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 liquid composition comprising an organic solvent having a hydroxyl group in its molecule, and a solid polymer electrolyte material made of a copolymer dissolved or dispersed in the organic solvent, said 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 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 3 M (1′)
wherein j is 0 or 1,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.
2. The liquid composition 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 3 M (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 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 liquid composition according to claim 1 , wherein the fluoromonomer A is perfluoro(2,2-dimethyl-1,3-dioxole).
4. The liquid composition 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 3 M (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 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 liquid composition according to claim 1 , wherein, the fluoromonomer A is perfluoro(1,3-dioxole).
6. The liquid composition according to claim 5 , wherein the fluoromonomer B′ is represented by the following formula (2′):
CF 2 ═CFO(CF 2 CFYO) k (CF 2 ) m SO 3 M (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 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 liquid composition according to claim 1 , wherein the fluoromonomer A is 2,2,4-trifluoro-5-trifluoromethoxy-1,3-dioxole.
8. The liquid composition 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 3 M (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 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 liquid composition according to claim 1 , wherein the solid polymer electrolyte material has an ion exchange capacity of from 0.9 to 1.5 meq/g dry resin.
10. The liquid composition according to claim 2 , wherein the solid polymer electrolyte material has an ion exchange capacity of from 0.9 to 1.5 meq/g dry resin.
11. The liquid composition according to claim 3 , wherein the solid polymer electrolyte material has an ion exchange capacity of from 0.9 to 1.5 meq/g dry resin.
12. The liquid composition according to claim 4 , wherein the solid polymer electrolyte material has an ion exchange capacity of from 0.9 to 1.5 meq/g dry resin.
13. The liquid composition according to claim 5 , wherein the solid polymer electrolyte material has an ion exchange capacity of from 0.9 to 1.5 meq/g dry resin.
14. The liquid composition according to claim 6 , wherein the solid polymer electrolyte material has an ion exchange capacity of from 0.9 to 1.5 meq/g dry resin.
15. The liquid composition according to claim 7 , wherein the solid polymer electrolyte material has an ion exchange capacity of from 0.9 to 1.5 meq/g dry resin.
16. The liquid composition according to claim 8 , wherein the solid polymer electrolyte material has an ion exchange capacity of from 0.9 to 1.5 meq/g dry resin.