CN112011051A - Heterocyclic ammonium ion polybenzimidazole and anion exchange membrane as well as preparation method and application thereof - Google Patents
Heterocyclic ammonium ion polybenzimidazole and anion exchange membrane as well as preparation method and application thereof Download PDFInfo
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- CN112011051A CN112011051A CN201910618015.7A CN201910618015A CN112011051A CN 112011051 A CN112011051 A CN 112011051A CN 201910618015 A CN201910618015 A CN 201910618015A CN 112011051 A CN112011051 A CN 112011051A
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- polybenzimidazole
- ammonium ion
- heterocyclic ammonium
- membrane
- drying
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- 239000004693 Polybenzimidazole Substances 0.000 title claims abstract description 110
- 229920002480 polybenzimidazole Polymers 0.000 title claims abstract description 110
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 title claims abstract description 55
- 125000000623 heterocyclic group Chemical group 0.000 title claims abstract description 42
- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 239000000446 fuel Substances 0.000 claims abstract description 12
- 238000000909 electrodialysis Methods 0.000 claims abstract description 7
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000012528 membrane Substances 0.000 claims description 72
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- 238000001035 drying Methods 0.000 claims description 42
- 239000000047 product Substances 0.000 claims description 42
- 238000001914 filtration Methods 0.000 claims description 33
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000002791 soaking Methods 0.000 claims description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000012065 filter cake Substances 0.000 claims description 14
- NTIGNJOEVBTPJJ-UHFFFAOYSA-N 3,3-dibromopentane Chemical compound CCC(Br)(Br)CC NTIGNJOEVBTPJJ-UHFFFAOYSA-N 0.000 claims description 13
- 238000005266 casting Methods 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229940125782 compound 2 Drugs 0.000 claims description 4
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims description 2
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 claims description 2
- 229910000103 lithium hydride Inorganic materials 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- 125000003003 spiro group Chemical group 0.000 abstract description 8
- 239000003513 alkali Substances 0.000 abstract description 6
- 239000003014 ion exchange membrane Substances 0.000 abstract description 4
- 238000010612 desalination reaction Methods 0.000 abstract description 3
- 239000013535 sea water Substances 0.000 abstract description 3
- 238000005342 ion exchange Methods 0.000 abstract description 2
- 239000005518 polymer electrolyte Substances 0.000 abstract description 2
- 229920006254 polymer film Polymers 0.000 abstract description 2
- RCXFJYVHZBXWRS-UHFFFAOYSA-N 8-pyrimidin-2-yl-8-aza-5-azoniaspiro[4.5]decane Chemical class C1CCC[N+]21CCN(C=1N=CC=CN=1)CC2 RCXFJYVHZBXWRS-UHFFFAOYSA-N 0.000 abstract 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 21
- 150000001450 anions Chemical class 0.000 description 21
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 16
- 238000012360 testing method Methods 0.000 description 12
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 10
- 210000004027 cell Anatomy 0.000 description 9
- 235000006408 oxalic acid Nutrition 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000001384 succinic acid Substances 0.000 description 5
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- VWBFKEUOPUBZJO-UHFFFAOYSA-N C.C1=CC=C(C=C1)C2=CC(=C(C(=C2N)N)N)N Chemical compound C.C1=CC=C(C=C1)C2=CC(=C(C(=C2N)N)N)N VWBFKEUOPUBZJO-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N malonic acid group Chemical group C(CC(=O)O)(=O)O OFOBLEOULBTSOW-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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- KSFAWAYSJUPRED-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetramine Chemical compound NC1=C(N)C(N)=CC(C=2C=CC=CC=2)=C1N KSFAWAYSJUPRED-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 210000000352 storage cell Anatomy 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/18—Polybenzimidazoles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/422—Electrodialysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/428—Membrane capacitive deionization
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
- B01J41/13—Macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
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Abstract
The invention discloses heterocyclic ammonium ion polybenzimidazole and an anion exchange membrane as well as a preparation method and application thereof, belonging to the technical field of polymer electrolytes and ion exchange membranes. Firstly, halogenated spiro ammonium salt is synthesized, then the halogenated spiro ammonium is introduced to a polybenzimidazole molecular chain through a grafting reaction to synthesize heterocyclic ammonium ion polybenzimidazole, and the heterocyclic ammonium ion polybenzimidazole anion exchange membrane is prepared through alkali ion exchange. The heterocyclic ammonium ion polybenzimidazole and the anion exchange membrane thereof prepared by the method have good polymer film forming property, high ionic conductivity, obviously improved mechanical property and alkali resistance stability and good dimensional stability, and are widely applied to the related fields of ion exchange membranes such as fuel cells, flow batteries, electrolysis, electrodialysis, seawater desalination and the like.
