Fluorine and/or silicone containing poly(alkylene-oxide)-block copolymer hydrogels and contact lenses thereof

• US 5,334,681 A
• Filed: 12/17/1993
• Issued: 08/02/1994
• Est. Priority Date: 06/20/1989
• Status: Expired due to Fees

• Current Assignee: Ciba-Geigy Corporation (Novartis Ag)
• Original Assignee: Ciba-Geigy Corporation (Novartis Ag)
• Inventors: Plankl, Walter L., Mueller, Karl F.
• Primary Examiner(s): Dean, Ralph H.
• Assistant Examiner(s): Dean, Karen A.
• Application Number:
  US08/168,979
• Time in Patent Office: 228 Days
• Field of Search: 526/279, 526/251, 526/247, 526/245, 526/243, 525/404, 525/455, 351/160 R, 351/160 H
• US Class Current: 526/243
• CPC Class Codes: C08F 290/062 Polyethers
• CPC Class Codes: C08F 290/147 Polyurethanes; Polyureas
• CPC Class Codes: C08G 18/4825 Polyethers containing two hydroxy groups C08G18/4833 - C08G18/5096 take precedence
• CPC Class Codes: C08G 18/4833 Polyethers containing oxyethylene units
• CPC Class Codes: C08G 18/5024 containing primary and/or secondary amino groups
• CPC Class Codes: C08G 18/8116 esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate group
• CPC Class Codes: C08L 51/08 grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
• CPC Class Codes: G02B 1/043 Contact lenses
• CPC Class Codes: G02C 7/04 Contact lenses for the eyes disinfection or sterilisation of contact lenses A61L12/00

Abstract

Fluorine and/or silicone containing block copolymers are described which are the copolymerization product of mono; di- or trivinyl substituted poly(ethylene oxide) prepolymers (A) and fluoroalkyl-alkylene acrylates or methacrylates (B1), oligosiloxy-silyl alkyl-acrylates or methacrylates (B2), ether copolymerizable comonomers (C), and 0.1 to 10% of a di- or polyvinyl crosslinking comonomer (D) of 200 to 1000 molecular weight. The novel block copolymers are prepared in solution or bulk and form hydrogels, which are characterized by high oxygen permeability, resiliency, flexibility and wettability and are therefore well suited as biocompatible polymers, especially as contact lenses.

Claims

1. A copolymer which is oxygen permeable, flexible, wettable, biocompatible and suitable for use in ophthalmic devices, such as contact lenses, which copolymer comprises the polymerization product of

(A) 15 to 69.9% by weight of a vinyl-telechelic polyether substantially free of fluorine , or a mixture thereof,

(B) 30 to 84.9% by weight of

(B-1) a fluorinated, ethylenically unsaturated monomer, or

(B-2) a silicone-containing ethylenically unsaturated monomer, or

a mixture of monomer (B-1) and monomer (B-2),

(C) 0 to 40% by weight of an ethylenically unsaturated monomer or mixture of monomers other than monomer (B-1) or monomer (B-2), and

(D) 0.1 to 10% by weight of a polyethylenically unsaturated comonomer of 200 to 1000 molecular weight.

2. A copolymer according to claim 1 wherein the vinyl-telechelic polyether is of formula (A) ##STR3## wherein PE has a number average molecular weight (MW_n) of about 500 to about 15,000 and has the formula:

##STR4## wherein n is 1 to 3, k, d, p are integers from 0 to 300, and

the sum of k+d+p is 7 to 300,

R₁, R₁ '"'"', R₁ " are independently of each other H or CH₃, with the proviso that when n = 3, R₁, R₁ '"'"', R₁ " are hydrogen,

a is zero or 1,

m is an integer from zero to 2,

q is zero or 1,

R₂ is an linear or branched alkylene with 2 to 4 carbon atoms,

Y is --CONH--R₃ --NHOC-- or --CO--, wherein

R₃ is a divalent aliphatic group of 2 to 14 carbon atoms, a divalent 5- or 6-membered cycloaliphatic group with 5 to 15 carbon atoms or an arylene group of 6 to 14 carbon atoms, with the proviso that when Y is --CO--, a is 1,

