초록 ▼

The invention provides a crosslinkable aromatic resin having a protonic acid group and a crosslinkable group, suitable for electrolytic membranes and binders used in fuel cells, etc., and electrolytic polymer membranes, binders and fuel cells using the resin. The crosslinkable aromatic resin has a c

The invention provides a crosslinkable aromatic resin having a protonic acid group and a crosslinkable group, suitable for electrolytic membranes and binders used in fuel cells, etc., and electrolytic polymer membranes, binders and fuel cells using the resin. The crosslinkable aromatic resin has a crosslinkable group, which is not derived from the protonic acid group and can form a polymer network without any elimination component. This resin exhibits excellent ion conductivity, heat resistance, water resistance, adhesion property and low methanol permeability. Preferably, the crosslinkable group is composed of a C1 to C10 alkyl group directly bonded to the aromatic ring and/or an alkylene group having 1 to 3 carbon atoms in the main chain in which at least one carbon atom directly bonded to the aromatic ring bonds to hydrogen, and a carbonyl group, or a carbon-carbon double bond or triple bond. The aromatic resins such as aromatic polyethers, aromatic polyamides, aromatic polyimides, aromatic polyamideimides, aromatic polyazoles, etc., which contain such a crosslinkable group, are preferred as the crosslinkable aromatic resins having a protonic acid group and a crosslinkable group.

대표청구항 ▼

What we claim is: 1. A crosslinkable aromatic resin having a protonic acid, which comprises that the crosslinkable aromatic resin contains a crosslinkable group, and that the crosslinkable group is not derived from the protonic acid group and can form a polymer network without forming any eliminati

