CN118580410A - Cross-linked hydrogen bond enhanced perfluoro conjugated cationic resin, and synthetic method and application thereof - Google Patents
Cross-linked hydrogen bond enhanced perfluoro conjugated cationic resin, and synthetic method and application thereof Download PDFInfo
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- 239000011347 resin Substances 0.000 title claims abstract description 133
- 229920005989 resin Polymers 0.000 title claims abstract description 133
- 239000001257 hydrogen Substances 0.000 title claims abstract description 124
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 124
- -1 perfluoro Chemical group 0.000 title claims abstract description 96
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 63
- 238000010189 synthetic method Methods 0.000 title abstract description 3
- 150000002500 ions Chemical class 0.000 claims abstract description 66
- 239000012528 membrane Substances 0.000 claims abstract description 59
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 50
- 229920000642 polymer Polymers 0.000 claims abstract description 46
- 150000001768 cations Chemical class 0.000 claims abstract description 39
- 238000005342 ion exchange Methods 0.000 claims abstract description 32
- 238000004132 cross linking Methods 0.000 claims abstract description 19
- 230000015556 catabolic process Effects 0.000 claims abstract description 18
- 238000006731 degradation reaction Methods 0.000 claims abstract description 18
- 239000003153 chemical reaction reagent Substances 0.000 claims description 162
- 239000000178 monomer Substances 0.000 claims description 94
- 239000000047 product Substances 0.000 claims description 89
- 238000006243 chemical reaction Methods 0.000 claims description 83
- 239000003011 anion exchange membrane Substances 0.000 claims description 80
- 239000003054 catalyst Substances 0.000 claims description 68
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 45
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical group CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 37
- 239000013067 intermediate product Substances 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000003960 organic solvent Substances 0.000 claims description 32
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 26
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 24
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 230000014759 maintenance of location Effects 0.000 claims description 15
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 14
- 239000000446 fuel Substances 0.000 claims description 14
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 claims description 13
- 125000001424 substituent group Chemical group 0.000 claims description 13
- 238000012360 testing method Methods 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- 229940124530 sulfonamide Drugs 0.000 claims description 10
- 150000003456 sulfonamides Chemical class 0.000 claims description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 125000003368 amide group Chemical group 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- USPTVMVRNZEXCP-UHFFFAOYSA-N sulfamoyl fluoride Chemical compound NS(F)(=O)=O USPTVMVRNZEXCP-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- SPQUPNFNFAQPOF-UHFFFAOYSA-L dipotassium;pyridine;carbonate Chemical compound [K+].[K+].[O-]C([O-])=O.C1=CC=NC=C1 SPQUPNFNFAQPOF-UHFFFAOYSA-L 0.000 claims description 4
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical group FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 3
- 125000005496 phosphonium group Chemical group 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 22
- 230000001105 regulatory effect Effects 0.000 abstract description 15
- 125000003010 ionic group Chemical group 0.000 abstract description 8
- 230000002035 prolonged effect Effects 0.000 abstract description 8
- 230000001276 controlling effect Effects 0.000 abstract description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 6
- 230000003014 reinforcing effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 55
- 239000003513 alkali Substances 0.000 description 24
- RCOVTJVRTZGSBP-UHFFFAOYSA-N 4-(chloromethyl)benzoyl chloride Chemical compound ClCC1=CC=C(C(Cl)=O)C=C1 RCOVTJVRTZGSBP-UHFFFAOYSA-N 0.000 description 23
- 238000001035 drying Methods 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 19
- 238000001308 synthesis method Methods 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 125000000524 functional group Chemical group 0.000 description 13
- 239000010453 quartz Substances 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 12
- 238000007731 hot pressing Methods 0.000 description 12
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- 238000005406 washing Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000004448 titration Methods 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 239000012046 mixed solvent Substances 0.000 description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 9
- 238000009792 diffusion process Methods 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000010907 mechanical stirring Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 229920006317 cationic polymer Polymers 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 6
- 239000005711 Benzoic acid Substances 0.000 description 6
- 239000005703 Trimethylamine hydrochloride Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 235000010233 benzoic acid Nutrition 0.000 description 6
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical compound Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 229920000831 ionic polymer Polymers 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 5
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 125000005997 bromomethyl group Chemical group 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000003014 ion exchange membrane Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- VUYGJYAPDGKPBF-UHFFFAOYSA-N 4-(bromomethyl)benzoyl bromide Chemical compound BrCC1=CC=C(C(Br)=O)C=C1 VUYGJYAPDGKPBF-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 125000002743 phosphorus functional group Chemical group 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical class C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- BGXNGARHYXNGPK-UHFFFAOYSA-N 2-[1-[(4-methoxyphenyl)methylsulfanyl]cyclohexyl]acetic acid Chemical compound C1=CC(OC)=CC=C1CSC1(CC(O)=O)CCCCC1 BGXNGARHYXNGPK-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical group OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000004433 infrared transmission spectrum Methods 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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Abstract
The invention relates to a cross-linking hydrogen bond enhanced perfluoro conjugated cationic resin, a synthetic method and application thereof. The cationic resin of the invention maintains the structural advantage of the perfluorinated ion resin in the chemical structure, and simultaneously adopts a chemical grafting mode to introduce a hydrogen bond reinforcing conjugated structure unit into the structure, so that the density of conjugated electron cloud can be effectively increased, and the degradation of the polymer is weakened or slowed down, thereby improving the chemical stability of the perfluorinated ion polymer. In addition, the C 2 position on the benzene ring connected with the cationic group does not contain beta hydrogen atoms, hoffman degradation can not occur, the degradation of the ionic group is further avoided, and the service life is prolonged. The hydrogen bond conjugated structural unit introduced in the cation resin structure has the function of regulating and controlling the ion exchange capacity of the perfluorinated ion polymer, and the perfluorinated ion polymer and the exchange membrane thereof can simultaneously realize the purpose of effectively regulating and controlling the ion exchange capacity and chemical stability.
Description
The invention is provided with the application number 202111552662.6, the application date 2021-12-17 and the name of a kind of hydrogen bond enhancement
Perfluoro conjugated cationic resin, its synthesis process, anion exchange membrane and its application
Technical Field
The invention relates to the field of high polymer materials, relates to a perfluorinated cation exchange resin, a synthesis method and application thereof, in particular to a crosslinked hydrogen bond enhanced perfluorinated conjugated cation resin, a synthesis method and application thereof.
Background
The cationic polymer is a high molecular functional material capable of conducting and exchanging anionic groups, and one of important applications is to prepare an Anionic Exchange Membrane (AEM) which is used in the fields of fuel cells, electrodialysis, bipolar membranes, alkaline electrolyzed water and chemical high-efficiency separation. AEM is required to have high chemical stability and ion conductivity as a core member of the above electrochemical device. However, at present, compared with perfluorinated sulfonic acid proton exchange membranes, AEMs have the common problem of low ionic conductivity, and the performance of AEMs cannot meet the requirements on the ionic membranes in the application process, so that the development of AEMs is greatly limited.
Currently, conventional comb-type cationic polymers are all implemented based on hydrocarbon-type cationic polymers, such as comb-type polyethersulfones (chinese patent document CN106893103 a), comb-type polyphenylene ethers (j.mater. Chem. A,2018,6,15456-1547; adv. Funct. Mater.,2018,28,1702758), or comb-type polystyrene (j.membr. Sci.,2017,536,133-140). However, as a traditional main chain, polysulfone, polyether and polyether ketone contain a large number of hydrocarbon bonds, such as-CH 3、-CH2 -, -C-O and the like, and under the condition of high-temperature alkali, an ion-delocalized beta hydrogen atom can be attacked by hydroxyl ions to generate Hoffman degradation, so that the AEMs membrane is degraded and failed. At present, no commercial AEMs membrane exists, so that the development of cationic polymers with high stability and high ionic conductivity and AEMs is an urgent problem to be solved.
The proton exchange membrane widely used at present is a perfluorosulfonic acid polymer proton exchange membrane which is invented by Dupont in last century 70, and the molecular structure of the proton exchange membrane comprises a perfluoro main chain skeleton- (CF 2CF2)m-(CF2 CF) n-, and a perfluoroether structure side chain taking a sulfonic acid group (-SO 3 H) as a terminal group. While (CF 2CF2)m-(CF2CF)n -has superior chemical stability under alkaline conditions) and is successfully applied by PFSA, researchers have tried to synthesize cationic polymers such as (J.Mater.Chem.,2011,21,6158;J.Mater.Chem.,2013,1,1018-1021;J.Polym.Sci.,Part B:Polym.Phys.,2019,57,700-712) by using perfluorosulfonyl fluoride precursor (PFSO 2F、Nafion-SO2 F.) on the one hand, since perfluorosulfonyl fluoride precursor is not dissolved in a conventional solvent, the reaction process is based on solid-liquid reaction, and the reaction degree is difficult to control, on the other hand, since the perfluorobackbone has superior electron withdrawing capability, the ionic groups of the side groups are more likely to be attacked by hydroxyl groups to be chemically degraded, and the ion conductivity is lost (J.Member. Sci., J.4,467:136-141; J.Mater. Chem. A.,2013,1 1018-1021). A great amount of manpower and materials are being put into study in the major countries at present, the PFSO 2F、Nafion-SO2 F-based perfluorocationic resins cannot meet the requirements of anion conductivity, alkali resistance, temperature resistance and the like, especially at high concentration of S/S far below 0.1 cm.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a hydrogen bond enhanced perfluoro conjugated cationic resin and a synthesis method thereof, wherein the perfluoro conjugated cationic resin retains the structural advantages of perfluoro ionic polymers in chemical structure, and simultaneously adopts a chemical grafting mode to introduce a hydrogen bond enhanced conjugated unit into the structure, thereby effectively increasing the power supply capacity of a side chain and reducing the electron withdrawing capacity of a perfluoro structure; in addition, the C 2 position connected with the cationic group does not contain beta hydrogen atoms, hoffman degradation does not occur, and the chemical stability of the ionic group is further enhanced. In addition, the hydrogen bond can enhance the acting force between ionic groups, increase the size of the ion clusters and greatly improve the ionic conductivity. Thus, the obtained perfluorinated ion polymer can simultaneously realize the purpose of effectively regulating and controlling the ion conductivity and the chemical stability.
The invention also provides an anion exchange membrane for the fuel cell, which is prepared from the hydrogen bond enhanced perfluoro conjugated cationic resin, the obtained anion exchange membrane has higher chemical stability and good ion conductivity, and the introduction of the hydrogen bond can effectively enhance the electron supply capacity of a side chain, so that the electron withdrawing capacity of a main chain is weakened or slowed down, the service life of the ion membrane is prolonged, and an important membrane material is provided for further research and application of the fuel cell.
