Polysiloxane prepolymers for biomedical devices

• US 7,632,876 B2
• Filed: 12/02/2005
• Issued: 12/15/2009
• Est. Priority Date: 12/29/2004
• Status: Expired due to Fees

• Current Assignee: Bausch & Lomb Incorporated (Bausch Health Cos., Inc.)
• Original Assignee: Bausch & Lomb Incorporated (Bausch Health Cos., Inc.)
• Inventors: Lai, Yu-Chin, Quinn, Edmond T., Lang, Weihong
• Primary Examiner(s): Gulakowski; Randy
• Assistant Examiner(s): Ojurongbe; Olatunde S
• Application Number:
  US11/293,575
• Publication Number:
  US 20060142526A1
• Time in Patent Office: 1,474 Days
• Field of Search: 528/28, 528 44- 45, 528/59, 523106-107, 428446-447
• US Class Current: 523/106
• CPC Class Codes: A61L 2430/16 for reconstruction of eye parts, e.g. intraocular lens, cornea
• CPC Class Codes: A61L 27/18 obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: C08F 283/12 on to polysiloxanes
• CPC Class Codes: C08F 290/06 Polymers provided for in subclass C08G
• CPC Class Codes: C08G 18/10 Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• CPC Class Codes: C08G 18/61 Polysiloxanes
• CPC Class Codes: C08G 18/672 Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
• CPC Class Codes: C08G 18/755 and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
• CPC Class Codes: C08G 2210/00 Compositions for preparing hydrogels
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 51/08 grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
• CPC Class Codes: C08L 51/085 on to polysiloxanes
• CPC Class Codes: C08L 53/00 Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 83/04 Polysiloxanes
• CPC Class Codes: G02B 1/043 Contact lenses
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane

Abstract

A polysiloxane prepolymer that is useful for forming biomedical devices has the formula:
M(*Dii*PS)_x*Dii*M  (I)
wherein:

• • each M is independently a polymerizable ethylenically unsaturated radical;
  • each Dii is independently a diradical residue of a diisocyanate;
  • each PS is independently a diradical residue of a polysiloxane-diol or a polysiloxane-diamine;
  • each * is independently —NH—CO—NH—, —NH—COO— or —OCO—NH—; and
  • x is at least 2.

Claims

1. A hydrogel copolymer that is the hydrated polymerization product of a monomeric mixture comprising a prepolymer represented by the general formula:

M(*Dii*PS)_x*Dii*M 

 

(I)

wherein;

each M is independently a polymerizable ethylenically unsaturated radical;

each Dii is independently a diradical residue of a diisocyanate;

each PS is independently a diradical residue of a polysiloxane-diol or a polysiloxane-diamine;

each * is independently —

NH—

CO—

NH—

, —

NH—

COO—

or OCO—

NH—

; and

x is at least 2, and a hydrophilic comonomer, and wherein the hydrogel copolymer has sufficient optical quality and an oxygen permeability of at least 150 barrers.

2. The hydrogel copolymer of claim 1, wherein each Dii is a diradical residue of a diisocyanate selected from the group consisting of isophorone diisocyanate, hexamethylene-1,6-diisocyanate, 4,4′

-dicyclohexylmethane diisocyanate, toluene diisocyanate, 4,4′

-diphenyl diisocyanate, 4,4′

-diphenylmethane diisocyanate, p-phenylene diisocyanate, 1,4-phenylene 4,4′

-diphenyl diisocyanate, 1,3-bis-(4,4′

-isocyanto methyl) cyclohexane, and cyclohexane diisocyanate.

3. The hydrogel copolymer of claim 1, wherein Mn of PS ranges from 1000 to 8000.

4. The hydrogel copolymer of claim 1, wherein x is at least 3.

5. The hydrogel copolymer of claim 1, wherein each M is independently a polymerizable ethylenically unsaturated radical of the formula:

6. The hydrogel copolymer of claim 1, wherein:

each M is 2-ethylenemethacrylate;

each Dii is the diradical residue of isophorone diisocyanate;

each PS is a diradical residue of a polydimethylsiloxane-diol having Mn of at least 2000 to 3600; and

each * is —

NH—

COO—

or —

OCO—

NH—

.

