CN113372596B - Alkaline anion exchange membrane based on chemical crosslinking and preparation method thereof - Google Patents
Alkaline anion exchange membrane based on chemical crosslinking and preparation method thereof Download PDFInfo
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- CN113372596B CN113372596B CN202110592582.7A CN202110592582A CN113372596B CN 113372596 B CN113372596 B CN 113372596B CN 202110592582 A CN202110592582 A CN 202110592582A CN 113372596 B CN113372596 B CN 113372596B
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- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 59
- 238000010382 chemical cross-linking Methods 0.000 title claims abstract description 36
- 238000005285 chemical preparation method Methods 0.000 title description 2
- 229920000642 polymer Polymers 0.000 claims abstract description 138
- 239000003960 organic solvent Substances 0.000 claims abstract description 93
- 239000000843 powder Substances 0.000 claims abstract description 71
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000005406 washing Methods 0.000 claims abstract description 31
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007787 solid Substances 0.000 claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 29
- 239000008367 deionised water Substances 0.000 claims abstract description 29
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 29
- 230000001590 oxidative effect Effects 0.000 claims abstract description 29
- 239000000126 substance Substances 0.000 claims abstract description 27
- 229920006254 polymer film Polymers 0.000 claims abstract description 18
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000005349 anion exchange Methods 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 238000005266 casting Methods 0.000 claims abstract description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 40
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 35
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 26
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 229920006037 cross link polymer Polymers 0.000 claims description 18
- 238000010791 quenching Methods 0.000 claims description 17
- 230000000171 quenching effect Effects 0.000 claims description 17
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000011521 glass Substances 0.000 claims description 14
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- HUUPVABNAQUEJW-UHFFFAOYSA-N 1-methylpiperidin-4-one Chemical group CN1CCC(=O)CC1 HUUPVABNAQUEJW-UHFFFAOYSA-N 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000004132 cross linking Methods 0.000 claims description 7
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 7
- 239000004695 Polyether sulfone Substances 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 5
- 229920000767 polyaniline Polymers 0.000 claims description 5
- 229920006393 polyether sulfone Polymers 0.000 claims description 5
- 229920002223 polystyrene Polymers 0.000 claims description 5
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000004693 Polybenzimidazole Substances 0.000 claims description 4
- 229920002480 polybenzimidazole Polymers 0.000 claims description 4
- 229920001088 polycarbazole Polymers 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- YHUNCTAOWLYFHG-UHFFFAOYSA-N 1,2,6-trimethylpiperidin-4-one Chemical compound CC1CC(=O)CC(C)N1C YHUNCTAOWLYFHG-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 abstract description 12
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 239000003513 alkali Substances 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 3
- 239000003014 ion exchange membrane Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 33
- 239000007788 liquid Substances 0.000 description 17
- 238000010521 absorption reaction Methods 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000012528 membrane Substances 0.000 description 15
- 150000001450 anions Chemical class 0.000 description 11
- 125000000524 functional group Chemical group 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 238000004108 freeze drying Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 7
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical group C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 125000003386 piperidinyl group Chemical group 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 238000005352 clarification Methods 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 230000037427 ion transport Effects 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 102100037709 Desmocollin-3 Human genes 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 101000968042 Homo sapiens Desmocollin-2 Proteins 0.000 description 1
- 101000880960 Homo sapiens Desmocollin-3 Proteins 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000000532 dioxanyl group Chemical group 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
- C08J5/2243—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231
- C08J5/225—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231 containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
- C08J5/2262—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2275—Heterogeneous membranes
- C08J5/2281—Heterogeneous membranes fluorine containing heterogeneous membranes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/08—Fuel cells with aqueous electrolytes
- H01M8/083—Alkaline fuel cells
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/02—Polyamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2381/06—Polysulfones; Polyethersulfones
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
An alkaline anion exchange membrane based on chemical crosslinking and a preparation method thereof are provided, wherein a polymer main chain is subjected to chemical crosslinking in strong oxidizing acid, piperidone and an organic solvent A at low temperature, quenched after the reaction is finished, washed and dried to obtain solid powder; adding the powder into an organic solvent B, adding methyl iodide, and performing a dark reaction at room temperature to obtain polymer powder; and (3) dissolving the polymer powder in an organic solvent C, casting into a film to obtain a polymer film, washing the polymer film with deionized water, and then performing anion exchange. According to the invention, the polymer main chain is subjected to self chemical crosslinking through the piperidone functional group for the first time, so that the mechanical strength and the chemical stability of the polymer main chain are improved; the synthesis path is simplified, the reaction flow is shortened, and the yield is improved; and the prepared alkaline anion exchange membrane is compact, transparent, high in ion exchange capacity, good in thermal stability and high in mechanical strength, and development of the polymer ion exchange membrane with high conductivity and strong alkali resistance is realized.
Description
Technical Field
The invention belongs to the field of polymer anion exchange membranes, and relates to an alkaline anion exchange membrane based on chemical crosslinking and a preparation method thereof.
Background
With the advent of energy crisis, hydrogen energy can be an effective alternative to traditional fossil fuels as a clean energy source. Hydrogen is successfully applied to Proton Exchange Membrane Fuel Cells (PEMFC) at present, and hydrogen automobiles and power generation devices have been commercialized gradually. PEMFCs have been successful in the market, but have disadvantages compared to Anion Exchange Membrane Fuel Cells (AEMFCs), which have increased production costs due to foreign monopolized proton exchange membranes and expensive noble metal catalysts. In contrast, AEMFC can obtain faster oxygen reduction reaction kinetics under alkaline conditions, the choice of catalyst is no longer limited to noble metal catalysts, and the electrooxidation of hydrogen and the electroreduction of oxygen are both better in non-strongly acidic environments. Thus, AEMFC generally performs better than PAFC and PEMFC using an acidic electrolyte; in addition, AEMFC operating temperature is low, and low temperature working property is good, and the battery starts soon. The anion exchange membrane is used as a core component of AEMFC, materials are all based on engineering plastics, and the manufacturing cost is low. The main problem at present is that the durability of the anion exchange membrane in a strongly alkaline environment is insufficient, so that it is necessary to provide a new anion exchange membrane.
