UV curable crosslinking agents useful in copolymerization

• US 5,310,779 A
• Filed: 07/30/1992
• Issued: 05/10/1994
• 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): Michl, Paul R.
• Assistant Examiner(s): CAIN, EDWARD J
• Application Number:
  US07/922,452
• Time in Patent Office: 649 Days
• Field of Search: 252/183.11
• US Class Current: 524/588
• 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 crosslinking composition having at least two different types of ethylenically polymerizable groups said crosslinking composition able to enhance the copolymerization of comonomers having differing rates of reactivity and wherein said composition is present in copolymeric systems in concentrations of from about 0.001 to about 10 weight percent and having the schematic representation:

##STR16## wherein V denotes a vinyl-containing group having the formula;

##STR17## A'"'"' denotes an acrylic-containing group having the formula;

##STR18## S denotes a styrene-containing group having the formula;

##STR19## wherein R_1'"'"' 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;

R_2'"'"' -R_10'"'"' 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'"'"' are greater than or equal to 1.

2. The composition of claim 1 wherein said composition comprises at least one acrylic-containing group and at least one vinyl-containing group.

3. The composition of claim 2 wherein said acrylic-containing group comprises at least one alkyl (meth)acrylate or alkyl (meth)acrylamide group.

4. The composition of claim 2 wherein said acrylic-containing group comprises at least one polysiloxanylalkyl (meth)acrylate or polysiloxanylalkyl (meth)acrylamide group.

5. The composition of claim 2 wherein said acrylic-containing group comprises at least one fluoroalkyl (meth)acrylate or fluoroalkyl (meth)acrylamide group.

6. The composition of claim 3 wherein said alkyl (meth)acrylate or alkyl (meth)acrylamide group is selected from the group consisting of derivatives of 2-hydroxyethyl methacrylate, glycerol methacrylate, hydroxyethyl methacrylamide, N,N-dimethylacrylamide, and 2-methacrylamido ethanol.

7. The composition of claim 2 wherein said acrylic-containing group is a monomer end-capped with (meth)acrylate or (meth)acrylamide groups.

8. The composition of claim 7 wherein said monomer is a polysiloxane-containing prepolymer.

9. The composition of claim 8 wherein said polysiloxane-containing prepolymer comprises at least one fluoroalkyl group.

10. The composition of claim 8 wherein said polysiloxane-containing prepolymer comprises at least one fluoroether group.

11. The composition of claim 8 wherein said polysiloxane-containing prepolymer comprises at least one alkyl ether group.

12. The composition of claim 8 wherein said polysiloxane-containing prepolymer comprises at least one alcohol group.

13. The composition of claim 7 wherein said monomer comprises at least one polyalkylene ether group.

14. The composition of claim 7 wherein said monomer comprises at least one polyfluorinated ether group.

15. The composition of claim 7 wherein said monomer comprises at least one polysiloxane-containing group linked to at least one polyalkylene ether-containing group through ester, carbonate, carbamate, urea or urethane linkages.

16. The composition of claim 7 wherein said monomer comprises at least one polysiloxane-containing group and at least one polyfluorinated ether-containing group linked by ester, carbonate, carbamate, urea or urethane linkages.

17. The composition of claim 7 wherein said monomer comprises at least one polyalkylene ether-containing group and at least one polyfluorinated ether-containing group linked by ether, carbonate, carbamate, urea or urethane linkages.

18. The composition of claim 2 wherein said vinyl-containing group is selected from the group consisting of vinyl carbonates, alkyl vinyl carbonates, polysiloxanylalkyl vinyl carbonates, fluoroalkyl vinyl carbonates, vinyl carbamates, alkylvinyl carbamates, polysiloxanylalkyl vinyl carbamates, fluoroalkyl vinyl carbamates, vinyl ureas, alkyl vinyl ureas, polysiloxanylalkyl vinyl ureas and fluoroalkyl vinyl ureas.

19. The composition of claim 2 wherein said vinyl-containing group is selected from the group consisting of N-vinylpyrrolidone derivatives, N-vinyl,N-methyl acetamide derivatives, N-vinyl,N-methyl formamide derivatives, N-vinyl acetamide derivatives, and N-vinyl formamide derivatives.

20. The composition of claim 2 wherein said vinyl-containing group is a prepolymer selected from the group consisting of vinyl carbonate-capped, vinyl carbamate-capped and vinyl urea-capped monomers.

21. The composition of claim 20 wherein said monomer is a polysiloxane-containing prepolymer.

22. The composition of claim 21 wherein said polysiloxane-containing prepolymer comprises at least one fluoroalkyl group.

23. The composition of claim 21 wherein said polysiloxane-containing prepolymer comprises at least one fluoroether group.

24. The composition of claim 21 wherein said polysiloxane-containing prepolymer comprises at least one alkyl ether group.

25. The composition of claim 21 wherein said polysiloxane-containing prepolymer comprises at least one alcohol group.

26. The composition of claim 20 wherein said monomer comprises at least one polyalkylene ether.

27. The composition of claim 20 wherein said monomer comprises at least one polyfluorinated ether.

28. The composition of claim 20 wherein said monomer comprises at least one polysiloxane-containing group and at least one polyalkylene ether-containing group linked by ester, carbonate, carbamate, urea or urethane linkages.

29. The composition of claim 20 wherein said monomer comprises at least one polysiloxane-containing group and at least one polyfluorinated ether-containing group linked by ester, carbonate, carbamate, urea or urethane linkages.

30. The composition of claim 20 wherein said monomer comprises at least one polyalkylene ether-containing group and at least one polyfluorinated ether-containing group linked by ester, carbonate, carbamate, urea or urethane linkages.

31. The composition of claim 1 wherein said composition comprises at least one vinyl-containing group and at least one styrene-containing group.

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

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

34. The composition of claim 1 wherein said composition is used to make biomedical devices.

35. The crosslinking composition of claim 1 wherein said crosslinking composition is selected from the group consisting of methacryloxyethyl vinyl carbonate, methacryloxyethyl vinyl carbamate, methacry-loxyethyl vinyl urea, 4-vinylphenyl vinyl carbamate, 4-vinylpenyl vinyl urea.

36. The crosslinking composition of claim 1 wherein said composition is used in copolymeric systems in concentrations of from about 0.01 to about 5 weight percent.