CN117106161A - Poly (aryl quinine) polymer, preparation method and prepared anion exchange membrane - Google Patents
Poly (aryl quinine) polymer, preparation method and prepared anion exchange membrane Download PDFInfo
- Publication number
- CN117106161A CN117106161A CN202311339045.7A CN202311339045A CN117106161A CN 117106161 A CN117106161 A CN 117106161A CN 202311339045 A CN202311339045 A CN 202311339045A CN 117106161 A CN117106161 A CN 117106161A
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- Prior art keywords
- polymer
- groups
- polyarylquinine
- anion exchange
- exchange membrane
- Prior art date
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- 229920000642 polymer Polymers 0.000 title claims abstract description 173
- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- LOUPRKONTZGTKE-WZBLMQSHSA-N Quinine Natural products C([C@H]([C@H](C1)C=C)C2)C[N@@]1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-WZBLMQSHSA-N 0.000 title claims description 71
- 229960000948 quinine Drugs 0.000 title claims description 41
- 235000001258 Cinchona calisaya Nutrition 0.000 title claims description 40
- LOUPRKONTZGTKE-UHFFFAOYSA-N cinchonine Natural products C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-UHFFFAOYSA-N 0.000 title claims description 40
- -1 Poly (aryl quinine Chemical compound 0.000 title description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 43
- 238000004132 cross linking Methods 0.000 claims abstract description 31
- 239000000446 fuel Substances 0.000 claims abstract description 18
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 7
- 150000001450 anions Chemical class 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims description 68
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 45
- 239000002904 solvent Substances 0.000 claims description 39
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 38
- 239000012528 membrane Substances 0.000 claims description 33
- 229920000412 polyarylene Polymers 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 229920006254 polymer film Polymers 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- SBYHFKPVCBCYGV-UHFFFAOYSA-N quinuclidine Chemical group C1CC2CCN1CC2 SBYHFKPVCBCYGV-UHFFFAOYSA-N 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 9
- 150000002576 ketones Chemical class 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
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- 230000008569 process Effects 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- 238000009792 diffusion process Methods 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 238000005956 quaternization reaction Methods 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 3
- 150000001350 alkyl halides Chemical class 0.000 claims description 3
- WACNXHCZHTVBJM-UHFFFAOYSA-N 1,2,3,4,5-pentafluorobenzene Chemical group FC1=CC(F)=C(F)C(F)=C1F WACNXHCZHTVBJM-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
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- WROMPOXWARCANT-UHFFFAOYSA-N tfa trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F.OC(=O)C(F)(F)F WROMPOXWARCANT-UHFFFAOYSA-N 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 150000001412 amines Chemical group 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 claims 1
- 230000000694 effects Effects 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 15
- 239000000126 substance Substances 0.000 abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
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- 229920001343 polytetrafluoroethylene Polymers 0.000 description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- XJKSTNDFUHDPQJ-UHFFFAOYSA-N 1,4-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 XJKSTNDFUHDPQJ-UHFFFAOYSA-N 0.000 description 8
- 238000011161 development Methods 0.000 description 7
- 229930184652 p-Terphenyl Natural products 0.000 description 7
- SXWIAEOZZQADEY-UHFFFAOYSA-N 1,3,5-triphenylbenzene Chemical compound C1=CC=CC=C1C1=CC(C=2C=CC=CC=2)=CC(C=2C=CC=CC=2)=C1 SXWIAEOZZQADEY-UHFFFAOYSA-N 0.000 description 6
- 125000002091 cationic group Chemical group 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- NGDCLPXRKSWRPY-UHFFFAOYSA-N Triptycene Chemical compound C12=CC=CC=C2C2C3=CC=CC=C3C1C1=CC=CC=C12 NGDCLPXRKSWRPY-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 239000013557 residual solvent Substances 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical compound CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 239000012634 fragment Substances 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- JXDYKVIHCLTXOP-UHFFFAOYSA-N isatin Chemical compound C1=CC=C2C(=O)C(=O)NC2=C1 JXDYKVIHCLTXOP-UHFFFAOYSA-N 0.000 description 4
- 238000000935 solvent evaporation Methods 0.000 description 4
- SLGBZMMZGDRARJ-UHFFFAOYSA-N triphenylene Chemical compound C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 4
- KZJRKRQSDZGHEC-UHFFFAOYSA-N 2,2,2-trifluoro-1-phenylethanone Chemical compound FC(F)(F)C(=O)C1=CC=CC=C1 KZJRKRQSDZGHEC-UHFFFAOYSA-N 0.000 description 3
- QJXCFMJTJYCLFG-UHFFFAOYSA-N 2,3,4,5,6-pentafluorobenzaldehyde Chemical compound FC1=C(F)C(F)=C(C=O)C(F)=C1F QJXCFMJTJYCLFG-UHFFFAOYSA-N 0.000 description 3
- 102000004310 Ion Channels Human genes 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- BSZXAFXFTLXUFV-UHFFFAOYSA-N 1-phenylethylbenzene Chemical compound C=1C=CC=CC=1C(C)C1=CC=CC=C1 BSZXAFXFTLXUFV-UHFFFAOYSA-N 0.000 description 2
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 2
- 238000005985 Hofmann elimination reaction Methods 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004693 Polybenzimidazole Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- 150000008378 aryl ethers Chemical class 0.000 description 2
- 238000000089 atomic force micrograph Methods 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002220 fluorenes Chemical class 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 229920000831 ionic polymer Polymers 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920002480 polybenzimidazole Polymers 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- PEQHIRFAKIASBK-UHFFFAOYSA-N tetraphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 PEQHIRFAKIASBK-UHFFFAOYSA-N 0.000 description 2
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 description 2
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 2
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalene Chemical group C1=CC=C2C(C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- SNFCXVRWFNAHQX-UHFFFAOYSA-N 9,9'-spirobi[fluorene] Chemical compound C12=CC=CC=C2C2=CC=CC=C2C21C1=CC=CC=C1C1=CC=CC=C21 SNFCXVRWFNAHQX-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- JIDUBFKLNRRLDT-UHFFFAOYSA-N [Ru].[Pt].[C] Chemical compound [Ru].[Pt].[C] JIDUBFKLNRRLDT-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
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- 238000005470 impregnation Methods 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
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- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical class O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 1
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- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
-
- 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
-
- 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
- H01M8/08—Fuel cells with aqueous electrolytes
- H01M8/083—Alkaline fuel cells
-
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention belongs to the technical field of hydrogen production by water electrolysis and fuel cells, and particularly relates to a polyarylquinine polymer, a preparation method and a prepared anion exchange membrane. According to the polyarylquinine polymer and the anion exchange membrane, a skeleton structure of a full carbon chain is adopted, a more stable functional cation functional group quinuclidine structure is introduced to serve as an anion conduction group, and the modification of the polymer is realized by using strategies such as copolymerization with a hydrophobic unit, hyperbranched, crosslinking and the like, so that the polymer with an ultrahigh stable chemical structure is formed, and the anion exchange membrane with ultrahigh stability is further prepared.
Description
Technical Field
The invention belongs to the technical field of hydrogen production by water electrolysis and fuel cells, and particularly relates to a polyarylquinine polymer, a preparation method and a prepared anion exchange membrane.
Background
The increasing energy crisis and environmental pollution are urgent to develop green efficient renewable energy sources, and hydrogen is receiving wide attention as an alternative energy source in order to replace fossil fuels and meet global climate change requirements. Hydrogen energy is recognized as the most ideal energy carrier in the future of humans because of its advantages of cleanliness, no carbon, easy transmission, high energy density, sustainability, no carbon, and renewable properties. However, most hydrogen is currently produced from fossil fuels by methane reforming, which produces large amounts of carbon dioxide. Thus, the development of low carbon clean hydrogen energy has become a global consensus.
The development of the technology of water electrolysis hydrogen production and fuel cells is a break-through of low-carbon clean hydrogen circulation, and the technology becomes an important field for supporting the development of high-proportion new energy and constructing a hydrogen-electricity cooperative pattern in the future. Three normal temperature water electrolysis hydrogen production technologies exist at present, including an alkaline aqueous solution electrolysis technology (ALK), a cation exchange membrane electrolysis water technology (PEM-WE) and an anion exchange membrane electrolysis water technology (AEM-WE). Wherein the AEM-WE electrolyzer is similar to the PEM-WE electrolyzer in structure, and the main structure is composed of an anion exchange membrane and two transition metal catalytic electrodes, and pure water or low-concentration alkaline solution is generally adopted as electrolyte. Meanwhile, AEM-WE is similar to an anion exchange membrane fuel cell (AEM-FC), and a cheaper non-Platinum Group Metal (PGM) electrocatalyst and a low-cost hydrocarbon-based membrane can be used, so that the AEM-WE has the advantages of low cost, high efficiency and the like, and is considered to be a hydrogen production technology with great development prospect.
