Perfluorocyclobutane copolymers
View Patent ↗The present invention provides copolymer having repeating units based on polyoxyalkylene radicals, polysiloxane radicals and perfluorocyclobutane radicals. The copolymers are useful as biomedical devices such as contact lenses or intraocular lenses.
1. A perfluorocyclobutane ring-containing copolymer which is obtained by copolymerization of at least two of the following prepolymers (a) T -(P) n -T, (b) T 1 -(P 1 ) n -T 1 and (c) T 2 -(P 2 ) n -T 2 wherein n is independently 1 to about 100,000 and T, T 1 and T 2 are independently of the general formula
wherein L is an optional linking group and is independently a straight or branched C 1 -C 30 alkyl group, a C 3 -C 30 cycloalkyl group, a C 5 -C 30 aryl group, an ether group, a C 1 -C 20 ester group, an amide group, a siloxanyl, an arylsiloxanyl or a fluorosiloxanyl, R 1 independently represents one or more inertly substituted groups; and each X is independently a group which links the inertly substituted groups and the trifluorovinyl group and is selected from the group consisting of a bond, an oxygen atom, a sulfur atom, a carboxylic ester group, a thiocarboxylic ester group, an amide group, a sulfone, a sulfoxide, a carbonate, a carbamate, a perfluoroalkylene, a perfluoroalkylene ether, an alkylene, an acetylene, a phosphine, a carbonyl group, a thiocarbonyl group, seleno, telluro, nitrido, a silanediyl group, a trisilanediyl group, a tetrasilanetetrayl group, a siloxanediyl group, a disiloxanediyl group, a trisiloxyldiyl group, a trisilazanyl group, a silythio group, a boranediyl group and combinations thereof; P is independently an oxyalkylene radical of the general formula
wherein R 2 and R 3 are independently hydrogen, a straight or branched C 1 -C 6 alkyl group, a C 3 -C 30 cycloalkyl group, a C 5 -C 30 aryl group, a straight or branched C 1 -C 6 fluoroalkyl group, a C 3 -C 30 fluorocycloalkyl group, a C 5 -C 30 fluoroaryl group, an ether group, a C 1 -C 20 ester group, an amide group, an amine group, fluorine, a vinyl group, or a hydroxyl group and m is 1 to about 10; P 1 is a polysiloxane radical of the general formula
wherein R 4 and R 5 are independently hydrogen, a straight or branched C 1 -C 6 alkyl group, a C 3 -C 30 cycloalkyl group, a C 5 -C 30 aryl group, a straight or branched C 1 -C 6 fluoroalkyl group, a C 3 -C 30 fluorocycloalkyl group, a C 5 -C 30 fluoroaryl group, an ether group, a C 1 -C 20 ester group, C 1 -C 6 alkoxy group, an amide group an amine group, fluorine, a vinyl group, or a hydroxyl group; and P 2 is a perfluorocyclobutane radical of the general formula
wherein R 6 independently represents one or more inertly substituted groups and X′ is independently a bond, an oxygen atom, a sulfur atom, a carboxylic or thiocarboxylic ester group, a sulfone, a sulfoxide, perfluoroalkylene, perfluoroalkylene ether, alkylene, acetylene, a phosphine, a carbonyl or thiocarbonyl group; seleno; telluro; nitrido; a silanediyl group, a trisilanedjyl group, a tetrasilanetetrayl group, a siloxanediyl group, a disiloxanediyl group, a trisiloxyl group, a trisilazanyl group, a silythio group, or a boranediyl group.
2. The perfluorocyclobutane ring-containing copolymer of claim 1 , wherein R 1 and R 6 are independently selected from the group consisting of
wherein R is independently hydrogen, a C 1 -C 20 alkyl group, a hydroxyl group, a C 1 -C 20 carboxylic acid group, a C 1 -C 20 ester group, a C 1 -C 20 alkoxy group, CO 2 − , SO 3 − , PO 3 − OPO 3 2− , F, Br, I, NA 2 or NA 3 30 wherein A is independently hydrogen, a C 1 -C 20 alkyl group, a hydroxyl group, a C 1 -C 20 carboxylic acid group, a C 1 -C 20 ester group, or a C 1 -C 20 alkoxy group, or two R groups together with the carbon atom to which they are bonded are joined together to form a cyclic structure optionally containing one or more heterocyclic groups; R 7 is a bond, a C 1 -C 20 alkylene or haloalkylene group optionally containing ether or ester linkages and wherein the X group and either the L or P or P 1 or P 2 group may independently be bonded to the aromatic group either ortho, meta and/or para with respect one another.
3. The perfluorocyclobutane ring-containing copolymer of claim 1 , wherein the prepolymer T-(P) n -T has a number average molecular weight of from about 100 about 100,000.
4. The perfluorocyclobutane ring-containing copolymer of claim 1 , wherein the prepolymer T 1 -(P 1 ) n -T 1 has a number average molecular weight of from about 100 about 100,000.