Disclosure of Invention
Aiming at the problem of durability of AEMFC in a strong alkaline environment at 60-120 ℃, the invention aims to prepare a chemically crosslinked alkaline anion exchange membrane with stronger mechanical strength, good chemical stability, stable heat resistance and high ion exchange capacity and a preparation method thereof.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for preparing a basic anion exchange membrane based on chemical crosslinking, comprising the following steps:
step a, chemically crosslinking a polymer main chain in strong oxidizing acid, piperidone and an organic solvent A at low temperature, quenching after the reaction is finished, washing and drying to obtain solid powder;
b, adding the powder obtained in the step a into an organic solvent B, adding methyl iodide, performing a dark reaction at room temperature for 18-36 hours, extracting, washing and drying to obtain polymer powder;
and C, after dissolving the polymer powder in the organic solvent C, casting the polymer powder into a film to obtain a polymer film, washing the polymer film with deionized water, and then performing anion exchange to obtain the alkaline anion exchange film based on chemical crosslinking.
The invention is further improved in that the main chain of the polymer in the step a is one or two of polystyrene, SEBS, polycarbazole, polysulfone, polybenzimidazole, polyaniline and polyethersulfone benzene rings.
The invention is further improved in that the strong oxidizing acid in step a is one or both of trifluoroacetic acid and trifluoromethanesulfonic acid.
The invention is further improved in that the organic solvent A is one of dichloromethane, chloroform, 1, 2-tetrachloroethane, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide;
the organic solvent B is one of dichloromethane, chloroform, 1, 2-tetrachloroethane, dioxane, toluene, dimethylbenzene, N-dimethylacetamide and dimethyl sulfoxide;
the organic solvent C is one or more of tetrahydrofuran, dimethylbenzene, toluene, chloroform, 1, 2-tetrachloroethane, dimethylacetamide, dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide;
the invention is further improved in that the volume ratio of the mass of the polymer backbone to the organic solvent A is 1g:30 mL-1 g:200mL.
The invention is further improved in that the volume ratio of the mass of the polymer backbone to the organic solvent A is 1g:50 mL-1 g:80mL.
The invention is further improved in that the ratio of the amount of polymer backbone to the amount of the substance of the strong oxidizing acid is 1:1 to 1:5.
the invention is further improved in that the ratio of the amount of polymer backbone to the amount of the substance of the strong oxidizing acid is 1:1.2 to 1:1.5.
the invention is further improved in that in the step B, the volume ratio of the mass of the solid powder to the organic solvent B is 1g:30 mL-1 g:200mL.
The invention is further improved in that the volume ratio of the mass of the solid powder to the organic solvent B is 1g:50 mL-1 g:80mL;
the invention is further improved in that the low-temperature reaction temperature in the step a is 0-15 ℃ and the reaction time is 1-12 h.
The invention is further improved in that the low-temperature reaction temperature is 3-6 ℃ and the time is 2-4 h
The invention is further improved in that the drying condition is freeze drying.
The invention is further improved in that the drying temperature in the step b is 30-80 ℃ (preferably 40-60 ℃), and the time is 6-24h (preferably 12-18 h).
The invention is further improved in that the specific process of the step c is as follows: dissolving polymer powder in an organic solvent C, wherein the mass fraction of the polymer powder is 25-60% (optimally 45%), refluxing at 20-40 ℃ for 3-6 h, dissolving until clarification to obtain a chemically crosslinked polymer solution, pouring the chemically crosslinked polymer solution into a glass tank, and volatilizing the organic solvent C for 4-12h at 20-50 ℃ to obtain a transparent polymer film;
the invention is further improved in that the dissolution mode is one or more than two of mechanical stirring, magnetic stirring, ultrasonic and cell crushing, preferably one or more than two of ultrasonic and cell crushing;
a chemically cross-linked basic anion exchange membrane prepared according to the above preparation method.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, after the polymer main chain is dissolved in the organic solvent A, piperidone is used for chemical crosslinking in a low-temperature environment, so that the strength of the membrane is improved, and the anion exchange site in an alkaline environment is protected through the steric hindrance of a piperidine structure. Compared with the existing anion exchange membrane, the invention carries out self chemical crosslinking on the polymer main chain through the piperidone functional group for the first time, thereby improving the mechanical strength and the chemical stability of the polymer main chain; the invention simplifies the synthesis path, shortens the reaction flow, improves the yield, and avoids the problems of low yield and gelation caused by the traditional multi-step reactions of grafting, reducing and then functional group, and the like; and the prepared alkaline anion exchange membrane is compact, transparent, high in ion exchange capacity, good in thermal stability and high in mechanical strength, and development of the polymer ion exchange membrane with high conductivity and strong alkali resistance is realized.
Further, the optimal reaction time is determined to be 45-130 min through deionized water quenching reaction, and the 100% functionalized alkaline anion exchange membrane is obtained.
Drawings
FIG. 1 is a schematic diagram of a basic anion exchange membrane prepared in example 1 of the present invention.
FIG. 2 is a nuclear magnetic resonance spectrum of the basic anion exchange membrane of examples 1 to 4 of the present invention.
FIG. 3 is an infrared spectrum of the basic anion exchange membranes of examples 1 to 4 of the present invention.
FIG. 4 is a drawing showing the tensile test of the basic anion exchange membrane of example 1 of the present invention.
FIG. 5 is a thermogravimetric analysis of the basic anion exchange membrane of example 1 of the present invention.
FIG. 6 is a 5 k-time plan scanning electron microscope image of the basic anion exchange membrane of example 1 of the present invention.
