Amphiphilic branched polydiorganosiloxane macromers

Patent metadata

Field	Value
Publication number	US-10597479-B2
Application number	US-201816175904-A
Country	US
Kind code	B2
Filing date	Oct 31, 2018
Priority date	Dec 15, 2015
Publication date	Mar 24, 2020
Grant date	Mar 24, 2020

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. A silicone hydrogel contact lens, comprising a crosslinked polymeric material which comprises units of an amphiphilic branched polydiorganosiloxane macromer, wherein the amphiphilic branched polydiorganosiloxane macromer comprises:
(1) at least first 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, 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,
wherein the silicone hydrogel contact lens, when being fully hydrated, has an oxygen permeability (Dk) of at least about 70 barrers, a water content of from about 25% to about 70% by weight, an elastic modulus of from about 0.20 MPa to about 1.2 MPa.

2. The silicone hydrogel contact lens of claim 1 , wherein the first and second hydrophilic polymr 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 silicone hydrogel contact lens 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 CI or Br.

4. The silicone hydrogel contact lens 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 CI or Br.

5. A method for producing silicone hydrogel contact lenses, comprising the steps of:
preparing a lens-forming composition which is clear at room temperature and optionally at a temperature of from about 0 to about 4° C., wherein the lens-forming composition comprises at least one amphiphilic branched polydiorganosiloxane macromer and at least one free-radical initiator, wherein the amphiphilic branched polydiorganosiloxane macromer comprises (1) at least first polydiorganosiloxane polymer chain having two terminal methacryloyl groups, (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

Assignees

• Novartis Ag
• Alcon Inc

Inventors

• Chang Frank
• Huang Jinyu
• Holland Troy Vernon

Classifications

• C08F2438/01

  Atom Transfer Radical Polymerization [ATRP] or reverse ATRP · CPC title

• C08G2210/00

  Compositions for preparing hydrogels · CPC title

• C08G77/20

  containing silicon bound to unsaturated aliphatic groups · CPC title

• C08L2312/06

  by radiation · CPC title

• C08F290/068 Primary

  Polysiloxanes · CPC title