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

• US 9,244,196 B2
• Filed: 05/22/2013
• Issued: 01/26/2016
• Est. Priority Date: 05/25/2012
• Status: Active Grant

• Current Assignee: Johnson & Johnson Vision Care Incorporated (Johnson & Johnson)
• Original Assignee: Johnson & Johnson Vision Care Incorporated (Johnson & Johnson)
• Inventors: Scales, Charles W., McCabe, Kevin P., Healy, Brent Matthew
• Primary Examiner(s): Salamon, Peter A.
• Application Number:
  US13/899,694
• Publication Number:
  US 20130317133A1
• Time in Patent Office: 979 Days
• Field of Search: None
• US Class Current: 1/1
• CPC Class Codes: C08L 101/14 the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels
• CPC Class Codes: C08L 81/00 Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 83/04 Polysiloxanes
• CPC Class Codes: G02B 1/043 Contact lenses
• CPC Class Codes: G02C 2202/16 Laminated or compound lenses
• CPC Class Codes: G02C 7/049 Contact lenses having special fitting or structural features achieved by special materials or material structures

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.

Claims

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

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

g/lens.

3. The ophthalmic device of claim 1 wherein said lipid uptake is about 10 μ

g/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 R₁ is selected from the group consisting of 4-cyanopentanoate, isobutanoic, or a benzylic group.

9. The ophthalmic device of claim 1, or 7 wherein R₁ is selected from the group consisting of a cyano-methy or cumyl group.

10. The ophthalmic device of claim 1 or 7 wherein R₁ 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, —

CH₂OH, —

CH₂CH₂OH, —

CH₂CH₂CH₂OH, —

CH₂—

CO₂⁻

, —

CH₂CH₂—

CO₂⁻

, —

CH₂CH₂CH₂—

CO₂⁻

, —

CH₂CH₂CH₂CH₂—

CO₂⁻

, —

CH₂CH₂CH₂CH₂CH₂—

CO₂⁻

, —

CH₂—

SO₃⁻

, —

CH₂CH₂—

SO₃⁻

, —

CH₂CH₂CH₂—

SO₃<sup>−

, —

CH</sup>₂CH₂CH₂CH₂—

SO₃⁻

, —

CH₂CH₂CH₂CH₂CH₂—

SO₃⁻

, —

(CH₃)₂—

CH₂—

CO₂⁻

, —

(CH₃)₂—

CH₂—

SO₃H, —

CH₂CH₂CH₂—

⁺N(CH₃)₂—

CH₂CH₂—

CO₂⁻

, —

CH₂CH₂—

⁺N(CH₃)₂—

CH₂CH₂CO₂⁻

, —

CH₂CH₂CH₂—

⁺N(CH₃)₂—

CH₂CH₂CH₂—

SO₃⁻

, —

CH₂CH₂—

⁺N(CH₃)₂—

CH₂CH₂CH₂—

SO₃⁻

, —

CH₂CH₂CH₂—

⁺N(CH₃)₂—

CH₂CH₂CH₂—

PO₃<sup>−

2</sup>, —

CH₂CH₂—

⁺N(CH₃)₂—

CH₂CH₂CH₂—

PO₃<sup>−

2</sup>, —

CH₂CH₂CH₂—

⁺N(CH₃)₂—

CH₂CH₂—

PO₃<sup>−

2</sup> —

CH₂CH₂—

⁺N(CH₃)₂—

CH₂CH₂—

PO₃<sup>−

2</sup>, 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—

—

(CH₃)₂, pyrrolidonyl, —

CON(CH₃)₂, N-(2-hydroxyethyl) amido or —

N(CH₃)COCH₃.

15. The ophthalmic device of claim 1 or 7 wherein R₁₅ and R₁₅′

cross-linking agents are free of dimethylsiloxane groups.

16. The ophthalmic device of claim 1 or 7 wherein R₁₅ and R₁₅′

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 R₁₅ 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 R₁₈ 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, crosslinked polymer has a degree of polymerization in the range of about 100 to about 1000.

24. The ophthalmic device of claim 1 or 7 wherein said water soluble, crosslinked polymer has a degree of polymerization in the range of about 100 to about 500.

25. The ophthalmic device of claim 1 or 7 wherein said water soluble, crosslinked polymer has a degree of polymerization in the range of about 100 to about 300.

26. The ophthalmic device of claim 1 or 7 wherein said water soluble, crosslinked polymer is free of substrate associative blocks.

27. The ophthalmic device of claim 1 or 7 wherein said primary chain, ζ

_l has a PDI of less than about 1.5.

28. The ophthalmic device of claim 1 or 7 wherein at least about 20% of V are derived from N-(2-hydroxypropyl) (meth)acrylamide.

29. The ophthalmic device of claim 1 or 7 wherein V comprises repeating units derived from comonomers.

30. The ophthalmic device of claim 1 or 7 wherein V is substantially free of anionic groups.

31. The ophthalmic device of claim 1 or 7 wherein V is free of anionic groups.

32. The ophthalmic device of claim 29 wherein said comonomers are selected from the group consisting of hydrophilic monomers, hydrophobic monomers, anionic monomers, cationic monomers, zwitterionic monomers, stimuli responsive monomers and combinations thereof.

33. The ophthalmic device of claim 29 wherein said comonomers are selected from the group consisting of anionic monomers, zwitterionic monomers and combinations thereof.