Chain-extended polysiloxane crosslinkers with dangling hydrophilic polymer chains

• US 9,052,440 B2
• Filed: 08/06/2014
• Issued: 06/09/2015
• Est. Priority Date: 10/06/2010
• Status: Active Grant

• Current Assignee: Alcon Incorporated
• Original Assignee: Novartis Ag
• Inventors: Kuyu, Selma, Smith, Dawn Alison, Huang, Jinyu, Chang, Frank, Scott, Robert, Medina, Arturo Norberto, Shankar, Venkat
• Primary Examiner(s): Schnizer, Richard
• Assistant Examiner(s): Pipic, Alma
• Application Number:
  US14/453,021
• Publication Number:
  US 20140350124A1
• Time in Patent Office: 307 Days
• Field of Search: 523/107, 525/479, 424/429
• US Class Current: 1/1
• CPC Class Codes: A61K 47/34 Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyesters, polyamino acids, polysiloxanes, polyphosphazines, copolymers of polyalkylene glycol or poloxamers A61K47/10 takes precedence
• CPC Class Codes: A61P 27/02 Ophthalmic agents
• CPC Class Codes: C08G 77/20 containing silicon bound to unsaturated aliphatic groups C08G77/045 takes precedence
• CPC Class Codes: C08G 77/38 Polysiloxanes modified by chemical after-treatment C08G77/045 takes precedence
• CPC Class Codes: C08G 77/42 Block-or graft-polymers containing polysiloxane sequences polymerising aliphatic unsaturated monomers on to a polysiloxane C08F283/12
• CPC Class Codes: C08G 77/442 containing vinyl polymer sequences
• CPC Class Codes: C08G 77/46 containing polyether sequences
• CPC Class Codes: C08L 83/10 Block- or graft-copolymers containing polysiloxane sequences obtained by polymerising a compound having a carbon-to-carbon double bond on to a polysiloxane C08L51/08, C08L53/00
• CPC Class Codes: C08L 83/12 containing polyether sequences
• CPC Class Codes: C08L 83/14 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms C08L83/10 takes precedence
• CPC Class Codes: G02B 1/043 Contact lenses
• CPC Class Codes: G02B 2207/109 Sols, gels, sol-gel materials

Abstract

The invention provide a class of linear chain-extended polysiloxane crosslinkers which comprises two terminal ethylenically unsaturated groups, at least two polysiloxane segments, and dangling hydrophilic polymer chains each covalently attached to a divalent organic radical separating each pair of adjacent polysiloxane segments. The present invention is also related to a polymer comprising crosslinking units derived from chain-extended polysiloxane crosslinker of the invention and to ophthalmic lenses comprising such a polymer.

Claims

1. A soluble amphiphilic prepolymer, which is obtained by:

first polymerizing a polymerizable composition including

(1) at least one chain-extended polysiloxane crosslinker,

(2) at least one hydrophilic vinylic monomer,

(3) a chain transfer agent with or without a first reactive functional group other than a thiol group and/or a vinylic monomer having a second reactive functional group other than an ethylenically unsaturated group,

(4) optionally a hydrophobic vinylic monomer, and

(5) optionally a polymerizable UV-absorbing agent, to form an intermediary copolymer; and

then ethylenically functionalizing the intermediary copolymer with an ethylenically functionalizing vinylic monomer having a third reactive functional group capable of reacting with the first or second reactive functional group to form a linkage in a coupling reaction in the presence or absence of a coupling agent to form the prepolymer, wherein the first, second and third reactive functional groups independent of each other are selected from the group consisting of amino group, hydroxyl group, carboxyl group, acid halide group, azlactone group, isocyanate group, epoxy group, aziridine group, and combination thereof

wherein the linear chain-extended polysiloxane crosslinker comprises (a) two terminal ethylenically unsaturated groups, (b) at least two polysiloxane segments, and (c) at least one dangling hydrophilic polymer chain covalently attached to a divalent organic radical separating said at least two polysiloxane segments, wherein the linear chain extended polysiloxane crosslinker is as set forth by formula (I)

2. The prepolymer of claim 1, wherein the polymerizable composition comprises the polymerizable UV-absorbing agent.

4. An ophthalmic lens, comprising a silicone hydrogel material that is obtained by curing a lens-forming composition including a soluble amphiphilic prepolymer of claim 1 in a mold, wherein the lens-forming composition further comprises one or more components selected from the group consisting of a hydrophilic vinylic monomer, a hydrophobic vinylic monomer, a polysiloxane-containing vinylic monomer, a polysiloxane-containing vinylic macromer, a crosslinking agent having a molecular weight of less than 700 Daltons, a polymerizable UV-absorbing agent, a visibility tinting agent, an antimicrobial agent, a bioactive agent, a leachable lubricant, a leachable tear-stabilizing agent, and mixtures thereof, wherein the ophthalmic lens has at least one property selected from the group consisting of:

an oxygen permeability of at least about 40 barrers;

an elastic modulus of from about 0.1 MPa to about 2.0 MPa;

an lonoflux Diffusion Coefficient, D, of at least about 1.0×

10<sup>−

5</sup> mm²/min;

a water content of from about 15% to about 55% by weight when fully hydrated; and

combinations thereof.

5. An ophthalmic lens, comprising a silicone hydrogel material that is obtained by curing a lens-forming composition including a soluble amphiphilic prepolymer of claim 2 in a mold, wherein the lens-forming composition further comprises one or more components selected from the group consisting of a hydrophilic vinylic monomer, a hydrophobic vinylic monomer, a polysiloxane-containing vinylic monomer, a polysiloxane-containing vinylic macromer, a crosslinking agent having a molecular weight of less than 700 Daltons, a polymerizable UV-absorbing agent, a visibility tinting agent, an antimicrobial agent, a bioactive agent, a leachable lubricant, a leachable tear-stabilizing agent, and mixtures thereof, wherein the ophthalmic lens has at least one property selected from the group consisting of:

an oxygen permeability of at least about 40 barrers;

an elastic modulus of from about 0.1 MPa to about 2.0 MPa;

an lonoflux Diffusion Coefficient, D, of at least about 1.0×

10<sup>−

5</sup> mm²/min;

a water content of from about 15% to about 55% by weight when fully hydrated; and

combinations thereof.

3. An ophthalmic lens, comprising a silicone hydrogel material that is obtained by curing, in a mold, a lens-forming composition including a linear chain-extended polysiloxane crosslinker comprising (a) two terminal ethylenically unsaturated groups, (b) at least two polysiloxane segments, and (c) at least one dangling hydrophilic polymer chain covalently attached to a divalent organic radical separating said at least two polysiloxane segments, wherein the linear chain extended polysiloxane crosslinker is as set forth by formula (I)