Q, shown as it is attached to V, is selected from the group consisting of

Q₁ V = --CO--V,

Q₂ V = --CONH--R₃ --NHOC--X--R₄ --X₁ --(CO)_b --V,

Q₃ V = --CONH--R₅ OOC--V, and

Q₄ C = --CONH--R₆ --V

wherein

R₄ is an alkylene of 2 to 4 carbon atoms,

R₅ is an alkylene of 2 to 10 carbon atoms,

R₆ is an arylene or alkyl-substituted arylene of 6 to 20 carbon atoms,

X is --O-- or --NR₇ --,

R₇ is an alkyl of 1 to 5 carbon atoms

X₁ is --O--, --NH-- or --NR₇ --,

b is zero or 1,

V is --(CH₂)_c CR₁ ═

CR₈ H

c is zero or 1,

V₁ has same meaning as V, or V₁ is H or R₉, when q is zero,

R₈ is H or --COOH, with the proviso that, if R₈ is COOH,

R₁ is H, c is zero, and Q is Q₁ ;

R₉ is an alkyl of 1 to 18 carbon atoms;

with the further proviso that

when Q is Q₂, a is zero;

when Q is Q₂, Q₃ or Q₄, R₈ is H;

when c is 1, b is zero, Q is Q₂ and R₁ and R₈ are H; and

when V₁ is R₉, m is zero.

3. A copolymer according to claim 2 wherein the polyether PE is a poly(ethylene oxide) of 500-12000 MW, a poly(propylene oxide) of 500-15000 MW a poly(ethylene oxide (A)-co-propylene oxide (B)) of random or block copolymer structure in ratios of A:

B from 1;

30 to 30;

1 of 500-15000 MW, or a poly(tetramethylene oxide) of 500-10000 MW wherein A is the amount of poly(ethylene oxide) and (B) is the amount of propylene oxide.

4. A copolymer according to claim 3 wherein the polyether PE is a poly(ethylene oxide) of 1500-10000 MW, or a poly(ethylene oxide-co-propylene oxide) of 1500-10000 MW and wherein a is 1 and R₂ is --CH₂ --CHCH₃ --.

5. A copolymer according to claim 3 wherein the polyether (PE) is an poly(propylene oxide) of 1000-8000 MW, a is 1 and R₂ is --CH₂ --CHCH₃ --.

6. A copolymer according to claim 3 wherein QV is Q₂ V, wherein R₃ is a divalent radical obtained by removing the two --NCO groups from a diisocyanate selected from the group consisting of ethylene diisocyanate, 1,2-diisocyanatopropane, 1,3-diisocyanatopropane, 1,6-diisocyanatohexane, 1,2-diisocyanatocyclo-hexane, 1,3-diisocyanatocyclohexane, 1,4-diisocyanato-benzene, bis(4-isocyanatocyclohexyl)methane, bis-(4-isocyanatocyclohexenyl)-methane, bis(4-isocyanatophenyl)-methane, 2,6- and 2,4-toluene diisocyanate;

3,3-dichloro-4,4'"'"'-diisocyanatobiphenyl;

tris(4-isocyanatophenyl)methane, 1,5-diisocyanatonaphthalene, hydrogenated toluene diisocyanate;

1-isocyanatomethyl-5-isocyanato-1,3-3-trimethylcyclohexane 1,3,5-tris (6-isocyanatohexyl)biuret, 1,6-diisocyanato-2,2-4-(2,4,4)-trimethylhexane (2,2,4-(2,4,4)-trimethylhexane-1-6-diisocyanate), 2,2'"'"'-diisocyanatodiethyl fumarate;

1,5-diisocyanato-1-carboxypentane;

