CN114395111A - Preparation method of anion exchange membrane imitating chemical structure of main side chain of Nafion - Google Patents
Preparation method of anion exchange membrane imitating chemical structure of main side chain of Nafion Download PDFInfo
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Abstract
The invention discloses a preparation method of a Nafion main side chain chemical structure-imitated anion exchange membrane, which comprises the steps of firstly synthesizing perfluorinated polydibiphenyl alkylidene high polymer and hydroxyl piperidine quaternary ammonium salt white solid with a long chain of a polyalkyl ether bond; NaH and tetrabutylammonium bromide (TBAB) were then dissolved in DMSO, N2Dripping dimethyl sulfoxide solution of the hydroxyl piperidine quaternary ammonium salt under the atmosphere, reacting for 2-3h at 50-60 ℃, dripping dimethyl sulfoxide solution of the perfluorinated polydibiphenyl alkylidene high molecular polymer, reacting for 6-10h at 50-60 ℃, precipitating with ethanol and washing for a plurality of times, drying to obtain target resin, dissolving with a polar solvent, pouring into a polytetrafluoroethylene mold, and drying to obtain the productAnd (3) obtaining the perfluorinated polydibiphenyl alkylidene bonded polyalkyl ether bonded side chain piperidine quaternary ammonium salt anion exchange membrane.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a preparation method of an anion exchange membrane.
Background
The polymer electrolyte membrane fuel cell has the advantages of high power density, high energy conversion efficiency, compact structure, quick start and the like, and can be widely applied to the fields of portable power supplies, emergency standby power supplies, electric automobiles and the like. OH-transport based alkaline Anion Exchange Membrane Fuel Cells (AEMFCs) as compared to H-based+Transport Proton Exchange Membrane Fuel Cells (PEMFCs) have received extensive attention and research with some advantages that further reduce the cost of the cell. However, the anion exchange membrane, which is one of the core components of the alkaline anion exchange membrane fuel cell, plays a role in transferring OH "and isolating direct contact between the anode and the cathode, and largely determines the performance and the service life of the cell. The low ionic conductivity and chemical stability of AEMFCs become key factors restricting the development of AEMFCs at present, and how to improve the alkali stability and hydroxide ion conductivity of AEMs is a problem to be solved urgently in AEMFC application.
In order to develop an anion exchange membrane with excellent performance and commercialization by comprehensively considering the research course of the anion exchange membrane in about 10 years, research directions of researchers of various countries mainly focus on the aspects of developing an OH-ion conduction group with stable alkali resistance, designing and synthesizing a polymer main chain with good alkali stability, selecting a proper connection mode to bond the OH-ion conduction group with the polymer main chain, and introducing a side chain between the polymer main chain and the OH-ion conduction group to regulate and control the hydrophilic/hydrophobic micro-phase separation form of the membrane.
In the research aspect of alkali-resistant stable polymer main chains, aromatic polymer main chains without ether bonds enter the research field of researchers, for example, ChulsungBae and Yu SeungKim topic in the U.S. also prepares poly (biphenyl alkylene) or poly (terphenyl alkylene) polymer without aryl ether bonds by Friedel-Crafts polycondensation reaction catalyzed by strong acid in 2015, and research results show that the polymer has high alkali-resistant chemical stability due to higher bond dissociation energy between phenyl-phenyl and phenyl-C, and compared with aryl ether bond polymers, the alkali-resistant stability of the polyphenylene main chain polymer is greatly improved, so that a new polymer is developed for preparing high alkali-resistant anion exchange membranes.
In the research aspect of the bonding mode of an OH-ion conducting group and a polymer main chain, a Frank subject group of the university of Stanford and a Haohong subject group of the university of the major continental engineering graft hydrophilic flexible alkyl side chains containing ether-oxygen bonds on a hydrophobic polysulfone main chain to respectively prepare quaternary ammonium type, imidazole type and spiro piperidine type anion exchange membranes.
