Amphiphilic, segmented copolymer of controlled morphology and ophthalmic devices including contact lenses made therefrom

• US 5,807,944 A
• Filed: 06/27/1996
• Issued: 09/15/1998
• Est. Priority Date: 06/27/1996
• Status: Expired due to Term

• Current Assignee: Novartis Ag
• Original Assignee: CIBA Vision Corporation (Bayer AG)
• Inventors: Hirt, Thomas, Lohmann, Dieter, Liu, Qin, Hopken, Jens
• Primary Examiner(s): Marquis, Melvyn I.
• Application Number:
  US08/671,278
• Time in Patent Office: 810 Days
• Field of Search: 526/279, 523/107, 525/937, 351/160 R
• US Class Current: 526/279
• CPC Class Codes: C08F 290/02 on to polymers modified by introduction of unsaturated end groups
• CPC Class Codes: G02B 1/043 Contact lenses
• CPC Class Codes: Y10S 525/937 Utility as body contact e.g. implant, contact lens or I.U.D.

Abstract

The subject matter of the present invention is an amphiphilic, segmented copolymer of controlled morphology comprising at least one segment having high oxygen permeability, at least one segment having high ion and water permeability, the segments being linked together through a non-hydrolizable bond, and at least one polymerizable unsaturated group; a process for the preparation of the copolymer; to polymeric products obtainable by further polymerizing and optionally cross-linking the amphiphilic segmented copolymer, and to mouldings, especially contact lenses and other ophthalmic devices comprising a polymeric product of the invention. In a specifically preferred embodiment, the present invention relates to a contact lens comprising a polymeric product of the invention which is suited for extended periods of wear.

Claims

1. An amphiphilic segmented copolymer comprising at least one segment A and at least one segment B wherein segment A comprises an oxygen-permeable polymer and segment B comprises an ion-permeable polymer, segments A and B being linked together through a non-hydrolyzable bond, and wherein the copolymer contains at least one polymerizable unsaturated group.

2. A copolymer according to claim 1, wherein segment A comprises a polysiloxane of Formula (I) ##STR11## in which n is an integer from 5 to 200;

Alk is alkylene having up to 20 carbon atoms;

80-100% of the radicals R₁, R₂, R₃ and R₄, independently of one another, are alkyl and 0-20% of the radicals R₁, R₂, R₃ and R₄, independently of one another, are alkenyl, aryl, fluoroalkyl or cycloalkyl.

3. A copolymer according to claim 2, wherein is an integer from 5 to 120.

4. A copolymer according to claim 2, wherein 85-100% of the radicals R₁, R₂, R₃, and R₄, independently of one another, are lower alkyl having up to 8 carbon atoms.

5. A copolymer according to claim 2, wherein 0-15% of the radicals R₁, R₂, R₃ and R₄, independently of one another, are lower alkenyl, phenyl which is unsubstituted or substituted by lower alkyl or lower alkoxy, fluoro(lower alkyl) or cyano(lower alkyl).

6. A copolymer according to claim 1, wherein segment A comprises a perfluoroalkyl polyether of Formula (II)

7. A copolymer according to claim 6, wherein Z is a bond, lower alkylene or --CONH-arylene, where the --CO-- moiety is linked to a CF₂ group.

8. A copolymer according to claim 6, wherein Z is lower alkylene.

9. A copolymer according to claim 6, wherein the indices x+y are a number in the range from 10 to 50.

10. A copolymer according to claim 6, wherein the ratio x:

y is in the range from 0.5 to 1.5.

