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

Claim 2

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).

Claim 3

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, R 1 , R 1 ', R 1 " are independently of each other H or CH 3 , with the proviso that when n=3, R 1 , R 1 ', R 1 " are hydrogen; a is zero or 1, m is an integer from zero to 2, l is zero or 1, R 2 is an linear or branched alkylene with 2 to 4 carbon atoms, ##STR14## wherein R 3 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 R 4 is an alkylene of 2 to 4 carbon atoms, R 5 is an alkylene of 2 to 10 carbon atoms, R 6 is an arylene or alkyl-substituted arylene of 6 to 20 carbon atoms, X is --O-- or --NR 7 --, R 7 is an alkyl of 1 to 5 carbon atoms, X 1 is --O--, --NH-- or --NR 7 --, b is zero or 1, V is ##STR17## c is zero or 1, V 1 has same meaning as V, or is H or R 9 , when l is zero, R 8 is H or --COOH, with the proviso that, if R 8 is --COOH, R 1 is H, c is zero, and Q is Q 1 ; R 9 is an alkyl of 1 to 18 carbon atoms; with the further proviso that when Q is Q 2 , a is zero; when Q is Q 2 , Q 3 or Q 4 , R 8 is H; when c is 1, b is zero, Q is Q 2 and R 1 and R 8 are H; and when V 1 is R 9 , m is zero.

Claim 4

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.

Claim 5

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 R 2 is ##STR18##

Claim 6

A copolymer according to claim 3 wherein the polyester (PE) is a poly(propylene oxide) of 1000-8000 MW, a is 1 and R 2 is ##STR19##

Claim 7

A copolymer according to claim 3 wherein QV is Q 2 V, wherein in Q 2 R 3 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 --X 1 --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.

Claim 8

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.

Claim 9

A copolymer according to claim 3 wherein QV is Q 3 V and V--COO--R 5 - 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.

Claim 10

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

Claim 11

A copolymer according to claim 3 wherein QV is Q 4 V and V--R 6 -- is the radical obtained by removing the --NCO group from 2-isocyanatobutyl vinyl ether, styrene isocyanate, or m-isopropenyl-alpha,alpha-dimethylbenzyl isocyanate.

Claim 12

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

Claim 13

A copolymer according to claim 4 wherein QV is Q 3 V and V--COO--R 5 - 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.

Claim 14

A copolymer according to claim 4 wherein QV is Q 4 V and V--R 6 -- is the radical obtained by removing the --NCO group from 2-isocyanatobutyl vinyl ether, styrene isocyanate, or m-isopropenyl-alpha,alpha-dimethylbenzyl isocyanate.

Claim 15

A copolymer according to claim 5 wherein QV is Q 3 V and V--COO--R 5 -- 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.

Claim 16

A copolymer according to claim 5 wherein QV is Q 4 V and V--R 6 -- is the radical obtained by removing the --NCO group from 2-isocyanatobutyl vinyl ether, styrene isocyanate, or m-isopropenyl-alpha,alpha-dimethylbenzyl isocyanate.

Claim 17

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

Claim 18

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

Claim 19

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

Claim 20

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 Q 2 V, Q 3 V or Q 4 V.

Claim 21

A copolymer according to claim 19 wherein QV is Q 3 V or Q 4 V and a is 1.

Claim 22

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 --(CF 2 ) t CF 2 L or --(CF 2 CF 2 ) q OCF(CF 3 ) 2 R 1 is hydrogen or methyl, X is oxygen or --NR 7 -- wherein R 7 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 --NR 7 --CO--; --NR 7 SO 2 --(CH 2 ) r --; --NR 7 SO 2 --; --S--(CH 2 ) r --; --NR 7 --(CH 2 ) r --NR 7 SO 2 --; or --NHCO--.

Claim 23

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.

Claim 24

A copolymer according to claim 21 wherein X is oxygen, W is a direct bond, R 1 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 R 1 is methyl, r is 2, t is 4 to 10 and L is fluorine.

Claim 25

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

Claim 26

A copolymer according to claim 21, wherein R 1 is methyl, r is 2 and t is 4 to 10 and L is fluorine.

Claim 27

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.

Claim 28

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.

Claim 29

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

Claim 30

A copolymer according to claim 1 wherein component (B) is 40 to 80% by weight of said copolymer.

Claim 31

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

Claim 32

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.

Claim 33

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.

Claim 34

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

Claim 35

A copolymer according to claim 33 wherein component (C) is 10 to 50% by weight of said copolymer.

Claim 36

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

Claim 37

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

Claim 38

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

Claim 39

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

Claim 40

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

Claim 41

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

Claim 42

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

Claim 43

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

Claim 44

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

Claim 45

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

Claim 46

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

Claim 47

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

Claim 48

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

Claim 49

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

Claim 50

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

Claim 51

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

Claim 52

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

Claim 53

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

Claim 54

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

Claim 55

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

Claim 56

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

Claim 57

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

Claim 58

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

Claim 59

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

Claim 60

A copolymer according to claim 2 wherein the polyether PE is a fluorinated polyether of MW 600-5000 of structure HO--CH 2 CF 2 (C 2 F 4 O)x(CF 2 O)yCF 2 CH 2 --OH, wherein x and y are independently of each other integers from 6 to 50.

Claim 61

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

Claim 62

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

Claim 63

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

Claim 64

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

Claim 65

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

Claim 66

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