Anion Exchange Membranes (AEMs) are an important component of AEM-WE and AEM-FC systems that function to conduct OH-from the cathode to the anode while blocking the direct transfer of gases and electrons between the electrodes. Meanwhile, AEM is also widely applied to new energy electrochemical devices in other fields such as electrodialysis, carbon dioxide reduction, flow batteries and the like. Compared with a cation exchange membrane, the anion exchange membrane has the disadvantages of complex preparation route, low hydroxide conductivity, poor mechanical stability and poor chemical stability, which are development bottlenecks; in addition, as AEM is in the working process, the local strong alkaline environment formed on the surface of the film can degrade AEM and generate perforation under the action of OH < - >, thereby causing electrode short circuit and affecting the service life. Thus, the development of novel anion exchange membranes is expected in the art, and how to enhance ionic conductivity, mechanical stability and alkaline stability is a key technical challenge for the further development of AEM-WE cells.
The new AEMs for AEM-WE or AEMFCs that have been developed today include most polymer backbones: such as Polyetheretherketone (PEEK), polysulfone (PSF), polyphenylene oxide (PPO), polybenzimidazole (PBI), and cationic groups (tetraalkylammonium, imidazolium, phosphonium, and organometallic cations). However, the research results show that the polymer skeleton and benzyl trimethyl ammonium cations connected by the aryl ether are easy to attack by OH-, and the degradation pathways such as nucleophilic substitution, hofmann elimination, ylide formation and the like lead to skeleton fracture and cation loss, so that the durability of AEM is seriously weakened, especially when AEM is used under high temperature conditions. Another major class of novel AEMs is the poly (aryl piperidine) copolymers synthesized by the catalyzed polycondensation of superacids, which are developed in recent years and are based on electron-rich phenyl monomers and piperidones, and although the basic stability of AEMs is further improved by the absence of an aryl ether backbone and cyclic quaternary ammonium structures, hofmann elimination (the main degradation route of piperidine cyclic quaternary ammonium salts) cannot be avoided.
In summary, the anion exchange membranes on the market still have a plurality of structural defects, which result in relatively poor chemical stability and cannot meet the requirements of special application scenes. Especially in large-scale and large-scale industrial applications, the higher alkaline stability directly determines the durability and efficiency of AEM-WE and AEM-FC devices. Therefore, there is a need in the art to develop an AEM that combines excellent mechanical strength, high ionic conductivity and ultra-high chemical stability, effectively pushing the mass production and industrialization of AEM-WE and AEM-FC.
Disclosure of Invention
Therefore, the first object of the present invention is to provide a polyarylquinine polymer and a quaternized polyarylquinine polymer, wherein the skeleton structure of the whole carbon chain of the polymer and the quinuclidine which is a more stable functional cation functional group can improve the chemical structural stability of AEM, and the modification of the polymer is realized by using strategies of copolymerization with a hydrophobic unit, hyperbranched, crosslinking and the like, so that the polymer has lower water absorption and swelling rate, the mechanical stability and the electrical conductivity of AEM can be further improved, and the polymer can be used for preparing an anion exchange membrane with high stability;
a second object of the present invention is to provide an anion exchange membrane prepared based on the above-mentioned polyarylene quinine polymer, which has ultra-high chemical stability, structural stability, and excellent conductivity and ionic conductivity, and has excellent performance in AEM-WE and AEMFCs applications, etc.;
a third object of the present invention is to provide a method for producing the above-mentioned polyarylene quinine polymer and an anion exchange membrane.
In order to solve the technical problems, the polyarylquinine polymer comprises a cross-linking group polymerization unit containing a quinuclidine structure and/or a linear structure polymerization unit containing a quinuclidine structure;
The cross-linking group polymerization unit containing the quinuclidine structure has a structure shown in the following formula (P1):
；
the quinuclidine structure-containing linear-structure polymeric unit has a structure represented by the following formula (P2):
；
wherein,
the Ar is as follows 1 Is a phenyl structural monomer with a plurality of crosslinking points;
the Ar is as follows 2 Phenyl structural monomers with linear structures.
Specifically, the polymer further comprises a linear hydrophobic polymeric unit;
the linear hydrophobic polymeric unit has a structure represented by the following formula (P3):
；
wherein,
the Ar is as follows 2 Phenyl structural monomers which are linear structures;
the R is 1 Is a hydrophobic copolymerized unit.
Specifically, the polymer comprises a crosslinking group polymerization unit and a linear structure polymerization unit; the polymer has a structure represented by the following formula (P):
；
wherein,
the Ar is as follows 1 Is a phenyl structural monomer with a plurality of crosslinking points;
the Ar is as follows 2 Phenyl structural monomers which are linear structures;
the R is 1 Is a hydrophobic copolymerized unit.
In particular, the polyarylquinine polymer, wherein,
x is the molar ratio of the cross-linking group polymeric units in the polymer,%;
y=y n +y m namely the mole ratio of the linear structure polymerization unit in the polymer,%;
Wherein x is 0-100%, y is 50% -100%, and x+y=100%.
Specifically, the polyarylquinine polymer, wherein the linear structure polymeric unit:
y n mole ratio of polymerized units containing the quinuclidine structure in the polymer,%;
y m to contain said hydrophobic comonomer R 1 Molar ratio,%;
wherein y is n 60% -100%, y m 0% -40% and y n +y m ≤100%。
Specifically, the polyarylene quinine polymer, the Ar 1 A planar or spatial structure formed by connecting phenyl structural monomers with a plurality of crosslinking points;
the Ar is as follows 1 Wherein the plurality of crosslinking points of the phenyl structural monomer are in a plane or space structure which is uniformly distributed or symmetrically distributed.
Preferably, the Ar 1 Wherein the plurality of crosslinking points of the phenyl structural monomer have the same substituted or unsubstituted phenyl structural monomer.
Preferably, the Ar 1 At least one of the phenyl structural monomers comprising the structure:
。
wherein, (a) is triphenylbenzene, (b) is triptycene, (c) is triphenylmethane, (d) is 9, 10-benzophenanthrene, (e) is 9,9 '-spirobifluorene, (f) is 9,9' -diphenylfluorene, (g) is tetraphenylmethane, and (h) is tetraphenylporphyrin.
Specifically, the polyarylene quinine polymer, the Ar 2 Wherein the phenyl structural monomers comprise 2-4 linear linked substituted or unsubstituted phenyl monomers.
Preferably, in the phenyl structural monomers, each benzene ring monomer is connected by a single bond, an unsaturated bond and/or forms a linear annular structure;
preferably, the Ar 2 Including diphenyl-substituted linear aromatic hydrocarbons.
Preferably, the Ar 2 At least one of the phenyl structural monomers comprising the structure:
；
wherein the R is 2 Is a C1-C10 alkyl group.
Wherein (a) is biphenyl, (b) is p-terphenyl, (c) is tetraterphenyl, (d) is m-terphenyl, (e) is diphenylethane, (f) is trans-1, 2-stilbene, (g) is cis-1, 2-stilbene, and (h) is dialkyl-substituted fluorene (R) 2 Is an alkyl chain C1-C10), (i) is N-R 2 Carbazole (R) 2 Is alkyl chain C1-C10), (j) is dibenzo-18-crown-6, (k) is 1,1' -binaphthyl, (l) is diphenyl ether, (m) is xanthene, (n) is 6,6' -dimethoxy-3, 3' -tetralinMethyl-1, 1 '-spiroindane, (o) is 9,9' -dialkyl-substituted-2, 7-diphenylfluorene (R) 2 Are alkyl chains C1-C10).
Specifically, the polyarylquinine polymer, the R 1 Wherein the hydrophobic copolymerization unit comprises a hydrophobic monomer containing an electron withdrawing group structure;
preferably, the hydrophobic co-polymer unit comprises a substituted or unsubstituted aromatic ring hydrophobic monomer, a substituted or unsubstituted saturated aliphatic hydrophobic monomer, or a substituted or unsubstituted ketone hydrophobic monomer.
Preferably, the hydrophobic co-units are selected from monomers comprising trifluoromethyl, carbonyl and/or pentafluorobenzene structures.