What we claim is: 1. A crosslinkable aromatic resin having a protonic acid, which comprises that the crosslinkable aromatic resin contains a crosslinkable group, and that the crosslinkable group is not derived from the protonic acid group and can form a polymer network without forming any elimination component, and further that the crosslinkable group is at least one selected from the group consisting of i) a crosslinkable group composed of a C1 to C10 alkyl group bonded to the aromatic ring and a carbonyl group, ii) a carbon-carbon double bond, and iii) a carbon-carbon triple bond. 2. The crosslinkable aromatic resin having a protonic acid group according to claim 1, wherein the crosslinkable group comprises an alkyl group having 1 to 10 carbon atoms directly bonded to the aromatic ring and a carbonyl group. 3. The crosslinkable aromatic resin having a protonic acid group according to claim 2, wherein the crosslinkable aromatic resin contains a crosslinkable group comprising an alkyl group having 1 to 10 carbon atoms directly bonded to the aromatic ring and a carbonyl group, and a protonic acid group, and can be crosslinked by light, heat and/or electron rays. 4. The crosslinkable aromatic resin having a protonic acid group according to claim 2, wherein the crosslinkable aromatic resin having a protonic acid group is an aromatic resin having a carbonyl group, an alkyl group having 1 to 10 carbon atoms directly bonded to the aromatic ring, and a protonic acid group, and being selected from the group consisting of aromatic polyethers, aromatic polyamides, aromatic polyimides, aromatic polyamideimides and aromatic polyazoles. 5. The crosslinkable aromatic resin having a protonic acid group according to claim 2, wherein the crosslinkable aromatic resin having a protonic acid group is a photo-crosslinkable polyether ketone containing a protonic acid group and an aromatic ring to which an alkyl group having 1 to 10 carbon atoms. 6. The crosslinkable aromatic resin having a protonic acid group according to claim 2, wherein the crosslinkable aromatic resin having a protonic acid group is an aromatic polyetherketone comprising, based on the total repeating structural units, 10 to 100% by mol of the repeating structural unit represented by the following formula (6) below, and 0 to 90% by mol of the repeating structural unit represented by the following formula (7) below, in which at least one of R1 to R10 is--CmH2m+1 (wherein m is an integer of 1 to 10) and at least one of X1 to X10 is a protonic acid group: [in formulas (6) and (7), each of R1 to R independently represents H or--CmH2m+1 (wherein m is an integer of 1 to 10), each of X1 to X10 independently represents H or a protonic acid group; each of A1 to A3 independently represents a direct bond,--CH2--,--C(CH3)2--,--C(CF3)2--,--O--,--SO2--or--CO--; each of i, j, k and l independently represents 0 or 1; and the hydrogen atom bonded to the aromatic rings in the formula (6) and (7) may be substituted with--CmH2m+1 (wherein m is an integer of 1 to 10), a protonic acid group, Cl, F or CF3.] 7. The crosslinkable aromatic resin having a protonic acid group according to claim 2, wherein the crosslinkable aromatic resin having a protonic acid group is an aromatic polyetherketone comprising, based on the total repeating structural units, 10 to 100% by mol of the repeating structural unit represented by the following formula (6') below, and 0 to 90% by mol of the repeating structural unit represented by the following formula (7') below, in which at least one of B1 to B3 is a group represented by the formula:--CH(CxHx+1){C(CyHy+1)(Cy'H y'30 1)}α{C(CzHz+1)(Cz'Hz'+1 )}β--, wherein x is an integer of 0 to 9, each of y, y', z and z' is independently an integer of 0 to 8, each of α and β is independently of 0 or 1 and x+y+y'+z+z'+α+β≦9, and at least one of X1 to X10 is a protonic acid group: [in formulas (6') and (7'), each of X1 to X10 independently represents H or a protonic acid group; each of B1 to B3 independently represents a direct bond,--C(CF3)2--,--SO2--,--CO--or a group represented by the formula:--CH(CxHx+1){C(CyHy+1)(Cy'H y'+1)}α{C(CzHz+1)(Cz'H z'+1)}β--, wherein x is an integer of 0 to 9, each of y, y', z and z' is independently an integer of 0 to 8, each of α and β is independently of 0 or 1 and x+y+y'+z+z'+α+β≦9; each of i, j, k and l independently represents 0 or 1; and the hydrogen atom bonded to the aromatic rings in the formula (6') and (7') may be substituted with--CmH2m+1 (wherein m is an integer of 1 to 10), a protonic acid group, Cl, F or CF3.] 8. The crosslinkable aromatic resin having a protonic acid group according to claim 2, wherein the crosslinkable aromatic resin having a protonic acid group comprises a carbonyl group-containing resin having a carbonyl group, and a resin containing an alkyl group having 1 to 10 carbon atoms directly bonded to the aromatic ring, and at least one of the carbonyl group-containing resin and the resin containing an alkyl group has a protonic acid group. 9. The crosslinkable aromatic resin having a protonic acid group according to claim 8, wherein each of the carbonyl group-containing resin and the resin containing an alkyl group independently is an aromatic resin selected from the group consisting of aromatic polyethers, aromatic polyamides, aromatic polyimides, aromatic polyamideimides and aromatic polyazoles. 10. The crosslinkable aromatic resin having a protonic acid group according to claim 8, wherein the crosslinkable aromatic resin having a protonic acid group comprises, based on the total repeating structural units, 20 to 80% by weight of the resin containing 10 to 100% by mol of the repeating structural unit represented by the following formula (6), and, 20 to 80% by weight of the resin containing 10 to 100% by mol of the repeating structural unit represented by the following formula (7), wherein at least one of R6 to R10 is--CmH2m+1 (wherein m is an integer of 1 to 10) and at least one of X1 to X10 is a protonic acid group: [in formula (6) and (7), each of R1 to R10 independently represents H or--CmH2m+1 (wherein m is an integer of 1 to 10), each of X1 to X10 independently represents H or a protonic acid group; each of A1 to A3 independently represents a direct bond,--CH2--,--C(CH3)2--,--C(CF3)2--,--O--,--SO2--or--CO--; each of i, j, k and l independently represents 0 or 1; and the hydrogen atom bonded to the aromatic rings in the formula (6) and (7) may be substituted with--CmH2m+1 (wherein m is an integer of 1 to 10), a protonic acid group, Cl, F or CF3.] 