CN113372596A - Alkaline anion exchange membrane based on chemical crosslinking and preparation method thereof - Google Patents
Alkaline anion exchange membrane based on chemical crosslinking and preparation method thereof Download PDFInfo
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- CN113372596A CN113372596A CN202110592582.7A CN202110592582A CN113372596A CN 113372596 A CN113372596 A CN 113372596A CN 202110592582 A CN202110592582 A CN 202110592582A CN 113372596 A CN113372596 A CN 113372596A
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- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 62
- 238000010382 chemical cross-linking Methods 0.000 title claims abstract description 39
- 238000005285 chemical preparation method Methods 0.000 title description 2
- 229920000642 polymer Polymers 0.000 claims abstract description 157
- 239000003960 organic solvent Substances 0.000 claims abstract description 93
- 239000000843 powder Substances 0.000 claims abstract description 73
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 239000007787 solid Substances 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000005406 washing Methods 0.000 claims abstract description 32
- 239000002253 acid Substances 0.000 claims abstract description 30
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- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000008367 deionised water Substances 0.000 claims abstract description 28
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 28
- 239000000126 substance Substances 0.000 claims abstract description 26
- 229920006254 polymer film Polymers 0.000 claims abstract description 17
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 238000005349 anion exchange Methods 0.000 claims abstract description 8
- 238000005266 casting Methods 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
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- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 26
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- 238000000034 method Methods 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 238000010791 quenching Methods 0.000 claims description 17
- 230000000171 quenching effect Effects 0.000 claims description 17
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- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 14
- 239000011521 glass Substances 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- HUUPVABNAQUEJW-UHFFFAOYSA-N 1-methylpiperidin-4-one Chemical group CN1CCC(=O)CC1 HUUPVABNAQUEJW-UHFFFAOYSA-N 0.000 claims description 11
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- 238000010992 reflux Methods 0.000 claims description 9
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- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 7
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- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
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- JWUXJYZVKZKLTJ-UHFFFAOYSA-N Triacetonamine Chemical compound CC1(C)CC(=O)CC(C)(C)N1 JWUXJYZVKZKLTJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920002480 polybenzimidazole Polymers 0.000 claims description 4
- 229920001088 polycarbazole Polymers 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- YHUNCTAOWLYFHG-UHFFFAOYSA-N 1,2,6-trimethylpiperidin-4-one Chemical compound CC1CC(=O)CC(C)N1C YHUNCTAOWLYFHG-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 abstract description 12
- 238000005342 ion exchange Methods 0.000 abstract description 12
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 238000011161 development Methods 0.000 abstract description 4
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 5
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 229910000510 noble metal Inorganic materials 0.000 description 2
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- 238000006722 reduction reaction Methods 0.000 description 2
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- QPFMBZIOSGYJDE-ZDOIIHCHSA-N 1,1,2,2-tetrachloroethane Chemical group Cl[13CH](Cl)[13CH](Cl)Cl QPFMBZIOSGYJDE-ZDOIIHCHSA-N 0.000 description 1
- 102100037709 Desmocollin-3 Human genes 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000005985 Hofmann elimination reaction Methods 0.000 description 1
- 101000968042 Homo sapiens Desmocollin-2 Proteins 0.000 description 1
- 101000880960 Homo sapiens Desmocollin-3 Proteins 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
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- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
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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
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
- C08J5/2243—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231
- C08J5/225—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231 containing fluorine
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- 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
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/08—Fuel cells with aqueous electrolytes
- H01M8/083—Alkaline fuel cells
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Abstract
A basic anion exchange membrane based on chemical crosslinking and a preparation method thereof, wherein a polymer main chain is subjected to chemical crosslinking in a strong oxidizing acid, piperidone and an organic solvent A at a low temperature, and after the reaction is finished, the polymer main chain is quenched, washed and dried to obtain solid powder; adding the powder into an organic solvent B, adding methyl iodide, and carrying out dark reaction at room temperature to obtain polymer powder; and (3) dissolving the polymer powder in an organic solvent C, casting to form a film to obtain a polymer film, washing the polymer film by deionized water, and then carrying out anion exchange. According to the invention, the polymer main chain is subjected to self-chemical crosslinking through piperidone type functional groups for the first time, so that the mechanical strength and the chemical stability of the polymer main chain are improved; the synthesis path is simplified, the reaction flow is shortened, and the yield is improved; the prepared alkaline anion exchange membrane is compact and transparent, has high ion exchange capacity, good thermal stability and high mechanical strength, and realizes the development of the polymer ion exchange membrane with high conductivity and strong alkali resistance.
Description
Technical Field
The invention belongs to the field of polymer anion exchange membranes, and relates to a chemical crosslinking-based alkaline anion exchange membrane and a preparation method thereof.
Background
With the arrival of the energy crisis, hydrogen energy as a clean energy source can effectively replace the traditional fossil fuel. At present, hydrogen is successfully applied to Proton Exchange Membrane Fuel Cells (PEMFCs), and hydrogen-powered automobiles and power generation devices are gradually commercialized. Although PEMFCs have been successful in the market, PEMFCs have disadvantages compared to Anion Exchange Membrane Fuel Cells (AEMFCs), and foreign monopoly of proton exchange membranes and expensive noble metal catalysts cause an increase in production costs. On the contrary, AEMFC can obtain faster oxygen reduction reaction kinetics under alkaline conditions, the selection of the catalyst is not limited to a noble metal catalyst, and hydrogen electro-oxidation and oxygen electro-reduction are better under a non-strong acid environment. Thus, the performance of AEMFC is generally better than PAFCs and PEMFCs that use acidic electrolytes; in addition, the AEMFC has low working temperature, good low-temperature working performance and quick start of the battery. The anion exchange membrane is used as the core component of the AEMFC, the selected materials are all based on engineering plastics, and the manufacturing cost is low. The current major problem is the insufficient durability of anion exchange membranes in strongly alkaline environments, so there is a need for new anion exchange membranes.