FIG. 7 is a 15 k-time plan scanning electron microscope image of the basic anion exchange membrane of example 1 of the present invention.
FIG. 8 is a 100-fold cross-sectional scanning electron microscope image of the basic anion exchange membrane of example 1 of the present invention.
FIG. 9 is a 250-fold cross-sectional scanning electron micrograph of a basic anion exchange membrane of example 1 of this invention.
FIG. 10 is a graph showing the results of conductivity testing of the basic anion exchange membrane of example 1 of the present invention.
Detailed Description
The invention will now be described in more detail by way of examples with reference to the accompanying drawings.
According to the invention, the main chain is directly crosslinked through the piperidine functional group, the influence of the Huffman effect is reduced from the perspective of steric hindrance by combining with the excellent heat resistance, chemical stability and mechanical strength of the main chain, and the film forming process of the solution volatile solvent is optimized, so that a polymer anion exchange film with strong mechanical strength, good chemical stability, stable heat resistance and high ion exchange capacity is obtained, and the polymer anion exchange film is characterized.
The development of the polymeric anionic membranes of the present invention starts with structural design and functional group selection. The main chain structure without unsaturated bonds is selected, and the functional group with strong alkali resistance is used, so that the long-term chemical stability, high conductivity, lower swelling rate, micro-phase separation form of ion transportation and strong mechanical strength can be realized.
Step a, chemically crosslinking a polymer main chain in strong oxidizing acid, piperidone and an organic solvent A at low temperature, quenching after the reaction is finished, washing and drying to obtain powder; piperidones are N-methyl-4-piperidone, 2, 6-tetramethyl-4-piperidone or 1,2, 6-trimethyl-4-piperidone.
B, adding the powder obtained in the step a into an organic solvent B, adding methyl iodide, performing a dark reaction at room temperature for 18-36 hours, extracting, washing and drying after the reaction is finished to obtain polymer powder;
and C, after dissolving the polymer powder in the organic solvent C, casting the polymer powder into a film to obtain a polymer film, washing the polymer film with deionized water, and then performing anion exchange to obtain the alkaline anion exchange film based on chemical crosslinking.
The polymer main chain contains aromatic structure (benzene ring) for chemical modification. Specifically, the polymer main chain is one or more than two of polystyrene, SEBS, polycarbazole, polysulfone, polybenzimidazole, polyaniline and polyethersulfone benzene rings.
The strong oxidizing acid in the step a is one or two of trifluoroacetic acid and trifluoromethanesulfonic acid;
the organic solvent A is: one of dichloromethane, chloroform, 1, 2-tetrachloroethane, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide;
the organic solvent B is one of dichloromethane, chloroform, 1, 2-tetrachloroethane, dioxane, toluene, dimethylbenzene, N-dimethylacetamide and dimethyl sulfoxide;
the organic solvent C is one or more than two of tetrahydrofuran, dimethylbenzene, toluene, chloroform, 1, 2-tetrachloroethane, dimethylacetamide, dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide;
the quenching is performed by deionized water, and the resistivity of the deionized water reaches 18MΩ.
The volume ratio of the mass of the polymer main chain to the organic solvent A is 1g:30 mL-1 g:200mL (preferably 1g:50 mL-1 g:80 mL);
the molar ratio of polymer backbone to piperidone was 1:0.5 to 1:2 (preferably 1:0.5 to 1:1.2).
The ratio of the amount of polymer backbone to the amount of the substance of the strong oxidizing acid was 1:1 to 1:5 (preferably 1:1.2 to 1:1.5).
In step B, the volume ratio of the mass of the powder to the organic solvent B is 1g:30 mL-1 g:200mL (preferably 1g:50 mL-1 g:80 mL);
the low-temperature reaction temperature in the step a is 0-15 ℃ (preferably 3-6 ℃), and the reaction time is 1-12 h (preferably 2-4 h); the drying condition is freeze drying.
In the step b, the drying temperature is 30-80 ℃ (preferably 40-60 ℃), and the time is 6-24h (preferably 12-18 h).
The process of step c is as follows: dissolving polymer powder in an organic solvent C, refluxing the polymer powder with the mass fraction of 25-60% (optimally 45%) at 20-40 ℃ for 3-6 h, completely dissolving the polymer powder until the polymer powder is clarified to obtain a chemically crosslinked polymer solution, pouring the chemically crosslinked polymer solution into a glass tank, and volatilizing the organic solvent C at 20-50 ℃ for 4-12h to obtain a transparent polymer film;
the dissolution mode is one or more than two of mechanical stirring, magnetic stirring, ultrasonic and cell crushing, preferably one or two of ultrasonic and cell crushing;
a chemically cross-linked basic anion exchange membrane prepared according to the above method having the structural formula:
wherein R1, R2 and R3 can be methyl or H.
Preferably, in the invention, the SEBS is a linear triblock copolymer which takes polystyrene as a terminal block and takes an ethylene-butene copolymer obtained by hydrogenation of polybutadiene as an intermediate elastic block, and the SEBS does not contain unsaturated double bonds, so the SEBS has high chemical stability, good heat resistance and high benzene ring content and is easy to modify. The N-piperidine structure can effectively reduce OH in alkaline environment due to the steric hindrance of the N-piperidine structure - Attack on the functional group site reduces the impact of the Huffman elimination reaction. Therefore, the piperidone is used for directly carrying out chemical crosslinking on the SEBS main chain, so that the mechanical strength and the chemical stability of the anion exchange membrane are improved, an ion transport channel is provided, and the two effects are realized by one-step reaction.
Preferably, the invention specifically comprises the following steps:
1) Weighing 4-8 g of SEBS, dissolving in 100-200 mL of organic solvent A, mechanically stirring, adding 3-4 mL of N-methyl-4-piperidone after the SEBS is completely dissolved, and changing the solution into clear pale yellow.
