Fluorosilicone hydrogels

• US 5,387,662 A
• Filed: 01/18/1994
• Issued: 02/07/1995
• Est. Priority Date: 02/12/1993
• Status: Expired due to Term

• Current Assignee: Bausch & Lomb Incorporated (Bausch Health Cos., Inc.)
• Original Assignee: Bausch & Lomb Incorporated (Bausch Health Cos., Inc.)
• Inventors: Kunzler, Jay, Ozark, Richard
• Primary Examiner(s): Michl, Paul R.
• Assistant Examiner(s): MERRIAM, ANDREW EDWIN
• Application Number:
  US08/183,220
• Time in Patent Office: 385 Days
• Field of Search: 526/242, 526/245, 526/246, 526/279, 528/26, 528/32, 523/107
• US Class Current: 526/245
• CPC Class Codes: C08F 30/08 containing silicon
• CPC Class Codes: C08G 77/045 containing less than 25 silicon atoms
• CPC Class Codes: C08G 77/385 containing halogens
• CPC Class Codes: C08L 43/04 Homopolymers or copolymers of monomers containing silicon
• CPC Class Codes: G02B 1/043 Contact lenses

Abstract

Novel fluorosiloxane-containing monomers are disclosed which are especially useful for the preparation of biomedical materials such as contact lenses.

Claims

1. In a method of making a fluorinated siloxane-containing polymer by preparing a monomer mix comprising a fluorinated siloxane-containing monomer, at least one vinyl- or acryl-containing hydrophilic monomer, and at least one initiator and curing the monomer mix, the improvement which comprises selecting the fluorinated siloxane-containing monomer from the group consisting of

(a) a monomer having the general schematic representation:

##STR15## wherein;

R is an alkyl or alkylene group having 1 to 10 carbon atoms and which may have ether linkages between carbon atoms;

R₁ -R₄ may independently be 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;

x is≧

0;

y is≧

z1;

x+y=2 to 1000;

R₅ is a fluorinated side group having the general schematic representation;

space="preserve" listing-type="equation">--D--(CF.sub.2).sub.z --H

wherein

z is 1 to 20;

D is an alkyl or alkylene group having 1 to 10 carbon atoms and which may have ether linkages between carbon atoms; and

A is an activated unsaturated group, such as an ester or amide of an acrylic or a methacrylic acid or is a group represented by the general formula;

##STR16## wherein Y is --O--, --S-- or --NH--; and

(b) a monomer having the general schematic representation;

##STR17## wherein A is an activated unsaturated group, such as an ester or amide of an acrylic or a methacrylic acid;

R₆ is CH₃ or H;

R is an alkyl or alkylene group having 1 to 10 carbon atoms and which may have ether linkages between carbon atoms;

D is an alkyl or alkylene group having 1 to 10 carbon atoms and which may have ether linkages between carbon atoms;

x is 1, 2 or 3;

y is 0, 1 or 2; and

x+y=3.

2. The method of claim 1 wherein said monomer mix further comprises at least one crosslinking agent.

3. The method of claim 1 wherein said siloxane-containing monomer mix comprises an additional siloxane-containing monomer.

4. The method of claim 1 wherein the siloxane-containing monomer comprises a repeating number of between from about 2 to about 200 siloxy units.

5. The method of claim 1 wherein the siloxane-containing monomer comprises about 100 repeating siloxy units.

6. The method of claim 1 wherein the fluorinated side group is comprised of an alkyloxyperfluoroalkyl group.

7. The method of claim 6 wherein the fluorinated side group is selected from the group consisting of propyloxyoctafluoropentanes, propyloxytetrafluoropropanes, and propyloxydodecafluoroheptanes.

8. The method of claim 6 wherein said fluorinated side group is represented by the formula:

space="preserve" listing-type="equation">--CH.sub.2 --CH.sub.2 --CH.sub.2 --O--CH.sub.2 --(CF.sub.2).sub.z --H

wherein

z is 1 to 20.

9. The method of claim 1 wherein said monomer mix further comprises more than one hydrophilic monomer.

10. The method of claim 1 wherein said hydrophilic monomers are N,N-dimethyl acrylamide and N-vinyl pyrrolidone.

11. In a fluorinated siloxane-containing polymerization product prepared by polymerizing a monomer mix comprising a fluorinated siloxane-containing monomer, at least one vinyl- or acryl-containing hydrophilic monomer, and at least one initiator and curing the monomer mix, the improvement which comprises selecting the fluorinated siloxane-containing monomer from the group consisting of

(a) a monomer having the general schematic representation:

##STR18## wherein;

R is an alkyl or alkylene group having 1 to 10 carbon atoms and which may have ether linkages between carbon atoms;

R₁ -R₄ may independently be 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;

x is≧

0;

y is≧

1;

x+y=2 to 1000;

R₅ is a fluorinated side group having the general schematic representation;

space="preserve" listing-type="equation">--D--(CF.sub.2).sub.z --H

wherein z is 1 to 20;

D is an alkyl or alkylene group having 1 to 10 carbon atoms and which may have ether linkages between carbon atoms; and

A is an activated unsaturated group, such as an ester or amide of an acrylic or a methacrylic acid or is a group represented by the general formula;

##STR19## wherein Y is --O--, --S-- or --NH--; and

(b) a monomer having the general schematic representation;

##STR20## wherein A is an activated unsaturated group, such as an ester or amide of an acrylic or a methacrylic acid;

R₆ is CH₃ or H;

R is an alkyl or alkylene group having 1 to 10 carbon atoms and which may have ether linkages between carbon atoms;

D is an alkyl or alkylene group having 1 to 10 carbon atoms and which may have ether linkages between carbon atoms;

x is 1, 2 or 3;

y is 0, 1 or 2; and

x+y=3.

12. The polymerization product of claim 11 wherein said monomer mix further comprises at least one additional siloxane-containing monomer.

13. The monomer mix of claim 11 wherein said monomer mix further comprises at least one additional crosslinking agent.

14. The polymerization product of claim 11 wherein said vinyl-containing hydrophilic monomer is selected from the group consisting of N-vinyl-N-methyl acetamide, N-vinyl-N-ethyl acetamide, N-vinyl-N-ethyl formamide, N-vinyl-formamide and N-vinyl pyrrolidone.

15. The polymerization product of claim 11 wherein said acrylic-containing hydrophilic monomer is selected from the group consisting of 2-hydroxyethyl methacrylate, glycerol methacrylate, 2-hydroxyethyl methacrylamide, methacrylic acid, acrylic acid and N,N-dimethylacrylamide.

16. The polymerization product of claim 11 wherein said polymerization product further comprises at least one additional siloxane-containing monomer.

17. The polymerization product of claim 11 wherein said monomer mix further comprises at least one additional siloxane-containing monomer.

18. The monomer mix of claim 11 wherein said monomer mix further comprises at least one additional crosslinking agent.

19. The polymerization product of claim 11 wherein said vinyl-containing hydrophilic monomer is selected from the group consisting of N-vinyl-N-methyl acetamide, N-vinyl-N-ethyl acetamide, N-vinyl-N-ethyl formamide, N-vinyl-formamide and N-vinyl pyrrolidone.

20. The polymerization product of claim 11 wherein said acrylic-containing hydrophilic monomer is selected from the group consisting of 2-hydroxyethyl methacrylate, glycerol methacrylate, 2-hydroxyethyl methacrylamide, methacrylic acid, acrylic acid and N,N-dimethylacrylamide.

21. The polymerization product of claim 11 wherein said polymerization product is a hydrogel.

22. The polymerization product of claim 11 wherein said polymerization product is a hydrogel.