Polyurethanes made from polysiloxane/polyol macromers

• US 6,271,332 B1
• Filed: 04/20/1999
• Issued: 08/07/2001
• Est. Priority Date: 12/22/1995
• Status: Expired due to Term

• Current Assignee: Novartis Ag
• Original Assignee: Novartis Ag
• Inventors: Domschke, Angelika, Lohmann, Dieter, Höpken, Jens
• Primary Examiner(s): Moore, Margaret G.
• Application Number:
  US09/091,394
• Time in Patent Office: 840 Days
• Field of Search: 528/28, 428/447, 351/160.R, 623/5, 623/6
• US Class Current: 528/28
• CPC Class Codes: C08G 18/61 Polysiloxanes
• CPC Class Codes: C08L 75/04 Polyurethanes
• CPC Class Codes: G02B 1/043 Contact lenses
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane

Abstract

The present invention describes a polymer and a precursor thereof; a prepolymer made essentially from a macromer that is cross-linked, for example, via its free hydroxy groups with a polyisocyanate, the macromer being made essentially from a polysiloxane and a polyol component; processes for the production of such prepolymers and polymers; the use of such polymers, for example, as artificial corneas, as molded articles, especially as contact lens material; also the use of a prepolymer or polymer for coating surfaces, especially functionalized polymer surfaces.

Claims

1. A polymer comprising a polymerisation product of at least one macromer that comprises at least one section of formula (I)

2. A polymer according to claim 1 wherein the polyisocyanate is a diisocyanate or a triisocyanate.

3. A polymer according to claim 2 wherein the triisocyanate is a compound

and T is an organic radical having up to 50 carbon atoms.

4. A polymer according to claim 2 wherein the diisocyanate is a compound OCN—

R—

NCO and R is a bivalent radical of an organic compound having up to 25 carbon atoms.

5. A polymer according to claim 4 wherein the di-radical R in the diisocyanate OCN—

R—

NCO is alkylene that may be interrupted one or more times by a bivalent structural unit Y, Y being selected from di-lower alkylsilyl and di-lower alkylsilyloxy, or R may be arylene, alkylenearylene, arylenealkylene or arylenealkylenearylene having up to 20 carbon atoms, a saturated bivalent cycloaliphatic group having from 6 to 20 carbon atoms, or cycloalkylenealkylenecycloalkylene having from 7 to 20 carbon atoms;

wherein lower alkyl is defined as having up to eight carbon atoms.

6. A polymer according to claim 5 wherein Y is dimethylsilyl or dimethylsilyloxy.

7. A polymer according to claim 4 wherein the di-radical R in the diisocyanate OCN—

R—

NCO is alkylene that may be interrupted one or more times by a bivalent structural unit Y, Y being selected from di-lower alkylsilyl and di-lower alkylsilyloxy, or R may be arylene, alkylenearylene, arylenealkylene or arylenealkylenearylene having up to 14 carbon atoms, or a saturated bivalent cycloaliphatic group having from 6 to 14 carbon atoms;

wherein lower alkyl is defined as having up to eight carbon atoms.

8. A polymer according to claim 4 wherein the di-radical R in the diisocyanate OCN—

R—

NCO is alkylene that may be interrupted one or more times by a bivalent structural unit Y, Y being selected from di-lower alkylsilyl and di-lower alkylsilyloxy, or R may be arylene, alkylenearylene or arylenealkylene having up to 14 carbon atoms, or a saturated bivalent cycloaliphatic group having from 6 to 14 carbon atoms;

wherein lower alkyl is defined as having up to eight carbon atoms.

9. A polymer according to claim 4 wherein the di-radical R in the diisocyanate OCN—

R—

NCO is alkylene or arylene having up to 12 carbon atoms, or a saturated bivalent cycloaliphatic group having from 6 to 14 carbon atoms.

10. A polymer according to claim 4 wherein the di-radical R in the diisocyanate OCN—

R—

NCO is alkylene or arylene having up to 10 carbon atoms, or a saturated bivalent cycloaliphatic group having from 6 to 10 carbon atoms.

11. A polymer accordingly to claim 1 wherein the content by weight of the macromer relative to the total polymer is in the range from 99 to 5%, and the balance to 100% by weight being formed by the polyisocyanate.

