CN111430763A - Ether oxygen group para quaternary ammonium structure anion exchange membrane without electron-withdrawing group and preparation method thereof - Google Patents
Ether oxygen group para quaternary ammonium structure anion exchange membrane without electron-withdrawing group and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of fuel cells, and particularly relates to an electron-withdrawing group-free ether oxygen group para quaternary ammonium structure anion exchange membrane and a preparation method thereof.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to an ether oxygen group para quaternary ammonium structure anion exchange membrane without electron-withdrawing groups and a preparation method thereof.
Background
To date, renewable energy is considered to be the most effective approach to environmental problems. Among the many renewable energy technologies, fuel cells are receiving attention because of their high efficiency and environmental friendliness. Among them, the anion exchange membrane fuel cell works under alkaline condition, can effectively enhance the electrode reaction kinetics, so that it can use non-noble metal catalyst and is widely concerned by academics. However, as a core component of an anion exchange membrane fuel cell, the anion exchange membrane has serious problems of rapid conductivity reduction, poor alkaline stability and the like under high-temperature (more than 80 ℃) and strong alkaline operating conditions.
The aromatic polyarylether polymer has the advantages of good mechanical and thermal stability, easy modification and the like, and is widely used for preparing anion exchange membranes. However, it has been found that under strongly alkaline conditions, the backbone is exposed to OH groups-The inventors have prepared a novel polyphenylene backbone structure by preparing an aromatic polymer without ether bonds as the backbone of an anion exchange membrane, thereby avoiding occurrence of cleavage of backbone ethers, such as in Macromolecules,2009,21,8316, a series of fluorenyl conjugated polymers are prepared by a Diels-Alder polymerization reaction, Macro L ett,2015,4,453, a series of fluorenyl conjugated polymers are synthesized by Suzuki coupling reaction, j. mater. chem.a,2015,3,21779 a perfluoroalkylene-phenylene backbone structure without heteroatom linkages is prepared by a nickel-catalyzed coupling reaction, ACS these anion exchange membranes show excellent stability, however, the above synthesis methods use a metal catalyst and the subsequent synthesis of a polymer using a simple and expensive anion exchange membrane, and thus the synthesis of a high-alkaline polymer is relatively complicated.
Disclosure of Invention
Firstly, converting electron-withdrawing linking group carbonyl in a main chain of polyaryletherketone into electron-donating group amino through L euckart reaction, eliminating the induction promotion of electron-withdrawing groups on ether cracking, and then carrying out one-step quaternization on the amino through a Menxiu gold reaction to prepare the anion exchange membrane with the ether oxygen para-quaternary ammonium structure.
The technical scheme of the invention is as follows:
an ether oxygen group para quaternary ammonium structure anion exchange membrane without electron-withdrawing groups has the following molecular structure:
the molecular weight of the material is 20-100kg mol-1. wherein-Ar-has the structure:
r1 is
Or ether-oxygen bonds are added into the carbon chain, and the total length is 0-12 atoms.
R2 is an introduced cationic functional group and may include:
an ether oxygen group para quaternary ammonium structure anion exchange membrane without electron-withdrawing groups and a preparation method thereof, the specific reaction formula is as follows:
the preparation method comprises the following specific steps:
(1) preparation of polyaryletherketone polymer material:
under the protection of nitrogen, dissolving 4, 4' -difluorobenzophenone, an aromatic dihydroxy monomer (HO-Ar-OH) and potassium carbonate in a solvent A, adding toluene, refluxing for 1-4 h at 120-170 ℃ until water and toluene are completely removed, then heating to 130-180 ℃, and reacting for 2-8 h. And pouring the reaction solution into a precipitator B, filtering, washing and drying at 80 ℃ for 12-48 h to obtain the polyaryletherketone.
