Polymerizable polysiloxanes with hydrophilic substituents

Patent metadata

Field	Value
Publication number	US-9720139-B2
Application number	US-201715446057-A
Country	US
Kind code	B2
Filing date	Mar 1, 2017
Priority date	Sep 26, 2014
Publication date	Aug 1, 2017
Grant date	Aug 1, 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. A contact lens comprising a silicone hydrogel material comprising repeating units of an actinically-polymerizable amphiphilic polysiloxane of formula (1) or (2)

in which:
υ1, υ2, 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,

wherein the contact lens has a water content of from about 20% to about 75% by weight when fully hydrated, an oxygen permeability (Dk) of at least about 40 barrers, and an elastic modulus of from about 0.1 MPa to about 2.0 MPa.

2. A method for making silicone hydrogel contact lenses, comprising the steps of: introducing a lens-forming formulation into a mold for making contact lenses, wherein the lens-forming formulation comprises
(a) a solvent selected from the group consisting of water, 1,2-propylene glycol, a polyethyleneglycol having a molecular weight of about 400 Daltons or less, and mixtures thereof,
(b) at least one amphiphilic siloxane-containing vinylic monomer of formula (1) or (2)

in which:
υ1, υ2, 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, (but preferably are methyl),
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 (preferably methy), 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 i

Assignees

• Novartis Ag

Inventors

• Chang Frank
• Huang Jinyu
• Shankar Venkat

Classifications

• C08G77/445

  containing polyester sequences · CPC title

• G02B1/043 Primary

  Contact lenses · CPC title

• C08F290/068

  Polysiloxanes · CPC title

• C08G77/20 Primary

  containing silicon bound to unsaturated aliphatic groups · CPC title

• C08G2210/00

  Compositions for preparing hydrogels · CPC title