Description
Technical Field
The invention relates to heterocyclic ammonium ion polybenzimidazole and an anion exchange membrane as well as a preparation method and application thereof, belonging to the technical field of polymer electrolytes and ion exchange membranes.
Background
In recent years, the urgent need of clean energy for various industries and civilians is caused by energy crisis and resource exhaustion, and the development of the clean energy is emphasized by countries in the world. The fuel cell has a series of advantages of environmental protection, high energy conversion rate and the like, and is paid more and more attention by scientific researchers, and meanwhile, the fuel cell also makes a series of great progress. The alkaline anion exchange membrane fuel cell is used as one of the fuel cells, has the advantages of no need of noble metal as a catalyst, simple water management and the like, and simultaneously faces the challenges of low ionic conductivity and poor alkaline resistance stability, which is also the place for improving the force of the invention.
Polybenzimidazole as an excellent special engineering plastic shows excellent mechanical stability, heat resistance and alkali resistance, attracts more and more attention of researchers, and is concerned to be applied to the fields of fuel cells, ion membranes for energy storage cells and the like. Currently, polybenzimidazole is used mostly in high temperature proton membranes, and the patent [ Wang Lei et al, patent publication No.: CN 106684415 a discloses a preparation of PBI doped phosphoric acid high temperature proton membrane, patent [ luggong et al, patent publication No.: CN 107887626 a discloses a cross-linked composite high-temperature proton membrane and its preparation method, patent [ patent publication No.: CN 107674417A discloses a non-ionic hydrophilic side chain polybenzimidazole and a preparation method thereof. However, there are few publications on the use of polybenzimidazole for basic anion exchange membranes, and patent [ cinnolin et al, patent publication No.: CN 108623806A discloses a polybenzimidazole with side amino, an anion exchange membrane thereof and a preparation method thereof.
Disclosure of Invention
Aiming at the problems of low ion conductivity and poor alkali resistance and stability of the existing alkaline anion resin and the ion exchange membrane thereof, the invention provides heterocyclic ammonium ion polybenzimidazole with good mechanical property, high alkali resistance and good size stability, an anion exchange membrane thereof and a preparation method thereof.
The invention is realized by adopting the following technical scheme:
a heterocyclic ammonium ion polybenzimidazole having the structure:
wherein n is 0-0.8;
z is Cl-,Br-Or OH-Ions, preferably OH-Ions;
a is a single bond, methylene-CH2-, an ether bond-O-or a carbonyl group-CO-, preferably A is a single bond or methylene-CH2-；
X takes the following structure:
wherein 2. ltoreq. n '.ltoreq.18, preferably X is 2. ltoreq. n' 8;
y has the following structure:
preferably Y is (a), (c), (e) and (f);
the invention provides a preparation method of the heterocyclic ammonium ion polybenzimidazole, which comprises the following steps:
The polybenzimidazole is synthesized by a tetramine monomer (II) and a diacid monomer (III) through solution polycondensation.
The tetramine monomer (II) has the following structure:
wherein A is a single bond or methylene-CH2-；
The structure of the diacid monomer (III) is as follows:
HOOC-X-COOH and HOOC-Y-COOH
Wherein, X takes the following structure:
wherein 2. ltoreq. n '.ltoreq.18, preferably X is 2. ltoreq. n' 8;
y has the following structure:
preferably Y is (a), (c), (e) and (f);
polyphosphoric acid is added into a reactor with stirring, and N is added2Under protection, adding tetramine monomer (II) and diacid monomer (III) HOOC-X-COOH and HOOC-Y-COOH in equal molar ratio, stirring and dissolving to make the total mass concentration of monomer II and monomer III be 1-20 wt%. Heating to 90-140 ℃, stirring for reaction for 0.5-10 h, heating to 140-160 ℃, stirring for reaction for 0.5-10 h, and heating to 160-190 ℃ for reaction for 8-30 h. After the polymerization reaction is finished, the product is poured into a large amount of deionized water, and excess NaHCO is added3And stirred overnight. Filtration and washing of the polymer with deionized water until neutral. The product was dried to give polybenzimidazole.
Step 2-1, Synthesis of heterocyclic ammonium ion polybenzimidazole (1)
Heating and dissolving a certain amount of polybenzimidazole in a solvent 2 to obtain a solution with the mass-volume ratio concentration of 0.5-10%, adding dibromopentane and an alkaline compound 2, and reacting at 30-150 ℃ for 8-100 h. And after the reaction is finished, adding a precipitating agent 1, filtering, washing a filter cake for 3 times by using deionized water, and drying a product to obtain the heterocyclic ammonium ion polybenzimidazole (1).