Preferably, said R 1 At least one of the hydrophobic co-units comprising the structure:
；
wherein the R is 3 Is alkyl; the R is 4 Is a hydrogen atom, an alkyl chain or an aryl group.
Wherein (a) is trifluoroacetophenone and (b) is trifluoroacetyl compound (R) 3 Is alkyl), (c) is 2, 3-butanedione, (d) is N-R 4 Isatin (R) 4 A hydrogen atom, an alkyl chain or an aryl group), (e) a pentafluorobenzaldehyde.
Preferably, the hydrophobic co-units are formed by the reaction of corresponding ketone monomers.
The invention also discloses a method for preparing the polyarylquinine polymer, which comprises the steps of taking a phenyl structural monomer Ar with a plurality of crosslinking points according to the selected structure of the polyarylquinine polymer 1 Phenyl structural monomer Ar with linear structure 2 3-quininone and hydrophobic comonomer R 1 Adding the corresponding ketone monomer into a first solvent, mixing, carrying out polymerization in the presence of a first catalyst, and adding a reaction solution into a second solvent, mixing, collecting the precipitated polymer, and preferably washing and drying the polymerAnd (5) processing.
Specifically, the preparation method of the polyarylquinine polymer comprises the following steps:
the phenyl structural monomer Ar with a plurality of crosslinking points 1 And the phenyl structural monomer Ar with the linear structure 2 The molar ratio of (1) to (50): (100-50); and/or the number of the groups of groups,
the molar ratio of the phenyl structural monomer with the linear structure to the 3-quininone is 1: (1-1.5); and/or the number of the groups of groups,
the hydrophobic copolymerization unit R 1 The molar ratio of the corresponding ketone monomer to the 3-quininone is (0-0.4): 1, a step of; and/or the number of the groups of groups,
the first solvent comprises at least one of dichloromethane, chloroform or tetrahydrofuran; and/or the number of the groups of groups,
the second solvent comprises at least one of ethyl acetate, methanol, ethanol, diethyl ether, tetrahydrofuran or acetone; and/or the number of the groups of groups,
the volume ratio of the first solvent to the second solvent is 1: (10-30); and/or the number of the groups of groups,
The addition amount of the 3-quininone based on the first solvent is 10-22.5mmol of the 3-quininone added per 10-15mL of the first solvent; and/or the number of the groups of groups,
the washing step comprises the step of adding a first alkali liquor for washing and the step of adding the first alkali liquor for washing; and/or the number of the groups of groups,
the primary alkali solution comprises K 2 CO 3 KOH, naOH or NaHCO 3 At least one of the solutions, preferably at a concentration of 0.5-2.0M; and/or the number of the groups of groups,
the drying step comprises the step of vacuum drying at 60-80 ℃; and/or the number of the groups of groups,
the first catalyst comprises trifluoroacetic acid (TFA) and/or trifluoromethanesulfonic acid (TFSA); wherein,
the molar ratio of the trifluoroacetic acid to the 3-quininone is (1-2): 1, a step of; and/or the number of the groups of groups,
the molar ratio of the trifluoromethanesulfonic acid to the 3-quininone is (10-20): 1.
the invention also discloses a quaternized polyarylquinine polymer, which has a structure shown in the following formula (Q):
；
wherein the Ar is 1 、Ar 2 、R 1 Is as defined in the polymer;
the R is 5 Including groups having a quaternized structure.
Preferably, said R 5 Including alkyl chains of quaternized structures.
Preferably, said R 5 C1-C10 alkyl chains which are quaternized structures.
The invention also discloses a method for preparing the quaternary amination polyarylquinine polymer, which comprises the steps of taking the polyarylquinine polymer, adding the polyarylquinine polymer into a third solvent, adding a second catalyst and halogenated alkane with a corresponding structure to carry out quaternary amination reaction, adding a reaction solution into a fourth solvent to mix, collecting a precipitate, and preferably washing and drying the precipitate.
Specifically, the preparation method of the quaternized polyarylquinine polymer comprises the following steps:
the solid to liquid ratio of the polyarylquinine polymer and the haloalkane is 1g: (1-3) mL; and/or the number of the groups of groups,
the mass ratio of the polyarylquinine polymer to the second catalyst is (2-3): 1, a step of; and/or the number of the groups of groups,
the second catalyst comprises K 2 CO 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or the number of the groups of groups,
the solid to liquid ratio of the polyarylquinine polymer and the third solvent is 1g: (10-20) mL; and/or the number of the groups of groups,
the third solvent comprises at least one of dimethyl sulfoxide, N-methyl pyrrolidone, N-dimethylformamide or N, N-dimethylacetamide; and/or the number of the groups of groups,
the fourth solvent comprises at least one of ethyl acetate, methanol, ethanol, acetone or diethyl ether; and/or the number of the groups of groups,
The volume ratio of the third solvent to the fourth solvent is 1: (6-10); and/or the number of the groups of groups,
the temperature of the quaternization reaction is 40-60 ℃; and/or the number of the groups of groups,
the drying step includes a step of vacuum drying at 60-80 ℃.
The invention also discloses a high-stability anion exchange membrane, which is OH - An anion exchange membrane having a structure represented by the following formula (T):
；
wherein the Ar is 1 、Ar 2 、R 1 Is the same as the defined features in the quaternized polyarylquinine polymer.
Specifically, the preparation raw materials of the anion exchange membrane comprise the polyarylquinine polymer and/or the quaternized polyarylquinine polymer.
The invention also discloses a method for preparing the high-stability anion exchange membrane, which comprises the following steps:
(1) Adding a fifth solvent into the quaternized poly (aryl quinine) polymer, mixing, and casting on the surface of a substrate to obtain a polymer film;
(2) The polymer film is placed in a second alkali solution for immersion to obtain OH - And (3) an anion exchange membrane.
Specifically, the preparation method of the high-stability anion exchange membrane comprises the following steps:
the solid to liquid ratio of the quaternized polyarylquinine polymer to the fifth solvent is 1g: (10-100) mL; and/or the number of the groups of groups,
The fifth solvent comprises at least one of dimethyl sulfoxide, N-methyl pyrrolidone, N-dimethylformamide or N, N-dimethylacetamide; and/or the number of the groups of groups,
the thickness of the polymer film is 20-60 mu m; and/or the number of the groups of groups,
the second alkaline solution comprises NaOH and/or KOH solution, and the preferable concentration is 0.5-2.0M; and/or the number of the groups of groups,
the temperature of the dipping step is 25-80 ℃ and the dipping time is 8-12h; and/or the number of the groups of groups,
the method further comprises the step of placing the anion exchange membrane in deionized water which is filled with a protective atmosphere for preservation.
Specifically, the method further comprises the step of preparing the desired quaternized polyarylquinine polymer from the polyarylquinine polymer according to the method.
The invention also discloses the use of the high-stability anion exchange membrane for preparing an alkaline water electrolysis cell and/or an alkaline fuel cell.
The invention also discloses an alkaline water electrolysis tank, an alkaline fuel cell and/or an alkaline fuel cell device prepared by the high-stability anion exchange membrane.
The invention also discloses the application of the polyarylquinine polymer and/or the quaternary aminated polyarylquinine polymer in preparing anion exchange membranes.
The invention also discloses the application of the polyarylquinine polymer and/or the quaternary aminated polyarylquinine polymer in preparing an anion membrane or a gas diffusion electrode coated by a catalytic layer.
The polyarylquinine polymer adopts a skeleton structure of a full carbon chain, takes a quinuclidine structure with more stable functional cations as an anion conduction group, and realizes modification of the polymer by using strategies such as copolymerization with a hydrophobic unit, hyperbranched, crosslinking and the like, so as to form the polymer with an ultrahigh stable chemical structure. The polyarylquinine polymer provided by the invention has lower water absorption and swelling rate, further improves the mechanical stability and the electrical conductivity of AEM, and has higher performance and stability in AEM-WE and AEM-FC tests.
The polyarylquinine polymer is prepared by introducing a hydrophobic structural unit R 1 The poly (aryl quinine) copolymer is obtained, the IEC of the polymer is regulated, and the water absorption rate of the anion exchange membrane is changed<25%) and the swelling ratio<10 percent) improves the mechanical strength and mechanical property of the polymer.
