CN114539578A - Physical crosslinking type polymer anion exchange membrane and preparation method thereof - Google Patents
Physical crosslinking type polymer anion exchange membrane and preparation method thereof Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 92
- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 238000004132 cross linking Methods 0.000 title claims abstract description 28
- BTVVEKSXUOEVAY-UHFFFAOYSA-N 4,4-diphenylpiperidine Chemical compound C1CNCCC1(C=1C=CC=CC=1)C1=CC=CC=C1 BTVVEKSXUOEVAY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 125000002091 cationic group Chemical group 0.000 claims abstract description 26
- 125000003003 spiro group Chemical group 0.000 claims abstract description 26
- 229920006037 cross link polymer Polymers 0.000 claims abstract description 13
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 74
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 72
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 60
- 239000002904 solvent Substances 0.000 claims description 50
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 36
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 32
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 28
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 26
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 25
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 229960001701 chloroform Drugs 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 16
- 238000002791 soaking Methods 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 14
- 238000007265 chloromethylation reaction Methods 0.000 claims description 13
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 12
- 235000010290 biphenyl Nutrition 0.000 claims description 12
- 239000004305 biphenyl Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- IBODDUNKEPPBKW-UHFFFAOYSA-N 1,5-dibromopentane Chemical compound BrCCCCCBr IBODDUNKEPPBKW-UHFFFAOYSA-N 0.000 claims description 11
- 239000012528 membrane Substances 0.000 claims description 11
- 230000007935 neutral effect Effects 0.000 claims description 10
- 230000001376 precipitating effect Effects 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 238000006068 polycondensation reaction Methods 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- 239000012265 solid product Substances 0.000 claims description 7
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 7
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical group OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 7
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003377 acid catalyst Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- XESLSYPFOYZAPG-UHFFFAOYSA-N piperidin-1-ium-2-one;chloride Chemical compound Cl.O=C1CCCCN1 XESLSYPFOYZAPG-UHFFFAOYSA-N 0.000 claims description 5
- 150000003512 tertiary amines Chemical class 0.000 claims description 5
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 4
- 238000010345 tape casting Methods 0.000 claims description 4
- RRSXICBKOPODSP-UHFFFAOYSA-N 1,4-bis(chloromethoxy)butane Chemical compound ClCOCCCCOCCl RRSXICBKOPODSP-UHFFFAOYSA-N 0.000 claims description 3
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 229920002866 paraformaldehyde Polymers 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims 1
- 239000000446 fuel Substances 0.000 abstract description 11
- 229920000867 polyelectrolyte Polymers 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 48
- 238000003756 stirring Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 125000006575 electron-withdrawing group Chemical group 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- -1 spiro cations Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- KVZQVTSNCUIGMU-UHFFFAOYSA-N 1,1'-biphenyl;piperidine Chemical compound C1CCNCC1.C1=CC=CC=C1C1=CC=CC=C1 KVZQVTSNCUIGMU-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-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
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- SXWRTZOXMUOJER-UHFFFAOYSA-N hydron;piperidin-4-one;chloride;hydrate Chemical compound O.Cl.O=C1CCNCC1 SXWRTZOXMUOJER-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical group Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
- NHLUVTZJQOJKCC-UHFFFAOYSA-N n,n-dimethylhexadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCN(C)C NHLUVTZJQOJKCC-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
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- 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
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- C—CHEMISTRY; METALLURGY
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
-
- 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
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1044—Mixtures of polymers, of which at least one is ionically conductive
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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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- 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
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Abstract
The invention relates to a physical cross-linking type polymer anion exchange membrane and a preparation method thereof, belonging to the technical field of fuel cell polyelectrolyte and anion exchange membranes; the structure of the physical cross-linking type polymer anion exchange membrane is as follows:
wherein: m 0.5-0.65, n 0.35-0.5, x 0.07-0.13, y 0-0.03, a0.12-0.17, b is 0.13-0.19. The main chain of the physically crosslinked polymer anion exchange membrane polymer does not contain polar groups such as aryl ether bonds and the like, has good main chain stability, improved film forming property, good dimensional stability and good mechanical property, and greatly improves the application of the load spiro cationic diphenyl piperidine polymer anion exchange membrane in fuel cells.
Description
Technical Field
The invention relates to a physical cross-linking type polymer anion exchange membrane and a preparation method thereof, belonging to the technical field of fuel cell polyelectrolyte and anion exchange membranes.
Technical Field
With the increase of non-renewable energy consumption and the worsening of environmental problems, hydrogen energy is considered as the most ideal renewable energy source in the future for human beings due to the advantages of high calorific value, good combustion performance, wide sources, various utilization forms and the like. Among the technologies, fuel cells are widely recognized as the best hydrogen energy conversion and storage device.
Proton Exchange Membrane Fuel Cells (PEMFCs) have been successfully used in automobiles and other fields, but the cost of the platinum-based noble metal catalyst is high, which hinders further development. In contrast, alkaline Anion Exchange Membrane Fuel Cells (AEMFCs) have been the focus of research due to their alkaline operating environment, rapid oxygen reduction reaction kinetics, and the use of non-noble metal catalysts. Anion Exchange Membranes (AEMs) as one of the core components of AEMFCs have been limited in their application due to insufficient chemical stability, low ionic conductivity, poor dimensional stability, and the like. Therefore, there is an urgent need to develop an anion exchange membrane having high chemical stability, high ion conductivity, and good dimensional stability.
At present, aromatic hydrocarbon alkaline anion exchange membranes reported in documents contain ether bonds in a polymer main chain, and electron-withdrawing groups near the ether bonds can accelerate chemical decomposition to cause degradation of a main chain structure, so that the service life of the anion exchange membrane is shortened, and stable operation of a fuel cell is not facilitated.