Step 2-2 Synthesis of heterocyclic ammonium ion polybenzimidazole (2)
Adding a quantity of piperidine to the dihaloalkane-containing P- (CH)2)mHeating P (P is Cl or Br atom, m is an integer more than 0 and less than or equal to 6, preferably m is more than or equal to 2 and less than or equal to 3) in a solvent 2, and stirring for reaction for 6-72 h at 30-90 ℃. After the reaction is finished, filtering and drying to obtain M';
heating and dissolving a certain amount of polybenzimidazole in a solvent 2 to obtain 0.5-10 wt% of solution, adding M' and reacting at 30-150 ℃ for 8-100 h. And after the reaction is finished, adding a precipitating agent 1, filtering, washing a filter cake for 3 times by using deionized water, and drying a product to obtain the heterocyclic ammonium ion polybenzimidazole (2).
Further, in the above technical scheme, Z is OH-Ions; a is a single bond or methylene-CH2-; n in X is not less than 2 and not more than 8;
y is selected from (a), (c), (e) or (f).
Further, in the above technical solution, the solvent 1 is one or a mixture of several of toluene, methanol, ethanol, dichloromethane, tetrahydrofuran, acetonitrile, acetone, ethyl acetate, N-dimethylacetamide, dimethyl sulfoxide, N-dimethylformamide, and N-methylpyrrolidone;
the solvent 2 is one or a mixture of more of toluene, dichloromethane, chloroform, N-dimethylacetamide, dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone;
further, in the technical scheme, the molar ratio of the polybenzimidazole to the dibromopentane in the step 2-1 is 0.1-1: 1, preferably 0.4-1: 1;
further, in the above technical scheme, in the step 2-2, piperidine and dihaloalkane P- (CH)2)mThe molar ratio of-P is 0.05 to 1:1, preferably 0.1 to 0.5: 1; the molar ratio of polybenzimidazole to M' is 0.1-1: 1.
A preparation method of heterocyclic ammonium ion polybenzimidazole and an anion exchange membrane thereof is characterized in that a precipitator 1 is one or a mixture of more of methanol, ethanol, diethyl ether, ethyl acetate, dichloromethane, tetrahydrofuran, acetone and water.
The alkaline compound 2 is selected from one or more of sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydride and lithium hydride.
Further, in the technical scheme, the viscosity average molecular weight of the polybenzimidazole is 10,000-450,000 g/mol, and the polymerization degree n is 20-1200.
The invention provides a preparation method of a heterocyclic ammonium ion polybenzimidazole anion exchange membrane, which comprises the steps of heating and dissolving heterocyclic ammonium ion polybenzimidazole (1) or heterocyclic ammonium ion polybenzimidazole (2) in a solvent 3 to prepare a 1-15 wt% solution, filtering, casting the filtrate on a clean flat plate, paving a membrane, and transferring the membrane into an oven for drying. And putting the prepared membrane into a 1M NaOH or 1M KOH solution for 24-48 h, taking out, soaking for 24h with water, taking out, and drying to obtain the heterocyclic ammonium ion polybenzimidazole anion exchange membrane (1) or the heterocyclic ammonium ion polybenzimidazole anion exchange membrane (2).
Further, in the above technical solution, the solvent 3 is selected from.
The invention provides the application of the heterocyclic ammonium ion polybenzimidazole as an electrolyte in fuel cells, flow batteries, water electrolysis, electrodialysis and membrane separation.
The invention provides application of the heterocyclic ammonium ion polybenzimidazole anion exchange membrane in the related fields of fuel cells, flow batteries, water electrolysis, electrodialysis and membrane separation.
The invention also aims to protect the application of the heterocyclic ammonium ion polybenzimidazole anion exchange membrane in the fields related to fuel cells, flow batteries, electrolysis and electrodialysis, and seawater desalination plasma membranes.
Compared with the prior art, the invention has the following advantages: the heterocyclic ammonium ion polybenzimidazole and the anion exchange membrane thereof prepared according to the invention and the preparation method thereof have the advantages of good polymer film forming property, high ionic conductivity, high membrane toughness and high alkali resistance stability, and are widely applied to the related fields of fuel cells, flow batteries, electrolysis, electrodialysis and seawater desalination plasma membranes.
Drawings
FIG. 1 is a hydrogen nuclear magnetic spectrum of a main chain spiro ammonium PBI anion exchange membrane prepared in example 9;
FIG. 2 is a photograph of the backbone spiro ammonium PBI anion exchange membrane prepared in example 9.
Detailed Description
The following examples further illustrate details of the heterocyclic ammonium ion polybenzimidazole anion exchange membrane of the present invention, its preparation method and application, but not intended to limit the scope of the present invention, and unless otherwise specified, the chemical reagents and pharmaceutical products of the present invention are commercially available, and if not specifically specified, the methods involved are conventional.