12. A polymer according to claim 1 wherein the polysiloxane segment (a) is the radical of a compound of formula (II)

wherein n is an integer from 5 to 500;

99.8-25% of the radicals R₁, R₂, R₃, R₄, R₅ and R₆ are each independently of the others alkyl and 0.2-75% of the radicals R₁, R₂, R₃, R₄, R₅ and R₆ are each independently of the others partially fluorinated alkyl, aminoalkyl, alkenyl, aryl, cyanoalkyl, Alk-NH-Alk-NH₂ or Alk-(OCH₂CH₂)_m—

(OCH₂)_p—

OR₇, wherein R₇ is hydrogen or lower alkyl, Alk is alkylene, m and p are each independently of the other an integer from 0-10; and

the compound of formula (II) contains at least one primary amino group or at least one hydroxy group.

13. A polymer according to claim 12 wherein the polysiloxane segment (a) is the radical of a compound of formula (II) wherein from 1 to 50 of the radicals R₁, R₂, R₃, R₄, R₅, and R₆ are each independently of the others, either terminal or pendant aminoalkyl or hydroxyalkyl.

14. A polymer according to claim 12 wherein the polysiloxane segment is the radical of a compound of formula (II) wherein 95-29% of the radicals R₁, R₂, R₃, R₄, R₅ and R₆ are each independently of the others alkyl and 5-71% of the radicals R₁, R₂, R₃, R₄, R₅ and R₆ are each independently of the others partially fluorinated alkyl, aminoalkyl, alkenyl, aryl, cyanoalkyl, Alk-NH-Alk-NH₂ or Alk-(OCH₂CH₂)_m—

(OCH₂)_p—

OR₇.

15. A polymer according to claim 12 wherein n is an integer from 5 to 400.

16. A polymer according to claim 12 wherein the two terminal radicals R₁ and R₆ are aminoalkyl or hydroxyalkyl.

17. A polymer according to claim 12 wherein from 1 to 50 of the radicals R₄ and R₅ are pendant aminoalkyl or hydroxyalkyl.

18. A polymer according to claim 1 wherein the polysiloxane segment (a) is linked a total of 1 to 50 times via a group Z to a segment (b) or to a further segment (a);

provided that if a segment (a) is linked to a further segment (a), then Z is a segment (c).

19. A polymer according to claim 1 wherein in a segment (a) the site of linkage to a group Z is an amino or hydroxy group reduced by a hydrogen atom.

20. A polymer according to claim 1 wherein Z is X₁ and X₁ is a bivalent radical having at least one carbonyl group.

21. A polymer according to claim 20 wherein the carbonyl group is flanked at most twice by +O—

, —

CONH—

, —

NHCO—

or —

NH—

.

22. A polymer according to claim 20 wherein the bivalent group Z is an ester, amide, urethane or urea group.

23. A polymer according to claim 1 wherein X₁ and X₂ independently an ester, amide, urethane, carbonate or urea group.

24. A polymer according to claim 1 wherein Z in formula (I) is X₁ and the polyol segment (b) is the radical of a carbohydrate, a carbohydrate monolactone or a carbohydrate dilactone.

25. A polymer according to claim 1 wherein the polyol segment (b) is the radical of a polyol that does not carry a lactone group and wherein the group Z is a segment (c).

26. A polymer according to claim 1 wherein in a segment (b) the site of linkage to a segment (c) is an amino or hydroxy group reduced by a hydrogen atom.

27. A polymer according to claim 1 wherein the di-radical R is alkylene that may be interrupted one or more times by a bivalent structural unit Y, Y being selected from di-lower alkylsilyl and di-lower alkylsilyloxy, or R may be arylene, alkylenearylene, arylenealkylene or arylenealkylenearylene having up to 20 carbon atoms, a saturated bivalent cycloaliphatic group having from 6 to 20 carbon atoms, or cycloalkylenealkylenecycloalkylene having from 7 to 20 carbon atoms;

wherein lower alkyl is defined as having up to eight carbon atoms.

28. A polymer according to claim 27 wherein Y is dimethylsilyl or dimethylsilyloxy.

29. A polymer according to claim 1 wherein R is alkylene that may be interrupted one or more times by a bivalent structural unit Y, Y being selected from di-lower alkylsilyl and di-lower alkylsilyloxy, or R may be arylene, alkylenearylene, arylenealkylene or arylenealkylenearylene having up to 14 carbon atoms, or a saturated bivalent cycloaliphatic group having from 6 to 14 carbon atoms;

wherein lower alkyl is defined as having up to eight carbon atoms.

30. A polymer according to claim 1 wherein R is alkylene or arylene having up to 12 carbon atoms, or a saturated bivalent cycloaliphatic group having from 6 to 14 carbon atoms.

