CN112574448A - Preparation method of side chain type polyphenyl ether anion exchange membrane containing double conduction sites for fuel cell - Google Patents
Preparation method of side chain type polyphenyl ether anion exchange membrane containing double conduction sites for fuel cell Download PDFInfo
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- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 57
- 229920013636 polyphenyl ether polymer Polymers 0.000 title claims abstract description 29
- 239000000446 fuel Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims description 17
- 229920001955 polyphenylene ether Polymers 0.000 claims abstract description 19
- UJNFDSOJKNOBIA-UHFFFAOYSA-M 4-[4-(dimethylamino)styryl]-N-methylpyridinium iodide Chemical class [I-].C1=CC(N(C)C)=CC=C1\C=C\C1=CC=[N+](C)C=C1 UJNFDSOJKNOBIA-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 230000031709 bromination Effects 0.000 claims abstract description 6
- 238000005893 bromination reaction Methods 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims description 25
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 22
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 15
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 230000005540 biological transmission Effects 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000010345 tape casting Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000002474 experimental method Methods 0.000 claims description 2
- 230000002209 hydrophobic effect Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 238000000643 oven drying Methods 0.000 claims 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 20
- 230000007774 longterm Effects 0.000 abstract description 13
- 230000008961 swelling Effects 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 9
- 238000002791 soaking Methods 0.000 abstract description 5
- -1 4-dimethylaminophenyl Chemical group 0.000 abstract description 4
- 230000000717 retained effect Effects 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- VKRWRNVGVPSVLA-UHFFFAOYSA-N n,n'-bis(2-phenylphenyl)oxamide Chemical compound C=1C=CC=C(C=2C=CC=CC=2)C=1NC(=O)C(=O)NC1=CC=CC=C1C1=CC=CC=C1 VKRWRNVGVPSVLA-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- AHKZTVQIVOEVFO-UHFFFAOYSA-N oxide(2-) Chemical group [O-2] AHKZTVQIVOEVFO-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 230000032258 transport Effects 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006053 organic reaction Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 125000005504 styryl group Chemical group 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 238000005985 Hofmann elimination reaction Methods 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920006260 polyaryletherketone Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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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
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
- C08G65/485—Polyphenylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
- C08J5/2287—After-treatment
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1046—Mixtures of at least one polymer and at least one additive
- H01M8/1048—Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
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- H01M8/1088—Chemical modification, e.g. sulfonation
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- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
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Abstract
The invention firstly provides a side chain type polyphenyl ether anion exchange membrane containing double conduction sites, which comprises: polyphenylene ether with 51% bromination rate and 4- (4-dimethylaminophenyl) with different grafting ratesVinyl) -1-methylpyridinium iodide (DASP), a series of 4- (4-dimethylaminostyryl) -1-methylpyridinium iodide quaternized polyphenylene ether anion exchange membranes were synthesized. The membranes were measured for ionic conductivity, thermal stability, water swelling rate and long term chemical stability. The results indicate that the side chain DASP monomers have unique hydrophilicity and steric hindrance. PPO-DASP7 at 30oC‑80oAnd C, the conductivity of hydroxide ions is 0.020-0.075S/cm. In addition, anion exchange membranes have good long-term chemical stability. At 80oAfter 300 hours of soaking in a 1M KOH solution of C, the PPO-DASP7 anion exchange membrane retained 56.4% of its initial conductivity. In addition, the obtained anion exchange membranes not only have good long-term stability and electrical conductivity, but also have limited water swelling rate, which indicates their potential for use in fuel cell devices. The investigated PPO-based anion exchange membranes are good candidates for AEMFC development. Is expected to be applied to the field of fuel cells.
Description
Technical Field
The invention belongs to the field of polymer chemistry and anion exchange membrane fuel cells, and particularly relates to a side chain type polyphenyl ether anion exchange membrane containing double conduction sites for a fuel cell and a preparation method thereof.
