A multi-cation photocrosslinked polyarylpiperidine anion exchange membrane and its preparation method and application

Abstract

The present invention discloses a polycationic photocrosslinked polyaryl piperidine anion exchange membrane and a preparation method and application thereof, belonging to the technical field of anion exchange membranes. The present invention designs a polyaryl piperidine main chain that does not contain polar groups such as ether bonds on the main chain, and its piperidine cyclic quaternary ammonium group has excellent cationic stability. The above main chain structure makes the material have excellent chemical stability, while improving the solubility of the anion exchange polymer, which is beneficial to the subsequent molding processability of the anion exchange polymer. In addition, in order to balance and ensure mechanical strength, stability and OH-ion conductivity, a flexible hydrophilic polycationic crosslinker is designed, and double bonds are introduced for functionalization, and an anion exchange membrane is prepared by an efficient and environmentally friendly ultraviolet curing method, which effectively improves the dimensional stability of the polyaryl piperidine anion exchange membrane while balancing the ion conductivity.

Description

Technical Field

[0001] The invention belongs to the technical field of anion exchange membranes, and in particular relates to a multi-cation photo-crosslinked polyaryl piperidine anion exchange membrane and a preparation method and application thereof. Background Art

[0002] Alkaline anion exchange membrane (AEM) fuel cells (AEMFCs) are devices that can use hydrogen energy to convert chemical energy into electrical energy through electrochemical reactions. As an environmentally friendly and efficient new energy technology, anion exchange membranes working in alkaline environments have higher redox reaction efficiency and can use non-precious metals such as nickel and silver as catalysts to greatly reduce costs. They have become a hot topic in scientific research. However, since anion exchange membranes work in a strong alkaline environment for a long time, the cationic groups and polymer main chains are easily affected by OH - The Hofmann elimination or SN2 nucleophilic substitution reaction occurs due to the attack of the ions, resulting in the degradation of membrane performance. In addition, the commercial development of AEMFCs is hampered by the difficulty in balancing ionic conductivity and dimensional stability.

[0003] The researchers found that the piperidine cation has a longer degradation half-life and improved alkali stability due to the steric hindrance and ring stress restraint brought by the ring structure. The main chain structure without aromatic ether bonds can also prevent OH - Attack on the main chain, thus showing good alkaline stability. Therefore, ether-free skeletons such as polyaryl piperidine have excellent alkaline stability and high structural rigidity. However, the main chain structure causes the cationic functional groups to be close to the polymer skeleton, and the water absorption rate and swelling degree are relatively high, which largely leads to poor mechanical properties of the membrane. Therefore, the ion conductivity and dimensional stability of the main chain polyaryl piperidine anion exchange membrane still need to be improved.

[0004] Increasing the ion exchange capacity (IEC) is a method to improve the ionic conductivity of AEMs, but this will also reduce the dimensional stability and mechanical properties of the membrane. At the same time, too high a concentration of ion exchange groups is also prone to more obvious chemical instability in alkaline working environments. Introducing cross-linked structures in polymer membranes has been shown to be an effective method for preparing AEMs with high ionic conductivity and dimensional stability. Cross-linking strategies are effective methods that help adjust ion transport channels, improve microphase separation, and regulate mechanical properties, which can better balance ionic conductivity, chemical stability, and mechanical strength. However, the rigid hydrophobic cross-linked structures commonly found in AEMs hinder the ion transport of OH-, resulting in a decrease in conductivity. In this regard, long and flexible multiple cationic cross-links are a good strategy that helps promote microphase separation in the membrane while maintaining mechanical stability, achieving the dual effects of ultra-high OH- ion conductivity and strong stability.

[0005] CN 117736415 A discloses a method for preparing a cyanuric chloride crosslinked and pyridine-terminated biphenylpiperidinium hydroxide ion exchange membrane, wherein a trifunctional cyanuric chloride crosslinking agent is used to react at 40-60°C for 48-96 hours to crosslink the biphenylpiperidinium polymer chain segments to regulate the dimensional stability of the membrane, and a cationic group is further introduced into the remaining functional sites to form an "ion-terminated segment" to promote the conduction of OH- ions. The reaction conditions are 60-80°C for 48-110 hours. The prepared cyanuric chloride crosslinked and pyridine-terminated biphenylpiperidinium hydroxide ion exchange membrane has both high stability and OH- - Ionic conductivity.