The aim of the invention can be achieved by the following technical scheme:
the structural unit of the perfluorinated conjugated cationic resin with hydrogen bond enhancement is as follows:
The structural units of formula (I) include a unit a (hydrogen bond enhancing conjugated structural unit) and a unit B (conjugated cationic unit); the A unit and the B unit both contain perfluoro ether groups and amide groups, both can form hydrogen bonds, both contain pi-pi conjugated structures, and the B unit also contains cationic groups; wherein, R 1～R5 groups in the A unit are-H, -CH 3、-O-CH3, -Ph (Ph represents one of benzene rings )、-O-Ph、-PhCH3、-OH、-CH2CH3、-(CH3)3C、-(CH3)2HC, and R 1～R5 are the same or different groups);
The R 11～R55 in the B unit contains 1 cationic group, and the position C 2 (the carbon atom connected with the cationic group is C 1, and the carbon atom adjacent to C 1 is C 2) on the benzene ring connected with the cationic group does not contain beta hydrogen atoms; the remaining substituents on the phenyl ring other than the cationic group are each independently-H, -CH 3、-O-CH3, -Ph (Ph represents one of phenyl rings )、-O-Ph、-OH、-PhCH3、-CH2CH3、-(CH3)3C、-(CH3)2HC;
m is an integer of 0 to 10, preferably m is an integer of 0 to 3; n is an integer of 1 to 6, preferably n is an integer of 1 to 3; most preferably, m=0, 1; n=2;
x is an integer of 1 to 30; y/(y+z) =0 to 0.5, preferably y/(y+z) =0 to 0.3; z/(y+z) =0.5 to 1.0, and preferably z/(y+z) =0.7 to 1.0.
Preferably, the R 1～R5 groups are all-H and the R 33 groups areR 11、R22、R44、R55 are H.
The hydrogen bond refers to a hydrogen bond formed between amides (-CONH-); the conjugation refers to pi-pi conjugation on benzene ring; the A units and the B units can form a hydrogen bond enhanced conjugated network structure, and the hydrogen bond enhanced conjugated network structure can be formed among the A units, the B units, the A units and the B units and between molecules or between molecules of the perfluorinated conjugated cation resin.
The hydrogen bond enhanced conjugated network structure is shown as a formula II:
The structure of the perfluoro ether group is shown in a formula III:
Wherein m in III structure is an integer from 0 to 10, preferably m is an integer from 0 to 3; n is an integer of 1 to 6, preferably n is an integer of 1 to 3; most preferably, m=0, 1; n=2.
Preferably, the cationic group structure contains one or more of the following structures:
Further preferred, the cationic group is of the structure of one of formula V:
in the cation resin provided by the invention, the formed hydrogen bond enhanced conjugated network can increase the density of conjugated electron cloud, weaken the electron withdrawing effect of the perfluoro units of the main chain and the side chain, weaken the attack of hydroxyl ions and prolong the service life of the ion membrane.
According to the present invention, the number average molecular weight of the perfluorinated ion polymer represented by formula (I) is preferably 20 to 100 ten thousand, more preferably 20 to 60 ten thousand, and most preferably 30 to 50 ten thousand.
In the invention, the perfluoro conjugated cationic resin shown in the formula (I) has the following advantages: (1) retaining a super-stable dominant unit- (CF 2CF2)x -) of the perfluorinated ion polymer, and ensuring sufficient chemical stability of the polymer; the invention has the advantages that (2) the end groups of the side chains of the perfluorinated ion polymer are utilized for chemical grafting, the introduced hydrogen bond enhanced conjugated structural unit can effectively increase the density of conjugated electron cloud, weaken or slow down the degradation of the polymer, and (3) the C 2 position connected with the cationic group does not contain beta hydrogen atoms and cannot be subjected to Hoffman degradation, so that the degradation of the ionic group is further avoided, the service life is prolonged, (4) the hydrogen bond enhanced conjugated network can enhance the acting force between the ionic groups, increase the size of an 'ion cluster', and greatly improve the ionic conductivity.
The invention also provides a synthesis method of the perfluoro conjugated cationic resin with the hydrogen bond enhancement function, and the perfluoro sulfonamide polymer (PFSO 2NH2), the N monomer reagent containing carbonyl groups and the H reagent are subjected to grafting reaction in an organic solvent under the action of a catalyst.
Preferably, the synthesis method of the perfluorinated conjugated cation resin with hydrogen bond enhancement is selected from one of the following methods:
The synthesis method comprises the following steps: (1) Performing grafting reaction on a perfluorinated sulfonamide polymer (PFSO 2NH2) and an M monomer reagent containing a carbonyl group in an organic solvent under the action of a catalyst to obtain an intermediate product;
(2) And (3) grafting the obtained intermediate product with an N monomer reagent containing carbonyl groups and an H reagent in an organic solvent to obtain the hydrogen bond enhanced perfluoro conjugated cation resin.
The synthesis method II comprises the following steps: (1) Performing grafting reaction on a perfluorinated sulfonamide polymer (PFSO 2NH2), a carbonyl group-containing N monomer reagent and an H reagent in an organic solvent to obtain an intermediate product;
(2) And (3) grafting the intermediate product and an M monomer reagent containing carbonyl groups in an organic solvent under the action of a catalyst to obtain the hydrogen bond enhanced perfluoro conjugated cation resin.
Preferably, the structure of the M reagent is as shown in formula VI:
Wherein, in the formula VI, the R 1～R5 group is as shown in the formula I; r x is one of-F, -Cl, -H, -Br and-OH;
Preferably, the R x groups are Cl, -Br, -OH.
The structure of the N reagent is shown in a formula VII:
Wherein, rxx group in the formula VII is one of-F, -Cl, -H, -Br and-OH; the R 111～R555 group contains at least one chloromethyl (-CH 2 Cl) or bromomethyl (-CH 2 Br) group, the remaining substituents are-H, -CH 3、-O-CH3, -Ph (Ph represents one of the benzene rings )、-O-Ph、-OH、-PhCH3、-CH2CH3、-(CH3)3C、-(CH3)2HC).
Preferably, R xx is-Cl, -Br, -OH.
The reagent H is a reagent containing one or more tertiary amine or tertiary phosphorus structures, and the structural general formula of the reagent H is as follows;
preferably, the structure of the H reagent in the invention is selected from one of the structures shown in formula VIII:
According to a preferred embodiment of the invention, the preparation of the perfluorinated sulfonamide polymer (PFSO 2NH2) is described in patents CN201510270702.6 and CN 201510094960.3.
According to the invention, the catalyst is preferably one of trimethylamine, N-diisopropylethylamine, 4-dimethylaminopyridine, triethanolamine, tetrabutylammonium bromide, triethylamine, alCl 3, pyridine potassium carbonate, ammonium carbonate and sodium carbonate.
According to a preferred embodiment of the present invention, the organic solvent is at least one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, toluene, methylene chloride, chloroform, tetrahydrofuran, ethanol, isopropanol, dimethyl sulfoxide, or ethyl acetate. Preferably, the organic solvent is one of N, N-dimethylformamide and N, N-dimethylacetamide.
According to the invention, the molar ratio of N monomer reagent to H reagent is preferably 1: 8-10.
According to a preferred embodiment of the invention, the molar ratio of the M monomer reagent to the catalyst is 1:3 to 15.
According to the invention, the grafting reaction is carried out at a temperature of 15 to 150 ℃, preferably 60 to 150 ℃; the reaction time is 1 to 48 hours, preferably 8 to 15 hours. Preferably, the reaction temperature of the grafting M monomer reagent is 60-80 ℃, the time is 9-11 h, and the reaction temperature of the grafting N monomer reagent is 80-150 ℃ and the reaction time is 10-15 h.
According to the invention, the catalyst is preferably added in step (1) or step (2) when the perfluorosulfonamide polymer (PFSO 2NH2) or intermediate product is reacted with the N monomer reagent and H reagent.
According to the invention, the molar ratio of PFSO 2NH2 to the M monomer reagent or N monomer reagent in step (1) is preferably 1:5 to 15. Preferably, the molar ratio of PFSO 2NH2 to M monomer reagent in step (1) is 1:7-13; 1:10 of PFSO 2NH2 to N monomer reagent.
In the step (2), the mol ratio of the intermediate product to the N monomer reagent or the M monomer reagent is 1:5-15, and the mol ratio of the N monomer reagent to the H monomer reagent is 1:3-15. Preferably, in step (2), the molar ratio of intermediate to M monomer reagent is 1:10; in the step (2), the molar ratio of the intermediate product to the N monomer reagent is 1:10;
according to the invention, the mass-volume ratio of PFSO 2NH2 to the organic solvent in the step (1) is preferably 1:1-30 g/mL; further preferably 1:1 to 25g/mL; most preferably 1:1 to 20g/mL. In the step (2), the mass-volume ratio of the intermediate product to the organic solvent is 1: 1-120 g/mL.
Preferably, the ionic resin obtained in the step (2) may be optionally subjected to alkali treatment. And (3) selecting whether to adopt alkali treatment to complete ion exchange according to the ion type of the carried cation clusters of the ion resin obtained in the step (2). When the ion type is Cl -、Br-、I-, the alkali treatment exchange can be performed to OH -.
According to the invention, the alkali treatment process in the step (2) is preferably that the obtained ion resin is soaked in a 2M KOH solution for 24-48 hours, so that the ion pair is completely converted into OH -.
The prepared hydrogen bond enhanced perfluoro conjugated cationic resin can determine the ion exchange capacity and the ratio of A, B units by acid-base titration. According to the requirements of product performance, the grafting rate of the reaction can be regulated and controlled by regulating and controlling the reaction time, the reaction temperature, the material proportion and the like in the steps (1) and (2), so that the ion exchange capacity of the perfluorinated ion polymer and the ratio of the two units are regulated and controlled.
Preferably, the synthesis method of the perfluorinated conjugated cation resin with hydrogen bond enhancement comprises the following steps:
Performing grafting reaction on a perfluorinated sulfonamide polymer (PFSO 2NH2) and an M monomer reagent containing carbonyl groups under the action of a catalyst to graft a hydrogen bond enhanced conjugated unit, performing grafting reaction in an organic reagent, washing the obtained product with the reagent, drying, and marking the product as an intermediate product M 1;
the reaction formula is as follows:
(II) grafting the intermediate product M 1 obtained in the step (I), an N monomer reagent and an H reagent to graft a conjugated cation unit, performing grafting reaction in an organic reagent, washing the obtained product with the reagent, and drying to obtain the hydrogen bond enhanced perfluoro conjugated cation resin;
chloromethyl group in N monomer structure and tertiary ammonia in H reagent structure in reaction process Or tertiary phosphorusThe groups react to produce quaternary ammoniaOr quaternary phosphorusThe reaction formula is as follows:
According to the invention, the washing in the step (I) is carried out by adopting absolute ethyl alcohol and chloroform, and the drying is carried out for 18-36 hours at 55-65 ℃.
