Polymerizable chain-extended polysiloxanes with pendant hydrophilic groups

• US 8,993,651 B2
• Filed: 10/05/2011
• Issued: 03/31/2015
• Est. Priority Date: 10/06/2010
• Status: Active Grant

• Current Assignee: Alcon Incorporated
• Original Assignee: Novartis Ag
• Inventors: Chang, Frank, Huang, Jinyu, Sanders, Laura Ann
• Primary Examiner(s): Schnizer, Richard
• Assistant Examiner(s): Pipic, Alma
• Application Number:
  US13/253,171
• Publication Number:
  US 20120088843A1
• Time in Patent Office: 1,273 Days
• Field of Search: 503/107, 525/479
• US Class Current: 523/107
• CPC Class Codes: A61P 27/02 Ophthalmic agents
• CPC Class Codes: C08F 290/068 Polysiloxanes
• CPC Class Codes: C08G 77/20 containing silicon bound to unsaturated aliphatic groups C08G77/045 takes precedence
• CPC Class Codes: C08G 77/28 sulfur-containing groups
• CPC Class Codes: C08G 77/46 containing polyether sequences
• CPC Class Codes: C08G 77/48 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms C08G77/42 takes precedence
• 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

Abstract

The invention provide a class of chain-extended polysiloxane crosslinkers which comprises (1) at least two polysiloxane segments, wherein each pair of adjacent polysiloxane segments is linked by one divalent organic radical which includes at least one pendant hydrophilic group (hydroxyl and/or carboxyl groups) or at least one dangling hydrophilic polymer chain and a di-thioether linkage —S-DR-S— in which DR is a divalent organic radical; and (2) two terminal ethylenically unsaturated groups. 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 chain-extended polysiloxane crosslinker, being represented by formula (I)

2. The chain-extended polysiloxane crosslinker of claim 1, wherein BG is a linear or branched C₃-C₇ alkylene divalent radical having at least one hydroxyl or carboxyl group or —

OC(O)(CH₂)_t1COOH in which t1 is an integer of 2 to 4,

a divalent radical of —

[CH₂CH(T)CH₂O]_r4—

[CH(R″

)CH₂O]_r3—

[CH₂CH(T)CH₂]_r5—

in which R″ and

r3 are as defined above, T is a hydroxyl or carboxyl group, and r4 and r5 independent of each other are 0 or 1, or combinations thereof.

3. The chain-extended polysiloxane crosslinker of claim 1, wherein the chain-extended polysiloxane crosslinker is obtained by reacting at least one polysiloxane crosslinker of formula (2) with at least one dimercaptan, under Michael Addition or thiol-ene reaction conditions,

4. The chain-extended polysiloxane crosslinker of claim 3, wherein said at least one polysiloxane crosslinker comprises at least one hydroxyl group and is obtained by ethylenically-functionalizing of:

(1) a di-epoxy terminated polysiloxane with use of an ethylenically-functionalizing vinylic monomer selected from the group consisting of C₂ to C₆ hydroxylalkyl (meth)acrylate, C₂ to C₆ hydroxyalkyl (meth)acrylamide, allyl alcohol, allylamine, amino-C₂-C₆ alkyl (meth)acrylate, C₁-C₆ alkylamino-C₂-C₆ alkyl (meth)acrylate, vinylamine, amino-C₂-C₆ alkyl (meth)acrylamide, C₁-C₆ alkylamino-C₂-C₆ alkyl (meth)acrylamide, acrylic acid, C₁-C₄ alkylacrylic acid, N-[tris(hydroxymethyl)-methyl]acrylamide, N,N-2-acrylamidoglycolic acid, beta methyl-acrylic acid (crotonic acid), alpha-phenyl acrylic acid, beta-acryloxy propionic acid, sorbic acid, angelic acid, cinnamic acid, 1-carboxy-4-phenyl-1,3-butadiene, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, maleic acid, fumaric acid, and a combination thereof;

(2) a polysiloxane having two terminal function groups selected from the group consisting of hydroxyl groups, amino groups, carboxyl groups, and a combination thereof with use of epoxy-containing vinylic monomer;

(3) a polysiloxane having two terminal function groups selected from the group consisting of hydroxyl groups, amino groups, carboxyl groups, and a combination thereof with use of an ethylenically-functionalizing vinylic monomer selected from the group consisting of C₂ to C₆ hydroxylalkyl (meth)acrylate, C₂ to C₆ hydroxyalkyl (meth)acrylamide, allylalcohol, allylamine, amino-C₂-C₆ alkyl (meth)acrylate, C₁-C₆ alkylamino-C₂-C₆ alkyl (meth)acrylate, vinylamine, amino-C₂-C₆ alkyl (meth)acrylamide, C₁-C₆ alkylamino-C₂-C₆ alkyl (meth)acrylamide, acrylic acid, C₁-C₄ alkylacrylic acid, N-[tris(hydroxymethyl)-methyl]acrylamide, N,N-2-acrylamidoglycolic acid, beta methyl-acrylic acid (crotonic acid), alpha-phenyl acrylic acid, beta-acryloxy propionic acid, sorbic acid, angelic acid, cinnamic acid, 1-carboxyl-4-phenyl butadiene-1,3, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, maleic acid, fumaric acid, and a combination thereof in the presence of a di-epoxy compound;

(4) a di-epoxy-terminated polysiloxane with use of glycidyl(meth)acrylate in the presence of a diol, di-amine compound, di-carboxylic acid compound, or a combination thereof;

or (5) combinations thereof.

