EP1481027A1 - Funktionalisierte hauptkettenpolymere - Google Patents
Funktionalisierte hauptkettenpolymereInfo
- Publication number
- EP1481027A1 EP1481027A1 EP02796506A EP02796506A EP1481027A1 EP 1481027 A1 EP1481027 A1 EP 1481027A1 EP 02796506 A EP02796506 A EP 02796506A EP 02796506 A EP02796506 A EP 02796506A EP 1481027 A1 EP1481027 A1 EP 1481027A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polymer
- group
- general formula
- functional groups
- radical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000005267 main chain polymer Substances 0.000 title abstract description 4
- 239000012528 membrane Substances 0.000 claims abstract description 69
- 239000000446 fuel Substances 0.000 claims abstract description 20
- 239000005518 polymer electrolyte Substances 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims description 126
- 239000002253 acid Substances 0.000 claims description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 125000000524 functional group Chemical group 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 27
- 125000003118 aryl group Chemical group 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 19
- 229920006037 cross link polymer Polymers 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 17
- -1 1,2-phenylene, 1, 3-phenylene, 1,4-phenylene, 4,4'-biphenyl Chemical group 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 125000001424 substituent group Chemical group 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 125000001072 heteroaryl group Chemical group 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 7
- 150000001768 cations Chemical class 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000005342 ion exchange Methods 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 229920002959 polymer blend Polymers 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical class [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 238000000502 dialysis Methods 0.000 claims description 3
- 238000009792 diffusion process Methods 0.000 claims description 3
- 238000000909 electrodialysis Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 150000002366 halogen compounds Chemical class 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 238000001728 nano-filtration Methods 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 238000005373 pervaporation Methods 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 238000001223 reverse osmosis Methods 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N antipyrene Natural products C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims description 2
- DOUHZFSGSXMPIE-UHFFFAOYSA-N hydroxidooxidosulfur(.) Chemical group [O]SO DOUHZFSGSXMPIE-UHFFFAOYSA-N 0.000 claims description 2
- 125000004437 phosphorous atom Chemical group 0.000 claims description 2
- 229920005597 polymer membrane Polymers 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- 239000003880 polar aprotic solvent Substances 0.000 claims 1
- 229920006393 polyether sulfone Polymers 0.000 abstract description 5
- 229920006260 polyaryletherketone Polymers 0.000 abstract description 3
- 229920002492 poly(sulfone) Polymers 0.000 description 17
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000002019 doping agent Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 229920003023 plastic Polymers 0.000 description 11
- 239000004033 plastic Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 235000011007 phosphoric acid Nutrition 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229920000557 Nafion® Polymers 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000008961 swelling Effects 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- 229920001643 poly(ether ketone) Polymers 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000004696 Poly ether ether ketone Substances 0.000 description 4
- 229920000265 Polyparaphenylene Polymers 0.000 description 4
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical group 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 229920002530 polyetherether ketone Polymers 0.000 description 4
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- 239000004693 Polybenzimidazole Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 229920001660 poly(etherketone-etherketoneketone) Polymers 0.000 description 3
- 229920000767 polyaniline Polymers 0.000 description 3
- 229920000323 polyazulene Polymers 0.000 description 3
- 229920002480 polybenzimidazole Polymers 0.000 description 3
- 229920001088 polycarbazole Polymers 0.000 description 3
- 229920000123 polythiophene Polymers 0.000 description 3
- 229920002717 polyvinylpyridine Polymers 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 150000003455 sulfinic acids Chemical class 0.000 description 3
- 125000001174 sulfone group Chemical group 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OIQCMCUFGWKBBV-UHFFFAOYSA-N 2,3-diiodobutane Chemical compound CC(I)C(C)I OIQCMCUFGWKBBV-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- 229920004459 Kel-F® PCTFE Polymers 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229920004428 Neoflon® PCTFE Polymers 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229920004695 VICTREX™ PEEK Polymers 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- ZSOMHSLKERBJSE-UHFFFAOYSA-N bromo methanesulfonate Chemical compound CS(=O)(=O)OBr ZSOMHSLKERBJSE-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- QPOWUYJWCJRLEE-UHFFFAOYSA-N dipyridin-2-ylmethanone Chemical compound C=1C=CC=NC=1C(=O)C1=CC=CC=N1 QPOWUYJWCJRLEE-UHFFFAOYSA-N 0.000 description 2
- 239000002003 electrode paste Substances 0.000 description 2
- 150000002390 heteroarenes Chemical class 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 150000002926 oxygen Chemical class 0.000 description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 229920000090 poly(aryl ether) Polymers 0.000 description 2
- 229920001652 poly(etherketoneketone) Polymers 0.000 description 2
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 229920002620 polyvinyl fluoride Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 description 2