Examples relate to test methods:
ion Exchange Capacity (IEC) test method: about 0.1g of 3 parts of monoammonium ion polybenzimidazole is respectively soaked in 100ml of NaOH with the concentration of 1M for 24h, then is respectively soaked in 100ml of deionized water for 24h and is washed to be neutral, and is dried in a vacuum oven at the temperature of 60 ℃, and is respectively soaked in 0.02002M of HCl for 24 h. A few drops of phenolphthalein were added and titrated to pink with 0.0182M NaOH and the amount of NaOH required was recorded. The IEC is determined by subtracting the moles of NaOH from the moles of HCl and dividing by 0.1 (g).
The examples relate to a test instrument:
and (3) conductivity test: the used electrochemical workstation is produced by Shanghai Chenghua apparatus Co., Ltd, and has the model number of chi660 c.
Nuclear magnetic testing: the NMR spectrometer used was a model number Bruker Avance II 400, 400MHz from Warran, USA. In nuclear magnetic spectrum, both salts are represented by D2O is used as a solvent, and DMSO-d6 is used as a solvent for the polymer after grafting.
Table 1 shows the chemical structures of the heterocyclic ammonium ion polybenzimidazole used in the examples.
TABLE 1
Example 1
Polyphosphoric acid is added into a reactor with stirring, and N is added2Adding biphenyltetramine methane (A is methylene-CH) under protection2-) and succinic acid and biphenyldicarboxylic acid (the total mole number of the succinic acid and the biphenyldicarboxylic acid is equal to the mole number of the biphenyltetramine methane), heating and stirring to dissolve, so that the monomer concentration is 10 wt%. Heating to 110 ℃, stirring for reaction for 5h, reacting at 140 ℃ for 0.5h, and then heating to 180 ℃ for reaction for 8h until the viscosity of the system is not increased any more. At the end of the polymerization, the product is poured into a large amount of deionized water and excess NaHCO is added3And stirred overnight. Filtration and washing of the polymer with deionized water until neutral. The product was dried to give polybenzimidazole.
10mol of the synthesized polybenzimidazole is heated and dissolved in DMSO to obtain a 5 wt% solution, 12mol of dibromopentane is added, and the reaction is carried out for 30h at 50 ℃. After the reaction is finished, pouring the mixture into a large amount of ethanol, filtering, washing a filter cake with deionized water for 3 times, and drying a product to obtain a polymerization product (1).
Dissolving the polymerization product (1) in DMSO to prepare a 4 wt% solution, vacuumizing for 0.5h, filtering, casting the filtrate on a clean flat plate, paving a membrane, and transferring to an oven for drying at 60 ℃. And soaking the prepared membrane in a 1M NaOH solution for 24h, taking out, soaking in water for 24h, taking out, and drying to obtain the double-ammonium ion PBI anion membrane.
The test shows that the double ammonium ion PBI anion membrane has OH at 80 DEG C-The conductivity is 42mS/cm, the ionic membrane has good toughness, and OH is obtained after the ionic membrane is soaked in KOH solution of 1M at the temperature of 80 ℃ for 1000h-The ionic conductivity remained 85%.
Example 2
Polyphosphoric acid is added into a reactor with stirring, and N is added2Under protection, adding biphenyltetramine, oxalic acid and terephthalic acid (the total mole number of the oxalic acid and the terephthalic acid)Equal to the mole number of the biphenyltetramine methane), heating, stirring and dissolving so that the monomer concentration is 10 wt%. Heating to 120 ℃, stirring and reacting for 10h, reacting for 2h at 145 ℃, and then heating to 180 ℃ and reacting for 20h until the viscosity of the system is not increased any more. At the end of the polymerization, the product is poured into a large amount of deionized water and excess NaHCO is added3And stirred overnight. Filtration and washing of the polymer with deionized water until neutral. The product was dried to give polybenzimidazole.
10mol of the synthesized polybenzimidazole is heated and dissolved in DMSO to obtain a 5 wt% solution, 10mol of dibromopentane is added, and the reaction is carried out for 30h at 50 ℃. After the reaction is finished, pouring the mixture into a large amount of ethanol, filtering, washing a filter cake with deionized water for 3 times, and drying a product to obtain a polymerization product (1).
Dissolving the polymerization product (1) in DMSO to prepare a 4 wt% solution, vacuumizing for 0.5h, filtering, casting the filtrate on a clean flat plate, paving a membrane, and transferring to an oven for drying at 60 ℃. And soaking the prepared membrane in a 1M NaOH solution for 24h, taking out, soaking in water for 24h, taking out, and drying to obtain the double-ammonium ion PBI anion membrane.