1,2-, 1,3-, 1,6-, 1,7-, 1,8-, 2,7- and 2,3-diisocyanato naphthalene;

2,4- and 2,7-diisocyanato-1-methylnaphthalene;

4,4'"'"'-diisocyanato-biphenyl;

4,4'"'"'-diisocyanato-3,3'"'"'-diisocyanato-6(7)-methyl-naphthalene;

4,4'"'"'-diisocyanato-2,2'"'"'-dimethyl biphenyl;

bis-(4-isocyanatophenyl) ethane and, bis(4-isocyanatophenyl ether; and

wherein V--(CO)_b --X₁ --R₄ -- is the radical obtained by removing the active hydrogen atom from a hydroxyl or amino group of a compound selected from the group consisting of 2-hydroxyethyl acrylate and methacrylate;

2- and 3-hydroxy-propyl acrylate and methacrylate;

4-hydroxybutyl acrylate and methacrylate;

glycerol dimethacrylate;

hydroxyethyl maleate and fumarate;

2-hydroxyethyl- and 4-hydroxy-butyl vinyl ether;

N-tert. -butylaminoethyl methacrylate,N-(3-hydroxypropyl)-methacrylamide;

vinyl-benzyl alcohol; and

allyl alcohol.

7. A copolymer according to claim 6 wherein the diisocyanate is 1-isocyanatomethyl-5-isocyanato-1,3-3-trimethylcyclohexane 2,2,4-(2,4,4)-trimethylhexane-1,6-diisocyanate, 2,4-toluene diisocyanate or 2,6-toluene diisocyanate, and the active hydrogen containing vinyl compound is 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate or N-tert. butyl-amino ethyl methacrylate.

8. A copolymer according to claim 3 wherein QV is Q₃ V and V--COO--R₅ -- is the radical obtained by removing the --NCO, group from an isocyanate compound selected from the group consisting of 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, 3-isocyanatopropyl methacrylate, 1-methyl-2-isocyanatoethyl methacrylate, and 1,1-dimethyl-2-isocyanatoethyl acrylate.

9. A copolymer according to claim 8 wherein the isocyanate compound is 2-isocyanatoethyl methacrylate.

10. A copolymer according to claim 3 wherein QV is Q₄ V and V--R₆ -- is the radical obtained by removing the --NCO group from 2-isocyanatobutyl vinyl ether, styrene isocyanate, or m-isopropenyl-α

,α

-dimethylbenzyl isocyanate.

11. A copolymer according to claim 10 wherein the isocyanate is m-isopropenyl-α

,α

-dimethylbenzyl isocyanate.

12. A copolymer according to claim 4 wherein QV is Q₃ V and V--COO--R₅ -- is the radical obtained by removing the --NCO group from an isocyanate compound selected from the group consisting of 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, 3-isocyanatopropyl methacrylate, 1-methyl-2-isocyanatoethyl methacrylate, and 1,1-dimethyl-2-isocyanatoethyl acrylate.

13. A copolymer according to claim 4 wherein QV is Q₄ V and V--R₆ -- is the radical obtained by removing the --NCO group from 2-isocyanatobutyl vinyl ether, styrene isocyanate, or m-isopropenyl-α

,α

-dimethylbenzyl isocyanate.

14. A copolymer according to claim 5 wherein QV is Q₃ V and V--COO--R₅ -- is the radical obtained by removing the --NCO group from an isocyanate compound selected from the group consisting of 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, 3-isocyanatopropyl methacrylate, 1-methyl-2-isocyanatoethyl methacrylate, and 1,1-dimethyl-2-isocyanatoethyl acrylate.

15. A copolymer according to claim 5 wherein QV is Q₄ V and V--R₆ -- is the radical obtained by removing the --NCO group from 2-isocyanatobutyl vinyl ether, styrene isocyanate, or m-isopropenyl-α

,α

-dimethylbenzyl isocyanate.

16. A copolymer according to claim 13, wherein the isocyanate is m-isopropenyl-α

,α

-dimethylbenzyl isocyanate.