According to the polyarylquinine polymer, a series of polymers with stable chemical structures are synthesized by introducing a monomer structure with large volume, rigidity and hydrophobicity and crosslinking points. The polymer has larger free volume, leads chains to be easier to move, leads cationic groups to be easier to mutually aggregate in the microphase separation process, is favorable for establishing an ion channel with lower transmission resistance, and has the conductivity of 55.56 mS cm at room temperature with b-QPAQ-5 percent -1 Compared with the common linear structure type anion exchange membrane QAPTP, the conductivity of the membrane at room temperature is only 20.60mS cm -1 The conductivity of the film is greatly improved.
The anion exchange membrane of the invention forms a quaternized polyarylene quinine polymer based on the polyarylene quinine polymer, and then forms OH by alkalization - An anion exchange membrane. The anion exchange membrane has ultrahigh chemical stability, structural stability, excellent conductivity and ion conductivity, and the ion loss rate is less than 2% after being soaked in a 1M KOH solution at 80 ℃ for more than 2000 hours, so that the stability of the anion exchange membrane is greatly improved. The anion exchange membrane has excellent performance in AEM-WE, AEMFCs and other applications.
The anion exchange membrane provided by the invention has the advantages of higher water absorption and high swelling rate in the practical application process, and greatly influences the long-time stability and efficiency of an electrochemical device, aiming at the defects of AEM applied to AEM-WE and AEM-FC in the prior art, namely the fracture of an aryl skeleton and the degradation of quaternary ammonium salt.
The anion exchange membrane provided by the invention directly carries out super acidic polymerization on the polymer monomer by a one-pot method, simplifies the synthesis steps of the membrane, has simple preparation process, and can be matched with mass production of the membrane.
The anion exchange membrane is used for preparing fuel cell devices, has higher device performance and stability, has higher performance in both the anion exchange membrane electrolyzed water and the anion exchange membrane fuel cell devices, and simultaneously stably operates for more than 1000 hours in the anion exchange membrane electrolyzed water devices, and has voltage rise less than 0.1 mv/h and exceeds most of anion exchange membranes reported at present.
The polyarylene quinine polymer of the invention, due to its excellent anionic conductivity, chemical stability, mechanical properties and solubility, its polymer solution can be formulated as an ionomer with catalyst, alcohol, water into a catalyst ink for preparing a catalytic layer coated anion membrane or gas diffusion electrode for electrolysis of water, fuel cells and CO 2 In the fields of reduction and the like, the running stability and durability of the device are improved.
The polyarylquinine polymer provided by the invention has ultrahigh-stability functional cationic groups, so that the polyarylquinine polymer can be used for preparing anion exchange membranes with high stability. In the anion exchange membrane with the structure, the water absorption and the swelling rate of the polymer are regulated and controlled by adding the copolymerized hydrophobic monomer, so that the mechanical strength of the polymer is improved; by adding the crosslinking groups, the polymer obtains larger free volume and reduces the expansion of the membrane, so that the inside of the polymer has more obvious microphase separation, and the aggregation of the cationic groups is also helpful to establish an ion channel with lower transmission resistance; and the polymer has very excellent performance by being applied to alkaline electrolyzed water and fuel cells, and has very important significance for realizing industrial application of AEM electrolyzed water.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which,
FIG. 1 is a graph showing the water absorption and swelling ratio of an anion exchange membrane in experimental example 1;
FIG. 2 shows the hydrogen nuclear magnetic resonance spectrum of the anion exchange membrane of Experimental example 2 1 H-NMR）；
FIG. 3 is an AFM image of the anion exchange membrane of Experimental example 2;
FIG. 4 shows ion conductivities of the anion exchange membrane and the QPAP membrane of Experimental example 2 at room temperature;
FIG. 5 is a graph showing LSV of the anion exchange membrane of experimental example 3 at various temperatures (25, 40, 60, 80 ℃) in an alkaline electrolytic cell;
FIG. 6 is an EIS graph of the anion exchange membrane of Experimental example 3 at 80℃in an alkaline electrolytic cell;
FIG. 7 is a graph showing stability data of an anion exchange membrane in experimental example 3 at room temperature under a constant current of 1A in an alkaline electrolytic cell;
fig. 8 is a polarization curve of an anion exchange membrane cell discharge assembled with an anion exchange membrane in experimental example 4.
Detailed Description
In the following examples of the invention, the polyarylene quinine polymer, the quaternized polyarylene quinine polymer, and OH - The anion exchange membranes have structures represented by the following formulas (P), (Q), and (T):
。
The above mentioned polyarylquinine polymers, quaternized polyarylquinine polymers and OH - Ar involved in the structure of anion exchange membrane 1 、Ar 2 、R 1 Representing the same group.
The above mentioned polyarylquinine polymers, quaternized polyarylquinine polymers and OH - In the structure of the anion exchange membrane, the Ar 1 For phenyl structural monomers having multiple crosslinking points, materials known in the art may be selected to form the desired structural features. In the following examples of the present invention, as an exemplary scheme, monomer structures such as triphenylbenzene, triptycene, triphenylmethane, 9, 10-benzophenanthrene, 9 '-spirobifluorene, 9' -diphenylfluorene, tetraphenylmethane or tetraphenylporphyrin may be selected as raw materials for the reaction.
The above mentioned polyarylquinine polymers, quaternized polyarylquinine polymers and OH - In the structure of the anion exchange membrane, the Ar 2 The phenyl structural monomer with linear structure can be selected from substances known in the art to form the required structural characteristics. In the following examples of the present invention, examples such as biphenyl, p-terphenyl, tetrabiphenyl, m-terphenyl, diphenylethane, trans-1, 2-stilbene, cis-o-biphenyl, and the like may be selected as illustrative embodiments 1, 2-stilbene, dialkyl substituted fluorene (alkyl is alkyl chain C1-C10), N-R 2 Carbazole (R) 2 Is alkyl chain C1-C10), dibenzo-18-crown ether-6, 1' -binaphthyl, diphenyl ether, xanthene, 6' -dimethoxy-3, 3' -tetramethyl-1, 1' -spiroindane, 9' -dialkyl substituted-2, 7-diphenyl fluorene (alkyl is alkyl chain C1-C10) and the like.
The above mentioned polyarylquinine polymers, quaternized polyarylquinine polymers and OH - In the structure of the anion exchange membrane, the R is 1 For hydrophobic co-units, materials known in the art may be selected to form the desired structural features. In the following examples of the invention, the hydrophobic co-units are formed by the reaction of corresponding ketone monomers. As an exemplary scheme, there may be selected, for example, trifluoroacetophenone, trifluoroacetyl compound (alkyl substituted), 2, 3-butanedione, N-R 4 Isatin (R) 4 Is hydrogen atom, alkyl chain and aryl group), and pentafluorobenzaldehyde is used as ketone monomer to form R through reaction 1 The hydrophobic co-polymer unit structure shown.
The above mentioned polyarylquinine polymers, quaternized polyarylquinine polymers and OH - The structure of the anion exchange membrane comprises a cross-linking group polymerization unit and a linear structure polymerization unit, wherein,
x is the molar ratio of the cross-linking group polymeric units in the polymer,%;
y=y n +y m namely the mole ratio of the linear structure polymerization unit in the polymer,%;
wherein x is 0-100%, y is 50% -100%, and x+y=100%;
specifically, in the linear structure polymerization unit:
y n mole ratio of polymerized units containing the quinuclidine structure in the polymer,%;
y m to contain said hydrophobic comonomer R 1 Molar ratio,%;
wherein y is n 60% -100%, y m Is 0 to-40%, and y n +y m ≤100%。
In the following examples, the method for synthesizing the polyarylquinine polymer can be carried out by regulating and controlling the phenyl monomer Ar with a crosslinking point 1 Phenyl monomer Ar with linear structure 2 3-quininone and hydrophobic comonomer R 1 The proportion of monomers is subjected to polycondensation reaction under the catalysis of trifluoromethanesulfonic acid to synthesize a series of homopolymers of polyarylquinine, polyarylquinine copolymers of different IEC and branched polyarylquinine copolymers, and the polymers are prepared into polymer films which are used in anion exchange membrane alkaline water electrolysis devices and anion exchange membrane fuel cell devices.
In the following examples, the process for the synthesis of the quaternized polyarylene quinine polymers is based on the polyarylene quinine polymers by adding K 2 CO 3 And the corresponding structure of the halogenated alkane are subjected to quaternization reaction to prepare the modified halogenated alkane.
In the following examples of the present invention, the high stability anion exchange membrane is OH - The synthetic method of the anion exchange membrane is to form a membrane by using a solvent volatilization mode on the basis of the quaternized poly aryl quinine polymer, and then to place the formed polymer membrane into an alkaline solvent for impregnation.