The molar ratio of the aromatic dihydroxy monomer to the 4, 4' -difluorobenzophenone to the potassium carbonate is 1 (0.5-2) to 1-2.5;
the mass concentration w/v (mass of a reaction substance/volume of a solvent, the same applies below) of the aromatic dihydroxy monomer, the 4, 4' -difluorobenzophenone and the potassium carbonate in the solvent A is 10-50 g/m L;
the volume ratio of the toluene to the solvent A is 3: 3-3: 5;
the solvent A is one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone;
the precipitator B is one or a mixture of deionized water, methanol and ethanol.
(2) Preparing a polyaryletheramine polymer material: dissolving polyaryletherketone, formamide and formic acid in a solvent C, and reacting for 10-40 h at 140-200 ℃. And pouring the reaction solution into a precipitator D, filtering, adding the precipitated solid product into a solvent E, dropwise adding 100ml of HCl solution while heating to 50-120 ℃, and reacting for 24-120 h. And filtering the reaction suspension, washing the reaction suspension to be neutral by using a KOH solution and deionized water, and drying the reaction suspension for 12-48 hours at the temperature of 60 ℃ to obtain the polyaryl ether amine.
The molar ratio of the polyaryletherketone to the formamide is 1: 30-1: 60;
the volume ratio of the formamide to the formic acid is 1: 1-2: 1;
the mass concentration w/v of the polyaryletherketone in the solvent C is 1-10 g/m L;
the volume ratio of the solvent C to the solvent E is 1: 3-2: 3;
the concentration of the HCl solution is 5-20%;
the concentration of the KOH solution is 10-40%;
the solvent C is one of N, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone;
the precipitator D is one or a mixture of deionized water, ethyl acetate, methanol and ethanol;
the solvent E is one of deionized water, methanol, ethanol and acetonitrile.
(3) Synthesis of halogenated aliphatic chain (cationic) ionic liquid: dissolving a dihalogen monomer containing an aliphatic chain and an ionizing reagent in a solvent F, reacting at 20-40 ℃ for 12-48 h to obtain a white suspension, and performing rotary evaporation on the filtered filtrate to obtain a mixed organic phase. And separating the mixed organic phase in a separating funnel to obtain a lower-layer product, and repeatedly washing the lower-layer product for 3-5 times by using a solvent G. And drying at 60 ℃ for 12-48 h to obtain the ionic liquid.
The dihalogen monomer of the aliphatic chain is a dibromo or dichloro monomer of a full carbon chain or an ether oxygen bond-containing carbon chain, and the total length of the carbon chain is 2-14 atoms;
the ionizing reagent is one of trimethylamine, 1-methylimidazole, 1, 2-dimethylimidazole, N-methylpiperidine, DABCO, pyridine and N-methylpiperazine;
the molar ratio of the dihalogen monomer containing the fatty chain to the ionizing reagent is 1: 2-1: 6;
the volume fraction of the dihalogen monomer containing the fatty chain and the ionizing agent in the solvent F is 40-60%;
the solvent F is one of acetone, ethyl acetate and acetonitrile;
the solvent G is one of acetone, ethyl acetate and acetonitrile.
(4) Dissolving polyaryletheramine in a solvent H, adding a quaternization reagent and a catalyst, reacting at 30-80 ℃ for 12-60H, pouring the reaction solution into a precipitator I, filtering, washing, drying at 60 ℃ for 10-30H, dissolving the product in a solvent J to prepare a casting solution, casting to form a membrane, soaking the membrane in a 1 mol/L potassium hydroxide solution for 24-48H, and soaking in deionized water to be neutral, thus obtaining the anion exchange membrane with the para-quaternary ammonium structure and without the electron-withdrawing group.
The quaternizing agent is one of ionic liquid and methyl iodide;
the catalyst is KOH, NaOH or K2CO3And NaH;
the molar ratio of the polyaryl ether amine to the quaternizing agent to the catalyst is 1 (1-6) to 0-3;
the mass concentration of the polyaryl ether amine in a solvent H is 1-15 g/m L;
the solvent H is one of N, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone;
the precipitant I is one of acetone, ethanol and ethyl acetate;
the mass concentration w/v of the casting solution is 2-8 g/m L.
The solvent J is one of N, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone.