Disclosure of Invention
At present, most of anion exchange membrane preparation processes are carried out through bonding connection of a benzene ring position and an N position of a quaternary ammonium cation group, so that the membrane alkali resistance is not high, one purpose of the invention is to select alkali-resistant stable piperidine quaternary ammonium cation and strong-hydrophobicity perfluoro polydibiphenyl alkylene polymer with a main chain without aryl ether bonds, the alkali-resistant stable piperidine quaternary ammonium cation and the strong-hydrophobicity perfluoro polydibiphenyl alkylene polymer are bonded to a C position of the main chain alkylene of the perfluoro polydibiphenyl alkylene polymer through a non-N position of piperidine, and the alkali resistance of an anion exchange membrane is greatly improved; the second purpose of the invention is to introduce a hydrophilic alkyl ether bond side chain with a certain length between a piperidine cationic group and a hydrophobic perfluoro polydibiphenyl alkylene polymer main chain, imitate a main side chain chemical structure of a Nafion membrane to construct a hydrophilic-hydrophobic microphase separation form in an anion exchange membrane, and further improve the OH-ion conductivity of the anion exchange membrane.
In order to achieve the purpose, the technical scheme is as follows:
a preparation method of an anion exchange membrane imitating a chemical structure of a main side chain of Nafion comprises the following steps:
(1) adding biphenyl, bromopentafluoroacetone, hexafluoroacetone and a solvent into a reactor, stirring, dissolving and mixing uniformly; in N2Adding rare earth trifluoromethanesulfonate under atmosphere, slowly adding trifluoromethanesulfonic acid (TSFA) dropwise, and controllingThe reaction temperature is 0-10 ℃, and the polycondensation reaction is stopped for 8-24 h; adding a product precipitated by methanol, repeatedly washing the product by using distilled water to obtain a white blocky solid, and drying the solid to obtain a perfluorinated polydibiphenyl alkylene high molecular polymer;
(2) 4-ethanol piperidine and CH3I and K2CO3Dissolving in dimethyl sulfoxide (DMSO), reacting at 36-41 deg.C for 24-48h, adding diethyl ether for precipitation, washing for several times, and drying to obtain 4-ethanol-N-dimethyl piperidine quaternary ammonium salt (OH-DMP); NaH and tetrabutylammonium bromide (TBAB) were dissolved in DMSO, N2Slowly dripping the obtained OH-DMP solution in the atmosphere, and reacting for 2-3h at the temperature of 50-60 ℃; continuously dropwise adding 2-chloro-1-propanol, reacting at 50-60 ℃ for 6-10h, precipitating with acetone, washing for several times, and drying to obtain a white solid of hydroxypiperidine quaternary ammonium salt with a long chain of a polyalkyl ether bond;
(3) NaH and tetrabutylammonium bromide (TBAB) were dissolved in DMSO, N2Dropwise adding a dimethyl sulfoxide solution of the hydroxyl piperidine quaternary ammonium salt under the atmosphere, reacting for 2-3h at 50-60 ℃, then dropwise adding a dimethyl sulfoxide solution of the perfluorinated polydibiphenyl alkylene high-molecular polymer, reacting for 6-10h at 50-60 ℃, precipitating with ethanol and washing for several times, drying to obtain perfluorinated polydibiphenyl alkylene bond polyalkyl ether bond side chain piperidine quaternary ammonium salt resin, dissolving with a polar solvent, pouring into a polytetrafluoroethylene mold, and drying to form a film to obtain the perfluorinated polydibiphenyl alkylene bond polyalkyl ether bond side chain piperidine quaternary ammonium salt anion exchange membrane.
According to the scheme, the trifluoromethanesulfonic acid rare earth salt is lanthanum trifluoromethanesulfonate La (CF)3SO3)3。
According to the scheme, one or more of biphenyl, bromopentafluoroacetone and hexafluoroacetone in the step 1 are replaced by 4H, 4' H-octafluorobiphenyl, trifluoroacetone and 3-bromo-1, 1, 1-trifluoroacetone correspondingly.
According to the scheme, the molar ratio of the biphenyl to the bromopentafluoroacetone to the hexafluoroacetone in the step 1 is 1: (0.55-0.85): (0.35-0.65); molar ratio of trifluoromethanesulfonic acid to biphenyl 1: (9-12).
According to the scheme, the 4-ethanol piperidine and CH in the step 23I ofThe molar ratio is 1 (3-5); the molar ratio of the 4-ethanol-N-dimethyl piperidine quaternary ammonium salt to the NaH to the 2-chloro-1-propanol is 1: (1-1.3): (1-1.5).
According to the scheme, the 2-chloro-1-propanol in the step 2 is replaced by different types of chlorinated ether alcohol to adjust the length of a long chain of a polyalkyl ether bond and the number of ether bonds; the chloroethanol comprises any one of 2-chloroethanol, 2-chloroethoxyethanol and 2-chloroethoxy-2-ethoxyethanol.