The test shows that the double ammonium ion PBI anion membrane has OH at 80 DEG C-The conductivity is 40mS/cm, the ionic membrane has good toughness, and OH is obtained after the ionic membrane is soaked in KOH solution of 1M at the temperature of 80 ℃ for 1400h-The ionic conductivity remained 85%.
Example 3
Backbone polybenzimidazole was synthesized as in example 2.
10mol of polybenzimidazole was dissolved in chloroform under heating to give a 12 wt% solution, and 10mol of dibromopentane was added to the solution to react at 40 ℃ for 15 hours. After the reaction is finished, pouring the mixture into a large amount of ethanol, filtering, washing a filter cake for 3 times by using deionized water, and drying a product to obtain a product (1).
Dissolving the product (1) in chloroform to prepare a 10 wt% solution, vacuumizing for 0.5h, filtering, casting the filtrate on a clean flat plate, paving a membrane, and transferring to a 60 ℃ oven for drying. And soaking the prepared membrane in a 1M NaOH solution for 24h, taking out, soaking in water for 24h, taking out, and drying to obtain the double-ammonium ion PBI anion membrane.
The test shows that the double ammonium ion PBI anion membrane has OH at 80 DEG C-A conductivity of 45mS/cm, theThe ionic membrane has good toughness, and OH is obtained after the ionic membrane is soaked in KOH solution of 1M at the temperature of 80 ℃ for 1300h-The ionic conductivity remained 87%.
Example 4
Backbone polybenzimidazole was synthesized as in example 2, wherein oxalic acid and terephthalic acid were replaced by pimelic acid and diphenyletherdiacid.
10mol of polybenzimidazole is heated and dissolved in DMSO to obtain a 7 wt% solution, 30mol of dibromopentane is added, and the reaction is carried out for 12 hours at 50 ℃. After the reaction is finished, pouring the mixture into a large amount of ethanol, filtering, washing a filter cake for 3 times by using deionized water, and drying a product to obtain a product (1).
Dissolving the product (1) in dimethyl sulfoxide (DMSO) to prepare 6 wt% solution, vacuumizing for 0.5h, filtering, casting the filtrate on a clean flat plate, spreading a membrane, and transferring to a 60 ℃ oven for drying. And soaking the prepared membrane in a 1M NaOH solution for 24h, taking out, soaking in water for 24h, taking out, and drying to obtain the double-ammonium ion PBI anion membrane.
The test shows that the double ammonium ion PBI anion membrane has OH at 80 DEG C-The conductivity is 42mS/cm, the ionic membrane has good toughness, and OH is obtained after the ionic membrane is soaked in KOH solution of 1M at the temperature of 80 ℃ for 1300h-The ionic conductivity remained 85%.
Example 5
Backbone polybenzimidazole was synthesized as in example 2, wherein oxalic acid and terephthalic acid were replaced by adipic acid and diphenylmethane diacid.
10mol of piperidine is added into acetone solution of 40mol of dibromoethane, and the temperature is raised to 40 ℃ to stir and react for 20 h. After the reaction is finished, filtering and drying to obtain M'; 10mol of polybenzimidazole was dissolved in DMSO under heating to give a 7 wt% solution, and 20mol of M' was added thereto, followed by reaction at 50 ℃ for 15 hours. After the reaction, the mixture was poured into a large amount of ethanol. Filtering, washing a filter cake with deionized water for 3 times, and drying a product to obtain a product (2).
Dissolving the product (2) in N-methylpyrrolidone (NMP) to prepare a 4 wt% solution, vacuumizing for 0.5h, filtering, casting the filtrate on a clean flat plate, paving a membrane, and transferring to a 60 ℃ oven for drying. And soaking the prepared membrane in a 1M NaOH solution for 24h, taking out, soaking in water for 24h, taking out, and drying to obtain the double-ammonium ion PBI anion membrane.
The test shows that the double ammonium ion PBI anion membrane has OH at 80 DEG C-The conductivity is 40mS/cm, the ionic membrane has good toughness, and OH is obtained after the ionic membrane is soaked in KOH solution of 1M at the temperature of 80 ℃ for 1200h-The ionic conductivity remained 85%.
Example 6
Backbone polybenzimidazole was synthesized as in example 1, in which succinic acid and biphenyldioic acid were replaced by succinic acid and isophthalic acid.
10mol of the synthesized polybenzimidazole is heated and dissolved in NMP to obtain a 15 wt% solution, 10mol of dibromopentane is added, and the reaction is carried out for 18h at 35 ℃. After the reaction is finished, pouring the mixture into a large amount of methanol, filtering, washing a filter cake with deionized water for 3 times, and drying a product to obtain a product (1).
