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

• US 5,115,056 A
• Filed: 02/28/1990
• Issued: 05/19/1992
• 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: Mueller, Karl F., Plankl, Walter L.
• Primary Examiner(s): Marquis, Melvyn I.
• Assistant Examiner(s): Hellender, Karen A.
• Application Number:
  US07/486,493
• Time in Patent Office: 811 Days
• Field of Search: 526/279, 526/251, 526/247, 526/245, 526/243, 526/404, 526/455, 351/160 R, 351/160 H
• US Class Current: 526/243
• CPC Class Codes: C08F 290/062 Polyethers
• 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

Abstract

Fluorine and/or silicone containing block copolymers are described which are the copolymerization product of mono; di- or trivinyl substituted poly(alkylene oxide) prepolymers (A) and fluoroalkyl-alkylene acrylates or methacrylates (B1), oligosiloxy-silyl alkyl-acrylates or methacrylates (B2), and optionally other copolymerizable comonomers (C). The novel block copolymers are prepared in solution or bulk and are characterized by high oxygen permeability, 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) 10 to 80% by weight of a vinyl-telechelic polyether, or a mixture thereof,

(B) 90 to 20% 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), and

(C) 0 to 60% by weight of an ethylenically unsaturated monomer or mixture of monomers other than monomer (B-1) or monomer (B-2).

2. A copolymer according to claim 1 wherein the vinyl-telechelic polyether is of formula (A) ##STR12## wherein:

PE has a number average molecular weight (MW) of about 500 to about 10,000 and has the formula;

##STR13## 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,

l is zero or 1,

R₂ is an linear or branched alkylene with 2 to 4 carbon atoms, ##STR14## 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 ##STR15## ##STR16## 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 ##STR17## c is zero or 1, V₁ has same meaning as V, or is H or R₉, when l 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 500-10000 MW, a poly(propylene oxide) of 500-10000 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 500-10000 MW, wherein A is the amount of poly(ethylene oxide) and (B) is the amount of propylene oxide or a poly(tetramethylene oxide) of 500-10000 MW.

4. A copolymer according to claim 3 wherein the polymer PE is a poly(ethylene oxide) of 1000-8000 MW, or a poly(ethylene oxide-co-propylene oxide) of 1000-10000 MW and wherein a is 1 and R₂ is ##STR18##

5. A copolymer according to claim 3 wherein the polyester (PE) is a poly(propylene oxide) of 1000-8000 MW, a is 1 and R₂ is ##STR19##

6. A copolymer according to claim 3 wherein QV is Q₂ V, wherein in Q₂ 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-diisocyanatobenzene, 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;

1,3,4-tris (6-isocyanatohexyl)biuret;

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)-methylnaphthalene;

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

bis-(4-isocyanatophenyl) ethane and;

bis(4-isocyanatophenyl) ether, and V-(CO)_b --X₁ --R.sub. 4 --X-- 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. -butyl-aminoethyl 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-alpha,alpha-dimethylbenzyl isocyanate.

11. A copolymer according to claim 10 wherein the isocyanate is m-isopropenyl-alpha, alpha-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-alpha,alpha-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-alpha,alpha-dimethylbenzyl isocyanate.

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

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

18. A copolymer according to claim 15, wherein the isocyanate is m-isopropenyl-alpha,alpha-dimethyl benzyl isocyanate.

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.