2) The ice water bath reaction is started: after the temperature is reduced to about 3-9 ℃, 15-25 mL of TFSA and 1-5 mL of TFA are slowly added for reaction for 45-270 min, the liquid becomes viscous, and the reaction is stopped to obtain light brown liquid.
3) Pouring the light brown liquid in deionized water for quenching reaction, mechanically stirring at high speed, crushing the viscous polymer, washing for 4-8 times with deionized water to neutrality, and vacuum drying to obtain the polymer solid after chemical crosslinking.
4) Weighing 300-3000 mg of polymer solid after chemical crosslinking in the last step, dissolving in 100-200 mL of organic solvent B, completely dissolving, putting the reaction system in a dark environment, and adding 270-2700 mg of K 2 CO 3 0.15-1 mL of methyl iodide and reacting for 12-36 h at room temperature.
5) The liquid in the flask of the previous step was poured into methanol/ethyl acetate (volume ratio 1:1-1:2, most preferably 1:1.5 And (3) extracting, adding deionized water for 4-8 times to obtain functionalized polymer, and vacuum drying to obtain functionalized polymer solid.
6) Weighing 100-600 mg of polymer solid after functionalization in the previous step, dissolving in an organic solvent C, magnetically stirring, ultrasonically clarifying the solution, pouring the solution onto a culture dish/glass plate, and slowly evaporating the solvent at 20-50 ℃ to obtain the anion exchange membrane.
7) And (3) standing the anion exchange membrane in the anion solution for 12-48 hours at room temperature to finish ion exchange. The chemical crosslinking and functionalization on the benzene ring of the polymer are quantitatively characterized by adopting AVANCE III HD MHz, and the resonance frequency is 600MHz. During the experiment, a small amount of sample to be detected is taken and dissolved in deuterated chloroform, and the sample is obtained on a nuclear magnetic resonance apparatus 1 H NMR spectrum, with Tetramethylsilane (TMS) as internal standard, the results are shown in FIG. 2, and the calculated results of Ion Exchange Capacity (IEC) are shown in Table1.
8) The prepared alkaline anion exchange membrane is arranged in a four-terminal probe conductivity test mould, and is tested by using an alternating current impedance method, and the frequency is 100000Hz to 10Hz. The electrical resistance was obtained from the ac impedance plot, and the electrical conductivity at different temperatures was calculated from the reference electrode spacing/(polymer cross-sectional area. Resistance) =electrical conductivity, and the results are shown in fig. 10.
Example 1
1) 4g of SEBS was weighed and dissolved in 150mL of dichloromethane, and after complete dissolution, 3mL of N-methyl-4-piperidone was added, and the solution turned to a clear pale yellow color.
2) The ice water bath reaction is started, 15mL of TFSA (trifluoromethanesulfonic acid) and 3mL of TFA (trifluoroacetic acid) are slowly added until the temperature is reduced to about 3-9 ℃, the reaction is carried out for 45min, the liquid becomes viscous, and the reaction is stopped.
3) Pouring the light brown liquid in deionized water for quenching reaction, mechanically stirring at high speed, crushing the viscous polymer, washing for 4-8 times with deionized water to neutrality, and vacuum drying to obtain the polymer solid after chemical crosslinking.
4) Weighing 300mg of polymer solid in the previous step, dissolving in 100mL of chloroform, putting the reaction system in a dark environment after the polymer solid is completely dissolved, and adding 270mg of K 2 CO 3 0.18mL of methyl iodide was reacted at room temperature for 24 hours.
5) And pouring the liquid in the flask in the previous step into methanol/ethyl acetate for extraction, adding deionized water for 4-8 times for washing to obtain a functionalized polymer, and drying in vacuum to obtain a functionalized polymer solid.
6) 400mg of polymer solid in the previous step is weighed and dissolved in chloroform, magnetically stirred, and poured into a culture dish/glass plate after ultrasonic treatment until the solution is clarified, and the solvent is slowly evaporated at 20-50 ℃ to obtain the anion exchange membrane.
7) And (3) standing the anion exchange membrane in the anion solution for 24 hours at room temperature to finish ion exchange to obtain the anion membrane.
FIG. 1 is a schematic representation of the basic anion exchange membrane prepared in example 1, showing that the anion exchange membrane is transparent and dense.
The nuclear magnetic resonance results and the characterization of the infrared spectrum of the basic anion exchange membrane prepared in example 1 are shown in fig. 2, the functional groups on the polymer are characterized by using a Nicolet iS50 fourier transform infrared spectrometer, and the mode iS ATR-IR. A small sample was taken for the experiment and the results are shown in FIG. 3. As can be seen from FIGS. 2 and 3, the flow rate is 2920cm -1 There appears an absorption peak of methylene contained in the structure due to abundant C-H stretching vibration and bending vibration in the all-carbon skeleton of SEBS and piperidine functional groups. At 1460cm -1 The absorption peak of (2) can be attributed. Characteristic absorption peaks due to benzene rings in SEBS. At 1030cm -1 Characteristic peaks of C-N bonds on N-piperidine appear. In addition, when the reaction time was 170min, the reaction time was 1227cm due to excessive crosslinking -1 There appears a C-N characteristic peak due to offset. In conclusion, the molecular structures of polymers, organic matters and membranes in the synthesis process are identified through two test analysis means of nuclear magnetism and infrared, and the successful synthesis of the anion membrane is proved.
The anion exchange membrane was subjected to a tensile test using a universal tensile machine, and the results are shown in fig. 4, and it can be seen that when the tensile deformation amount is 190%, the membrane breaks, and the mechanical strength and elasticity of the membrane are proved to be good.
The results of the thermal stability analysis using METTLER TOLEDO TGA/DSC3+ under nitrogen atmosphere at room temperature-800 ℃ (800 ℃ C., heating rate of 10 ℃/min) are shown in FIG. 5. It can be seen that the anionic membrane is structurally decomposed at about 500 ℃ and has better thermal stability.