- 125000000626 sulfinic acid group Chemical group 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 2
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 2
- ROUYUBHVBIKMQO-UHFFFAOYSA-N 1,4-diiodobutane Chemical compound ICCCCI ROUYUBHVBIKMQO-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ZPLCXHWYPWVJDL-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)methyl]-1,3-oxazolidin-2-one Chemical compound C1=CC(O)=CC=C1CC1NC(=O)OC1 ZPLCXHWYPWVJDL-UHFFFAOYSA-N 0.000 description 1
- WVSYONICNIDYBE-UHFFFAOYSA-N 4-fluorobenzenesulfonic acid Chemical group OS(=O)(=O)C1=CC=C(F)C=C1 WVSYONICNIDYBE-UHFFFAOYSA-N 0.000 description 1
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000005967 Finkelstein reaction Methods 0.000 description 1
- 229920005372 Plexiglas® Polymers 0.000 description 1
- 229920008285 Poly(ether ketone) PEK Polymers 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920003295 Radel® Polymers 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- WGZNLHRYNZYPRX-UHFFFAOYSA-M [Br+].CCS([O-])(=O)=O Chemical compound [Br+].CCS([O-])(=O)=O WGZNLHRYNZYPRX-UHFFFAOYSA-M 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000005418 aryl aryl group Chemical group 0.000 description 1
- 238000006254 arylation reaction Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000001566 impedance spectroscopy Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- JDNTWHVOXJZDSN-UHFFFAOYSA-N iodoacetic acid Chemical compound OC(=O)CI JDNTWHVOXJZDSN-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000006263 metalation reaction Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920001657 poly(etheretherketoneketone) Polymers 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- QJZUKDFHGGYHMC-UHFFFAOYSA-N pyridine-3-carbaldehyde Chemical compound O=CC1=CC=CN=C1 QJZUKDFHGGYHMC-UHFFFAOYSA-N 0.000 description 1
- 238000011158 quantitative evaluation Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229910052645 tectosilicate Inorganic materials 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/18—Macromolecular compounds
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Definitions
- Functionalized fluorine-free main chain polymers such as sulfonated polyaryl ether ketones and polyether sulfones have been developed in the past by DuPont as an alternative to fluorinated cation exchangers such as Nafion®.
- Such polymers processed into membranes, are used in membrane processes, in particular in fuel cells.
- PEM fuel cells polymer electrolyte membrane fuel cells
- the former convert hydrogen and the latter methanol.
- Direct methanol fuel cells (DMFC) place higher demands on the membranes than on fuel cells that are operated exclusively with hydrogen.
- Ionically cross-linked membranes were developed by Kerres et. al. developed. These are acid-base polymer blends and polymer (blend) membranes.
- An advantage of the ionically crosslinked acid-base blend membranes is the greater flexibility of the ionic bonds and that these polymers / membranes do not dry out so easily at higher temperatures and consequently the membranes do not become brittle as quickly.
- the ionic bonds have the disadvantage that they start to open at temperatures above 60 ° C., which leads to a strong swelling up to the dissolution of the membrane.
- the polymer should have the best possible mechanical stability and improved swelling behavior.
- the swelling behavior based on the dimension (length, width, height), should increase at a temperature of 90 ° C. in deionized water by less than 90% compared to the control value at 30 ° C.
- Another object was to provide a polymer that can be processed into a membrane and used in fuel cells.
- the crosslinked polymer should be suitable for use in fuel cells above 80 ° C., in particular above 100 ° C.
- Membranes made from the polymer are said to be particularly suitable in direct methanol fuel cells.
- fluorine-free polymeric cation exchangers such as sulfonated polyaryl ether ketones and sulfonated polysulfones
- a polymeric fluorinated sulfonic acid e.g. Nafion® from DuPont
- the polymer according to the invention is a polymer with a proton-releasing group, such as sulfonic acid, phosphonic acid and or carboxylic acid, the acid strength of which has been increased in accordance with the invention in accordance with the task, covalent and / or ionic crosslinking is not mandatory.
- a proton-releasing group such as sulfonic acid, phosphonic acid and or carboxylic acid
- the uncrosslinked, covalently and / or possibly ionically crosslinked polymer in the present invention has recurring units of the general formula (1)
- the present invention relates to polymers having fluorine in the main chain, such as polyvinylidene difluoride (PVDF), poly (vinyl fluoride) (PVF) and polychlorotrifluorethylene and analogs, such as Kel-F® and Neoflon®.
- PVDF polyvinylidene difluoride
- PVF poly (vinyl fluoride)
- PVF polychlorotrifluorethylene
- Kel-F® and Neoflon® such as Kel-F® and Neoflon®.
- polymers according to the invention are accessible through one or more modification steps of the starting polymers of the general formula (1).
- Polymers of the general formula (1) are already known. These are polyarylenes, such as polyphenylene and polypyrene, aromatic polyvinyl compounds, such as polystyrene and polyvinylpyridine, polyphenylene vinylene, aromatic polyethers, such as polyphenylene oxide, aromatic thioethers, such as polyphenylene sulfide, polysulfones such as ⁇ Radel R and Ultrason®, and polyether ketones such as PEK, PEEK, PEKK and PEKEKK.
- polyarylenes such as polyphenylene and polypyrene
- aromatic polyvinyl compounds such as polystyrene and polyvinylpyridine
- polyphenylene vinylene aromatic polyethers, such as polyphenylene oxide, aromatic thioethers, such as polyphenylene sulfide, polysulfones such as ⁇ Radel R and
- polyporroles such as polybenzimidazole, polyanilines, polyazulenes, polycarbazoles, polyindophenines, polyvinylendifluoride (PVDF) and polychlorotrifluorethylenes and analogues, such as Kel-F® and Neoflon®.