According to the scheme, the ratio of the using amount of the hydroxypiperidine quaternary ammonium salt in the step 3 to the molar weight of the bromopentafluoroacetone structure in the perfluorinated polydibiphenyl alkylene high molecular polymer is 1: (1-1.2).
According to the scheme, the polar solvent in the step 3 is one or more of DMSO, NMP, DMAc and DMF.
The invention has the beneficial effects that:
the invention discloses an anion exchange membrane imitating a chemical structure of a main side chain of Nafion, which is a polymer with excellent alkali stability, wherein the main chain skeleton of the polymer has a perfluoro structure, and the side chain of the polymer has a long chain of a polyalkyl ether bond; the alkali-resistant stable piperidine quaternary ammonium cation and the strong-hydrophobicity perfluorinated polydibiphenyl alkylene polymer with the main chain free from aryl ether bonds are selected and bonded to the C site of the main chain alkylene of the perfluorinated polydibiphenyl alkylene polymer through the non-N site of piperidine, so that the alkali-resistant performance of the anion exchange membrane is greatly improved; by introducing the chlorinated ether alcohols with different structures into the piperidine cationic group, hydrophilic alkyl ether bond side chains with different lengths can be introduced into the main chain of the hydrophobic perfluorinated polydibiphenyl alkylene polymer, the number of ether bonds can be adjusted, the main side chain chemical structure of a Nafion membrane is simulated to construct a hydrophilic-hydrophobic microphase separation form in an anion exchange membrane, and the OH-ion conductivity of the anion exchange membrane is further improved.
The anion exchange membrane obtained by the invention has good thermal stability and alkali resistance, the decomposition temperature of the polymer can reach 400-600 ℃, the degradation does not occur when the membrane is soaked in a simulated fuel cell operating environment (such as almost anhydrous KOH crown ether solution) for 30 days, and the reduction of the OH-ion conductivity is not more than 5%.
Drawings
FIG. 1: example 1 reaction scheme for step 1.
FIG. 2: example 1 reaction scheme for step 2.
FIG. 3: example 1 reaction scheme for step 3.
Detailed Description
The following examples further illustrate the technical solutions of the present invention, but should not be construed as limiting the scope of the present invention.
The preparation process of the anion exchange membrane imitating the Nafion main side chain chemical structure in the specific embodiment is as follows:
(1) adding 4H, 4' H-octafluorobiphenyl, bromopentafluoroacetone, hexafluoroacetone and a solvent dichloromethane into a four-mouth bottle provided with a stirrer, a thermometer, a reflux condenser and a dropping funnel, starting stirring and dissolving at room temperature; in N2Adding rare earth triflate (such as lanthanum triflate La (CF) under protection3SO3)3) Slowly dropwise adding trifluoromethanesulfonic acid (TSFA) and controlling the reaction temperature at 0-10 ℃, after polycondensation reaction is carried out for 8-24h, the product becomes viscous, and the reaction is stopped; adding a product precipitated by methanol, repeatedly washing the product by using distilled water to obtain a white blocky solid, and drying the white blocky solid in vacuum at the temperature of 80 ℃ to obtain a perfluorinated polydibiphenyl alkylene high molecular polymer; wherein one or more of biphenyl, bromopentafluoroacetone and hexafluoroacetone are replaced by 4H, 4' H-octafluorobiphenyl, trifluoroacetone and 3-bromo-1, 1, 1-trifluoroacetone respectively; the molar ratio of the biphenyl to the bromopentafluoroacetone to the hexafluoroacetone is 1: (0.55-0.85): (0.35-0.65); molar ratio of trifluoromethanesulfonic acid to biphenyl 1: (9-12).
