Amphiphilic branched polydiorganosiloxane macromers

• US 10,138,316 B2
• Filed: 12/13/2016
• Issued: 11/27/2018
• Est. Priority Date: 12/15/2015
• Status: Active Grant

• Current Assignee: Alcon Incorporated
• Original Assignee: Novartis Ag
• Inventors: Chang, Frank, Huang, Jinyu, Holland, Troy Vernon
• Primary Examiner(s): Salamon, Peter A
• Application Number:
  US15/376,707
• Publication Number:
  US 20170166675A1
• Time in Patent Office: 714 Days
• Field of Search: None
• CPC Class Codes: C08F 220/40 Esters of unsaturated alcohols , e.g. allyl (meth)acrylate
• CPC Class Codes: C08F 222/102 of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
• CPC Class Codes: C08F 222/38 Amides
• CPC Class Codes: C08F 2438/01 Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
• CPC Class Codes: C08F 283/124 on to polysiloxanes having carbon-to-carbon double bonds
• CPC Class Codes: C08F 290/068 Polysiloxanes
• CPC Class Codes: C08G 2210/00 Compositions for preparing hydrogels
• CPC Class Codes: C08G 77/20 containing silicon bound to unsaturated aliphatic groups C08G77/045 takes precedence
• CPC Class Codes: C08L 2312/06 by radiation
• CPC Class Codes: G02B 1/043 Contact lenses

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.

Claims

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-C₂-C₄ alkoxy group, (meth)acrylamido-C₂-C₄ alkoxy group, (meth)acryloxy-C₂-C₄ alkylamino group, (meth)acrylamido-C₂-C₄ alkylamino group, C₁-C₆ substituted or unsubstituted alkoxy group, C₂-C₆ substituted or unsubstituted alkanoyloxy group, or C₁-C₆ 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 C₁-C₄-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 C₁-C₄-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)

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)