Background
Fuel cells are electrochemical devices that convert chemical energy into electrical energy; from the viewpoint of clean energy and ecological environment, fuel cells are considered as one of the most promising power generation technologies; alkaline anionic membrane fuel cells have attracted a great deal of scholars' attention in terms of their efficient electrical conversion technology and low cost; in the alkaline anion fuel cell, an anion exchange membrane is a key part; the important role of the anion exchange membrane is to block fuel and oxidant between the anode and the cathode and to transport OH simultaneously through the membrane-Ions;
in anion exchange membranes, the chemical nature of the polymer backbone can affect the long-term stability of the membrane; in previous researches, a large number of used main chain materials comprise polyphenyl ether, polyaryletherketone and polysulfone, and the main chain of the membrane can be obviously degraded in a high-pH environment, so that the long-term stability of the membrane is greatly reduced; at the same time, the ion transport site Quaternary Ammonium (QA) groups on the anion exchange membrane are also exposed to OH-Attack by ions, organic degradation reactions such as Hofmann elimination and nucleophilic Substitution (SN)2) And the like; the anion exchange membrane can be degraded and damaged; many studies have shown that when polyphenylene ether is used as an anion exchange membrane polymer backbone material, it has good dimensional stability and alkali resistance, which are indistinguishable from its unique molecular structure; in the structural formula of polyphenylene ether, it can be seen that oxygen in ether bond has a lone electron pair, which forms a strong conjugated state with benzene ring, and thus can be maintained in a stable state for a long period of time under acidic or basic conditions; by combining the main chain and side chain monomers of the polyphenyl ether, a novel anion exchange membrane is synthesized, and the side chain type polyphenyl ether anion exchange membrane containing double conduction sites is formed.
Disclosure of Invention
The invention aims to provide a side chain type polyphenyl ether anion exchange membrane containing double conduction sites for a fuel cell and a preparation method thereof, aiming at improving the ionic conductivity and the thermal stability on the basis of different grafting rates, keeping better dimensional stability and simultaneously having simple process;
the invention firstly provides a preparation method of a side chain type polyphenyl ether anion exchange membrane containing double conduction sites for a fuel cell, which comprises the following steps:
A. firstly, preparing brominated polyphenylene oxide;
B. then preparing polyphenyl ether polymers with different grafting ratios;
C. finally, spreading the prepared polymers with different grafting ratios;
in the preparation method of the side chain type polyphenylene oxide anion exchange membrane containing the double conduction sites, the step A specifically comprises the following steps: preparing brominated polyphenylene oxide by taking polyphenylene oxide, N-bromosuccinimide and azobisisobutyronitrile as raw materials through an organic reaction, wherein the brominated polyphenylene oxide is named as BPPO; regulating the proportion of the N-bromosuccinimide to the polyphenyl ether to prepare brominated polyphenyl ethers with different bromination rates; the bromination rate is 51 percent;
in the preparation method of the polyphenylene ether polymer with different grafting ratios, the step B specifically comprises the following steps: taking 4- (4-dimethylaminostyryl) -1-methylpyridinium iodide (DASP) and brominated polyphenylene oxide as raw materials, synthesizing polymers with different grafting rates by an organic substitution reaction method, and naming the polymers as PPO-DASP5, PPO-DASP7, PPO-DASP10 and PPO-DASP 13;
in the preparation method of the side chain type polyphenylene ether anion exchange membrane containing the double conduction sites, the step C specifically comprises the following steps:
c1 mixing 80 Polymer and 4- (4-Dimethylaminostyryl) -1-methylpyridinium iodideoC, stirring for 96 hours;
c2, pouring the mixed liquid on a dry and clean glass plate, and then carrying out vacuum drying for 24-48 h;
c3, performing alkalization treatment on the dried membrane, and washing the membrane with deionized water for later use;
in the preparation of the side chain type polyphenylene oxide anion exchange membrane containing the double conduction sites, the molar ratio of DASP to BPPO is 0.05:1, 0.07:1, 0.1:1 and 0.13: 1.