(2) 4-Ethanolpiperidine and CH in a three-neck flask3I and K2CO3Dissolving in dimethyl sulfoxide (DMSO), reacting at 36-41 deg.C for 24-48h, washing with diethyl ether precipitate for several times after reaction, and drying at 80 deg.C for 24h to obtain 4-ethanol-N-dimethylpiperidine quaternary ammonium salt (OH-DMP); NaH and tetrabutylammonium bromide (TBAB) were dissolved in DMSO in N2Adding OH-DMP (dissolved in DMSO) dropwise into the above solution under protection, reacting at 50-60 deg.C for 2-3h to obtain 4-sodium ethoxide-N-dimethylpiperidine quaternary ammonium salt, and adding 2-chloro-1-propanol dropwise into the above solutionReacting at 50-60 ℃ for 6-10h, precipitating with acetone, washing for several times, and vacuum drying at 80 ℃ for 24h to obtain a white solid of hydroxypiperidine quaternary ammonium salt with a long chain of polyalkyl ether bond; wherein the 4-ethanol piperidine and CH3The molar ratio of I is 1 (3-5); the molar ratio of the 4-ethanol-N-dimethyl piperidine quaternary ammonium salt to the NaH to the 2-chloro-1-propanol is 1: (1-1.3): (1-1.5); the 2-chloro-1-propanol is replaced by different types of chlorinated ether alcohol and is used for adjusting the length of a long chain of a polyalkyl ether bond and the number of ether bonds; the chloroethanol comprises any one of 2-chloroethanol, 2-chloroethoxyethanol and 2-chloroethoxy-2-ethoxyethanol.
(3) NaH and tetrabutylammonium bromide (TBAB) were dissolved in DMSO, N2Dripping the hydroxyl piperidine quaternary ammonium salt (dissolved in DMSO) with the long chain of the polyalkyl ether bond prepared in the step (2) into the solution under the condition, reacting for 2-3h at the temperature of 50-60 ℃, dripping the perfluorinated polydibiphenyl alkylene high molecular polymer (dissolved in DMSO) prepared in the step (1) into the solution, and continuing to perform reaction under the condition of N2Reacting for 6-10h at 50-60 ℃, precipitating with ethanol and washing for several times after the reaction is finished, vacuum drying for 24h at 80 ℃ to obtain perfluoro polydibiphenyl alkylene bond polyalkyl ether bond side-chain piperidine quaternary ammonium salt resin, dissolving the polymer by adopting a polar solvent, pouring into a polytetrafluoroethylene mold, and forming a film in an oven to obtain the perfluoro polydibiphenyl alkylene bond polyalkyl ether bond side-chain piperidine quaternary ammonium salt anion exchange membrane; wherein, the ratio of the using amount of the hydroxypiperidine quaternary ammonium salt in the step 3 to the molar weight of the bromopentafluoroacetone structure in the perfluorinated polydibiphenyl alkylene high molecular polymer is 1: (1-1.2). (ii) a The polar solvent is one or more of DMSO, NMP, DMAc and DMF.
Example 1
A preparation method of an anion exchange membrane imitating a chemical structure of a main side chain of Nafion comprises the following steps:
(1) adding 4H, 4' H-octafluorobiphenyl, bromopentafluoroacetone, hexafluoroacetone and a solvent dichloromethane into a four-mouth bottle provided with a stirrer, a thermometer, a reflux condenser and a dropping funnel, starting stirring and dissolving at room temperature; the molar ratio of two monomers of bromopentafluoroacetone and hexafluoroacetone is 3:1, andthe molar ratio of the sum of the amounts of the monomer species to the 4H, 4' H-octafluorobiphenyl is 1.2: 1; in N2Adding rare earth triflate (such as lanthanum triflate La (CF) under protection3SO3)3) Slowly dripping trifluoromethanesulfonic acid (TSFA) and controlling the reaction temperature at 0-10 ℃, after polycondensation reaction is carried out for 8-24h, the product becomes viscous, and the reaction is stopped; adding a product precipitated by methanol, repeatedly washing the product by using distilled water to obtain a white blocky solid, and drying the white blocky solid in vacuum at the temperature of 80 ℃ to obtain a perfluorinated polydibiphenyl alkylene high molecular polymer; the process flow diagram of the step is shown in the attached figure 1.
(2) 4-Ethanolpiperidine and CH in a three-neck flask3I and K2CO3Dissolving in dimethyl sulfoxide (DMSO), reacting at 40 deg.C for 48h, washing with diethyl ether precipitate for several times after reaction, and drying at 80 deg.C for 24h to obtain 4-ethanol-N-dimethylpiperidine quaternary ammonium salt (OH-DMP); NaH and tetrabutylammonium bromide (TBAB) were dissolved in DMSO in N2Under protection, OH-DMP (dissolved in DMSO) is dripped into the solution to react for 2h at 60 ℃ to obtain 4-sodium ethoxide-N-dimethyl piperidine quaternary ammonium salt, 2-chlorine-1-propanol is dripped into the solution to react for 6-10h at 60 ℃, acetone is used for precipitation and washing for a plurality of times, and vacuum drying is carried out at 80 ℃ for 24h to obtain hydroxyl piperidine quaternary ammonium salt white solid with a long chain of a polyalkyl ether bond; the process flow diagram of this step is shown with reference to FIG. 2.