5. The perfluorocyclobutane ring-containing copolymer of claim 1 , wherein the prepolymer T 2 -(P 2 ) n -T 2 has a number average molecular weight of from about 100 about 100,000.
6. The perfluorocyclobutane ring-containing copolymer of claim 1 , which is obtained by copolymerizing one or more of the prepolymer T-(P) n T with one or more of the prepolymer T 1 -(P 1 ) n -T 1 .
7. The perfluorocyclobutane ring-containing copolymer of claim 1 , which is obtained by copolymerizing one or more of the prepolymer T 1 -(P 1 ) n -T 1 with one or more of the prepolymer T 2 -(P 2 ) n -T 2 .
8. The perfluorocyclobutane ring-containing copolymer of claim 1 , which is obtained by copolymerizing one or more of the prepolymer T 1 -(P 1 ) n -T 1 with one or more of the prepolymer T 2 -(P 2 ) n -T 2 .
9. The perfluorocyclobutane ring-containing copolymer of claim 1 , which is obtained by copolymerizing one or more of the prepolymer T-(P) n -T with one or more of the prepolymer T 1 -(P 1 ) n -T 1 and with one or more of the prepolymer T 2 -(P 2 ) n -T 2 .
10. A process for preparing a copolymer comprising polymerizing at least two of the following prepolymers (a) T-(P) n -T, (b) T 1 -(P 1 ) n -T 1 and (c) T 2 -(P 2 ) n -T 2 for a sufficient time to form the perfluoro containing copolymer, wherein n is independently 1 to about 100,000 and T, T 1 and T 2 are independently of the general formula
wherein L is an optional linking group and is independently a straight or branched C 1 -C 30 alkyl group, a C 3 -C 30 cycloalkyl group, a C 5 -C 30 aryl group, an ether group, a C 1 -C 20 ester group, an amide group, a siloxanyl, an arylsiloxanyl or a fluorosiloxanyl, R 1 independently represents one or more inertly substituted groups; and each X is independently a group which links the inertly substituted groups and the trifluorovinyl group and is selected from the group consisting of a bond, an oxygen atom, a sulfur atom, a carboxylic ester group, a thiocarboxylic ester group, an amide group, a sulfone, a sulfoxide, a carbonate, a carbamate, a perfluoroalkvlene, a perfluoroalkylene ether, an alkylene, an acetylene, a phosphine, a carbonyl group, a thiocarbonyl group, seleno, telluro, nitrido, a silanediyl group, a trisilanedivl group, a tetrasilanetetrayl group, a siloxanediyl group, a disiloxanedjyl group, a trisiloxyldiyl group, a trisilazanyl group, a silythio group, a boranediyl group and combinations thereof; P is independently an oxyalkylene radical of the general formula
wherein R 2 and R 3 are independently hydrogen, a straight or branched C 1 -C 6 alkyl group, a C 3 -C 30 cycloalkyl group, a C 5 -C 30 aryl group, a straight or branched C 1 -C 6 fluoroalkyl group, a C 3 -C 30 fluorocycloalkyl group, a C 5 -C 30 fluoroaryl group, an ether group, a C 1 -C 20 ester group, an amide group, an amine group, fluorine, a vinyl group, or a hydroxyl group and m is 1 to about 10; P 1 is a polysiloxane radical of the general formula
wherein R 4 and R 5 are independently hydrogen, a straight or branched C 1 -C 6 alkyl group, a C 3 -C 30 cycloalkyl group, a C 5 -C 30 aryl group, a straight or branched C 1 -C 6 fluoroalkyl group, a C 3 -C 30 fluorocycloalkyl group, a C 5 -C 30 fluoroaryl group, an ether group, a C 1 -C 20 ester group, C 1 -C 6 alkoxy group, an amide group an amine group, fluorine, a vinyl group, or a hydroxyl group; and P 2 is a perfluorocyclobutane radical of the general formula
wherein X′ is independently a bond, an oxygen atom, a sulfur atom, a carboxylic or thiocarboxylic ester group, a sulfone, a sulfoxide, perfluoroalkylene, perfluoroalkylene ether, alkylene, acetylene, a phosphine, a carbonyl or thiocarbonyl group; seleno; telluro; nitrido; a silanedjyl group, a trisilanediyl group, a tetrasilanetetrayl group, a siloxanediyl group, a disiloxanediyl group, a trisiloxyl group, a trisilazanyl group, a silythio group, or a boranediyl group and R 6 independently represents one or more inertly substituted groups and wherein the perfluorocyclobutane prepolymer (c) T 2 -P 2 -T 2 can be generated in situ from one or more monomers having two dimerizable perfluorovinyl groups.
11. A biomedical device comprising the perfluorocyclobutane ring-containing copolymer of claim 1 .
12. The biomedical device of claim 11 , which is an ophthalmic lens.
13. The biomedical device of claim 12 , wherein the ophthalmic lens is a contact lens.
14. The biomedical device of claim 13 , wherein the contact lens is a rigid gas permeable lens.