Preferably, the synthesis method of the perfluorinated conjugated cation resin with hydrogen bond enhancement comprises the following steps:
① The perfluoro sulfonamide polymer (PFSO 2NH2), N monomer reagent and H reagent are grafted with conjugated cation unit through grafting reaction, grafting reaction is carried out in organic reagent, and the obtained product is dried after being washed by the reagent and is recorded as intermediate product N 1; chloromethyl group in N monomer structure and tertiary ammonia in H reagent structure in reaction process Or tertiary phosphorusThe groups react to produce quaternary ammoniaOr quaternary phosphorusThe reaction formula is as follows:
② Grafting reaction is carried out on the intermediate product N 1 obtained in the step (1) and an M monomer reagent under the action of a catalyst so as to graft a hydrogen bond enhancement conjugated unit, the grafting reaction is carried out in an organic reagent, and the obtained product is washed by the reagent and dried to obtain the hydrogen bond enhancement type perfluorinated conjugated cation resin, wherein the reaction formula is as follows:
A perfluorinated conjugated cationic resin with enhanced crosslinking hydrogen bond is characterized in that a perfluorinated main chain is connected with a perfluorinated ether group, an amide group and a side chain of a benzene ring conjugated structure, wherein the benzene ring conjugated structure of one side chain contains a cationic group; the benzene ring conjugated structure is connected with an amide group through a carbonyl group; the conjugated structure of the benzene ring on at least one side chain contains at least two carbonyl groups directly connected with the benzene ring.
Preferably, the number of carbonyl groups directly connected with the benzene ring conjugated structure is 2-3.
Preferably, the carbonyl group directly attached to the conjugated structure of the benzene ring is attached at any carbon atom position of the benzene ring. Further preferably, the number of carbonyl groups directly bonded to the conjugated structure of the benzene ring is two, and the carbonyl groups are bonded to the para position of the benzene ring.
Preferably, the structure of the cross-linked hydrogen bond enhanced perfluoro conjugated cationic resin is shown in the following formula (1), (2) or (3):
By adopting the preparation method, the M, N monomer reagent contains two or more than two-COCl, -COBr, -COOH functional groups in the structure, and the H reagent contains a tertiary ammonia or tertiary phosphorus group.
Preferably, the M monomer reagent used in the structure of formula (1) contains two of the above-mentioned functional groups, the N monomer reagent used in the structure of formula (2) contains two of the above-mentioned functional groups, and the monomer reagent M, N used in the structure of formula (3) contains two functional groups, respectively.
The synthesis method of the cross-linking hydrogen bond enhanced perfluoro conjugated cationic resin is selected from one of the following methods:
The synthesis method comprises the following steps: (1) Performing grafting reaction on a perfluorinated sulfonamide polymer (PFSO 2NH2) and an M monomer reagent containing a carbonyl group in an organic solvent under the action of a catalyst to obtain an intermediate product;
(2) And (3) grafting the obtained intermediate product with an N monomer reagent containing carbonyl groups and an H reagent in an organic solvent to obtain the cross-linking hydrogen bond enhanced perfluoro conjugated cationic resin.
The synthesis method II comprises the following steps: (1) Performing grafting reaction on a perfluorinated sulfonamide polymer (PFSO 2NH2), a carbonyl group-containing N monomer reagent and an H reagent in an organic solvent to obtain an intermediate product;
(2) And (3) grafting the intermediate product and an M monomer reagent containing carbonyl groups in an organic solvent under the action of a catalyst to obtain the cross-linking hydrogen bond enhanced perfluoro conjugated cationic resin.
Preferably, the structure of the M reagent is shown in a formula VI, wherein the R 1～R5 group in the formula VI contains a-COCl, -COBr, -COOH functional group, and other groups are the same as the formula I; r x is one of-F, -Cl, -H, -Br and-OH; preferably, the R x groups are Cl, -Br, -OH.
The structure of the N reagent is shown in a formula VII:
Wherein, rxx group in the formula VII is one of-F, -Cl, -H, -Br and-OH; the R 111～R555 group contains a chloromethyl (-CH 2 Cl) or bromomethyl (-CH 2 Br) group, contains a-COCl, -COBr, -COOH functional group, and the remaining substituents are-H, -CH 3、-O-CH3, -Ph (Ph represents one of the benzene rings )、-O-Ph、-OH、-PhCH3、-CH2CH3、-(CH3)3C、-(CH3)2HC. Preferably, R xx is-Cl, -Br, -OH.
The reagent H is a reagent containing a tertiary amine or tertiary phosphorus structure, and the structural general formula of the reagent H is as follows;
in the invention, the structure of the H reagent is one of structures shown in a formula VIII.
According to the invention, the catalyst is preferably one of trimethylamine, N-diisopropylethylamine, 4-dimethylaminopyridine, triethanolamine, tetrabutylammonium bromide, triethylamine, alCl 3, pyridine potassium carbonate, ammonium carbonate and sodium carbonate.
According to a preferred embodiment of the present invention, the organic solvent is at least one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, toluene, methylene chloride, chloroform, tetrahydrofuran, ethanol, isopropanol, dimethyl sulfoxide, or ethyl acetate. Preferably, the organic solvent is one of N, N-dimethylformamide and N, N-dimethylacetamide.
According to the invention, the molar ratio of N monomer reagent to H reagent is preferably 1: 8-10.
According to a preferred embodiment of the invention, the molar ratio of the M monomer reagent to the catalyst is 1:3 to 15.
According to the invention, the grafting reaction is carried out at a temperature of 15 to 150 ℃, preferably 60 to 150 ℃; the reaction time is 1 to 48 hours, preferably 8 to 15 hours. Preferably, the reaction temperature of the grafting M monomer reagent is 60-80 ℃, the time is 9-11 h, and the reaction temperature of the grafting N monomer reagent is 80-150 ℃ and the reaction time is 10-15 h.
According to the invention, the catalyst is preferably added in step (1) or step (2) when the perfluorosulfonamide polymer (PFSO 2NH2) or intermediate product is reacted with the N monomer reagent and H reagent.
According to the invention, the molar ratio of PFSO 2NH2 to the M monomer reagent or N monomer reagent in step (1) is preferably 1:5 to 15. Preferably, the molar ratio of PFSO 2NH2 to M monomer reagent in step (1) is 1:7-13; 1:10 of PFSO 2NH2 to N monomer reagent.
In the step (2), the mol ratio of the intermediate product to the N monomer reagent or the M monomer reagent is 1:5-15, and the mol ratio of the N monomer reagent to the H monomer reagent is 1:3-15. Preferably, in step (2), the molar ratio of intermediate to M monomer reagent is 1:10; in the step (2), the molar ratio of the intermediate product to the N monomer reagent is 1:10;
according to the invention, the mass-volume ratio of PFSO 2NH2 to the organic solvent in the step (1) is preferably 1:1-30 g/mL; further preferably 1:1 to 25g/mL; most preferably 1:1 to 20g/mL. In the step (2), the mass-volume ratio of the intermediate product to the organic solvent is 1: 1-120 g/mL.
Preferably, the ionic resin obtained in the step (2) may be optionally subjected to alkali treatment. And (3) selecting whether to adopt alkali treatment to complete ion exchange according to the ion type of the carried cation clusters of the ion resin obtained in the step (2). When the ion type is Cl -、Br-、I-, the alkali treatment exchange can be performed to OH -.
According to the invention, the alkali treatment process in the step (2) is preferably that the obtained ion resin is soaked in a 2M KOH solution for 24-48 hours, so that the ion pair is completely converted into OH -.
The hydrogen bond enhanced crosslinked perfluoro conjugated multi-cation group resin has a repeating unit structure containing 2-3 side chains of benzene ring conjugated structures, wherein the benzene ring conjugated structures are connected through two quaternary ammonium or quaternary phosphonium structures; the benzene ring conjugated structure is connected with the amide group through carbonyl.
Preferably, the number of carbonyl groups directly connected with the benzene ring conjugated structure is 2-3.
Preferably, the carbonyl group directly attached to the conjugated structure of the benzene ring is attached at any carbon atom position of the benzene ring. Further preferably, the number of carbonyl groups directly bonded to the conjugated structure of the benzene ring is two, and the carbonyl groups are bonded to the para position of the benzene ring.
Preferably, the structure of the hydrogen bond enhanced crosslinked perfluorinated conjugated cationic resin is shown in the following formula (1) or (2):
By adopting the preparation method, the N reagent contains a-CH 2Cl、-CH2 Br group and a-COBr, -COH, -COCl and-COOH functional group; the H reagent contains two or more tertiary ammonia or tertiary phosphorus groups, and the M reagent contains 1 or more functional groups of-COBr, -COH, -COCl and-COOH.
Preferably, the M monomer reagent and the N reagent used in the structure of the formula (1) respectively contain 1 functional group with carbonyl, the N reagent contains a-CH 2 Cl or-CH 2 Br group, and the H reagent contains two functional groups of tertiary ammonia or tertiary phosphorus; the M monomer reagent used in the structure of the formula (2) contains 2 functional groups with carbonyl groups, the N reagent contains 1 functional group with carbonyl groups and one-CH 2 Cl or-CH 2 Br group, and the H reagent contains two functional groups of tertiary ammonia or tertiary phosphorus.
In addition, a cross-linked network structure can be formed between the A units and between the B units and the B units.
The synthesis method of the hydrogen bond enhanced crosslinked perfluorinated conjugated cationic resin is selected from one of the following methods:
The synthesis method comprises the following steps: (1) Performing grafting reaction on a perfluorinated sulfonamide polymer (PFSO 2NH2) and an M monomer reagent containing a carbonyl group in an organic solvent under the action of a catalyst to obtain an intermediate product;
(2) And (3) grafting the obtained intermediate product with an N monomer reagent containing carbonyl groups and an H reagent in an organic solvent to obtain the hydrogen bond enhanced crosslinking perfluorinated conjugated cation resin.
The synthesis method II comprises the following steps: (1) Performing grafting reaction on a perfluorinated sulfonamide polymer (PFSO 2NH2), a carbonyl group-containing N monomer reagent and an H reagent in an organic solvent to obtain an intermediate product;
(2) And (3) grafting the intermediate product and an M monomer reagent containing carbonyl groups in an organic solvent under the action of a catalyst to obtain the hydrogen bond enhanced crosslinking perfluorinated conjugated cation resin.
Preferably, the structure of the M reagent is shown as a formula VI, wherein R 1～R5 in the formula VI contains 0-1-COCl, -COBr, -COOH groups, and other groups are shown as a formula I; r x is one of-F, -Cl, -H, -Br and-OH; preferably, the R x groups are Cl, -Br, -OH.
The structure of the N reagent is shown as a formula VII, wherein Rxx groups in the formula VII are one of-F, -Cl, -H, -Br and-OH; the R 111～R555 group contains a chloromethyl (-CH 2 Cl) or bromomethyl (-CH 2 Br) group, the remaining substituents are-H, -CH 3、-O-CH3, -Ph (Ph represents one of the benzene rings )、-O-Ph、-OH、-PhCH3、-CH2CH3、-(CH3)3C、-(CH3)2HC. Preferably, R xx is-Cl, -Br, -OH.
The H reagent is a reagent containing a plurality of (2-3) tertiary amines or tertiary phosphorus structures, and the structural general formula is shown in the specification;
According to the invention, the catalyst is preferably one of trimethylamine, N-diisopropylethylamine, 4-dimethylaminopyridine, triethanolamine, tetrabutylammonium bromide, triethylamine, alCl 3, pyridine potassium carbonate, ammonium carbonate and sodium carbonate.
According to a preferred embodiment of the present invention, the organic solvent is at least one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, toluene, methylene chloride, chloroform, tetrahydrofuran, ethanol, isopropanol, dimethyl sulfoxide, or ethyl acetate. Preferably, the organic solvent is one of N, N-dimethylformamide and N, N-dimethylacetamide.