(3) NaH and tetrabutylammonium bromide (TBAB) were dissolved in DMSO, N2Dripping the hydroxyl piperidine quaternary ammonium salt (dissolved in DMSO) with the long chain of the polyalkyl ether bond prepared in the step (2) into the solution under the condition, reacting for 2 hours at the temperature of 60 ℃, then dripping the perfluorinated polydibiphenyl alkylene high molecular polymer (dissolved in DMSO) prepared in the step (1) into the solution, and continuing to perform reaction under the condition of N2Reacting for 6-10h at 60 ℃, precipitating with ethanol and washing for several times after the reaction is finished, vacuum drying for 24h at 80 ℃ to obtain perfluoro poly-biphenyl alkylene bond polyalkyl ether bond side-chain piperidine quaternary ammonium salt resin, dissolving the polymer by adopting a polar solvent, pouring into a polytetrafluoroethylene mold, and forming a film in an oven to obtain the perfluoro poly-biphenyl alkylene bond polyalkyl ether bond side-chain piperidine quaternary ammonium salt anion exchange membraneAs shown in fig. 3. The relevant properties of the films are shown in table 1.
Example 2
Adding 4H, 4' H-octafluorobiphenyl, bromopentafluoroacetone, hexafluoroacetone and a solvent dichloromethane into a four-mouth bottle provided with a stirrer, a thermometer, a reflux condenser and a dropping funnel, starting stirring and dissolving at room temperature; the molar ratio of bromopentafluoroacetone to hexafluoroacetone was 4:1, and the molar ratio of the sum of the amounts of the two monomer species to 4H, 4' H-octafluorobiphenyl was 1.2: 1. The rest of the experimental procedure was the same as in example 1.
Example 3
Adding 4H, 4' H-octafluorobiphenyl, bromopentafluoroacetone, hexafluoroacetone and a solvent dichloromethane into a four-mouth bottle provided with a stirrer, a thermometer, a reflux condenser and a dropping funnel, starting stirring and dissolving at room temperature; the molar ratio of the two monomers bromopentafluoroacetone and hexafluoroacetone was 5:1, and the molar ratio of the sum of the amounts of the two monomer species to 4H, 4' H-octafluorobiphenyl was 1.2: 1. The rest of the experimental procedure was the same as in example 1.
Example 4
(1) Adding 4H, 4' H-octafluorobiphenyl, bromopentafluoroacetone, hexafluoroacetone and a solvent dichloromethane into a four-mouth bottle provided with a stirrer, a thermometer, a reflux condenser and a dropping funnel, starting stirring and dissolving at room temperature; the molar ratio of two monomers of bromopentafluoroacetone and hexafluoroacetone is 3:1, and the molar ratio of the sum of the two monomer substances to 4H, 4' H-octafluorobiphenyl is 1.2: 1; in N2Adding rare earth triflate (such as lanthanum triflate La (CF) under protection3SO3)3) Slowly dripping trifluoromethanesulfonic acid (TSFA) and controlling the reaction temperature at 0-10 ℃, after polycondensation reaction is carried out for 8-24h, the product becomes viscous, and the reaction is stopped; adding a product precipitated by methanol, repeatedly washing the product by using distilled water to obtain a white blocky solid, and drying the white blocky solid in vacuum at the temperature of 80 ℃ to obtain a perfluorinated polydibiphenyl alkylene high molecular polymer;
(2) 4-Ethanolpiperidine and CH in a three-neck flask3I and K2CO3Dissolving in dimethyl sulfoxide (DMSO), reacting at 40 deg.C for 36h, precipitating with diethyl ether, washing several times, drying at 80 deg.C for 36h to obtain 4-ethanol-N-dimethylpiperidineQuaternary ammonium salts (OH-DMP); NaH and tetrabutylammonium bromide (TBAB) were dissolved in DMSO in N2Under protection, OH-DMP (dissolved in DMSO) is dripped into the solution to react for 4h at 60 ℃ to obtain 4-sodium ethoxide-N-dimethyl piperidine quaternary ammonium salt, 2-chloroethanol is dripped into the solution to react for 8h at 60 ℃, acetone is used for precipitation and washing for a plurality of times, and vacuum drying is carried out for 4h at 80 ℃ to obtain hydroxyl piperidine quaternary ammonium salt white solid with a long chain of a polyalkyl ether bond;
