Polysiloxane prepolymers for biomedical devices
View Patent ↗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.
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:
wherein:
R 23 is hydrogen or methyl;
each R 24 is hydrogen, an alkyl radical having 1 to 6 carbon atoms, or a —CO—Y—R 26 radical wherein Y is —O—, —S— or —NH—;
R 25 is a divalent alkylene radical having 1 to 10 carbon atoms;
R 26 is a alkyl radical having 1 to 12 carbon atoms;
Q is —CO—, —OCO— or —COO—;
X is —O— or —NH—;
Ar is an aromatic radical having 6 to 30 carbon atoms;
b is 0 to 6; c is 0 or 1; d is 0 or 1; and e is 0 or 1.
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/mm 2 .
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/mm 2 .
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/mm 2 .
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/mm 2 .
24. The contact lens of claim 22 wherein x is at least 2 to 5.