Dissolving the product (1) in NMP to prepare 6 wt% solution, vacuumizing for 0.5h, filtering, casting the filtrate on a clean flat plate, paving a membrane, and transferring to a 60 ℃ oven for drying. And soaking the prepared membrane in a 1M NaOH solution for 24h, taking out, soaking in water for 24h, taking out, and drying to obtain the double-ammonium ion PBI anion membrane.
The test shows that the double ammonium ion PBI anion membrane has OH at 80 DEG C-The conductivity is 42mS/cm, the ionic membrane has good toughness, and OH is obtained after the ionic membrane is soaked in KOH solution of 1M at the temperature of 80 ℃ for 1350h-The ionic conductivity remained 86%.
Example 7
Backbone polybenzimidazole was synthesized as in example 1, wherein succinic acid and biphenyldioic acid were replaced with malonic acid and diphenyletherdioic acid.
10mol of the synthesized polybenzimidazole is heated and dissolved in chloroform to obtain a 10 wt% solution, 8mol of dibromopentane is added, and the reaction is carried out for 10 hours at 60 ℃. After the reaction is finished, pouring the mixture into a large amount of ethanol, filtering, washing a filter cake for 3 times by using deionized water, and drying a product to obtain a product (1).
Dissolving the product (1) in N, N-dimethylacetamide (DMAc) to prepare a 10 wt% solution, vacuumizing for 0.5h, filtering, casting the filtrate on a clean flat plate to spread a membrane, and transferring the membrane to a 60 ℃ oven for drying. And soaking the prepared membrane in a 1M NaOH solution for 24h, taking out, soaking in water for 24h, taking out, and drying to obtain the double-ammonium ion PBI anion membrane.
The test shows that the double ammonium ion PBI anion membrane has OH at 80 DEG C-The conductivity is 40mS/cm, the ionic membrane has good toughness, and OH is obtained after the ionic membrane is soaked in KOH solution of 1M at the temperature of 80 ℃ for 1400h-The ionic conductivity was maintained at 84%.
Example 8
Backbone polybenzimidazole was synthesized as in example 2, wherein oxalic acid and terephthalic acid were replaced by suberic acid and terephthalic acid.
10mol of the synthesized polybenzimidazole is heated and dissolved in DMAc to obtain a 5 wt% solution, 15mol of dibromopentane is added, and the reaction is carried out for 12h at 70 ℃. After the reaction is finished, pouring the mixture into a large amount of methanol, filtering, washing a filter cake with deionized water for 3 times, and drying a product to obtain a product (1).
Dissolving the product (1) in DMAc to prepare a 12 wt% solution, vacuumizing for 0.5h, filtering, casting the filtrate on a clean flat plate, paving a film, and transferring the film to a 60 ℃ oven for drying. And soaking the prepared membrane in a 1M NaOH solution for 24h, taking out, soaking in water for 24h, taking out, and drying to obtain the double-ammonium ion PBI anion membrane.
The test shows that the double ammonium ion PBI anion membrane has OH at 80 DEG C-The conductivity is 50mS/cm, the ionic membrane has good toughness, and OH is obtained after the ionic membrane is soaked in KOH solution of 1M at the temperature of 80 ℃ for 1300h-The ionic conductivity remained 87%.
Example 9
Backbone polybenzimidazole was synthesized as in example 2, wherein oxalic acid and terephthalic acid were replaced by diphenyl ether diacid.
10mol of the synthesized polybenzimidazole is heated and dissolved in DMSO to obtain a 10 wt% solution, 20mol of dibromopentane is added, and the reaction is carried out for 20 hours at 45 ℃. After the reaction is finished, pouring the mixture into a large amount of ethanol, filtering, washing a filter cake for 3 times by using deionized water, and drying a product to obtain a product (1).
Dissolving the product (1) in DMSO to prepare a 10 wt% solution, vacuumizing for 0.5h, filtering, casting the filtrate on a clean flat plate, paving a membrane, and transferring to an oven for drying at 60 ℃. And soaking the prepared membrane in a 1M NaOH solution for 24h, taking out, soaking in water for 24h, taking out, and drying to obtain the double-ammonium ion PBI anion membrane.
Tested at 80 DEG COH of the double-ammonium ion PBI anion membrane-The conductivity is 45mS/cm, the ionic membrane has good toughness, and OH is obtained after the ionic membrane is soaked in KOH solution of 1M at the temperature of 80 ℃ for 1200h-The ionic conductivity remained 86%.
