EP3478750A1 - Cross-linked high stable anion exchange blend membranes with polyethyleneglycols as hydrophilic membrane phase - Google Patents
Cross-linked high stable anion exchange blend membranes with polyethyleneglycols as hydrophilic membrane phaseInfo
- Publication number
- EP3478750A1 EP3478750A1 EP17767982.6A EP17767982A EP3478750A1 EP 3478750 A1 EP3478750 A1 EP 3478750A1 EP 17767982 A EP17767982 A EP 17767982A EP 3478750 A1 EP3478750 A1 EP 3478750A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polymer
- groups
- halomethylated
- membrane
- room temperature
- 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.)
- Pending
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 131
- 239000000203 mixture Substances 0.000 title claims abstract description 50
- 229920001223 polyethylene glycol Polymers 0.000 title claims abstract description 40
- 238000005349 anion exchange Methods 0.000 title claims abstract description 27
- 229940068917 polyethylene glycols Drugs 0.000 title 1
- 229920000642 polymer Polymers 0.000 claims abstract description 96
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 18
- 239000011159 matrix material Substances 0.000 claims abstract description 18
- 125000004970 halomethyl group Chemical group 0.000 claims abstract description 15
- 150000001768 cations Chemical class 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000446 fuel Substances 0.000 claims abstract description 10
- 150000002118 epoxides Chemical class 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- DOUHZFSGSXMPIE-UHFFFAOYSA-N hydroxidooxidosulfur(.) Chemical compound [O]SO DOUHZFSGSXMPIE-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 8
- 238000000909 electrodialysis Methods 0.000 claims abstract description 5
- 150000002460 imidazoles Chemical class 0.000 claims abstract description 5
- 238000000502 dialysis Methods 0.000 claims abstract description 4
- 238000009792 diffusion process Methods 0.000 claims abstract description 4
- 230000002378 acidificating effect Effects 0.000 claims abstract 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 27
- 239000003011 anion exchange membrane Substances 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000011780 sodium chloride Substances 0.000 claims description 22
- 125000003118 aryl group Chemical group 0.000 claims description 21
- 229920002480 polybenzimidazole Polymers 0.000 claims description 15
- 239000004693 Polybenzimidazole Substances 0.000 claims description 14
- 239000000010 aprotic solvent Substances 0.000 claims description 14
- 229920006393 polyether sulfone Polymers 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 125000000524 functional group Chemical group 0.000 claims description 10
- 238000000265 homogenisation Methods 0.000 claims description 10
- 229920000570 polyether Polymers 0.000 claims description 10
- 238000005956 quaternization reaction Methods 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 9
- 229920006254 polymer film Polymers 0.000 claims description 9
- 150000003512 tertiary amines Chemical class 0.000 claims description 9
- -1 1H-imidazole 1H-pyrazole 1, 2-dimethyl-4,5-diphenyl-1H-imidazoles Chemical class 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 150000003217 pyrazoles Chemical class 0.000 claims description 8
- 239000004793 Polystyrene Substances 0.000 claims description 7
- 229920002223 polystyrene Polymers 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229920002492 poly(sulfone) Polymers 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- 229960004592 isopropanol Drugs 0.000 claims description 4
- SZZYAOCSMNDGPI-UHFFFAOYSA-N methylsulfinylmethane;thiolane 1,1-dioxide Chemical compound CS(C)=O.O=S1(=O)CCCC1 SZZYAOCSMNDGPI-UHFFFAOYSA-N 0.000 claims description 4
- 229920006255 plastic film Polymers 0.000 claims description 4
- 239000002985 plastic film Substances 0.000 claims description 4
- 238000005341 cation exchange Methods 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000005267 main chain polymer Substances 0.000 claims description 3
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 230000000712 assembly Effects 0.000 claims description 2
- 238000000429 assembly Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229920002959 polymer blend Polymers 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 2
- 150000001556 benzimidazoles Chemical class 0.000 claims 2