The invention has the beneficial effects that:
(1) the main chain without the electron-withdrawing group in the membrane structure can effectively avoid the inducing and promoting effect of the electron-withdrawing linking group on ether cracking. Meanwhile, compared with the conventional ortho-quaternary ammonium group, the para-quaternary ammonium group far away from the ether oxygen group can further inhibit the acceleration effect of the cationic group on the ether cleavage.
(2) The preparation of the main chain of the polyaryletheramine does not need to use a noble metal catalyst, and the quaternization process is completed in one step, so that the method is an economic and simple synthetic route.
(3) The ether oxygen group para quaternary ammonium structure anion exchange membrane without the electron-withdrawing group has stronger alkali stability, and the main chain is not degraded after the membrane is soaked in 1M KOH solution at the temperature of 80 ℃ for 192 hours. Meanwhile, the grafted ionic liquid side chain enables the membrane to have good micro-phase separation and excellent conductivity.
Drawings
FIG. 1 shows a hydrogen nuclear magnetic spectrum diagram of an anion exchange membrane with an ether oxygen-based para-quaternary ammonium structure and without an electron-withdrawing group (1H-NMR)。
FIG. 2 shows the trend of ether bond content in the main chain of the polymer changing with time when the ether oxygen group para-quaternary ammonium structure anion exchange membrane without electron-withdrawing groups is soaked in 1MKOH solution at 80 ℃.
FIG. 3 shows the trend of the conductivity of the anion exchange membrane with the ether oxygen-based para-quaternary ammonium structure and without the electron-withdrawing group along with the temperature.
Detailed Description
The following describes in detail specific embodiments of the present invention with reference to the technical solutions, but the embodiments of the present invention are not limited thereto.
Example 1:
(1) preparation of polyaryletherketone polymer material: under the protection of nitrogen, 2.28g of bisphenol A, 2.18g of 44' -Difluorobenzophenone and 1.73g K2CO3Adding the mixture into a three-neck flask with the volume of 100m L, adding 15m L toluene and 20m L N, N-dimethylacetamide to prepare a mixed solution, gradually heating to 160 ℃, reacting for 2 hours, removing water generated in the system by using toluene azeotropy during the reaction, distilling to remove toluene, heating to 170 ℃, continuing to react for 3 hours, cooling the mixture to room temperature after the reaction is finished, adding 10m L N, N-dimethylacetamide to dissolve, slowly pouring the solution into 100m L methanol, washing the separated polymer with deionized water, and finally vacuum-drying at 80 ℃ for 24 hours to obtain the polyaryletherketone product.
(2) The preparation method of the polyaryletheramine polymer material comprises the steps of dissolving 1g of polyaryletherketone in 20m L N, N-dimethylacetamide, adding 5m L formamide, heating an oil bath to 160 ℃, dropwise adding 4.5m L formic acid into the mixture solution, continuously reacting for 20 hours, cooling to room temperature, precipitating, filtering and washing the obtained solution with ethanol, adding the filtered product into a 250m L three-neck flask filled with 50m L ethanol solution, slowly dropwise adding 100ml of 15% HCl solution, reacting for 72 hours at 80 ℃, cooling the suspension to room temperature, filtering, washing the filtered product with 30% KOH solution and deionized water to be neutral, and vacuum drying at 60 ℃ for 12 hours to obtain the polyaryletheramine product.
(3) Preparing an ether oxygen group para-quaternary ammonium structure polymer material without an electron-withdrawing group: dissolving polyaryletheramine in dimethyl sulfoxide to prepare 11 wt% solution, adding 4.5 times of molar equivalent of methyl iodide, and reacting at 40 ℃ for 48 h. Adding sodium bicarbonate powder with the molar equivalent of the polyaryl ether amine, and continuing the reaction for 24 hours at the same temperature. The reaction solution is precipitated by ethyl acetate, filtered and washed by deionized water for a plurality of times, and the product is dried for 12 hours in vacuum at 60 ℃.