31. A polymer according to claim 1 wherein a segment (c) is the bivalent radical of hexane-1,6-diisocyanate, 2,2,4-trimethylhexane-1,6-diisocyanate, 1,3-bis(3-isocyanatopropyl)tetramethyldisiloxane, tetramethylene diisocyanate, phenylene-1,4-diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, m- or p-xylene diisocyanate, isophorone diisocyanate, cyclohexane-1,4-diisocyanate, 1,5-naphthylene diisocyanate, 4,4′

-diphenylmethane diisocyanate, 4,4′

-diphenylsulfone diisocyanate or 4,4′

-dicyclohexylmethane diisocyanate.

32. A polymer according to claim 4 wherein the diisocyanate is hexane-1,6-diisocyanate, 2,2,4-trimethylhexane-1,6-diisocyanate, 1,3-bis(3-isocyanatopropyl)tetramethyldisiloxane, tetramethylene diisocyanate, phenylene-1,4-diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, m- or p-xylene diisocyanate, isophorone diisocyanate, cyclohexane-1,4-diisocyanate, 1,5-naphthylene diisocyanate, 4,4′

-diphenylmethane diisocyanate, 4,4′

-diphenylsulfone diisocyanate or 4,4′

-dicyclohexylmethane diisocyanate.

33. A polymer according to claim 1 wherein the mean molecular weight of the macromer is in the range from approximately 300 to approximately 30 000.

34. A polymer according to claim 1 wherein the ratio of segments (a) and (b) in the macromer is in a range of (a):

(b)=3;

4, 2;

3, 1;

2, 1;

1, 1;

3 or 1;

5.

35. A polymer according to claim 1 wherein the sum total of segments (a) and (b) or, where appropriate, (a) and (b) and (c) is in a range from 2 to 50.

36. A moulded article consisting essentially of a polymer according to claim 1.

37. A moulded article according to claim 36 which is a contact lens.

38. A moulded article according to claim 36 which is a soft contact lens having a water content of from 1 to 40% by weight.

39. A moulded article according to claim 36 which is a low water content flexible gas permeable contact lens.

40. A moulded article according to claim 36 which is an intraocular lens.

41. A biomedical article consisting essentially of a polymer according to claim 1.

42. A coating on the surface of an article comprising the polymer of claim 1.

43. A corneal implant consisting essentially of a polymer according to claim 1.

44. A corneal implant according to claim 43 which can be used in surgical implants on or in the cornea of a warm-blooded animal, wherein the mentioned implant has in the region over the optical axis an optical property that is suitable for imparting sharpness of vision, and also a porosity that is sufficient to allow the passage of components of tissue fluid having a molecular weight greater than 100 000 dalton, the passage of tissue fluid from cells outside the implant to cells inside the implant being ensured, and wherein the porosity in the region over the optical axis is such that the passage of components of tissue fluid is possible but the growth of ocular tissue is excluded.

45. A corneal implant according to claim 43, the implant being coated with one or more components that promote the growth of tissue in the vicinity of the implant and/or that promote the adherence of cells to the implant.

46. A corneal implant according to claim 43 wherein the porosity of the implant is provided by a plurality of pores the size of which is sufficient to ensure the passage through the implant of protein components of tissue fluid having a molecular weight greater than 10 000 dalton, but the size of which excludes the possibility of the growth of tissue.

47. A corneal implant according to claim 46 wherein the majority of the pores have a diameter of from 15 nanometres to 0.5 micrometres, preferably from 150 nanometres to 0.5 micrometres.

48. A cell growth substrate comprising a polymer as defined in claim 1.

49. A medical implant comprising a polymer as defined in claim 1.

50. A process for the preparation of a prepolymer which process comprises adding to a macromer as defined in claim 1 a polyisocyanate, in the presence or absence of a solvent.

51. A process for the preparation of a polymer which comprises mixing a macromer as defined in claim 1 with a polyisocyanate in the presence or absence of a solvent, if necessary adding a suitable catalyst and then, if necessary, heating the reaction mixture.

52. A prepolymer containing at least one free isocyanato group, consisting of the addition product of a macromer containing at least one section of formula (I)

53. A process for the preparation of a polymer wherein a prepolymer according to claim 52 is crosslinked.

54. A process according to claim 53 wherein the the prepolymer is crosslinked by an increase in pressure or in temperature or both.

55. A coating on the surface of an article comprising the prepolymer of claim 52.