20. A copolymer according to claim 19 wherein QV is Q₃ V or Q₄ V and a is 1.

21. A copolymer according to claim 1 wherein (B-1) is a fluorine containing monomer containing at least three fluorine atoms and comprising hexafluoroisopropyl acrylate and methacrylate, perfluorocyclohexyl acrylate and methacrylate, pentafluorostyrene or the acrylate or methacrylate esters or amides of the formula ##STR20## wherein R_f is --(CF₂)_t CF₂ L or --(CF₂ CF₂)_q OCF(CF₃)₂

R₁ is hydrogen or methyl,

X is oxygen or --NR₇ -- wherein R₇ is an alkyl group with 1-5 carbon atoms.

r is an integer from 1-4,

t is an integer from 0-14,

q is an integer from 1-3,

L is hydrogen or fluorine, with the proviso that, when t is 0, L is fluorine, and

W is a direct bond or a divalent group of the structure --NR₇ --CO--;

--NR₇ SO₂ --(CH₂)_r --;

--NR₇ SO₂ --;

--S--(CH₂)_r --;

--NR₇ --(CH₂)_r --NR₇ SO₂ --;

or --NHCO--.

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

23. A copolymer according to claim 21 wherein X is oxygen, W is a direct bond, R₁ is hydrogen, r is 2, t is 6 to 10 and L is fluorine;

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

24. A copolymer according to claim 21, wherein r is 1 or 2, t is 1 to 4 and L is fluorine.

25. A copolymer according to claim 21, wherein R₁ is methyl, r is 2 and t is 4 to 10 and L is fluorine.

26. A copolymer according to claim 1 wherein (B-2) is a silicone-containing vinyl monomer which is an oligosiloxanyl-silyl-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(trimethylsiloxy-silyl)propyl (meth)acrylate, triphenyldimethyl-disiloxanylmethyl (meth)acrylate, pentamethyl-disiloxanyl-methyl (meth)acrylate, tert-butyl-tetramethyldisiloxanylethyl (meth)-acrylate, methyl-di(trimethylsiloxy)silylpropylglyceryl (meth)acrylate;

pentamethyldisiloxanyl-methyl methacrylate;

heptamethyl-cyclotetrasiloxy methyl methacrylate;

heptamethyl-cyclotetrasiloxy-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 40 to 80% by weight of said copolymer.

30. A copolymer according to claim 29 wherein component (B) is 50 to 70% by weight of said copolymer.

31. A copolymer according to claim 1 wherein component (C) is a monomer selected from the group consisting of methyl acrylate, ethyl acrylate, n- and isopropyl acrylate, cyclohexyl acrylate, trimethylcyclohexyl acrylate, phenyl acrylate, benzyl acrylate and the corresponding methacrylate;

furfuryl acrylate and methacrylate;

methoxy-ethyl-, ethoxy-ethyl-, and ethoxy-ethoxy ethyl acrylate and methacrylate;

2-hydroxyethyl acrylate and methacrylate, 3-hydroxypropyl acrylate, methacrylate and methacrylamide;

N,N-dimethylacrylamide;

N-isopropyl- acrylamide;

N-vinylacetamide;

N-vinyl-pyrrolidone;

dimethylamino-ethyl methacrylate and methacrylamide;

acrylic and methacrylic acid, vinyl sulfonic acid, 4-styrene sulfonic acid and 2-methacrylamido-2-methyl-propane-sulfonic acid and their salts, and mixtures thereof.

32. A copolymer according to claim 31 wherein the monomer is methoxyethyl 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-dimethyl-acrylamide and styrene, or mixtures thereof.

33. A copolymer according to claim 1 wherein component (C) is 5 to 60% by weight of said copolymer.

34. A copolymer according to claim 33 wherein component (C) is 10 to 50% 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.

59. A copolymer according to claim 2 wherein the polyether PE is a fluorinated polyether of MW 600-5000 of structure HO--CH₂ CF₂ (C₂ F₄ O)x(CF₂ O)yCF₂ CH₂ --OH, wherein x and y are independently of each other integers from 6 to 50.

60. A copolymer according to claim 4 wherein the amount of component (C) is zero.

61. A copolymer according to claim 4 wherein component (A) is 15-30% by weight of said copolymer.

62. A copolymer according to claim 5 wherein component (A) is 30-60% by weight of said copolymer.

63. A copolymer according to claim 60, which is a contact lens.

64. A copolymer according to claim 61, which is a contact lens.

65. A copolymer according to claim 62, which is a contact lens.