Fluorinated poly(ether)s end-capped with polymerizable cationic hydrophilic groups
View Patent ↗The present invention relates to polymeric compositions useful in the manufacture of biocompatible medical devices. More particularly, the present invention relates to certain cationic monomers capable of polymerization to form polymeric compositions having desirable physical characteristics useful in the manufacture of ophthalmic devices. The polymer compositions comprise polymerized fluorinated polyether monomer end-capped with ethylenically unsaturated cationic hydrophilic groups.
1. A medical device comprising a polymerization product of a mixture comprising a fluorinated polyether monomer, wherein the fluorinated polyether monomer is end-capped with ethylenically unsaturated cationic hydrophilic groups, and further wherein the medical device is selected from the group consisting of heart valves, intraocular lenses, films, surgical devices, vessel substitutes, intrauterine devices, membranes, diaphragms, surgical implants, blood vessels, artificial ureters, artificial breast tissue, membranes for kidney dialysis machines, membranes for heart/lung machines, catheters, mouth guards, denture liners, ophthalmic devices, and contact lenses.
2. The device of claim 1 wherein the fluorinated polyether monomer is a monomer of formula (I):
wherein L can be the same or different and is selected from the group consisting of a bond, hydrogen, urethanes, carbonates, carbamates, carboxyl ureidos, sulfonyls, a straight or branched C1-C30 alkyl group, a C1-C30 fluoroalkyl group, a C1-C20 ester-containing group, an alkyl ether, cycloalkyl ether, cycloalkenyl ether, aryl ether, arylalkyl ether, a polyether containing group, an ureido group, an amide group, an amine group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C3-C30 cycloalkylalkyl group, a substituted or unsubstituted C3-C30 cycloalkenyl group, a substituted or unsubstituted C5-C30 aryl group, a substituted or unsubstituted C5-C30 arylalkyl group, a substituted or unsubstituted C5-C30 heteroaryl group, a substituted or unsubstituted C3-C30 heterocyclic ring, a substituted or unsubstituted C4-C30 heterocyclolalkyl group, a substituted or unsubstituted C6-C30 heteroarylalkyl group, a C5-C30 fluoroaryl group, or a hydroxyl substituted alkyl ether and combinations thereof; X − is at least a single charged counter ion; m is 1-5, and n is 1-10,000; each Rf is independently hydrogen, fluorine, a C5-C30 fluoroaryl group, a C1-C30 fluoroalkyl group, or combinations thereof with the proviso that at least some, but not all, Rf is hydrogen; R is independently hydrogen, a straight or branched C1-C30 alkyl group, a C1-C20 ester-containing group, an alkyl ether, cycloalkyl ether, cycloalkenyl ether, aryl ether, arylalkyl ether, a polyether containing group, an ureido group, an amide group, an amine group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C3-C30 cycloalkylalkyl group, a substituted or unsubstituted C3-C30 cycloalkenyl group, a substituted or unsubstituted C5-C30 aryl group, a substituted or unsubstituted C5-C30 arylalkyl group, a substituted or unsubstituted C5-C30 heteroaryl group, a substituted or unsubstituted C3-C30 heterocyclic ring, a substituted or unsubstituted C4-C30 heterocyclolalkyl group, a substituted or unsubstituted C6-C30 heteroarylalkyl group or a hydroxyl group; Z, when present, is R or V; and V is independently a polymerizable ethylenically unsaturated organic radical.
3. The device of claim 2 wherein X − of the monomer of formula I is selected from the group consisting of Cl − , Br − , I − , CF 3 CO 2 − , CH 3 CO 2 − , HCO 3 − , CH 3 SO 4 − , p-toluenesulfonate, HSO 4 − , H 2 PO 4 − , NO 3 − , CH 3 CH(OH)CO 2 − , SO 4 2− , CO 3 2− , HPO 4 2− and mixtures thereof.
4. The device of claim 2 wherein X − of the monomer of formula I is at least a single charged counter ion and is selected from the group consisting of Cl − , Br − , I − , CF 3 CO 2 − , CH 3 CO 2 − , HCO 3 − , CH 3 SO 4 − , p-toluenesulfonate, HSO 4 − , H 2 PO 4 − , NO 3 − , and CH 3 CH(OH)CO 2 − and mixtures thereof.
5. The device of claim 1 wherein the mixture further comprises at least one second monomer.
6. The device of claim 1 wherein the mixture further comprises a hydrophobic monomer, a hydrophilic monomer or both.
7. The device of claim 1 wherein the mixture further comprises a second monomer selected from the group consisting of unsaturated carboxylic acids, acrylic substituted alcohols, vinyl lactams, acrylamides, methacrylates, hydrophilic vinyl carbonates, hydrophilic vinyl carbamate monomers, hydrophilic oxazolone monomers, and mixtures thereof.
8. The device of claim 1 wherein the mixture further comprises a second monomer selected from the group consisting of methacrylic acids, acrylic acids, 2-hydroxyethylmethacrylate, 2-hydroxyethylacrylate, N-vinyl pyrrolidone (NVP) N-vinyl caprolactone, methacrylamide, N,N-dimethylacrylamide, ethylene glycol dimethacrylate, methyl methacrylate, 3-methacryloyloxypropyl tris(trimethylsiloxy)silane, ethylene glycol dimethacrylate (EGDMA), allyl methacrylate (AMA) and mixtures thereof.
9. The device of claim 1 wherein the device is a contact lens.
10. The device of claim 9 wherein the contact lens is a rigid gas permeable contact lens.
11. The device of claim 9 wherein the contact lens is a soft contact lens.
12. The device of claim 9 wherein the contact lens is a hydrogel contact lens.
13. The device of claim 1 wherein the device is an intraocular lens.
14. The device of claim 13 wherein the intraocular lens is a phakic intraocular lens.
15. The device of claim 13 wherein the intraocular lens is an aphakic intraocular lens.
16. The device of claim 1 wherein the device is a corneal implant.