11. A copolymer according to claim 1, wherein segment A comprises an unsaturated polymer comprising repeating units selected from units of Formulae (III) and (IV) ##STR12## wherein R₅ is hydrogen, alkyl or trialkyl-silyl;

R₆ is alkyl, unsubstituted or substituted by alkoxy, alkoxycarbonyl, hydroxy, carboxyl, halogen or aryl;

alkenyl, unsubstituted or substituted by alkoxy, alkoxycarbonyl, carboxyl, halogen or aryl;

or alkenyl, unsubstituted or substituted by alkoxy, alkoxycarbonyl, carboxyl, halogen or aryl; and

R₇ and R₈, independently of one another, are hydrogen or alkyl;

or R₆ and R₇, taken together, are --(CH₂)_p --, wherein p is an integer of 3 to 5,

or R₆ and R₇, taken together, are a divalent residue of Formula (V) ##STR13## wherein r and s, independently of one another, are an integer of 1 to 3, but do not have at the same time the value 1;

R₇ and R₈, taken together, are --(CH₂)_p --, wherein p is as defined above;

m and o, independently of one another, are an integer of 10 to 100,000; and

the sum of m and o is an integer of 20 to 100,010.

12. A copolymer according to claim 11, wherein the unsaturated polymer comprises repeating units selected from units of Formula (III) and (IV), wherein R₅, R₇ and R₈ are hydrogen and R₆ is lower alkenyl or lower alkenyl substituted by halogen, preferably lower alkenyl having up to 4 carbon atoms.

13. A copolymer according to claim 11, wherein the unsaturated polymer comprises repeating units of Formula (IV) wherein R₅ is tri lower alkylsilyl and R₆ is lower alkyl.

14. A copolymer according to claim 11, wherein the unsaturated polymer comprises alternating repeating units of Formula (III) and (IV), wherein R₅, R₇ and R₈ are hydrogen and R₆ is lower alkyl or lower alkenyl having up to 4 carbon atoms.

15. A copolymer according to claim 11, wherein the unsaturated polymer is selected from syndiotactic poly-1,2-butadiene, poly-1,4-butadiene and polyisoprene.

16. A copolymer according to claim 1, wherein segment A comprises a polysulfone comprising at least one of the structural elements VIa) to VId) ##STR14## wherein R is structural element VIa) is alkylene or arylene and R in structural elements VIb), VIc) and VId) is arylene, especially phenylene.

17. A copolymer according to claim 1, wherein segment A comprises two or more subsegments selected from polysiloxanes of Formula (I) as defined in claim 2, perfluoroalkyl polyethers of Formula (II) as defined in claim 6, unsaturated polymers comprising repeating units of Formulae (III) and (IV) as defined in claims 11, and polysulfones as defined in claim 16.

18. A copolymer according to claim 1, wherein segment A comprises perfluoroalkyl polyether or polybutadiene subsegments (a) and polysiloxane subsegments (b).

19. A copolymer according to claim 1, wherein segment B is derived from a cyclic imino ether compound of Formula (VII) ##STR15## wherein R₉ is hydrogen, alkyl, hydroxyalkyl or alkenyl having up to 22 carbon atoms and optionally containing ether, ester or urethane groups, cycloalkyl, aralkyl or aryl;

and t is 2 or 3.

20. A copolymer according to claim 19, wherein the cyclic imino ether compound is a 2-alkyl, or 2-alkenyl oxazoline or a 2-(hydroxyalkyl)oxazoline or a 2-isocyanatoethyl methacrylate adduct thereof.

21. A copolymer according to claim 20, wherein the cyclic imino ether compound is 2-methyl oxazoline, 2-(hydroxymethyl)oxazoline or 2-(hydroxyethyl)oxazoline.

22. A copolymer according to claim 1, wherein segment B is derived from a vinyl ether of Formula (VIII)

23. A copolymer according to claim 22, wherein the vinyl ether is methyl vinyl ether, ethyl vinyl ether or methoxy ethyl vinyl ether.

24. A copolymer according to claim 22, wherein the cyclic ether is oxetane.

25. A copolymer according to claim 22, wherein the cyclic ether is ethylene oxide or propylenoxide.

26. A copolymer according to claim 22, wherein the cyclic ether is methyl glycidyl ether, vinyl glycidyl ether, allyl glycidyl ether or ethoxyethyl glycidyl ether.

27. A copolymer according to claim 1, wherein segment B is derived from an N-substituted aziridine, β

-lactone or β

-lactame.