And (3) performing morphology observation by adopting a GEMINI 500 scanning electron microscope, placing the anion exchange membrane in liquid nitrogen for 4-24 hours, quenching to obtain a cross section, and observing the surface and the cross section by using multiples of 100, 250,5k and 15k respectively, wherein the result is shown in fig. 6-9, and the surface is smooth.
The dried alkaline anion exchange membrane was weighed, measured for mass and diameter, soaked in deionized water for 12 to 24 hours, and then the surface moisture was sucked with filter paper, again measured for mass and diameter, and the difference/dry film=swelling ratio and water absorption after drying and water absorption, and the results are shown in table 1.
TABLE 1 ion exchange Capacity, swelling Rate, water absorption of anion exchange Membrane
As can be seen from Table 1, the ion exchange capacity of the polymer film was 2.04mmol g -1 The water absorption rate is 18.42%, the swelling rate is 7.95%, and the performance of the anion membrane is proved to be good.
The prepared alkaline anion exchange membrane is arranged in a four-terminal probe conductivity test mould, and is tested by using an alternating current impedance method, and the frequency is 100000Hz to 10Hz. The electrical resistance was obtained from the ac impedance chart, and the electrical conductivity at temperatures of 25 ℃ to 80 ℃ was calculated from the reference electrode spacing/(polymer cross-sectional area. Resistance) =electrical conductivity, respectively, and the results are shown in fig. 10. It can be seen that the conductivity of the alkaline anion exchange membrane is 41.78mS/cm at 25 ℃, 167.54mS/cm at 80 ℃ and is not obviously reduced after being soaked in 5M NaOH strong alkaline solution for 200 hours, which indicates that the structure has strong alkali resistance.
Example 2
1) 4g of SEBS was weighed and dissolved in 150mL of dichloromethane, and after complete dissolution, 3mL of N-methyl-4-piperidone was added, and the solution turned to a clear pale yellow color.
2) And (3) starting an ice water bath reaction, slowly adding 15mL TFSA,3mL TFA when the temperature is reduced to about 3-9 ℃, reacting for 65min, changing the liquid into a viscous state, and stopping the reaction.
3) Pouring the light brown liquid in deionized water for quenching reaction, mechanically stirring at high speed, crushing the viscous polymer, washing for 4-8 times with deionized water to neutrality, and vacuum drying to obtain the polymer solid after chemical crosslinking.
4) Weighing 300mg of polymer solid in the previous step, dissolving in 200mL of chloroform, putting the reaction system in a dark environment after the polymer solid is completely dissolved, and adding 270mg of K 2 CO 3 0.18mL of methyl iodide was reacted at room temperature for 24 hours.
5) And pouring the liquid in the flask in the previous step into methanol/ethyl acetate for extraction, adding deionized water for 4-8 times for washing to obtain a functionalized polymer, and drying in vacuum to obtain a functionalized polymer solid.
6) 400mg of polymer solid in the previous step is weighed and dissolved in chloroform, magnetically stirred, and poured into a culture dish/glass plate after ultrasonic treatment until the solution is clarified, and the solvent is slowly evaporated at 20-50 ℃ to obtain the anion exchange membrane.
7) The anion exchange membrane was allowed to stand in the anion solution for 24 hours at room temperature to complete the ion exchange.
The nuclear magnetic resonance results and the characterization of the infrared spectrum versus the structure of the basic anion exchange membrane prepared in example 2 are shown in fig. 2 and 3. In FIG. 2, the chemical shift of the functional group structure due to chemical crosslinking occurs at the position where the chemical shift is 6.5-8.0 1 H. Illustrating the success of the synthesis of the product and the chemical shift of the different structures, FIG. 3 at 2920cm -1 There appears an absorption peak of methylene contained in the structure due to abundant C-H stretching vibration and bending vibration in the all-carbon skeleton of SEBS and piperidine functional groups. At 1460cm -1 The absorption peak of (2) is attributable to the characteristic absorption peak caused by the benzene ring in SEBS. At 1030cm -1 Characteristic peaks of C-N bonds on N-piperidine appear. In addition, when the reaction time was 170min, the reaction time was 1227cm due to excessive crosslinking -1 The appearance of the C-N characteristic peaks due to the shift shows that the functional groups of the synthesized product conform to the designed structure.
Example 3
1) 4g of SEBS was weighed and dissolved in 150mL of dichloromethane, and after complete dissolution, 3mL of N-methyl-4-piperidone was added, and the solution turned to a clear pale yellow color.
2) And (3) starting an ice water bath reaction, slowly adding 15mL TFSA,3mL TFA when the temperature is reduced to about 3-9 ℃, reacting for 110min, changing the liquid into a viscous state, and stopping the reaction.
3) Pouring the light brown liquid in deionized water for quenching reaction, mechanically stirring at high speed, crushing the viscous polymer, washing for 4-8 times with deionized water to neutrality, and vacuum drying to obtain the polymer solid after chemical crosslinking.
4) Weighing 300mg of polymer solid in the previous step, dissolving in 150mL of chloroform, putting the reaction system in a dark environment after the polymer solid is completely dissolved, and adding 270mg of K 2 CO 3 0.18mL of methyl iodide was reacted at room temperature for 24 hours.
5) And pouring the liquid in the flask in the previous step into methanol/ethyl acetate for extraction, adding deionized water for 4-8 times for washing to obtain a functionalized polymer, and drying in vacuum to obtain a functionalized polymer solid.
6) 400mg of polymer solid in the previous step is weighed and dissolved in chloroform, magnetically stirred, and poured into a culture dish/glass plate after ultrasonic treatment until the solution is clarified, and the solvent is slowly evaporated at 20-50 ℃ to obtain the anion exchange membrane.