According to the invention, the molar ratio of N monomer reagent to H reagent is preferably 1: 8-10.
According to a preferred embodiment of the invention, the molar ratio of the M monomer reagent to the catalyst is 1:3 to 15.
According to the invention, the grafting reaction is carried out at a temperature of 15 to 150 ℃, preferably 60 to 150 ℃; the reaction time is 1 to 48 hours, preferably 8 to 15 hours. Preferably, the reaction temperature of the grafting M monomer reagent is 60-80 ℃, the time is 9-11 h, and the reaction temperature of the grafting N monomer reagent is 80-150 ℃ and the reaction time is 10-15 h.
According to the invention, the catalyst is preferably added in step (1) or step (2) when the perfluorosulfonamide polymer (PFSO 2NH2) or intermediate product is reacted with the N monomer reagent and H reagent.
According to the invention, the molar ratio of PFSO 2NH2 to the M monomer reagent or N monomer reagent in step (1) is preferably 1:5 to 15. Preferably, the molar ratio of PFSO 2NH2 to M monomer reagent in step (1) is 1:7-13; 1:10 of PFSO 2NH2 to N monomer reagent.
In the step (2), the mol ratio of the intermediate product to the N monomer reagent or the M monomer reagent is 1:5-15, and the mol ratio of the N monomer reagent to the H monomer reagent is 1:3-15. Preferably, in step (2), the molar ratio of intermediate to M monomer reagent is 1:10; in the step (2), the molar ratio of the intermediate product to the N monomer reagent is 1:10;
according to the invention, the mass-volume ratio of PFSO 2NH2 to the organic solvent in the step (1) is preferably 1:1-30 g/mL; further preferably 1:1 to 25g/mL; most preferably 1:1 to 20g/mL. In the step (2), the mass-volume ratio of the intermediate product to the organic solvent is 1: 1-120 g/mL.
Preferably, the ionic resin obtained in the step (2) may be optionally subjected to alkali treatment. And (3) selecting whether to adopt alkali treatment to complete ion exchange according to the ion type of the carried cation clusters of the ion resin obtained in the step (2). When the ion type is Cl -、Br-、I-, the alkali treatment exchange can be performed to OH -.
According to the invention, the alkali treatment process in the step (2) is preferably that the obtained ion resin is soaked in a 2M KOH solution for 24-48 hours, so that the ion pair is completely converted into OH -.
The use of the three types of hydrogen bond enhanced perfluorinated conjugated cationic resins in one or more of the following: 1) Use in the manufacture of ion exchange membranes in fuel cells or electrolysers; 2) Preparing an anion exchange membrane application and a membrane electrode for alkaline electrolysis water; 3) Use in electrodialysis; 4) Application in sea water desalination; 5) Application to antibacterial materials; 6) The application in preparing the membrane electrode for the fuel cell; 7) The application in sewage treatment.
The invention also provides a hydrogen bond enhanced perfluoro conjugated anion exchange membrane, and the anion exchange membrane component comprises the hydrogen bond enhanced perfluoro conjugated cation resin.
According to the invention, the anion exchange membrane has an ion exchange capacity of 0.8-1.9 mmol/g, an ion conductivity of 50-200 mS/cm, a thermal degradation temperature of 280-320 ℃ and an ion conductivity retention rate of more than 90% after a 6M KOH decay test for 500 h.
The preparation method of the anion exchange membrane comprises the following steps:
dissolving the hydrogen bond enhanced perfluoro conjugated cation resin in an organic solvent to prepare perfluoro conjugated ion resin solution, and directly preparing an anion exchange membrane by adopting a solution casting method;
according to the invention, the concentration of the perfluorinated conjugated cation resin solution is preferably 2-20wt%, preferably 2-15wt%.
According to the present invention, the organic solvent is preferably at least one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, ethanol, an ethanol/water mixed solvent, an isopropanol/water mixed solvent, dimethylsulfoxide, or ethyl acetate.
Further preferably, the volume ratio of the ethanol to the water in the ethanol/water mixed solvent is 8-9:1-2; the volume ratio of the isopropanol to the water in the isopropanol/water mixed solvent is 8-9:1-2.
According to the present invention, preferably, the solution casting method comprises the steps of: coating the perfluoro conjugated cation resin solution on a quartz surface dish, pre-drying at 80-90 ℃, drying at 140-150 ℃ for 90-100 min, taking out and demoulding.
According to the invention, when the anion exchange membrane is prepared, the ionic conductivity and the chemical stability of the anion exchange membrane can be regulated and controlled by regulating the A, B unit ratio in the perfluorinated conjugated cation resin according to the requirement of product performance, so that the service life of the anion exchange membrane is regulated and controlled.
The invention also provides a membrane electrode applied to alkaline electrolyzed water and fuel cells, and the catalyst mixture component of the catalyst layer of the membrane electrode comprises the perfluoro conjugated ion resin with hydrogen bond enhancement.
The preparation method of the membrane electrode comprises the following steps:
(1) Dissolving the hydrogen bond enhanced perfluoro conjugated cationic resin in a water/alcohol mixed solvent to prepare a solution with the weight percent of 2-15%, then adding a Pt/C or IrO 2 catalyst into the solution, and dispersing to obtain a catalyst mixture;
(2) Spraying the catalyst mixture onto the gas diffusion layer subjected to the hydrophobic treatment by using a spray gun to form a catalytic layer, and performing heat treatment to obtain an electrode layer;
(3) And placing electrode layers with proper cutting sizes on the upper side and the lower side of the anion exchange membrane, and performing hot pressing treatment to obtain the membrane electrode.
According to the invention, the alcohol in the water/alcohol mixed solvent in the step (1) is ethanol or isopropanol, and the volume ratio of water to alcohol is 1-2:8-9.
According to the invention, in the step (1), the ultrasonic dispersion is carried out, and the ultrasonic time is 30-200 min.
According to a preferred embodiment of the present invention, in the step (1), the concentration of the perfluoro conjugated cation resin solution is 2 to 15wt%.
According to the present invention, preferably, the temperature of the heat treatment in step (2) is: the temperature is 80-130 ℃ and the time is 30-200 min.
According to the invention, the dry weight content of IrO 2 or Pt/C in the catalytic layer in step (2) is preferably 2.5mg/cm 2 or 0.4mg/cm 2, respectively, and the dry weight content of the hydrogen bond enhanced perfluoro conjugated cationic resin is 1.5mg/cm 2.
According to a preferred embodiment of the present invention, the anion exchange membrane in step (3) is an anion exchange membrane or other anion exchange membrane as described above in the present invention.
According to the invention, the pressure of the hot pressing treatment in the step (3) is 0.1-5 MPa, the hot pressing temperature is 80-140 ℃, and the hot pressing treatment time is 30-150 s.
According to the invention, the chemical stability of the membrane electrode can be regulated and controlled by regulating and controlling the A, B unit proportion in the perfluorinated conjugated cation resin according to the requirements of product performance, so that the service life of the membrane electrode can be regulated and controlled.
The beneficial effects are that:
compared with the prior perfluorinated cationic polymers (CN 201510270702.6 and CN 201510094960.3), the hydrogen bond enhanced perfluorinated conjugated cationic resin, the synthesis method thereof, the anion exchange membrane and the membrane electrode provided by the invention have the following advantages:
(1) The hydrogen bond-enhanced conjugated network introduced in the polymer structure can effectively increase the density of conjugated electron cloud and weaken or slow down the degradation of the polymer;
(2) The C 2 position on the benzene ring connected with the cationic group does not contain beta hydrogen atoms, hoffman degradation does not occur, the degradation of the ionic group is further avoided, and the service life is prolonged.
(3) The hydrogen bond enhanced conjugated network can enhance acting force among ionic groups, increase the size of an ion cluster and greatly improve the ionic conductivity.
(4) The cation resin synthesized by the invention has wide application, and can be used for preparing an anion exchange membrane and a corresponding membrane electrode to be applied to fuel cells and alkaline electrolyzed water.
(5) The A, B units in the perfluoro conjugated cation resin can regulate and control the ion conductivity and chemical stability of the anion exchange membrane, thereby regulating and controlling the service life of the anion exchange membrane.
(6) The perfluoro conjugated cation resin prepared by the invention can prepare corresponding ion exchange membranes and membrane electrodes; in the polymer synthesis process, A, B units can be effectively regulated and controlled according to the product requirement, and the values of y and z are controlled by regulating and controlling the ratio of reactants and the reaction time.
(7) The ion exchange membrane and the membrane electrode prepared by the invention can be applied to alkaline water electrolysis and fuel cell devices.
After the perfluorinated conjugated cation resin prepared by the method is subjected to alkali attenuation test for 500 hours, the retention rate of Ion Exchange Capacity (IEC) is up to more than 90%, and the obtained resin has higher capability of resisting hydroxyl attack, so that the service life of perfluorinated cation polymer and products thereof can be effectively prolonged. After the anion exchange membrane is tested for 500 hours by a 6M KOH decay test, the retention rate of the ion exchange capacity is more than 90 percent, and the retention rate of the ion conductivity is more than 90 percent. The membrane electrode provided by the invention takes the ion resin or the ion membrane prepared by the invention as a raw material, so that the service life of the membrane electrode can be effectively prolonged.
Drawings
FIG. 1 is an infrared spectrum of PFSO 2NH2, the target products A1 and A2 of example 1.
Fig. 2 is a graph of ionic conductivity retention of the anion exchange membrane prepared in example 2.
FIG. 3 is a graph showing the retention of ion exchange capacity of the anion exchange membrane prepared in example 2.
Detailed Description
The present invention is described in detail below with reference to specific examples, which are only for the purpose of illustrating the invention in detail and are not to be construed as limiting the scope of the invention. The invention is not limited to the following embodiments, but other combinations derived on the basis of the invention are all within the scope of the invention. The raw materials and reagents involved in the examples are all common commercial products unless specified; the experimental methods referred to in the examples are conventional in the art unless otherwise specified.
In the embodiment, a 6M KOH decay experiment is adopted to accelerate the invasion of the target product so as to achieve the aim of investigating the chemical stability of the target product. The chemical stability of the target product was evaluated by the retention (RV%) of the Ion Exchange Capacity (IEC) of the target product before and after the test decay experiment.
The specific conditions of the alkali attenuation experiment are as follows: the target product is soaked in 6M KOH solution, maintained at 80 ℃ for 500 hours, the KOH solution is replaced every 3 hours, the product is taken out after the experiment is finished and washed by deionized water for multiple times, and finally the product is dried at 60 ℃ for 4 hours.
Titration of Ion Exchange Capacity (IEC): accurately weighing a certain weight of dry target product, then carrying out ion exchange for more than 12 hours by using NaCl aqueous solution with the concentration of about 1M, collecting the ion exchanged solution, titrating by using 0.1M NaOH standard solution with phenolphthalein as an indicator until the solution turns pink, wherein the Ion Exchange Capacity (IEC) value of the target product can be calculated according to the following formula:
IEC＝(VNaOH×CNaOH)/m
Wherein: v NaOH -the volume of NaOH standard solution consumed, mL; c NaOH -molar concentration of NaOH standard solution, mmol/mL; m-mass of dry target product, g.