(3) NaH and tetrabutylammonium bromide (TBAB) were dissolved in DMSO, N2Dripping the hydroxyl piperidine quaternary ammonium salt (dissolved in DMSO) with the long chain of the polyalkyl ether bond prepared in the step (2) into the solution under the condition, reacting for 3h at the temperature of 55 ℃, then dripping the perfluorinated polydibiphenyl alkylene high molecular polymer (dissolved in DMSO) prepared in the step (1) into the solution, and continuing to perform reaction under the condition of N2Reacting for 10 hours at 55 ℃, precipitating with ethanol and washing for several times after the reaction is finished, vacuum drying for 48 hours at 80 ℃ to obtain perfluoro polydibiphenyl alkylene bonded polyalkyl ether bond side chain piperidine quaternary ammonium salt resin, dissolving the polymer by adopting a polar solvent, pouring into a polytetrafluoroethylene mould disc, and forming a film in an oven to obtain the perfluoro polydibiphenyl alkylene bonded polyalkyl ether bond side chain piperidine quaternary ammonium salt anion exchange membrane.
Example 5
The procedure of example 4 was followed except that 2-chloroethanol in step (2) was replaced with 2-chloroethoxy-2-ethoxyethanol.
Example 6
The procedure of example 4 was followed except that 2-chloroethanol in step (2) was replaced with 2-chloroethoxyethanol.
Comparative example
The polymer prepared using fluorine-free biphenyl in copolymerization was used as a comparative example in this example: at room temperature, firstly, dissolving biphenyl in dichloromethane to prepare a transparent solution, then adding trifluoroacetone and 3-bromo-1, 1, 1-trifluoroacetone, wherein the molar ratio of two monomers is 3:1, the molar ratio of the sum of the two monomer substances to the biphenyl is 1.2:1, and dissolving biphenyl in the solution in a molar ratio of 1: 1.2, the rest of the experimental procedure is the same as example 1.
The relevant properties of the anion exchange membranes prepared in examples 1-6 above are shown in table 1, where the conductivity was measured at 80 ℃ and 100% RH; the swelling degree is measured by soaking for 48 hours at 25 ℃; the conductivity is at 80 ℃ and 2mol L-1After soaking in NaOH solution for 480h, the conductivity was measured at 80 ℃.
TABLE 1
The raw materials listed in the invention, the upper and lower limits and interval values of the raw materials of the invention, and the upper and lower limits and interval values of the process parameters (such as temperature, time and the like) can all realize the invention, and the examples are not listed.
Claims (8)
1. A preparation method of an anion exchange membrane imitating a chemical structure of a main side chain of Nafion is characterized by comprising the following steps:
(1) adding biphenyl, bromopentafluoroacetone, hexafluoroacetone and a solvent into a reactor, stirring, dissolving and mixing uniformly; in N2Adding rare earth trifluoromethanesulfonate under the atmosphere, slowly dropwise adding trifluoromethanesulfonic acid (TSFA), controlling the reaction temperature to be 0-10 ℃, and stopping the reaction for 8-24h in a polycondensation reaction; adding a product precipitated by methanol, repeatedly washing the product by using distilled water to obtain a white blocky solid, and drying the solid to obtain a perfluorinated polydibiphenyl alkylene high molecular polymer;
(2) 4-ethanol piperidine and CH3I and K2CO3Dissolving in dimethyl sulfoxide (DMSO), reacting at 36-41 deg.C for 24-48h, adding diethyl ether for precipitation, washing for several times, and drying to obtain 4-ethanol-N-dimethyl piperidine quaternary ammonium salt (OH-DMP); NaH and tetrabutylammonium bromide (TBAB) were dissolved in DMSO, N2Slowly dripping the obtained OH-DMP solution in the atmosphere, and reacting for 2-3h at the temperature of 50-60 ℃; continuously dropwise adding 2-chloro-1-propanol, reacting at 50-60 ℃ for 6-10h, precipitating with acetone, washing for several times, and drying to obtain a white solid of hydroxypiperidine quaternary ammonium salt with a long chain of a polyalkyl ether bond;
(3) NaH and tetrabutylammonium bromide (TBAB) were dissolved in DMSO, N2Dropwise adding under the atmosphereReacting the dimethyl sulfoxide solution of the hydroxyl piperidine quaternary ammonium salt for 2-3h at 50-60 ℃, then dropwise adding the dimethyl sulfoxide solution of the perfluorinated polydibiphenyl alkylene high molecular polymer, reacting for 6-10h at 50-60 ℃, precipitating with ethanol and washing for several times, drying to obtain perfluorinated polydibiphenyl alkylene bonding polyalkyl ether bond side chain piperidine quaternary ammonium salt resin, dissolving by adopting a polar solvent, pouring into a polytetrafluoroethylene mold, and drying to form a film to obtain the perfluorinated polydibiphenyl alkylene bonding polyalkyl ether bond side chain piperidine quaternary ammonium salt anion exchange membrane.