- 150000002170 ethers Chemical class 0.000 claims 2
- 229920001470 polyketone Polymers 0.000 claims 2
- BWLRYJKJWCDIDR-UHFFFAOYSA-N 1,4-diazabicyclo[2.2.2]octane 1H-imidazole Chemical compound C1=CNC=N1.C1CN2CCN1CC2 BWLRYJKJWCDIDR-UHFFFAOYSA-N 0.000 claims 1
- LAXWTHPUJQUILB-UHFFFAOYSA-N 1h-benzimidazole;1h-imidazole Chemical compound C1=CNC=N1.C1=CC=C2NC=NC2=C1 LAXWTHPUJQUILB-UHFFFAOYSA-N 0.000 claims 1
- 239000004642 Polyimide Substances 0.000 claims 1
- 125000003700 epoxy group Chemical group 0.000 claims 1
- 229920002313 fluoropolymer Polymers 0.000 claims 1
- 238000001728 nano-filtration Methods 0.000 claims 1
- 230000007935 neutral effect Effects 0.000 claims 1
- 229920002490 poly(thioether-sulfone) polymer Polymers 0.000 claims 1
- 229920003251 poly(α-methylstyrene) Polymers 0.000 claims 1
- 229920002577 polybenzoxazole Polymers 0.000 claims 1
- 229920001601 polyetherimide Polymers 0.000 claims 1
- 229920001721 polyimide Polymers 0.000 claims 1
- 229920002620 polyvinyl fluoride Polymers 0.000 claims 1
- 238000001223 reverse osmosis Methods 0.000 claims 1
- 150000003568 thioethers Chemical class 0.000 claims 1
- 238000000108 ultra-filtration Methods 0.000 claims 1
- 238000004132 cross linking Methods 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 150000001450 anions Chemical class 0.000 abstract description 8
- 150000002500 ions Chemical class 0.000 abstract description 6
- 238000005804 alkylation reaction Methods 0.000 abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 3
- 108091006522 Anion exchangers Proteins 0.000 abstract 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical class C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 abstract 1
- 125000003785 benzimidazolyl group Chemical class N1=C(NC2=C1C=CC=C2)* 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 247
- 239000000243 solution Substances 0.000 description 52
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 18
- 239000004721 Polyphenylene oxide Substances 0.000 description 17
- 238000001757 thermogravimetry curve Methods 0.000 description 17
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 238000003860 storage Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000004695 Polyether sulfone Substances 0.000 description 11
- 238000006731 degradation reaction Methods 0.000 description 11
- 238000005342 ion exchange Methods 0.000 description 11
- GNCJRTJOPHONBZ-UHFFFAOYSA-N 4,4,5,5-tetramethyl-1h-imidazole Chemical compound CC1(C)NC=NC1(C)C GNCJRTJOPHONBZ-UHFFFAOYSA-N 0.000 description 10
- 238000000605 extraction Methods 0.000 description 10
- 238000010348 incorporation Methods 0.000 description 10
- 229920006380 polyphenylene oxide Polymers 0.000 description 10
- WLUJHMKCLOIRSK-UHFFFAOYSA-N 1,2,4,5-tetramethylimidazole Chemical compound CC=1N=C(C)N(C)C=1C WLUJHMKCLOIRSK-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000012512 characterization method Methods 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 7
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 239000004971 Cross linker Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- ROUYUBHVBIKMQO-UHFFFAOYSA-N 1,4-diiodobutane Chemical compound ICCCCI ROUYUBHVBIKMQO-UHFFFAOYSA-N 0.000 description 2
- SLBOQBILGNEPEB-UHFFFAOYSA-N 1-chloroprop-2-enylbenzene Chemical group C=CC(Cl)C1=CC=CC=C1 SLBOQBILGNEPEB-UHFFFAOYSA-N 0.000 description 2
- 238000010464 Blanc reaction Methods 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000006734 Wohl-Ziegler bromination reaction Methods 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical compound C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000004985 diamines Chemical group 0.000 description 2
- 239000012973 diazabicyclooctane Substances 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000002847 impedance measurement Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- VAOCPAMSLUNLGC-UHFFFAOYSA-N metronidazole Chemical compound CC1=NC=C([N+]([O-])=O)N1CCO VAOCPAMSLUNLGC-UHFFFAOYSA-N 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical group 0.000 description 2
- WKGDNXBDNLZSKC-UHFFFAOYSA-N oxido(phenyl)phosphanium Chemical compound O=[PH2]c1ccccc1 WKGDNXBDNLZSKC-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920003208 poly(ethylene sulfide) Polymers 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- ISNICOKBNZOJQG-UHFFFAOYSA-N 1,1,2,3,3-pentamethylguanidine Chemical compound CN=C(N(C)C)N(C)C ISNICOKBNZOJQG-UHFFFAOYSA-N 0.000 description 1