- polyporroles such as polybenzimidazole, polyanilines, polyazulenes, polycarbazoles, polyindophenines, polyvinylendifluoride (PVDF) and polychlorotrifluorethylenes and analogues, such as Kel-F® and Neoflon®.
- PVDF polyvinylendifluoride
- Neoflon® such as Kel-F® and Neoflon®.
- radicals R 1 independently of one another have the general formula (888-1) or (888-2) ß ⁇ .
- M is independently hydrogen, a mono- or polyvalent cation, preferably Li + , Na + , K + , Rb + , Cs + , TiO 2+ , ZrO 2+ , Ti 4+ , Zr 4+ , Ca 2+ , Mg 2+ or an optionally alkylated ammonium ion and X is a halogen or an optionally alkylated amino group, and wherein R 2 , R 3 , R, R 5 independently of one another are hydrogen, (4A), (4B), (4C), (4D) , (4E), (4F), (4G), (4H), (41), (4J), (4K), (4L), (4M), (4N), (40), (4P), ( 4Q) and / or (4R) or a group having 1 to 40 carbon atoms, preferably a branched or unbranched alkyl, cycloalkyl or an optionally alkylated aryl or heteroaryl group, which can be fluorinated or partially fluorinated
- radical R optionally has bridges of the general formula (6A), (6B) and or (6C)
- Y is a group having 1 to 40 carbon atoms, preferably a branched or unbranched alkyl, cycloalkyl or optionally alkylated aryl group
- Z is hydroxyl, a group of the general formula (7)
- the doped plastic membranes have a lower volume resistance, preferably less than or equal to 100 Ohm x cm at 20 ° C.
- the doped plastic membranes have only a low permeability for hydrogen, oxygen and methanol.
- the doped plastic membrane is suitable for use in fuel cells above 80 ° C, in some cases above 100 ° C and in special cases also above 110 ° C.
- The. doped plastic membrane is suitable for use in fuel cells above 82 ° C, especially under normal pressure
- the doped plastic membrane can be produced on an industrial scale. occur both through the formation of covalent and via the formation of ionic bonds.
- the crosslinked polymer according to the invention is preferably doped with acid.
- doped polymers refer to those polymers which, owing to the presence of doping agents, have an increased proton conductivity in comparison with the undoped polymers.
- Dopants for the polymers according to the invention are acids.
- acids include all known Lewis and Bronsted acids, preferably inorganic Lewis and Bronsted acids. It is also possible to use polyacids, in particular isopolyacids and heterolpolyacids, and also mixtures of different acids.
- heteropolyacids refer to inorganic polyacids with at least two different central atoms, each consisting of weak, polybasic oxygen acids of a metal (preferably Cr, Mo, V, W) and a non-metal (preferably As, I, P, Se, Si, Te) arise as partially mixed anhydrides.
- a metal preferably Cr, Mo, V, W
- a non-metal preferably As, I, P, Se, Si, Te
- Doping agents which are particularly preferred according to the invention are sulfuric acid and
- Phosphoric acid A very particularly preferred dopant is phosphoric acid
- zirconium phosphate and titanium sulfate via methods known to the person skilled in the art are particularly preferred, and modified and unmodified layered and framework silicates are also preferred. Montmorillonite, which is added during membrane production, is particularly preferred in this modification method.
- the dopants are optionally fixed in the membrane by a calcination process and converted into the strongly Lewis acid form.
- the calcination of titanium sulfate and zirconium phosphate in the membrane is particularly preferred.
- the calcination is followed by a new and / or further doping.
- Phosphoric acid, sulfuric acid and the heteropolyacids mentioned above are particularly preferred as dopants. If necessary, the process can be repeated several times.
- the temperature range from 60 ° C. to just below the thermal decomposition temperature of the polymer to be doped is suitable as the calcining temperature.
- the temperature range from 100 ° C. to 300 ° C. is particularly preferred.
- the calcination fixes some dopants in the membrane for a technically applicable time.
- the crosslinked polymer according to the invention has recurring units of the general formula (1), in particular recurring units corresponding to the general formulas (IA), (1B), (IC), (ID), (1E), (IF), (1G), ( 1H), (II), (IT), (1K), (1L), (IM), (IN), (10), (1P), (IQ), (1R), (IS) and / or ( IT), on:
- the radicals R ⁇ are, independently of one another, the same or different 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 4,4'-biphenyl, a divalent radical of a heteroaromatic, a divalent radical of a Cjo aromatic, a divalent radical of a C 14 aromatics and / or a divalent pyrene radical.
- a C 10 aromatics is naphthalene, for a C 14 aromatics phenanthrene.
- the substitution pattern of the aromatic and / or heteroaromatic is arbitrary, in the case of phenylene, for example, R 6 can be ortho-, meta- and para-phenylene.
- radicals R ⁇ R 8 and R 9 denote single-, four- or three-bonded aromatic or heteroaromatic groups and the radicals U, which are the same within a repeating unit, stand for an oxygen atom, a sulfur atom or an amino group, which is a hydrogen atom, a Group having 1-20 carbon atoms, preferably a branched or unbranched alkyl or alkoxy group, or an aryl group as a further radical.