[0006] CN 113871671 A discloses a method for preparing a polycationic long flexible chain cross-linked polyindigo biphenyl anion exchange membrane, which comprises fully dissolving the polymer at 60°C, then adding a polycationic cross-linking agent and reacting at 80°C for 24 hours, and finally forming a polycationic cross-linked anion exchange membrane by casting and drying at 80°C for 12 hours, wherein the polycationic cross-linked anion exchange membrane has an ion conductivity of up to 0.075S / cm (80°C).

[0007] CN 117327314 A discloses a method for preparing a multi-cation cross-linked anion exchange membrane for an ammonia fuel cell. The method comprises the following steps: firstly dissolving a polyaryl piperidine polymer and adding a halogenated primary amine, and subjecting the polyaryl piperidine polymer to a quaternary amination reaction at 40 to 80° C. for 24 to 48 hours. The obtained primary amine polymer is further reacted with a halogenated olefin at 30 to 60° C. for 24 to 48 hours. Finally, the poly-cation cross-linked anion exchange membrane is obtained by reacting the polymer at 120 to 160° C. for 48 to 72 hours through an in-situ thermal cross-linking method. The obtained poly-cation cross-linked anion exchange membrane has low water absorption and swelling and high ion conductivity.

[0008] However, the above patents all use traditional thermal cross-linking methods, which require heating to initiate the polymerization reaction, have a long polymerization time and high energy consumption. Summary of the invention

[0009] In order to solve the above technical problems, the present invention proposes a multi-cationic photocross-linked polyaryl piperidine anion exchange membrane and a preparation method and application thereof. The present invention adopts ultraviolet light curing to form the film, which is energy-saving, environmentally friendly and clean, greatly shortens the curing time, and improves the mechanical properties and dimensional stability while taking into account the ionic conductivity.

[0010] To achieve the above object, the present invention provides the following technical solutions:

[0011] One of the technical solutions of the present invention:

[0012] A multi-cation photo-crosslinked polyaryl piperidine anion exchange membrane, wherein the multi-cation photo-crosslinked polyaryl piperidine anion exchange membrane has the following structure:

[0013]

[0014] Wherein, Ar is any one of the following monomers:

[0015]

[0016] R is any of the following structures:

[0017]

[0018] X represents the molar content of the double-bond functionalized dicationic crosslinking agent, and the value is 20 to 80%.

[0019] Preferably, the value of X is 20%, 40%, 60% or 80%.

[0020] The second technical solution of the present invention:

[0021] The present invention also provides a method for preparing the multi-cation photo-crosslinked polyaryl piperidine anion exchange membrane, comprising the following steps:

[0022] In a nitrogen atmosphere, a benzene ring-containing aromatic monomer and a piperidone monomer are dissolved in dichloromethane, and a viscous liquid is obtained after a low-temperature reaction, and an aromatic piperidine polymer is obtained by precipitation and washing;

[0023] The polyaryl piperidine polymer is dissolved in solvent A, stirred and reacted at 50-90° C. for 15-45 minutes, then an excess of 6-bromo-1-hexene and an excess of a polymerization inhibitor are added, reacted at 50-90° C. for 24-48 hours, then the product is extracted with ethyl acetate, the precipitate is centrifuged and dried to obtain a double-bond functionalized polyaryl piperidine;

[0024] In a light-proof environment, the double-bond functionalized polyaryl piperidine and the cross-linking agent are added to the solvent A, stirred evenly to obtain a mixed solution, and then the photoinitiator is dissolved in the solvent A and then added dropwise to the mixed solution, stirred evenly, and then dropped into a mold, vacuum dried, and photocured to obtain a light yellow film, and then the light yellow film is immersed in a NaOH solution to obtain OH - The polycationic photo-crosslinked polyaryl piperidine anion exchange membrane is obtained after washing.

[0025] Preferably, the benzene ring-containing aromatic monomer is biphenyl, 1,2-diphenylethane, p-terphenyl, m-terphenyl or p-quaterphenyl; the piperidone monomer is N-methyl-4-piperidone; and the low temperature is 0°C.

[0026] Preferably, the solvent A is at least one of N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), N,N-dimethylacetamide (DMAC), N,N-dimethylformamide (DMF) and monostyrene sulfone (MSDS).

[0027] Preferably, the molar ratio of the polyaryl piperidine to the 6-bromo-1-hexene is 1:(1.5-20), more preferably 1:(2-7).