The invention is further illustrated by the following specific experimental procedures. The following examples are intended to illustrate the invention without further limiting it.
Example 1
This example provides an OH group of a polyarylene quinine homopolymer - An anion exchange membrane has the following specific structure:
。
the anion exchange membrane described in this example is prepared by the following method:
(1) In a 100mL single-neck flask, adding p-terphenyl (1.1545 g,5.0 mmol) and 3-quininone (0.9662 g,6.0 mmol) into dichloromethane (5 mL), stirring for 10min under ice-water bath and air atmosphere by using a magnetic stirrer to obtain a light yellow mixed solution, then dropwise adding TFSA (5.0 mL,56.50 mmol) into the white mixed solution, stirring and reacting for 72h after the dropwise adding, changing the color of the solution from light yellow to red and finally changing the color into dark blue during the reaction, and pouring the obtained viscous solution into 200ml+200mL of mixed solution of water and methanol to precipitate yellow polymer;
(2) The yellow polymer was crushed and the fragments were collected by filtration using 1M K 2 CO 3 Stirring and washing the solution at room temperature for 12 hours to neutralize acid remained in the reaction, washing the solution with deionized water for three times, and drying the solution in a vacuum oven at 80 ℃ for 12 hours to obtain a poly (aryl quinine) homopolymer (PAQ);
(3) In a flask, PAQ (2.8 g) was dissolved in DMSO (30 mL), stirred at room temperature for 30min, then K was added 2 CO 3 (0.637 g) and methyl iodide (5.0 mL), stirring at room temperature in the dark for 12h, then heating to 60℃and stirring for 6h, adding 200mL diethyl ether to the resulting viscous solution, filtering the yellow precipitate, rinsing 3 times with deionized water, and drying in a vacuum oven at 80℃for 12h to give a quaternized polyarylene quinine homopolymer (QPAQ (I) - ））；
(4) QPAQ (I) - ) (0.5 g) was dissolved in DMSO (15 mL), the polymer solution was filtered through a 0.45 μm Polytetrafluoroethylene (PTFE) filter, cast onto a flat, clean glass plate, and then dried on a solvent evaporation heating table at 120deg.C for 6h to give a 40 μm thick I after complete removal of residual solvent - A polymer film of the type;
(5) Will I - Stripping the polymer film from the glass plate, soaking in 1M KOH solution, and ion-exchanging at 60deg.C for 12 hr to obtain OH - The shaped film was then washed 3 times with deionized water to avoid CO 2 And carbonate formation, the membranes were immersed in deionized water purged with nitrogen for storage.
Example 2
This example provides a low IEC OH of a polyarylene quinine copolymer - An anion exchange membrane has the following specific structure:
。
the anion exchange membrane described in this example is prepared by the following method:
(1) In a 100mL single-neck flask, p-terphenyl (1.1545 g,5.0 mmol), 3-quininone (0.7247 g,4.5 mmol) and trifluoroacetophenone (0.2612 g,1.5 mmol) are added into dichloromethane (5 mL), a magnetic stirrer is used for stirring for 10min under the ice-water bath and air atmosphere to obtain a light yellow mixed solution, TFSA (5.0 mL,56.50 mmol) is then dropwise added into the white mixed solution, stirring is carried out for 72h after the dropwise addition, the color of the solution is changed from light yellow to red and finally changed to dark blue in the reaction process, and the obtained viscous solution is poured into 200mL+200mL of mixed solution of water and methanol to precipitate yellow polymer;
(2) The yellow polymer was crushed and the fragments were collected by filtration using 1M K 2 CO 3 Stirring and washing for 12 hours at room temperature to neutralize acid remained in the reaction, then washing with deionized water for three times, and drying for 12 hours in a vacuum oven at 80 ℃ to obtain a poly (aryl quinine) copolymer (co-PAQ, IEC=2.56 mmol/g);
(3) In a flask, co-PAQ (3.0 g) was dissolved in DMSO (30 mL), stirred at room temperature for 30min, then K was added 2 CO 3 (0.687 g) and methyl iodide (5.0 mL), stirring at room temperature in the dark for 12h, then heating to 60deg.C and stirring for 6h, adding 200mL diethyl ether to the viscous solution, filtering the yellow precipitate, washing with deionized water 3 times, and vacuum oven drying at 80deg.C for 12h to obtain quaternized polyarylquinine copolymer (co-QPAQ (I) - ））；
(4) co-QPAQ (I) - ) (0.5 g) was dissolved in DMSO (15 mL), the polymer solution was filtered through a 0.45 μm Polytetrafluoroethylene (PTFE) filter, cast onto a flat, clean glass plate, and then dried on a solvent evaporation heating table at 120deg.C for 6h to give a 40 μm thick I after complete removal of residual solvent - A polymer film of the type;
(5) Will I - Stripping the polymer film from the glass plate, soaking in 1M KOH solution, and ion-exchanging at 60deg.C for 12 hr to obtain OH - The shaped film was then washed 3 times with deionized water to avoid CO 2 And carbonate formation, the membranes were immersed in deionized water purged with nitrogen for storage.
In this example, OH is finally obtained - Poly (arylquinine) copolymer co-QPAQ of type.
Example 3
This example provides a branched polyarylquinine anion exchange membrane prepared by:
。
the anion exchange membrane described in this example is prepared by the following method:
(1) In a 100mL single-neck flask, p-terphenyl (1.0968 g,4.75 mmol), triphenylbenzene (0.0766 g,0.25 mmol) and 3-quininone (0.9662 g,6.0 mmol) are added into dichloromethane (5 mL), and stirred for 10min under an ice-water bath and air atmosphere by a magnetic stirrer to obtain a light yellow mixed solution, TFSA (5.0 mL,56.50 mmol) is then dropwise added into the white mixed solution, and stirring reaction is carried out for 36h after the dropwise addition, wherein the color of the solution is changed from white to red to dark blue finally in the reaction process, and the obtained viscous solution is poured into 200mL+200mL of mixed solution of water and methanol to precipitate a yellow polymer;
(2) The yellow polymer was crushed and the fragments were collected by filtration using 1M K 2 CO 3 Stirring and washing for 12 hours at room temperature to neutralize acid remained in the reaction, washing with deionized water for three times, and drying in a vacuum oven at 80 ℃ for 12 hours to obtain a branched polyarylquinine polymer (b-PAQ);
(3) In a flask, b-PAQ (2.8 g) was dissolved in DMSO (30 mL), stirred at room temperature for 30min, then K was added 2 CO 3 (0.637 g) and methyl iodide (5.0 mL), stirred at room temperature in the dark for 12h, followed byHeating to 60deg.C, stirring for 6 hr, adding 200mL diethyl ether into the viscous solution, filtering the yellow precipitate, washing with deionized water for 3 times, and vacuum oven drying at 80deg.C for 12 hr to obtain quaternized polyarylquinine polymer (b-QPAQ (I) - ））；
(4) b-QPAQ (I) - ) (0.5 g) was dissolved in DMSO (15 mL), the polymer solution was filtered through a 0.45 μm Polytetrafluoroethylene (PTFE) filter, cast onto a flat, clean glass plate, and then dried on a solvent evaporation heating table at 120deg.C for 6h to give a 40 μm thick I after complete removal of residual solvent - A polymer film of the type;
(5) Will I - Stripping the polymer film from the glass plate, soaking in 1M KOH solution, and ion-exchanging at 60deg.C for 12 hr to obtain OH - The shaped film was then washed 3 times with deionized water to avoid CO 2 And carbonate formation, the membranes were immersed in deionized water purged with nitrogen for storage.
In this example, a branched anion exchange membrane b-QPAQ-5% was finally obtained, wherein 5.0% is the molar amount of triphenylbenzene as a percentage of the total molar amount of triphenylbenzene and para-terphenyl. The anion exchange membrane b-QPAQ-5% prepared in this example (tested as a 20 cm. Times.20 cm membrane) was tested to have a uniform thickness and transparent texture.