Disclosure of Invention
Aiming at the problem of durability of AEMFC working in a strong alkaline environment at 60-120 ℃, the invention aims to prepare a chemically crosslinked alkaline anion exchange membrane with strong mechanical strength, good chemical stability, stable heat resistance and high ion exchange capacity and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a basic anion-exchange membrane based on chemical crosslinking comprises the following steps:
a, chemically crosslinking a polymer main chain in a strong oxidizing acid, piperidone and an organic solvent A at a low temperature, quenching after the reaction is finished, washing and drying to obtain solid powder;
b, adding the powder obtained in the step a into an organic solvent B, adding methyl iodide, carrying out dark reaction at room temperature for 18-36 hours, then extracting, washing and drying to obtain polymer powder;
and C, dissolving the polymer powder in an organic solvent C, casting to form a film to obtain a polymer film, washing the polymer film by deionized water, and then carrying out anion exchange to obtain the alkaline anion exchange film based on chemical crosslinking.
The invention further improves that the polymer main chain in the step a is one or two of polystyrene, SEBS, polycarbazole, polysulfone, polybenzimidazole, polyaniline and polyether sulfone benzene rings.
In a further improvement of the invention, the strong oxidizing acid in step a is one or both of trifluoroacetic acid and trifluoromethanesulfonic acid.
The further improvement of the invention is that the organic solvent A is one of dichloromethane, chloroform, 1,2, 2-tetrachloroethane, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide;
the organic solvent B is one of dichloromethane, chloroform, 1,2, 2-tetrachloroethane, dioxane, toluene, xylene, N-dimethylacetamide and dimethyl sulfoxide;
the organic solvent C is one or more of tetrahydrofuran, xylene, toluene, chloroform, 1,2, 2-tetrachloroethane, dimethylacetamide, dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide;
a further improvement of the invention is that the ratio of the mass of the polymer backbone to the volume of the organic solvent a is 1 g: 30 mL-1 g: 200 mL.
A further improvement of the invention is that the ratio of the mass of the polymer backbone to the volume of the organic solvent a is 1 g: 50 mL-1 g: 80 mL.
A further improvement of the invention is that the ratio of the amount of substance of the polymer main chain to the strongly oxidizing acid is 1: 1-1: 5.
a further improvement of the invention is that the ratio of the amount of substance of the polymer main chain to the strongly oxidizing acid is 1: 1.2-1: 1.5.
in a further improvement of the invention, in step B, the ratio of the mass of the solid powder to the volume of the organic solvent B is 1 g: 30 mL-1 g: 200 mL.
The invention is further improved in that the ratio of the mass of the solid powder to the volume of the organic solvent B is 1 g: 50 mL-1 g: 80 mL;
the invention has the further improvement that the low-temperature reaction temperature in the step a is 0-15 ℃, and the reaction time is 1-12 h.
The further improvement of the invention is that the low-temperature reaction temperature is 3-6 ℃ and the time is 2-4 h
In a further development of the invention, the drying conditions are freeze drying.
The invention is further improved in that the drying temperature in the step b is 30-80 ℃ (preferably 40-60 ℃), and the drying time is 6-24h (preferably 12-18 h).
The invention has the further improvement that the specific process of the step c is as follows: dissolving polymer powder in an organic solvent C, wherein the mass fraction of the polymer powder is 25-60% (optimally 45%), refluxing for 3-6 h at 20-40 ℃, dissolving until the polymer powder is clear to obtain a chemically crosslinked polymer solution, pouring the polymer solution into a glass tank, and volatilizing the organic solvent C for 4-12h at 20-50 ℃ to obtain a transparent polymer film;
the further improvement of the invention is that the dissolving mode is one or more than two of mechanical stirring, magnetic stirring, ultrasonic and cell crushing, preferably one or two of ultrasonic and cell crushing;
a basic anion-exchange membrane with a chemical crosslinking structure prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects: according to the invention, after the main chain of the polymer is dissolved in the organic solvent A, the piperidone is used for chemical crosslinking in a low-temperature environment, so that the strength of the membrane is improved, and the anion exchange sites in an alkaline environment are protected by steric hindrance of a piperidine structure. Compared with the existing anion exchange membrane, the invention carries out self chemical crosslinking on the main chain of the polymer through the piperidone functional group for the first time, thereby improving the mechanical strength and the chemical stability of the polymer; the invention simplifies the synthesis path, shortens the reaction flow, improves the yield, and avoids the problems of low yield and gelation caused by multi-step reactions such as grafting, reducing, functional group post-treatment and the like in the prior art; the prepared alkaline anion exchange membrane is compact and transparent, has high ion exchange capacity, good thermal stability and high mechanical strength, and realizes the development of the polymer ion exchange membrane with high conductivity and strong alkali resistance.
Further, quenching reaction is carried out through deionized water, and the optimal reaction time is 45-130 min, so that the 100% functionalized alkaline anion exchange membrane is obtained.
Drawings
FIG. 1 is a schematic diagram of a basic anion exchange membrane prepared in example 1 of the present invention.
FIG. 2 is a nuclear magnetic spectrum of the basic anion exchange membrane of examples 1 to 4 of the present invention.
FIG. 3 is an IR spectrum of the basic anion exchange membrane of examples 1-4 of the present invention.
FIG. 4 is a tensile test chart of the basic anion-exchange membrane of example 1 of the present invention.
FIG. 5 is a thermogravimetric analysis of the basic anion exchange membrane of example 1 of the present invention.
FIG. 6 is a 5 k-fold planar SEM image of the basic anion-exchange membrane of example 1 of the present invention.
FIG. 7 is a 15 k-fold planar SEM image of the basic anion-exchange membrane of example 1 of the present invention.
FIG. 8 is a 100-fold cross-sectional scanning electron micrograph of the basic anion-exchange membrane of example 1 of the present invention.
FIG. 9 is a scanning electron micrograph of a cross section of 250 times the basic anion exchange membrane of example 1 of the present invention.
FIG. 10 is a graph of the conductivity test results for the basic anion exchange membrane of example 1 of the present invention.
Detailed Description
The present invention will be described in detail below by way of examples with reference to the accompanying drawings.
According to the invention, the main chain is directly crosslinked through the piperidine functional group, the influence of the Hofmann effect is reduced from the perspective of steric hindrance by combining the excellent heat resistance, chemical stability and mechanical strength of the main chain, and the membrane preparation process of the solution volatile solvent is optimized, so that the polymer anion exchange membrane with strong mechanical strength, good chemical stability, stable heat resistance and high ion exchange capacity is obtained and characterized.