[0028] Preferably, the molar ratio of the cross-linking agent to 6-bromo-1-hexene is 1:(5-20), more preferably 1:(6-10).

[0029] Preferably, the inhibitor is at least one of hydroquinone (HQ), 4-methoxyphenol (MEHQ) and 2,6-di-tert-butyl-p-cresol (BHT); and the photoinitiator is at least one of TPO, 184, 1173, 819, ITX and 907.

[0030] Preferably, the cross-linking agent is a double-bond functionalized dicationic cross-linking agent, and the preparation method is as follows: dissolving 1,6-dibromohexane and a secondary amine compound in acetonitrile, and adding an alkaline reagent B, reacting at 50-80° C. for 24-48 hours, adding water after the reaction is completed, and extracting with solvent C, then adding anhydrous magnesium sulfate to dry, and finally evaporating the solvent to concentrate to obtain a cross-linking agent containing a tertiary amine group;

[0031] 6-bromo-1-hexene and the cross-linking agent containing tertiary amine group or N 1 ,N 1 ,N 6 ,N 6 -Tetramethyl-1,6-hexanediamine is dissolved in solvent D, a polymerization inhibitor is added, and the mixture is stirred at 50-90°C for 24-48 hours. After the reaction is completed, the product is extracted and washed with solvent E, and the solid product is vacuum dried to obtain a double-bond functionalized dicationic crosslinker;

[0032] The invention first synthesizes a double-bond functionalized main chain, then synthesizes a cross-linking agent containing a tertiary amine group, then double-bond functionalizes the dication, and finally prepares a photo-cross-linked anion exchange membrane, which effectively improves the dimensional stability of the polyaryl piperidine anion exchange membrane while balancing the ion conductivity.

[0033] Preferably, the secondary amine compound is piperidine, 4-methylpiperidine or 2-methylimidazole.

[0034] Preferably, the alkaline reagent B is one of sodium carbonate (Na2CO3) and potassium carbonate (K2CO3);

[0035] The solvent C is at least one of ethyl acetate, butyl acetate and chloroform;

[0036] The solvent D is at least one of methanol, ethanol, acetonitrile and tetrahydrofuran;

[0037] The solvent E is at least one of petroleum ether, ethyl ether and ethyl acetate.

[0038] Preferably, when preparing the double-bond functionalized polyaryl piperidine, the solid product is dried under vacuum at 50 to 90° C. for 4 to 6 hours;

[0039] When preparing the double-bond functionalized dicationic crosslinking agent, the solid product is vacuum dried at 40-70° C. for 12-24 hours.

[0040] The principle of the present invention is that the introduction of a cross-linking agent into the AEM membrane can form a highly cross-linked network structure, making the molecular connections within the membrane more closely connected, and increasing the mechanical strength, stability and chemical corrosion resistance of the membrane. However, the cross-linked structure inside the membrane will reduce the free space inside the membrane, restrict the movement of the polymer chains, and the rigid hydrophobic cross-linked network will inhibit the penetration of water molecules and hinder OH - The long flexible chain polycationic hydrophilic cross-linked structure introduced in the present invention can improve the OH while ensuring mechanical strength and stability. - The present invention designs a polyaryl piperidine main chain that does not contain polar groups such as ether bonds on the main chain. Its piperidine cyclic quaternary ammonium group has excellent cationic stability. The above main chain structure makes the material have excellent chemical stability and improves the solubility of the anion exchange polymer, which is beneficial to the subsequent molding processability of the anion exchange polymer. In addition, in order to balance the mechanical strength, stability and OH - Ionic conductivity, a flexible hydrophilic polycationic cross-linker was designed, and double bonds were introduced for functionalization. Anion exchange membranes were prepared using an efficient and environmentally friendly UV curing method, which effectively improved the dimensional stability of the polyaryl piperidine anion exchange membrane while balancing the ionic conductivity.