7) The anion exchange membrane was allowed to stand in the anion solution for 24 hours at room temperature to complete the ion exchange.
The nuclear magnetic resonance results and the characterization of the infrared spectrum versus the structure of the basic anion exchange membrane prepared in example 3 are shown in fig. 2 and 3. In FIG. 2, the chemical shift of the functional group structure due to chemical crosslinking occurs at the position where the chemical shift is 6.5-8.0 1 H. Illustrating the success of the synthesis of the product and the chemical shift of the different structures, FIG. 3 at 2920cm -1 There appears an absorption peak of methylene contained in the structure due to abundant C-H stretching vibration and bending vibration in the all-carbon skeleton of SEBS and piperidine functional groups. At 1460cm -1 The absorption peak of (2) is attributable to the characteristic absorption peak caused by the benzene ring in SEBS. At 1030cm -1 Characteristic peaks of C-N bonds on N-piperidine appear. In addition, when the reaction time was 170min, the reaction time was 1227cm due to excessive crosslinking -1 The appearance of the C-N characteristic peaks due to the shift shows that the functional groups of the synthesized product conform to the designed structure.
Example 4
1) 4g of SEBS was weighed and dissolved in 150mL of dichloromethane, and after complete dissolution, 3mL of N-methyl-4-piperidone was added, and the solution turned to a clear pale yellow color.
2) And (3) starting an ice water bath reaction, slowly adding 15mL TFSA,3mL TFA when the temperature is reduced to about 3-9 ℃, reacting for 170min, changing the liquid into a viscous state, and stopping the reaction.
3) Pouring the light brown liquid in deionized water for quenching reaction, mechanically stirring at high speed, crushing the viscous polymer, washing for 4-8 times with deionized water to neutrality, and vacuum drying to obtain the polymer solid after chemical crosslinking.
4) Weighing 300mg of polymer solid in the previous step, dissolving in 120mL of chloroform, putting the reaction system in a dark environment after the polymer solid is completely dissolved, and adding 270mg of K 2 CO 3 0.18mL of methyl iodide was reacted at room temperature for 24 hours.
5) And pouring the liquid in the flask in the previous step into methanol/ethyl acetate for extraction, adding deionized water for 4-8 times for washing to obtain a functionalized polymer, and drying in vacuum to obtain a functionalized polymer solid.
6) 400mg of the polymer solid in the previous step is weighed, dissolved in chloroform, magnetically stirred, ultrasonically treated until the solution is clarified, poured into a culture dish/glass plate, and the solvent is slowly evaporated at 20-50 ℃ to obtain the anion exchange membrane, as shown in figure 1.
7) The anion exchange membrane was allowed to stand in the anion solution for 24 hours at room temperature to complete the ion exchange.
The nuclear magnetic resonance results and the characterization of the infrared spectrum versus the structure of the basic anion exchange membrane prepared in example 4 are shown in fig. 2 and 3. In FIG. 2, the chemical shift of the functional group structure due to chemical crosslinking occurs at the position where the chemical shift is 6.5-8.0 1 H. Illustrating the success of the synthesis of the product and the chemical shift of the different structures, FIG. 3 at 2920cm -1 There appears an absorption peak of methylene contained in the structure due to abundant C-H stretching vibration and bending vibration in the all-carbon skeleton of SEBS and piperidine functional groups. At 1460cm -1 The absorption peak of (2) is attributable to the characteristic absorption peak caused by the benzene ring in SEBS. At 1030cm -1 Characteristic peaks of C-N bonds on N-piperidine appear. In addition, when the reaction time was 170min, the reaction time was 1227cm due to excessive crosslinking -1 The appearance of the C-N characteristic peaks due to the shift shows that the functional groups of the synthesized product conform to the designed structure.
Example 5
Step a, carrying out chemical crosslinking reaction on 4g of polymer main chain in strong oxidizing acid, piperidone and an organic solvent A at 0 ℃ for 1h, quenching by deionized water with the resistivity reaching 18MΩ cm after the reaction is finished, washing, and freeze-drying to obtain powder; wherein the polymer backbone is polystyrene.
The strong oxidizing acid is trifluoroacetic acid;
piperidone is N-methyl-4-piperidone;
the organic solvent A is chloroform;
the volume ratio of the mass of the polymer main chain to the organic solvent A is 1g:30mL;
the molar ratio of polymer backbone to piperidone was 1:1.
the ratio of the amount of polymer backbone to the amount of the substance of the strong oxidizing acid was 1:1.
b, adding the powder obtained in the step a into an organic solvent B, adding methyl iodide, performing a dark reaction at room temperature for 18 hours, extracting, washing after the reaction is finished, and drying at 30 ℃ for 24 hours to obtain polymer powder; wherein the organic solvent B is chloroform;
the volume ratio of the mass of the powder to the organic solvent B was 1g:30mL;
step c, the process of the step c is as follows: dissolving polymer powder in an organic solvent C, wherein the mass fraction of the polymer powder is 25%, refluxing for 6 hours at 20 ℃, stirring, completely dissolving until clarification to obtain a chemically crosslinked polymer solution, pouring the chemically crosslinked polymer solution into a glass tank, and volatilizing the organic solvent C for 4 hours at 50 ℃ to obtain a transparent polymer film;
wherein the organic solvent C is a mixture of chloroform and tetrahydrofuran.