The development of the polymeric anionic membranes of the present invention starts with structural design and functional group selection. The main chain structure without unsaturated bonds is selected, and the functional group with strong alkali resistance is used, so that long-term chemical stability, high conductivity, low swelling rate, ion transportation microphase separation form and strong mechanical strength can be realized.
A, chemically crosslinking a polymer main chain in a strong oxidizing acid, piperidone and an organic solvent A at a low temperature, quenching after the reaction is finished, washing and drying to obtain powder; the piperidone is N-methyl-4-piperidone, 2,6, 6-tetramethyl-4-piperidone or 1,2, 6-trimethyl-4-piperidone.
B, adding the powder obtained in the step a into an organic solvent B, adding methyl iodide, carrying out dark reaction at room temperature for 18-36 hours, extracting after the reaction is finished, washing, and drying to obtain polymer powder;
and C, dissolving the polymer powder in an organic solvent C, casting to form a film to obtain a polymer film, washing the polymer film by deionized water, and then carrying out anion exchange to obtain the alkaline anion exchange film based on chemical crosslinking.
Chemical modification with aromatic structure (benzene ring) in the main chain of the polymer. Specifically, the polymer main chain is one or more than two of polystyrene, SEBS, polycarbazole, polysulfone, polybenzimidazole, polyaniline and polyether sulfone benzene rings.
In the step a, the strong oxidizing acid is one or two of trifluoroacetic acid and trifluoromethanesulfonic acid;
the organic solvent A is: one of dichloromethane, chloroform, 1,2, 2-tetrachloroethane, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide;
the organic solvent B is one of dichloromethane, chloroform, 1,2, 2-tetrachloroethane, dioxane, toluene, xylene, N-dimethylacetamide and dimethyl sulfoxide;
the organic solvent C is one or more than two of tetrahydrofuran, dimethylbenzene, methylbenzene, chloroform, 1,2, 2-tetrachloroethane, dimethylacetamide, dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide;
quenching was performed with deionized water, which reached a resistivity of 18M Ω cm.
The volume ratio of the mass of the polymer main chain to the organic solvent A is 1 g: 30 mL-1 g: 200mL (preferably 1 g: 50 mL-1 g: 80 mL);
the molar ratio of the polymer backbone to piperidone was 1: 0.5-1: 2 (preferably 1: 0.5 to 1: 1.2).
The ratio of the amount of substance of the polymer main chain to the strong oxidizing acid is 1: 1-1: 5 (preferably 1: 1.2 to 1: 1.5).
In step B, the volume ratio of the mass of the powder to the organic solvent B is 1 g: 30 mL-1 g: 200mL (preferably 1 g: 50 mL-1 g: 80 mL);
in the step a, the low-temperature reaction temperature is 0-15 ℃ (preferably 3-6 ℃), and the reaction time is 1-12 h (preferably 2-4 h); the drying condition is freeze drying.
In the step b, the drying temperature is 30-80 ℃ (preferably 40-60 ℃), and the time is 6-24h (preferably 12-18 h).
The process of the step c is as follows: dissolving polymer powder in an organic solvent C, wherein the mass fraction of the polymer powder is 25-60% (optimally 45%), refluxing for 3-6 h at 20-40 ℃, completely dissolving until the polymer powder is clear to obtain a chemically crosslinked polymer solution, pouring the chemically crosslinked polymer solution into a glass tank, and volatilizing the organic solvent C at 20-50 ℃ for 4-12h to obtain a transparent polymer film;
the dissolving mode is one or more than two of mechanical stirring, magnetic stirring, ultrasonic and cell crushing, preferably one or two of ultrasonic and cell crushing;
the alkaline anion exchange membrane with the chemical crosslinking structure prepared by the method has the following structural formula:
wherein R1, R2 and R3 can be methyl or H.
Preferably, the SEBS in the present invention is a linear triblock copolymer having polystyrene as a terminal block and an ethylene-butene copolymer obtained by hydrogenating polybutadiene as an intermediate elastic block, and has high chemical stability, good heat resistance, and a high benzene ring content, because it does not contain an unsaturated double bond. The N-piperidine structure can effectively reduce OH in alkaline environment due to steric hindrance-The attack on functional group sites reduces the influence of Hofmann elimination reaction. Therefore, the SEBS main chain is directly subjected to chemical crosslinking by using piperidone, so that the mechanical strength and the chemical stability of the anion exchange membrane are improved, an ion transportation channel is provided, and two effects are realized by one-step reaction.
Preferably, the method specifically comprises the following steps:
1) weighing 4-8 g of SEBS, dissolving in 100-200 mL of organic solvent A, mechanically stirring, adding 3-4 mL of N-methyl-4-piperidone after completely dissolving, and changing the solution into clear light yellow.
2) Starting an ice-water bath reaction: and (3) when the temperature is reduced to about 3-9 ℃, slowly adding 15-25 mL of TFSA and 1-5 mL of TFA, reacting for 45-270 min, and stopping the reaction to obtain light brown liquid.
3) And pouring the light brown liquid in the last step into deionized water for quenching reaction, mechanically stirring at a high speed, crushing the viscous polymer, washing for 4-8 times by using the deionized water until the viscous polymer is neutral, and drying in vacuum to obtain the polymer solid after chemical crosslinking.
4) Weighing 300-3000 mg of the polymer solid after chemical crosslinking in the previous step, dissolving the polymer solid in 100-200 mL of organic solvent B, putting the reaction system in a dark environment after the polymer solid is completely dissolved, and adding 270-2700 mg of K2CO3And 0.15-1 mL of methyl iodide, and reacting at room temperature for 12-36 h.
5) The liquid in the flask in the previous step was poured into methanol/ethyl acetate (volume ratio 1: 1-1: 2, optimally 1: 1.5), adding deionized water for washing for 4-8 times to obtain a functionalized polymer, and drying in vacuum to obtain a functionalized polymer solid.