Example 4
This example provides a space-type polyarylene quinine polymer OH - An anion exchange membrane has a specific structure shown in the following figure:
。
the anion exchange membrane described in this example is prepared by the following method:
(1) In a 100mL single-neck flask, p-terphenyl (1.0391 g,4.5 mmol), triptycene (0.1271 g,0.5 mmol) and 3-quinine (0.9662 g,6.0 mmol) are added into dichloromethane (5 mL), and the mixture is stirred for 10min under ice-water bath and air atmosphere by a magnetic stirrer to obtain a light yellow mixed solution, TFSA (5.0 mL,56.50 mmol) is then dropwise added into the white mixed solution, and stirring reaction is carried out for 36h after the dropwise addition, wherein the color of the solution is changed from white to red to dark blue finally during the reaction, and the obtained viscous solution is poured into 200mL+200mL of mixed solution of water and methanol to precipitate yellow polymer;
(2) The yellow polymer was crushed and the fragments were collected by filtration using 1M K 2 CO 3 Stirring and washing for 12 hours at room temperature to neutralize acid remained in the reaction, washing with deionized water for three times, and drying in a vacuum oven at 80 ℃ for 12 hours to obtain a space-type poly (aryl quinine) polymer (s-PAQ);
(3) In a flask, s-PAQ (2.6 g) was dissolved in DMSO (30 mL), stirred at room temperature for 30min, then K was added 2 CO 3 (0.637 g) and methyl iodide (5.0 mL), stirring at room temperature in the dark for 12 hours, then heating to 60℃and stirring for 6 hours, adding 200mL of diethyl ether to the viscous solution obtained, filtering the yellow precipitate, washing 3 times with deionized water, and drying in a vacuum oven at 80℃for 12 hours to obtain a quaternized polyarylene quinine polymer (s-QPAQ (I) - ））；
(4) Will s-QPAQ (I) - ) (0.5 g) was dissolved in DMSO (15 mL), the polymer solution was filtered through a 0.45 μm Polytetrafluoroethylene (PTFE) filter, cast onto a flat, clean glass plate, and then dried on a solvent evaporation heating table at 120deg.C for 6h to give a 40 μm thick I after complete removal of residual solvent - A polymer film of the type;
(5) Will I - Stripping the polymer film from the glass plate, soaking in 1M KOH solution, and ion-exchanging at 60deg.C for 12 hr to obtain OH - The shaped film was then washed 3 times with deionized water to avoid CO 2 And carbonate formation, the membranes were immersed in deionized water purged with nitrogen for storage.
In this example, the space type anion exchange membrane s-QPAQ-10% is finally obtained, wherein 10% is the percentage of the mole amount of triptycene to the total mole amount of triptycene and p-terphenyl.
Example 5
The embodiment provides a multi-element regulation and controlHydrophilic and hydrophobic polyarylene quinine polymers OH - An anion exchange membrane has a specific structure shown in the following figure:
。
the anion exchange membrane described in this example is prepared by the following method:
(1) In a 100mL single-neck flask, dibenzo-18-crown-6 (1.719 g,4.75 mmol), triphenylbenzene (0.0766 g,0.25mmol, 3-quininone (0.82313 g,5.1 mmol) and pentafluorobenzaldehyde (111. Mu.L, 0.9 mmol) were added to methylene chloride (5 mL), stirred with a magnetic stirrer under an ice-water bath and air atmosphere for 10min to obtain a pale yellow mixed solution, TFSA (5.0 mL,56.50 mmol) was then added dropwise to the above white mixed solution, and stirred for 36h after the dropwise addition, during the reaction, the color of the solution was changed from white to red and finally changed to dark blue, and the obtained viscous solution was poured into 200mL+200mL of a mixed solution of water and methanol to precipitate a white polymer;
(2) The white polymer was crushed, and the crushed pieces were collected by filtration, using 1M K 2 CO 3 Stirring and washing for 12 hours at room temperature to neutralize acid remained in the reaction, washing with deionized water for three times, and drying in a vacuum oven at 80 ℃ for 12 hours to obtain a branched polyarylquinine polymer (m-PAQ);
(3) In a flask, b-PAQ (3.5 g) was dissolved in DMSO (30 mL), stirred at room temperature for 30min, then K was added 2 CO 3 (0.637 g) and methyl iodide (5.0 mL), stirring at room temperature in the dark for 12 hours, then heating to 60℃and stirring for 6 hours, adding 200mL diethyl ether to the viscous solution obtained, filtering the yellow precipitate, washing 3 times with deionized water, and drying in a vacuum oven at 80℃for 12 hours to obtain a quaternized polyarylene quinine polymer (m-QPAQ (I) - ））；
(4) The m-QPAQ (I) - ) (0.5 g) dissolved in DMSO (15 mL), the polymer solution was filtered through a 0.45 μm Polytetrafluoroethylene (PTFE) filter, cast onto a flat, clean glass plate, and then on a glass plateDrying the mixture on a solvent volatilization heating table at 120 ℃ for 6 hours, and completely removing residual solvent to obtain the I with the thickness of 40 mu m - A polymer film of the type;
(5) Will I - Stripping the polymer film from the glass plate, soaking in 1M KOH solution, and ion-exchanging at 60deg.C for 12 hr to obtain OH - The shaped film was then washed 3 times with deionized water to avoid CO 2 And carbonate formation, the membranes were immersed in deionized water purged with nitrogen for storage.
In the embodiment, the multi-element regulated hydrophilic-hydrophobic anion exchange membrane m-QPAQ (OH) - ）。
Experimental example
1. Water absorption and swelling test
In this experimental example, OH obtained in example 2 was taken - The polyarylquinine copolymer co-QPAQ and the resulting film was tested for water absorption and swelling.
Taking the OH - The anion exchange membrane after exchange is soaked in deionized water with different temperatures to reach adsorption equilibrium. After the surface water was blotted dry, the weight (Wwet) and length (Lwet) of the wet sample were measured. The films were then dried in a vacuum oven at 80 ℃ for 24 hours to measure the weight (Wdry) of each film in the dry state. WU and SR are calculated by the following formulas, and the calculation results are shown in fig. 1.
WU（%）=；/>
SR（%）=。
As can be seen from the results of FIG. 1, the co-QPAQ films prepared in this example had water absorption (80 ℃, < 25%) and swelling (80 ℃, < 10%) at different temperatures (25, 40, 50, 60, 70, 80 ℃). The membrane has lower water absorption and swelling rate, ensures mechanical properties, and meets the established standard (swelling rate is less than or equal to 10 percent) of the national 2023 anion exchange membrane water electrolysis hydrogen production electrolysis stack technology.
2. Conductivity test
In this experimental example, the anion exchange membrane obtained in example 3 was further subjected to a conductivity test.
The method comprises the steps of testing the conductivity of a branched anion exchange membrane at room temperature by adopting an alternating current impedance method (EIS), measuring by adopting a CHI760e electrochemical workstation, wherein the test frequency is 1Mhz-0.01Hz, in order to reduce the error caused by contact resistance to a measurement result, cutting the membrane into 5mm multiplied by 5mm in an experiment, placing the membrane into a polytetrafluoroethylene clamp for testing at 25 ℃, and finally calculating the ion conductivity sigma of the sample according to the following formula;
σ＝d/（SR）；
wherein d is the thickness (cm) of the electrode membrane and S is the contact area (cm) of the membrane with the electrode 2 ) R is the measured resistance (Ω) of the film.
FIG. 2 is a diagram showing I in the present embodiment - Form of anion exchange membrane b-QPAQ-5% nuclear magnetic resonance hydrogen spectrum.
FIG. 3 is an AFM image of the anion exchange membrane of this example, showing good phase separation inside the polymer.
FIG. 4 shows the ionic conductivities of the anion exchange membranes and QPAP membranes prepared in this example at room temperature. As can be seen, the b-QPAQ-5% membrane has a conductivity of 55.56mS cm at room temperature -1 Conductivity higher than that of QPAP film at the same temperature (20.60 mS cm -1 ) The branched anion exchange membrane on the surface has good application prospect.
Therefore, the three-dimensional structure phenyl monomer has the characteristics of three-dimensional space structure, rigidity, hydrophobicity and the like, and the material can be introduced into the traditional linear structure polymer to obtain larger free volume and reduce the swelling of the membrane, so that the ion conductivity and the dimensional stability of the membrane can be improved.
3. Electrode performance test
The experimental example further performs electrochemical tests on the performance of the electrode formed by the anion exchange membrane.
Taking the b-QPAQ-5% anion exchange membrane prepared in example 3 and anode catalyst NiFe catalyst and cathode catalyst Ni 4 Mo/MoO 2 And assembling a film-forming electrode, installing the film-forming electrode in an AEM electrolytic cell, and performing electrochemical tests at an Autolab electrochemical workstation.
In this experimental example, the anode and cathode catalysts were 1cm by 1cm in size, and the electrolyte solution of the AEM cell was 1M KOH solution.