In order to solve the above problems, researchers have proposed: the use of an all-carbon chain polymer without heteroatoms and electron-withdrawing groups as a backbone, the all-carbon chain polymer exhibits outstanding base stability compared to polymers containing heteroatoms and electron-withdrawing groups. Researchers have also proposed: the anion exchange membrane shows excellent stability after an alkali stability test by adopting Poly Biphenyl Piperidine (PBP) without heteroatoms as a framework of the anion exchange membrane. However, the mechanical properties of the film are brittle due to the strong rigid structure of the polybiphenylpiperidine. Researchers have proposed that hydrogenated styrene-butadiene block copolymer (SEBS) which also does not contain heteroatoms and electron-withdrawing groups is used as the framework of the anion exchange membrane, has excellent chemical stability, and the characteristic of soft and hard block distribution of the hydrogenated styrene-butadiene block copolymer (SEBS) per se can better promote the formation of a micro phase separation structure in the anion exchange membrane; however, the ionic conductivity is poor due to the restriction of the conduction sites of the hydrogenated styrene-butadiene block copolymer (SEBS) film.
Therefore, the development of a novel high-performance anion exchange membrane, combined with the advantages of hydrogenated styrene-butadiene block copolymer (SEBS) and Poly Biphenyl Piperidine (PBP) frameworks, has a developed ion transport channel, good dimensional stability, higher ion conductivity and chemical stability, thereby meeting the material requirements under different application conditions, and becomes a technical problem to be solved urgently in the technical field.
Disclosure of Invention
The invention aims to select polybiphenylpiperidine with good alkali resistance and high conduction site as one of main frameworks of an anion exchange membrane to prepare a spiro cationic load type polybiphenylpiperidine anion exchange membrane with strong alkali resistance and high conduction site according to the problems of low ionic conductivity, poor chemical stability and insufficient dimensional stability of the existing anion exchange membrane, and simultaneously selects comb-shaped hydrogenated styrene-butadiene block copolymer (SEBS) with strong chemical stability, high elasticity and flexibility and polybiphenylpiperidine framework crosslinking complementary enhancement of various performances of the membrane, so that the membrane has a developed ion transmission channel, good dimensional stability, higher ionic conductivity and chemical stability, and can be applied to an alkaline membrane fuel cell.
The above object of the present invention is achieved by the following technical solutions:
a physical cross-linking type polymer anion exchange membrane has the following structure:
wherein: m is 0.5-0.65, n is 0.35-0.5, x is 0.07-0.13, y is 0-0.03, a is 0.12-0.17, and b is 0.13-0.19.
Preferably, the physically crosslinked polymeric anion exchange membrane has an ionic conductivity of 86.53% after soaking in 2M sodium hydroxide solution at 80 ℃ for approximately 1600 hours.
The preparation method of the physical crosslinking type polymer anion exchange membrane comprises the following steps:
(1) preparation of Polybiphenylpiperidine (PBP) polymers
The method comprises the following steps of (1) carrying out strong acid catalyzed continuous polycondensation reaction on a biphenyl monomer and a piperidone hydrochloride monomer under the action of an organic solvent and a strong acid catalyst, after the continuous polycondensation reaction is finished, precipitating in a sodium hydroxide solution, washing the product with deionized water to be neutral, soaking the obtained white solid product in a hydrochloric acid solution, washing the product after acid soaking with deionized water to be neutral to obtain a yellow solid, and drying to obtain a polybiphenyl piperidine polymer;
(2) preparation of spiro-cationic-supported diphenyl piperidine polymer (PB-ASU)
Dissolving the polybiphenyl piperidine polymer prepared in the step (1) in a dimethyl sulfoxide solvent, adding 1, 5-dibromopentane and an acid-binding agent potassium carbonate into the obtained solution, reacting at 80 ℃ to obtain a solution of the load spiro cationic polybiphenyl piperidine polymer, precipitating in an ethyl acetate solvent after the reaction is finished, washing with deionized water, removing the potassium carbonate, and drying to obtain the load spiro cationic polybiphenyl piperidine polymer;
(3) preparation of chloromethylated hydrogenated styrene-butadiene Block Copolymer (CMSEBS)
Dissolving hydrogenated styrene-butadiene block copolymer in a trichloromethane solvent, adding a chloromethylation reagent and a catalyst of anhydrous stannic chloride, carrying out chloromethylation reaction, separating out in a washing solvent after the reaction is finished, dissolving again, and repeating for three times to obtain chloromethylated hydrogenated styrene-butadiene block copolymer;
(4) preparation of comb-shaped hydrogenated styrene-butadiene Block copolymer (Cn-SEBS)
Reacting the chloromethylated hydrogenated styrene-butadiene block copolymer prepared in the step (3) with tertiary amine with a long alkyl chain, after the reaction is finished, precipitating in a precipitation solvent, washing and drying to obtain the comb-shaped hydrogenated styrene-butadiene block copolymer;
(5) preparation of alkaline anion exchange membrane (PB-ASU-Cn-SEBS)
Dissolving the load spiro cationic diphenyl piperidine polymer prepared in the step (2) in a dimethyl sulfoxide solvent to obtain a load spiro cationic diphenyl piperidine polymer solution; dissolving the comb-shaped hydrogenated styrene-butadiene block copolymer prepared in the step (4) in a chloroform solvent to obtain a comb-shaped hydrogenated styrene-butadiene block copolymer solution; and mixing the loaded spiro cationic diphenyl piperidine polymer solution with the comb hydrogenated styrene-butadiene block copolymer solution in a slow dropwise manner to obtain an alkaline anion exchange membrane (PB-ASU-Cn-SEBS), forming a membrane in a tape casting manner, drying the obtained alkaline anion exchange membrane (PB-ASU-Cn-SEBS), and soaking the membrane in a sodium hydroxide solution to obtain the hydroxide form alkaline anion exchange membrane (physical crosslinking polymer anion exchange membrane).