[0041] More preferably, the preparation method of the multi-cationic photo-crosslinked polyarylpiperidine anion exchange membrane is:

[0042] (1) Synthesis of double bond functionalized polyaryl piperidine:

[0043] Under a nitrogen atmosphere, a polyaryl piperidine is dissolved in a solvent A, and the mixture is stirred and reacted at 50 to 90° C. for 15 to 45 minutes, and then an excess of 6-bromo-1-hexene and a polymerization inhibitor are added, and the mixture is reacted at 50 to 90° C. for 24 to 48 hours, and then the product is extracted with an alkaline reagent B, and the precipitate is centrifuged and separated, and the solid product is collected and dried under vacuum at 50 to 90° C. for 4 to 6 hours to obtain a double-bond functionalized polyaryl piperidine;

[0044] (2) Synthesis of cross-linking agents containing tertiary amine groups:

[0045] Dissolve 1,6-dibromohexane and a secondary amine compound in acetonitrile, add an alkaline reagent B, react at 50-80° C. for 24-48 hours, add deionized water after the reaction is completed, extract with solvent C for multiple times, then add anhydrous magnesium sulfate for drying, and finally, evaporate and concentrate the solvent to obtain a cross-linking agent containing a tertiary amine group;

[0046] (3) Synthesis of double bond functionalized polycationic crosslinkers:

[0047] 6-bromo-1-hexene is crosslinked with a tertiary amine group-containing crosslinking agent or N 1 ,N 1 ,N 6 ,N 6 -Tetramethyl-1,6-hexanediamine is dissolved in solvent D, and a polymerization inhibitor is added, and the reaction is stirred at 50-90° C. for 24-48 hours. After the reaction is completed, the product is extracted with solvent E and washed multiple times, and the solid product is collected and placed at 40-70° C. for vacuum drying for 12-24 hours to obtain a double-bond functionalized dicationic crosslinker;

[0048] (4) Synthesis of photo-crosslinked polyarylpiperidine anion exchange membrane:

[0049] In a light-proof environment, the double-bond functionalized polyaryl piperidine is added to solvent A and stirred for 1 to 2 hours to be completely dissolved to obtain a mixed solution, and then the photoinitiator is dissolved in solvent A and added dropwise to the mixed solution, stirred for 2 to 4 hours to make the solution evenly mixed, and then dropped into the mold, placed in an oven at 50 to 90° C. and dried in a light-proof vacuum oven for 1 to 3 hours, and finally placed in a UV curing instrument for curing for 30 to 90 seconds to obtain a light yellow film, and then the prepared film is immersed in a 1 to 3 M NaOH solution for 24 to 48 hours to complete the ion exchange and obtain OH - The membrane was washed with deionized water for 3 times to obtain a photo-crosslinked polyaryl piperidine anion exchange membrane. Similarly, adding different amounts of double-bond functionalized dicationic crosslinking agents into the double-bond functionalized polyaryl piperidine polymer can prepare a multi-cationic photo-crosslinked polyaryl piperidine anion exchange membrane, and the molar content of the double-bond functionalized dicationic crosslinking agent is preferably 20%, 40%, 60% and 80%.

[0050] The third technical solution of the present invention:

[0051] The present invention also provides the use of the multi-cation photo-crosslinked polyaryl piperidine anion exchange membrane in the preparation of an alkaline anion exchange membrane fuel cell.

[0052] Compared with the prior art, the present invention has the following advantages and technical effects:

[0053] The present invention provides a multi-cation photo-crosslinked polyaryl piperidine anion exchange membrane, by introducing carbon-carbon double bonds into the polyaryl piperidine matrix polymer, preparing carbon-carbon double bond functionalized long alkyl chain dications as crosslinking agents, and then preparing the photo-crosslinked polyaryl piperidine anion exchange membrane by ultraviolet light curing and crosslinking method, so as to achieve the purpose of balancing ion conductivity and effectively improving the dimensional stability of the polyaryl piperidine anion exchange membrane. Compared with the side group modified oxygen-free polymer anion exchange membrane disclosed in CN 109280198 A, which has a water absorption rate of 50% and a swelling degree of 16%, the crosslinked structure introduced in the present invention can effectively improve the water absorption and swelling of the membrane and improve the dimensional stability of the membrane. Compared with the piperidine-functionalized ether-free polyarylindole anion exchange membrane and its preparation method and application disclosed in CN 115466422 A, the present invention adopts efficient, energy-saving and environmentally friendly ultraviolet light curing technology, combined with a multi-cation cross-linking strategy, to reduce the water absorption and swelling of the anion exchange membrane, and improve the dimensional and mechanical stability. At the same time, the introduction of multi-cations provides a guarantee for the construction of efficient ion transport channels, thereby ensuring good ion conductivity. BRIEF DESCRIPTION OF THE DRAWINGS