Example 6
Step a, carrying out chemical crosslinking reaction on 4g of polymer main chain in strong oxidizing acid, piperidone and an organic solvent A at 15 ℃ for 12 hours, quenching by deionized water with the resistivity reaching 18MΩ cm after the reaction is finished, washing, and freeze-drying to obtain powder; wherein the polymer main chain is a mixture of SEBS and polycarbazole. The strong oxidizing acid is trifluoromethanesulfonic acid;
the organic solvent A is 1, 2-tetrachloroethane;
piperidone is 2, 6-tetramethyl-4-piperidone;
the volume ratio of the mass of the polymer main chain to the organic solvent A is 1g:200mL;
the molar ratio of polymer backbone to piperidone was 1:2.
the ratio of the amount of polymer backbone to the amount of the substance of the strong oxidizing acid was 1:5.
b, adding the powder obtained in the step a into an organic solvent B, adding methyl iodide, performing a dark reaction at room temperature for 36 hours, extracting, washing after the reaction is finished, and drying at 40 ℃ for 20 hours to obtain polymer powder; wherein the organic solvent B is 1, 2-tetrachloroethane;
the volume ratio of the mass of the powder to the organic solvent B was 1g:200mL;
step c, the process of the step c is as follows: dissolving polymer powder in an organic solvent C, wherein the mass fraction of the polymer powder is 50%, refluxing for 3 hours at 40 ℃, completely dissolving under magnetic force ultrasonic until the polymer powder is clarified to obtain a chemically crosslinked polymer solution, pouring the chemically crosslinked polymer solution into a glass tank, and volatilizing the organic solvent C for 12 hours at 20 ℃ to obtain a transparent polymer film;
wherein the organic solvent C is a mixture of dichloromethane and dimethylbenzene.
Example 7
Step a, carrying out chemical crosslinking reaction on 4g of polymer main chain in strong oxidizing acid, piperidone and an organic solvent A at 3 ℃ for 2 hours, quenching by deionized water with the resistivity reaching 18MΩ cm after the reaction is finished, washing, and freeze-drying to obtain powder; wherein the polymer backbone is polybenzimidazole.
The strong oxidizing acid is trifluoroacetic acid;
piperidone is 1,2, 6-trimethyl-4-piperidone;
the organic solvent A is N, N-dimethylformamide;
the volume ratio of the mass of the polymer main chain to the organic solvent A is 1g:50mL;
the molar ratio of polymer backbone to piperidone was 1:0.5.
the ratio of the amount of polymer backbone to the amount of the substance of the strong oxidizing acid was 1:1.2.
b, adding the powder obtained in the step a into an organic solvent B, adding methyl iodide, performing a dark reaction at room temperature for 20 hours, extracting, washing after the reaction is finished, and drying at 80 ℃ for 6 hours to obtain polymer powder; wherein, the organic solvent B is dioxane;
the volume ratio of the mass of the powder to the organic solvent B was 1g:50mL;
step c, the process of the step c is as follows: dissolving polymer powder in an organic solvent C, wherein the mass fraction of the polymer powder is 60%, refluxing for 4 hours at 30 ℃, completely dissolving until clarification is achieved under ultrasound to obtain a chemically crosslinked polymer solution, pouring the chemically crosslinked polymer solution into a glass tank, and volatilizing the organic solvent C for 10 hours at 30 ℃ to obtain a transparent polymer film;
wherein the organic solvent C is a mixture of 1, 2-tetrachloroethane and dimethylacetamide.
Example 8
Step a, carrying out chemical crosslinking reaction on 4g of polymer main chain in strong oxidizing acid, piperidone and an organic solvent A at 6 ℃ for 3 hours, quenching by deionized water with the resistivity reaching 18MΩ cm after the reaction is finished, washing, and freeze-drying to obtain powder; wherein the main chain of the polymer is polyethersulfone benzene ring.
The strong oxidizing acid is trifluoromethanesulfonic acid;
piperidone is N-methyl-4-piperidone;
the organic solvent A is N, N-dimethylacetamide;
the volume ratio of the mass of the polymer main chain to the organic solvent A is 1g:80mL;
the molar ratio of polymer backbone to piperidone was 1:1.2.
the ratio of the amount of polymer backbone to the amount of the substance of the strong oxidizing acid was 1:1.5.
b, adding the powder obtained in the step a into an organic solvent B, adding methyl iodide, performing a dark reaction at room temperature for 25 hours, extracting, washing after the reaction is finished, and drying at 60 ℃ for 10 hours to obtain polymer powder; wherein the organic solvent B is toluene;
the volume ratio of the mass of the powder to the organic solvent B was 1g:80mL;
step c, the process of the step c is as follows: dissolving polymer powder in an organic solvent C, wherein the mass fraction of the polymer powder is 45%, refluxing for 5 hours at 30 ℃, completely dissolving the polymer powder until the polymer powder is clarified after cell crushing to obtain a chemically crosslinked polymer solution, pouring the chemically crosslinked polymer solution into a glass tank, and volatilizing the organic solvent C for 7 hours at 40 ℃ to obtain a transparent polymer film;
wherein the organic solvent C is a mixture of dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide.
Example 9
Step a, carrying out chemical crosslinking reaction on 4g of polymer main chain in strong oxidizing acid, piperidone and an organic solvent A at 5 ℃ for 4 hours, quenching by deionized water with the resistivity reaching 18MΩ cm after the reaction is finished, washing, and freeze-drying to obtain powder; wherein the polymer main chain is a mixture of polyaniline and polyethersulfone benzene ring.
The strong oxidizing acid is a mixture of trifluoroacetic acid and trifluoromethanesulfonic acid;
piperidone is N-methyl-4-piperidone;
the organic solvent A is dimethyl sulfoxide;
the volume ratio of the mass of the polymer main chain to the organic solvent A is 1g:60/mL;
the molar ratio of polymer backbone to piperidone was 1:0.8.
the ratio of the amount of polymer backbone to the amount of the substance of the strong oxidizing acid was 1:1.3.
b, adding the powder obtained in the step a into an organic solvent B, adding methyl iodide, performing a dark reaction at room temperature for 30 hours, extracting, washing and drying at 50 ℃ for 15 hours after the reaction is finished to obtain polymer powder; wherein, the organic solvent B is N, N-dimethylacetamide;
the volume ratio of the mass of the powder to the organic solvent B was 1g:60mL;
step c, the process of the step c is as follows: dissolving polymer powder in an organic solvent C, wherein the mass fraction of the polymer powder is 40%, refluxing for 5 hours at 25 ℃, stirring, completely dissolving until clarification to obtain a chemically crosslinked polymer solution, pouring the chemically crosslinked polymer solution into a glass tank, and volatilizing the organic solvent C for 10 hours at 20 ℃ to obtain a transparent polymer film;
wherein the organic solvent C is dimethyl sulfoxide.