2. The method for preparing the Nafion-like anion exchange membrane with the main side chain chemical structure as in claim 1, wherein the rare earth triflate is lanthanum triflate La (CF)3SO3)3。
3. The method for preparing an anion exchange membrane imitating the chemical structure of a main side chain of Nafion as claimed in claim 1, wherein in the step 1, one or more of biphenyl, bromopentafluoroacetone and hexafluoroacetone are replaced by 4H, 4' H-octafluorobiphenyl, trifluoroacetone and 3-bromo-1, 1, 1-trifluoroacetone respectively.
4. The method for preparing an anion-exchange membrane imitating the chemical structure of a main side chain of Nafion as claimed in claim 1, wherein the molar ratio of the biphenyl, the bromopentafluoroacetone and the hexafluoroacetone in the step 1 is 1: (0.55-0.85): (0.35-0.65); molar ratio of trifluoromethanesulfonic acid to biphenyl 1: (9-12).
5. The method for preparing the anion exchange membrane imitating the chemical structure of the main side chain of Nafion as claimed in claim 1, wherein the 4-ethanol piperidine and CH in the step 23The molar ratio of I is 1 (3-5); the molar ratio of the 4-ethanol-N-dimethyl piperidine quaternary ammonium salt to the NaH to the 2-chloro-1-propanol is 1: (1-1.3): (1-1.5).
6. The method for preparing the anion-exchange membrane imitating the chemical structure of the main side chain of Nafion as claimed in claim 1, wherein the 2-chloro-1-propanol in the step 2 is replaced by different types of chlorinated ether alcohol to adjust the length of the long chain of the polyalkyl ether bond and the number of ether bonds; the chloroethanol comprises any one of 2-chloroethanol, 2-chloroethoxyethanol and 2-chloroethoxy-2-ethoxyethanol.
7. The method for preparing an anion exchange membrane imitating a chemical structure of a main side chain of Nafion as claimed in claim 1, wherein the ratio of the amount of the hydroxypiperidine quaternary ammonium salt to the molar weight of the bromopentafluoroacetone structure in the perfluoro polydibiphenyl alkylene high molecular polymer in the step 3 is 1: (1-1.2).
8. The method for preparing the anion exchange membrane imitating the chemical structure of the main side chain of Nafion as claimed in claim 1, wherein the polar solvent in the step 3 is one or more of DMSO, NMP, DMAc and DMF.
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| US20200308341A1 (en) * | 2019-03-28 | 2020-10-01 | University Of Delaware | Polymers having stable cationic pendant groups for use as anion exchange membranes |
| CN112920441A (en) * | 2021-03-23 | 2021-06-08 | 武汉理工大学 | Preparation method of cross-linked polyfluorene piperidine anion exchange membrane |
| CN113583279A (en) * | 2021-08-11 | 2021-11-02 | 中国科学院山西煤炭化学研究所 | Anion exchange membrane containing strong rigid structure, preparation method and application |
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| CN112920441A (en) * | 2021-03-23 | 2021-06-08 | 武汉理工大学 | Preparation method of cross-linked polyfluorene piperidine anion exchange membrane |
| CN113583279A (en) * | 2021-08-11 | 2021-11-02 | 中国科学院山西煤炭化学研究所 | Anion exchange membrane containing strong rigid structure, preparation method and application |
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| CN115109391B (en) * | 2022-08-03 | 2023-05-05 | 宿迁时代储能科技有限公司 | Preparation method and application of polyarylpiperidine anion-exchange membrane with quaternary ammonium side chain |
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