11. The crosslinkable aromatic resin having a protonic acid group according to claim 8, wherein the crosslinkable aromatic resin having a protonic acid group comprises, based on the total repeating structural units, 20 to 80% by weight of the resin containing 10 to 100% by mol of the repeating structural unit represented by the following formula (6'), and, 20 to 80% by weight of the resin containing 10 to 100% by mol of the repeating structural unit represented by the following formula (7'), wherein at least one of B1 to B3 is a group represented by the formula:--CH(CxHx+1){C(CyHy+1)(Cy'H y'+1)}α{C(CzHz+1)(Cz'H z'+1)}β--, wherein x is an integer of 0 to 9, each of y, y', z and z' is independently an integer of 0 to 8, each of α and β is independently of 0 or 1 and x+y+y'+z+z'+α+β≦9, and at least one of X1 to X10 is a protonic acid group: [in formula (6') and (7'), each of X1 to X10 independently represents H or a protonic acid group; each of B1 to B3 independently represents a direct bond,--C(CF3)2--,--SO2--,--CO--, or a group represented by the formula:--CH(CxHx+1){C(CyHy+1)(Cy'H y'+1)}α{C(CzHz+1)(Cz'H z'+1)}β--, wherein x is an integer of 0 to 9, each of y, y', z and z' is independently an integer of 0 to 8, each of α and β is independently of 0 or 1 and x+y+y'+z+z'+α+β≦9; each of i, j, k and l independently represents 0 or 1; and the hydrogen atom bonded to the aromatic rings in the formula (6') and (7') may be substituted with--CmH2m+1 (wherein m is an integer of 1 to 10), a protonic acid group, Cl, F or CF3.] 12. The crosslinkable aromatic resin having a protonic acid group according to claim 1, wherein the crosslinkable aromatic resin having a protonic acid group is an aromatic resin having a carbon-carbon double bond or a carbon-carbon triple bond, which is selected from the group consisting of aromatic polyethers, aromatic polyamides, aromatic polyimides, aromatic polyamideimides and aromatic polyazoles. 13. The crosslinkable aromatic resin having a protonic acid group according to claim 1, wherein the crosslinkable group is a carbon-carbon double bond or a carbon-carbon triple bond. 14. The crosslinkable aromatic resin having a protonic acid group according to claim 13, wherein the crosslinkable aromatic resin having a protonic acid group is an aromatic resin having a carbon-carbon double bond or a carbon-carbon triple bond, which is selected from the group consisting of aromatic polyethers, aromatic polyamides, aromatic polyimides, aromatic polyamideimides and aromatic polyazoles. 15. The crosslinkable aromatic resin having a protonic acid group according to claim 13, wherein the crosslinkable aromatic resin having a protonic acid group comprises an aromatic resin containing 20 to 100% by mol, based on the total repeating structural units, of the repeating structural unit represented by the following formula (34), wherein at least one of R11 to R15 is--CmH2m--CH═CH--R or--CmH2m--C≡C--R (wherein m is an integer of 0 to 10, and R is H or phenyl) and at least one of X11 to X15 is a protonic acid group: [wherein each of R11 to R15 independently represents H,--CmH2m--CH═CH--R or--CmH2m--C≡C--R (wherein m is an integer of 0 to 10, and R is H or phenyl); V independently represents CH, C--CN or N; each of X11 to X15 independently represents H or a protonic acid group; each of A4 and A5 independently represents a direct bond,--CH2--,--C(CH3)2--,--C(CF3)2--,--O--,--SO2--or--CO--; each of k, l and n independently represents 0 or 1; the hydrogen atom bonded to the aromatic rings in formula (34) may be substituted with--CmH2m--CH═CH--R or--CmH2m--C≡C--R (wherein m is an integer of 0 to 10, and R is H or phenyl), a protonic acid group, Cl, F or CF3]. 16. The crosslinkable aromatic resin having a protonic acid group according to claim 13, wherein the crosslinkable aromatic resin having a protonic acid group comprises 20 to 100% by mol, based on the total repeating structural units, of the repeating structural unit shown by the following formula (35), wherein at least one of X16 to X20 is a protonic acid group and the molecular end is--Ra--CH═CH--Rb or--Ra--C≡C--Rb (wherein Ra is phenylene and Rb is H or phenyl: [wherein each of X16 to X20 independently represents H or a protonic acid group; V independently represents CH, C--CN or N; each of A6 and A7 independently represents a direct bond,--CH2--,--C(CH3)2--,--C(CF3)2--,--O--,--SO2--or--CO--; each of k, l and n independently represents 0 or 1; the hydrogen atoms bonded to the aromatic rings in formula (35) may be substituted with a protonic acid group, Cl, F or CF3]. 17. The crosslinkable aromatic resin having a protonic acid group according to claim 1, wherein the protonic acid group is--CnH2n--SO3Y (wherein n is an integer of 0 to 10; and Y is H, Na or K). 18. A crosslinked product, which is obtained by crosslinking the crosslinkable aromatic resin having a protonic acid group defined in claim 1. 19. A polymer membrane, which is obtained using the crosslinkable aromatic resin having a protonic acid group defined in claim 1. 20. An ion conductive polymer membrane for fuel cells, which is obtained by crosslinking the polymer membrane defined in claim 19. 21. The ion conductive polymer membrane for fuel cells according to claim 20, wherein the ion-exchange equivalent weight is not greater than 1000 g/mol and the methanol solubility is less than 15% by weight. 22. An ion conductive binder for fuel cells, which contains the crosslinkable aromatic resin having a protonic acid group defined in claim 1. 23. A composition for forming electrodes comprising the binder defined in claim 22 and electrode materials. 24. An electrode, which is obtained by using the binder defined in claim 22. 25. A fuel cell, which is obtained by using the polymer membrane defined in claim 19. 26. A fuel cell, which is obtained by using the binder defined in claim 22. 27. A fuel cell, which is obtained by using the electrode defined in claim 24. 28. A crosslinked product, which is obtained by crosslinking the crosslinkable aromatic resin having a protonic acid group defined in claim 17. 29. A polymer membrane, which is obtained using the crosslinkable aromatic resin having a protonic acid group defined in claim 17. 30. An ion conductive binder for fuel cells, which contains the crosslinkable aromatic resin having a protonic acid group defined in claim 17. 31. An electrode, which is obtained by using the binder defined in claim 30. 32. A fuel cell, which is obtained by using the polymer membrane defined in claim 29. 33. A fuel cell, which is obtained by using the binder defined in claim 30. 34. A fuel cell, which is obtained by using the electrode defined in claim 31.