Polymerizable polysiloxanes with hydrophilic substituents

• US 9,637,582 B2
• Filed: 09/21/2015
• Issued: 05/02/2017
• Est. Priority Date: 09/26/2014
• Status: Active Grant

• Current Assignee: Alcon Incorporated
• Original Assignee: Novartis Ag
• Inventors: Chang, Frank, Huang, Jinyu, Shankar, Venkat
• Primary Examiner(s): Salamon, Peter A
• Application Number:
  US14/859,486
• Publication Number:
  US 20160090432A1
• Time in Patent Office: 589 Days
• Field of Search: None
• CPC Class Codes: B29D 11/00134 Curing of the contact lens material
• CPC Class Codes: B29D 11/00192 Demoulding, e.g. separating lenses from mould halves
• CPC Class Codes: B29K 2083/00 Use of polymers having silicon, with or without sulfur, nitrogen, oxygen, or carbon only, in the main chain, as moulding material
• CPC Class Codes: B29K 2105/0061 Gel or sol
• CPC Class Codes: C08F 220/00 Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
• CPC Class Codes: C08F 220/58 containing oxygen in addition to the carbonamido oxygen , e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
• CPC Class Codes: C08F 220/585 and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
• CPC Class Codes: C08F 230/08 containing silicon
• 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: C08G 77/26 nitrogen-containing groups
• CPC Class Codes: C08G 77/28 sulfur-containing groups
• 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 77/445 containing polyester 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: C08J 3/03 in aqueous media
• CPC Class Codes: C08J 3/075 Macromolecular gels
• CPC Class Codes: C08J 3/28 : Treatment by wave energy or particle radiation
• CPC Class Codes: C08L 101/14 : the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels
• CPC Class Codes: C08L 51/085 : on to polysiloxanes
• CPC Class Codes: C08L 83/04 : Polysiloxanes
• CPC Class Codes: C08L 83/06 : containing silicon bound to oxygen-containing groups C08L83/12 takes precedence
• 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 83/14 : 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: G02C 7/04 : Contact lenses for the eyes disinfection or sterilisation of contact lenses A61L12/00

Abstract

The invention provides an actinically-polymerizable amphiphilic polysiloxane which comprises a polysiloxane polymer chain comprising a polylsiloxane segments comprising at least one siloxane unit having a low molecular weight hydrophilic polymer chain connected with a silicone atom of the siloxane unit, and (meth)acrylamido groups each covalently bonded to one of the ends of the polysiloxane polymer chain and/or to the end of one of low molecular weight hydrophilic polymer chains each connected with one silicone atom. The present invention is also related to a polymer, an actinically-crosslinkable silicone-containing prepolymer, a silicone hydrogel polymeric material, or a silicone hydrogel contact lens, which comprises repeating units derived from an actinically-polymerizable amphiphilic polysiloxane of the invention. In addition, the invention provides a method for making silicone hydrogel contact lenses using a water-based lens-forming formulation comprising an actinically-polymerizable amphiphilic polysiloxane of the invention and/or an actinically-crosslinkable silicone-containing prepolymer of the invention.

Claims

1. An actinically-polymerizable amphiphilic polysiloxane of formula (1) or (2)

2. The actinically-polymerizable amphiphilic polysiloxane of claim 1, wherein E₁ and E₂ are an polymerizable group of

3. The actinically-polymerizable amphiphilic polysiloxane of claim 1, wherein E₁ and E₂ are hydrogen, substituted or unsubstituted C₁-C₈-alkyl, C₁-C₈-alkoxy, —

NH₂, —

NHR′

with R′

being C₁-C₁₀ alkyl, hydroxyl, carboxyl, Br, Cl, or thiol while E₃ is an polymerizable group polymerizable group of

4. The actinically-polymerizable amphiphilic polysiloxane of claim 1, wherein E₁, E₂ and E₃ are an polymerizable group polymerizable group of

5. The actinically-polymerizable amphiphilic polysiloxane of claim 1, wherein R₁₂, R₁₃, R₁₄, R₁₅, R₁₆, and R₁₇ are methyl.

6. The actinically-polymerizable amphiphilic polysiloxane of claim 1, wherein ν

2 is an integer of an integer of from 3 to 350 while ω

2 is an integer of from 1 to 10.

7. The actinically-polymerizable amphiphilic polysiloxane of claim 1, wherein hPC is a hydrophilic polymer segment composed of hydrophilic monomeric units derived from at least one hydrophilic vinylic monomer selected from the group consisting of N-vinylpyrrolidone, N,N-dimethyl (meth)acrylamide, (meth)acrylamide, N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide, N-vinyl-N-methyl acetamide, N-methyl-3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone, and combinations thereof, and combinations thereof.

8. The actinically-polymerizable amphiphilic polysiloxane of claim 7, being represented by formula (1).

9. The actinically-polymerizable amphiphilic polysiloxane of claim 8, wherein ν

1;

ω

1 is from about 7;

3 to about 9.5;

0.5.

10. The actinically-polymerizable amphiphilic polysiloxane of claim 1, wherein hPC is a polyoxazoline segment.

11. The actinically-polymerizable amphiphilic polysiloxane of claim 10, being represented by formula (1).

12. The actinically-polymerizable amphiphilic polysiloxane of claim 11, wherein ν

1;

ω

1 is from about 7;

3 to about 9.5;

0.5.

13. The actinically-polymerizable amphiphilic polysiloxane of claim 7, being represented by formula (2).

14. The actinically-polymerizable amphiphilic polysiloxane of claim 10, being represented by formula (2).

15. A polymer comprising repeating units of an actinically-polymerizable amphiphilic polysiloxane of claim 1.

16. The polymer of claim 15, wherein the polymer is an actinically-crosslinkable silicone-containing prepolymer which further comprises hydrophilic units of at least one hydrophilic vinylic monomer.