Preferably, the molar ratio of the biphenyl monomer to the piperidone hydrochloride monomer in step (1) is 1:1.2 to 1: 1.3.
Preferably, the organic solvent in the step (1) is dichloromethane, and the volume ratio of the mass of the biphenyl monomer to the dichloromethane solvent is 1:1.7-1:2.3 g/mL.
Preferably, the strong acid catalyst in the step (1) is trifluoromethanesulfonic acid and trifluoroacetic acid, and the molar ratio of the biphenyl monomer to the trifluoroacetic acid is 1:1-1:1.05 and the molar ratio to the trifluoromethanesulfonic acid is 1:11-1: 12.
Preferably, in step (1), the continuous polycondensation reaction is carried out under ice bath conditions for 3 to 4 hours.
Preferably, in the step (1), the concentration of the sodium hydroxide solution is 3.0-5.0 mol/L.
Preferably, in the step (1), the hydrochloric acid solution has a concentration of 1M, is soaked for 3 days, and is dried in an oven at 80 ℃ under vacuum for 24 hours.
Preferably, in the step (2), the molar ratio of the polybiphenylpiperidine polymer to the 1, 5-dibromopentane is 1:1.3-1: 1.4; the polybiphenylpiperidine polymer with K2CO3In a molar ratio of 1: 1.1; the volume ratio of the mass of the polybiphenylpiperidine polymer to the dimethyl sulfoxide solvent is 1:20-1:25 g/mL.
Preferably, in the step (3), the chloromethylation reagent is one or more of 1, 4-dichloromethoxybutane, trimethylchlorosilane or paraformaldehyde which are mixed in any proportion; the mass ratio of the mass of the hydrogenated styrene-butadiene block copolymer to the mass of the trichloromethane is 1:25-1:30 g/mL; the molar ratio of the hydrogenated styrene-butadiene block copolymer to the chloromethylation reagent is 1:1.8-1: 2.2; the molar ratio of the hydrogenated styrene-butadiene block copolymer to the anhydrous tin tetrachloride is 1:0.3 to 1: 0.4.
Preferably, in step (3), the temperature of the chloromethylation reaction is 0-55 ℃ and the reaction time is 3-24 hours.
Preferably, in step (3), the washing solvent is methanol and/or ethanol, and tetrahydrofuran.
Preferably, in step (4), in the tertiary amine with a long alkyl chain, the length of the alkyl chain is 8, 12 or 16 carbon atoms.
Preferably, in step (4), the precipitation solvent selected is petroleum ether or ethyl acetate.
Preferably, in the step (5), the volume ratio of the mass of the loaded spiro cationic diphenyl piperidine polymer to the volume of the dimethyl sulfoxide solvent is 0.02-0.03 g/mL; the volume ratio of the mass of the comb-shaped hydrogenated styrene-butadiene block copolymer to the chloroform solvent is 0.02-0.03 g/mL.
Preferably, in the step (5), the temperature of the film forming is room temperature to 80 ℃; the concentration of the sodium hydroxide solution is 1M-2M.
Compared with the prior art, the invention has the following beneficial effects:
the physically crosslinked polymer anion exchange membrane and the preparation method thereof provided by the invention are characterized in that the physically crosslinked polymer anion exchange membrane is obtained by dropwise mixing the polybiphenyl piperidine polymer modified by spiro cations and the chloromethylated hydrogenated styrene-butadiene block copolymer modified by long-chain alkylamine through tape casting film forming and alkalization, and the main chain of the anion exchange membrane polymer does not contain polar groups such as aryl ether bonds and the like, so that the anion exchange membrane has good main chain stability; the physically crosslinked polymer anion exchange membrane improves the film-forming property of the load spiro cationic diphenyl piperidine polymer by using the flexible comb hydrogenated styrene-butadiene block copolymer; in addition, the physical crosslinking polymer anion-exchange membrane has good dimensional stability and good mechanical properties, and the application of the load spiro cationic diphenyl piperidine polymer anion-exchange membrane in fuel cells is greatly improved.
The invention is further illustrated by the following figures and specific examples, which are not meant to limit the scope of the invention.
Drawings
FIG. 1 is a schematic diagram of the synthesis of a physically cross-linked anion exchange membrane of the present invention.
FIG. 2 is the 1H NMR nuclear magnetic spectrum of the polybiphenylpiperidine polymer and the spiro cationic-supported biphenylpiperidine polymer in example 1 of the present invention.
FIG. 3 is a 1H NMR nuclear magnetic spectrum of a hydrogenated styrene-butadiene block copolymer or a chloromethylated hydrogenated styrene-butadiene block copolymer in example 1 of the present invention.
FIG. 4 is a 1H NMR nuclear magnetic spectrum of a comb-like hydrogenated styrene-butadiene block copolymer in example 1 of the present invention.
FIG. 5 is a graph showing the hydroxide ion conductivity of the physically crosslinked anion-exchange membrane at 30 to 80 ℃ in example 1 of the present invention.
FIG. 6 is a graph of the percentage of residual ionic conductivity to initial ionic conductivity as a function of time after soaking a physically crosslinked anion exchange membrane in 2M sodium hydroxide solution at 80 ℃ in example 1 of the present invention.
Detailed Description
Unless otherwise stated, the raw materials used in the examples of the present invention are conventional raw materials available on the market, the equipment used is conventional in the art, and the methods used are conventional in the art; the present invention will be described in further detail with reference to examples for the purpose of understanding the present invention, but the present invention should not be construed as being limited thereto. The present invention is exemplified as follows.