- BTSDBXHMQFVTNJ-UHFFFAOYSA-N 1,2-dimethyl-4,5-diphenylimidazole Chemical class CN1C(C)=NC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 BTSDBXHMQFVTNJ-UHFFFAOYSA-N 0.000 description 1
- DOFSYYJDRYGRAT-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine;ruthenium(2+) Chemical compound [Ru+2].N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 DOFSYYJDRYGRAT-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 229910002546 FeCo Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- QSRFYFHZPSGRQX-UHFFFAOYSA-N benzyl(tributyl)azanium Chemical compound CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 QSRFYFHZPSGRQX-UHFFFAOYSA-N 0.000 description 1
- VBQDSLGFSUGBBE-UHFFFAOYSA-N benzyl(triethyl)azanium Chemical compound CC[N+](CC)(CC)CC1=CC=CC=C1 VBQDSLGFSUGBBE-UHFFFAOYSA-N 0.000 description 1
- VNHUAJSDMAVHFQ-UHFFFAOYSA-N benzyl(tripentyl)azanium Chemical compound CCCCC[N+](CCCCC)(CCCCC)CC1=CC=CC=C1 VNHUAJSDMAVHFQ-UHFFFAOYSA-N 0.000 description 1
- BCCDCNCWUHICFM-UHFFFAOYSA-N benzyl(tripropyl)azanium Chemical compound CCC[N+](CCC)(CCC)CC1=CC=CC=C1 BCCDCNCWUHICFM-UHFFFAOYSA-N 0.000 description 1
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- ISNICOKBNZOJQG-UHFFFAOYSA-O guanidinium ion Chemical group C[NH+]=C(N(C)C)N(C)C ISNICOKBNZOJQG-UHFFFAOYSA-O 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 231100001223 noncarcinogenic Toxicity 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000005208 trialkylammonium group Chemical group 0.000 description 1
- JQKHNBQZGUKYPX-UHFFFAOYSA-N tris(2,4,6-trimethoxyphenyl)phosphane Chemical compound COC1=CC(OC)=CC(OC)=C1P(C=1C(=CC(OC)=CC=1OC)OC)C1=C(OC)C=C(OC)C=C1OC JQKHNBQZGUKYPX-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
-
- 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
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
- B01J41/13—Macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/28—Polymers of vinyl aromatic compounds
- B01D71/281—Polystyrene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/52—Polyethers
- B01D71/521—Aliphatic polyethers
- B01D71/5211—Polyethylene glycol or polyethyleneoxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/52—Polyethers
- B01D71/522—Aromatic polyethers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/52—Polyethers
- B01D71/522—Aromatic polyethers
- B01D71/5222—Polyetherketone, polyetheretherketone, or polyaryletherketone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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- 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
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
- B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
- C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/42—Ion-exchange membranes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2481/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2481/06—Polysulfones; Polyethersulfones
Definitions
- AEMs anion exchange membranes
- APEFCs alkaline polymer electrolyte fuel cells
- AEE alkaline polymer electrolyte electrolysis
- RFBs redox flow batteries
- RED Reverse electrodialysis
- MFCs microwave fuel cells
- DD diffusion dialysis
- a major advantage of using AEM in electrochemical conversion processes such as fuel cells or electrolysis is that when using AEMs for the electrocatalytic reactions at the electrodes no precious metal catalysts consisting of platinum group metals (PGM) are required, thus containing AEM Membrane electrode assemblies (MEAs) are significantly less expensive than cation exchange membrane (CEM) containing MEAs.
- PGM platinum group metals
- AEMs have the following major drawbacks compared to CEMs:
- Ion conductivity is significantly lower for most AEM types than for CEMs of comparable ion exchange capacity (IEC), in part because most of the AEMs have a hydrocarbon backbone that is significantly less hydrophobic than perfluorinated ones, for example Polymer backbone of perfluorinated membranes of the Nafion ® type, so that it comes in the AEM to a lower separation between ionic groups and polymer backbone, which leads to lower ionic conductivity because of the then lower local density of the anion exchange groups, especially for most AEM types the Festkationen merely attached to the polymer backbone via a CH 2 bridge [20].