- polymers having recurring units of the general formula (1) belong to homopolymers and copolymers, for example random copolymers, such as Victrex ® 720 P and Astrel ®.
- Very particularly preferred polymers are polyaryl ethers, polyaryl thioethers, polysulfones, polyether ketones, poly pyrroles, polythiophenes, polyazoles, polyphenylenes, polyphenylene vinylenes, polyanilines, polyazulenes, polycarbazoles, polypyrenes, polyindiprienines and polyvinylpyridines, in particular:
- polyaniline polyazulene:
- Cross-linked polymers with recurring units of the general formula (1A-1), (1B-1), (1C-1), (II-1), (1G-1), (1E-1), (1E-1), ( 1H-1), (11-1), (1F-1), (Ul), (1K-1), (1L-1), (1M-1) and / or (1N : 1).
- n denotes the number of repeating units along a macromolecule chain of the crosslinked polymer.
- This number of repeating units of the general formula (1) along a macromolecule chain of the crosslinked polymer is preferably an integer greater than or equal to 10, in particular greater than or equal to 100.
- the number of repeating units of the general formula (1A), (1B) (1Q , (ID), (1E), (IF), (IG), (1H), (II), (1J), (1K), (1L), (IM), (IN), (lO) > ( 1P), (IQ), (1R), (IS) and / or (IT) along a macromolecule chain of the crosslinked polymer an integer greater than or equal to 10, in particular greater than or equal to 100.
- the number average molecular weight of the macromolecule chain is greater than 25,000 g / mol, advantageously greater than 50,000 g / mol, in particular greater than 100,000 g / mol.
- the crosslinked polymer according to the invention can also have different repeating units along a markromolecule chain.
- 'it has, along a Makromolekiilkette only identical recurring units of the general formula (1A), (1B), (IC), (ID), (1E), (IF), (IG), (1H), (II) , (13), (1K), (1L), (IM), (IN), (10), (1P), (IQ), (1R), (IS) and / or (IT).
- the radical R has at least partially substituents of the general formula (4A), (4B), (4C), (4D), (4E), (4F), (4G), (4H), (41) , (43), (4K), (4L), (4M), (4N), (40), (4P), (4Q) and / or (4R) preferably of the general formula (4A), (4B), (4C), (4D), (4J), (4K), (4L) and / or (4M), suitably of the general formula (4A), (4B), (4C), (4J), (4K) and / or (4L), in particular of the general formula (4J) and / or (4K).
- O ox the general formula (4A), (4B), (4C), (4D), (4E), (4F), (4G), (4H), (41) , (43), (4K), (4L), (4M), (4N), (40), (4P), (4Q) and / or (4R) preferably of the general formula (4A), (4B), (4C), (4D), (4J), (4K), (4L) and / or (4M), suit
- the R 1 radicals independently denote a bond or a 1
- M stands for hydrogen, a mono- or polyvalent metal cation, preferably Li + , Na + , K + , Rb + , Cs + , Zr 4+ , Ti 4+ , Zr0 2+ or an optionally alkylated ammonium ion, advantageously for hydrogen or Li + , especially for hydrogen.
- X is a halogen or an optionally alkylated amino group. and / or the radical R is USflS ⁇ partially a group of the general formula (5G) and / or (5Mlor preferably Hfc [Fa ⁇
- radicals R 2 , R 3 , R 4 and R 5 independently of one another denote a group having 1 to 40 carbon atoms, preferably a branched or unbranched alkyl, cycloalkyl or an optionally alkylated aryl group, at least two of the radicals R 2 , R 3 and R 4 can be closed to form an optionally aromatic ring.
- R at least partially has substituents of the general formula (5A-1) and / or (5A-2).
- the radicals R 10 here denotes an optionally alkylated aryl group which has at least one optionally alkylated amino group, or an optionally alkylated heteroaromatic compound which either has at least one optionally alkylated amino group or has at least one nitrogen atom in the heteroaromatic core.
- R n is hydrogen, an alkyl, a cycl ⁇ alkyl, an aryl, or a heteroaryl group or a radical R 10 with the abovementioned meaning, where R 10 and R 11 can be identical or different.
- Substituents of the formula (5A-1) in which R 10 is an optionally alkylated aniline residue or pyridine residue, preferably an alkylated aniline residue, are very particularly preferred according to the invention.
- substituents of the formula (5A-2) in which R 10 and R n are optionally alkylated aniline residues or pyridine residues, preferably alkylated aniline residues are also particularly preferred.
- the radical R z-ssa ⁇ t partially bridges the general formula (6) on ⁇ / € ⁇ & Ci combine the at least two radicals R, where Y is a group having 1 to 40 carbon atoms, preferably a branched or unbranched alkyl, cycloalkyl or optionally alkylated aryl group, advantageously a linear or branched alkyl group having 1 to 6 carbon atoms.
- vH polymer according to the invention is preferably doped with acid.
- doped polymers refer to those polymers which, owing to the presence of doping agents, have an increased proton conductivity in comparison with the undoped polymers.