As shown in fig. 1, a schematic synthesis diagram of the physically cross-linked anion exchange membrane of the present invention; wherein: 0.65-0.5% for m, 0.35-0.5 for n, 0.07-0.13 for x, 0-0.03 for y, 0.12-0.17 for a, 0.13-0.19 for b;
the preparation method of the physical crosslinking type polymer anion exchange membrane comprises the following steps:
(1) preparation of Polybiphenylpiperidine (PBP) polymers
The method comprises the following steps of (1) carrying out strong acid catalyzed continuous polycondensation reaction on a biphenyl monomer and a piperidone hydrochloride monomer under the action of an organic solvent and a strong acid catalyst, after the continuous polycondensation reaction is finished, precipitating in a sodium hydroxide solution, washing the product with deionized water to be neutral, soaking the obtained white solid product in a hydrochloric acid solution, washing the product after acid soaking with deionized water to be neutral to obtain a yellow solid, and drying to obtain a polybiphenyl piperidine polymer;
(2) preparation of spiro-cationic-supported diphenyl piperidine polymer (PB-ASU)
Dissolving the polybiphenyl piperidine polymer prepared in the step (1) in a dimethyl sulfoxide solvent, adding 1, 5-dibromopentane and an acid-binding agent potassium carbonate into the obtained solution, reacting at 80 ℃ to obtain a solution of the load spiro cationic polybiphenyl piperidine polymer, precipitating in an ethyl acetate solvent after the reaction is finished, washing with deionized water, removing the potassium carbonate, and drying to obtain the load spiro cationic polybiphenyl piperidine polymer;
(3) preparation of chloromethylated hydrogenated styrene-butadiene Block Copolymer (CMSEBS)
Dissolving hydrogenated styrene-butadiene block copolymer in a trichloromethane solvent, adding a chloromethylation reagent and a catalyst of anhydrous stannic chloride, carrying out chloromethylation reaction, separating out in a washing solvent after the reaction is finished, dissolving again, and repeating for three times to obtain chloromethylated hydrogenated styrene-butadiene block copolymer;
(4) preparation of comb-shaped hydrogenated styrene-butadiene Block copolymer (Cn-SEBS)
Reacting the chloromethylated hydrogenated styrene-butadiene block copolymer prepared in the step (3) with tertiary amine with a long alkyl chain, after the reaction is finished, precipitating in a precipitation solvent, washing and drying to obtain the comb-shaped hydrogenated styrene-butadiene block copolymer;
(5) preparation of alkaline anion exchange membrane (PB-ASU-Cn-SEBS)
Dissolving the load spiro cationic diphenyl piperidine polymer prepared in the step (2) in a dimethyl sulfoxide solvent to obtain a load spiro cationic diphenyl piperidine polymer solution; dissolving the comb-shaped hydrogenated styrene-butadiene block copolymer prepared in the step (4) in a chloroform solvent to obtain a comb-shaped hydrogenated styrene-butadiene block copolymer solution; and mixing the loaded spiro cationic diphenyl piperidine polymer solution with the comb hydrogenated styrene-butadiene block copolymer solution in a slow dropwise manner to obtain an alkaline anion exchange membrane (PB-ASU-Cn-SEBS), forming a membrane in a tape casting manner, drying the obtained alkaline anion exchange membrane (PB-ASU-Cn-SEBS), and soaking the membrane in a sodium hydroxide solution to obtain the hydroxide form alkaline anion exchange membrane (physical crosslinking polymer anion exchange membrane).
Example 1
A preparation method of a physical cross-linking type polymer anion exchange membrane comprises the following steps:
(1) preparation of Polybiphenylpiperidine (PBP) polymers
Dissolving 3.0g of a commercial biphenyl monomer in 6mL of a commercial dichloromethane solvent to obtain a colorless transparent solution, adding 3.88g of a commercial 4-piperidone hydrochloride hydrate into the colorless transparent solution under mechanical stirring, fully dispersing under normal-temperature magnetic stirring, slowly adding 1.5mL of commercial trifluoroacetic acid under an ice bath condition, then slowly dropwise adding 19.0mL of commercial trifluoromethanesulfonic acid, reacting, keeping an ice-water bath, and continuing for 5 hours under magnetic stirring; after the reaction is finished, slowly pouring the obtained reaction product into a 5M sodium hydroxide solution to separate out a white blocky solid, washing the product obtained by precipitation with deionized water to be neutral, soaking the obtained white solid product in a 1M hydrochloric acid solution for 3 days to completely protonate N atoms on piperidine rings in a PBP framework, washing the product subjected to acid soaking with deionized water to be neutral to obtain a yellow solid, and placing the yellow solid in an oven at 80 ℃ for vacuum drying for 24 hours to obtain the polybiphenylpiperidine polymer;
(2) preparation of spiro cationic diphenyl piperidine (PB-ASU) -loaded polymer
