Polysiloxane prepolymers for biomedical devices

• US 7,423,074 B2
• Filed: 12/02/2005
• Issued: 09/09/2008
• 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): Zimmer; Marc S
• Application Number:
  US11/292,817
• Publication Number:
  US 20060142524A1
• Time in Patent Office: 1,012 Days
• Field of Search: None
• 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 290/06 Polymers provided for in subclass C08G
• CPC Class Codes: C08F 290/067 Polyurethanes; Polyureas
• CPC Class Codes: C08F 290/068 Polysiloxanes
• CPC Class Codes: C08F 290/14 Polymers provided for in subclass C08G
• CPC Class Codes: C08F 290/147 Polyurethanes; Polyureas
• CPC Class Codes: C08F 290/148 Polysiloxanes
• CPC Class Codes: C08F 293/00 Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule on to polymers modified by introduction of unsaturated end groups C08F290/02
• CPC Class Codes: C08F 293/005 using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
• 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 18/12 using two or more compounds having active hydrogen in the first polymerisation step
• CPC Class Codes: C08G 18/3206 aliphatic
• 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 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 75/16 : having terminal carbon-to-carbon unsaturated bonds
• CPC Class Codes: C08L 83/04 : Polysiloxanes
• CPC Class Codes: C08L 83/08 : containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
• CPC Class Codes: G02B 1/043 : Contact lenses

Abstract

A polysiloxane copolymer that is useful for forming biomedical devices comprises blocks (I) and (II) and is terminated at each end with an ethylenically unsaturated radical:
(*Dii*Diol*Dii*PS)_x   (I)
(*Dii*PS)_y   (II)
wherein:

• • each Dii is independently a diradical residue of a diisocyanate;
  • each Diol is independently a diradical residue of a diol having 1 to 10 carbon atoms;
  • each PS is independently a diradical residue of a polysiloxane-containing diol or diamine;
  • each * is independently —NH—CO—NH—, —NH—COO— or —OCO—NH—:
  • x represents the number of blocks (I) and is at least 2, and
  • y represents the number of blocks (II) and is at least 1.

Claims

1. A copolymer that is the polymerization product of a monomeric mixture comprising a copolymer represented by the general formulae,

M(*Dii*Diol*Dii*PS)_x(*Dii*PS)_y*Dii*M or

M(*Dii*Diol*Dii*PS)_x(*Dii*PS)_y*Dii*Diol*Dii*M

wherein:

each M is independently a polymerizable ethylenically unsaturated radical;

each Dii is independently a diradical residue of a diisocyanate;

each Diol is independently a diradical residue of a diol having 1 to 10 carbon atoms;

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—

;

x is at least 2, and

y is at least 1; and

a hydrophilic comonomer and a monofunctional silicone-containing monomer.

2. The copolymer of claim 1, wherein each Dii is independently a diradical residue of an aliphatic or an aromatic diisocyanate having 6 to 30 carbon atoms in the aliphatic or aromatic moiety.

3. The copolymer of claim 2, 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.

4. The copolymer of claim 1, wherein each Diol is independently selected from the group consisting of an alkyl diol, a cycloalkyl diol, an alkyl cycloalkyl diol, an aryl diol or an alkylaryl diol having 1 to 10 carbon atoms and which may contain ether, thio or amine linkages in the main chain.

5. The copolymer of claim 4, wherein each Diol is independently selected from the group consisting of 2,2-(4,4′

-dihydroxydiphenyl)propane (bisphenol-A), 4,4′

-iso-propylidine dicyclohexanol, ethoxylated and propoxylated bisphenol-A, 2,2-(4,4′

-dihydroxydiphenyl)pentane, 1,1′

-(4,4′

-dihydroxydiphenyl)-p-diisopropyl benzene, 1,3-cyclohexane diol, 1,4-cyclohexane diol, 1-4-cyclohexane dimethanol, neopentyl glycol, 1,4-butanediol, 1,3-propanediol, 1,5-pentanediol, ethylene glycol, diethylene glycol and triethylene glycol.

6. The copolymer of claim 1, wherein each PS is independently a diradical residue of a polysiloxane represented by the formula:

7. The copolymer of claim 6, wherein each R is alkylene, and each R′

is independently alkyl or fluoroalkyl optionally including ether linkages.

8. The copolymer of claim 6, wherein Mn of PS ranges from 1000 to 8000.

9. The copolymer of claim 1, wherein the ratio of x to y is at least 0.6.

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

11. The copolymer of claim 1, wherein:

each M is methacryloxyethyl;

each Dii is the diradical residue of isophorone diisocyanate;

each Diol is the diradical residue of diethyleneglycol;

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

each * is —

NH—

COO—

or —

OCO—

NH—

.

12. The copolymer of claim 1, wherein the hydrophilic monomer selected form the group consisting of:

ethylenically unsaturated carboxylic acids;

(meth)acrylic substituted alcohols;

vinyl lactams; and

(meth)acrylamides.

13. The copolymer of claim 12, wherein the hydrophilic monomer selected form the group consisting of:

methacrylic acid;

acrylic acid;

2-hydroxyethylmethacrylate;

glyceryl methacrylate;

N-vinyl pyrrolidone;

methacrylamide; and

N,N-dimethylacrylamide.

14. The copolymer of claim 1, wherein the monofunctional silicone-containing monomer is methacryloxypropyl tris(trimethylsiloxy)silane.

15. A hydrogel copolymer that is the hydrated polymerization product of a monomeric mixture comprising a copolymer represented by the general formulae,

M(*Dii*Diol*Dii*PS)_x(*Dii*PS)_y*Dii*M or

M(*Dii*Diol*Dii*PS)_x(*Dii*PS)_y*Dii*Diol*Dii*M

wherein;

each M is independently a polymerizable ethylenically unsaturated radical;

each Dii is independently a diradical residue of a diisocyanate;

each Diol is independently a diradical residue of a diol having 1 to 10 carbon atoms;

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—

;

x is at least 2, and

y is at least 1; and

a hydrophilic comonomer and a monofunctional silicone-containing monomer.

16. The hydrogel copolymer of claim 15, having a water content of at least 20 weight percent.

17. The hydrogel copolymer of claim 15, having a modulus no greater than 100 g/mm².

18. The hydrogel copolymer of claim 17, having a modulus between about 40 and 80 g/mm².

19. The hydrogel copolymer of claim 15, having an oxygen permeability of at least 100 barrers.

20. The hydrogel copolymer of claim 19, having an oxygen permeability of at least 150 barrers.

21. The hydrogel copolymer of claim 15, having a water content of at least 20 weight percent, a modulus between about 40 and 80 g/mm², and an oxygen permeability of at least 150 barrers.

22. A biomedical device comprising a copolymer of claim 15.

23. An ophthalmic device comprising a copolymer of claim 15.

24. The ophthalmic device of claim 23, that is a contact lens or an intraocular lens.