Retention of Ion Exchange Capacity (IEC):
RV％＝(IEC1-IEC0)/IEC0
Wherein: IEC 1 and IEC 0 represent the Ion Exchange Capacities (IEC) of the target product after and before the Fenton experiment.
Ion conductivity measurement of anion exchange membrane: the resistance R of the sample is tested by adopting a two-electrode method, an electrochemical workstation Autolab PGSTA is adopted as an instrument, the frequency interval is 106Hz-10Hz, and the conductivity is calculated by a calculation formula:
σ＝L/RS
wherein: l is the thickness (cm) of the membrane, R is the resistance (Ω) of the membrane, σ is the conductivity (S/cm) of the sample, and S is the test part area (cm 2) of the sample.
Retention of anion exchange membrane conductivity:
RV％＝(σ1-σ0)/σ0
Wherein: σ 1 and σ 0 represent the ion conductivity of the anion exchange membrane after and before the Fenton experiment, respectively.
Thermal degradation temperature (defined as the temperature at which the polymer degrades by 5%): and (3) testing by adopting a thermogravimetric analyzer, wherein the testing instrument is in the TAQ50 and N 2 atmosphere produced by PERKIN ELMER company in the United states, the temperature rising speed is 10 ℃/min, the temperature range is 50-800 ℃, and the sample is dried for 24 hours at 60 ℃ before testing.
Membrane electrode durability test:
The durability or chemical stability of the membrane electrode samples was evaluated at 30% Relative Humidity (RH) and 90℃at Open Circuit Voltage (OCV) to provide hydrogen and air gas flow rates of 3.43slpm and 8.37slpm, respectively. The OCV of each cell in the stack was monitored over time. The test was terminated when the OCV of any one of the 5 cells in the stack reached 0.8V or H 2 Crossover was greater than 10mA/cm 2.
Example 1
The synthesis of hydrogen bond enhanced perfluoro conjugated cation resin adopts benzoyl chloride as M monomer reagent (R 1～R5 is-H and R x is-Cl); 4-chloromethylbenzoyl chloride is selected as an N reagent for providing chloromethyl (R xx is-Cl, R 333 is-CH 2 Cl, and the rest substituents are-H); trimethylamine (TMA) is selected as an H reagent and a catalyst to carry out grafting reaction to graft a hydrogen bond reinforcing conjugated unit. PFSO 2NH2 resin (m=1, n=2, number average molecular weight 42 ten thousand, x' value 10, molar equivalent ew=870 g/mol) was reacted to synthesize the target product, specifically as follows:
(1) After a 500mL closed reaction kettle is cleaned, vacuumized and filled with high-purity nitrogen for three times, 10g of PFSO 2NH2 resin and 200mL of dried N, N-dimethylacetamide are added, a stirring device is started, after the mixture is slowly heated to 80 ℃, 0.02g of 4-chloromethylbenzoyl chloride is added after the mixture is completely dissolved, and the molar ratio of PFSO 2NH2 to 4-chloromethylbenzoyl chloride is about 1:5, finally adding 0.05g TMA as catalyst and reactant, the molar ratio of 4-chloromethylbenzoyl chloride to TMA is about 1:8, 8; after the material addition is completed, the mixture is reacted for 10 hours at 80 ℃ under mechanical stirring, then cooled to room temperature, the product is filtered, unreacted 4-chloromethylbenzoyl chloride is removed through absolute ethyl alcohol and chloroform washing, excessive TMA and corresponding hydrochloride are obtained through deionized water washing (the product HCl and TMA form trimethylamine hydrochloride in the reaction process); finally, the intermediate product is dried at 60 ℃, and the obtained intermediate product is marked as A1, and has the following reaction formula:
Measurement of infrared transmission spectrum of intermediate A1, FIG. 1 is a graph showing infrared results of PFSO 2NH2 and A1 (FIG. 1B) in the present invention, wherein it can be seen that characteristic peaks (-NH 2 group) belonging to primary amine of PFSO 2NH2 between 3304-3400cm -1 and 1548cm -1 are reduced in area after reaction, demonstrating that-NH 2 group participates in reaction; at the same time, -CH-, -CH 2,-CH3 appears at 3000cm -1, a characteristic peak of carbonyl appears at 1710cm -1 and a characteristic peak of quaternary amine group appears at 1478cm -1, which prove that the intermediate product A1 is successfully synthesized.
(2) Cleaning a 500mL closed reaction kettle, vacuumizing, filling high-purity nitrogen, replacing for three times, adding 200mL of dried N, N-dimethylacetamide, slowly heating to 60 ℃ by starting a stirring device, adding 10g of intermediate A1 in the step (1), and adding 0.03g of 4-chloromethylbenzoyl chloride after the intermediate A1 is completely dissolved, wherein the molar ratio of A1 to benzoyl chloride is about 1:10, finally adding 0.21g of AlCl 3 as a catalyst (the molar ratio of benzoyl chloride to the catalyst is 1:10), reacting for 10 hours at 60 ℃ under mechanical stirring after the completion of the addition, cooling to room temperature, generating trimethylamine hydrochloride from HCl and trimethylamine generated in the reaction process, filtering the product, washing the product by absolute ethyl alcohol, chloroform and deionized water to remove unreacted benzoyl chloride and trimethylamine hydrochloride, finally soaking the product in 2M KOH solution for 24 hours, and recording the target product obtained by completely converting chloride ions into hydroxyl ions as A2, wherein the reaction formula is as follows:
The Ion Exchange Capacity (IEC) measurement shows that the IEC of the obtained target product A1 is 0.98mmol/g, and the z/y+z=0.85 and the y/y+z=0.15 in the structure of the obtained target product A1.
The target product A2 is determined to be 1.00mmol/g by titration, the theoretical IEC=0.85× (1000/870) mmol/g=0.98 mmol/g of the target product A2 can be calculated from the values of z/y+z=0.85 and y/y+z=0.15 in the step (1), and the IEC obtained by the titration method is close to the IEC obtained by theoretical solution, so that the complete reaction of all amino groups is proved. Based on this, the latter examples of the application all use titration IEC to calculate the z/y+z and the y/y+z ratios.
The infrared spectrum of the target product A2 is measured, the infrared spectrum result of the A2 is shown in a figure 1C, the characteristic peak belonging to primary amine of PFSO 2NH2 at the position 1548cm -1 can be seen to completely disappear after reaction, and y in the A5 structure is proved to be 0; meanwhile, -CH-, -CH 2,-CH3 appears at 3000cm -1, a characteristic peak of carbonyl appears at 1710cm -1 and a characteristic peak of quaternary amine group appears at 1478cm -1, and the results prove that the hydrogen bond enhanced perfluoro conjugated cationic resin A2 is successfully synthesized.
Example 2
The preparation of the hydrogen bond enhanced perfluoro conjugated anion exchange membrane comprises the following specific steps:
The target product A2 prepared in the example 1 is dissolved in N, N-dimethylformamide to prepare 10wt% of perfluoro-cation resin solution, then the resin solution is coated on a clean and smooth quartz surface dish, pre-dried at 80 ℃, dried in an oven at 145 ℃ for 90 minutes, taken out and demoulded, and the hydrogen bond enhanced perfluoro-conjugate anion exchange membrane is prepared.
The ion exchange capacity IEC of the above anion exchange membrane was 1.03mmol/g as determined by titration.
The ion conductivity of the above anion exchange membrane at room temperature (25 ℃) was 60.2mS/cm.
The stability of the anion exchange membrane is tested by an alkali attenuation test, and the result is shown in figure 2, and after the ion membrane is tested by the alkali attenuation test for 105 days, the ionic conductivity and the retention rate of the ion exchange capacity are both up to more than 90%, so that the obtained anion exchange membrane has higher capability of resisting hydroxyl attack, the alkali stability of the anion exchange membrane is improved, and the service life of the anion exchange membrane can be effectively prolonged.
Example 3
A hydrogen bond enhanced perfluoro conjugated cationic resin is synthesized by selecting benzoic acid as an M monomer reagent (R 1～R5 is-H, rx is-OH) for providing carbonyl groups, selecting 4-chloromethylbenzoyl chloride as an N monomer reagent (R xx is-Cl, R 33 is-CH 2 Cl, and other substituents are-H) for providing chloromethyl groups, and selecting 1-methylimidazole as an H reagent and a catalyst for grafting hydrogen bond enhanced conjugated units through grafting reaction. PFSO 2NH2 resin (m=0, n=2, number average molecular weight 40 ten thousand, x' value 10, molar equivalent ew=800 g/mol) was reacted to synthesize the target product, specifically as follows:
(1) After a 500mL reaction kettle is cleaned, 200mL of dry N, N-dimethylformamide is added, a stirring device is started, the mixture is slowly heated to 80 ℃, 30g of PFSO 2NH2 resin is added, the stirring device is started, after the PFSO 2NH2 resin is completely dissolved, 0.14g of benzoic acid is added after three times of high-purity nitrogen replacement, and the molar ratio of PFSO 2NH2 to the benzoic acid is about 1:15, finally adding 1.16g of Triethylamine (TEA) as a catalyst (the molar ratio of benzoic acid to TEA is 1:10), reacting for 10 hours at 80 ℃ under mechanical stirring after the completion of the addition, cooling to room temperature, filtering the product, washing the product by absolute ethyl alcohol, chloroform and deionized water to remove unreacted benzoic acid, and drying to obtain an intermediate product, namely A3; the reaction formula is as follows:
(2) Cleaning a 500mL closed reaction kettle, vacuumizing, filling high-purity nitrogen for replacement for three times, adding 200mL of dried N, N-dimethylformamide, starting a stirring device, slowly heating to 80 ℃, adding 10g of the product A3 in the step 1, adding 0.1g of p-bromomethylbenzoyl bromide (the molar ratio of the A3 to the N monomer reagent is 1:10) after the product A3 is completely dissolved, and finally adding 0.24g of 1-methylimidazole as a catalyst and a reaction H reagent, wherein the molar ratio of the p-bromomethylbenzoyl bromide to the 1-methylimidazole is 1:8, after the addition, the mixture is reacted for 15 hours at 80 ℃ under mechanical stirring, then cooled to room temperature, the product is filtered, unreacted benzoyl chloride and 1-methylimidazole are removed through washing by absolute ethyl alcohol, chloroform and deionized water, finally, the mixture is soaked in a 2M KOH solution for 24 hours, and the target product obtained by completely converting chloride ions into hydroxide ions is recorded as A4, wherein the reaction formula is as follows:
The target product A4 is titrated to have the IEC of 1.15mmol/g; iec= (z/y+z) ×1.25 mmol/g=1.15 mmol/g, thereby calculating z/y+z=0.92, y/y+z=0.08.
Example 4
The preparation of the hydrogen bond enhanced perfluoro conjugated anion exchange membrane comprises the following specific steps:
The target product A4 prepared in the example 3 is dissolved in dimethyl sulfoxide to prepare 8wt% of perfluoro cation resin solution, then the resin solution is coated on a clean and smooth quartz surface dish, and after pre-drying at 80 ℃, the resin solution is placed in an oven at 145 ℃ to be dried for 90 minutes, and taken out for demoulding, so that the hydrogen bond enhanced perfluoro conjugated anion exchange membrane is prepared.