7. The hydrogel copolymer of claim 1, wherein the hydrophilic monomer is selected from the group consisting of:

unsaturated carboxylic acids;

(meth)acrylic substituted alcohols;

vinyl lactams; and

(meth)acrylamides.

8. The hydrogel copolymer of claim 7, wherein the hydrophilic monomer is selected from the group consisting of:

methacrylic acid;

acrylic acid;

2-hydroxyethylmethacrylate;

glyceryl methacrylate;

N-vinyl pyrrolidone;

methacrylamide; and

N,N-dimethylacrylamide.

9. The hydrogel copolymer of claim 1, wherein the monomeric mixture further comprises a monofunctional silicone-containing monomer.

10. The hydrogel copolymer of claim 9, wherein the monomeric mixture further comprises methacryloxypropyl tris(trimethylsiloxy)silane.

11. The hydrogel copolymer of claim 1, having a water content of at least 20 weight percent.

12. The hydrogel copolymer of claim 1, having a modulus no greater than 100 g/mm².

13. The hydrogel copolymer of claim 1, having a water content of at least 20 weight percent, and a modulus no greater than 100 g/mm².

14. A biomedical device comprising a hydrogel copolymer of claim 1.

15. The hydrogel copolymer of claim 1, wherein x is at least 2 to about 5.

16. The hydrogel copolymer of claim 1 wherein each PS is a diradical residue of a polydimethylsiloxane-diol having Mn of at least 2000 to 3600.

17. An ophthalmic device comprising a hydrogel copolymer that is the hydrated polymerization product of a monomeric mixture comprising a prepolymer represented by the general formula:

M(*Dii*PS)_x*Dii*M 

 

(I)

wherein;

each M is independently a polymerizable ethylenically unsaturated radical;

each Dii is independently a diradical residue of a diisocyanate;

each PS is independently a diradical residue of a polysiloxane-diol or a polysiloxane-diamine;

each * is independently —

NH—

CO—

NH—

, —

NH—

COO—

or OCO—

NH—

; and

x is at least 2, and a hydrophilic comonomer, and wherein the hydrogel copolymer has sufficient optical quality and an oxygen permeability of at least 150 barrers, wherein the ophthalmic device is a contact lens or an intraocular lens.

18. The ophthalmic device of claim 17, wherein x is at least 2 to about 5.

19. The ophthalmic device of claim 17, wherein the monomeric mixture further comprises a monofunctional silicone-containing monomer.

20. The ophthalmic device of claim 17, wherein each PS is a diradical residue of a polydimethylsiloxane-diol having Mn of at least 2000 to 3600.

21. The ophthalmic device of claim 17, having a water content of at least 20 weight percent, a modulus no greater than 100 g/mm².

22. A contact lens comprising a hydrogel copolymer that is the hydrated polymerization product of a monomeric mixture comprising a prepolymer represented by the general formula:

M(*Dii*PS)_x*Dii*M 

 

(I)

wherein;

each M is independently a polymerizable ethylenically unsaturated radical;

each Dii is independently a diradical residue of a diisocyanate;

each PS is a diradical residue of a polydimethylsiloxane-diol having Mn of at least 2000 to 3600;

each * is independently —

NH—

CO—

NH—

, —

NH—

COO—

or OCO—

NH—

; and

x is at least 2, and a hydrophilic comonomer, and wherein the hydrogel copolymer has sufficient optical quality and an oxygen permeability of at least 100 barrers.

23. The contact lens of claim 22 having a water content of at least 20 weight percent, and a modulus no greater than 100 g/mm².

24. The contact lens of claim 22 wherein x is at least 2 to 5.