Silicone-containing macromonomers and low water materials

• US 5,981,675 A
• Filed: 12/07/1998
• Issued: 11/09/1999
• Est. Priority Date: 12/07/1998
• 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., Ozark, Richard M.
• Primary Examiner(s): Wu, David W.
• Assistant Examiner(s): LU, C CAIXIA
• Application Number:
  US09/206,470
• Time in Patent Office: 337 Days
• Field of Search: 526/279, 525/302
• US Class Current: 526/279
• CPC Class Codes: C08F 290/04 Polymers provided for in subclasses C08C or C08F
• CPC Class Codes: C08F 290/12 Polymers provided for in subclasses C08C or C08F
• CPC Class Codes: C08L 51/00 Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds for ABS polymers C08L55/02; Compositions of derivatives of such polymers
• CPC Class Codes: G02B 1/043 Contact lenses

Abstract

Low water siloxane macromonomer are disclosed. This macromonomer can be copolymerized with unsaturated silicone containing monomers to prepare polymeric materials useful as biomedical devices. These macromonomers are particularly suited for soft contact lens applications.

Claims

1. A low water polymeric silicone composition which is the polymerization product of a mixture comprising:

(A) a macromonomer of the general Formula (I);

space="preserve" listing-type="equation">(X)(E).sub.n (I)

wherein;

X is derived from a copolymer prepared by reacting the following components;

(a) at least 50 mole % of an ethylenically unsaturated silicon-containing monomer,

(b) 2.5 to 20 mole % of an ethylenically unsaturated monomer containing a hydroxyl, amino or carboxylic acid radical,

(c) 0 to 15 mole % of an ethylenically unsaturated monomer other than monomers (a) or (b),

(d) 2.5 to 20 mole % of a chain transfer agent, and

the mole percent of components (a), (b), (c) and (d) being based on the total amount of said components;

E is a polymerizable, ethylenically unsaturated radical;

n is at least 2; and

(B) an ethylenically unsaturated silicone-containing monomer other than the macromonomer of Formula (I).

2. The composition of claim 1, which is the polymerization product of a mixture that includes the macromonomer of Formula (I) and (B), wherein the ethylenically unsaturated silicone-containing monomer is selected from the group consisting of monofunctional ethylenically unsaturated silicone-containing monomers and difunctional ethylenically unsaturated silicone-containing monomers.

3. The composition of claim 2, which is the polymerization product of a mixture that includes the macromonomer of Formula (I), a monofunctional ethylenically unsaturated silicone-containing monomer and a difunctional ethylenically unsaturated silicone-containing monomer.

4. The composition of claim 2, wherein the macromonomer of formula I includes a compound of Formula (II):

##STR10## wherein;

X denotes --COO--, --CONR⁴ --, --OCOO--, or --OCONR⁴ -- where each where R⁴ is H or lower alkyl;

R³ denotes hydrogen or methyl;

h is 1 to 10; and

each R² independently denotes a lower alkyl radical, a phenyl radical or a radical of the formula

space="preserve" listing-type="equation">--Si(R.sup.5).sub.3

wherein each R⁵ is independently a lower alkyl radical or a phenyl radical.

5. The composition of claim 4, wherein the ethylenically unsaturated silicone-containing monomer further includes a compound of the formula:

##STR11##

6. The composition of claim 1, wherein component (a) of the macromonomer is derived from methacryloxypropyl tris (trimethylsiloxy) silane.

7. The composition of claim 1, wherein component (b) of the macromonomer is derived from a monomer selected from the group consisting of hydroxyl-substituted (meth)acrylates, hydroxyl-substituted (meth)acrylamides, amino-substituted (meth)acrylates, and amino-substituted (meth)acrylamides.

8. The composition of claim 7, wherein the component (b) of the macromonomer is derived from at least one hydroxyl-substituted (meth)acrylate selected from the group consisting of 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, glycerol methacrylate, glycerol acrylate, polyethylene glycol methacrylate, and polyethylene glycol acrylate.

9. The composition of claim 8, wherein component (c) of the macromonomer is derived from 2-mercaptoethanol, thioglycolic acid or 2-aminoethanethiol.

10. The composition of claim 1, wherein X the macromonomer is based on a copolymer of methacryloxypropyl tris (trimethylsiloxy) silane, 2-hydroxyethyl methacrylate and mercaptoethanol.