- Dopants for the polymers according to the invention are acids.
- acids include all known Lewis and Br ⁇ nsted acids, preferably inorganic Lewis and Bransted acids. It is also possible to use polyacids, in particular isopolyacids and heteropolyacids, and mixtures of different acids.
- heteropolyacids denote inorganic polyacids with at least two different central atoms, each of which consists of weak, polybasic oxygen acids of a metal (preferably . Cr, Mo, V, W) and a non-metal (preferably As, I, P, Se , Si, Te) arise as partially mixed anhydrides. They include, among others, 12-molybdate phosphoric acid and 12-tungsten phosphoric acid.
- Dopants which are particularly preferred according to the invention are sulfuric acid and phosphoric acid.
- a very particularly preferred dopant is phosphoric acid (H 3 PO 4 ).
- the conductivity of the plastic membrane according to the invention can be influenced via the degree of doping.
- the conductivity increases with increasing dopant concentration until a maximum value is reached.
- the degree of doping is stated as mole of acid per mole of repeating unit of the polymer. In the context of the present invention, a degree of doping between 3 and 15, in particular between 6 and 12, is preferred.
- Processes for producing doped plastic membranes are known.
- they are obtained by a polymer according to the invention for a suitable time, preferably 0.5-96 hours, particularly preferably 1-72 hours, at temperatures between room temperature and 100 ° C. and, if appropriate, increased pressure with concentrated acid , preferably wetted with highly concentrated phosphoric acid.
- the spectrum of properties of the crosslinked polymer according to the invention can be changed by varying its ion exchange capacity.
- the ion exchange capacity is preferably between 0.5 meq / g and 1.9 meq / g, in each case based on the total mass of the polymer.
- the polymer according to the invention has a low volume resistivity, preferably of at most 100 ⁇ cm, expediently of at most 50 ⁇ cm, in particular of at most 20 ⁇ cm, in each case at 25 ° C.
- the properties of the plastic membrane according to the invention can be controlled in part by their overall thickness.
- the total thickness of the doped plastic membrane according to the invention is preferably between 5 and 100 ⁇ m, advantageously between 10 and 90 ⁇ m, in particular between 20 and 80 ⁇ m.
- the present invention swells at a temperature of 90 ° C. in deionized water by less than 100%.
- L is a leaving group, preferably an F, Cl, Br, I, tosylate, and n is an integer greater than or equal to 2, preferably 2.
- Each reactant polymer preferably has recurring units of the general formula (1). Furthermore, it is expediently not covalently crosslinked.
- the reaction with the compound (7) can also be used to form Lead bridges of the general formula (8) and / or (9).
- a polymer mixture is formed 1) at least one starting polymer having functional groups a),
- a polymer mixture is made from
- the starting polymer (s) to be used according to the invention can fundamentally have different repeating units of the general formula (1). However, they preferably have only the same recurring units of the general formula (1A), (IB), (IC), (ID), (1E), (IF), (IG), (1H), (II), (U), (1K), ( 1L), (IM), (IN), (10), (1P), (IQ), (1R), (IS) and / or (IT).
- the number of repeating units of the general formula (1A), (IB), (IC), (ID), (1E), (IF), (IG), (1H), (II), (1J), (1K ), (1L), (IM), (IN), (10), (1P), (IQ), (1R), (IS) and / or (IT) is preferably an integer greater than or equal to 10, preferably at least 100 recurring units.
- the number average of the molecular weight of the starting polymer or polymers is greater than 25,000 g / mol, advantageously greater than 50,000 g / mol, in particular greater than 100,000 g / mol.
- the synthesis of the starting polymer having functional groups of the general formula a), b) and / or d) is already known. It can be carried out, for example, by reacting a polymer of the general formula (1) with n-butyllithium in a dried aprotic solvent, preferably tetrahydrofuran (THF), under an inert gas atmosphere, preferably argon, and in this way Iithiating.
- a polymer of the general formula (1) with n-butyllithium in a dried aprotic solvent, preferably tetrahydrofuran (THF), under an inert gas atmosphere, preferably argon, and in this way Iithiating.
- THF tetrahydrofuran
- the lithiated polymer is known in a manner known per se with suitable functionalizing agents, preferably with alkylating agents of the general formula
- Subst. Is the substituent to be introduced, with ketones and / or aldehydes, which are converted to the corresponding alcoholates, and / or with carboxylic acid residues and / or carboxylic acid halides, which are converted to the corresponding ketones.
- the introduction of sulfonate groups can also be achieved by the reaction of the lithiated polymer with SO 3 , the introduction of Sulfate groups also occur through the reaction of the lithiated polymer with SO 2 .
- the degree of functionalization of the precursor polymers is preferably in the range '• from 0.1 to 3 groups per recurring unit, preferably from 0.2 to 2.2 groups per repeating unit.
- Starting polymers with 0.2 to 0.8 groups a), preferably sulfonate groups, per repeat unit are particularly preferred.
- reactant polymers with 0.8 to 2.2 groups b) per repeat unit have proven particularly useful.
- particularly advantageous results are achieved with starting polymers which have 0.8 to 1.3 groups d) per repeating unit.