Dissolving 0.6g of the polybiphenylpiperidine polymer completely protonated by hydrochloric acid prepared in step (1) in 20mL of a commercial dimethyl sulfoxide solvent under magnetic stirring, after completely dissolving, raising the temperature to 80 ℃, dropwise adding 0.13mL of commercial 1, 5-dibromopentane into the reaction for the first time, adding 0.10g of commercial potassium carbonate into the reaction as an acid-binding agent, continuously stirring for 16 hours, dropwise adding 0.13mL of commercial 1, 5-dibromopentane into the reaction for the second time, adding 0.10g of commercial potassium carbonate into the reaction as an acid-binding agent, continuously stirring for 16 hours, dropwise adding 0.13mL of commercial 1, 5-dibromopentane into the reaction for the third time, adding 0.10g of commercial potassium carbonate into the reaction as an acid-binding agent, continuously stirring for 16 hours, after the reaction is finished, gradually deepening the color of the solution along with the progress of the reaction, slowly pouring the reaction solution into a commercially available ethyl acetate solvent to separate out yellow flocculent solids, filtering the obtained ethyl acetate suspension under reduced pressure to obtain solid precipitates, washing the obtained solid precipitates with ethyl acetate for three times to remove redundant reactants, washing the solid precipitates with deionized water for three times to remove inorganic salts to obtain yellow solid products, and performing vacuum drying in an oven at the temperature of 80 ℃ for 48 hours to obtain a load spiro cationic diphenyl piperidine polymer (PB-ASU);
(3) preparation of chloromethylated hydrogenated styrene-butadiene Block Copolymer (CMSEBS)
4.0g of a hydrogenated styrene-butadiene block polymer (A1535, Mw 70000, styrene block content 58 wt%) sold by Koteng, USA was dissolved in 120mL of a commercially available chloroform solution, and after complete dissolution, 18.4mL of commercially available 1, 4-dichloromethoxybutane and 2.8mL of commercially available anhydrous tin tetrachloride were added dropwise at a rate of 1 drop/sec using a dropping funnel, and the reaction was continued stirring at 55 ℃ for 3 hours, and after completion of the reaction, the reaction solution was slowly poured into 300mL of a commercially available mixed solvent of anhydrous ethanol and methanol (volume ratio 2:1) to precipitate a pale purple solid; dissolving the light purple solid in 100mL of a commercial tetrahydrofuran solvent, then precipitating by using a mixed solvent of absolute ethyl alcohol and methanol (the volume ratio is 2:1), repeating the operation for three times, and after the light purple solid becomes a white solid, placing the white solid in a vacuum oven at 40 ℃ for drying for 48 hours to obtain a chloromethylated hydrogenated styrene-butadiene block Copolymer (CMSEBS);
(4) preparation of comb-shaped hydrogenated styrene-butadiene Block copolymer (C16-SEBS)
Dissolving 0.6g of chloromethylated hydrogenated styrene-butadiene block copolymer prepared in the step (3) in 25mL of commercial chloroform solvent, completely dissolving under stirring, adding 0.66mL of commercial N, N-dimethyl-1-hexadecylamine by using a pipette, reacting at 50 ℃ for 48 hours, pouring the reacted solution into commercial petroleum ether solvent after the reaction is completely finished, separating out a solid, and drying in an oven at 40 ℃ for 24 hours to obtain a comb-shaped hydrogenated styrene-butadiene block copolymer (C16-SEBS);
(5) preparation of physical crosslinking type alkaline anion exchange membrane (PB-ASU-C16-SEBS)
Dissolving 0.21g of the supported spiro cationic diphenyl piperidine polymer prepared in the step (2) in 11mL of commercial dimethyl sulfoxide solvent, 0.03g of the comb-shaped hydrogenated styrene-butadiene block copolymer prepared in step (4) was dissolved in 2mL of a commercially available chloroform solvent, slowly dripping dimethyl sulfoxide solution loaded with the spiro cationic diphenyl piperidine polymer into a chloroform solvent containing the comb hydrogenated styrene-butadiene block copolymer through a dropping funnel, directly pouring the mixed solution into a super-flat dish, placing the casting solution in an oven at 40 ℃, slowly evaporating the solvent to dryness, forming a film, soaking in 1M sodium hydroxide solution to obtain a hydroxyl-form alkaline anion exchange membrane (physical crosslinking polymer anion exchange membrane) (PB-ASU-C16-SEBS), and carrying out various tests on the alkaline anion exchange membrane.
The polybiphenylpiperidine polymer, the spiro-supported cationic biphenylpiperidine polymer, the chloromethylated hydrogenated styrene-butadiene block copolymer and the comb hydrogenated styrene-butadiene block copolymer synthesized in each step in example 1 were respectively subjected to structural characterization by a Bruker Advance III 400M nuclear magnetic resonance spectrometer:
in the experiment, 5mg of polybiphenylpiperidine (PBP) and 5mg of a polymer sample loaded with spiro cationic biphenylpiperidine (PB-ASU) were dissolved in 0.55mL of deuterated dimethyl sulfoxide, 5mg of chloromethylated hydrogenated styrene-butadiene block Copolymer (CMSEBS) and 5mg of comb hydrogenated styrene-butadiene block copolymer (C16-SEBS) were dissolved in 0.55mL of deuterated chloroform, Tetramethylsilane (TMS) was used as an internal standard, and samples were obtained on a Bruker advanced III 400M nuclear magnetic resonance spectrometer1H NMR spectrum; as shown in fig. 2, it is a 1H NMR nuclear magnetic spectrum of the polybiphenylpiperidine polymer and the spiro cationic-supported biphenylpiperidine polymer in example 1 of the present invention; FIG. 3 shows 1H NMR nuclear magnetic spectra of the hydrogenated styrene-butadiene block copolymer and the chloromethylated hydrogenated styrene-butadiene block copolymer in example 1 of the present invention; in this example, the cationic grafting degree of the loaded spiro cationic diphenyl piperidine polymer is 100%, the functionalization degree of the comb hydrogenated styrene-butadiene block copolymer is 100%, and the molar ratio of the loaded spiro cationic diphenyl piperidine (PB-ASU) polymer to the comb hydrogenated styrene-butadiene block copolymer (C16-SEBS) in the physically crosslinked polymer anion exchange membrane is 1.86: 1.