The invention has the advantages of
The invention firstly provides a side chain type polyphenyl ether anion exchange membrane containing double conduction sites for a fuel cell, which comprises: the polyphenylene ether containing 51% of brominating rate and 4- (4-dimethylaminostyryl) -1-methylpyridinium iodide with different grafting rates were 5%, 7%, 10% and 13%, respectively. Long side chains containing amino and pyridinium groups are introduced into polyphenylene oxide to form quaternary ammonium type and pyridinium type transmission sites, so that the double transmission sites can increase the hydrophilicity of the membrane, improve the IEC value of the membrane and improve the ionic conductivity of the anionic membrane; when long side chain type substituent containing styryl is introduced into the main chain, the main chain with hydrophobicity and the styryl can be microphase separated from hydrophilic cationic groups to form hydrophilic and hydrophobic ion channels; by combining a PPO main chain and a side chain containing double transmission sites, a novel anion exchange membrane is synthesized; forming a PPO-based side-chain type polyphenylene oxide anion exchange membrane containing double conduction sites;
in this work, we used a simple two-step synthesis reaction to obtain an anion exchange membrane; the polyphenylene ether is brominated and then substituted; synthesizing a series of 4- (4-dimethylaminostyryl) -1-methylpyridinium iodide quaternized polyphenyl ether anion exchange membranes; measuring the ionic conductivity, mechanical properties, water swelling rate and long-term chemical stability of the membrane; the results show that the temperature range of PPO-DASP7 is 30oC-80oC, the conductivity of hydroxide ions is 0.020-0.075S/cm; in addition, anion exchange membranes have good long-term chemical stability; after soaking in 80 ℃ 1M KOH solution for 300 hours, the PPO-DASP7 anion exchange membrane retained 56.4% of its initial conductivity; in addition, the anion exchange membranes obtained not only have good long-term stability and electrical conductivity, but also have a limited water swelling rate, which indicates that they are useful in the field of water treatmentPotential for use in fuel cell devices. The studied PPO-based anion exchange membrane is a good candidate material for AEMFC development; is expected to be applied to the field of fuel cells.
Drawings
FIG. 1 is a diagram of the infrared spectra of PPO-DASP7 and PPO-DASP 10;
FIG. 2 is a graph of conductivity versus temperature for a film sample;
FIG. 3 is a graph of the thermal weight loss of a film sample;
FIG. 4 is a graph of the alkali resistance stability of film samples;
table 1 shows the water absorption and swelling at 25 ℃ and 80 ℃ for the film samples.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the present invention by way of examples, but it is to be understood that the description is intended to illustrate further features and advantages of the invention, and not to limit the scope of the claims which follow;
preferably, step a specifically comprises: shown as a formula I, the method comprises the steps of preparing brominated polyphenylene oxide by taking polyphenylene oxide, N-bromosuccinimide and azobisisobutyronitrile as raw materials through an organic reaction, wherein the brominated polyphenylene oxide is named as BPPO; regulating the proportion of the N-bromosuccinimide to the polyphenyl ether to prepare brominated polyphenyl ethers with different bromination rates; the bromination rate is 51 percent; the reaction formula is as follows:
formula I
Preferably, step B specifically comprises: as shown in formula II, 4- (4-dimethylaminostyryl) -1-methylpyridinium iodide (DASP) and brominated polyphenylene oxide are used as raw materials, and polymers with different grafting rates are synthesized by an organic substitution reaction method, and are named as PPO-DASP5, PPO-DASP7, PPO-DASP10 and PPO-DASP 13; the reaction formula is as follows:
formula II
Wherein x is the number of repeating units, and x is an integer of more than or equal to 1;
in the preparation method of the side chain type polyphenylene ether anion exchange membrane containing the double conduction sites, the step C specifically comprises the following steps:
c1 mixing 80 Polymer and 4- (4-Dimethylaminostyryl) -1-methylpyridinium iodideoC, stirring for 96 hours;
c2, pouring the mixed liquid on a dry and clean glass plate, and then carrying out vacuum drying for 24-48 h;
c3, performing alkalization treatment on the dried membrane, and washing the membrane with deionized water for later use;
in the preparation of the side chain type polyphenyl ether anion exchange membrane containing the double conduction sites, the molar ratio of DASP to BPPO is 0.05:1, 0.07:1, 0.1:1 and 0.13: 1;
based on the method, the invention provides a side chain type polyphenyl ether anion exchange membrane containing double conduction sites, which is prepared by adopting the preparation method as described in any one of the above; the side chain type polyphenyl ether anion exchange membrane containing the double conduction sites has excellent performances of good long-term stability, good ion conduction performance, good size stability and the like.