Weighing 0.2g of the product, dissolving the product in 5m L dimethyl sulfoxide, centrifuging the casting solution, casting the casting solution in a glass mold, drying at 60 ℃ for 48h to obtain an anion exchange membrane, soaking the anion exchange membrane in 1 mol/L KOH solution at room temperature for 48h, and then repeatedly cleaning and soaking the anion exchange membrane in deionized water to be neutral to obtain the ether oxygen group para-quaternary ammonium structure anion exchange membrane without electron-withdrawing groups.
The anion-exchange membrane obtained in this example had the following structure:
fig. 2 shows that the ether oxygen based para-quaternary ammonium structure anion exchange membrane prepared in this example and not containing electron-withdrawing groups has excellent main chain stability, 96.1% of ether bond content in the membrane still remains after the membrane is soaked in 1 mol/L KOH solution at 80 ℃ for 192 hours, and almost no polymer main chain degradation occurs.
Example 2:
(1) preparation of polyaryletherketone polymer material: under nitrogen protection, 2.85g of bisphenol A, 2.73g of 4, 4' -difluorobenzophenone and 2.59g K2CO3Adding the mixture into a three-neck flask with the volume of 100m L, adding 20m L toluene and 25m L N, N-dimethylformamide to prepare a mixed solution, gradually heating to 140 ℃, reacting for 3 hours, removing water generated in the system by using the toluene in an azeotropic manner, distilling to remove the toluene, heating to 150 ℃, continuing to react for 5 hours, cooling the mixture to room temperature after the reaction is finished, adding 10m L N, N-dimethylformamide to dissolve, slowly pouring the solution into 100m L ethanol and water mixed solution (the volume ratio is 1:1), washing the separated polymer with deionized water, and finally vacuum-drying at 80 ℃ for 36 hours to obtain the polyaryletherketone product.
(2) The preparation method of the polyaryletheramine polymer material comprises the steps of dissolving 1.2g of polyaryletherketone in 20m L N, N-dimethylformamide, adding 5.5m L formamide, heating an oil bath to 145 ℃, dropwise adding 5.5m L formic acid into the mixture solution, continuously reacting for 30h, cooling to room temperature, precipitating, filtering and washing the obtained solution with ethanol, adding the filtered product into a 250m L three-neck flask filled with 50m L methanol solution, slowly dropwise adding 100ml of 15% HCl solution, reacting for 84h at 60 ℃, cooling the suspension to room temperature, filtering, washing the filtered product with 30% KOH solution and deionized water to be neutral, and vacuum drying for 24h at 60 ℃ to obtain the polyaryletheramine product.
(3) Synthesis of 6-Br-TMA ionic liquid, which is to dissolve 5.0m L1, 6-dibromohexane (30mmol) in a 250m L three-neck flask containing 50m L acetone solution, slowly dropwise add 21.5m L trimethylamine alcohol solution (120mmol), react at room temperature for 24 hours to obtain white suspension, filter to remove white solid, rotatably evaporate the filtrate to remove acetone to obtain a mixed organic phase, separate a lower layer product in a separating funnel, repeatedly wash the lower layer product with ethyl acetate for 3-5 times, and dry the product in vacuum at 60 ℃ for 24 hours to obtain the ionic liquid.
(4) Dissolving polyaryletheramine in dimethyl sulfoxide to prepare a 4 wt% solution, adding 6-Br-TMA ionic liquid (164.8mg) and 30.0mg NaOH in equal molar equivalents, reacting at 60 ℃ for 15h, cooling to room temperature, centrifuging the reaction solution, casting in a glass mold, drying at 60 ℃ for 48h to obtain an anion exchange membrane, soaking in 1 mol/L KOH solution at room temperature for 48h, repeatedly washing with deionized water, and soaking to neutrality to obtain the ether oxygen para-quaternary ammonium structure anion exchange membrane without the electron-withdrawing groups.
The anion-exchange membrane obtained in this example had the following structure:
as can be seen from FIG. 1, in example 2, the characteristic peak at 3.0ppm is the proton signal on the quaternary ammonium group, and the peak corresponding to hydrogen on the methylene group in the alkyl chain appears at 1.1 to 2.0ppm, indicating successful preparation. Tests show that the ether oxygen group para-quaternary ammonium structure anion-exchange membrane without the electron-withdrawing group prepared in the embodiment shows good conductivity, and the ionic conductivity at 80 ℃ is 84.5 mS/cm.