- a dipolar aprotic solvent preferably in N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide or sulfolane and react with the halogen compound with stirring.
- the polymer solution is spread as a film on a base, preferably on a glass plate, a fabric or a nonwoven, and b) the solvent is evaporated, if appropriate at elevated temperature above 25 ° C. and / or reduced pressure below 1000 mbar, and in this way receives a polymer membrane.
- the properties of the polymer according to the invention can also be improved by treating the polymer a) with an acid in a first step and b) with deionized water in a further step. wherein the polymer is optionally treated with an alkali before the first step.
- Gas separation, pervaporation, perstraction, reverse osmosis, nanofiltration, electrodialysis and diffusion dialysis can be used in a particularly advantageous manner.
- the specific volume resistance R sp of the membranes was determined by means of impedance spectroscopy (IM6 impedance measuring device, Zahner electrics) in a Plexiglas unit with gold-coated copper electrodes (electrode area 0.25 cm 2 ). According to the invention, the impedance at which the phase angle between current and voltage was 0 denotes the specific volume resistance.
- the specific measuring conditions were as follows: 0.5 N HC1 was used, the membrane to be measured was packed between two Nafion 117 membranes, the multi-layer arrangement Nafion 117 / membrane / Nafion 117 membrane was pressed between the two electrodes.
- the interface resistances between the membrane and the electrode were eliminated by first measuring the multilayer arrangement of all 3 membranes and then the two Nafion 117 membranes alone. The impedance of the Nafion membranes was subtracted from the impedance of all 3 membranes. In the context of the present invention, the specific volume resistances at 25 ° C were determined.
- Lithium salt of sulfonated polyether ketone PEK Lithium salt of sulfonated polyether ketone PEK
- PSU Udel ® was first dissolved in dry THF and cooled to -75 ° C under argon. Traces of water in the reaction mixture were removed with 2.5 M n-butyllithium (n-BuLi). The dissolved polymer was then lithiated with 10 M n-BuLi. The reaction was allowed to react for one hour and then pyridine-3-aldehyde or 4,4'-bis (N, N-diethylamino) benzophenone was added. The reaction temperature was then raised to -20 ° C for one hour. For the reaction with SO 2 , the mixture was then cooled again to -75 ° C. and the SO 2 was introduced.
- n-BuLi n-butyllithium
- the polymers PEK-SO 3 Li, PSU-P3-SO 2 Li, PSU-EBD-SO 2 Li, PSU-DPK and / or PSUSO2L1 were dissolved in NMP according to Table 2 and filtered. The polymer solution was then degassed in vacuo and then 1,4-diiodobutane was added. After that, it was poured onto a glass plate and knife out. The glass plate was then in an oven at 60 ° C for one hour
- the polymers according to the invention and the membranes produced therefrom are suitable for producing membrane electrode assemblies. If the sulfinic acid group does not react completely, the electrodes applied to the membrane, e.g. in the form of a paste, ink or via powder coating processes, with reactive groups covalently crosslinked with the membrane via alkylation crosslinkers. Both the membrane and the applied electrodes contain sulfic acid groups which have not yet reacted before the reaction, the sulfinates being particularly preferred.
- the electrode paste which contains both precursors of polymeric cation exchangers and polymeric sulfinates, di- or oligohalogen crosslinkers, which may contain functional groups from ⁇ ) to ( ⁇ R)
- the polymeric sulfinates of the electrode paste react with the free polymeric sulfinates of the membrane .
- the resulting covalent crosslinking solves an existing problem in the insufficient connection of the electrodes to the membrane.
- polymers according to the invention can be used in other membrane processes, preferably in gas separation, pervaporation, reverse osmosis, nanofiltration, electrodialysis, perstraction and diffusion dialysis.
- the new polymers can be made by various methods.
- polymeric sulfinic acids are, inter alia, those described by Guiver et.al. and also by Kerres et.al. described procedures accessible.
- the polymeric sulfinic acid salt reacts with elimination of Li halide with a mono- or oligohalogen compound with sulfur alkylation or sulfur arylation, which also carry at least one further functional group from ⁇ A.) to (jfirj.
- the halogen compound preferably contains the halogens fluorine, chlorine, bromine and / or iodine as a removable anion, iodide can be split off at room temperature (25 ° C.), bromine at temperatures above 30 ° C.
- Sulfinated PSU-SO-Li polysulfone is prepared as described under a-3).
- the IEC of the protonated form is 1.95 meq SO 2 Li / g. It is dissolved in NMP and an equivalent amount of the sodium salt of bromomethanesulfonate is added. After heating, the following compound is obtained dissolved in NMP PSU-SO 2 -CH 2 -SO 3 " Na + with an IEC of 1.95 meq SO 3 Li / g.
- bromine-efansulfonate (sodium salt) is reacted with PSU-SO 2 -Li.
- the reaction proceeds smoothly and after evaporation of the solvent and recrystallization, the pure compound PSU-SO 2 -CH 2 CH 2 -SO 3 " Na + is obtained .
- the solvent is evaporated in a drying cabinet at a temperature of approx. 80 ° C. until the solution has a concentration of approx. 10-15% by weight. Has.