[0054] The drawings constituting a part of the present application are used to provide a further understanding of the present application. The illustrative embodiments and descriptions of the present application are used to explain the present application and do not constitute an improper limitation on the present application. In the drawings:

[0055] Figure 1 The present invention is a flow chart for preparing a multi-cation photo-crosslinked polyarylpiperidine anion exchange membrane;

[0056] Figure 2 Total reflection infrared spectra of multi-cationic photo-crosslinked polyarylpiperidine anion exchange membranes prepared with different contents of dicationic crosslinkers;

[0057] Figure 3 OH of multi-cationic photocrosslinked polyarylpiperidine anion exchange membranes prepared with different contents of dicationic crosslinkers - Conductivity;

[0058] Figure 4 Mechanical properties of multi-cationic photocrosslinked polyarylpiperidine anion exchange membranes prepared with different contents of dicationic crosslinkers. DETAILED DESCRIPTION

[0059] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0060] It should be understood that the terms described in the present invention are only for describing special embodiments and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. Each smaller range between the intermediate value in any stated value or stated range and any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0061] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0062] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to those skilled in the art. The present invention description and examples are exemplary only.

[0063] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0064] In the present invention, the test method of membrane performance is as follows:

[0065] (1) Ion exchange capacity test (IEC)

[0066] The membrane was tested for IEC by acid-base back titration. The specific operation steps were as follows: first, the membrane sample was repeatedly washed with deionized water until it was neutral and completely dried to measure its weight (m d , g), and then the membrane was immersed in 50 mL 0.01 mol·L -1 HCl solution for 48 hours to replace all counterions with Cl - Then, phenolphthalein was added to the membrane sample as a titration indicator; a certain volume of 0.01 mol·L -1The NaOH solution was placed in the alkaline burette to calibrate the remaining volume of hydrochloric acid. The IEC of the membrane (mmol·g) was calculated by formula (I): -1 ) value. HCl and V HCl Respectively represent the concentration of hydrochloric acid solution (mol·L -1 ) and volume (L); C NaOH and V NaOH Respectively represent the concentration of sodium hydroxide solution (mol·L -1 ) and volume (L); m d Indicates the weight of the dry film (g).

[0067]

[0068] (2) Water absorption and swelling test

[0069] The water absorption (WU, %) and swelling rate (SR, %) of AEM were characterized by the weight change and size change of the film before and after drying. The film of 1 cm × 4 cm was cut out and placed in an oven at 80 ° C for 24 h to completely remove the water. The weight of the dry film (m d , g) and the length of the dry film (L d , cm); then the membranes to be tested were placed in deionized water and soaked for 12 h; the water on the membrane surface was quickly absorbed with filter paper, and the weight of the wet membrane was weighed and recorded (m w , g) and the length of the wet film (L w , cm); the water absorption and swelling degree of the membrane are calculated by formula (II) and formula (III):

[0070]

[0071] (3) Mechanical properties test

[0072] The tensile strength, Young's modulus and elongation at break of the membrane were tested using an electronic universal testing machine (UTM 4203). Test conditions: At room temperature (25±2°C), the membrane in the hydrated state was taken out and the surface moisture was quickly wiped with filter paper, and the sample was cut into a dumbbell shape. The tensile rate of the sample was set to 5 mm·min -1 .

[0073] (4)OH - Conductivity test

[0074] Ionic conductivity of membrane (σ, mS·cm -1) was measured by the AC impedance method. The model of the electrochemical workstation used was Shanghai CHI 760E, with a frequency range of 1MHz~1Hz and a potential amplitude of 10mA. The test method is as follows: First: immerse the membrane to be tested in distilled water under N2 atmosphere for 24h to balance its water absorption, and then quickly assemble the membrane between the homemade electrode plates to measure its AC impedance value (R, kΩ) at 30℃~80℃. The test temperature range is 30℃~80℃, and a group of measurements are taken every 10℃ to calculate the average value. In order to stabilize the impedance value, each specific temperature needs to be balanced for more than 2h. The ionic conductivity of the membrane is calculated by formula (Ⅳ), where L is the distance between the two electrode plates (cm); A is the effective cross-sectional area of ​​the membrane to be tested (cm 2 ); R is the impedance of the film to be tested (kΩ).

[0075]

[0076] All raw materials used in the embodiments of the present invention are commercially available.