Example 3:
(1) preparation of polyaryletherketone polymer material: under nitrogen protection, 2.62g of bisphenol A, 2.51g of 4, 4' -difluorobenzophenone and 2.0g K2CO3Adding into a three-neck flask of 100m L, adding 20m L toluene and 20m L N-methyl pyrrolidone to prepare a mixed solution, gradually heating to 160 ℃, reacting for 2h, removing water generated in the system by using toluene azeotropy during the reaction, distilling to remove toluene, heating to 175 ℃, continuing to react for 2.5h, cooling the mixture to room temperature after the reaction is finished, adding 10m LDissolving N-methylpyrrolidone, slowly pouring the solution into 100m L ethanol, washing the precipitated polymer with deionized water, and finally carrying out vacuum drying at 80 ℃ for 36h to obtain the polyaryletherketone product.
(2) The preparation method of the polyaryletheramine polymer material comprises the steps of dissolving 0.8g of polyaryletherketone in 20m L N, N-dimethylacetamide, adding 5.0m L formamide, heating an oil bath to 150 ℃, dropwise adding 5.0m L formic acid into the mixture solution, continuously reacting for 24 hours, cooling to room temperature, precipitating, filtering and washing the obtained solution with ethanol, adding the filtered product into a 250m L three-neck flask filled with 60m L ethanol solution, slowly dropwise adding 100ml of 20% HCl solution, reacting for 60 hours at 80 ℃, cooling the suspension to room temperature, filtering, washing the filtered product with 30% KOH solution and deionized water to be neutral, and vacuum drying for 24 hours at 60 ℃ to obtain the polyaryletheramine product.
(3) Synthesis of 6-Br-TMA ionic liquid, which is to dissolve 5.0m L1, 6-dibromohexane (30mmol) in a 250m L three-neck flask containing 50m L acetonitrile solution, slowly dropwise add 16.1m L trimethylamine alcohol solution (90mmol), react at room temperature for 20 hours to obtain white suspension, filter to remove white solid, rotatably evaporate the filtrate to remove acetonitrile to obtain a mixed organic phase, separate a lower layer product in a separating funnel, repeatedly wash the lower layer product with acetone for 3-5 times, and dry the product in vacuum at 60 ℃ for 24 hours to obtain the ionic liquid.
(4) Dissolving polyaryletheramine in N-methylpyrrolidone to prepare a 4 wt% solution, adding 3 molar equivalents of 6-Br-TMA ionic liquid (494.5mg) and 18.5mg of NaH, reacting at 80 ℃ for 24h, cooling to room temperature, centrifuging the reaction solution, casting in a glass mold, drying at 60 ℃ for 48h to obtain an anion exchange membrane, soaking in 1 mol/L KOH solution at room temperature for 48h, repeatedly cleaning with deionized water, and soaking to neutrality to obtain the ether oxygen-based para-quaternary ammonium structure anion exchange membrane without the electron-withdrawing group.
The anion-exchange membrane obtained in this example had the following structure:
tests show that the anion exchange membrane with the ether oxygen para-quaternary ammonium structure and without the electron-withdrawing group prepared in the embodiment shows excellent conductivity, and as can be seen from figure 3, the ionic conductivity at 80 ℃ is as high as 106.2 mS/cm.
Table 1 shows the ion exchange capacity values of the ether oxygen based para-quaternary ammonium structure anion exchange membrane without electron withdrawing group, wherein the ion exchange amount of example 3 is much larger than that of example 2 and is close to the ideal value (grafting ratio 100%).
TABLE 1
a. Ideally (grafting ratio 100%) IEC value; b. the IEC values were determined by titration.
