Organo-modified silicone polymers and hydrogels comprising the same

• US 9,890,234 B2
• Filed: 09/22/2014
• Issued: 02/13/2018
• Est. Priority Date: 03/22/2012
• Status: Active Grant

• Current Assignee: Momentive Performance Materials Incorporated
• Original Assignee: Momentive Performance Materials Incorporated
• Inventors: Saxena, Anubhav, Naik, Sandeep Shashikant, Phukan, Monjit, Bhat, Shreedhar
• Primary Examiner(s): Salamon, Peter A
• Application Number:
  US14/492,646
• Publication Number:
  US 20150011671A1
• Time in Patent Office: 1,240 Days
• Field of Search: None
• CPC Class Codes: C07F 7/1804 Compounds having Si-O-C linkages Si-O-acyl linkages C07F7/1896
• CPC Class Codes: C07F 7/21 Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
• CPC Class Codes: C08F 230/08 containing silicon
• CPC Class Codes: C08F 283/124 on to polysiloxanes having carbon-to-carbon double bonds
• CPC Class Codes: C08G 2210/00 Compositions for preparing hydrogels
• CPC Class Codes: C08G 77/38 Polysiloxanes modified by chemical after-treatment C08G77/045 takes precedence
• 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: C08G 77/50 by carbon linkages C08G77/485 takes precedence
• CPC Class Codes: C08K 3/20 Oxides; Hydroxides graphene oxides C08K3/042
• CPC Class Codes: C08L 101/14 the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels
• CPC Class Codes: C08L 71/00 Compositions of polyethers obtained by reactions forming an ether link in the main chain of polyacetals C08L59/00; of epoxy resins C08L63/00; of polythioether-ethers C08L81/02; of polyether-sulfones C08L81/06; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 83/04 Polysiloxanes
• 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

A hydrophilic silicone polymer composition suitable for use in producing hydrogel polymer films disclosed. In one aspect, a hydrophilic silicone monomer is of the Formula 1:
wA_mB_nw  (1)
where A is a divalent block comprising a silicone-containing pendant group. In one embodiment, the silicone-containing pendant group comprises polyalkylene oxide groups. The structure of the polymer can be controlled and tuned to provide a material with excellent wettability and oxygen permeability. The polymers are suitable for use in a variety of applications including in providing a film for forming contact lenses.

Claims

1. A hydrogel composition comprising a siloxane pre-polymer of the formula:

wA_mB_nw

where m is a positive integer from 2 to about 100, and n is a positive integer from 0 to about 100;

A is a divalent block having a formula;

2. The pre-polymer in the composition of claim 1, wherein L is a hydrophilic residue chosen from a polyalkyleneoxide, optionally a polyalkyleneoxide chosen from —

CH₂CH₂O—

, —

CH₂CH(CH₃)O—

, —

CH₂CH₂CH₂O—

, and their analogues with up to 6 carbon atoms.

3. The pre-polymer in the composition of claim 1, wherein L is a cyclic hydrocarbon residue with the structure:

4. The pre-polymer in the composition of claim 1 wherein R₉, R₁₀, R₁₁, R₁₃, R₁₄, R₁₅, R₁₆, R₁₈, and R₂₀ in the unit G of group E are independently selected from a hydrocarbon radical chosen from methyl, ethyl, propyl, iso-propyl, butyl, isobutyl, phenyl, naphthyl, an aralkyl radical with 8 to 20 carbon atoms, trifluoromethylpropyl, and combinations of two or more thereof.

5. The pre-polymer in the composition of claim 1, wherein the mono-functional group E has a structure chosen from any of the formulas:

6. The pre-polymer in the composition of claim 1, where R₂₅ and R₂₆ are hydrogen, R₂₇ is chosen from hydrogen or a methyl radical, and R₂₈ is a part of an ethylenically-unsaturated hydrophilic monomer or a hydrophobic monomer.

7. The composition of claim 1, wherein the siloxane pre-polymer has at least one terminal reactive group.

8. The composition of claim 1 where the siloxane pre-polymer is (a) a homopolymer or (b) a copolymer.

9. The composition of claim 8, wherein the pre-polymer is a copolymer further comprising a free-radical polymerizable organic monomer chosen from a vinylic monomer, an acrylide monomer, an acrylic monomer, or a combination of two or more thereof.

10. The copolymer of claim 8, wherein the vinylic monomer is chosen from N-vinyl-pyrrolidone, N-vinyl-caprolactam, N-vinyl-acetamide, N-vinyl-formamide and N-vinyl-isopropylamide, vinyl benzene, vinyl naphthalene, vinyl pyridine, vinyl alcohol, vinyl containing silicones, or a combination of two or more thereof.

11. The copolymer of claim 8, wherein the acrylic monomers are chosen from 2-hydroxy-ethyl-methacrylate (HEMA), 2-hydroxy-ethyl-acrylate (HEA), hydroxyl propyl methacrylate, trimethylammonium 2-hydroxy propyl methacrylate hydrochloride, dimethylaminoethyl methacrylate, glycerol methacrylate, N,N-Dimethylacrylamide, N-isopropylacrylamide, acrylamide, methacrylamide, acrylic acid, methacrylic acid, acrylated hydrophilic or hydrophobic organo-silicones, or c combination of two or more thereof.

12. The copolymer of claim 8 optionally comprises a cross-linker selected from ethylene glycol dimethacrylate, trimethyloylpropane trimethacrylate, diethyleneglycol dimethacrylate, bisphenol A dimethacrylate, diglycidyl bisphenol A dimethacrylate and dimethacrylate-terminated polyethylene glycol and reactive linear or pendant polyether modified silicones.

13. The composition of claim 1, wherein the initiator is a thermal or a photo initiator chosen from 2,2′

-azobis (2,4-dimethylpentanenitrile), 2,2′

-azobis (2-methylpropanenitrile), 2,2′

-azobis (2-methylbutanenitrile), peroxides such as benzoyl peroxide, benzoin methyl ether, diethoxyacetophenone, a benzoylphosphine oxide, 2-hydroxy-2-methyl propiophenone (HMPP), 1-hydroxycyclohexyl phenyl ketone, an α

-hydroxyketone type, a phenylglyoxylate type, a benysldimethyl-ketal type, an α

-aminoketone type, a mono-acyl phosphine type, a bis-acyl phosphine type, a phosphine oxide, a metallocene type, and an iodonium salt.

14. A contact lens comprising the hydrogel film of claim 1.

15. The contact lens according to claim 14 comprising a limited extraction protocol that further comprises a green or aqueous solvent chosen from water, an organic or inorganic salt solution, a buffer, an emulsion, a commercial lens cleaning solution, or an ophthalmically compatible solvent in the temperature range of 15-125°

C. for extraction.

16. The hydrogel composition of claim 1, wherein the composition is a film forming additive in a textile, paper, leather, personal care, health care, home care, coating, painting, or seed treatment formulations.