- IEC ion exchange capacity
- AEM A monomer having aromatic groups
- polystyrene polystyrene
- polyphenylene ethers or other aromatic polyethers
- polyethersulfones polyether ketones o. ⁇ .
- the first step in the preparation of AEM is the synthesis of a polymer with halomethyl side groups.
- Halomethylation is achieved by (1) chloro- or bromomethylation with hydrogen, formaldehyde and a Lewis acid such as ZnCl 2 or AICI 3 (Blanc reaction [23,24]), or (2) bromination of the CH 3 side group of aromatic polymers with N-bromo-succinimide (NBS) by the well-Ziegler bromination reaction [25].
- the Blanc reaction is associated with the appearance of the highly carcinogenic by-product bis (chloromethyl) ether. For this reason, the Wohl-Ziegler reaction is now preferably used in the production of halomethylated aromatic polymers.
- Literature examples for the preparation of bromomethylated aromatic polymers by the Wohl-Ziegler reaction are the bromomethylation of polyphenylene oxide [26] or the bromomethylation of a methylated polyethersulfone [27].
- Phase-segregated AEMs with improved ionic conductivity are obtainable by the preparation of linear block copolymers from hydrophobic and ionic blocks [31] or by graft copolymers with an anion exchange group-containing grafting side chain [32] (example: grafting of vinylbenzyl chloride side chains onto e " irradiated ETFE, and quaternization of the chloromethylated side chains with trimethylamine [33]).
- a sterically hindered chemically stabilized cationic functional group is the tris (2,4,6-trimethoxyphenyl) phosphonium cation [40], which was attached to polyvinylbenzyl chloride graft chains after storage for 75 hours in IN NaOH at 60 ° C had no degradation.
- a positively charged bis (terpyridine) ruthenium (II) complex was attached to a norbornene polymer [41].
- the AEM thus prepared showed excellent stability in an alkaline environment: incorporation of the polymer in IN NaOH at room temperature showed no degradation even after half a year.
- AK ionically and covalently cross-linked AEM blends from bromomethylated PPO or a bromomethylated and partially fluorinated arylene main chain polymer and a partially fluorinated PBI (FePBI) as a mechanically and chemically stable matrix and a sulfonated polyethersulfone sPPSU added in excess [46].
- the halomethylated blend component was quaternized with N-methylmorpholine (NMM) to form the anion exchange group [47].
- AEMs were synthesized consisting of rigid / flexible semi-interpenetrating networks of triethylamine quaternized PPO and a polyethylene glycol network. It was found that this AEM has high ionic conductivity ( ⁇ 0 ⁇ - up to 80 mS / cm) and a high alkali stability (degradation of ionic conductivity between 25 and 30% within 30 days of storage in IM NaOH at 80 ° C) [52].
- polyethylene glycols were grafted onto chloromethylated SEBS polymers and the resulting copolymers were then quaternized with trimethylamine.
- the resulting AEMs showed very high mechanical and chemical stabilities in 2.5M KOH at 60 ° C (increasing the ionic conductivity during storage in the KOH from 20 to 24 mS / cm) and high ionic conductivities ( ⁇ 0 ⁇ - up to 52 mS / cm) to [53].
- anion-exchange blend membranes of the following blend components are present in anion-exchange blend membranes of the following blend components:
- x 0-12, for example chloromethylated polystyrene or bromomethylated polyphenylene oxide;
- sterically hindered tertiary nitrogen compounds are:
- halomethylated polymers 1, 2-dimethyl-4,5-diphenyl-1H-imidazoles
- Bromomethylated partially fluorinated aromatic polyether II a matrix polymer, for example, a basic polybenzimidazole;
- a matrix polymer for example, a basic polybenzimidazole;
- Examples of basic matrix polymers are:
- a sulfonated aryl polymer as an ionic macromolecular crosslinker (ionic crosslinking with the basic functional groups of the matrix polymer and with the anion exchange groups of the quaternized halomethylated polymer.