- the mixture is then left to cool to room temperature (25 ° C.) and an equivalent amount of diiodobutane is added. The amount of diiodobutane is calculated on the crosslinking of the free sulfinate groups.
- the solution is then doctored to a membrane on a glass plate and the remaining solvent NMP is evaporated in a drying cabinet. A covalently crosslinked membrane is obtained whose proton-releasing group has a significantly greater acid strength than the control.
- the membrane is converted into the acid form by an aftertreatment in aqueous mineral acid and water.
- the salts formed are removed.
- the following graphic explains an embodiment of the polymers according to the invention.
- polymers are provided which have one of the following groupings:
- R 1 is defined as in the description of R 1 for the ⁇ Substituents A),), C), D),
- ⁇ ⁇ DD is one of your duusi ⁇ u ineiLaus [? F) 3 y D (SL), M),, g), # > ), #Q) or # 1).
- polymers are sulfinic acids.
- the polymeric sulfinic acid is according to the general formula
- Polysulfone is metallized with butyllithium at -60 ° C according to the prior art, described for example by Guiver et al. Then it is mixed with the equivalent amount of methyl iodide. The mixture is allowed to warm to -10 ° C. so that the polysulfone is completely methylated. The methylated polysulfone is cooled again to -60 ° C. and the equivalent amount of butyllithium is added to the metalation. Now you add the equivalent amount of one molecule of SO 2 CI 2 each at least more than a simply methylated methyl group and then you inject iodine dissolved in THF. The procedure is described in detail in the published patent application DE 3636854 AI. The resulting polymer is fluorinated via the well-known Finkelstein reaction via the halogen exchange and freed from the solvent. The polymer is then hydrolyzed in water, acid and / or alkali and the sulfonic acid is released.
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- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
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Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10158006 | 2001-11-22 | ||
DE10158006 | 2001-11-22 | ||
DE10208679 | 2002-02-28 | ||
DE10208679 | 2002-02-28 | ||
PCT/DE2002/004414 WO2003060012A1 (de) | 2001-11-22 | 2002-11-22 | Funktionalisierte hauptkettenpolymere |
Publications (1)
Publication Number | Publication Date |
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EP1481027A1 true EP1481027A1 (de) | 2004-12-01 |
Family
ID=26010656
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP02796506A Withdrawn EP1481027A1 (de) | 2001-11-22 | 2002-11-22 | Funktionalisierte hauptkettenpolymere |
Country Status (6)
Country | Link |
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US (4) | US8710175B2 (pl) |
EP (1) | EP1481027A1 (pl) |
JP (4) | JP4237631B2 (pl) |
AU (2) | AU2002363823A1 (pl) |
DE (2) | DE10296292D2 (pl) |
WO (2) | WO2003060011A2 (pl) |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
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AU2002363823A1 (en) * | 2001-11-22 | 2003-07-30 | Haring, Rima | Modified covalently cross-linked polymers |
JP4827044B2 (ja) * | 2002-02-28 | 2011-11-30 | ウニヴェルズィテート シュトゥットガルト | スルフィナート基を含むオリゴマー及びポリマー、並びにその製造方法 |
KR100542228B1 (ko) * | 2004-06-30 | 2006-01-10 | 삼성에스디아이 주식회사 | 연료전지용 고분자 막/전극 접합체 및 이를 포함하는연료전지 |
US20100063168A1 (en) * | 2004-08-20 | 2010-03-11 | Haring Thomas | Ionomers with ionogenic groups in the sidechain |
JP2007012375A (ja) * | 2005-06-29 | 2007-01-18 | Toyota Motor Corp | 燃料電池、燃料電池用電極触媒層の製造方法、及び燃料電池の運転方法 |
EP1906473B1 (en) | 2005-07-15 | 2014-02-12 | JSR Corporation | Electrode paste for use in solid polymer fuel cell |
EP2527156A1 (en) * | 2011-05-25 | 2012-11-28 | RLS Merilna Tehnika D.O.O. | Apparatus and method for writing a pattern in a substrate |
GB2552986B (en) | 2016-08-17 | 2020-09-16 | Nifco Inc | A device for separating oil from a blow-by gas |
CN110194838B (zh) * | 2019-05-28 | 2021-07-06 | 上海大学 | 1-芘基官能化聚砜材料及其制备方法 |
US11505671B1 (en) | 2021-06-16 | 2022-11-22 | Avanpore LLC | Preparation of mesoporous poly (aryl ether ketone) articles and use thereof |
US11491464B1 (en) | 2021-06-24 | 2022-11-08 | Avanpore LLC | Mesoporous poly (aryl ether ketone) hollow fiber membranes and use thereof in mass transfer processes |
