Amphiphilic branched polydiorganosiloxane macromers

Patent metadata

Field	Value
Publication number	US-10138316-B2
Application number	US-201615376707-A
Country	US
Kind code	B2
Filing date	Dec 13, 2016
Priority date	Dec 15, 2015
Publication date	Nov 27, 2018
Grant date	Nov 27, 2018

Abstract

The invention provides a class of amphiphilic branched macromers and the uses thereof. An amphiphilic branched polydiorganosiloxane macromer of the invention is produced from an α,ω-dimethacryloyl-terminated polydiorganosiloxane vinylic crosslinker comprising one or more ATRP-containing siloxane units having one substituent having an ATRP initiator by ATRP polymerization of one or more hydrophilic vinylic monomers. It comprises at least two polydiorganosiloxane polymer chains each having at most two terminal methacryloxy groups, dangling hydrophilic polymer chains each having a polymerizable or non-polymerizable terminal group, and one or more hydrophilic polymer chains as linkages between two polydiorganosiloxane chains. The present invention is also related to a silicone hydrogel contact lens, which comprises units derived from a polydiorganosiloxane-containing amphiphilic branched macromer of the invention.

First claim

What is claimed is:

1. An amphiphilic branched polydiorganosiloxane macromer, comprising:
(1) at least first one polydiorganosiloxane polymer chain having two terminal methacryloyl groups; and
(2) at least one first hydrophilic chain;
(3) at least one second hydrophilic polymer chain; and
(4) at least one second polydiorganosiloxane polymer chain at least one end of which is covalently connected to the second hydrophilic polymer chain,
wherein the first and second polydiorganosiloxane chains are derived from an α,ω-dimethacryloyl-terminated polydiorganosiloxane vinylic crosslinker comprising one or more ATRP-containing siloxane units having one substituent having an ATRP initiator,
wherein the first hydrophilic chain is anchored covalently onto one single ATRP-containing siloxane unit of the first or second polydiorganosiloxane chain at one of the two ends of the first hydrophilic polymer chain and has one first terminal group at the other one of the two ends of the first hydrophilic polymer chain,
wherein the second hydrophilic polymer chain is (a) anchored covalently onto one single ATRP-containing siloxane unit of the first polydiorganosiloxane chain at one of the two ends of the second hydrophilic polymer chain, (b) has one second terminal group at the other one of the two ends of the second hydrophilic polymer chain, and (c) is covalently connected to covalently connected to one of the two ends of the second polydiorganosiloxane chain,
wherein the first and second terminal groups independent of each other are (meth)acryloxy group, (meth)acryloxy-C 2 -C 4 alkoxy group, (meth)acrylamido-C 2 -C 4 alkoxy group, (meth)acryloxy-C 2 -C 4 alkylamino group, (meth)acrylamido-C 2 -C 4 alkylamino group, C 1 -C 6 substituted or unsubstituted alkoxy group, C 2 -C 6 substituted or unsubstituted alkanoyloxy group, or C 1 -C 6 substituted or unsubstituted alkylamino group, wherein the first and second hydrophilic polymer chains are composed of monomeric units of 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, hydroxyethyl (meth)acrylate, hydroxyethyl (meth)acrylamide, hydroxypropyl (meth)acrylamide, glycerol methacrylate (GMA), polyethylene glycol (meth)acrylate, polyethylene glycol C 1 -C 4 -alkyl ether (meth)acrylate having a number average molecular weight of up to 1500, and mixtures thereof.

2. The amphiphilic branched polydiorganosiloxane macromer of claim 1 , wherein the first and second hydrophilic polymer chains are composed of monomeric units of at least one hydrophilic vinylic monomer selected from the group consisting of selected from the group consisting of N,N-dimethyl (meth)acrylamide, (meth)acrylamide, N-vinyl-N-methyl acetamide, N-vinylpyrrolidone, hydroxyethyl (meth)acrylate, hydroxyethyl (meth)acrylamide, glycerol methacrylate, polyethylene glycol C 1 -C 4 -alkyl ether (meth)acrylate having a number average molecular weight of up to 1500, and combinations thereof.

3. The amphiphilic branched polydiorganosiloxane macromer of claim 2 , wherein the α,ω-dimethacryloxy-terminated polydiorganosiloxane vinylic crosslinker comprising one or more ATRP-containing siloxane units having one substituent having an ATRP initiator has formula (1)

in which: X 0 is O or NR′ in which R′ is hydrogel or C 1 -C 10 alkyl, υ1 is an integer of from 30 to 500 and ω1 is an integer of from 1 to 75, provided that ω1/υ1 is from about 0.003 to about 0.20; R 2 and R 3 independently of each other are a substituted or unsubstituted C 2 -C 6 alkylene divalent radical or a divalent radical of —R 5 —O—R 6 — in which R 5 and R 6 independently of each other are a substituted or unsubstituted C 2 -C 6 alkylene divalent radical; R 4 is of formula (2) or (3)

in which: q1 is zero or 1; n1 is an integer of 3 to 9; R 7 is C 2 -C 6 substituted or unsubstituted alkylene diradical; R 8 and R 9 independent of each other are hydrogen or methyl; Hal is Cl or Br.

4. The amphiphilic branched polydiorganosiloxane macromer of claim 1 , wherein the α,ω-dimethacryloxy-terminated polydiorganosiloxane vinylic crosslinker comprising one or more ATRP-containing siloxane units having one substituent having an ATRP initiator has formula (1)

in which: X 0 is O or NR′ in which R′ is hydrogel or C 1 -C 10 alkyl, υ1 is an integer of from 30 to 500 and ω1 is an integer of from 1 to 75, provided that ω1/υ1 is from about 0.003 to about 0.20; R 2 and R 3 independently of each other are a substituted or unsubstituted C 2 -C 6 alkylene divalent radical or a divalent radical of —R 5 —O—R 6 — in which R 5 and R 6 independently of each other are a substituted or unsubstituted C 2 -C 6 alkylene divalent radical; R 4 is of formula (2) or (3)

in which: q1 is zero or 1; n1 is an integer of 3 to 9; R 7 is C 2 -C 6 substituted or unsubstituted alkylene diradical; R 8 and R 9 independent of each other are hydrogen or methyl; Hal is Cl or Br.

Assignees

• Novartis Ag

Inventors

• Chang Frank
• Huang Jinyu
• Holland Troy Vernon

Classifications

• C08L2312/06

  by radiation · CPC title

• C08F290/068 Primary

  Polysiloxanes · CPC title

• C08F220/40

  Esters of unsaturated alcohols {, e.g. allyl (meth)acrylate} · CPC title

• C08F283/124

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

• C08G2210/00

  Compositions for preparing hydrogels · CPC title