Example 2
A preparation method of a physical cross-linking type polymer anion exchange membrane comprises the following steps:
(1) preparation of Polybiphenylpiperidine polymers (PBPs)
3.0g of a commercially available biphenyl monomer was dissolved in 6mL of a commercially available methylene chloride solvent, and after the dissolution, 3.88g of a commercially available 4-piperidone hydrochloride hydrate was added; under the ice bath condition, slowly dropwise adding 1.5mL of commercially available trifluoroacetic acid and 12mL of commercially available trifluoromethanesulfonic acid, after the reaction is carried out for 1 hour, supplementing 6mL of trifluoromethanesulfonic acid, continuously stirring the reaction in an ice water bath for 3.5 hours until the reaction mixture is deep red and reaches the most viscous degree, stopping the reaction, slowly pouring the reaction mixture into a 5M sodium hydroxide solution to separate out a white blocky solid, washing the solid to be neutral through deionized water, soaking 1M hydrochloric acid, washing the solid to be neutral through the deionized water, and drying the solid to obtain a poly (diphenyl-piperidine) polymer (PBP);
(2) preparation of spiro-cationic-supported diphenyl piperidine polymer (PB-ASU)
Dissolving 0.6g of the polybiphenylpiperidine polymer completely protonated by hydrochloric acid prepared in step (1) in 20mL of a commercial dimethyl sulfoxide solvent under magnetic stirring, after completely dissolving, raising the temperature to 80 ℃, dropwise adding 0.13mL of commercial 1, 5-dibromopentane into the reaction for the first time, adding 0.10g of commercial potassium carbonate as an acid-binding agent into the reaction, continuously stirring for 16 hours, dropwise adding 0.13mL of commercial 1, 5-dibromopentane into the reaction for the second time, adding 0.10g of commercial potassium carbonate as an acid-binding agent into the reaction, continuously stirring for 16 hours, dropwise adding 0.13mL of commercial 1, 5-dibromopentane into the reaction for the third time, adding 0.10g of commercial potassium carbonate as an acid-binding agent into the reaction, continuously stirring for 16 hours, wherein the color of the solution gradually deepens after the reaction is finished, slowly pouring the reaction solution into a commercially available ethyl acetate solvent to separate out yellow flocculent solids, filtering the obtained ethyl acetate suspension under reduced pressure to obtain solid precipitates, washing the obtained solid precipitates with ethyl acetate for three times to remove redundant reactants, then washing the solid precipitates with deionized water for three times to remove inorganic salts to obtain yellow solid products, and drying the yellow solid products in an oven at the temperature of 80 ℃ for 48 hours in vacuum to obtain a load spiro cationic diphenyl piperidine polymer (PB-ASU);
(3) preparation of chloromethylated hydrogenated styrene-butadiene Block Copolymer (CMSEBS)
Dissolving 4.0G of hydrogenated styrene-butadiene block copolymer model G1652 sold by Keteng of America in 120mL of commercial trichloromethane, adding 22.8mL of commercial trimethylchlorosilane and 5.4G of commercial paraformaldehyde in an ice-water bath, adding 2.8mL of commercial anhydrous stannic chloride after complete dissolution, keeping the ice bath for 30 minutes, removing the ice bath, stirring for 8 hours at room temperature, separating out the reaction solution in commercial anhydrous methanol to obtain a light yellow solid, repeating the processes of dissolving tetrahydrofuran and separating out methanol three times to obtain a white solid, and drying the white solid in a vacuum oven at 40 ℃ for 48 hours to obtain a chloromethylated hydrogenated styrene-butadiene block Copolymer (CMSEBS);
(4) preparation of comb-shaped hydrogenated styrene-butadiene Block copolymer (C12-SEBS)
Dissolving 0.6g of chloromethylated hydrogenated styrene-butadiene block Copolymer (CMSEBS) prepared in the step (3) in 25mL of commercial chloroform, adding 0.66mL of commercial N, N-dimethyl-1-dodecylamine after the chloromethylated hydrogenated styrene-butadiene block copolymer is completely dissolved, reacting at 50 ℃ for 48 hours, slowly pouring the reaction liquid into a commercial ethyl acetate solvent for precipitation, and drying the obtained solid in an oven at 40 ℃ for 24 hours to obtain a comb-shaped hydrogenated styrene-butadiene block copolymer (C12-SEBS);
(5) preparation of physical crosslinking type alkaline anion exchange membrane (PB-ASU-C12-SEBS)
Dissolving 0.21g of the loaded spiro cationic diphenyl piperidine polymer prepared in the step (2) in 7mL of commercial dimethyl sulfoxide solvent, dissolving 0.027g of the comb hydrogenated styrene-butadiene block copolymer prepared in the step (4) in 2mL of commercial chloroform solvent, slowly dripping the dimethyl sulfoxide solvent loaded with the spiro cationic diphenyl piperidine polymer into the chloroform solution containing the comb hydrogenated styrene-butadiene block copolymer through a dropping funnel, uniformly mixing the solution through an ultrasonic crusher, coating the mixed solvent on a coating platform of a scraper coater, uniformly coating the solution through a coating rod, heating to 50 ℃, evaporating the solvent to form a film, removing the obtained film from the coating platform after the film is dried, soaking the film in 1M sodium hydroxide solution to obtain a hydroxide-form alkaline anion exchange membrane (physically crosslinked polymer anion exchange membrane) (PB-ASU- C12-SEBS) and subjected to various tests.
In this example, the degree of spiro cation loading in the polybiphenylpiperidine polymer was 100%, the degree of chloromethylation in the chloromethylated hydrogenated styrene-butadiene block polymerization was 78%, the degree of quaternization in the comb hydrogenated styrene-butadiene block copolymer was 100%, and the molar ratio of PB-ASU to C12-SEBS was 1.5: 1.