5. The chain-extended polysiloxane crosslinker of claim 3, wherein said at least one polysiloxane crosslinker is:

α

,ω

-bis[3-(meth)acryloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α

,ω

-bis[3-(meth)acryloxyethoxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α

,ω

-bis[3-(meth)acryloxyethylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α

,ω

-bis[3-(meth)acrylamidoethoxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α

,ω

-bis[(meth)acrylamidoethylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α

,ω

-bis[3-(meth)acryloxypropoxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α

,ω

-bis[3-(meth)acryloxypropylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α

,ω

-bis[3-(meth)acrylamidopropoxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α

,ω

-bis[3-(meth)acrylamidopropylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α

,ω

-bis[3-(meth)acrylamidoisopropoxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α

,ω

-bis(allyloxy-2-hydroxypropyl-oxyethoxypropyl)-terminated polydimethylsiloxane, α

,ω

-bis(allylamino-2-hydroxypropyloxypropyl)-terminated polydimethylsiloxane, α

,ω

-bis(vinylamino-2-hydroxypropyloxypropyl)-terminated polydimethylsiloxane, α

,ω

-bis(allyloxy-2-hydroxypropyl-oxypropyl)-terminated polydimethylsiloxane, α

,ω

-bis(vinyloxy-2-hydroxypropyl-oxyethoxypropyl)-terminated polydimethylsiloxane, α

,ω

-bis[(meth)acryloxy-2-hydroxypropyloxy-ethoxypropyl]-terminated polydimethylsiloxane, α

,ω

-bis[(meth)acryloxy-2-hydroxypropyl-N-ethylaminopropyl]-terminated polydimethylsiloxane, α

,ω

-bis[(meth)acryloxy-2-hydroxypropyl-aminopropyl]-polydimethylsiloxane, α

,ω

-bis[allyloxy-2-hydroxypropyl-N-ethylaminopropyl]-terminated polydimethylsiloxane, α

,ω

-bis[vinyloxy-2-hydroxypropyl-N-ethylaminopropyl]-terminated polydimethylsiloxane, α

,ω

-bis[(meth)acryloxy-2-hydroxypropyl-oxycabonylpropyl]-terminated polydimethylsiloxane, α

,ω

-bis[allyloxy-2-hydroxypropyl-oxycabonylpropyl]-terminated polydimethylsiloxane, α

,ω

-bis[vinyloxy-2-hydroxypropyl-oxycabonylpropyl]-terminated polydimethylsiloxane, α

,ω

bis[(meth)acryloxy-2-hydroxypropyl-oxy-pentylcabonyloxyalkyl]-terminated polydimethylsiloxane, α

,ω

-bis[allyloxy-2-hydroxypropyl-oxy-pentylcabonyloxyalkyl]-terminated polydimethylsiloxane, α

,ω

-bis[vinyloxy-2-hydroxypropyl-oxy-pentylcabonyloxyalkyl]-terminated polydimethylsiloxane, α

,ω

-bis(allyloxy-2-hydroxypropyl-oxy(polyethylenoxy)propyl)-terminated polydimethylsiloxane, α

,ω

-bis(vinyloxy-2-hydroxypropyl-oxy(polyethylenoxy)propyl)-terminated polydimethylsiloxane, α

,ω

-bis[(meth)acryloxy-2-hydroxypropyl-oxy(polyethylenoxy)propyl]-terminated polydimethylsiloxane, a coupling product of C₂-C₄ hydroxyalkyl(meth)acrylate or C₂-C₄ hydroxyalkyl(meth)acrylamide or (meth)acrylic acid with α

,ω

-bis(hydroxyethoxypropyl)-polydimethylsiloxane through a di-epoxy compound, or combinations thereof.

6. The chain-extended polysiloxane crosslinker of claim 5, wherein said at least one dimercaptan is selected from the group consisting of C₂-C₁₂ alkyl dimercaptans, ethylcyclohexyl dimercaptan, dipentene dimercaptan, benzenedithiol, methyl-substituted benzenedithiol, benzenedimethanethiol, glycol dimercaptoacetate, ethyl ether dimercaptan, triglycol dimercaptan, tetraglycol dimercaptan, and combinations thereof.

7. The chain-extended polysiloxane crosslinker of claim 5, wherein said at least one dimercaptan comprises at least one hydroxy and/or carboxyl group.

8. The chain-extended polysiloxane crosslinker of claim 3, wherein said at least one polysiloxane crosslinker is free of any hydroxy or carboxyl group, wherein said at least one dimercaptan comprises at least one hydroxy and/or carboxyl group.

9. The chain-extended polysiloxane crosslinker of claim 8, wherein said at least one dimercaptan is dimercaprol, dimercaptobutanol, dimercaptopentanol, dithiothreitol, dimercaptopropionic acid, dihydrolipoic acid, dimercaptosuccinic acid, or combinations thereof.

10. The chain-extended polysiloxane crosslinker of claim 8, wherein said at least one dimercaptan comprises at least one carboxyl group.

11. The chain-extended polysiloxane crosslinker of claim 10, wherein said at least one dimercaptan is dimercaptopropionic acid, dihydrolipoic acid, dimercaptosuccinic acid, or combinations thereof.