17. A copolymer according to claim 14, wherein the isocyanate is 2-isocyanatoethyl methacrylate.

18. A copolymer according to claim 14, wherein the isocyanate is m-isopropenyl-α

,α

-dimethyl benzylisocyanate.

19. A copolymer according to claim 2 where in PE is poly(ethylene oxide), poly(propylene oxide) or poly(ethylene oxide-co-propylene oxide) and QV is Q₂ V, Q₃ V or Q₄ V.

21. A copolymer according to claim 1 wherein (B-1) is a fluorine containing monomer containing at least three fluorine atoms consisting of the acrylate or methacrylate esters of the formula

22. A copolymer according to claim 1 wherein (B-1) is a fluorinated monomer selected from the group consisting of hexafluoroisopropyl acrylate, hexafluoroisopropyl methacrylate, or of a compound of structure (I), wherein W is a direct bond, X is oxygen, R_f is --(CF₂)_t CF₂ L and L is fluorine.

23. A copolymer according to claim 22 wherein in the compound of structure (I), R₁ is hydrogen, r is 2 and t is 6 to 10;

or in which R₁ is hydrogen, r is 1 or 2 and t is 1-4, or in which R₁ is methyl, r is 2 and t is 4-10.

24. A copolymer according to claim 22, wherein in the compound of structure (I) r is 1 or 2 and t is 4-8.

25. A copolymer according to claim 22, wherein in the compound of structure (I) R is methyl, r is 2 and t is 4 to 10.

26. A copolymer according to claim 1 wherein (B-2) is a silicone containing vinyl monomer which is an oligosiloxanylsilyl-alkyl acrylate or methacrylate containing 2 to 10 silicon atoms.

27. A copolymer according to claim 26 wherein the monomer is selected from the group consisting of tris(trimethylsiloxysilyl)propyl (meth) acrylate, triphenyldimethyldisiloxanylmethyl (meth)acrylate, pentamethyl-disiloxanylmethyl (meth)acrylate, tert-butyl-tetramethyl-disiloxanylethyl (meth)-acrylate, methyl-di(trimethylsiloxy)silylpropylglyceryl (meth)acrylate;

pentamethyldisiloxanyl-methyl methacrylate, heptamethyl-cyclotetrasiloxy methyl methacrylate;

heptamethyl-cyclotetra-siloxy-propyl methacrylate;

(trimethylsilyl)-decamethyl-pentasiloxy-propyl methacrylate; and

dodecamethyl pentasiloxypropyl methacrylate.

28. A copolymer according to claim 27 wherein the monomer is tris(trimethylsiloxy-silyl) propyl methacrylate.

29. A copolymer according to claim 1 wherein component (B) is 50 to 84.5% by weight of said copolymer, component (C) is 0 to 20% by weight and component (D) is 0.5 to 7% by weight.

30. A copolymer according to claim 2, wherein component (A) is 15 to 50% by weight and the polyether PE is a poly(ethylene oxide) of 1500-10000 MW, or a poly(ethylene oxide-co-propylene oxide) of 1500-10000 MW and wherein a is 1 and R₂ is --CH₂ --CHCH₃ --, wherein QV is Q₃ V or Q₄ V, and V--COO--R₅ -- is the radical obtained by removing the --NCO group from 2-isocyanatoethyl methacrylate or 2-isocyanatoethyl acrylate, and wherein V--R₆ -- is the radical obtained by removing the --NCO group from styrene isocyanate or m-isopropenyl-α

,α

-dimethylbenzyl isocyanate;

component (B) is 50 to 84.5% by weight of component (B-1), wherein (B-1) is a fluorinated monomer selected from the group consisting of hexafluoroisopropyl acrylate, hexafluoroisopropyl methacrylate, or is a fluorine containing monomer containing at least three fluorine atoms and having the formula

space="preserve" listing-type="equation">CH.sub.2 ═

CR.sub.1 --COX(CH.sub.2).sub.r --W--R.sub.f

wherein

W is a direct bond, X is oxygen and R_f is --(CF₂)_t CF₂ L

R₁ is hydrogen or methyl,

r is an integer from 1-4,

t is an integer from 0-10,

L is hydrogen or fluorine, with the proviso that, when t is O, L is fluorine, and

component (C) is 0 to 20% by weight and component (D) is 0.5 to 7% by weight.