- sulfonated aryl polymers examples include sulfonation SFS001)
- sulfonated aromatic poly (phenylphosphine oxide) II optionally a sulfonated polymer as a covalent macromolecular crosslinker whose sulfinate groups undergo covalent crosslinking via the sulfinate-S-alkylation with the halomethyl groups of the halomethylated polymer.
- a covalent crosslinking reaction between a sulfonated aromatic poly (phenylphosphine oxide) II optionally a sulfonated polymer as a covalent macromolecular crosslinker whose sulfinate groups undergo covalent crosslinking via the sulfinate-S-alkylation with the halomethyl groups of the halomethylated polymer.
- the membrane properties such as conductivity and thermal and chemical stability, in particular stability in strongly alkaline solutions, such as aqueous potassium hydroxide solution or sodium hydroxide solution
- the sulfinate groups of the sulfinated polymer with epoxy or halomethyl end groups of the polyethylene glycol are capable of reaction, presumably under sulfinate S-alkylation of the sulfinate groups by the epoxide or halomethyl groups.
- the reaction of the sulfinate groups of the sulfinated polymer with the epoxide end groups of the polyethylene glycol are shown below:
- anion-exchange blend membranes AEBM
- polymeric blend components halomethylated polymer, matrix polymer (eg.
- Polybenzimidazole polyethylene glycol with epoxide or halomethyl end groups, optionally sulfonated polymer and / or sulfinated polymer) are together in a dipoiar-aprotic solvent or in a mixture of different dipoiar-aprotic solvents (examples: ⁇ , ⁇ -dimethylacetamide, N-methylpyrrolidinone, N-ethyl pyrrolidinone, dimethyl sulfoxide sulfolane).
- the polymer solutions are doctored or cast on a support (glass plate, metal plate, plastic film, etc.), and the solvent is evaporated in a circulating air dryer or a vacuum oven at temperatures between room temperature and 150 ° C.
- Polybenzimidazole polyethylene glycol with epoxide or halomethyl end groups, optionally sulfonated polymer and / or sulfinated polymer) are together in a dipoiar-aprotic solvent or in a mixture of different dipoiar-aprotic solvents (examples: ⁇ , ⁇ -dimethylacetamide, N-methylpyrrolidinone, N-ethyl pyrrolidinone, dimethyl sulfoxide sulfolane).
- the tertiary amine or the N-monoalkylated (benz) imidazole or N-monoalkylated pyrazole is added to the solution .
- the polymer solutions are doctored or cast on a support (glass plate, metal plate, plastic film, etc.), and the solvent is evaporated in a circulating air dryer or a vacuum oven at temperatures between room temperature and 150 ° C.
- Figure 1 shows the chloride conductivities of the membranes 2175 and 2176 in the temperature range between 30 and 90 ° C with a constant relative humidity of 90%.
- Figure 2 shows the chloride conductivity of the membrane 2176 before and after 10, 20 and 30 days of incorporation in IM KOH in a temperature range of 30 to 90 ° C and a relative humidity of 90%.
- Figure 3 shows the TGA curves of membranes 2175 and 2176 before and after 10 days treatment in IM KOH at 90 ° C
- Figure 4 shows the TGA curves of membrane 2176 before and after 10, 20 and 30 days treatment in IM KOH at 90 ° C
- Figure 5 shows the chloride conductivity of the membrane 2190A before and after 10 days storage in IM KOH in the temperature range 30-90 ° C at a relative humidity of 90%
- Figure 6 shows the TGA curves of membrane 2190A before and after 10 days of storage in IM KOH at 90 ° C
- Figure 7 shows the chloride conductivity of membrane 2215 before and after 10 days storage in IM KOH in the temperature range 30-90 ° C at a relative humidity of 90%
- Figure 8 shows the TGA curves of membrane 2215 before and after 10 days storage in IM KOH at 90 ° C
- Figure 9 shows the chloride conductivity of the membrane 2179B before and after 10 days storage in IM KOH in the temperature range 30-90 ° C at a relative humidity of 90%
- Figure 10 shows the chloride conductivity of membrane 2216 before and after 10 days storage in IM KOH in the temperature range 30-90 ° C at a relative humidity of 90%
- Figure 11 shows the chloride conductivity of the commercial anion exchange membrane Tokuyama A201 in the temperature range 30-80 ° C at a relative humidity of 90%
- membrane 2175 0.25 g of epoxide-terminated polyethylene glycol (molecular mass 500 daltons, ALDRICH product no. 475696) are added to this mixture after homogenization, in the case of membrane 2176 0.25 g of epoxide-terminated polyethylene glycol (Molecular mass 6000 daltons, ALDRICH product no. 731803).