The ion exchange capacity IEC of the above anion exchange membrane was 1.22mmol/g as determined by titration.
The ion conductivity of the above anion exchange membrane at room temperature (25 ℃) was 75.5mS/cm.
Example 5
A hydrogen bond enhanced perfluoro conjugated cationic resin is synthesized by selecting 4-chloromethylbenzoyl chloride as N monomer reagent for providing chloromethyl (R xx is-Cl, R 33 is-CH 2 Cl, and other substituents are-H) and selecting TMA as H reagent and catalyst to carry out grafting reaction to graft hydrogen bond enhanced conjugated unit. PFSO 2NH2 resin (m=1, n=2, number average molecular weight 42 ten thousand, x' value 10, molar equivalent ew=870 g/mol) was reacted to synthesize the target product, specifically as follows:
After a 500mL reaction vessel was cleaned, 200mL of dry N, N-dimethylacetamide was added, the reaction vessel was slowly heated to 80℃and 10g of PFSO 2NH2 resin was added, after the reaction vessel was completely dissolved by turning on a stirring apparatus, 0.06g of 4-chloromethylbenzoyl chloride was added after three replacements with high-purity nitrogen, and the molar ratio of PFSO 2NH2 to 4-chloromethylbenzoyl chloride was about 1:13, finally 0.2g TMA was added as catalyst and H reagent, the molar ratio of 4-chloromethylbenzoyl chloride to TMA being about 1:10; after the completion of the addition, the reaction was refluxed at 150℃for 15 hours and then cooled to room temperature. HCI and trimethylamine generated in the reaction process generate trimethylamine hydrochloride, the filtered product is washed by absolute ethyl alcohol, chloroform and deionized water to remove unreacted 4-chloromethylbenzoyl chloride and trimethylamine hydrochloride, and finally the filtered product is soaked in 2M KOH solution for 24 hours to completely convert chloride ions into hydroxide ions, and the obtained target product is denoted as A5, and the reaction formula is as follows:
The target product A5 is measured by Ion Exchange Capacity (IEC), IEC is 1.12mmol/g, y in the structure of the target product A5 is 0, and z/y+z=1.0. The embodiment is modified by N monomer reagent, the cationic group content is high, that is IEC is high, and the conductivity of the corresponding ionic membrane is high.
Example 6
The preparation of the hydrogen bond enhanced perfluoro conjugated anion exchange membrane comprises the following specific steps:
The target product A5 prepared in the example 7 is dissolved in dimethyl sulfoxide to prepare 8wt% of perfluoro cation resin solution, then the resin solution is coated on a clean and smooth quartz surface dish, and after pre-drying at 80 ℃, the resin solution is placed in an oven at 145 ℃ to be dried for 90 minutes, and taken out for demoulding, so that the hydrogen bond enhanced perfluoro conjugated anion exchange membrane is prepared.
The ion exchange capacity IEC of the above anion exchange membrane was 1.11mmol/g as determined by titration.
The ion conductivity of the above anion exchange membrane at room temperature (25 ℃) was 65.2mS/cm.
Example 7
A hydrogen bond enhanced perfluoro conjugated cationic resin is synthesized by selecting 4-chloromethylbenzoyl chloride as N monomer reagent for providing chloromethyl (R xx is-Cl, R 33 is-CH 2 Cl, and other substituents are-H) and selecting TMA as H reagent and catalyst to carry out grafting reaction to graft hydrogen bond enhanced conjugated unit. PFSO 2NH2 resin (m=0, n=2, number average molecular weight 40 ten thousand, x' value 10, molar equivalent ew=800 g/mol) was reacted to synthesize the target product, specifically as follows:
After a 500mL reaction vessel was purged, 200mL of dry N, N-dimethylformamide was added, slowly heated to 80℃and 10g of PFSO 2NH2 resin was added, after complete dissolution, the stirring apparatus was turned on and high purity nitrogen was replaced three times and 0.06g of 4-chloromethylbenzoyl chloride was added, the molar ratio of PFSO 2NH2 to 4-chloromethylbenzoyl chloride was about 1:13, finally, 0.2g of 1-methylimidazole as catalyst and H reagent were added, the molar ratio of 4-chloromethylbenzoyl chloride to 1-methylimidazole being approximately 1:10; after the completion of the addition, the reaction was refluxed at 80℃for 15 hours and then cooled to room temperature. Filtering the product, washing the product by absolute ethyl alcohol, chloroform and deionized water to remove unreacted benzoyl chloride and trimethylamine hydrochloride, and finally soaking the product in a 2M KOH solution for 24 hours to completely convert chloride ions into hydroxide ions, wherein the obtained target product is denoted as A6, and the reaction formula is as follows:
The target product A6 is measured by Ion Exchange Capacity (IEC), IEC is 1.23mmol/g, y in the structure of the target product A6 is 0, and z/y+z=1.0.
Example 8
The preparation of the hydrogen bond enhanced perfluoro conjugated anion exchange membrane comprises the following specific steps:
The target product A6 prepared in the example 7 is dissolved in dimethyl sulfoxide to prepare 8wt% of perfluoro cation resin solution, then the resin solution is coated on a clean and smooth quartz surface dish, and after pre-drying at 80 ℃, the resin solution is placed in an oven at 145 ℃ to be dried for 90 minutes, and taken out for demoulding, so that the hydrogen bond enhanced perfluoro conjugated anion exchange membrane is prepared.
The ion exchange capacity IEC of the above anion exchange membrane was 1.22mmol/g as determined by titration.
The ion conductivity of the above anion exchange membrane at room temperature (25 ℃) was 77.5mS/cm.
Example 9
A cross-linking hydrogen bond enhanced perfluoro conjugated cationic resin is synthesized by selecting terephthaloyl chloride as an M monomer reagent for providing a cross-linking carbonyl group (Rx and R 3 are both-COCl and the rest are-H), selecting 4-chloromethylbenzoyl chloride as an N monomer reagent for providing chloromethyl (R xx is-Cl, R 333 is-CH 2 Cl and the other substituents are-H), and selecting TMA as an H reagent and a catalyst to carry out grafting reaction to graft the cross-linking hydrogen bond enhanced conjugated unit. PFSO 2NH2 resin (m=1, n=2, number average molecular weight 42 ten thousand, x' value 10, molar equivalent ew=870 g/mol) was reacted to synthesize the target product, specifically as follows:
After a 500mL reaction vessel was washed, 200mL of dried N, N-dimethylacetamide was added, and after the stirring apparatus was started to slowly heat to 80 ℃, 15g of A1 in example 1 was added, and after the stirring apparatus was started to completely dissolve the same, 0.08g of terephthaloyl chloride was added as an M monomer reagent providing a cross-linking carbonyl group after three times of high purity nitrogen substitution, the molar ratio of A1 to terephthaloyl chloride was about 1:10, finally 0.53g of AlCl 3 was added as catalyst, the molar ratio of terephthaloyl chloride to AlCl 3 was about 1:10. after the addition, the mixture is reacted for 12 hours at 80 ℃ under mechanical stirring, then cooled to room temperature, the product is filtered, unreacted terephthaloyl chloride is removed through washing by absolute ethyl alcohol, chloroform and deionized water, and finally the mixture is soaked in a 2M KOH solution for 24 hours, and the target product obtained by completely converting chloride ions into hydroxide ions is recorded as A7; the reaction formula is as follows:
The target product A7 is titrated to 0.92mmol/g; iec= (z/y+z) × (1000/870) mmol/g=0.92 mmol/g, thus calculating z/y+z=0.80, y/y+z=0.20 in the structure of the target product A7.
Example 10
The preparation of the cross-linking hydrogen bond enhanced perfluoro conjugated anion exchange membrane comprises the following specific steps:
The target product A7 prepared in the example 7 is dissolved in dimethyl sulfoxide to prepare a 5wt% perfluoro cation resin solution, then the resin solution is coated on a clean and smooth quartz surface dish, is pre-dried at 80 ℃, is dried in an oven at 145 ℃ for 90 minutes, and is taken out for demolding, so that the cross-linked hydrogen bond enhanced perfluoro conjugated anion exchange membrane is prepared.
The ion exchange capacity IEC of the above anion exchange membrane was determined by titration to be 0.91mmol/g.
The ion conductivity of the above anion exchange membrane at room temperature (25 ℃) was 50.5mS/cm.
Example 11
The synthesis of cross-linked polyion hydrogen bond enhanced perfluoro conjugated cationic resin adopts benzoic acid as M monomer reagent for providing carbonyl group (R1-R5 are-H, rx is-OH), 4-chloromethylbenzoyl chloride as N monomer reagent for providing chloromethyl group (R xx is-Cl, R 33 is-CH 2 Cl, other substituent groups are-H), tetramethyl-1, 6-hexamethylenediamine is used as cross-linking H reagent and catalyst to make grafting reaction to graft cross-linked polyion hydrogen bond enhanced conjugated unit. PFSO 2NH2 resin (m=0, n=2, number average molecular weight 40 ten thousand, x' value 10, molar equivalent ew=800 g/mol) was reacted to synthesize the target product, specifically as follows:
After a 500mL reaction vessel was washed, 200mL of dried N, N-dimethylacetamide was added, a stirring device was turned on, and 15g of A3 in example 3 was added after slowly heating to 80℃and after turning on the stirring device until it was completely dissolved, 0.08g of 4-chloromethylbenzoyl chloride was added as an N monomer reagent providing chloromethyl group after three replacements with high-purity nitrogen, and the molar ratio of A3 to 4-chloromethylbenzoyl chloride was about 1:10, finally, 0.73g of tetramethyl-1, 6-hexamethylenediamine is added as crosslinking H reagent and catalyst, the molar ratio of 4-chloromethylbenzoyl chloride to tetramethyl-1, 6-hexamethylenediamine being about 1:10. after the material addition, the mixture is reacted for 13 hours at the temperature of 100 ℃ under mechanical stirring, then cooled to room temperature, the product is filtered, unreacted 4-chloromethylbenzoyl chloride is removed through washing by absolute ethyl alcohol, chloroform and deionized water, and finally the product is soaked in a 2M KOH solution for 24 hours, so that the chloride ions are completely converted into hydroxide ions, and the target product obtained is recorded as A8; the reaction formula is as follows:
The target product A8 is titrated to have the IEC of 1.75mmol/g; because the B unit contains two quaternary amine ions, the IEC calculation process needs to be multiplied by 2; iec= (z/y+z) × (1000/800) ×2 mmol/g=1.75 mmol/g, whereby z/y+z=0.70, y/y+z=0.30 in the structure of the target product A7 was calculated. From this calculation it can be seen that the introduction of a cross-linked polyionic structure in the B unit can significantly improve the IEC of the resin.
Example 12
The preparation of the cross-linked polyion hydrogen bond enhanced perfluorinated conjugated anion exchange membrane comprises the following specific steps:
the target product A8 prepared in example 11 is dissolved in dimethyl sulfoxide to prepare a 5wt% perfluoro cation resin solution, then the resin solution is coated on a clean and smooth quartz surface dish, and after pre-drying at 80 ℃, the resin solution is placed in an oven at 145 ℃ to be dried for 90 minutes, and taken out for demoulding, so that the hydrogen bond enhanced perfluoro conjugated anion exchange membrane is prepared.