6) Weighing 100-600 mg of the polymer solid after the functionalization in the previous step, dissolving the polymer solid in an organic solvent C, stirring by magnetic force, performing ultrasonic treatment until the solution is clarified, pouring the solution onto a culture dish/glass plate, and slowly evaporating the solvent at 20-50 ℃ to obtain the anion exchange membrane.
7) And standing the anion exchange membrane in an anion solution, and finishing the ion exchange at room temperature for 12-48 hours. The chemical crosslinking and the functionalization on the benzene ring of the polymer are quantitatively characterized by using AVANCE III HD 600MHz, and the resonance frequency is 600 MHz. During experiment, a small amount of sample to be tested is dissolved in deuterated chloroform, and the sample is obtained on a nuclear magnetic resonance apparatus1The H NMR spectrum was obtained using Tetramethylsilane (TMS) as an internal standard, and the results are shown in FIG. 2 and the results of calculating the Ion Exchange Capacity (IEC) are shown in Table 1.
8) The prepared alkaline anion-exchange membrane is arranged in a four-terminal probe conductivity test mould and is tested by using an alternating current impedance method, and the frequency is 100000Hz to 10 Hz. The resistance was obtained from the ac impedance plot, and the conductivity at different temperatures was calculated from the reference electrode spacing/(polymer cross-sectional area resistance) — conductivity, and the results are shown in fig. 10.
Example 1
1) 4g of SEBS are weighed out and dissolved in 150mL of dichloromethane, the mixture is stirred mechanically, 3mL of N-methyl-4-piperidone are added after the SEBS is completely dissolved, and the solution becomes clear and light yellow.
2) And starting ice-water bath reaction, slowly adding 15mL of TFSA (trifluoromethanesulfonic acid) and 3mL of TFA (trifluoroacetic acid) when the temperature is reduced to about 3-9 ℃, reacting for 45min, and stopping the reaction when the liquid becomes viscous.
3) And pouring the light brown liquid in the last step into deionized water for quenching reaction, mechanically stirring at a high speed, crushing the viscous polymer, washing for 4-8 times by using the deionized water until the viscous polymer is neutral, and drying in vacuum to obtain the polymer solid after chemical crosslinking.
4) Weighing 300mg of the polymer solid in the previous step, dissolving the polymer solid in 100mL of trichloromethane, keeping the reaction system in a dark environment after the polymer solid is completely dissolved, and adding 270mg of K2CO30.18mL of methyl iodide was reacted at room temperature for 24 hours.
5) And pouring the liquid in the flask in the last step into methanol/ethyl acetate for extraction, adding deionized water for washing for 4-8 times to obtain a functionalized polymer, and performing vacuum drying to obtain a functionalized polymer solid.
6) Weighing 400mg of the polymer solid in the previous step, dissolving the polymer solid in chloroform, magnetically stirring, performing ultrasonic treatment until the solution is clarified, pouring the solution onto a culture dish/glass plate, and slowly evaporating the solvent at 20-50 ℃ to obtain the anion exchange membrane.
7) And standing the anion exchange membrane in an anion solution, and finishing ion exchange at room temperature for 24 hours to obtain the anion membrane.
FIG. 1 is a schematic representation of the basic anion exchange membrane prepared in example 1, showing that the anion exchange membrane is transparent and dense.
The nuclear magnetic results and the infrared spectrum of the basic anion-exchange membrane prepared in example 1 are used for characterizing the structure as shown in fig. 2, and a Nicolet iS50 Fourier transform infrared spectrometer iS used for characterizing the functional groups on the polymer, and ATR-IR iS used as the mode. A small amount of sample was taken for the test at the time of the experiment, and the results are shown in FIG. 3. As can be seen from fig. 2 and 3, at 2920cm-1The absorption peak of methylene contained in the structure appears due to C-H stretching vibration and bending vibration which are abundant in the all-carbon skeleton of SEBS and piperidine functional groups. At 1460cm-1The absorption peak of (A) can be classified. Characteristic absorption peaks due to the benzene ring in SEBS. At 1030cm-1The characteristic peak of C-N bond on N-piperidine appears. Furthermore, when the reaction time was 170min, the reaction time was 1227cm due to excessive crosslinking-1The C-N characteristic peak due to the shift appears. In conclusion, the molecular structures of the polymer, the organic matter and the membrane in the synthesis process are identified by two test analysis means of nuclear magnetism and infrared, and the anionic membrane is successfully synthesized.
The anion exchange membrane is subjected to tensile test by using a universal tensile machine, and the result is shown in fig. 4, and it can be seen that when the tensile deformation is 190%, the membrane is broken, and the mechanical strength and elasticity of the membrane are proved to be good.
Thermal stability analysis was performed using METTLER TOLEDO TGA/DSC3+, and the results are shown in FIG. 5, where the temperature was set at room temperature to 800 ℃ under a nitrogen atmosphere (including 800 ℃ C., and the rate of temperature increase was 10 ℃/min). It can be seen that the anionic membrane is structurally decomposed at about 500 ℃, which proves its good thermal stability.
And (3) performing morphology observation by adopting a GEMINI 500 scanning electron microscope, placing the anion exchange membrane in liquid nitrogen for 4-24 hours, quenching to obtain a cross section, observing the surface and the cross section by using multiples of 100, 250, 5k and 15k respectively, and observing the result as shown in figures 6-9, wherein the surface is smooth.
Weighing the dried alkaline anion-exchange membrane, measuring the mass and the diameter, soaking the membrane in deionized water for 12-24 h, absorbing surface moisture by using filter paper, measuring the mass and the diameter again, and obtaining the difference value/dry membrane after drying and water absorption, namely swelling rate and water absorption, wherein the results are shown in table 1.
TABLE 1 ion exchange Capacity, swelling Rate, Water absorption of anion exchange membranes
As can be seen from Table 1, the ion exchange capacity of the polymer membrane was 2.04mmol g-1The water absorption rate was 18.42% and the swelling rate was 7.95%, demonstrating that the anionic membrane performance was good.