[0077] The preparation flow chart of the multi-cation photo-crosslinked polyaryl piperidine anion exchange membrane of the present invention is shown in Figure 1 .

[0078] The technical solution of the present invention is further illustrated by the following embodiments.

[0079] Example 1

[0080] 1) Synthesis of poly(biphenyl-methyl-4-piperidone) (PBP): Under a nitrogen atmosphere, biphenyl (0.5 g, 3.24 mmol) and N-methyl-4-piperidone (0.4403 g, 3.89 mmol) were added to 2 mL of dichloromethane and stirred at 0°C for 10 min. After complete dissolution, 0.0289 mL of trifluoroacetic acid (TFA) and 2.6 mL of trifluoromethanesulfonic acid (TFSA) were added dropwise in sequence. After reacting for 4 h, the obtained viscous solution was poured into a 5 mol / L NaOH solution. After stirring and soaking for 15 min, the precipitated blocky polymer solid was taken out, cut into pieces, and then fully soaked and washed three times with deionized water. It was vacuum dried at 60°C for 24 h to obtain poly(biphenyl-methyl-4-piperidone) (PBP).

[0081] 2) Synthesis of double bond functionalized biphenyl piperidine polymer (QPBPi): Under nitrogen atmosphere, (1.2 g, 4.54 mmol) PBP was added to 20 mL dimethyl sulfoxide (DMSO), and the reaction was stirred at 60°C for 30 min. Subsequently, an excess of 6-bromo-1-hexene (9.1 mmol, 1.48 g) and 0.008 g inhibitor MEHQ (mass fraction of 3‰) were added, and the reaction was carried out at 60°C for 48 h. The product was then extracted with ethyl acetate, the precipitate was centrifuged, and the solid product was collected and dried under vacuum at 60°C for 4 h to obtain the double bond functionalized biphenyl piperidine polymer backbone QPBPi.

[0082] 3) Preparation of photo-crosslinked anion exchange membrane: In a light-proof environment, add 0.5g QPBPi to 5mL DMSO and stir for 1h to completely dissolve it to obtain a mixed solution. Then take 3% TPO photoinitiator by mass and dissolve it in 3mL DMSO and drop it into the above mixed solution. Stir for 2h, then drop it into a polytetrafluoroethylene (PTFE) mold, put it in a 60℃ oven in a light-proof vacuum dryer for 1h, and finally put it in a UV curing instrument to cure for 40s to obtain a light yellow film. Then soak the prepared membrane in 1M NaOH solution for 48h to obtain OH - The membrane was washed three times with deionized water to obtain a photo-crosslinked polyarylpiperidine anion exchange membrane, denoted as QPBP, with the following structure:

[0083]

[0084] Example 2

[0085] 1) Synthesis of PBP: Under a nitrogen atmosphere, biphenyl (0.5 g, 3.24 mmol) and N-methyl-4-piperidone (0.4403 g, 3.89 mmol) were added to 2 mL of dichloromethane and stirred at 0°C for 10 min. After complete dissolution, 0.0289 mL of TFA and 2.6 mL of TFSA were added dropwise in sequence. After reacting for 4 h, the obtained viscous solution was poured into a 5 mol / L NaOH solution. After stirring and soaking for 15 min, the precipitated block polymer solid was taken out, cut into pieces, and then fully soaked and washed three times with deionized water. It was vacuum dried at 60°C for 24 h to obtain PBP.

[0086] 2) Synthesis of QPBPi: Under a nitrogen atmosphere, PBP (1.2 g, 4.54 mmol) was added to 20 mL DMSO and stirred at 60 °C for 30 min. Subsequently, an excess of 6-bromo-1-hexene (9.1 mmol, 1.48 g) and 0.008 g of inhibitor MEHQ (mass fraction of 3‰) were added and reacted at 60 °C for 48 h. The product was then extracted with ethyl acetate, the precipitate was centrifuged, and the solid product was collected and dried under vacuum at 60 °C for 4 h to obtain the double-bond functionalized biphenyl piperidine polymer backbone QPBPi.

[0087] 3) Synthesis of double-bond functionalized dicationic crosslinker HETD: 6-bromo-1-hexene (15 mmol, 2.45 g) was dissolved in 15 mL of ethanol, and 0.00735 g of inhibitor MEHQ (mass fraction 3‰) was added to obtain a reaction solution; then N 1 ,N 1 ,N 6 ,N 6 -Tetramethyl-1,6-hexanediamine (TMHDA) (2.5mmol, 0.43g) was mixed with 5mL of ethanol, added dropwise to the above reaction solution, and stirred at 60°C for 48h. After the reaction was completed, the product was extracted with ether and washed several times. The solid product was collected and placed at 40°C for vacuum drying for 24h to obtain the dicationic crosslinker HETD.