Hydrogen nuclear magnetic spectrum analysis of fig. 1:
FIG. 1 is the hydrogen nuclear magnetic spectrum diagram of the anion exchange membrane of spiro benzimidazole with DMSO-d6 as solvent and 400MHz as nuclear magnetic instrument frequency. As shown in FIG. 1, no characteristic peak of N-H on imidazole ring in main chain appeared between chemical shift 11-13ppm, and no Br-CH appeared around 3.5ppm2The characteristic peak of the methylene indicates that the imidazole N-H of the polymer main chain is successfully cyclized into a spiro ring structure. The chemical shifts 3.51ppm and 2.41ppm are characteristic peaks of trace water molecules and solvent DMSO molecules. Chemical shifts of 8.30 ppm and 7.36ppm are characteristic peaks of H2 and H1 on benzene rings of diphenyl ether in polymer structural units. The chemical shifts of 7.91ppm, 7.73ppm and 7.64ppm are the characteristic peaks of H3, H4 and H5 of the benzene ring connected with the polymer structural unit tetramine. Chemical shift 4.40ppm is spiro ring connected directly with N positive ion-CH2The upper H6 characteristic peak is that the chemical shift at 1.79ppm is the spiro ring is located at the N positive ion meta-CH2Characteristic peak of upper H7. From the above analysis, it can be known that the PBI main chain imidazole structure is successfully cyclized to a spiro ammonium structure, and the main chain spiro ammonium PBI anion exchange membrane is prepared.
Example 10
Backbone polybenzimidazole was synthesized as in example 2, wherein oxalic acid and terephthalic acid were replaced by isophthalic acid.
10mol of the synthesized polybenzimidazole is heated and dissolved in NMP to obtain a 15 wt% solution, 15mol of dibromopentane is added, and the reaction is carried out for 15h at 45 ℃. After the reaction is finished, pouring the mixture into a large amount of ethanol, filtering, washing a filter cake for 3 times by using deionized water, and drying a product to obtain a product (1).
Dissolving the product (1) in NMP to prepare a 10 wt% solution, vacuumizing for 0.5h, filtering, casting the filtrate on a clean flat plate, paving a membrane, and transferring to a 60 ℃ oven for drying. And soaking the prepared membrane in a 1M NaOH solution for 24h, taking out, soaking in water for 24h, taking out, and drying to obtain the double-ammonium ion PBI anion membrane.
The test shows that the double ammonium ion PBI anion membrane has OH at 80 DEG C-The conductivity is 40mS/cm, the ionic membrane has good toughness, and OH is obtained after the ionic membrane is soaked in KOH solution of 1M at the temperature of 80 ℃ for 1300h-The ionic conductivity was maintained at 84%.
Claims (10)
1. A heterocyclic ammonium ion polybenzimidazole characterized by the following structure:
wherein n is 0-0.8;
z is Cl-,Br-Or OH-Ions;
a is a single bond, methylene-CH2-, an ether bond-O-or a carbonyl group-CO-;
x takes the following structure:
wherein n' is more than or equal to 2 and less than or equal to 18;
y has the following structure:
2. the method of claim 1, comprising the steps of: step 1, Synthesis of polybenzimidazole
The polybenzimidazole is synthesized by a tetramine monomer (II) and a diacid monomer (III) through solution polycondensation;
the tetramine monomer (II) has the following structure:
wherein A is a single bond, methylene-CH2-, an ether bond-O-or carbonyl-CO-;
the structure of the diacid monomer (III) is as follows:
HOOC-X-COOH and HOOC-Y-COOH
Wherein, X takes the following structure:
wherein n' is more than or equal to 2 and less than or equal to 18;
y has the following structure:
polyphosphoric acid is added into a reactor with stirring, and N is added2Under protection, adding a tetramine monomer (II) and diacid monomers (III) HOOC-X-COOH and HOOC-Y-COOH in an equimolar ratio, and stirring for dissolving to ensure that the total mass concentration of the monomers II and III is 1-20 wt%; heating to 90-140 ℃, stirring for reaction for 0.5-10 h, heating to 140-160 ℃, stirring for reaction for 0.5-10 h, and heating to 160-190 ℃ for reaction for 8-30 h; after the polymerization reaction is finished, the product is poured into a large amount of deionized water, and excess NaHCO is added3Stirring overnight; filtering, washing the polymer with deionized water until the polymer is neutral; drying the product to obtain polybenzimidazole;
step 2-1, Synthesis of heterocyclic ammonium ion polybenzimidazole (1)
Heating and dissolving a certain amount of polybenzimidazole in a solvent 2 to obtain a solution with the mass-volume ratio concentration of 0.5-10%, adding dibromopentane and an alkaline compound 2, and reacting at 30-150 ℃ for 8-100 h; after the reaction is finished, adding a precipitating agent 1, filtering, washing a filter cake for 3 times by using deionized water, and drying a product to obtain heterocyclic ammonium ion polybenzimidazole (1);
step 2-2 Synthesis of heterocyclic ammonium ion polybenzimidazole (2)
Adding a quantity of piperidine to the dihaloalkane-containing P- (CH)2)mHeating the mixture to 30-90 ℃ in the solvent 2 of the-P, and stirring for reacting for 6-72 hours; after the reaction is finished, filtering and drying to obtain M';
heating and dissolving a certain amount of polybenzimidazole in a solvent 2 to obtain 0.5-10 wt% of solution, adding M' and reacting at 30-150 ℃ for 8-100 h; after the reaction is finished, adding a precipitating agent 1, filtering, washing a filter cake for 3 times by using deionized water, and drying a product to obtain heterocyclic ammonium ion polybenzimidazole (2); wherein, P is selected from Cl or Br atoms, and m is more than 0 and less than or equal to 6.
