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

• US 9,726,906 B2
• Filed: 11/23/2015
• Issued: 08/08/2017
• 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: Healy, Brent Matthew, Scales, Charles W., McCabe, Kevin P.
• Primary Examiner(s): Salamon, Peter A
• Application Number:
  US14/948,474
• Publication Number:
  US 20160077360A1
• Time in Patent Office: 624 Days
• Field of Search: None
• 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. A process comprising contacting a contact lens with a solution comprising a lipid uptake reducing amount of at least one water soluble, crosslinked copolymer under contacting conditions suitable to associate said copolymer with said contact lens;

wherein said cross-linked copolymer comprises a plurality of crosslinked primary polymer chains each having a degree of polymerization in the range of about 10 to about 10,000, wherein said cross-linked copolymer does not comprise repeating units derived from a substituted or unsubstituted acrylic acid bonded directly to the polymer backbone.

2. The process of claim 1 wherein said contact lens comprises a silicone hydrogel contact lens.

3. The process of claim 1 wherein said water soluble, cross-linked copolymer has a cross-linker to primary polymer chain molar ratio in the range of about 0.01 to about 3.

4. The process of claim 1 wherein said lipid uptake reducing amount is at least about 10 ppm.

5. The process of claim 1 wherein said lipid uptake reducing amount is in the range of about 10 ppm to about 10,000 ppm.

6. The process of claim 1 wherein the lipid uptake by the lens is no more than about 10 μ

g/lens.

7. The process of claim 1, wherein said primary polymer chains are selected from the group consisting of hydrophilic polymers and copolymers, proton donating polymers and copolymers, proton accepting polymers and copolymers, ionic polymers and copolymers, complexing polymers and copolymers, stimuli responsive polymers and copolymers and mixtures thereof.

8. The process of claim 7, wherein the proton donating polymers and copolymers comprise one or more alcohols.

9. The process of claim 7, wherein the proton accepting polymers and copolymers comprise one or more amides.

10. The process of claim 7, wherein the ionic polymers and copolymers comprise one or more of the following:

a carboxylate, a sulfonate, an ammonium salt, and a phosphonium salt.

11. The process of claim 7, wherein the complexing polymers and copolymers comprise one or more boronic acid functionalities and/or hydroxyl functionalities.

12. The process of claim 7, wherein the stimuli responsive polymers and copolymers comprise a polymer selected from the group consisting of temperature-responsive polymers, pH responsive polymers, electrolyte responsive polymers, light responsive polymers and mixtures thereof.

13. The process of claim 12, wherein the temperature-responsive polymer is poly(N-isopropylacrylamide).

14. The process of claim 7 wherein the copolymers are both hydrophilic and proton donating.

15. The process of claim 14 wherein the copolymers comprise repeating units derived from the polymerization of at least one monomer selected from the group consisting of N-vinyl pyrrolidone, N,N-dimethyl acrylamide, and N-hydroxypropyl methacrylamide.

16. The process of claim 1 wherein the copolymers are formed from monomers selected from the group consisting of vinyl amides, vinyl lactones, vinylimides, vinyl lactams, hydrophilic (meth)acrylates, (meth)acrylamides, and mixtures thereof.

17. The process of claim 1 wherein said primary polymer chains are cross-linked by at least one cross-linking agent selected from the group consisting of an N,N′

-alkylenebis(meth)acrylamide, polyalkyleneglycoldi(meth)acrylate, polyalkyleneglycoldi(meth)acrylamide, and combinations thereof.

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

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

20. The process of claim 1 wherein said primary polymer chains independently have a degree of polymerization in the range of about 100 to about 500.

21. The process of claim 1 wherein said primary polymer chains independently have a degree of polymerization in the range of about 100 to about 300.

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

23. The process of claim 1 wherein said primary polymer chains are cross-linked to other primary polymer chains of said hydrophilic nanogel having polydispersity indices (PDIs) of less than about 1.5.

24. The process of claim 22 wherein said primary polymer chains are cross-linked by covalent bonding, ionic bonding, hydrogen bonding, or a combination thereof.

25. The process of claim 1 wherein said primary polymer chains, ζ

, are represented by the formula

26. The process of claim 25 wherein said primary polymer chains, ζ

, are represented by the formula

27. The process of claim 25 or 26 wherein R₁ is selected from the group consisting of 4-cyanopentanoate, isobutanoic, or a benzylic group.

28. The process of claim 25 or 26 wherein R₁ is selected from the group consisting of a cyano-methy or cumyl group.

29. The process of claim 25 or 26 wherein R₁ is polyvalent.

30. The process of claim 25 or 26 wherein U is selected from H or methyl.

31. The process of claim 25 or 26 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⁻

, —

CH₂CH₂CH₂CH₂—

SO₃⁻

, —

CH₂CH₂CH₂CH₂CH₂—

SO₃⁻

, —

(CH₃)₂—

CH₂—

CO₂⁻

, —

(CH₃)₂—

CH₂—

SO₃H, —

CH₂CH₂CH₂—

⁺N(CH₃)₂—

CH₂CH₂—

CO₂⁻

, —

CH₂CH₂—

⁺N(CH₃)₂—

CH₂CH₂—

CO₂⁻

, —

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.

32. The process of claim 30 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-2-caprolactam, 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,N′

-dimethylurea, and the like, and mixtures thereof.

33. The process of claim 30 wherein V is selected from the group consisting of —

N—

(CH₃)₂, pyrrolidonyl, —

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

N(CH₃)COCH₃.

34. The process of claim 25 or 26 wherein R₁₅ and R₁₅′

cross-linking agents are free of dimethylsiloxane groups.

35. The process of claim 25 or 26 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.

36. The process of claim 25 or 26 wherein R₁₅ and R₁₅′

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.

37. The process of claim 25 or 26 wherein R₁₈ is a RAFT or ATRP control agent.

38. The process of claim 25 or 26 wherein a 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.

39. The process of claim 25 or 26 wherein a 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.

40. The process of claim 25 or 26 wherein a 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.

41. The process of claim 25 or 26 wherein said water soluble, crosslinked polymer is free of substrate associative blocks.

42. The process of claim 25 or 26 wherein at least about 20% of V are derived from N-(2-hydroxypropyl) (meth)acrylamide.

43. The process of claim 25 or 26 wherein V comprises repeating units derived from comonomers.

44. The process of claim 25 or 26 wherein V is substantially free of anionic groups.

45. The process of claim 25 or 26 wherein V is free of anionic groups.

46. The process of claim 43 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.

47. The process of claim 43 wherein said comonomers are selected from the group consisting of anionic monomers, zwitterionic monomers and combinations thereof.