Solid polymer electrolyte material, liquid composition, solid polymer fuel cell and fluoropolymer
View Patent ↗A solid polymer electrolyte material made of a copolymer comprising a repeating unit based on a fluoromonomer A which gives a polymer having an alicyclic structure in its main chain by radical polymerization, and a repeating unit based on a fluoromonomer B of the following formula (1): CF 2 ═CF(R f ) j SO 2 X (1) wherein j is 0 or 1, X is a fluorine atom, a chlorine atom or OM {wherein M is a hydrogen atom, an alkali metal atom or a group of NR 1 R 2 R 3 R 4 (wherein each of R 1 , R 2 , R 3 and R 4 which may be the same or different, is a hydrogen atom or a monovalent organic group)}, and R f is a C 1-20 polyfluoroalkylene group having a straight chain or branched structure which may contain ether oxygen atoms.
1. A solid polymer electrolyte material made of a copolymer comprising a repeating unit based on a fluoromonomer A which gives a polymer having an alicyclic structure in its main chain by radical polymerization, and a repeating unit based on a fluoromonomer B of the following formula (1), wherein the repeating unit based on a fluoromonomer A is represented by the following formula (4):
wherein s is 0 or 1, each of R f4 , R f5 , R f6 and R f7 , which may be the same or different, is a fluorine atom or to a C 1-5 perfluoroalkyl group (provided that R f4 and R f5 may be connected to form a spiro ring when s is 0), and R f8 is a fluorine atom, a C 1-5 perfluoroalkyl group or a C 1-5 perfluoroalkoxy group;
CF 2 ═CF(R f ) j SO 2 X (1)
wherein j is 0 or 1, X is a fluorine atom, a chlorine atom or OM {wherein M is a hydrogen atom, an alkali metal atom or a group of NR 1 R 2 R 3 R 4 (wherein each of R 1 , R 2 , R 3 and R 4 which may be the same or different, is a hydrogen atom or a monovalent organic group)}, and R f is a C 1-20 polyfluoroalkylene group having a straight chain or branched structure which optionally contains at least one ether oxygen atom.
2. The solid polymer electrolyte material according to claim 1 , wherein the fluoromonomer B is represented by the following formula (2):
CF 2 ═CFO(CF 2 CFYO) k (CF 2 ) m SO 2 X (2)
wherein k is an integer of from 0 to 2, m is an integer of from 1 to 12, Y is a fluorine atom or a trifluoromethyl group, and X is a fluorine atom, a chlorine atom or OM {wherein M is a hydrogen atom, an alkali metal atom or a group of NR 1 R 2 R 3 R 4 (wherein each of R 1 , R 2 , R 3 and R 4 which may be the same or different, is a hydrogen atom or a monovalent organic group)}.
3. The solid polymer electrolyte material according to claim 1 , wherein the fluoromonomer A is perfluoro(2,2-dimethyl-1,3-dioxole).
4. The solid polymer electrolyte material according to claim 3 , wherein the fluoromonomer B is represented by the following formula (2):
CF 2 ═CFO(CF 2 CFYO) k (CF 2 ) m SO 2 X (2)
wherein k is an integer of from 0 to 2, m is an integer of from 1 to 12, Y is a fluorine atom or a trifluoromethyl group, where X is a fluorine atom, a chlorine atom or OM {wherein M is a hydrogen atom, an alkali metal atom or a group of NR 1 R 2 R 3 R 4 (wherein each of R 1 , R 2 , R 3 and R 4 which may be the same or different, is a hydrogen atom or a monovalent organic group)}.
5. The solid polymer electrolyte material according to claim 1 , wherein the fluoromonomer A is perfluoro(1,3-dioxole).
6. The solid polymer electrolyte material according to claim 5 , wherein the fluoromonomer B is represented by is the following formula (2):
CF 2 ═CFO(CF 2 CFYO) k (CF 2 ) m SO 2 X (2)
wherein k is an integer of from 0 to 2, m is an integer of from 1 to 12, Y is a fluorine atom or a trifluoromethyl group, and X is a fluorine atom, a chlorine atom or OM {wherein M is a hydrogen atom, an alkali metal atom or a group of NR 1 R 2 R 3 R 4 (wherein each of R 1 , R 2 , R 3 and R 4 which may be the same or different, is a hydrogen atom or a monovalent organic group)}.
7. The solid polymer electrolyte material according to claim 1 , wherein the fluoromonomer A is 2,2,4-trifluoro-5-trifluoromethoxy-1,3-dioxole.
8. The solid polymer electrolyte material according to claim 7 , wherein the fluoromonomer B is represented by the following formula (2):
CF 2 ═CFO(CF 2 CFYO) k (CF 2 ) m SO 2 X (2)
wherein k is an integer of from 0 to 2, m is an integer of from 1 to 12, Y is a fluorine atom or a trifluoromethyl group, and X is a fluorine atom. a chlorine atom or OM {wherein M is a hydrogen atom, an alkali metal atom or a group of NR 1 R 2 R 3 R 4 {wherein each of R 1 , R 2 , R 3 and R 4 which may be the same or different, is a hydrogen atom or a monovalent organic group)}.
9. The solid polymer electrolyte material according to claim 1 , which has an ion exchange capacity of from 0.9 to 1.5 meq/g dry resin.
10. The solid polymer electrolyte material according to claim 2 , which has an ion exchange capacity of from 0.9 to 1.5 meq/g dry resin.
11. The solid polymer electrolyte material according to claim 3 , which has an ion exchange capacity of from 0.9 to 1.5 meq/g dry resin.
12. The solid polymer electrolyte material according to claim 4 , which has an ion exchange capacity of from 0.9 to 1.5 meq/g dry resin.
13. The solid polymer electrolyte material according to claim 5 , which has an ion exchange capacity of from 0.9 to 1.5 meq/g dry resin.
14. The solid polymer electrolyte material according to claim 6 , which has an ion exchange capacity of from 0.9 to 1.5 meq/g dry resin.
15. The solid polymer electrolyte material according to claim 7 , which has an ion exchange capacity of from 0.9 to 1.5 meq/g dry resin.
16. The solid polymer electrolyte material according to claim 8 , which has an ion exchange capacity of from 0.9 to 1.5 meq/g dry resin.