11. The composition of claim 10, wherein B of the macromonomer is derived from 2-isocyanatoethyl methacrylate.

13. The medical device of claim 1, which is the polymerization product of a mixture that includes the macromonomer of Formula (I) and (B), wherein the ethylenically unsaturated silicone-containing monomer is selected from the group consisting of monofunctional ethylenically unsaturated silicone-containing monomers and difunctional ethylenically unsaturated silicone-containing monomers.

14. The medical device of claim 2, which is the polymerization product of a mixture that includes the macromonomer of Formula (I), a monofunctional ethylenically unsaturated silicone-containing monomer and a difunctional ethylenically unsaturated silicone-containing monomer.

15. The medical device of claim 2, wherein the macromonomer of formula I includes a compound of Formula (II):

##STR12## wherein;

X denotes --COO--, --CONR⁴ --, --OCOO--, or --OCONR⁴ -- where each where R⁴ is H or lower alkyl;

R³ denotes hydrogen or methyl;

h is 1 to 10; and

each R² independently denotes a lower alkyl radical, a phenyl radical or a radical of the formula

space="preserve" listing-type="equation">--Si(R.sup.5).sub.3

wherein each R⁵ is independently a lower alkyl radical or a phenyl radical.

16. The medical device of claim 4, wherein the ethylenically unsaturated silicone-containing monomer further includes a compound of the formula:

##STR13##

17. The medical device of claim 1, wherein component (a) of the macromonomer is derived from methacryloxypropyl tris (trimethylsiloxy) silane.

18. The medical device of claim 1, wherein component (b) of the macromonomer is derived from a monomer selected from the group consisting of hydroxyl-substituted (meth)acrylates, hydroxyl-substituted (meth)acrylamides, amino-substituted (meth)acrylates, and amino-substituted (meth)acrylamides.

19. The medical device of claim 7, wherein the component (b) of the macromonomer is derived from at least one hydroxyl-substituted (meth)acrylate selected from the group consisting of 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, glycerol methacrylate, glycerol acrylate, polyethylene glycol methacrylate, and polyethylene glycol acrylate.

20. The medical device of claim 8, wherein component (c) of the macromonomer is derived from selected from 2-mercaptoethanol, thioglycolic acid or 2-aminoethanethiol.

21. The medical device of claim 1, wherein the macromonomer is based on a copolymer of methacryloxypropyl tris (trimethylsiloxy) silane, 2-hydroxyethyl methacrylate and mercaptoethanol.

22. The medical device of claim 1, wherein B of the macromonomer is derived from 2-isocyanatoethyl methacrylate.

23. The medical device of claim 1, wherein the medical device is a soft contact lens.

24. The medical device of claim 1, wherein the medical device is a rigid gas permeable contact lens.

25. The medical device of claim 1, wherein the medical device is an intraocular lens.

12. A medical device formed from a low water composition which is the polymerization product of a mixture comprising:

(A) a macromonomer of the general Formula (I);

space="preserve" listing-type="equation">(X)(E).sub.n (I)

wherein;

X is derived from a copolymer prepared by reacting the following components;

(a) at least 50 mole % of an ethylenically unsaturated silicon-containing monomer,

(b) 2.5 to 20 mole % of an ethylenically unsaturated monomer containing a hydroxyl, amino or carboxylic acid radical,

(c) 0 to 15 mole % of an ethylenically unsaturated monomer other than monomers (a) or (b),

(d) 2.5 to 20 mole % of a chain transfer agent, and

the mole percent of components (a), (b), (c) and (d) being based on the total amount of said components;

E is a polymerizable, ethylenically unsaturated radical;

n is at least 2; and

(B) an ethylenically unsaturated silicone-containing monomer other than the macromonomer of Formula (I).

26. A macromonomer useful in the preparation of a low water polymeric silicone composition consisting of the following Formula (Ia):

space="preserve" listing-type="equation">(X)(E).sub.n (Ia)

wherein;

X is derived from a copolymer prepared by reacting the following components;

(a) at least 80 mole % of an ethylenically unsaturated silicon-containing monomer,

(b) 2.5 to 20 mole % of an ethylenically unsaturated monomer containing an active hydrogen atom,

(c) 0 to 15 mole % of an ethylenically unsaturated monomer other than monomers (a) or (b), and

(d) 2.5 to 20 mole % of a chain transfer agent,

the weight percent of components (a), (b), (c) and (d) being based on the total amount of said components;

E is a polymerizable, ethylenically unsaturated radical; and

n is at least 2;

wherein the low water polymeric silicone composition when cured absorbs maximumly 5% or less of water base on the total weight of the polymeric silicone and water.