28. A copolymer according to claim 1, which is a di-block comprising one segment A and one segment B.

29. A copolymer according to claim 1, which is a tri-block comprising one segment A and two segments B which are attached to the ends of segment A, or comprising one segment B and two segments A which are attached to the ends of segment B.

30. A copolymer according to claim 1, which is a comb-type copolymer of the Formula (XII) or (XII'"'"') ##STR17## wherein the segments B are pendent from segment A or segments A are pendent from segment B;

and v is an integer of 0 to 20.

31. A copolymer according to claim 29, wherein further hydrophobic segments A'"'"' and/or further hydrophilic segments B'"'"' which are composed of the same or different monomers as segments A and B are attached to the ends of segments A or B.

32. A copolymer according to claim 1, wherein the at least one polymerizable unsaturated group is present within any one of segments A, B, A'"'"' or B'"'"' or is present at the end of the terminal segment.

33. A process for the preparation of a copolymer according to claim 1, comprising the steps of

a) providing at least one thermally or photochemically activable cationic or radical initiator group on at least one end or pendent from a compound serving as segment A or segment B in the copolymer;

b) conducting a graft polymerization at the initiator group present on the said segment A or segment B using a monomer from which segment B or segment A, respectively, is derived;

c) optionally changing the monomer and conducting further graft polymerization using a hydrophobic or hydrophilic monomer which is the same or different from the monomer making up segments A and B to produce further hydrophobic segments A'"'"' and/or further hydrophilic segments B'"'"', and if a polymerizable final unsaturated group should be provided at the end of the growing segment;

d) reacting the segmented copolymer thus obtained or a suitable derivative therefrom with a functionalized compound carrying a polymerizable unsaturated group.

34. A polymeric product which is obtainable by further polymerizing a copolymer according to claim 1 through the polymerizable unsaturated group(s), optionally in the presence of further vinylic comonomers and optionally of cross-linking agents containing at least two unsaturated groups.

35. A polymeric product according to claim 34, wherein the vinyl comonomer comprises at least one hydrophobic comonomer.

36. A polymeric product according to claim 35, wherein the hydrophobic comonomer is selected from methyl methacrylate, TRIS, DSPMA and acrylonitrile.

37. A polymeric product according to claim 34, wherein the vinyl comonomer comprises at least one hydrophilic comonomer.

38. A polymeric product according to claim 37, wherein the vinylic comonomer is selected from hydroxy ethyl methacrylate, N-vinyl pyrolidone, N,N-dimethylacrylamid, (meth)-acrylic acid, dihydroxypropyl-methacrylate and acrylamide.

39. A polymeric product according to claim 34, wherein the vinylic comonomer comprises at least one hydrophobic and at least one hydrophilic comonomer.

40. A polymeric product according to claim 34, which is obtainable by further polymerizing a copolymer according to claim 1 through the polymerizable unsaturated group in the presence of a crosslinking agent containing at least two unsaturated groups.

41. A polymeric product according to claim 34, which comprises at least one vinylic comonomer and at least one cross-linking agent.

42. A moulding essentially comprising a polymeric product according to claim 34.

43. A moulding according to claim 42, which is an ophthalmic device for vision correction.

44. A moulding according to claim 42, which is a contact lens.

45. A moulding according to claim 44, which is a water-containing soft contact lens.

46. A moulding according to claim 44, which is low-water-content flexible, gas-permeable (RGP) contact lens.

47. A moulding according to claim 44 which is a highly O₂ -- permeable extended wear lens with favorable water permeability and good on-eye mobility.

48. A contact lens according to claim 47 having a bulk water content of 5 to 30, based on the total lens weight.

49. A moulding according to claim 42, which is an intraocular lens.

50. A moulding according to claim 42, which is a lenticular corneal implant (artificial cornea).

51. A biomedical article comprising a polymeric product according to claim 34.

52. A coating of an article, comprising the copolymer according to claim 1.

53. A coating of an article, comprising the polymeric product according to claim 34.

54. A contact lens comprising the copolymer according to claim 1.