The ion exchange capacity IEC of the above anion exchange membrane was 1.71mmol/g as determined by titration.
The ion conductivity of the above anion exchange membrane at room temperature (25 ℃) was 100.5mS/cm.
Example 13
The preparation of the hydrogen bond enhanced perfluoro conjugated membrane electrode for the fuel cell comprises the following specific steps:
(1) Dissolving a target product A4 in the embodiment 3 in a mixed solvent of water and isopropanol (volume ratio is 2:8) to prepare a perfluorinated ion polymer solution with the weight percent of 5%, adding a Pt/C catalyst into 10mL of the perfluorinated ion polymer solution, and carrying out ultrasonic treatment for 100min to obtain a catalyst mixture;
(2) Coating the perfluorinated ion polymer solution in the step (1) on a clean and smooth quartz surface dish, pre-drying at 80 ℃, drying in an oven at 145 ℃ for 90 minutes, taking out and demolding to prepare the anion exchange membrane;
(3) Spraying the catalyst mixture obtained in the step (1) onto the 2cm multiplied by 2cm gas diffusion layer subjected to the hydrophobic treatment by using a spray gun to form a catalyst layer, and performing heat treatment at 130 ℃ for 90min to obtain an electrode layer consisting of the gas diffusion layer and the catalyst layer, wherein the electrode layer is divided into a hydrogen electrode and an oxygen electrode due to different contact between fuel hydrogen and oxygen in a membrane electrode, wherein the platinum loading amount on the surface of the catalyst layer is 0.4mg/cm 2;
(4) Placing the hydrogen electrode and the oxygen electrode which are cut into proper sizes on the upper side and the lower side of the anion exchange membrane (3 cm multiplied by 3 cm) in the step (2), aligning up and down, performing hot pressing treatment by a press, wherein the pressure of the press is 0.8MPa, the hot pressing temperature is 140 ℃, the duration time is 60 seconds, opening the press, and taking out the hydrogen bond enhanced perfluorinated conjugated membrane electrode for the fuel cell after natural cooling.
Example 14
The preparation of the hydrogen bond enhanced perfluoro conjugated membrane electrode for the electrolyzed water comprises the following specific steps:
(1) Dissolving a target product A5 in the embodiment 5 in a mixed solvent of water/isopropanol (volume ratio is 2:8) to prepare a perfluorinated ion polymer solution with the weight percent of 5%, then respectively adding Pt/C and IrO 2 catalysts into two groups of 10mL perfluorinated ion polymer solutions, and carrying out ultrasonic treatment for 100min to obtain a catalyst mixture; irO 2 is used as a catalyst for an anode and Pt/C is used for a cathode in the alkaline water electrolysis device;
(2) Coating the perfluorinated ion polymer solution in the step (1) on a clean and smooth quartz surface dish, pre-drying at 80 ℃, drying in an oven at 145 ℃ for 90 minutes, taking out and demolding to prepare the anion exchange membrane;
(3) Spraying the catalyst mixture obtained in the step (1) onto the 2cm multiplied by 2cm gas diffusion layer subjected to the hydrophobic treatment by using a spray gun to form a catalyst layer, and performing heat treatment at 130 ℃ for 90min, wherein the dry weight content of IrO 2 and Pt/C in the catalyst layer is 2.5mg/cm 2 and 0.4mg/cm 2 respectively, so as to obtain an electrode layer consisting of the gas diffusion layer and the catalyst layer.
(4) And (3) placing membrane electrodes with proper cutting sizes on the upper side and the lower side of the anion membrane (3 cm multiplied by 3 cm) in the step (2), aligning up and down, performing hot pressing treatment by a press, wherein the pressure of the press is 0.8MPa, the hot pressing temperature is 140 ℃, the duration is 60s, opening the press, and taking out the prepared hydrogen bond enhanced perfluoro conjugated membrane electrode for electrolyzed water after natural cooling.
Comparative example 1
A non-hydrogen bond enhanced perfluorinated cation resin and an anion exchange membrane thereof specifically comprise the following steps:
Glycidyl trimethyl ammonium chloride (GCI) and PFSO 2NH2 resin (m=1, n=2, number average molecular weight is 40 ten thousand, x' value is 10, and molar equivalent Ew=870 g/mol) are selected for reaction to synthesize a target product, and the specific steps are as follows:
(1) After a 100mL reaction kettle is cleaned, 50mL of dry N, N-dimethylformamide is added, a stirring device is started, after three times of replacement by high-purity nitrogen gas is pumped in vacuum, 0.1g of GCI is added, after the reaction kettle is slowly heated to 60 ℃,30 g of PFSO 2NH2 resin is added after the reaction kettle is completely dissolved, and the molar ratio of PFSO 2NH2 to GCI is about 1:10, after reacting for 10 hours at 80 ℃ under mechanical stirring, cooling to room temperature, filtering the product, washing by deionized water to remove unreacted GCI, finally soaking in 2M KOH solution for 24 hours, completely converting chloride ions into hydroxide ions, and drying the product at 60 ℃ to obtain a target product, namely A11, wherein the reaction formula is as follows:
The target product A11 was measured by Ion Exchange Capacity (IEC), and IEC was 1.02mmol/g.
And (3) dissolving A11 in dimethyl sulfoxide to prepare 8wt% of perfluoro cation resin solution, coating the resin solution on a clean and smooth quartz surface dish, pre-drying at 80 ℃, drying in an oven at 145 ℃ for 90 minutes, taking out, and demolding to prepare the anion exchange membrane.
The ion exchange capacity IEC of the above anion exchange membrane was 1.05mmol/g as determined by titration.
The ion conductivity of the above anion exchange membrane at room temperature (25 ℃) was 40.5mS/cm.
Comparative example 2
The preparation of the composite anion exchange membrane comprises the steps of firstly, soaking a product obtained by reacting 4-chloromethylbenzoyl chloride with trimethylamine in A2M KOH solution for 24 hours, marking the obtained product as A22 (the structure is shown in the specification), then directly adding the product into PFSO 2NH2 (m=1, n=2, the number average molecular weight is 40 ten thousand, the x value is 10, the molar equivalent Ew=870 g/mol), uniformly mixing the product with the solution in a mechanical stirring mode, coating the obtained mixed solution on a clean and smooth quartz surface dish, pre-drying the product at 80 ℃, drying the product in an oven at 145 ℃ for 90 minutes, taking out and demoulding, and thus obtaining the anion exchange membrane.
The Ion Exchange Capacity (IEC) of the resulting anion exchange membrane was determined to be 0.25mmol/g.
The ion conductivity of the above anion exchange membrane at room temperature (25 ℃) was 10.5mS/cm.
Comparative example 3
The non-hydrogen bond enhanced membrane electrode for the fuel cell comprises the following specific steps:
(1) Diluting the perfluoro cationic resin A11 of the comparative example 1 in an isopropanol/water (volume ratio is 8:2) mixed solvent to prepare a perfluoro cationic polymer solution with the weight percent of 5%, adding 10mL of the solution into a Pt/C catalyst, and carrying out ultrasonic treatment for 100min to obtain a catalyst mixture;
(2) Coating the 5wt% of the perfluorinated polymer solution in the step (1) on a clean and smooth quartz surface dish, pre-drying at 80 ℃, drying in an oven at 145 ℃ for 80 minutes, taking out and demolding to prepare the perfluorinated anion exchange membrane;
(3) Spraying the membrane electrode slurry obtained in the step (1) onto the 2cm multiplied by 2cm gas diffusion layer subjected to the hydrophobic treatment by using a spray gun to form a catalyst layer, and performing heat treatment at 130 ℃ for 90min to obtain an electrode layer consisting of the gas diffusion layer and the catalyst layer, wherein the platinum loading amount on the surface of the catalyst layer is 0.4mg/cm 2, and the electrode layer is divided into a hydrogen electrode and an oxygen electrode due to different contact between fuel hydrogen and oxygen in the membrane electrode;
(4) Placing the hydrogen electrode and the oxygen electrode which are cut into proper sizes on the upper side and the lower side of the anion exchange membrane (3 cm multiplied by 3 cm) in the step (2), aligning up and down, well matching, performing hot pressing treatment by a press, wherein the pressure of the press is 0.8MPa, the hot pressing temperature is 140 ℃, the duration is 60 seconds, opening the press, and taking out the prepared membrane electrode after natural cooling.
Comparative example 4
The preparation of the non-hydrogen bond enhanced membrane electrode for the electrolyzed water comprises the following specific steps:
(1) Dissolving a target product A11 in the implementation comparative example 1 in a mixed solvent of water and isopropanol (volume ratio is 2:8) to prepare a perfluorinated ion polymer solution with the concentration of 5wt%, and then respectively adding Pt/C and IrO 2 catalysts into two groups of 10mL perfluorinated ion polymer solutions, and carrying out ultrasonic treatment for 100min to obtain a catalyst mixture; irO 2 is used as a catalyst for an anode and Pt/C is used for a cathode in the alkaline water electrolysis device;
(2) Coating the perfluorinated ion polymer solution in the step (1) on a clean and smooth quartz surface dish, pre-drying at 80 ℃, drying in an oven at 145 ℃ for 90 minutes, taking out and demolding to prepare the anion exchange membrane;
(3) Spraying the catalyst mixture obtained in the step (1) onto the 2cm multiplied by 2cm gas diffusion layer subjected to the hydrophobic treatment by using a spray gun to form a catalyst layer, and performing heat treatment at 130 ℃ for 90min, wherein the dry weight content of IrO 2 and Pt/C in the catalyst layer is 2.5mg/cm 2 and 0.4mg/cm 2 respectively, so as to obtain an electrode layer consisting of the gas diffusion layer and the catalyst layer.
(4) And (3) placing membrane electrodes with proper cutting sizes on the upper side and the lower side of the anion membrane (3 cm multiplied by 3 cm) in the step (2), aligning up and down, performing hot pressing treatment by a press, wherein the pressure of the press is 0.8MPa, the hot pressing temperature is 140 ℃, the duration is 60s, opening the press, and taking out the prepared hydrogen bond enhanced perfluoro conjugated membrane electrode for electrolyzed water after natural cooling.
Performance test:
the performance of the perfluorinated cation resin, the anion exchange membrane and the membrane electrode prepared above was tested, and the results are shown in tables 1 to 3:
TABLE 1 alkali stability test results of Hydrogen bond enhanced perfluoro conjugated cationic resin
As shown in Table 1, after the alkali attenuation experiment for 500 hours, the IEC of the hydrogen bond enhanced perfluoro conjugated cationic resin prepared by the invention is over 90%, the thermal degradation temperature is over 300 ℃, and compared with the non-hydrogen bond enhanced cationic resin, the IEC retention rate and the thermal degradation temperature are obviously improved. In addition, the introduction of the cross-linking structure in the A unit and the B unit can further effectively improve the retention rate of IEC, and the alkali resistance is effectively improved; the heat stability of the cross-linking pair resin is also obviously improved, which proves that the hydrogen bond enhanced perfluoro conjugated cationic resin prepared by the invention has higher chemical stability, reduces or slows down the degradation of the polymer, and has enough heat stability.