The prepared alkaline anion-exchange membrane is arranged in a four-terminal probe conductivity test mould and is tested by using an alternating current impedance method, and the frequency is 100000Hz to 10 Hz. The resistance was obtained from the ac impedance plot, and the conductivities were calculated at temperatures from 25 ℃ to 80 ℃ from the reference electrode spacing/(polymer cross-sectional area resistance) — conductivity, respectively, and the results are shown in fig. 10. It can be seen that the conductivity of the alkaline anion exchange membrane at 25 ℃ is 41.78mS/cm, the conductivity at 80 ℃ is 167.54mS/cm, and after soaking in 5M NaOH strong alkaline solution for 200h, the conductivity is not obviously reduced, which indicates that the alkaline resistance of the structure is strong.
Example 2
1) 4g of SEBS are weighed out and dissolved in 150mL of dichloromethane, the mixture is stirred mechanically, 3mL of N-methyl-4-piperidone are added after the SEBS is completely dissolved, and the solution becomes clear and light yellow.
2) Starting ice-water bath reaction, slowly adding 15mL of TFSA and 3mL of TFA when the temperature is reduced to about 3-9 ℃, reacting for 65min, and stopping the reaction when the liquid becomes viscous.
3) And pouring the light brown liquid in the last step into deionized water for quenching reaction, mechanically stirring at a high speed, crushing the viscous polymer, washing for 4-8 times by using the deionized water until the viscous polymer is neutral, and drying in vacuum to obtain the polymer solid after chemical crosslinking.
4) Weighing 300mg of the polymer solid in the previous step, dissolving the polymer solid in 200mL of trichloromethane, keeping the reaction system in a dark environment after the polymer solid is completely dissolved, and adding 270mg of K2CO30.18mL of methyl iodide was reacted at room temperature for 24 hours.
5) And pouring the liquid in the flask in the last step into methanol/ethyl acetate for extraction, adding deionized water for washing for 4-8 times to obtain a functionalized polymer, and performing vacuum drying to obtain a functionalized polymer solid.
6) Weighing 400mg of the polymer solid in the previous step, dissolving the polymer solid in chloroform, magnetically stirring, performing ultrasonic treatment until the solution is clarified, pouring the solution onto a culture dish/glass plate, and slowly evaporating the solvent at 20-50 ℃ to obtain the anion exchange membrane.
7) The anion exchange membrane was left standing in the anion solution at room temperature for 24 hours to complete the ion exchange.
The nuclear magnetic results and the infrared spectrum of the basic anion-exchange membrane prepared in example 2 are shown in fig. 2 and fig. 3 for the structural characterization. Chemical shifts of benzene rings and structures of functional groups due to chemical crosslinking appear at chemical shifts 6.5-8.0 in FIG. 21H. Illustrating the success of the synthesis of the product and the chemical shifts of the different structures, at 2920cm in FIG. 3-1The absorption peak of methylene contained in the structure is shown, and the C-H stretching vibration is abundant in the all-carbon skeleton of the SEBS and the piperidine functional groupAnd bending vibration. At 1460cm-1Can be attributed to the characteristic absorption peak caused by the benzene ring in SEBS. At 1030cm-1The characteristic peak of C-N bond on N-piperidine appears. Furthermore, when the reaction time was 170min, the reaction time was 1227cm due to excessive crosslinking-1The appearance of characteristic peaks of C-N due to shifts indicates that the functional groups of the synthesized product conform to the designed structure.
Example 3
1) 4g of SEBS are weighed out and dissolved in 150mL of dichloromethane, the mixture is stirred mechanically, 3mL of N-methyl-4-piperidone are added after the SEBS is completely dissolved, and the solution becomes clear and light yellow.
2) Starting ice-water bath reaction, slowly adding 15mL of TFSA and 3mL of TFA when the temperature is reduced to about 3-9 ℃, reacting for 110min, and stopping the reaction when the liquid becomes viscous.
3) And pouring the light brown liquid in the last step into deionized water for quenching reaction, mechanically stirring at a high speed, crushing the viscous polymer, washing for 4-8 times by using the deionized water until the viscous polymer is neutral, and drying in vacuum to obtain the polymer solid after chemical crosslinking.
4) Weighing 300mg of the polymer solid in the previous step, dissolving the polymer solid in 150mL of trichloromethane, keeping the reaction system in a dark environment after the polymer solid is completely dissolved, and adding 270mg of K2CO30.18mL of methyl iodide was reacted at room temperature for 24 hours.
5) And pouring the liquid in the flask in the last step into methanol/ethyl acetate for extraction, adding deionized water for washing for 4-8 times to obtain a functionalized polymer, and performing vacuum drying to obtain a functionalized polymer solid.
6) Weighing 400mg of the polymer solid in the previous step, dissolving the polymer solid in chloroform, magnetically stirring, performing ultrasonic treatment until the solution is clarified, pouring the solution onto a culture dish/glass plate, and slowly evaporating the solvent at 20-50 ℃ to obtain the anion exchange membrane.
7) The anion exchange membrane was left standing in the anion solution at room temperature for 24 hours to complete the ion exchange.
The nuclear magnetic results and the infrared spectrum of the basic anion-exchange membrane prepared in example 3 are shown in fig. 2 and fig. 3 for the structural characterization. Appears at chemical shifts of 6.5-8.0 in FIG. 2Chemical shifts of the structure of the benzene ring and the functional groups arising from chemical crosslinking1H. Illustrating the success of the synthesis of the product and the chemical shifts of the different structures, at 2920cm in FIG. 3-1The absorption peak of methylene contained in the structure appears due to C-H stretching vibration and bending vibration which are abundant in the all-carbon skeleton of SEBS and piperidine functional groups. At 1460cm-1Can be attributed to the characteristic absorption peak caused by the benzene ring in SEBS. At 1030cm-1The characteristic peak of C-N bond on N-piperidine appears. Furthermore, when the reaction time was 170min, the reaction time was 1227cm due to excessive crosslinking-1The appearance of characteristic peaks of C-N due to shifts indicates that the functional groups of the synthesized product conform to the designed structure.
Example 4
1) 4g of SEBS are weighed out and dissolved in 150mL of dichloromethane, the mixture is stirred mechanically, 3mL of N-methyl-4-piperidone are added after the SEBS is completely dissolved, and the solution becomes clear and light yellow.
