Organosilicon-containing materials useful for biomedical devices

• US 5,616,757 A
• Filed: 04/08/1993
• Issued: 04/01/1997
• Est. Priority Date: 04/08/1993
• 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 F., Bambury, Ronald E.
• Primary Examiner(s): Shaver, Paul F.
• Application Number:
  US08/045,459
• Time in Patent Office: 1,454 Days
• Field of Search: 556/439, 552/419, 552/420, 528/17, 528/18, 528/26, 528/28, 528/32, 528/33, 528/35, 528/38, 528/41
• US Class Current: 523/107
• CPC Class Codes: A61L 27/16 obtained by reactions only involving carbon-to-carbon unsaturated bonds
• 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 290/06 Polymers provided for in subclass C08G
• CPC Class Codes: C08G 63/6956 Dicarboxylic acids and dihydroxy compounds
• CPC Class Codes: C08G 63/6958 Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
• CPC Class Codes: C08G 69/26 derived from polyamines and polycarboxylic acids
• CPC Class Codes: C08G 69/42 Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen C08G69/12, C08G69/32 take precedence
• CPC Class Codes: C08L 43/04 Homopolymers or copolymers of monomers containing silicon
• CPC Class Codes: C08L 67/00 Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain of polyester-amides C08L77/12; of polyester-imides C08L79/08; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 77/00 Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain of polyhydrazides C08L79/06; of polyamideimides or polyamide acids C08L79/08; Compositions of derivatives of such polymers
• CPC Class Codes: G02B 1/043 Contact lenses

Abstract

Organosilicon-containing materials are useful in articles such as biomedical devices, including contact lenses.

Claims

1. A polymer containing repeating units of the formula:

##STR25## wherein;

each Y is --O-- or --NR³⁰ -- wherein R³⁰ is H or C₁ -C₆ alkyl;

each R¹, R², R³, R⁴ and R⁵ is independently selected from the group consisting of H, C₁ -C₆ alkyl, C₁ -C₆ haloalkyl, C₂ -C₆ alkyl wherein at least one methylene group is replaced with --O--, C₂ -C₆ haloalkyl wherein at least one methylene group is replaced with --O--, and --R^Si ;

m and n are independently 0 or an integer of 1 to 6;

each R^Si is independently an organosilicon radical; and

R is the divalent residue of an α

,ω

-dihydroxyl compound or an α

,ω

-diamino compound.

2. A polymer of claim 1, wherein each Y is --O--.

3. A polymer of claim 1, wherein each of Y is --NR³⁰.

4. A polymer of claim 1, wherein R is selected from the group consisting of C₁ -C₁₀ alkylene, C₁ -C₁₀ haloalkylene, C₂ -C₁₀ alkylene ethers, C₆ -C₁₀ arylene, C₆ -C₁₀ haloarylene, C₇ -C₁₀ aralkylene, C₇ -C₁₀ haloaralkylene, C₅ -C₁₀ cycloalkylene and C₆ -C₁₂ alkylcycloalkylene.

5. A polymer of claim 1, wherein m is 0 and n is 0 or 1.

6. A polymer of claim 1, wherein each R^Si is independently an organosilicon radical of the formula:

##STR26## wherein each R¹⁰ is independently selected from the group consisting of C₁ -C₈ alkyl, phenyl and a group of the formula ##STR27## wherein each R¹¹ is independently selected from the group consisting of C₁ -C₈ alkyl, phenyl and --O--Si(R¹²)₃, wherein each R¹² is independently selected from the group consisting of C₁ -C₈ alkyl and phenyl; and

L is selected from the group consisting of a single bond and a divalent linking radical.

7. A polymer of claim 6, wherein each L is independently a divalent linking group of the formula:

##STR28## wherein;

q is an integer of 2 to 6; and

R⁷ and R⁸ are independently selected from the group consisting of H, C₁ -C₆ alkyl, C₁ -C₆ haloalkyl, C₂ -C₆ alkyl wherein at least one methylene group is replaced with --O--, and C₂ -C₆ haloalkyl wherein at least one methylene group is replaced with --O--.