31. A copolymer according to claim 29 wherein component (D) is 0.5 to 7% by weight of the diacrylates and dimethacrylates of 1,2-ethylene glycol, 1,2- and 1,3-propanediol and of 1,3- and 1,4-butane-, 1,5-pentane- and 1,6-hexanediol;

the diacrylates and dimethacrylates of diethylene, triethylene- and tetraethylene glycol, and of neopentyl glycol, di-(2-hydroxyethyl) sulfone and thiodiethylene glycol;

trimethylolpropane triacrylate and trimethacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate and tetramethacrylate, di-pentaerythritol monohydroxy pentaacrylate;

bisphenol-A- and ethoxylated bisphenol-A-dimethacrylate, tris(2-hydroxyethyl)-isocyanurate triacrylate;

allyl methacrylate;

methylene-bisacrylamide, ethylene-bismethacrylamide, divinylbenzene, allyl methacrylate and butanediol divinylether and the reaction products of equivalent amounts of aliphatic, cycloaliphatic and aromatic diisocyanates or of vinyl-unsaturated isocyanates with hydroxy or amino substituted acrylates and methacrylates.

32. A copolymer according to claim 1 wherein component (C) is is methoxy-ethyl acrylate and methoxy-ethyl methacrylate, ethoxy-ethyl acrylate and ethoxy-ethyl methacrylate;

ethoxy-ethoxy-ethyl acrylate, methyl methacrylate;

methyl acrylate, 2-hydroxyethyl methacrylate;

N-vinylpyrrolidone;

N,N-dimethylacrylamide, styrene, or mixtures thereof and component-(D) is ethyleneglycol diacrylate or dimethacrylate, trimethylolpropane triacrylate or methacrylate, neopentyl glycol diacrylate or methacrylate, allyl methacrylate or divinyl benzene.

33. A copolymer according to claim 1 wherein component (D) is 0.5 to 7% by weight of said copolymer.

34. A copolymer according to claim 1 wherein component (D) is 0.1 to 0.5% by weight of said copolymer.

35. A copolymer according to claim 1 which is a contact lens.

36. A copolymer according to claim 2 which is a contact lens.

37. A copolymer according to claim 4 which is a contact lens.

38. A copolymer according to claim 5 which is a contact lens.

39. A copolymer according to claim 7 which is a contact lens.

40. A copolymer according to claim 8 which is a contact lens.

41. A copolymer according to claim 9 which is a contact lens.

42. A copolymer according to claim 10 which is a contact lens.

43. A copolymer according to claim 11 which is a contact lens.

44. A copolymer according to claim 12 which is a contact lens.

45. A copolymer according to claim 13 which is a contact lens.

46. A copolymer according to claim 16 which is a contact lens.

47. A copolymer according to claim 17 which is a contact lens.

48. A copolymer according to claim 18 which is a contact lens.

49. A copolymer according to claim 19 which is a contact lens.

50. A copolymer according to claim 21 which is a contact lens.

51. A copolymer according to claim 22 which is a contact lens.

52. A copolymer according to claim 23 which is a contact lens.

53. A copolymer according to claim 24 which is a contact lens.

54. A copolymer according to claim 25 which is a contact lens.

55. A copolymer according to claim 26 which is a contact lens.

56. A copolymer according to claim 29 which is a contact lens.

57. A copolymer according to claim 32 which is a contact lens.

58. A copolymer according to claim 34 which is a contact lens.

20. A copolymer according to claim 20 wherein QV is Q₃ V or Q₄ V and a is 1.