US11673099B2 (en) | 2021-07-14 | 2023-06-13 | Avanpore LLC | Composite poly (aryl ether ketone) membranes, their preparation and use thereof |
US11511238B1 (en) | 2021-07-20 | 2022-11-29 | Avanpore LLC | Composite covalent organic framework membranes |
DE102022121273A1 (de) * | 2022-08-23 | 2024-02-29 | Acs Coating Systems Gmbh | Pulvermischung für Teflon freie Antihaftbeschichtung |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
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US4713426A (en) * | 1984-09-28 | 1987-12-15 | Amoco Corporation | Blends of a biphenyl containing poly(aryl ether sulfone) and a poly(aryl ether ketone) |
JPS62148525A (ja) * | 1985-12-24 | 1987-07-02 | Asahi Chem Ind Co Ltd | 変性ポリフエニレンエ−テル樹脂 |
IL89213A0 (en) * | 1988-02-08 | 1989-09-10 | Ici Plc | Substituted aromatic polymers |
US5140064A (en) * | 1988-03-10 | 1992-08-18 | Mitsubishi Rayon Co., Ltd. | Thermoplastic resin composition |
JPH0574467A (ja) * | 1991-09-12 | 1993-03-26 | Showa Denko Kk | 高分子固体電解質 |
EP0574791B1 (de) * | 1992-06-13 | 1999-12-22 | Aventis Research & Technologies GmbH & Co. KG | Polymerelektrolyt-Membran und Verfahren zu ihrer Herstellung |
GB9324731D0 (en) * | 1993-12-02 | 1994-01-19 | North West Water Group Plc | Aromatic polysulphones |
JPH09245801A (ja) * | 1996-03-11 | 1997-09-19 | Tanaka Kikinzoku Kogyo Kk | 高分子固体電解質型燃料電池用電極及びその製造方法 |
DE19622337C1 (de) * | 1996-06-04 | 1998-03-12 | Dlr Deutsche Forschungsanstalt | Vernetzung von modifizierten Engineering Thermoplasten |
DE19632285A1 (de) * | 1996-08-09 | 1998-02-19 | Hoechst Ag | Protonenleiter mit einer Temperaturbeständigkeit in einem weiten Bereich und guten Protonenleitfähigkeiten |
JP4326179B2 (ja) * | 1999-08-27 | 2009-09-02 | パナソニック株式会社 | 高分子電解質型燃料電池 |
KR100437293B1 (ko) * | 1999-09-21 | 2004-06-25 | 마쯔시다덴기산교 가부시키가이샤 | 고분자 전해질형 연료전지 및 그 제조방법 |
DE10024576A1 (de) * | 2000-05-19 | 2001-11-22 | Univ Stuttgart | Kovalent und ionisch vernetzte Polymere und Polymermembranen |
AU2002363823A1 (en) * | 2001-11-22 | 2003-07-30 | Haring, Rima | Modified covalently cross-linked polymers |
-
2002
- 2002-11-21 AU AU2002363823A patent/AU2002363823A1/en not_active Abandoned
- 2002-11-21 DE DE10296292T patent/DE10296292D2/de not_active Ceased
- 2002-11-21 WO PCT/DE2002/004344 patent/WO2003060011A2/de not_active Application Discontinuation
- 2002-11-22 EP EP02796506A patent/EP1481027A1/de not_active Withdrawn
- 2002-11-22 AU AU2002361930A patent/AU2002361930A1/en not_active Abandoned
- 2002-11-22 WO PCT/DE2002/004414 patent/WO2003060012A1/de active Application Filing
- 2002-11-22 JP JP2003560104A patent/JP4237631B2/ja not_active Expired - Fee Related
- 2002-11-22 DE DE10296279T patent/DE10296279D2/de not_active Expired - Lifetime
-
2008
- 2008-10-01 JP JP2008256892A patent/JP2009035743A/ja active Pending
-
2011
- 2011-03-14 US US13/047,655 patent/US8710175B2/en not_active Expired - Fee Related
-
2012
- 2012-04-20 JP JP2012097132A patent/JP5715085B2/ja not_active Expired - Fee Related
-
2014
- 2014-02-10 US US14/176,815 patent/US20140155502A1/en not_active Abandoned
- 2014-11-20 JP JP2014235744A patent/JP2015057496A/ja active Pending
-
2016
- 2016-08-15 US US15/237,537 patent/US20170095809A1/en not_active Abandoned
-
2017
- 2017-05-30 US US15/608,990 patent/US10328425B2/en not_active Expired - Fee Related
Non-Patent Citations (2)
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None * |
See also references of WO03060012A1 * |
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US20170095809A1 (en) | 2017-04-06 |
US20140155502A1 (en) | 2014-06-05 |
AU2002363823A8 (en) | 2003-07-30 |
AU2002363823A1 (en) | 2003-07-30 |
US10328425B2 (en) | 2019-06-25 |
JP4237631B2 (ja) | 2009-03-11 |
US8710175B2 (en) | 2014-04-29 |
DE10296292D2 (de) | 2004-12-23 |
WO2003060012A1 (de) | 2003-07-24 |
JP2009035743A (ja) | 2009-02-19 |
JP2005530860A (ja) | 2005-10-13 |
WO2003060011A3 (de) | 2003-11-13 |
AU2002361930A1 (en) | 2003-07-30 |
US20170266652A1 (en) | 2017-09-21 |
JP2012162732A (ja) | 2012-08-30 |
WO2003060011A2 (de) | 2003-07-24 |
DE10296279D2 (de) | 2004-12-23 |
US20120004330A1 (en) | 2012-01-05 |
JP2015057496A (ja) | 2015-03-26 |
JP5715085B2 (ja) | 2015-05-07 |
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