The physical crosslinking type alkaline anion exchange membrane (PB-ASU-C12-SEBS) prepared in the embodiment has high ionic conductivity, and the physical crosslinking type alkaline anion exchange membrane (PB-ASU-C12-SEBS) shows good alkaline stability after being soaked in a 2M sodium hydroxide solution at 80 ℃ for 1580 hours.
In the physical crosslinking type alkaline anion exchange membrane (PB-ASU-C12-SEBS) prepared by the invention, the anion exchange membrane comprises a rigid diphenyl piperidine polymer and a flexible hydrogenated styrene butadiene block copolymer on the chemical structure of a main chain, and the main chain does not contain electron-withdrawing groups such as aryl ether bonds, carbon-oxygen double bonds and the like, so that the chemical stability of the framework is ensured; the invention has good film forming property, low swelling property and good ionic conductivity. The physical cross-linking type alkaline anion-exchange membrane is soaked in a 2M sodium hydroxide solution at the temperature of 80 ℃ for 1580 hours, and the residual rate of ion conductivity is still higher than 86.53 percent. The preparation method of the physical crosslinking type polymer anion exchange membrane is efficient, convenient and fast, and is easy for large-area preparation.
The physical crosslinking type polymer anion exchange membrane has the following advantages:
(1) the prepared physical crosslinking type polymer anion exchange membrane uses an all-carbon chain type polymer framework, has excellent alkali stability, and still has 86.53 percent of ion conductivity after being soaked in 2M sodium hydroxide solution for nearly 1600 hours at 80 ℃;
(2) the rigid load spiro cationic diphenyl piperidine polymer and the comb hydrogenated styrene-butadiene block copolymer are blended, so that the prepared material has relatively excellent mechanical strength, and the tensile strength at room temperature is higher than 10 MPa;
(3) the prepared physical crosslinking anion exchange membrane has uniform and compact surface, the conductivity of hydroxyl ions of the membrane can reach 77.2mS/cm at the temperature of 80 ℃, and the high-performance anion exchange membrane can meet the application of fuel cells;
(4) the prepared physical cross-linking type anion exchange membrane has thermal stability completely capable of meeting the working temperature (about 80 ℃) of an anion exchange membrane fuel cell.
The above-mentioned embodiments are further detailed to explain the objects, technical solutions and advantages of the present invention, but the present invention is not limited thereto, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A physical cross-linking type polymer anion exchange membrane has the following structure:
wherein: m is 0.5-0.65, n is 0.35-0.5, x is 0.07-0.13, y is 0-0.03, a is 0.12-0.17, and b is 0.13-0.19.
2. The physically crosslinked polymeric anion exchange membrane of claim 1, wherein: the physically crosslinked polymeric anion exchange membrane has an ionic conductivity of 86.53% after immersion in 2M sodium hydroxide solution at 80 ℃ for approximately 1600 hours.
3. The method for preparing the physically crosslinked polymer anion exchange membrane of any one of claims 1 to 2, comprising the steps of:
(1) preparation of Poly-Biphenyl-piperidine (PBP) polymers
The method comprises the following steps of (1) carrying out strong acid catalyzed continuous polycondensation reaction on a biphenyl monomer and a piperidone hydrochloride monomer under the action of an organic solvent and a strong acid catalyst, after the continuous polycondensation reaction is finished, precipitating in a sodium hydroxide solution, washing the product with deionized water to be neutral, soaking the obtained white solid product in a hydrochloric acid solution, washing the product after acid soaking with deionized water to be neutral to obtain a yellow solid, and drying to obtain a polybiphenyl piperidine polymer;
(2) preparation of spiro-cationic-supported diphenyl piperidine polymer (PB-ASU)
Dissolving the polybiphenyl piperidine polymer prepared in the step (1) in a dimethyl sulfoxide solvent, adding 1, 5-dibromopentane and an acid-binding agent potassium carbonate into the obtained solution, reacting at 80 ℃ to obtain a solution of the load spiro cationic polybiphenyl piperidine polymer, precipitating in an ethyl acetate solvent after the reaction is finished, washing with deionized water, removing the potassium carbonate, and drying to obtain the load spiro cationic polybiphenyl piperidine polymer;
(3) preparation of chloromethylated hydrogenated styrene-butadiene Block Copolymer (CMSEBS)
Dissolving hydrogenated styrene-butadiene block copolymer in a trichloromethane solvent, adding a chloromethylation reagent and a catalyst of anhydrous stannic chloride, carrying out chloromethylation reaction, separating out in a washing solvent after the reaction is finished, dissolving again, and repeating for three times to obtain chloromethylated hydrogenated styrene-butadiene block copolymer;
(4) preparation of comb-shaped hydrogenated styrene-butadiene Block copolymer (Cn-SEBS)
Reacting the chloromethylated hydrogenated styrene-butadiene block copolymer prepared in the step (3) with tertiary amine with a long alkyl chain, after the reaction is finished, precipitating in a precipitation solvent, washing and drying to obtain the comb-shaped hydrogenated styrene-butadiene block copolymer;
(5) preparation of alkaline anion exchange membrane (PB-ASU-Cn-SEBS)
Dissolving the load spiro cationic diphenyl piperidine polymer prepared in the step (2) in a dimethyl sulfoxide solvent to obtain a load spiro cationic diphenyl piperidine polymer solution; dissolving the comb-shaped hydrogenated styrene-butadiene block copolymer prepared in the step (4) in a chloroform solvent to obtain a comb-shaped hydrogenated styrene-butadiene block copolymer solution; and mixing the loaded spiro cationic diphenyl piperidine polymer solution with the comb hydrogenated styrene-butadiene block copolymer solution in a slow dropwise manner to obtain an alkaline anion exchange membrane (PB-ASU-Cn-SEBS), forming a membrane in a tape casting manner, drying the obtained alkaline anion exchange membrane (PB-ASU-Cn-SEBS), and soaking the membrane in a sodium hydroxide solution to obtain the hydroxide form alkaline anion exchange membrane (physical crosslinking polymer anion exchange membrane).