8. A polymer of claim 1, wherein the repeating units are of the formula:

##STR29## wherein R^o is the divalent residue of an α

,ω

-dihydroxyl compound.

9. A polymer of claim 8, wherein R^Si is

10. A polymer of claim 1, having the formula:

##STR30## wherein x has an average value greater than 1, and R^o is the divalent residue of an α

,ω

-dihydroxyl compound.

11. A polymer of claim 1, having the formula:

##STR31## wherein x has an average value greater than 1, and R^N is the divalent residue of an α

,ω

-diamino compound.

12. A shaped article which is formed of a polymer containing repeating units of the formula:

##STR32## wherein;

each Y is --O-- or --NR³⁰ -- wherein R³⁰ is H or C₁ -C₆ alkyl;

each R¹, R², R³, R⁴ and R⁵ is independently selected from the group consisting of H, C₁ -C₆ alkyl, C₁ -C₆ haloalkyl, C₂ -C₆ alkyl wherein at least one methylene group is replaced with --O--, C₂ -C₆ haloalkyl wherein at least one methylene group is replaced with --O--, and --R^Si ;

m and n are independently 0 or an integer of 1 to 6;

each R^Si is independently an organosilicon radical; and

R is the divalent residue of an α

,ω

-dihydroxyl compound or an α

,ω

-diamino compound.

13. The article of claim 12, which is the polymerization product of a mixture comprising:

(a) a macromonomer comprising repeating units of the formula;

##STR33## said macromonomer endcapped with at least one ethylenically unsaturated radical, wherein each Y is --O-- or --NR³⁰ --, wherein R³⁰ is H or C₁ -C₆ alkyl,

each R¹, R², R³, R⁴ and R⁵ is independently selected from the group consisting of H, C₁ -C₆ alkyl, C₁ -C₆ haloalkyl, C₂ -C₆ alkyl wherein at least one methylene group is replaced with --O--, C₂ -C₆ haloalkyl wherein at least one methylene group is replaced with --O--, and --R^Si,

m and n are independently 0 or an integer of 1 to 6,

each R^Si is independently an organosilicon radical, and

R is the divalent residue of an α

,ω

-dihydroxyl compound or an α

,ω

-diamino compound; and

(b) a hydrophilic monomer.

14. The article of claim 12, which is optically clear and shaped as a contact lens.

15. The article of claim 12, which is the polymerization product of a mixture comprising:

(a) a monomer having the formula;

##STR34## wherein;

each Y is --O-- or --NR³⁰ --, wherein R³⁰ is H or C₁ -C₆ alkyl,

each R¹, R², R³, R⁴ and R⁵ is independently selected from the group consisting of H, C₁ -C₆ alkyl, C₁ -C₆ haloalkyl, C₂ -C₆ alkyl wherein at least one methylene group is replaced with --O--, C₂ -C₆ haloalkyl wherein at least one methylene group is replaced with --O--, and --R^Si,

m and n are independently 0 or an integer of 1 to 6,

each R^Si is independently an organosilicon radical,

R is the divalent residue of an α

,ω

-dihydroxyl compound or an α

,ω

-diamino compound, and

R⁵⁰ is an ethylenically unsaturated radical; and

(b) at least one hydrophilic monomer.

16. The article of claim 14, wherein each Y in the formula is --O--.

17. The article of claim 14, wherein each Y in the formula is --NR³⁰ --.

18. The article of claim 14, wherein R in the formula is selected from the group consisting of C₁ -C₁₀ alkylene, C₁ -C₁₀ haloalkylene, C₂ -C₁₀ alkylene ethers, C₆ -C₁₀ arylene, C₆ -C₁₀ haloarylene, C₇ -C₁₀ aralkylene, C₇ -C₁₀ haloaralkylene, C₅ -C₁₀ cycloalkylene and C₆ -C₁₂ alkylcycloalkylene.