2) Starting ice-water bath reaction, slowly adding 15mL of TFSA and 3mL of TFA when the temperature is reduced to about 3-9 ℃, reacting for 170min, and stopping the reaction when the liquid becomes viscous.
3) And pouring the light brown liquid in the last step into deionized water for quenching reaction, mechanically stirring at a high speed, crushing the viscous polymer, washing for 4-8 times by using the deionized water until the viscous polymer is neutral, and drying in vacuum to obtain the polymer solid after chemical crosslinking.
4) Weighing 300mg of the polymer solid in the previous step, dissolving the polymer solid in 120mL of trichloromethane, keeping a reaction system in a dark environment after the polymer solid is completely dissolved, and adding 270mg of K2CO30.18mL of methyl iodide was reacted at room temperature for 24 hours.
5) And pouring the liquid in the flask in the last step into methanol/ethyl acetate for extraction, adding deionized water for washing for 4-8 times to obtain a functionalized polymer, and performing vacuum drying to obtain a functionalized polymer solid.
6) Weighing 400mg of the polymer solid in the last step, dissolving the polymer solid in chloroform, magnetically stirring, performing ultrasonic treatment until the solution is clarified, pouring the solution onto a culture dish/glass plate, and slowly evaporating the solvent at 20-50 ℃ to obtain the anion exchange membrane, wherein the anion exchange membrane is shown in figure 1.
7) The anion exchange membrane was left standing in the anion solution at room temperature for 24 hours to complete the ion exchange.
The nuclear magnetic results and the infrared spectrum of the basic anion-exchange membrane prepared in example 4 are shown in fig. 2 and fig. 3 for the structural characterization. Chemical shifts of benzene rings and structures of functional groups due to chemical crosslinking appear at chemical shifts 6.5-8.0 in FIG. 21H. Illustrating the success of the synthesis of the product and the chemical shifts of the different structures, at 2920cm in FIG. 3-1The absorption peak of methylene contained in the structure appears due to C-H stretching vibration and bending vibration which are abundant in the all-carbon skeleton of SEBS and piperidine functional groups. At 1460cm-1Can be attributed to the characteristic absorption peak caused by the benzene ring in SEBS. At 1030cm-1The characteristic peak of C-N bond on N-piperidine appears. Furthermore, when the reaction time was 170min, the reaction time was 1227cm due to excessive crosslinking-1The appearance of characteristic peaks of C-N due to shifts indicates that the functional groups of the synthesized product conform to the designed structure.
Example 5
A, carrying out chemical crosslinking reaction on 4g of a polymer main chain in a strong oxidizing acid, piperidone and an organic solvent A at 0 ℃ for 1h, quenching by using deionized water with the resistivity of 18M omega cm after the reaction is finished, washing, and freeze-drying to obtain powder; wherein the polymer main chain is polystyrene.
The strong oxidizing acid is trifluoroacetic acid;
the piperidone is N-methyl-4-piperidone;
the organic solvent A is chloroform;
the volume ratio of the mass of the polymer main chain to the organic solvent A is 1 g: 30 mL;
the molar ratio of the polymer backbone to piperidone was 1: 1.
the ratio of the amount of substance of the polymer main chain to the strong oxidizing acid is 1: 1.
b, adding the powder obtained in the step a into an organic solvent B, adding methyl iodide, carrying out dark reaction at room temperature for 18 hours, extracting after the reaction is finished, washing, and drying at 30 ℃ for 24 hours to obtain polymer powder; wherein the organic solvent B is chloroform;
the ratio of the mass of the powder to the volume of the organic solvent B was 1 g: 30 mL;
step c, the process of step c is: dissolving polymer powder in an organic solvent C, wherein the mass fraction of the polymer powder is 25%, refluxing for 6h at 20 ℃, completely dissolving the polymer powder to be clear under stirring to obtain a chemically crosslinked polymer solution, pouring the chemically crosslinked polymer solution into a glass tank, and volatilizing the organic solvent C at 50 ℃ for 4h to obtain a transparent polymer film;
wherein the organic solvent C is a mixture of trichloromethane and tetrahydrofuran.
Example 6
A, carrying out chemical crosslinking reaction on 4g of a polymer main chain in a strong oxidizing acid, piperidone and an organic solvent A at 15 ℃ for 12h, quenching by using deionized water with the resistivity of 18M omega cm after the reaction is finished, washing, and freeze-drying to obtain powder; wherein, the polymer main chain is a mixture of SEBS and polycarbazole. The strong oxidizing acid is trifluoromethanesulfonic acid;
the organic solvent A is 1,1,2, 2-tetrachloroethane;
the piperidone is 2,2,6, 6-tetramethyl-4-piperidone;
the volume ratio of the mass of the polymer main chain to the organic solvent A is 1 g: 200 mL;
the molar ratio of the polymer backbone to piperidone was 1: 2.
the ratio of the amount of substance of the polymer main chain to the strong oxidizing acid is 1: 5.
b, adding the powder obtained in the step a into an organic solvent B, adding methyl iodide, carrying out dark reaction at room temperature for 36 hours, extracting after the reaction is finished, washing, and drying at 40 ℃ for 20 hours to obtain polymer powder; wherein the organic solvent B is 1,1,2, 2-tetrachloroethane;
the ratio of the mass of the powder to the volume of the organic solvent B was 1 g: 200 mL;
step c, the process of step c is: dissolving polymer powder in an organic solvent C, wherein the mass fraction of the polymer powder is 50%, refluxing for 3h at 40 ℃, completely dissolving the polymer powder under magnetic force ultrasound until the polymer powder is clear to obtain a chemically crosslinked polymer solution, pouring the chemically crosslinked polymer solution into a glass tank, and volatilizing the organic solvent C at 20 ℃ for 12h to obtain a transparent polymer film;
wherein, the organic solvent C is a mixture of dichloromethane and xylene.
Example 7
A, carrying out chemical crosslinking reaction on 4g of a polymer main chain in a strong oxidizing acid, piperidone and an organic solvent A at 3 ℃ for 2h, quenching by using deionized water with the resistivity of 18M omega cm after the reaction is finished, washing, and freeze-drying to obtain powder; wherein the polymer main chain is polybenzimidazole.