- the polymer solutions are doctored on a glass plate. Thereafter, the solvent is evaporated in a convection oven at 130 ° C for a period of 2 hours. The polymer films are then removed under water and after-treated as follows: at 60 ° C for 24 hours in a 10% strength by weight solution of tetramethylimidazole in ethanol
- Membrane 2175 ion exchange capacity before / after KOH treatment * [meq OH ⁇ / g membrane]: 2.92 / 2.96
- Membrane 2176 ion exchange capacity before / after KOH treatment * [meq OH ⁇ / g membrane]:
- FIG. 2 shows the chloride conductivities of the membrane 2176 before and after 10, 20 and 30 days incorporation in IM KOH in the temperature range from 30 to 90 ° C.
- TGA curves of the 2176 were recorded before and after 10, 20 and 30 days of incorporation in KOH. These TGA curves are shown in Figure 4. From Figure 4, it can be seen that the TGA curves of all 4 samples are nearly congruent up to a temperature of about 430 ° C, from which one can conclude that the 2176 still shows no sign of significant degradation even after 30 days of incorporation into KOH which confirms the results of the conductivity tests.
- Application Example 2 AEM blend of PVBCI, PBIOO, a sulfonated polyethersulfone (SAC098, see description), tetramethylimidazole for quaternizing the PVBCI and an epoxide-terminated polyethylene glycol having a lower AEM content than in Application Example 1 but the same molar ratio between PBIOO and PEG -Diepoxid 6000 (Membrane MJK2190A)
- epoxide-terminated polyethylene glycol molecular mass 6000 daltons, ALDRICH product no. 731803
- the polymer solution is doctored onto a glass plate. Thereafter, the solvent is evaporated in a convection oven at 130 ° C for a period of 2 hours.
- the polymer film is then removed under water and after-treated as follows: at 60 ° C for 24 hours in a 10 wt% solution of tetramethylimidazole in ethanol
- Part of the membrane is placed in an aqueous IM KOH solution for a period of 10 days at a temperature of 90 ° C.
- the chloride conductivity was also determined in this membrane as a function of the temperature between 30 and 90 ° C at a relative humidity of 90%.
- the conductivity curves are shown in Figure 5.
- the conductivity of the 2190A membrane also increases during KOH treatment.
- TGA curves of the membrane were recorded before and after 10 days of KOH treatment.
- the TGA curves are shown in Figure 6. Even with this membrane, the TGA curves before and after 10 days of KOH treatment almost congruent, at least up to a temperature of about 350 ° C, what indicates that after 10 days of incorporation in IM KOH at 90 ° C, no significant degradation of the membranes has yet occurred.
- the solvent is evaporated in a convection oven at 140 ° C for a period of 2 hours.
- the polymer film is then removed under water and after-treated as follows: at 60 ° C for 24 hours in a 10 wt% solution of tetramethylimidazole in ethanol
- Part of the membrane is placed in an aqueous IM KOH solution for a period of 10 days at a temperature of 90 ° C *
- the chloride conductivity was also determined in this membrane as a function of the temperature between 30 and 90 ° C at a relative humidity of 90%.
- the conductivity curves are shown in Figure 7.
- the chloride conductivity after lOd storage in IM KOH at 90 ° C is higher than before.
- TGA curves of the membrane were recorded before and after 10 days of KOH treatment. The TGA curves are shown in Figure 8.
- the TGA curves before and after 10 days KOH treatment almost congruent, at least up to a temperature of about 350 ° C, indicating that after 10 days of incorporation in IM KOH at 90 ° C, no significant Degradation of the membranes has taken place.
