produced in b) to form a hydrogel.

85. The method of claim 84 wherein said crosslinking agent is methacryloxyethyl vinyl carbonate.

86. The method of claim 84 wherein said hydrogel comprises methacryloxyethyl vinyl carbonate, N-vinyl pyrrolidone, and 2-hydroxyethyl methacrylate.

87. The method of claim 84 wherein said hydrogel comprises N-vinyl pyrrolidone, 2-vinyl-4,4-dimethyl-2-oxazoline-5-one, N,N-dimethyl acrylamide, and methacryloxyethyl vinyl carbonate.

88. The method of claim 84 wherein said hydrogel comprises α

,ω

-Bis(methacryloxyalkyl) polysiloxane, 3-methacryloxypropyl tris(trimethylsiloxy)silane, N-vinyl pyrrolidone, and methacryloxyethyl vinyl carbonate.