The strong oxidizing acid is trifluoroacetic acid;
the piperidone is 1,2, 6-trimethyl-4-piperidone;
the organic solvent A is N, N-dimethylformamide;
the volume ratio of the mass of the polymer main chain to the organic solvent A is 1 g: 50 mL;
the molar ratio of the polymer backbone to piperidone was 1: 0.5.
the ratio of the amount of substance of the polymer main chain to the strong oxidizing acid is 1: 1.2.
b, adding the powder obtained in the step a into an organic solvent B, adding methyl iodide, carrying out dark reaction at room temperature for 20 hours, extracting after the reaction is finished, washing, and drying at 80 ℃ for 6 hours to obtain polymer powder; wherein the organic solvent B is dioxane;
the ratio of the mass of the powder to the volume of the organic solvent B was 1 g: 50 mL;
step c, the process of step c is: dissolving polymer powder in an organic solvent C, wherein the mass fraction of the polymer powder is 60%, refluxing for 4h at 30 ℃, completely dissolving the polymer powder to be clear under ultrasonic waves to obtain a chemically crosslinked polymer solution, pouring the chemically crosslinked polymer solution into a glass tank, and volatilizing the organic solvent C at 30 ℃ for 10h to obtain a transparent polymer film;
wherein the organic solvent C is a mixture of 1,1,2, 2-tetrachloroethane and dimethylacetamide.
Example 8
A, carrying out chemical crosslinking reaction on 4g of a polymer main chain in a strong oxidizing acid, piperidone and an organic solvent A at 6 ℃ for 3h, quenching by using deionized water with the resistivity of 18M omega cm after the reaction is finished, washing, and freeze-drying to obtain powder; wherein, the main chain of the polymer is polyether sulfone benzene ring.
The strong oxidizing acid is trifluoromethanesulfonic acid;
the piperidone is N-methyl-4-piperidone;
the organic solvent A is N, N-dimethylacetamide;
the volume ratio of the mass of the polymer main chain to the organic solvent A is 1 g: 80 mL;
the molar ratio of the polymer backbone to piperidone was 1: 1.2.
the ratio of the amount of substance of the polymer main chain to the strong oxidizing acid is 1: 1.5.
b, adding the powder obtained in the step a into an organic solvent B, adding methyl iodide, carrying out dark reaction at room temperature for 25 hours, extracting after the reaction is finished, washing, and drying at 60 ℃ for 10 hours to obtain polymer powder; wherein the organic solvent B is toluene;
the ratio of the mass of the powder to the volume of the organic solvent B was 1 g: 80 mL;
step c, the process of step c is: dissolving polymer powder in an organic solvent C, wherein the mass fraction of the polymer powder is 45%, refluxing for 5h at 30 ℃, completely dissolving the polymer powder until the polymer powder is clear after cell crushing to obtain a chemically crosslinked polymer solution, pouring the chemically crosslinked polymer solution into a glass tank, and volatilizing the organic solvent for 7h at 40 ℃ to obtain a transparent polymer film;
wherein the organic solvent C is a mixture of dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide.
Example 9
A, carrying out chemical crosslinking reaction on 4g of a polymer main chain in a strong oxidizing acid, piperidone and an organic solvent A at 5 ℃ for 4h, quenching by using deionized water with the resistivity of 18M omega cm after the reaction is finished, washing, and freeze-drying to obtain powder; wherein the main chain of the polymer is a mixture of polyaniline and polyether sulfone benzene rings.
The strong oxidizing acid is a mixture of trifluoroacetic acid and trifluoromethanesulfonic acid;
the piperidone is N-methyl-4-piperidone;
the organic solvent A is dimethyl sulfoxide;
the volume ratio of the mass of the polymer main chain to the organic solvent A is 1 g: 60/mL;
the molar ratio of the polymer backbone to piperidone was 1: 0.8.
the ratio of the amount of substance of the polymer main chain to the strong oxidizing acid is 1: 1.3.
b, adding the powder obtained in the step a into an organic solvent B, adding methyl iodide, carrying out dark reaction at room temperature for 30 hours, extracting after the reaction is finished, washing, and drying at 50 ℃ for 15 hours to obtain polymer powder; wherein the organic solvent B is N, N-dimethylacetamide;
the ratio of the mass of the powder to the volume of the organic solvent B was 1 g: 60 mL;
step c, the process of step c is: dissolving polymer powder in an organic solvent C, wherein the mass fraction of the polymer powder is 40%, refluxing for 5h at 25 ℃, completely dissolving the polymer powder to be clear under stirring to obtain a chemically crosslinked polymer solution, pouring the chemically crosslinked polymer solution into a glass tank, and volatilizing the organic solvent C at 20 ℃ for 10h to obtain a transparent polymer film;
wherein the organic solvent C is dimethyl sulfoxide.
Example 10
A, carrying out chemical crosslinking reaction on 4g of a polymer main chain in a strong oxidizing acid, piperidone and an organic solvent A at 4 ℃ for 5 hours, quenching by using deionized water with the resistivity of 18M omega cm after the reaction is finished, washing, and freeze-drying to obtain powder; wherein the main chain of the polymer is polyaniline.
The strong oxidizing acid is trifluoroacetic acid;
the piperidone is N-methyl-4-piperidone;
the organic solvent A is dichloromethane;
the volume ratio of the mass of the polymer main chain to the organic solvent A is 1 g: 70 mL;
the molar ratio of the polymer backbone to piperidone was 1: 1.
the ratio of the amount of substance of the polymer main chain to the strong oxidizing acid is 1: 1.4.
b, adding the powder obtained in the step a into an organic solvent B, adding methyl iodide, carrying out dark reaction at room temperature for 32 hours, extracting after the reaction is finished, washing, and drying at 55 ℃ for 18 hours to obtain polymer powder; wherein the organic solvent B is dimethyl sulfoxide;
the ratio of the mass of the powder to the volume of the organic solvent B was 1 g: 70 mL;
step c, the process of step c is: dissolving polymer powder in an organic solvent C, wherein the mass fraction of the polymer powder is 30%, refluxing for 4h at 30 ℃, completely dissolving the polymer powder to be clear under stirring to obtain a chemically crosslinked polymer solution, pouring the chemically crosslinked polymer solution into a glass tank, and volatilizing the organic solvent C at 50 ℃ for 5h to obtain a transparent polymer film;
wherein the organic solvent C is a mixture of xylene and toluene.