The present invention will be described in detail below with reference to specific examples;
a. preparation of brominated polyphenylene ethers
(1) Installing a three-neck flask with a reflux device on a heating sleeve, installing a mechanical stirrer on the flask, weighing 6g of polyphenyl ether on a balance, and adding the weighed medicine into the flask;
(2) under nitrogen protection, 60ml of chlorobenzene solution and 0.25g of initiator 2,2' azo (2-methylpropionitrile) (AIBN) and 9.8g N-bromosuccinimide (NBS) were added to the flask, respectively;
(3) refluxing with a condenser under nitrogen, heating to 135 deg.CoC, reacting for 4 hours;
(4) introducing the obtained viscous polymer into ethanol to cool the polymer into filaments; washing for multiple times until the ethanol solution is clear;
(5) cutting the obtained filamentous solid polymer into small pieces by using scissors;
(6) the resulting small blocks are at 60oC, drying in an oven for 24 hours;
(7) dissolving the dried polymer in chloroform solvent;
(8) introducing the completely dissolved liquid into ethanol again to obtain yellow filamentous polymer; washing for multiple times until the ethanol is clear;
(9) shearing the obtained polymer and drying; obtaining a final product, namely brominated polyphenylene oxide; the bromide ratio was 75.7%;
b. preparing anion exchange membrane polymers with different grafting ratios;
(1) dissolving 0.15g of brominated polyphenylene oxide serving as a raw material in an organic solvent;
(2) adding 4- (4-dimethylaminostyryl) -1-methylpyridinium iodide organic monomers in different proportions; the molar ratio of 4- (4-dimethylaminostyryl) -1-methylpyridinium iodide to brominated polyphenylene ether is 0.05:1, 0.07:1, 0.1:1, 0.13: 1; synthesizing polymers with different grafting ratios, namely PPO-DASP5, PPO-DASP7, PPO-DASP10 and PPO-DASP 13;
c. preparing a side chain type polyphenyl ether anion exchange membrane containing double conduction sites;
(1) mixing the obtained mixed solution 80oStirring for 96 hours at the temperature of C to obtain a film-forming solution, wherein the molar ratio of the 4- (4-dimethylaminostyryl) -1-methylpyridinium iodide to the brominated polyphenylene oxide in the film-forming solution is 0.05:1, 0.07:1, 0.1:1 and 0.13: 1;
(2) the obtained film-forming solution is subjected to film forming by adopting a tape casting method, the film-forming solution is placed on a flat glass plate for film forming by tape casting, and then the film-forming solution is placed into an oven and heated to 60 DEG for film formingoDrying for 24-48 hours under C; naturally cooling to room temperature, and demoulding in water;
(3) soaking the obtained membrane in a potassium hydroxide solution with the concentration of 1M for ion exchange for 24 hours, then cleaning the membrane by deionized water until the pH value is neutral, and soaking the membrane in the deionized water for 24 hours to obtain a side chain type polyphenyl ether anion exchange membrane containing double conduction sites for a fuel cell;
d. the prepared film samples PPO-DASP5, PPO-DASP7, PPO-DASP10 and PPO-DASP13 are subjected to structural characterization and performance characterization;
(1) structural characterization
Infrared spectrogram
FIG. 1 is an FT-IR spectrum with characteristic peaks recorded as follows; at 2934cm-1The tensile vibration peak at (A) is attributed to the methyl group (-CH) on the main chain structure3）； 1184cm-1The vibration of (a) is due to the C-O-C bond of the main chain; 1017 cm-1The peak at (A) is the tensile vibration of the C-N bond; 1558 and 1598cm-1The vibration of (a) is due to the vibration of the pyridine ring; the above observations indicate successful synthesis of anion exchange membranes;
(2) performance characterization
Water absorption, swelling ratio and proton conductivity
Table 1 shows the values of water absorption and swelling capacity at 25 ℃ and 80 ℃ for the film samples, the water absorption of the film samples increasing with increasing temperature, since the water absorption increases with increasing temperature, since the water diffusion rate in the polymer increases with increasing temperature; as can be seen from the table, the swelling results substantially match the water absorption, and as the water absorption increases, the swelling ratio of the film samples also increases;
TABLE 1
FIG. 2 is a graph showing the ion conductivity of the membrane samples as a function of temperature, and it can be seen that the conductivity of each membrane sample gradually increases with the temperature, and ranges from 30 to 80oThe conductivity of the membrane in the C range is positively correlated with the temperature; the PPO-DASP5, PPO-DASP7, PPO-DASP10 and PPO-DASP13 films are coated on the surface of the membrane at 30oThe conductivity at C was 5.1, 19.9, 12.2 and 10.6 mS/cm, respectively; at 80oAt C, they are 22.2, 75.0, 50.9 and 37.4mS/cm, respectively; it can be seen that the DASP monomer provides more cation transport sites, thereby facilitating the transport of hydroxide in AEM;
thermal analysis
FIG. 3 is TGA plot of film samplesLine graph showing the thermal stability of the film, measured as the final OH "form of the film; the thermal decomposition process of the membrane was analyzed by TGA, and due to its same compositional structure, the PPO-DASPx membranes all showed similar thermal decomposition process; as shown in fig. 3, at 50-700 foC, the first stage (200-oC) Due to degradation of the cationic groups; the first stage (400)oC or above) is the degradation of the main chain polyphenylene ether; all four PPO-DASPx membranes had excellent thermal stability.