- Comparative Example 1 AEM blend of PVBCI, PBIOO, a sulfonated polyethersulfone (SAC098, see description), tetramethylimidazole for quaternization of the PVBCI with the same calculated IEC as the membranes MJK2175 and MJK2176, but without PEG diglycidyl ether (membrane 2179B)
- the polymer solutions are doctored on a glass plate. Thereafter, the solvent is evaporated in a convection oven at 140 ° C for a period of 2 hours.
- the polymer films are then dissolved in water and after-treated as follows: at 60 ° C for 24 hours in a 10 wt% solution of tetramethylimidazole in ethanol
- Parts of the membranes are placed in an aqueous IM KOH solution for a period of 10 days at a temperature of 90 ° C *
- Water uptake is significantly lower than at 2175 and 2176. This can be explained by the lower hydrophilicity of the control membrane.
- the impedance of the 2179B was higher in conductivity measurement at room temperature and in 0.5N NaCl as at 2175 and 2176 after the KOH treatment, the impedance of the 2179B again became function of the temperature at a relative humidity of 90 % measured.
- the conductivity curve of the 2179B under these conditions is shown in Figure 9.
- the chloride conductivity is much lower than that of the 2175 and 2176 containing a PEG phase, and the impedance after the KOH treatment is significantly lower than before.
- the solvent is evaporated in a convection oven at 140 ° C for a period of 2 hours.
- the polymer film is then removed under water and after-treated as follows: at 60 ° C for 24 hours in a 10 wt% solution of tetramethylimidazole in ethanol
- Portions of the membranes are placed in an aqueous IM KOH solution for a period of 10 days at a temperature of 90 ° C
- the cr conductivity at room temperature in 0.5N NaCl is significantly lower than in the case of the membrane 2215 according to the invention. This shows the positive influence that the addition of a hydrophilic PEG phase has to the membrane.
- the water uptake is significantly lower than at 2215. This can be explained by the lower hydrophilicity of the control membrane. Since the Cl " conductivity of the 2216 was higher at the room temperature and 0.5N NaCl than at 2215 after the KOH treatment, the impedance of the 2215 again became 90% relative to the temperature at a relative humidity of 90%. The conductivity curve of the 2215 under these conditions is shown in Figure 10.
- Comparative Example 3 Commercial anion exchange membrane A201 (development code A006) of the manufacturer Tokuyama
- This membrane is company secret.
- the anion exchange group of this membrane is the trimethylammonium group. But it is obviously a cross-linked membrane because the extraction of the membrane gave a gel content of 95%.
- this membrane is company secret. But it is obviously a cross-linked membrane, as the extraction of the membrane gave a gel content of 93.3%.
- the chloride conductivity of this membrane is substantially lower than that of most of the membranes of this invention listed as examples, which u. A. is also because this membrane is fabric reinforced.
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Abstract
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DE102016007815.4A DE102016007815A1 (en) | 2016-06-22 | 2016-06-22 | Crosslinked highly stable anion exchange blend membranes with polyethylene glycols as the hydrophilic membrane phase |
PCT/DE2017/000179 WO2017220065A1 (en) | 2016-06-22 | 2017-06-22 | Cross-linked high stable anion exchange blend membranes with polyethyleneglycols as hydrophilic membrane phase |
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DE102016007815A1 (en) * | 2016-06-22 | 2017-12-28 | Universität Stuttgart | Crosslinked highly stable anion exchange blend membranes with polyethylene glycols as the hydrophilic membrane phase |
CN109316979B (en) * | 2018-11-02 | 2021-04-16 | 绿邦膜分离技术(江苏)有限公司 | Continuous preparation method of high-compactness polystyrene cation exchange membrane |
CN109701400A (en) * | 2019-03-11 | 2019-05-03 | 福州大学 | A kind of preparation method of the porous anion exchange membrane based on polyether sulfone |