In the AEM cell assembly process, the electrolyte solution is heated to a specific temperature (25, 40, 50, 60, 70, 80 ℃) by a heating rod, and then the heated electrolyte solution is respectively conveyed to an anode and a cathode of the AEM cell by a peristaltic pump.
Before electrochemical testing, the electrolyte solution is circulated for 20min to ensure the constant temperature of the whole testing system, then the whole electrolytic cell is subjected to scanning activation of a cyclic voltammetry Curve (CV), and after the CV curve is kept stable, the linear voltammetry scanning (LSV) test is performed.
Wherein, the voltage range of LSV test is 1.0-2.6V, the sweeping speed is 10mV/s, and the test temperature (25, 40, 60, 80 ℃).
Subsequently, the AEM cell was tested for alternating current impedance (EIS) at 1.8V at 80℃using a two electrode method, wherein the impedance was tested at a frequency in the range of 100KHz-0.1hz and an amplitude of 10mV at test temperatures (25, 40, 60, 80 ℃).
FIG. 5 is a LSV curve based on the polymer film (b-QPAQ-5%) of example 3 at various temperatures (25, 40, 60, 80 ℃). It can be seen that at 80℃: at 2V overpotential, the current density can reach 8.0A/cm 2 。
FIG. 6 is an EIS curve at 80℃based on the polymer film (b-QPAQ-5%) in example 3. It can be seen that the electrochemical impedance is 0.045Ω at 80 ℃, and has higher current density and lower electrochemical impedance performance, which is superior to most anion exchange membranes in the market at present.
Fig. 7 is a graph showing the long-term device stability results at room temperature for devices assembled according to this example. It can be seen that the operation time in the period exceeds 1000 hours, the device stability is very excellent, the voltage attenuation rate is less than 5.5%, and the method meets the established standard of the national 2023 anion exchange membrane water electrolysis hydrogen production electrolysis reactor technology (the voltage attenuation rate is less than or equal to 10% after 1000 hours of operation).
4. Performance test of anion exchange membrane fuel cell
The experimental example is used for testing the performance of the anion exchange membrane fuel cell prepared by the anion exchange membrane.
Preparation of a membrane electrode: the polymer (co-QPAQ) of Synthesis example 2 was used as the ionic polymer binder for the catalytic layer, the membrane (bQPAQ-5%) obtained in example 3 was used as the anion exchange membrane, the thickness was 50. Mu.m, platinum carbon and platinum ruthenium carbon were used as the cathode and anode catalysts, respectively, and the metal platinum loading was 1mg/cm 2 The mass ratio of the catalyst to the ionic polymer is 4:1, preparing the membrane electrode by adopting a spraying method.
Battery assembly and performance testing: sealing gaskets, graphite flow fields, gold-plated current collectors, insulating gaskets, heating end plates and the like are sequentially assembled on two sides of the membrane electrode to obtain a single cell, and the effective area of the electrode is 1cm 2 . The cathode and the anode of the battery are respectively filled with humidified oxygen and hydrogen (the purity is more than 99 percent, the humidification is 100 percent), the flow is 500mL/min, and after the battery operates stably, the current-voltage polarization curve of the battery under the condition of 60 ℃ is tested.
Fig. 8 is a polarization curve of an anion exchange membrane cell discharge based on the anion exchange membrane assembly in example 3. It can be seen that the open circuit voltage of the battery was 1.01V and the maximum power density was 528mW/cm 2 The corresponding current density was 700mA/cm when the maximum power density was reached 2 The voltage was 0.66V. The single cell maintains good running stability in the observation time interval of the test.
The polymer solution can be used as ionomer to be prepared into catalyst ink together with catalyst, alcohol and water for preparing an anion membrane or a gas diffusion electrode coated by a catalytic layer, so that the stability and durability of the operation of the device can be improved.
In summary, the polyarylquinine polymer provided by the invention has ultrahigh-stability functional cationic groups, so that the polyarylquinine polymer can be used for preparing anion exchange membranes with high stability. In the anion exchange membrane with the structure, the water absorption and the swelling rate of the polymer are regulated and controlled by adding the copolymerized hydrophobic monomer, so that the mechanical strength of the polymer is improved; by adding the crosslinking groups, the polymer obtains larger free volume and reduces the expansion of the membrane, so that the inside of the polymer has more obvious microphase separation, and the aggregation of the cationic groups is also helpful to establish an ion channel with lower transmission resistance; and the polymer has very excellent performance by being applied to alkaline electrolyzed water and fuel cells, and has very important significance for realizing industrial application of AEM electrolyzed water.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (28)
1. A polyarylquinine polymer, wherein the polymer comprises cross-linking group polymeric units comprising a quinuclidine structure and/or linear structure polymeric units comprising a quinuclidine structure;
the cross-linking group polymerization unit containing the quinuclidine structure has a structure shown in the following formula (P1):
；
the quinuclidine structure-containing linear-structure polymeric unit has a structure represented by the following formula (P2):
；
wherein,
the Ar is as follows 1 Is a phenyl structural monomer with a plurality of crosslinking points;
the Ar is as follows 2 Phenyl structural monomers with linear structures.
2. The polyarylene quinine polymer of claim 1, wherein the polymer further comprises linear hydrophobic polymeric units;
the linear hydrophobic polymeric unit has a structure represented by the following formula (P3):
；
Wherein,
the Ar is as follows 2 Phenyl structural monomers which are linear structures;
the R is 1 Is a hydrophobic copolymerized unit.
3. The polyarylene quinine polymer of claim 2, wherein the polymer comprises cross-linking group polymeric units and linear structure polymeric units;
the polymer has a structure represented by the following formula (P):
；
wherein,
the Ar is as follows 1 Is a phenyl structural monomer with a plurality of crosslinking points;
the Ar is as follows 2 Phenyl structural monomers which are linear structures;
the R is 1 Is a hydrophobic copolymerized unit.
4. The polyarylene quinine polymer of claim 3 wherein in the polymer:
x is the molar ratio of the cross-linking group polymeric units in the polymer,%;
y=y n +y m namely the mole ratio of the linear structure polymerization unit in the polymer,%;
wherein x is 0-100%, y is 50% -100%, and x+y=100%.
5. The polyarylene quinine polymer of claim 4, wherein in the linear structural polymeric units:
y n mole ratio of polymerized units containing the quinuclidine structure in the polymer,%;
y m to contain said hydrophobic comonomer R 1 Molar ratio,%;
Wherein y is n 60% -100%, y m 0% -40% and y n +y m ≤100%。
6. The polyarylene quinine polymer of any of claims 1-5, wherein Ar 1 A planar or spatial structure formed by connecting phenyl structural monomers with a plurality of crosslinking points;
the Ar is as follows 1 Wherein the plurality of crosslinking points of the phenyl structural monomer are in a plane or space structure which is uniformly distributed or symmetrically distributed.
7. The polyarylquinine polymer of claim 6, wherein the Ar 1 Wherein the plurality of crosslinking points of the phenyl structural monomer have the same substituted or unsubstituted phenyl structural monomer.
8. The polyarylquinine polymer of claim 7, wherein the Ar 1 At least one of the phenyl structural monomers comprising the structure:
。
9. the polyarylene quinine polymer of any of claims 1-5, wherein Ar 2 Wherein the phenyl structural monomers comprise 2-4 linear linked substituted or unsubstituted phenyl monomers.
10. The polyarylene quinine polymer of claim 9, wherein each of the phenyl monomers is connected by a single bond, an unsaturated bond, or forms a linear cyclic structure.
11. The polyarylquinine polymer of claim 10, wherein the Ar 2 At least one of the phenyl structural monomers comprising the structure:
；
wherein the R is 2 Is a C1-C10 alkyl group.
12. The polyarylene quinine polymer of any of claims 1-5, wherein R 1 Wherein the hydrophobic copolymerization unit comprises a hydrophobic monomer containing an electron withdrawing group structure;
the hydrophobic copolymerized unit includes a substituted or unsubstituted aromatic ring hydrophobic monomer, a substituted or unsubstituted saturated aliphatic hydrophobic monomer, or a substituted or unsubstituted ketone hydrophobic monomer.
13. The polyarylene quinine polymer of claim 12, wherein the hydrophobic co-polymerized units are selected from monomers comprising trifluoromethyl, carbonyl and/or pentafluorobenzene structures.
14. The polyarylquinine polymer of claim 13, wherein R 1 At least one of the hydrophobic co-units comprising the structure:
；
wherein the R is 3 Is alkyl; the R is 4 Is hydrogen, an alkyl chain or an aryl group.