When the anion membrane is applied to an alkaline fuel cell, the specific process is as follows: the anion membrane is hermetically assembled in the membrane module and is installed in the fuel cell. When the alkaline fuel cell works, water is transported to the membrane component through the flow channel, the membrane component is wetted, and the directional mass transfer is started. As a solid electrolyte layer, under the action of an electric field, anions pass through an ion channel of the polymer membrane to provide ion transmission necessary for the operation of the battery.
Claims (10)
1. A preparation method of a basic anion-exchange membrane based on chemical crosslinking is characterized by comprising the following steps:
a, chemically crosslinking a polymer main chain in a strong oxidizing acid, piperidone and an organic solvent A at a low temperature, quenching after the reaction is finished, washing and drying to obtain solid powder;
b, adding the powder obtained in the step a into an organic solvent B, adding methyl iodide, carrying out dark reaction at room temperature for 18-36 hours, then extracting, washing and drying to obtain polymer powder;
and C, dissolving the polymer powder in an organic solvent C, casting to form a film to obtain a polymer film, washing the polymer film by deionized water, and then carrying out anion exchange to obtain the alkaline anion exchange film based on chemical crosslinking.
2. The method for preparing the basic anion-exchange membrane based on chemical crosslinking according to claim 1, wherein the polymer main chain in the step a is one or two of polystyrene, SEBS, polycarbazole, polysulfone, polybenzimidazole, polyaniline and polyether sulfone benzene rings.
3. The method of claim 1, wherein the piperidone is N-methyl-4-piperidone, 2,6, 6-tetramethyl-4-piperidone or 1,2, 6-trimethyl-4-piperidone; the strong oxidizing acid is one or two of trifluoroacetic acid and trifluoromethanesulfonic acid.
4. The method for preparing the alkaline anion-exchange membrane based on chemical crosslinking according to claim 1, wherein the organic solvent A is one of dichloromethane, chloroform, 1,2, 2-tetrachloroethane, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide;
the organic solvent B is one of dichloromethane, chloroform, 1,2, 2-tetrachloroethane, dioxane, toluene, xylene, N-dimethylacetamide and dimethyl sulfoxide;
the organic solvent C is one or more of tetrahydrofuran, xylene, toluene, chloroform, 1,2, 2-tetrachloroethane, dimethylacetamide, dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide.
5. The method for preparing the alkaline anion-exchange membrane based on chemical crosslinking according to claim 1, wherein the volume ratio of the mass of the polymer main chain to the volume of the organic solvent A is 1 g: (30-200) mL.
6. The method for preparing a basic anion-exchange membrane based on chemical crosslinking according to claim 1, wherein the ratio of the amount of the polymer main chain to the amount of the substance of strong oxidizing acid is 1: 1-1: 5.
7. the method for preparing the basic anion-exchange membrane based on chemical crosslinking according to claim 1, wherein in the step B, the ratio of the mass of the solid powder to the volume of the organic solvent B is 1 g: (30-200) mL.
8. The preparation method of the alkaline anion-exchange membrane based on chemical crosslinking according to claim 1, wherein the low temperature reaction temperature in step a is 0-15 ℃ and the reaction time is 1-12 h.
9. The method for preparing the alkaline anion-exchange membrane based on chemical crosslinking according to claim 1, wherein the specific process of the step c is as follows: dissolving polymer powder in an organic solvent C, wherein the mass fraction of the polymer powder is 25-60%, refluxing for 3-6 h at 20-40 ℃, dissolving until the polymer powder is clear to obtain a chemically crosslinked polymer solution, pouring the polymer solution into a glass tank, and volatilizing the organic solvent C for 4-12h at 20-50 ℃ to obtain the transparent polymer film.
10. A basic anion-exchange membrane of a chemically cross-linked structure prepared by the preparation method according to any one of claims 1 to 9.
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| CN114395112A (en) * | 2022-01-12 | 2022-04-26 | 北京化工大学 | Hydrophobic block-containing polycarbazole anion exchange membrane and preparation method thereof |
| CN117343290A (en) * | 2023-12-04 | 2024-01-05 | 宿迁时代储能科技有限公司 | Alkali-resistant and oxidation-resistant anion exchange resin and application thereof |
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| CN110690486A (en) * | 2019-11-07 | 2020-01-14 | 大连理工大学 | Preparation method of crosslinking type alkaline anionic membrane based on flexible long-side-chain multi-cation structure |
| US20210009726A1 (en) * | 2017-09-28 | 2021-01-14 | University Of Delaware | Poly(aryl piperidinium) polymers including those with stable cationic pendant groups for use as anion exchange membranes and ionomers |
| CN112608503A (en) * | 2020-11-23 | 2021-04-06 | 大连理工大学 | Piperidine anion exchange membrane for alkaline electrolytic cell and preparation method thereof |
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| US20210009726A1 (en) * | 2017-09-28 | 2021-01-14 | University Of Delaware | Poly(aryl piperidinium) polymers including those with stable cationic pendant groups for use as anion exchange membranes and ionomers |
| CN110690486A (en) * | 2019-11-07 | 2020-01-14 | 大连理工大学 | Preparation method of crosslinking type alkaline anionic membrane based on flexible long-side-chain multi-cation structure |
| CN112608503A (en) * | 2020-11-23 | 2021-04-06 | 大连理工大学 | Piperidine anion exchange membrane for alkaline electrolytic cell and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114395112A (en) * | 2022-01-12 | 2022-04-26 | 北京化工大学 | Hydrophobic block-containing polycarbazole anion exchange membrane and preparation method thereof |
| CN114395112B (en) * | 2022-01-12 | 2023-01-24 | 北京化工大学 | Hydrophobic block-containing polycarbazole anion exchange membrane and preparation method thereof |
| CN117343290A (en) * | 2023-12-04 | 2024-01-05 | 宿迁时代储能科技有限公司 | Alkali-resistant and oxidation-resistant anion exchange resin and application thereof |
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