Example 10
Step a, carrying out chemical crosslinking reaction on 4g of polymer main chain in strong oxidizing acid, piperidone and an organic solvent A at 4 ℃ for 5 hours, quenching by deionized water with the resistivity reaching 18MΩ cm after the reaction is finished, washing, and freeze-drying to obtain powder; wherein the polymer main chain is polyaniline.
The strong oxidizing acid is trifluoroacetic acid;
piperidone is N-methyl-4-piperidone;
the organic solvent A is methylene dichloride;
the volume ratio of the mass of the polymer main chain to the organic solvent A is 1g:70mL;
the molar ratio of polymer backbone to piperidone was 1:1.
the ratio of the amount of polymer backbone to the amount of the substance of the strong oxidizing acid was 1:1.4.
b, adding the powder obtained in the step a into an organic solvent B, adding methyl iodide, performing a dark reaction at room temperature for 32 hours, extracting, washing and drying at 55 ℃ for 18 hours after the reaction is finished to obtain polymer powder; wherein the organic solvent B is dimethyl sulfoxide;
the volume ratio of the mass of the powder to the organic solvent B was 1g:70mL;
step c, the process of the step c is as follows: dissolving polymer powder in an organic solvent C, wherein the mass fraction of the polymer powder is 30%, refluxing for 4 hours at 30 ℃, stirring, completely dissolving until clarification to obtain a chemically crosslinked polymer solution, pouring the chemically crosslinked polymer solution into a glass tank, and volatilizing the organic solvent C for 5 hours at 50 ℃ to obtain a transparent polymer film;
wherein the organic solvent C is a mixture of xylene and toluene.
When the anion membrane is applied to an alkaline fuel cell, the specific process is as follows: the anion membrane is hermetically assembled in a membrane module and installed in a fuel cell. When the alkaline fuel cell works, moisture is transported into the membrane component through the runner, and is wetted, and directional mass transfer is started. As a solid electrolyte layer, anions are transported through the ion channels of the polymer membrane by the electric field, providing the necessary ion transport for the operation of the cell.
Claims (8)
1. A method for preparing a basic anion exchange membrane based on chemical cross-linking, which is characterized by comprising the following steps:
step a, chemically crosslinking a polymer main chain in strong oxidizing acid, piperidone and an organic solvent A at low temperature, quenching after the reaction is finished, washing and drying to obtain solid powder;
wherein the polymer main chain is one or two of polystyrene, SEBS, polycarbazole, polysulfone, polybenzimidazole, polyaniline and polyethersulfone benzene ring;
the ratio of the amount of polymer backbone to the amount of the substance of the strong oxidizing acid was 1:1-1: 5, a step of;
the molar ratio of polymer backbone to piperidone was 1: 0.5-1: 2;
b, adding the powder obtained in the step a into an organic solvent B, adding methyl iodide, performing a dark reaction at room temperature for 18-36 hours, extracting, washing and drying to obtain polymer powder;
and C, after dissolving the polymer powder in the organic solvent C, casting the polymer powder into a film to obtain a polymer film, washing the polymer film with deionized water, and then performing anion exchange to obtain the alkaline anion exchange film based on chemical crosslinking.
2. The method for preparing a basic anion exchange membrane based on chemical cross-linking according to claim 1, wherein the piperidone is N-methyl-4-piperidone, 2, 6-tetramethyl-4-piperidone or 1,2, 6-trimethyl-4-piperidone; the strong oxidizing acid is one or two of trifluoroacetic acid and trifluoromethanesulfonic acid.
3. The method for preparing a basic anion exchange membrane based on chemical cross-linking according to claim 1, wherein the organic solvent A is one of dichloromethane, chloroform, 1, 2-tetrachloroethane, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide;
the organic solvent B is one of dichloromethane, chloroform, 1, 2-tetrachloroethane, dioxane, toluene, dimethylbenzene, N-dimethylacetamide and dimethyl sulfoxide;
the organic solvent C is one or more of tetrahydrofuran, xylene, toluene, chloroform, 1, 2-tetrachloroethane, dimethylacetamide, dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide.
4. The method for preparing a basic anion exchange membrane based on chemical cross-linking according to claim 1, wherein the volume ratio of the mass of the polymer main chain to the organic solvent a is 1g: (30-200) mL.
5. The method for preparing a basic anion exchange membrane based on chemical cross-linking according to claim 1, wherein in step B, the volume ratio of the mass of the solid powder to the organic solvent B is 1g: (30-200) mL.
6. The preparation method of the alkaline anion exchange membrane based on chemical crosslinking according to claim 1, wherein the low-temperature reaction temperature in the step a is 0-15 ℃ and the reaction time is 1-12 h.
7. The method for preparing a basic anion exchange membrane based on chemical cross-linking according to claim 1, wherein the specific process of step c is: and (3) dissolving the polymer powder in an organic solvent C, wherein the mass fraction of the polymer powder is 25-60%, refluxing at 20-40 ℃ for 3-6 h, dissolving until the polymer powder is clarified to obtain a chemically crosslinked polymer solution, pouring the chemically crosslinked polymer solution into a glass tank, and volatilizing the organic solvent C at 20-50 ℃ for 4-12h to obtain the transparent polymer film.
8. A chemically cross-linked basic anion exchange membrane prepared according to the method of any one of claims 1 to 7.
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