Siloxane macromonomers

• US 5,336,797 A
• Filed: 12/30/1992
• Issued: 08/09/1994
• Est. Priority Date: 12/30/1992
• Status: Expired due to Term

• Current Assignee: Bausch & Lomb Incorporated (Bausch Health Cos., Inc.)
• Original Assignee: Bausch & Lomb Incorporated (Bausch Health Cos., Inc.)
• Inventors: McGee, Joseph A., Valint, Paul L. Jr.
• Primary Examiner(s): Michl, Paul R.
• Assistant Examiner(s): MERRIAM, ANDREW EDWIN
• Application Number:
  US07/998,346
• Time in Patent Office: 587 Days
• Field of Search: 526/279, 526/286, 556/419, 556/422, 556/437, 556/440, 528/26, 528/28, 528/29, 528/25
• US Class Current: 556/419
• CPC Class Codes: C08F 2/38 Polymerisation using regulators, e.g. chain terminating agents , e.g. telomerisation
• CPC Class Codes: C08F 290/04 Polymers provided for in subclasses C08C or C08F
• CPC Class Codes: C08L 51/085 on to polysiloxanes
• CPC Class Codes: G02B 1/043 Contact lenses

Abstract

Siloxane macromonomers are disclosed which can be copolymerized with hydrophilic monomers or hydrophobic monomers to prepare polymeric materials useful as biomedical devices. The copolymers made from hydrophilic monomers exhibit good oxygen permeability and are particularly suitable for use in contact lenses.

Claims

1. An oil soluble, non-surface active siloxane macromonomer represented by the following structural formula:

space="preserve" listing-type="equation">B--E--(T).sub.m

wherein each B is a polymerizable end group containing at least one ethylenically unsaturated group and a functional group which reacts to form an ester, amide, urea, urethane, carbonate or epoxy type linkage with the rest of the macromonomer;

E is a functionalized chain transfer agent;

T has the following structural formula;

##STR13## wherein n is an integer from 1 to 6, A is O, ##STR14## NH or ##STR15## R¹ is H or CH₃ ; and

each R² is independently selected from a C₁ -C₈ alkyl group, a phenyl group and a group of the following structural formula;

##STR16## wherein each Y is independently selected from a C₁ -C₈ alkyl group, a phenyl group and a (R)₃ OSi-group wherein each R is independently a lower alkyl group; and

m is an integer from 1 to 120.

2. The macromonomer of claim 1 wherein A is selected from O, ##STR17##

3. The macromonomer of claim 2 wherein R² is independently selected from a C₂ -C₄ alkyl group and a (CH₃)₃ OSi-group.

4. The macromonomer of claim 3 wherein R² is a (CH₃)₃ OSi-group.

5. The macromonomer of claim 4 wherein m is 2 to 25.

6. The macromonomer of claim 5 wherein E is compound selected from mercapto carboxylic acids, mercapto alcohols and aminomercaptans.

7. The macromonomer of claim 6 wherein E is selected from mercapto carboxyclic acids and mercapto alcohols.

8. The macromonomer of claim 6 wherein B contains at least one group selected from the following functional groups:

##STR18##

9. The macromonomer of claim 8 wherein the precursor to T is selected from the group 3-methacryloxypropyltris (trimethyl siloxy) silane, N-(tris(trimethylsiloxy)silylpropyl)methacryloxyethyl carbonate and 3(tris(trimethylsilyloxy)silyl)propyl vinyl carbonate.

10. The macromonomer of claim 9 wherein the precursor to T is 3-methacryloxypropyltris (trimethyl siloxy) silane.

11. The macromonomer of claim 1 wherein A is selected from NH and ##STR19##

12. The macromonomer of claim 11 wherein R² is independently selected from a C₂ -C₄ alkyl group and a (CH₃)₃ OSi-group.

13. The macromonomer of claim 12 wherein each R² is a (CH₃)₃ OSi-group.

14. The macromonomer of claim 13 wherein m is 2 to 25.

15. The macromonomer of claim 14 wherein E is derived from a compound selected from mercapto carboxylic acids, mercapto alcohols and aminomercaptans.

16. The macromonomer of claim 11 wherein E is selected from mercapto carboxyclic acids and mercapto alcohols.

17. The macromonomer of claim 15 wherein B contains at least one group selected from the following functional groups:

##STR20##

18. The macromonomer of claim 17 wherein the precursor to T is selected from the group N(tris(trimethylsiloxy)silylpropyl)methacrylamide, N-tris(trimethylsiloxy) silyl)prop) acrylamide, and 3(tris(trimethylsilyloxy)silyl)propyl vinyl carbamate.

19. The macromonomer of claim 18 wherein the precursor to T is N-(Tris(trimethylsiloxy)silylpropyl)acrylamide.

20. An in soluble intermediate polymer useful in the preparation of siloxane macromonomers comprised of the following structural formula:

space="preserve" listing-type="equation">E(T).sub.m

wherein E is a functional chain transfer agent and T has the following structural formula;

##STR21## wherein n is an integer, from i to 6, A is O, ##STR22## NH or ##STR23## R is H or CH₃ ; and

each R² is independently selected from a C₁ -C₈ alkyl group, a phenyl group and a group of the following structural formula;

##STR24## whereln each Y is independently selected from a C₁ -C₈ alkyl group, a phenyl group and a (R)₃ OSi- group wherein each R is independently a lower alkyl group;

and m is an integer from I to 120.

21. The polymer of claim 20 wherein A is selected from O, ##STR25## each R² is independently selected from a C₂ to C₄ alkyl group and a ((CH₃)₃ OSi-) group and n is an integer from 2 to 4.

22. The polymer of claim 21 which is the reaction product of the polymerization of a chain transfer agent selected from mercapto carboxylic acids, mercapto alcohols and aminomercaptans with a siloxane macromonomer selected from 3-methacryloxypropyltris (trimethyl siloxy) silane, N-(tris(trimethylsiloxy)silylpropyl)methacryloxyethyl carbonate and 3(tris(trimethylsilyloxy)silyl)propyl vinyl carbonate.

23. The polymer of claim 22 wherein the siloxane macromonomer is a 3-methacryloxypropyltris (trimethyl siloxy) silane.

24. The polymer of claim 23 wherein m is an integer from 2 to 25.

25. The polymer of claim 20 wherein A is selected from NH and ##STR26## each X is independently selected from a C₂ to C₄ alkyl group and a ((CH₃)₃ OSi) group and n is an integer from 2 to 4.

26. The polymer of claim 25 which is the reaction product of the polymerization of a chain transfer agent selected from mercapto carboxylic acids, mercapto alcohols and aminomercaptans with a siloxane monomer selected from the group N(tris(trimethyl siloxy)silylpropyl)methacrylamide, N-(tris(trimethylsiloxy)silylpropyl)acrylamide, and 3(tris(trimethylsilyloxy)silyl)propyl vinyl carbamate.