TABLE 2 results of Performance test of anion exchange Membrane
As can be seen from Table 2, after the anion exchange membrane prepared by the hydrogen bond enhanced perfluoro conjugated cation resin is subjected to an alkali attenuation experiment for 500 hours, the IEC is over 90%, the ion conductivity retention rate is over 90%, and the thermal degradation temperature of the anion exchange membrane is over 300 ℃; compared with a non-hydrogen bond enhanced anion exchange membrane (comparative example), the chemical stability and the thermal stability of the ionic membrane are obviously improved, and the service life of the ionic membrane is effectively prolonged. In addition, the introduction of the cross-linking structure can further effectively improve the alkali resistance and the thermal stability of the ion membrane, wherein in the comparative example 2, small molecules are directly added into a conventional perfluorinated polymer to prepare the composite anion exchange membrane, and although the small molecules can directly form a hydrogen bond structure, the small molecules are easy to agglomerate and run off and have poor compatibility with the polymer, so that the mechanical property and the electrical conductivity of the anion exchange membrane are reduced, and the service life is influenced.
TABLE 3 Performance test results of Membrane electrode
| Example 13 | Example 14 | Comparative example 3 | Comparative example 4 | |
| Duration (h) | 225.3 | 230.5 | 90.6 | 70.8 |
As can be seen from Table 3, the duration of the membrane electrode prepared by the hydrogen bond enhanced perfluoro conjugated cationic resin of the present invention can reach 220h or more at the Open Circuit Voltage (OCV), 30% Relative Humidity (RH) and 90 ℃, while the duration of the membrane electrode prepared by the non-hydrogen bond enhanced resin (comparative examples 3 and 4) is lower than 100h, which indicates that the durability of the membrane electrode prepared by the present invention is effectively improved.
Claims (10)
1. A cross-linking hydrogen bond enhanced perfluoro conjugated cationic resin is characterized in that a perfluoro main chain is connected with a perfluoro ether group, an amide group and a side chain of a benzene ring conjugated structure, wherein the benzene ring conjugated structure of one side chain contains a cationic group; the benzene ring conjugated structure is connected with an amide group through a carbonyl group; the conjugated structure of the benzene ring on at least one side chain contains at least two carbonyl groups directly connected with the benzene ring.
2. The crosslinked hydrogen bond reinforced perfluoro conjugated cationic resin according to claim 1, wherein the number of carbonyl groups directly connected to the benzene ring conjugated structure is 2 to 3.
Preferably, the carbonyl group directly attached to the conjugated structure of the benzene ring is attached at any carbon atom position of the benzene ring. Further preferably, the number of carbonyl groups directly bonded to the conjugated structure of the benzene ring is two, and the carbonyl groups are bonded to the para position of the benzene ring.
Further preferably, the structure of the crosslinked hydrogen bond enhanced perfluoro conjugated cationic resin is represented by the following formula (1), (2) or (3):
Wherein:
R 1～R5 is one of -H、-CH3、-O-CH3、-Ph、-O-Ph、-PhCH3、-OH、-CH2CH3、-(CH3)3C、-(CH3)2HC, and R 1～R5 are the same or different groups; r 11～R55 contains 1 cationic group; the rest substituent groups outside the cation groups on the benzene ring are respectively and independently-H, -CH 3、-O-CH3 and-Ph (Ph represents one of benzene rings )、-O-Ph、-OH、-PhCH3、-CH2CH3、-(CH3)3C、-(CH3)2HC), m is an integer of 0-10, n is an integer of 1-6, x is an integer of 1-30, and y/(y+z) =0-0.5.
Preferably, m is an integer from 0 to 3; n is an integer of 1 to 3; further preferred, m=0, 1; n=2; y/(y+z) =0 to 0.3.
3. The crosslinked hydrogen bond reinforced perfluorinated conjugated cationic resin according to claim 1, wherein said cationic group structure contains one or more of the following structures:
preferably, the cross-linked hydrogen bond enhanced perfluorinated conjugated cationic resin has the following structural formula:
Wherein:
m is an integer of 0 to 10, and n is an integer of 1 to 6; x is an integer of 1 to 30; y/(y+z) =0 to 0.5.
4. The method for preparing the cross-linked hydrogen bond enhanced perfluoro conjugated cationic resin according to claim 3, comprising the following steps:
① The perfluorinated sulfonamide polymer, an N monomer reagent and an H reagent are subjected to grafting reaction, a conjugated cation unit is grafted, grafting reaction is carried out in an organic reagent, and the obtained product is washed by the reagent and dried and then is marked as an intermediate product A1; chloromethyl group in N monomer structure and tertiary ammonia in H reagent structure in reaction process The groups react to produce quaternary ammoniaThe reaction formula is as follows:
② Grafting reaction is carried out on the intermediate product A1 obtained in the step ① and an M monomer reagent under the action of a catalyst so as to graft a hydrogen bond enhanced conjugated unit, grafting reaction is carried out in an organic reagent, and the obtained product is washed by the reagent and dried to obtain the hydrogen bond enhanced perfluoro conjugated cationic resin, wherein the reaction formula is as follows:
The structure of the M reagent is shown in a formula VI:
wherein Rx and R 3 in the formula VI are both-COCl, and the rest are-H;
The structure of the N reagent is shown in a formula VII:
Wherein R xx in the formula VII is-Cl, R 333 is-CH 2 Cl, and the rest substituents are-H; the H reagent is trimethylamine.
5. The method according to claim 4, wherein the catalyst is one of trimethylamine, N-diisopropylethylamine, 4-dimethylaminopyridine, triethanolamine, tetrabutylammonium bromide, triethylamine, alCl 3, pyridine potassium carbonate, ammonium carbonate and sodium carbonate.
Preferably, the organic solvent is at least one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, toluene, methylene chloride, chloroform, tetrahydrofuran, ethanol, isopropanol, dimethyl sulfoxide or ethyl acetate. Preferably, the organic solvent is one of N, N-dimethylformamide and N, N-dimethylacetamide.
Preferably, the molar ratio of N monomer reagent to H reagent is 1: 8-10.
Preferably, the molar ratio of M monomer reagent to catalyst is 1:3 to 15.
Preferably, the temperature of the grafting reaction is 15-150 ℃, preferably 60-150 ℃; the reaction time is 1 to 48 hours, preferably 8 to 15 hours. Preferably, the reaction temperature of the grafting M monomer reagent is 60-80 ℃, the time is 9-11 h, and the reaction temperature of the grafting N monomer reagent is 80-150 ℃ and the reaction time is 10-15 h.
Preferably, the molar ratio of perfluorosulfonamide polymer to N monomer reagent in step ① is 1:5-15. In step ②, the molar ratio of the intermediate product A1 to the M monomer reagent is 1:5-15, and the molar ratio of the N monomer reagent to the H monomer reagent is 1:3-15. Preferably, the mass to volume ratio of the perfluorinated sulfonamide polymer to the organic solvent in the step ① is 1:1-30 g/mL; further preferably 1:1 to 25g/mL; most preferably 1:1 to 20g/mL. In step ②, the mass-to-volume ratio of intermediate product A1 to organic solvent is 1: 1-120 g/mL.
6. A kind of hydrogen bond enhanced crosslinking perfluoro conjugated multi-cation group resin is characterized in that,
The repeating unit structure contains 2-3 side chains of benzene ring conjugated structures, and the benzene ring conjugated structures are connected through two quaternary ammonium or quaternary phosphonium structures; the benzene ring conjugated structure is connected with the amide group through carbonyl.
7. The hydrogen bond-enhanced crosslinked perfluoro conjugated polycation group resin according to claim 6, wherein the number of carbonyl groups directly connected to the benzene ring conjugated structure is 2 to 3.
Preferably, the carbonyl group directly attached to the conjugated structure of the benzene ring is attached at any carbon atom position of the benzene ring. Further preferably, the number of carbonyl groups directly bonded to the conjugated structure of the benzene ring is two, and the carbonyl groups are bonded to the para position of the benzene ring.
Further preferably, the structure of the hydrogen bond enhanced crosslinked perfluorinated conjugated cationic resin is represented by the following formula (1) or (2):
Wherein:
R 1～R5 is one of -H、-CH3、-O-CH3、-Ph、-O-Ph、-PhCH3、-OH、-CH2CH3、-(CH3)3C、-(CH3)2HC, and R 1～R5 are the same or different groups; r 11～R55 contains 1 cationic group; the rest substituent groups outside the cation groups on the benzene ring are respectively and independently-H, -CH 3、-O-CH3 and-Ph (Ph represents one of benzene rings )、-O-Ph、-OH、-PhCH3、-CH2CH3、-(CH3)3C、-(CH3)2HC), m is an integer of 0-10, n is an integer of 1-6, x is an integer of 1-30, and y/(y+z) =0-0.5.
Preferably, m is an integer from 0 to 3; n is an integer of 1 to 3; further preferred, m=0, 1; n=2; y/(y+z) =0 to 0.3.
8. The hydrogen bond enhanced crosslinked perfluorinated conjugated polycationic group resin according to claim 7, wherein the hydrogen bond enhanced crosslinked perfluorinated conjugated polycationic group resin has the structure:
Wherein:
m is an integer of 0 to 10, and n is an integer of 1 to 6; x is an integer of 1 to 30; y/(y+z) =0 to 0.5.
9. A crosslinked hydrogen bond enhanced perfluoro conjugated anion exchange membrane, characterized in that the anion exchange membrane component comprises the crosslinked hydrogen bond enhanced perfluoro conjugated cation resin of any one of claims 1 to 3 or the hydrogen bond enhanced crosslinked perfluoro conjugated polycationic group resin of any one of claims 6 to 8.
Preferably, the ion exchange capacity of the anion exchange membrane is 0.8-1.9 mmol/g, the ion conductivity is 50-200 mS/cm, the thermal degradation temperature is 280-320 ℃, and after the 6M KOH decay test is carried out for 500 hours, the ion exchange capacity retention rate is above 90%, and the ion conductivity retention rate is above 90%.
Preferably, the preparation method of the hydrogen bond enhanced perfluorinated conjugate anion exchange membrane comprises the following steps:
Dissolving the cross-linked hydrogen bond enhanced perfluoro conjugated cationic resin according to any one of claims 1 to 3 or the hydrogen bond enhanced cross-linked perfluoro conjugated polycation group resin according to any one of claims 6 to 8 in an organic solvent to prepare a perfluoro conjugated ionic resin solution, and directly preparing an anion exchange membrane by adopting a solution casting method; preferably, the concentration of the perfluorinated conjugated cation resin solution is 2-20wt%, preferably 2-15wt%.
10. A membrane electrode for alkaline electrolyzed water and fuel cell, characterized in that the catalyst mixture component of the catalyst layer of the membrane electrode comprises the crosslinked hydrogen bond enhanced perfluoro conjugated cationic resin according to any one of claims 1 to 3 or the hydrogen bond enhanced crosslinked perfluoro conjugated polycationic group resin according to any one of claims 6 to 8.
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