Polymers and nanogel materials and methods for making and using the same

Patent metadata

Field	Value
Publication number	US-9244196-B2
Application number	US-201313899694-A
Country	US
Kind code	B2
Filing date	May 22, 2013
Priority date	May 25, 2012
Publication date	Jan 26, 2016
Grant date	Jan 26, 2016

Abstract

Provided are articles such as medical devices which comprise at least one water soluble, crosslinked copolymer. The primary polymer chains of the copolymer are hydrophilic and independently have a degree of polymerization in the range of about 10 to about 10,000. The water soluble, crosslinked copolymers of the present invention are free from terminal substrate associating segments. The copolymers may be incorporated into a formulation from which the article is made or may be contacted with the article post-formation.

First claim

What is claimed is:

1. An ophthalmic device comprising a silicone-containing polymer and at least one water soluble, cross-linked copolymer comprising a plurality of primary polymer chains, ζ, each having a degree of polymerization in the range of about 10 to about 10,000, wherein ζ is represented by the formula

wherein R 1 is a divalent group selected from the group consisting of optionally substituted benzyl, optionally substituted phenyl, ethanoate, optionally substituted propionate, 4-cyanopentanoate, or isobutyroate functionalities;
U is independently selected from the group consisting of hydrogen, halogen, C 1 -C 4 alkyl which may be optionally substituted with hydroxyl, alkoxy, aryloxy (OR″), carboxy, acyloxy, aroyloxy (O 2 CR″), alkoxy-carbonyl, aryloxy-carbonyl (CO 2 R″) and combinations thereof;
V is independent selected from the group consisting of R″, —CO 2 R″, —COR″, —CN, —CONH 2 , —CONHR″, —CONR″ 2 , —O 2 CR″, —OR″, cyclic and acyclic N-vinyl amides and combinations thereof;
R″i s independently selected from the group consisting of optionally substituted C 1 -C 18 alkyl, C 2 -C 18 alkenyl, aryl, heterocycl, alkaryl wherein the substituents are independently selected from the group that consists of epoxy, hydroxyl, alkoxy, acyl, acyloxy, carboxy, carboxylate, sulfonic acid, and sulfonate, alkoxy-or aryloxy-carbonyl, isocyanato, cyano, silyl, halo, dialkylamino; phosphoric acids, phosphates, phosphonic acids, phosphonates and combinations thereof;
R 15 ′ and R 15 are residues of hydrophilic, free radical reactive cross-linking agents;
R 18 is a controlled radical polymerization agent;
ζ l is another primary chain, are mole fractions, and α is equal to about 0.85 to about 0.999, β is not 0, and the mole fractions of β and γ combined are about 0.15 to about 0.001, and
wherein said copolymer is associated with at least one surface of said ophthalmic device and provides said ophthalmic device with a reduction in lipid uptake compared to the silicone-containing polymer of at least about 20%.

2. The ophthalmic device of claim 1 wherein said lipid uptake is less than about 12 μg/lens.

3. The ophthalmic device of claim 1 wherein said lipid uptake is about 10 μg/lens or less.

4. The ophthalmic device of claim 1 wherein said copolymer has a cross-linker to primary polymer chain molar ratio in the range of about 0.01 to about 3.

5. The ophthalmic device of claim 1 wherein said primary polymer chains independently have a degree of polymerization in the range of about 50 to about 5,000.

6. The ophthalmic device of claim 1 wherein said primary polymer chains independently have a degree of polymerization in the range of about 100 to about 1000.

7. The ophthalmic device of claim 1 wherein said water soluble, crosslinked copolymer has primary chains, ζ, represented by the formula.

8. The ophthalmic device of claim 1 or 7 wherein R 1 is selected from the group consisting of 4-cyanopentanoate, isobutanoic, or a benzylic group.

9. The ophthalmic device of claim 1 , or 7 wherein R 1 is selected from the group consisting of a cyano-methy or cumyl group.

10. The ophthalmic device of claim 1 or 7 wherein R 1 is polyvalent.

11. The ophthalmic device of claim 1 or 7 wherein R″ is selected from H or methyl.

12. The ophthalmic device of claim 1 or 7 wherein R″ is selected from the group consisting of methyl, —CH 2 OH, —CH 2 CH 2 OH, —CH 2 CH 2 CH 2 OH, —CH 2 —CO 2 − , —CH 2 CH 2 —CO 2 − , —CH 2 CH 2 CH 2 —CO 2 − , —CH 2 CH 2 CH 2 CH 2 —CO 2 − , —CH 2 CH 2 CH 2 CH 2 CH 2 —CO 2 − , —CH 2 —SO 3 − , —CH 2 CH 2 —SO 3 − , —CH 2 CH 2 CH 2 —SO 3 −, —CH 2 CH 2 CH 2 CH 2 —SO 3 − , —CH 2 CH 2 CH 2 CH 2 CH 2 —SO 3 − , —(CH 3 ) 2 —CH 2 —CO 2 − , —(CH 3 ) 2 —CH 2 —SO 3 H, —CH 2 CH 2 CH 2 — + N(CH 3 ) 2 —CH 2 CH 2 —CO 2 − , —CH 2 CH 2 — + N(CH 3 ) 2 —CH 2 CH 2 CO 2 − , —CH 2 CH 2 CH 2 — + N(CH 3 ) 2 —CH 2 CH 2 CH 2 —SO 3 − , —CH 2 CH 2 — + N(CH 3 ) 2 —CH 2 CH 2 CH 2 —SO 3 − , —CH 2 CH 2 CH 2 — + N(CH 3 ) 2 —CH 2 CH 2 CH 2 —PO 3 −2 , —CH 2 CH 2 — + N(CH 3 ) 2 —CH 2 CH 2 CH 2 —PO 3 −2 , —CH 2 CH 2 CH 2 — + N(CH 3 ) 2 —CH 2 CH 2 —PO 3 −2 —CH 2 CH 2 — + N(CH 3 ) 2 —CH 2 CH 2 —PO 3 −2 , and combinations thereof.