CN110280149A (en) * | 2019-07-02 | 2019-09-27 | 中国科学院宁波材料技术与工程研究所 | Super hydrophilic polymer microporous film, preparation method and application |
LT3770201T (en) * | 2019-07-22 | 2023-08-25 | Evonik Operations Gmbh | Polymeric anion-conducting membrane |
CN110560181B (en) * | 2019-09-04 | 2022-08-02 | 中国科学技术大学先进技术研究院 | Preparation method of anion exchange membrane |
CN110550788A (en) * | 2019-09-12 | 2019-12-10 | 欧润吉生态环保(浙江)有限公司 | Zero release water treatment facilities |
CN111303436B (en) * | 2020-03-06 | 2022-03-18 | 珠海冠宇电池股份有限公司 | Polyolefin-g-hyperbranched polybenzimidazole graft copolymer and preparation method and application thereof |
CN111359453A (en) * | 2020-03-21 | 2020-07-03 | 山东科技大学 | Imidazole-doped ionic liquid/modified chitosan homogeneous anion exchange membrane and preparation method thereof |
CN112316988A (en) * | 2020-10-23 | 2021-02-05 | 天津市大陆制氢设备有限公司 | Efficient anion exchange membrane and preparation method thereof |
CN113041850A (en) * | 2021-04-07 | 2021-06-29 | 福州大学 | Preparation method of porous cross-linked anion exchange membrane for diffusion dialysis |
CN113600026B (en) * | 2021-09-09 | 2022-07-22 | 浙江工业大学 | Preparation method of anti-pollution cross-linking type anion exchange membrane based on polyvinyl alcohol |
CN114456393B (en) * | 2022-01-19 | 2023-06-27 | 武汉理工大学 | Preparation method of SEBS grafted polyphenyl ether anion exchange membrane |
DE102022120196A1 (en) | 2022-08-10 | 2024-02-15 | Forschungszentrum Jülich GmbH | Side chain functionalized polystyrenes as membrane materials for alkaline water electrolyzers, fuel cells and flow batteries |
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JP5301466B2 (en) * | 2007-12-21 | 2013-09-25 | 株式会社トクヤマ | Membrane for polymer electrolyte fuel cell, and membrane-catalyst electrode assembly |
JP5959046B2 (en) * | 2012-03-07 | 2016-08-02 | 国立研究開発法人日本原子力研究開発機構 | Anion conducting electrolyte membrane and method for producing the same |
WO2015122320A1 (en) * | 2014-02-14 | 2015-08-20 | 株式会社トクヤマ | Partially quaternized styrene-based copolymer, ionic-conductivity imparter, catalytic electrode layer, membrane/electrode assembly and process for producing same, gas diffusion electrode and process for producing same, and fuel cell of anion exchange membrane type |
DE102014009170A1 (en) * | 2014-06-12 | 2015-12-17 | Universität Stuttgart | Combinatorial material system for ion exchange membranes and its use in electrochemical processes |
DE102016007815A1 (en) * | 2016-06-22 | 2017-12-28 | Universität Stuttgart | Crosslinked highly stable anion exchange blend membranes with polyethylene glycols as the hydrophilic membrane phase |
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2016
- 2016-06-22 DE DE102016007815.4A patent/DE102016007815A1/en not_active Withdrawn
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2017
- 2017-06-22 AU AU2017280451A patent/AU2017280451A1/en not_active Abandoned
- 2017-06-22 EP EP17767982.6A patent/EP3478750A1/en active Pending
- 2017-06-22 US US16/312,975 patent/US11278879B2/en active Active
- 2017-06-22 DE DE112017003141.9T patent/DE112017003141A5/en not_active Withdrawn
- 2017-06-22 JP JP2019520195A patent/JP2019522887A/en active Pending
- 2017-06-22 WO PCT/DE2017/000179 patent/WO2017220065A1/en unknown
-
2022
- 2022-03-21 US US17/700,325 patent/US12083511B2/en active Active
- 2022-07-01 JP JP2022107354A patent/JP2022160413A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111040156A (en) * | 2019-11-28 | 2020-04-21 | 李南文 | Solvent-resistant and high-dimensional-stability cross-linked polyimide film |
Also Published As
Publication number | Publication date |
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JP2019522887A (en) | 2019-08-15 |
US12083511B2 (en) | 2024-09-10 |
WO2017220065A1 (en) | 2017-12-28 |
JP2022160413A (en) | 2022-10-19 |
US20200023348A1 (en) | 2020-01-23 |
DE102016007815A1 (en) | 2017-12-28 |
DE112017003141A5 (en) | 2019-03-07 |
US11278879B2 (en) | 2022-03-22 |
AU2017280451A1 (en) | 2019-02-14 |
US20220212183A1 (en) | 2022-07-07 |
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