Polymerizable polysiloxanes with hydrophilic substituents
View Patent ↗The invention provides an actinically-polymerizable amphiphilic polysiloxane which comprises a polysiloxane polymer chain comprising a polylsiloxane segments comprising at least one siloxane unit having a low molecular weight hydrophilic polymer chain connected with a silicone atom of the siloxane unit, and (meth)acrylamido groups each covalently bonded to one of the ends of the polysiloxane polymer chain and/or to the end of one of low molecular weight hydrophilic polymer chains each connected with one silicone atom. The present invention is also related to a polymer, an actinically-crosslinkable silicone-containing prepolymer, a silicone hydrogel polymeric material, or a silicone hydrogel contact lens, which comprises repeating units derived from an actinically-polymerizable amphiphilic polysiloxane of the invention. In addition, the invention provides a method for making silicone hydrogel contact lenses using a water-based lens-forming formulation comprising an actinically-polymerizable amphiphilic polysiloxane of the invention and/or an actinically-crosslinkable silicone-containing prepolymer of the invention.
1. An actinically-polymerizable amphiphilic polysiloxane of formula (1) or (2)
in which:
ν1, ν2, and ω1 independently of one another are an integer of from 1 to 500;
ω2 independent of each other are an integer of from 1 to 10;
R 3 and R 4 , independently of each other, are a direct bond or a substituted or unsubstituted C 1 -C 10 alkylene divalent radical;
R 10 and R 11 , independently of each other, are a substituted or unsubstituted C 1 -C 10 alkylene divalent radical;
R 5 , R 6 , R 7 , R 8 , R 9 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 , independently of one another, are C 1 -C 8 -alkyl, C 1 -C 4 alkyl- or C 1 -C 4 alkoxy-substituted phenyl, or fluoro-substituted C 1 -C 18 -alkyl;
L 1 is a divalent radical of
in which R 18 is a substituted or unsubstituted C 1 -C 10 alkylene divalent radical and R 18 ′ is a direct bond or a substituted or unsubstituted C 1 -C 10 alkylene divalent radical, X 1 is a direct bond, a thio ether bond (—S—), —NR 20 — in which R 20 is a substituted or unsubstituted C 1 -C 10 alkyl, or a divalent radical of
in which R 19 is a substituted or unsubstituted C 1 -C 10 alkylene divalent radical and R 20 is a substituted or unsubstituted C 1 -C 10 alkyl;
L 2 is a direct bond or a substituted or unsubstituted C 1 -C 10 alkylene divalent radical;
E 1 , E 2 and E 3 , independent of one another, are hydrogen, substituted or unsubstituted C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, —NH 2 , —NHR′ with R′ being C 1 -C 10 alkyl, hydroxyl, carboxyl, Br, Cl, thiol, or a polymerizable group which is
in which r1 and r2 independent of each other are integer of 0 or 1, R″ is hydrogen or methyl, R 21 is a substituted or unsubstituted C 1 -C 10 alkylene divalent radical, X 2 is
in which R 22 and R 23 independent of each other are C 1 -C 8 alkyl, and R 19 is a substituted or unsubstituted C 1 -C 10 alkylene divalent radical, provided that either (i) E 1 and E 2 both are a polymerizable group or (ii) E 3 is a polymerizable group; and
hPC is a hydrophilic polymer segment selected from the group consisting of (1) polyoxazoline segment
in which R 1 is hydrogen, methyl or ethyl group, and q is an integer from 3 to 500) which is obtained in a ring-opening polymerization of oxazoline, (2) a polypeptide segment composed of at least one amino acid selected from the group consisting of asparagine, glutamine, alanine, glycine, and combinations thereof, and (3) a hydrophilic polymer segment composed of hydrophilic monomeric units derived from at least one hydrophilic vinylic monomer selected from the group consisting of (meth)acrylamide, N,N-dimethyl (meth)acrylamide, dimethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylamide, N-vinyl-2-pyrrolidone, N-vinyl-N-methyl isopropylamide, N-vinyl-N-methyl acetamide, N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide, N-vinyl-N-methyl acetamide, N-methyl-3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone, 1-n-propyl-3-methylene-2-pyrrolidone, 1-n-propyl-5-methylene-2-pyrrolidone, 1-isopropyl-3-methylene-2-pyrrolidone, 1-isopropyl-5-methylene-2-pyrrolidone, 1-n-butyl-3-methylene-2-pyrrolidone, 1-tert-butyl-3-methylene-2-pyrrolidone, and mixtures thereof.
2. The actinically-polymerizable amphiphilic polysiloxane of claim 1 , wherein E 1 and E 2 are an polymerizable group of
in which R″, R 21 , X 2 , r1 and r2 are as defined above while E 3 is hydrogen, substituted or unsubstituted C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, —NH 2 , —NHR′ with R′ being C 1 -C 10 alkyl, hydroxyl, carboxyl, Br, CI, or thiol.
3. The actinically-polymerizable amphiphilic polysiloxane of claim 1 , wherein E 1 and E 2 are hydrogen, substituted or unsubstituted C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, —NH 2 , —NHR′ with R′ being C 1 -C 10 alkyl, hydroxyl, carboxyl, Br, Cl, or thiol while E 3 is an polymerizable group polymerizable group of
in which R″, R 21 , X 2 , r1 and r2 are as defined above.
4. The actinically-polymerizable amphiphilic polysiloxane of claim 1 , wherein E 1 , E 2 and E 3 are an polymerizable group polymerizable group of
in which R″, R 21 , X 2 , r1 and r2 are as defined above.
5. The actinically-polymerizable amphiphilic polysiloxane of claim 1 , wherein R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 are methyl.
6. The actinically-polymerizable amphiphilic polysiloxane of claim 1 , wherein ν2 is an integer of an integer of from 3 to 350 while ω2 is an integer of from 1 to 10.
7. The actinically-polymerizable amphiphilic polysiloxane of claim 1 , wherein hPC is a hydrophilic polymer segment composed of hydrophilic monomeric units derived from at least one hydrophilic vinylic monomer selected from the group consisting of N-vinylpyrrolidone, N,N-dimethyl (meth)acrylamide, (meth)acrylamide, N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide, N-vinyl-N-methyl acetamide, N-methyl-3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone, and combinations thereof, and combinations thereof.
8. The actinically-polymerizable amphiphilic polysiloxane of claim 7 , being represented by formula (1).
9. The actinically-polymerizable amphiphilic polysiloxane of claim 8 , wherein ν1:ω1 is from about 7:3 to about 9.5:0.5.
10. The actinically-polymerizable amphiphilic polysiloxane of claim 1 , wherein hPC is a polyoxazoline segment.
11. The actinically-polymerizable amphiphilic polysiloxane of claim 10 , being represented by formula (1).
12. The actinically-polymerizable amphiphilic polysiloxane of claim 11 , wherein ν1:ω1 is from about 7:3 to about 9.5:0.5.
13. The actinically-polymerizable amphiphilic polysiloxane of claim 7 , being represented by formula (2).
14. The actinically-polymerizable amphiphilic polysiloxane of claim 10 , being represented by formula (2).
15. A polymer comprising repeating units of an actinically-polymerizable amphiphilic polysiloxane of claim 1 .
16. The polymer of claim 15 , wherein the polymer is an actinically-crosslinkable silicone-containing prepolymer which further comprises hydrophilic units of at least one hydrophilic vinylic monomer.