[0088] 4) Preparation of polycationic photo-crosslinked polyaryl piperidine anion exchange membrane: In a light-proof environment, add 0.5g QPBPi and 0.049g crosslinker HETD to 5mL DMSO (the amount of HETD is calculated based on the designed crosslinker molar dose of 20%), stir the reaction for 1h until it is completely dissolved to obtain a mixed solution, then take 3% of the mass fraction of 819 photoinitiator dissolved in 3mL DMSO and drop it into the above mixed solution, stir for 2h, then drop it into the PTFE mold, put it in a 60℃ oven in a light-proof vacuum dryer for 1h, and finally put it in a UV curing instrument for curing for 40s to obtain a light yellow film. Then soak the prepared membrane in 1M NaOH solution for 48h to obtain OH - The membrane was washed three times with deionized water to obtain a multi-cation photo-crosslinked polyarylpiperidine anion exchange membrane, denoted as QPBP-HETD-20%, with the following structure:

[0089]

[0090] Example 3

[0091] The same as Example 2, except that the amount of the crosslinking agent HETD added is 0.098 g, and the obtained multi-cationic photo-crosslinked polyarylpiperidine anion exchange membrane is denoted as QPBP-HETD-40%, and the structure is as follows:

[0092]

[0093] Example 4

[0094] The same as Example 2, except that the amount of the crosslinking agent HETD added was 0.147 g, and the obtained multi-cationic photo-crosslinked polyarylpiperidine anion exchange membrane was denoted as QPBP-HETD-60%, and the structure was as follows:

[0095]

[0096] Example 5

[0097] The same as Example 2, except that the amount of the crosslinking agent HETD added was 0.196 g, and the obtained multi-cationic photo-crosslinked polyarylpiperidine anion exchange membrane was denoted as QPBP-HETD-80%, and the structure was as follows:

[0098]

[0099] Example 6

[0100] 1) Synthesis of the main chain: Under a nitrogen atmosphere, 1,2-diphenylethane (0.92 g, 5 mmol) and N-methyl-4-piperidone (0.68 g, 6 mmol) were added to 5 mL of dichloromethane and stirred at 0°C for 10 min. After complete dissolution, 0.45 mL of TFA and 4 mL of TFSA were added dropwise in sequence. After reacting for 4 h, the obtained viscous solution was poured into a 1 mol / L NaOH solution. After stirring and soaking for 15 min, the precipitated block polymer solid was taken out, cut into pieces, and fully soaked and washed three times with deionized water. It was vacuum dried at 60°C for 24 h to obtain PDiP.

[0101] 2) Synthesis of double bond functionalized main chain: PDiP (1.2 g, 4.1 mmol) was added to 20 mL NMP and stirred at 60 °C for 30 min. Then, an excess of 6-bromo-1-hexene (16.4 mmol, 2.674 mmol) and 0.0116 g of inhibitor MEHQ (mass fraction of 3‰) were added and reacted at 60 °C for 48 h. The product was then extracted with ethyl acetate, the precipitate was centrifuged, and the solid product was collected and dried under vacuum at 60 °C for 4 h to obtain a double bond functionalized aryl piperidine polymer main chain QPDiP.

[0102] 3) Synthesis of double bond functionalized dicationic crosslinker HETD: Excess 6-bromo-1-hexene (17.5 mmol, 2.85 g) was dissolved in 15 mL of methanol, and 0.0086 g of inhibitor MEHQ (mass fraction of 3‰) was added to obtain a reaction solution; then TMHDA (2.5 mmol, 0.43 g) was mixed with 5 mL of methanol, and added dropwise to the above reaction solution, and the reaction was stirred at 60°C for 48 hours. After the reaction was completed, the product was extracted with petroleum ether and washed several times, and the solid product was collected and dried in vacuum at 40°C for 24 hours to obtain the dicationic crosslinker HETD.

