Polymerizable polysiloxanes with hydrophilic substituents

Patent metadata

Field	Value
Publication number	US-9637582-B2
Application number	US-201514859486-A
Country	US
Kind code	B2
Filing date	Sep 21, 2015
Priority date	Sep 26, 2014
Publication date	May 2, 2017
Grant date	May 2, 2017

Abstract

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.

First claim

What is claimed is:

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.

Assignees

• Novartis Ag

Inventors

• Chang Frank
• Huang Jinyu
• Shankar Venkat

Classifications

• C08J3/28

  Treatment by wave energy or particle radiation · CPC title

• C08G77/38

  Polysiloxanes modified by chemical after-treatment · CPC title

• C08F220/585

  and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS] · CPC title

• C08J3/03

  in aqueous media · CPC title

• C08F290/068

  Polysiloxanes · CPC title