Hydrophilized carbosiloxane vinylic monomers

Patent metadata

Field	Value
Publication number	US-10082604-B2
Application number	US-201715598652-A
Country	US
Kind code	B2
Filing date	May 18, 2017
Priority date	Apr 25, 2014
Publication date	Sep 25, 2018
Grant date	Sep 25, 2018

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 polymer comprising monomeric units derived in a free-radical polymerization from a carbosiloxane vinylic monomer of any one of formula (I), (I-1-g), (I-1-h), (I-1-i), (I-2-g), and (I-2 h)

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-pyrolidone, 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 —;
R º is H or C 1 -C 10 alkyl;
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;
g1 is an integer from 3 to 500;
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;
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).

2. The polymer of claim 1 , wherein the polymer is an actinically-crosslinkable prepolymer having two or more ethylenically unsaturated groups.

3. The polymer of claim 2 , wherein the actinically-crosslinkable prepolymer further comprises hydrophilic units derived in the free radical polymerization from at least one hydrophilic vinylic monomer.

4. The polymer of claim 1 , wherein the polymer is a silicone hydrogel material which further comprises hydrophilic units derived in the free radical polymerization from at least one hydrophilic vinylic monomer.

5. A silicone hydrogel contact lens, comprising a silicone hydrogel material of claim 4 .

6. A silicone hydrogel contact lens which is obtained by polymerizing a polymerizable composition comprising an actinically-crosslinkable prepolymer of claim 3 .

7. The silicone hydrogel contact lens of claim 5 , 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 40 barrers, an elastic modulus of from about 0.1 MPa to about 2.0 MPa, and a relatively-long thermal stability as defined by having an average change in elastic modulus of about 10% or less in accelerated shelf life studies carried out at an elevated temperature for a period of 60 days relative to the elastic modulus of control silicone hydrogel contact lenses before being stored at the elevated temperature.

8. The silicone hydrogel contact lens of claim 5 , wherein the silicone hydrogel material comprises monomeric units of a carbosiloxane monomer of formula (I) in which Q is a (meth)acryloyloxy or (meth)acrylamido group.

9. The silicone hydrogel contact lens of claim 5 , wherein the silicone hydrogel material comprises monomeric units of a carbosiloxane monomer of any one of formula (I-1-c)-(I-1-h), (I-2-c)-(I-2-h), (I-3-c)-(I-3-h), (I-4-c)-(I-4-h), and (I-5-c)-(I-5-h)

10. The silicone hydrogel contact lens of claim 8 , wherein G 1 , G 2 , G 3 , and G 4 are phosphocholine groups.

11. The silicone hydrogel contact lens of claim 8 , wherein G 1 , G 2 , G 3 , and G 4 are poly(oxazoline) chains.

12. The silicone hydrogel contact lens of claim 8 , wherein G 1 , G 2 , G 3 , and G 4 are poly(ethyleneglycol) chains.

13. The silicone hydrogel contact lens of claim 8 , 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).

14. The polymer of claim 3 , wherein the silicone hydrogel material comprises monomeric units of a carbosiloxane monomer of formula (I) in which Q is a (meth)acryloyloxy or (meth)acrylamido group.

15. The polymer of claim 3 , wherein the silicone hydrogel material comprises monomeric units of a carbosiloxane monomer of any one of formula (I-1-c)-(I-1-h), (I-2-c)-(I-2-h), (I-3-c)-(I-3-h), (I-4-c)-(I-4-h), and (I-5-c)-(I-5-h)

16. The polymer of claim 14 , wherein G 1 , G 2 , G 3 , and G 4 are phosphocholine groups.

17. The polymer of claim 14 , wherein G 1 , G 2 , G 3 , and G 4 are poly(oxazoline) chains.

18. The polymer of claim 14 , wherein G 1 , G 2 , G 3 , and G 4 are poly(ethyleneglycol) chains.

19.

Assignees

• Novartis Ag

Inventors

• Huang Jinyu
• Chang Frank

Classifications

• C08G77/50

  by carbon linkages · CPC title

• C08F283/124

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

• C08G77/395

  containing phosphorus · CPC title

• C08G77/392

  containing sulfur · CPC title

• C07F9/092

  substituted by B, Si or a metal · CPC title