4. The method for preparing the physically crosslinked polymer anion exchange membrane according to claim 3, wherein: the molar ratio of the biphenyl monomer to the piperidone hydrochloride monomer in the step (1) is 1:1.2-1: 1.3; the organic solvent is dichloromethane, and the volume ratio of the mass of the biphenyl monomer to the dichloromethane solvent is 1:1.7-1:2.3 g/mL; the strong acid catalyst is trifluoromethanesulfonic acid and trifluoroacetic acid, the molar ratio of the biphenyl monomer to the trifluoroacetic acid is 1:1-1:1.05, and the molar ratio of the biphenyl monomer to the trifluoromethanesulfonic acid is 1:11-1: 12; the continuous polycondensation is carried out under the ice-bath condition, and the reaction time is 3-4 hours; the concentration of the sodium hydroxide solution is 3.0-5.0 mol/L; the concentration of the hydrochloric acid solution is 1M, the hydrochloric acid solution is soaked for 3 days, and the drying is vacuum drying in an oven at the temperature of 80 ℃ for 24 hours.
5. The method for preparing the physically crosslinked polymer anion exchange membrane according to claim 4, wherein: in the step (2), the molar ratio of the polybiphenylpiperidine polymer to the 1, 5-dibromopentane is 1:1.3-1: 1.4; the polybiphenylpiperidine polymer with K2CO3In a molar ratio of 1: 1.1; the volume ratio of the mass of the polybiphenylpiperidine polymer to the dimethyl sulfoxide solvent is 1:20-1:25 g/mL.
6. The method for preparing the physically crosslinked polymer anion exchange membrane according to claim 5, wherein: in the step (3), the chloromethylation reagent is one or more of 1, 4-dichloromethoxybutane, trimethylchlorosilane or paraformaldehyde which are mixed in any proportion; the mass ratio of the mass of the hydrogenated styrene-butadiene block copolymer to the mass of the trichloromethane is 1:25-1:30 g/mL; the molar ratio of the hydrogenated styrene-butadiene block copolymer to the chloromethylation reagent is 1:1.8-1: 2.2; the molar ratio of the hydrogenated styrene-butadiene block copolymer to the anhydrous tin tetrachloride is 1:0.3-1: 0.4; the temperature of the chloromethylation reaction is 0-55 ℃, and the reaction time is 3-24 hours; the washing solvent is methanol and/or ethanol and tetrahydrofuran.
7. The method for preparing the physically crosslinked polymer anion exchange membrane according to claim 6, wherein: in the tertiary amine with the long alkyl chain in the step (4), the length of the alkyl chain is 8, 12 or 16 carbon atoms; the selected precipitation solvent is petroleum ether or ethyl acetate.
8. The method for preparing the physically crosslinked polymer anion exchange membrane according to claim 7, wherein: in the step (5), the volume ratio of the mass of the loaded spiro cationic diphenyl piperidine polymer to the dimethyl sulfoxide solvent is 0.02-0.03 g/mL; the volume ratio of the mass of the comb-shaped hydrogenated styrene-butadiene block copolymer to the chloroform solvent is 0.02-0.03 g/mL.
9. The method for preparing the physically crosslinked polymer anion exchange membrane according to claim 8, wherein: in the step (5), the film forming temperature is between room temperature and 80 ℃; the concentration of the sodium hydroxide solution is 1M-2M.
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| CN115028956A (en) * | 2022-07-08 | 2022-09-09 | 北京化工大学 | Anion exchange membrane, preparation method thereof, and preparation and application of alkaline anion exchange membrane |
| CN116554621A (en) * | 2023-04-19 | 2023-08-08 | 江苏耀鸿电子有限公司 | High-frequency high-heat-conductivity fluorine-containing resin-based copper-clad plate and preparation method thereof |
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| CN109411788A (en) * | 2018-09-28 | 2019-03-01 | 北京化工大学 | Poly- biphenyl alkaline membrane of azaspiro cation support type and preparation method thereof |
| KR20200023822A (en) * | 2018-08-27 | 2020-03-06 | 인천대학교 산학협력단 | Anion exchange membrane and method for preparing the same |
| CN111276723A (en) * | 2020-02-19 | 2020-06-12 | 北京化工大学 | Comb-structured alkaline anion exchange membrane and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20200023822A (en) * | 2018-08-27 | 2020-03-06 | 인천대학교 산학협력단 | Anion exchange membrane and method for preparing the same |
| CN109411788A (en) * | 2018-09-28 | 2019-03-01 | 北京化工大学 | Poly- biphenyl alkaline membrane of azaspiro cation support type and preparation method thereof |
| CN111276723A (en) * | 2020-02-19 | 2020-06-12 | 北京化工大学 | Comb-structured alkaline anion exchange membrane and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115028956A (en) * | 2022-07-08 | 2022-09-09 | 北京化工大学 | Anion exchange membrane, preparation method thereof, and preparation and application of alkaline anion exchange membrane |
| CN116554621A (en) * | 2023-04-19 | 2023-08-08 | 江苏耀鸿电子有限公司 | High-frequency high-heat-conductivity fluorine-containing resin-based copper-clad plate and preparation method thereof |
| CN116554621B (en) * | 2023-04-19 | 2023-09-29 | 江苏耀鸿电子有限公司 | High-frequency high-heat-conductivity fluorine-containing resin-based copper-clad plate and preparation method thereof |
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