15. A process for preparing the polyarylene quinine polymer of any of claims 3-14, comprising taking phenyl structural monomer Ar having a plurality of cross-links according to the selected structure of the polyarylene quinine polymer 1 Phenyl structural monomer Ar with linear structure 2 3-quininone and hydrophobic comonomer R 1 The method comprises the steps of adding the corresponding ketone monomer into a first solvent, mixing, carrying out polymerization reaction in the presence of a first catalyst, adding a reaction solution into a second solvent, mixing, and collecting precipitated polymer.
16. The method of preparing a polyarylene quinine polymer of claim 15, wherein:
the phenyl structural monomer Ar with a plurality of crosslinking points 1 And the phenyl structural monomer Ar with the linear structure 2 The molar ratio of (1) to (50): (100-50); and/or the number of the groups of groups,
the molar ratio of the phenyl structural monomer with the linear structure to the 3-quininone is 1: (1-1.5); and/or the number of the groups of groups,
the hydrophobic copolymerization unit R 1 The molar ratio of the corresponding ketone monomer to the 3-quininone is (0-0.4): 1, a step of; and/or the number of the groups of groups,
the first solvent comprises at least one of dichloromethane, chloroform or tetrahydrofuran; and/or the number of the groups of groups,
the second solvent comprises at least one of ethyl acetate, methanol, ethanol, diethyl ether, tetrahydrofuran or acetone; and/or the number of the groups of groups,
the volume ratio of the first solvent to the second solvent is 1: (10-30); and/or the number of the groups of groups,
The addition amount of the 3-quininone based on the first solvent is 10-22.5mmol of the 3-quininone added per 10-15mL of the first solvent; and/or the number of the groups of groups,
the washing step comprises the step of adding a first alkali liquor for washing and the step of adding the first alkali liquor for washing; and/or the number of the groups of groups,
the primary alkali solution comprises K 2 CO 3 KOH, naOH or NaHCO 3 At least one of the solutions; and/or the number of the groups of groups,
the drying step comprises the step of vacuum drying at 60-80 ℃; and/or the number of the groups of groups,
the first catalyst comprises trifluoroacetic acid (TFA) and/or trifluoromethanesulfonic acid (TFSA); wherein,
the molar ratio of the trifluoroacetic acid to the 3-quininone is (1-2): 1, a step of;
the molar ratio of the trifluoromethanesulfonic acid to the 3-quininone is (10-20): 1.
17. a quaternized polyarylquinine polymer, wherein the polymer has a structure represented by formula (Q):
；
wherein the Ar is 1 、Ar 2 、R 1 Is as defined in any one of claims 1 to 14;
the R is 5 Including groups having a quaternized structure.
18. The quaternized polyarylquinine polymer of claim 17 wherein R 5 Including alkyl chains of quaternized structures.
19. A process for preparing the quaternized polyarylquinine polymer of claim 17 or 18, comprising the steps of taking the polyarylquinine polymer of any of claims 1-14 into a third solvent and adding a second catalyst and a haloalkane of corresponding structure to effect a quaternization reaction, and adding the reaction solution into a fourth solvent to mix and collect a precipitate, depending on the structure of the quaternized polyarylquinine polymer selected.
20. The method of making a quaternized polyarylquinine polymer of claim 19, wherein:
the solid to liquid ratio of the polyarylquinine polymer and the haloalkane is 1g: (1-3) mL; and/or the number of the groups of groups,
the mass ratio of the polyarylquinine polymer to the second catalyst is (2-3): 1, a step of; and/or the number of the groups of groups,
the second catalyst comprises K 2 CO 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or the number of the groups of groups,
the solid to liquid ratio of the polyarylquinine polymer and the third solvent is 1g: (10-20) mL; and/or the number of the groups of groups,
the third solvent comprises at least one of dimethyl sulfoxide, N-methyl pyrrolidone, N-dimethylformamide or N, N-dimethylacetamide; and/or the number of the groups of groups,
the fourth solvent comprises at least one of ethyl acetate, methanol, ethanol, acetone or diethyl ether; and/or the number of the groups of groups,
The volume ratio of the third solvent to the fourth solvent is 1: (6-10); and/or the number of the groups of groups,
the temperature of the quaternization reaction is 40-60 ℃; and/or the number of the groups of groups,
the drying step includes a step of vacuum drying at 60-80 ℃.
21. A high-stability anion exchange membrane is characterized in that the anion exchange membrane is OH - An anion exchange membrane having a structure represented by the following formula (T):
；
wherein the Ar is 1 、Ar 2 、R 1 The limiting features are as defined in claim 17 or18, and a polymeric quaternary amine.
22. A method of making the high stability anion exchange membrane of claim 21 comprising the steps of:
(1) Adding the quaternized polyarylquinine polymer of claim 17 or 18 into a fifth solvent, mixing, casting onto a substrate surface to obtain a polymer film;
(2) The polymer film is placed in a second alkali solution for immersion to obtain OH - And (3) an anion exchange membrane.
23. The method for preparing a high-stability anion exchange membrane according to claim 22, wherein:
the solid to liquid ratio of the quaternized polyarylquinine polymer to the fifth solvent is 1g: (10-100) mL; and/or the number of the groups of groups,
The fifth solvent comprises at least one of dimethyl sulfoxide, N-methyl pyrrolidone, N-dimethylformamide or N, N-dimethylacetamide; and/or the number of the groups of groups,
the thickness of the polymer film is 20-60 mu m; and/or the number of the groups of groups,
the second alkali solution comprises NaOH and/or KOH solution; and/or the number of the groups of groups,
the temperature of the dipping step is 25-80 ℃ and the dipping time is 8-12h; and/or the number of the groups of groups,
the method further comprises the step of placing the anion exchange membrane in deionized water which is filled with a protective atmosphere for preservation.
24. The process for preparing a highly stable anion exchange membrane according to claim 22 or 23, further comprising the step of preparing the desired quaternized polyarylene quinine polymer according to the process of claim 15 or 16 starting from the polyarylene quinine polymer of any one of claims 1-14.
25. Use of the high stability anion exchange membrane of claim 21 for the preparation of alkaline water electrolysis cells and/or alkaline fuel cells.
26. An alkaline water electrolyzer, an alkaline fuel cell and/or an alkaline fuel cell device prepared from the high stability anion exchange membrane of claim 21.
27. Use of the polyarylquinine polymer of any of claims 1-14 and/or the quaternized polyarylquinine polymer of claim 17 or 18 for preparing an anion exchange membrane.
28. Use of the polyarylquinine polymer of any of claims 1-14 and/or the quaternized polyarylquinine polymer of claim 17 or 18 for preparing a catalytic layer coated anion membrane or gas diffusion electrode.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112552488A (en) * | 2020-05-28 | 2021-03-26 | 合肥工业大学 | Ionomer containing alkali-resistant cation groups and fluorocarbon side chains and preparation method and application thereof |
| KR20220061829A (en) * | 2020-11-06 | 2022-05-13 | 인천대학교 산학협력단 | A copolymer having quaternary ammonium functional group, a polymer membrane comprising the same, an anion exchange membrane comprising the polymer membrane, a fuel cell comprising the anion exchange membrane, and a method for manufacturing the copolymer |
| CN115521445A (en) * | 2022-11-08 | 2022-12-27 | 河北工业大学 | Branched polyaryl piperidine polymer and anion exchange membrane |
| CN116693785A (en) * | 2022-09-20 | 2023-09-05 | 武汉立膜科技有限公司 | Nitrogen-containing heterocyclic polymer, polymer film and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112552488A (en) * | 2020-05-28 | 2021-03-26 | 合肥工业大学 | Ionomer containing alkali-resistant cation groups and fluorocarbon side chains and preparation method and application thereof |
| KR20220061829A (en) * | 2020-11-06 | 2022-05-13 | 인천대학교 산학협력단 | A copolymer having quaternary ammonium functional group, a polymer membrane comprising the same, an anion exchange membrane comprising the polymer membrane, a fuel cell comprising the anion exchange membrane, and a method for manufacturing the copolymer |
| CN116693785A (en) * | 2022-09-20 | 2023-09-05 | 武汉立膜科技有限公司 | Nitrogen-containing heterocyclic polymer, polymer film and application thereof |
| CN115521445A (en) * | 2022-11-08 | 2022-12-27 | 河北工业大学 | Branched polyaryl piperidine polymer and anion exchange membrane |
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