13. The ophthalmic device of claim 11 wherein V is selected from the group consisting of pyrrolidonyl, piperidonyl, 2-caprolactam, 3-methyl 2- caprolactam, 3-methyl-2-piperidonyl, 4-methyl-2- piperidonyl, 4-methyl-2caprolactam, 3-ethyl-2- pyrrolidonyl, 4,5-dimethyl-2-pyrrolidonyl, imidazolyl, N—N-dimethylamido, amido, N,N-bis(2-hydroxyethyl)amido, -cyano, N-isopropyl amido, acetate, carboxypolyethylene glycol, N-(2-hydroxypropyl) amido, N-(2-hydroxyethyl) amido, carboxyethyl phosphorylcholine, 3-(dimethyl(4-benzyl)ammonio)propane-1-sulfonate 3-((3-amidopropyl)dimethylammonio)propane-1-sulfonate 3-((3-(carboxy)propyl)dimethylammonio)propane-1-sulfonate N-methylacetamide, -acetamide, N-methylpropionamide, N-methyl-2-methylpropionamide, 2-methylpropionamide, N,N2-dimethylurea, and the like, and mixtures thereof.

14. The ophthalmic device of claim 11 wherein V is selected from the group consisting of —N——(CH 3 ) 2 , pyrrolidonyl, —CON(CH 3 ) 2 , N-(2-hydroxyethyl) amido or —N(CH 3 )COCH 3 .

15. The ophthalmic device of claim 1 or 7 wherein R 15 and R 15 ′ cross-linking agents are free of dimethylsiloxane groups.

16. The ophthalmic device of claim 1 or 7 wherein R 15 and R 15 ′ are polymerization residues of at least one crosslinking agent selected from the group consisting of N,N′-alkylenebis(meth)acrylamides;
polyalkyleneglycoldi(meth)acrylates, polyalkyleneglycoldi(meth)acrylamides, triallyl cyanurate, 1,3-divinylimidazolidin-2-one, and 3,3″alkylenebis(1-vinylpyrrolidin-2-one), wherein the alkylene has 1-12 carbons, and mixtures thereof.

17. The ophthalmic device of claim 1 or 7 wherein R 15 and R 15′ are polymerization residues of at least one crosslinking agent selected from the group consisting of N,N′-methylenebis(meth)acrylamide; N,N′-ethylenebis(meth)acrylamide; N,N′-propylenebis(meth)acrylamide; N,N′-butylenebis(meth)acrylamide; N,N′-pentamethylenebis(meth)acrylamide; N,N′-hexamethylenebis(meth)acrylamide; ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetra-ethylene glycol di(meth)acrylate; N,N′-(oxybis(ethane-2,1-diyl))diacrylamide N,N′-(((oxybis(ethane-2,1-diyl))bis(oxy))bis(ethane-2,1-diyl))diacrylamide, triallyl cyanurate, 1,3-divinylimidazolidin-2-one and mixtures thereof.

18. The ophthalmic device of claim 1 or 7 wherein R 18 is a RAFT or ATRP control agent.

19. The ophthalmic device of claim 1 or 7 wherein α is about 0.92 to about 0.999, and the combined mole fraction of β and γ is about 0.08 to about 0.001.

20. The ophthalmic device of claim 1 or 7 wherein α is about 0.95 to about 0.999, and the combined mole fraction of β and γ is about 0.05 to about 0.001.

21. The ophthalmic device of claim 1 or 7 wherein α is about 0.97 to about 0.999, and the combined mole fraction of β and γ is about 0.025 to about 0.001.

22. The ophthalmic device of claim 1 or 7 wherein said water soluble, crosslinked polymer has a degree of polymerization in the range of about 25 to about 5,000.

23. The ophthalmic device of claim 1 wherein said water soluble, cross

Assignees

• Johnson & Johnson Vision Care

Inventors

• Scales Charles W
• Mccabe Kevin P
• Healy Brent Matthew

Classifications

• G02C7/049 Primary

  Contact lenses having special fitting or structural features achieved by special materials or material structures · CPC title

• G02B1/043 Primary

  Contact lenses · CPC title

• G02C2202/16

  Laminated or compound lenses · CPC title

• C08L101/14

  the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels · CPC title

• C08L83/04

  Polysiloxanes · CPC title