Hydrophilized carbosiloxane vinylic monomers

Patent metadata

Field	Value
Publication number	US-9684095-B2
Application number	US-201514694150-A
Country	US
Kind code	B2
Filing date	Apr 23, 2015
Priority date	Apr 25, 2014
Publication date	Jun 20, 2017
Grant date	Jun 20, 2017

Abstract

The invention provides a hydrophilized carbosiloxane vinylic monomer which comprises (1) a poly(carbosiloxane) segment, (2) one sole ethylenically unsaturated group, and (3) at least one terminal or pendant group which is a hydrophilic group or hydrophilic polymer chain. 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 monomeric units derived from a hydrophilized carbosiloxane vinylic monomer of the invention.

First claim

What is claimed is:

1. A carbosiloxane vinylic monomer of formula (I)

in which
e1, e2, e3, and e4 independent of one another are an integer of 0 or 1, provided that at least one of e1, e2, e3, and e4 is an integer of 1 and (e1+e2+e3)≦2,
n1 is an integer of 2 or 3,
n2 is an integer of from 2 to 100,
E is C 1 -C 6 alkyl radical or

in which R 7 , R 8 or R 9 independent of one another is a C 1 -C 6 alkyl,
G 1 , G 2 , G 3 , and G 4 independent of one another are selected from the group consisting of phosphocholine group, a poly(oxazoline) chain, a poly(ethyleneglycol) chain, a linear hydrophilic polymer chain 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,
L 1 is a covalent bond or a C 1 -C 6 alkyl diradical,
L 2 is a C 1 -C 6 alkyl diradical,
L 3 is a C 1 -C 6 alkyl diradical if e4 is an integer of 1 or a covalent bond if e4 is an integer of 0,
R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 independent of one another are a C 1 -C 6 alkyl radical, Q is the ethylenically unsaturated group,
T 1 , T 2 , and T 3 independent of one another are a C 1 -C 6 alkyl tri-radical
X 1 , X 2 , and X 3 independent of one another is —O—, —NR o —, —CO—NR o —, —NR o —CO—, —NR o —CO—NH—, —NH—CO—NR o —, —O—CO—NH—, —NH—CO—O—, —O—CO—, —CO—O—, —NR o —CO—NH-L 4 -NH—CO—NR o —, —O—CO—NH-L 4 -NH—CO—O—, —NR o —CO—NH-L 4 -NH—CO—O—, or —O—CO—NH-L 4 -NH—CO—NR o — in which R o is H or C 1 -C 10 alkyl and L 4 is an alkyl diradical, a cycloalkyl diradical, an alkylcycloalkyl diradical, an alkylaryl diradical, or an aryl diradical with up to 40 carbon atoms.

2. The carbosiloxane vinylic monomer of claim 1 , wherein Q is a (meth)acryloyloxy or (meth)acrylamido group.

3. The carbosiloxane vinylic monomer of claim 1 , wherein the carbosiloxane vinylic monomer is represented by one of formula (I-1-c)-(I-1-f), (I-2-c)-(I-2-f), (I-3-c)-(I-3-h), (I-4-c)-(I-4-h), and (I-5-c)-(I-5-h)

in which
n2 is an integer of from 2 to 100;
q1 is an integer from 3 to 500;
R o is hydrogen or C 1 -C 10 -alkyl;
R 1 ″, R 2 ″ and R 3 ″ independently of one another are C 1 -C 8 alkyl or C 1 -C 8 hydroxyalkyl;
R 4 ″ and R 5 ″ independently of one another are methyl or ethyl;
PC is a phosphocholine group of

in which R 1 ″, R 2 ″ and R 3 ″ are as defined above;
POZO is a polyoxazoline polymer chain of

in which q1 is as defined above;
Dii is a diurethane linkage of

in which L 4 is an alkyl diradical, a cycloalkyl diradical, an alkylcycloalkyl diradical, an alkylaryl diradical, or an aryl diradical with up to 40 carbon atoms;
HPC is a hydrophilic polymer chain selected from the group consisting of a poly(ethyleneglycol) chain, a poly(N-vinylpyrrolidone) chain, a poly[N,N-dimethyl (meth)acrylamide] chain, a poly[(meth)acrylamide] chain, a poly(N-vinyl-N-methyl acetamide) chain, a poly(N-vinyl acetamide) chain, a poly(N-vinyl formamide) chain, and a poly(N-methyl-3-methylene-2-pyrrolidone).

4. The carbosiloxane vinylic monomer of claim 1 , wherein G 1 , G 2 , G 3 , and G 4 are phosphocholine groups.

5. The carbosiloxane vinylic monomer of claim 1 , wherein G 1 , G 2 , G 3 , and G 4 are poly(oxazoline) chains.

6. The carbosiloxane vinylic monomer of claim 1 , wherein G 1 , G 2 , G 3 , and G 4 are poly(ethyleneglycol) chains.

7. The carbosiloxane vinylic monomer of claim 1 , wherein G 1 , G 2 , G 3 , and G 4 independent of one another are selected from the group consisting of a poly(N-vinylpyrrolidone) chain, a poly[N,N-dimethyl (meth)acrylamide] chain, a poly[(meth)acrylamide] chain, a poly(N-vinyl-N-methyl acetamide) chain, a poly(N-vinyl acetamide) chain, a poly(N-vinyl formamide) chain, and a poly(N-methyl-3-methylene-2-pyrrolidone).

8. A carbosiloxane vinylic monomer of any one of formula (I-1-g), (I-1-h), (I-1-i), (I-2-g), and (I-2-h)

in which
n2 is an integer of from 2 to 100;
R o is hydrogen or C 1 -C 10 -alkyl;
R 4 ″ and R 5 ″ independently of one another are methyl or ethyl;
Dii is a diurethane linkage of

in which L 4 is an alkyl diradical, a cycloalkyl diradical, an alkylcycloalkyl diradical, an alkylaryl diradical, or an aryl diradical with up to 40 carbon atoms;
HPC is a hydrophilic polymer chain selected from the group consisting of a poly(ethyleneglycol) chain, a poly(N-vinylpyrrolidone) chain, a poly[N,N-dimethyl (meth)acrylamide] chain, a poly[(meth)acrylamide] chain, a poly(N-vinyl-N-methyl acetamide) chain, a poly(N-vinyl acetamide) chain, a poly(N-vinyl formamide) chain, and a poly(N-methyl-3-methylene-2-pyrrolidone).

Assignees

• Novartis Ag

Inventors

• Huang Jinyu
• Chang Frank

Classifications

• C08G77/38

  Polysiloxanes modified by chemical after-treatment · CPC title

• C08G77/395

  containing phosphorus · CPC title

• C07F9/092

  substituted by B, Si or a metal · CPC title

• C08G77/392

  containing sulfur · CPC title

• C08F283/124

  on to polysiloxanes having carbon-to-carbon double bonds · CPC title