Claims (8)
1. An electron-withdrawing group-free ether oxygen-based para-quaternary ammonium structure anion exchange membrane is characterized in that the electron-withdrawing group-free ether oxygen-based para-quaternary ammonium structure anion exchange membrane has the following molecular structure:
the molecular weight of the material is 20-100kg mol-1(ii) a wherein-Ar-has the structure:
r1 is
Or ether oxygen bonds are added into the carbon chain, and the total length is 0 to 12 atoms;
r2 is an introduced cationic functional group.
2. The anion exchange membrane of ether oxygen based para-quaternary ammonium structure without electron withdrawing group of claim 1, wherein R2 is an introduced cationic functional group and can comprise:
3. the preparation method of the anion exchange membrane with the ether oxygen-based para-quaternary ammonium structure and without the electron-withdrawing group, according to the claim 1 or 2, is characterized by comprising the following specific preparation steps:
(1) preparation of polyaryletherketone polymer material:
under the protection of nitrogen, dissolving 4, 4' -difluorobenzophenone, an aromatic dihydroxy monomer (HO-Ar-OH) and potassium carbonate in a solvent A, adding toluene, refluxing for 1-4 h at 120-170 ℃ until water and toluene are completely removed, then heating to 130-180 ℃, and reacting for 2-8 h; pouring the reaction solution into a precipitator B, filtering, washing and drying at 80 ℃ for 12-48 h to obtain polyaryletherketone;
the molar ratio of the aromatic dihydroxy monomer to the 4, 4' -difluorobenzophenone to the potassium carbonate is 1 (0.5-2) to 1-2.5;
the mass concentration w/v (mass of a reaction substance/volume of a solvent, the same applies below) of the aromatic dihydroxy monomer, the 4, 4' -difluorobenzophenone and the potassium carbonate in the solvent A is 10-50 g/m L;
the volume ratio of the toluene to the solvent A is 3: 3-3: 5;
(2) preparing a polyaryletheramine polymer material: dissolving polyaryletherketone, formamide and formic acid in a solvent C, and reacting for 10-40 h at 140-200 ℃; pouring the reaction solution into a precipitator D, filtering, adding the precipitated solid product into a solvent E, dropwise adding 100ml of HCl solution while heating to 50-120 ℃, and reacting for 24-120 h; filtering the reaction suspension, washing the reaction suspension to be neutral by using a KOH solution and deionized water, and drying the reaction suspension for 12-48 hours at the temperature of 60 ℃ to obtain polyaryletheramine;
the molar ratio of the polyaryletherketone to the formamide is 1: 30-1: 60;
the volume ratio of the formamide to the formic acid is 1: 1-2: 1;
the mass concentration w/v of the polyaryletherketone in the solvent C is 1-10 g/m L;
the volume ratio of the solvent C to the solvent E is 1: 3-2: 3;
the concentration of the HCl solution is 5-20%;
the concentration of the KOH solution is 10-40%;
(3) synthesis of halogenated aliphatic chain (cationic) ionic liquid: dissolving a dihalogen monomer containing an aliphatic chain and an ionizing reagent in a solvent F, reacting at 20-40 ℃ for 12-48 h to obtain a white suspension, and performing rotary evaporation on the filtered filtrate to obtain a mixed organic phase; separating the mixed organic phase in a separating funnel to obtain a lower-layer product, and repeatedly cleaning for 3-5 times by using a solvent G; drying at 60 ℃ for 12-48 h to obtain ionic liquid;
the dihalogen monomer of the fatty chain is a dibromo or dichloro monomer of a full carbon chain or a carbon chain containing an ether oxygen bond, and the total length is 2-14 atoms;
the ionizing reagent is one of trimethylamine, 1-methylimidazole, 1, 2-dimethylimidazole, N-methylpiperidine, DABCO, pyridine and N-methylpiperazine;
the molar ratio of the dihalogen monomer containing the fatty chain to the ionizing reagent is 1: 2-1: 6;
the volume fraction of the dihalogen monomer containing the fatty chain and the ionizing agent in the solvent F is 40-60%;
(4) preparing an anion exchange membrane with a para-quaternary ammonium structure and no electron-withdrawing group, namely dissolving polyaryletheramine in a solvent H, adding a quaternizing agent and a catalyst, reacting for 12-60 hours at 30-80 ℃, then pouring the reaction solution into a precipitator I, filtering, washing, drying for 10-30 hours at 60 ℃, dissolving the product in a solvent J to prepare a casting solution, casting into a membrane, soaking the membrane in a 1 mol/L potassium hydroxide solution for 24-48 hours, and soaking in deionized water to be neutral to obtain the anion exchange membrane with the para-quaternary ammonium structure and no electron-withdrawing group;
the quaternizing agent is one of ionic liquid and methyl iodide;
the molar ratio of the polyaryl ether amine to the quaternizing agent to the catalyst is 1 (1-6) to 0-3;
the mass concentration of the polyaryl ether amine in a solvent H is 1-15 g/m L;
the mass concentration w/v of the casting solution is 2-8 g/m L.