19. The article of claim 14, wherein m is 0 and n is 0 or 1.

20. The article of claim 14, wherein each R^Si is independently an organosilicon radical of the formula ##STR35## wherein each R¹⁰ is independently selected from the group consisting of C₁ -C₈ alkyl, phenyl and a group of the formula ##STR36## wherein each R¹¹ is independently selected from the group consisting of C₁ -C₈ alkyl, phenyl and --O--Si(R¹²)₃, wherein each R¹² is independently selected from the group consisting of C₁ -C₈ alkyl and phenyl;

and

L is selected from the group consisting of a single bond and a divalent linking radical.

21. The article of claim 20, wherein each L is independently a dvialent linking group of the formula ##STR37## wherein q is an integer of 2 to 6, and R⁷ and R⁸ are independently selected from the group consisting of H, C₁ -C₆ alkyl, C₁ -C₆ haloalkyl, C₂ -C₆ alkyl wherein at least one methylene group is replaced with --O--, and C₂ -C₆ haloaalkyl wherein at least one methylene group is replaced with --O--.

22. The article of claim 14, wherein the repeating units are of the formula:

##STR38## wherein R^o is the divalent residue of an α

,ω

-dihydroxyl compound.

23. The article of claim 22, wherein R^Si is

24. The article of claim 13, which is optically clear and shaped as a contact lens.

25. The article of claim 24, wherein each of said at least one ethylenically unsaturated radicals is independently a radical of the formula:

##STR39## wherein;

R³¹ is hydrogen or methyl;

R³² is selected from the group consisting of hydrogen, an alkyl radical having 1 to 6 carbon atoms, and an --CO--Y'"'"'--R³⁴ radical wherein Y'"'"' is --O-- or --NH--;

each of R³⁴ and R³⁵ is independently selected from the group consisting of--COO--, --CONH--, --NHCO--, --OCOO--, --NHCOO-- and --OCO--NH--;

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

each of t and y is independently 0 or an integer of 1 to 6; and

each of u, v and w is independently 0 or 1.

26. The article of claim 25, wherein said macromonomer is endcapped with two ethylenically unsaturated radicals.

27. The article of claim 25, wherein each of said at least one ethylenically unsaturated radicals is independently a radical of the formula:

##STR40##

28. The article of claim 24, wherein each Y is --O--.

29. The article of claim 24, wherein each Y is --NR³⁰ --.

30. The article of claim 24, wherein R is selected from the group consisting of C₁ -C₁₀ alkylene, C₁ -C₁₀ haloalkylene, C₂ -C₁₀ alkylene ethers, C₆ -C₁₀ arylene, C₆ -C₁₀ haloarylene, C₇ -C₁₀ aralkylene, C₇ -C₁₀ haloaralkylene, C₅ -C₁₀ cycloalkylene and C₆ -C₁₂ alkylcycloalkylene.

31. The article of claim 24, wherein m is 0 and n is 0 or 1.

32. The article of claim 24, wherein each R^Si is independently an organosilicon radical of the formula ##STR41## wherein each R¹⁰ is independently selected from the group consisting of C₁ -C₈ alkyl, phenyl and a group of the formula ##STR42## wherein each R¹¹ is independently selected from the group consisting of C₁ -C₈ alkyl, phenyl and --O--Si(R¹²)₃, wherein each R¹² is independently selected from the group consisting of C₁ -C₈ alkyl and phenyl;

and

L is selected from the group consisting of a single bond and a divalent linking radical.

33. The article of claim 32, wherein each L is independently a dvialent linking group of the formula ##STR43## wherein q is an integer of 2 to 6, and R⁷ and R⁸ are independently selected from the group consisting of H, C₁ -C₆ alkyl, C₁ -C₆ haloalkyl, C₂ -C₆ alkyl wherein at least one methylene group is replaced with --O--, and C₂ -C₆ haloalkyl wherein at least one methylene group is replaced with --O--.

34. The article of claim 24, wherein the macromonomer has the formula:

##STR44## wherein R^o is the divalent residue of an α

,ω

-dihydroxyl compound, and R⁵⁰ is the ethylenically unsaturated radical.

35. The article of claim 24, wherein the macromonomer has the formula:

##STR45## wherein R^N is the divalent residue of an α

,ω

-diamino compound, and R⁵⁰ is the ethylenically unsaturated radical.

36. The article of claim 15, which is optically clear and shaped as a contact lens.