Analysis of alkali resistance stability
FIG. 4 is a graph of alkali resistance stability test of the film; to test the long-term chemical stability of the anion exchange membrane in this experiment, which limited its practical application in fuel cells, the membrane was placed at 80 foC in 1MKOH solution for 300 hours; the alkali resistance stability of the anion exchange membranes was evaluated by the ion conductivity retained by the membrane.
In summary, the invention provides a side chain type polyphenyl ether anion exchange membrane containing double conduction sites and a preparation method thereof, the invention firstly prepares brominated polyphenyl ether, and then synthesizes an anion exchange membrane polymer; a series of 4- (4-dimethylaminostyryl) -1-methylpyridinium iodide quaternized polyphenyl ether anion exchange membranes are synthesized. Measuring the ionic conductivity, thermal stability, water swelling rate and long term chemical stability of the membrane; the results indicate that the side chain DASP monomers have unique hydrophilicity and steric hindrance. PPO-DASP7 at 30oC-80oAnd C, the conductivity of hydroxide ions is 0.020-0.075S/cm. In addition, anion exchange membranes have good long-term chemical stability. At 80oAfter 300 hours of soaking in a 1M KOH solution of C, the PPO-DASP7 anion exchange membrane retained 56.4% of its initial conductivity. In addition, the obtained anion exchange membranes not only have good long-term stability and electrical conductivity, but also have limited water swelling rate, which indicates their potential for use in fuel cell devices. The investigated PPO-based anion exchange membranes are good candidates for AEMFC development.
The above description of the embodiments is only for the purpose of assisting understanding of the method of the present invention and the core idea thereof, and it should be noted that those skilled in the art can make several improvements and modifications to the present invention without departing from the principle of the present invention, and these improvements and modifications also fall into the protection scope of the claims of the present invention.
Claims (5)
1. The side chain type polyphenyl ether anion exchange membrane containing double conduction sites for the fuel cell is characterized by comprising the following steps:
A. firstly preparing brominated polyphenylene oxide (BPPO);
B. then preparing polyphenylene ether type anion exchange membrane polymers with different grafting ratios;
C. finally, the prepared polymers with different grafting ratios are spread into a film.
2. The method for preparing a side-chain type polyphenylene ether anion exchange membrane containing double conduction sites for a fuel cell according to claim 1, comprising the following steps:
the method comprises the following steps: respectively dissolving organic monomers 4- (4-dimethylaminostyryl) -1-methylpyridinium iodide (DASP) and bromine-containing polyphenyl ether in a solvent, and then mixing the two to obtain a mixed solution;
step two: stirring the mixed solution obtained in the step one for 96 hours to obtain a film-forming solution, wherein the film-forming solution contains an organic monomer 4- (4-dimethylaminostyryl) -1-methylpyridinium iodide (DASP) and brominated polyphenylene oxide in a molar ratio of 0.05:1;
step three: and (4) forming the film by adopting a tape casting method from the film forming solution obtained in the step two to obtain the side chain type polyphenyl ether anion exchange membrane containing the double conduction sites for the fuel cell.
3. The method for preparing a side-chain type polyphenylene ether anion-exchange membrane for a fuel cell according to claim 2, wherein the organic monomer 4- (4-dimethylaminostyryl) -1-methylpyridinium iodide: contains quaternary ammonium salt and pyridinium salt double transmission sites and hydrophobic functional group styryl.