3. The method for preparing heterocyclic ammonium ion polybenzimidazole according to claim 2, where in the solvent 1 is one or a mixture of several of toluene, methanol, ethanol, dichloromethane, tetrahydrofuran, acetonitrile, acetone, ethyl acetate, N-dimethylacetamide, dimethylsulfoxide, N-dimethylformamide, and N-methylpyrrolidone;
the solvent 2 is one or a mixture of more of toluene, dichloromethane, chloroform, N-dimethylacetamide, dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone.
4. The heterocyclic ammonium ion polybenzimidazole and its preparation method according to claim 2, characterized in that in step 2-1, the molar ratio of polybenzimidazole to dibromopentane is 0.1-1: 1;
in step 2-2, piperidine and dihaloalkane P- (CH)2)m-the molar ratio of-P is 0.05 to 1: 1; the molar ratio of polybenzimidazole to M' is 0.1-1: 1.
5. The method for preparing heterocyclic ammonium ion polybenzimidazole according to claim 2, where in said precipitant 1 is one or more of methanol, ethanol, diethyl ether, ethyl acetate, dichloromethane, tetrahydrofuran, acetone and water;
the alkaline compound 2 is selected from one or more of sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydride and lithium hydride.
6. The method for preparing heterocyclic ammonium ion polybenzimidazole according to claim 2, where polybenzimidazole has viscosity average molecular weight of 10,000 to 450,000g/mol and degree of polymerization n of 20 to 1200.
7. A preparation method of a heterocyclic ammonium ion polybenzimidazole anion exchange membrane is characterized by comprising the following steps:
heating and dissolving the heterocyclic ammonium ion polybenzimidazole (1) or the heterocyclic ammonium ion polybenzimidazole (2) in a solvent 3 to prepare a 1-15 wt% solution, filtering, casting the filtrate on a clean flat plate, paving a film, and transferring the film into an oven for drying; and putting the prepared membrane into a 1M NaOH or 1M KOH solution for 24-48 h, taking out, soaking for 24h with water, taking out, and drying to obtain the heterocyclic ammonium ion polybenzimidazole anion exchange membrane (1) or the heterocyclic ammonium ion polybenzimidazole anion exchange membrane (2).
8. The method according to claim 7, wherein the solvent 3 is one or more selected from the group consisting of toluene, methanol, ethanol, dichloromethane, tetrahydrofuran, acetonitrile, acetone, ethyl acetate, N-dimethylacetamide, dimethylsulfoxide, N-dimethylformamide, and N-methylpyrrolidone.
9. Use of the heterocyclic ammonium ionic polybenzimidazole according to claim 1 as an electrolyte in fuel cells, flow batteries, water electrolysis, electrodialysis and membrane separation.
10. Use of the heterocyclic ammonium ion polybenzimidazole anion exchange membrane according to claim 7 or 8 in the fields of fuel cells, flow batteries, water electrolysis, electrodialysis and membrane separation.
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| CN113856502A (en) * | 2021-10-18 | 2021-12-31 | 大连理工大学 | Quaternary amine type anion exchange membrane for reverse electrodialysis technology, preparation method and application thereof |
| CN116606438A (en) * | 2022-02-08 | 2023-08-18 | 大连理工大学 | Preparation method and application of polybenzimidazole with spiro-ammonified main chain, anion exchange membrane and ionomer solution thereof |
| CN117209760A (en) * | 2023-11-09 | 2023-12-12 | 国家电投集团氢能科技发展有限公司 | Sulfonated benzimidazole polymer and preparation method and application thereof |
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| CN113773491B (en) * | 2021-08-11 | 2023-08-01 | 华南师范大学 | Polybenzimidazole derivative and application thereof in fluorescent probe field |
| CN114163641B (en) * | 2021-11-12 | 2022-09-20 | 大连理工大学 | Ammonium polybenzimidazole and alkaline ion exchange membrane thereof, and preparation method and application of ionomer |
| CN114524919B (en) * | 2022-03-15 | 2023-08-29 | 北京化工大学 | Polyarylene anion exchange membrane and preparation method thereof |
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