4. The method for preparing an anion exchange membrane with an ether oxygen-based para-quaternary ammonium structure and without an electron-withdrawing group according to claim 3,
the solvent A is one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone;
the solvent C is one of N, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone;
the solvent E is one of deionized water, methanol, ethanol and acetonitrile;
the solvent F is one of acetone, ethyl acetate and acetonitrile;
the solvent G is one of acetone, ethyl acetate and acetonitrile;
the solvent H is one of N, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone;
the solvent J is one of N, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone.
5. The method for preparing an anion exchange membrane with an ether oxygen-based para-quaternary ammonium structure and without an electron-withdrawing group according to claim 3,
the precipitator B is one or a mixture of deionized water, methanol and ethanol;
the precipitator D is one or a mixture of deionized water, ethyl acetate, methanol and ethanol;
the precipitant I is one of acetone, ethanol and ethyl acetate.
6. The method for preparing an anion exchange membrane with an ether oxygen-based para-quaternary ammonium structure without an electron-withdrawing group according to claim 4,
the precipitator B is one or a mixture of deionized water, methanol and ethanol;
the precipitator D is one or a mixture of deionized water, ethyl acetate, methanol and ethanol;
the precipitant I is one of acetone, ethanol and ethyl acetate.
7. The method for preparing the anion exchange membrane with the ether oxygen-based para-quaternary ammonium structure and without the electron-withdrawing group as claimed in claim 3, wherein the catalyst is KOH, NaOH or K2CO3And NaH.
8. The method for preparing the anion exchange membrane with the ether oxygen-based para-quaternary ammonium structure without the electron-withdrawing group according to claim 4, 5 or 6, wherein the catalyst is KOH, NaOH or K2CO3And NaH.
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| CN112290068A (en) * | 2020-09-21 | 2021-01-29 | 长春工业大学 | Two quaternary ammonium side chain type anion exchange membranes for fuel cell and preparation method thereof |
| CN112521535A (en) * | 2020-12-17 | 2021-03-19 | 南京理工大学 | Anion exchange membrane with high alkali stability and preparation method thereof |
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| CN112290068A (en) * | 2020-09-21 | 2021-01-29 | 长春工业大学 | Two quaternary ammonium side chain type anion exchange membranes for fuel cell and preparation method thereof |
| CN112521535A (en) * | 2020-12-17 | 2021-03-19 | 南京理工大学 | Anion exchange membrane with high alkali stability and preparation method thereof |
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| CN113471498A (en) * | 2021-07-07 | 2021-10-01 | 长春工业大学 | Multi-quaternary ammonium side long-chain type polysulfone anion-exchange membrane and preparation method thereof |
| CN115010824A (en) * | 2022-06-20 | 2022-09-06 | 集美大学 | Preparation method of laminarin extract |
| CN115010824B (en) * | 2022-06-20 | 2023-04-25 | 集美大学 | Preparation method of laminarin extract |
| CN115627001A (en) * | 2022-11-07 | 2023-01-20 | 大连理工大学 | Ether-containing piperidine type anion exchange membrane, preparation method and application |
| CN116371478A (en) * | 2023-03-16 | 2023-07-04 | 同济大学 | Anion exchange membrane, preparation method and application thereof |
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