4. The preparation method of the side chain type polyphenylene ether anion exchange membrane containing the double conduction sites for the fuel cell as claimed in claim 2, wherein the preparation method of the brominated polyphenylene ether comprises the following steps: under the protection of nitrogen, 6g of polyphenylene ether, 0.25g of azobisisobutyronitrile and 9.8g of N-bromosuccinimide, and 60ml of chlorobenzene solution were added into a flask; slowly heating to 135 ℃, and refluxing for 4h at constant temperature; pouring the obtained viscous liquid polymer into ethanol, and cooling the polymer into filaments; cutting the obtained filamentous solid polymer, drying, and dissolving in chloroform solution again; pouring the obtained liquid into ethanol again, cutting yellow filamentous solid into pieces, and oven drying; experiment can adjust the bromination rate by adjusting the molar ratio of the polyphenyl ether to the N-bromosuccinimide.
5. A side chain type polyphenylene ether anion exchange membrane containing double conduction sites, which is prepared by the preparation method of the anion exchange membrane with high alkali resistance stability as claimed in any one of claims 1 to 4.
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|---|---|---|---|---|
| CN117720721A (en) * | 2024-02-18 | 2024-03-19 | 国家电投集团氢能科技发展有限公司 | Anion exchange polymer, ion exchange membrane, and preparation methods and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140107237A1 (en) * | 2012-10-09 | 2014-04-17 | University Of Delaware | Cation-strung side chain polymers useful in hydroxide/anion exchange membranes |
| CN104151590A (en) * | 2013-05-15 | 2014-11-19 | 北京化工大学 | Polyphenylene oxide anion exchange membrane for alkaline membrane fuel cells |
| CN105367782A (en) * | 2015-11-02 | 2016-03-02 | 国网吉林省电力有限公司电力科学研究院 | 2-methyl-3-alkyl imidazole onium salt polyarylether comb type polymer and preparation and application thereof |
| CN106147197A (en) * | 2016-06-30 | 2016-11-23 | 北京化工大学 | A kind of fuel cell many conduction sites polyphenyl ether anion exchange membrane and preparation method thereof |
| CN110694698A (en) * | 2019-10-21 | 2020-01-17 | 华南理工大学 | Anion exchange membrane with high anion permeability and high ion selectivity as well as preparation method and application thereof |
| CN110739478A (en) * | 2019-11-07 | 2020-01-31 | 大连理工大学 | Preparation method of long-short side chain blended anion exchange membranes |
-
2020
- 2020-12-30 CN CN202011597870.3A patent/CN112574448A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140107237A1 (en) * | 2012-10-09 | 2014-04-17 | University Of Delaware | Cation-strung side chain polymers useful in hydroxide/anion exchange membranes |
| CN104151590A (en) * | 2013-05-15 | 2014-11-19 | 北京化工大学 | Polyphenylene oxide anion exchange membrane for alkaline membrane fuel cells |
| CN105367782A (en) * | 2015-11-02 | 2016-03-02 | 国网吉林省电力有限公司电力科学研究院 | 2-methyl-3-alkyl imidazole onium salt polyarylether comb type polymer and preparation and application thereof |
| CN106147197A (en) * | 2016-06-30 | 2016-11-23 | 北京化工大学 | A kind of fuel cell many conduction sites polyphenyl ether anion exchange membrane and preparation method thereof |
| CN110694698A (en) * | 2019-10-21 | 2020-01-17 | 华南理工大学 | Anion exchange membrane with high anion permeability and high ion selectivity as well as preparation method and application thereof |
| CN110739478A (en) * | 2019-11-07 | 2020-01-31 | 大连理工大学 | Preparation method of long-short side chain blended anion exchange membranes |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117720721A (en) * | 2024-02-18 | 2024-03-19 | 国家电投集团氢能科技发展有限公司 | Anion exchange polymer, ion exchange membrane, and preparation methods and application thereof |
| CN117720721B (en) * | 2024-02-18 | 2024-04-30 | 国家电投集团氢能科技发展有限公司 | Anion exchange polymer, ion exchange membrane, and preparation methods and application thereof |
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