[0103] 4) Preparation of polycationic photo-crosslinked polyaryl piperidine anion exchange membrane: In a light-proof environment, 0.5g QPDiP and 0.045g crosslinker HETD were added to 5mL NMP (the amount of HETD was calculated based on the designed crosslinker molar dosage of 20%), stirred for 1h to completely dissolve, and a mixed solution was obtained. Then, 3% of 184 photoinitiator was dissolved in 3mL NMP and added dropwise to the mixed solution, stirred for 2h, and then dropped into a PTFE mold, placed in a 60°C oven and dried in a vacuum for 1h in a light-proof environment, and finally placed in a UV curing instrument for curing for 40s to obtain a light yellow film. The prepared membrane was then immersed in a 1M NaOH solution for 48h to obtain an OH-type membrane, which was washed 3 times with deionized water to obtain a polycationic photo-crosslinked polyaryl piperidine anion exchange membrane, denoted as QPDiP-HETD-20%, with the following structure:

[0104]

[0105] Example 7

[0106] 1) Synthesis of the main chain: Under a nitrogen atmosphere, p-terphenyl (1.16 g, 5 mmol) and N-methyl-4-piperidone (0.68 g, 6 mmol) were added to 5 mL of dichloromethane and stirred at 0°C for 10 min. After complete dissolution, 0.45 mL of TFA and 4 mL of TFSA were added dropwise in sequence. After reacting for 4 h, the obtained viscous solution was poured into a 1 mol / L NaOH solution. After stirring and soaking for 15 min, the precipitated block polymer solid was taken out, cut into pieces, and fully soaked and washed three times with deionized water. It was vacuum dried at 60°C for 24 h to obtain PTP.

[0107] 2) Synthesis of double bond functionalized main chain: PTP (1.2 g, 3.5 mmol) was added to 20 mL DMAC, stirred and reacted at 60 °C for 30 min, then an excess of 6-bromo-1-hexene (17.5 mmol, 2.85 g) and 0.01215 g of inhibitor HQ (mass fraction of 3‰) were added, and the reaction was carried out at 60 °C for 48 h. The product was then extracted with ethyl acetate, the precipitate was centrifuged, and the solid product was collected and dried under vacuum at 60 °C for 4 h to obtain a double bond functionalized aryl piperidine polymer main chain QPTP.

[0108] 3) Synthesis of double-bond functionalized dicationic crosslinker QDHP: 6-hydropyridine (HP, 0.85 g, 10 mmol), K2CO3 (2 g, 15 mmol) and acetonitrile (8 mL) were stirred and mixed at 70°C, and then acetonitrile (8 mL) and 1,6-dibromohexane (1.22 g, 5 mmol) were mixed and added dropwise to the above solution. The reaction was stirred at 70°C for 48 h. The resulting solution was poured into deionized water and extracted with ethyl acetate. The organic phase was collected, dried over MgSO4, and concentrated on a rotary evaporator to obtain a yellow DHP liquid. Excess 6-bromo-1-hexene (20 mmol, 3.26 g) was dissolved in 15 mL of acetonitrile, and 0.0098 g of inhibitor HQ (mass fraction of 3‰) was added to obtain a reaction solution; then DHP (2.5 mmol, 0.63 g) was dissolved in 8 mL of acetonitrile and added dropwise to the above reaction solution, and the reaction was carried out at 60°C for 24 h. After the reaction was completed, the mixture was precipitated and washed in ether, and vacuum dried for 24 h to obtain white QDHP powder.

[0109] 4) Preparation of polycationic photo-crosslinked polyaryl piperidine anion exchange membrane: In a light-proof environment, 0.5g QPTP and 0.097g crosslinker QDHP were added to 5mL DMAC (the amount of QDHP was calculated based on the designed crosslinker molar dose of 40%), and the mixture was stirred for 1h until it was completely dissolved to obtain a mixed solution. Then, 3% of the mass fraction of 907 photoinitiator was dissolved in 3mL DMAC and added dropwise to the above mixed solution, stirred for 2h, and then dropped into a PTFE mold, placed in a 60°C oven and dried in a vacuum at 60°C for 1h, and finally placed in a UV curing instrument for curing for 40s to obtain a light yellow film. The prepared membrane was then immersed in a 1M NaOH solution for 48h to obtain an OH-type membrane, and washed with deionized water 3 times to obtain a polycationic photo-crosslinked polyaryl piperidine anion exchange membrane, denoted as QPTP-QDHP-40%, with the following structure:

[0110]

[0111] Example 8

[0112] 1) Synthesis of the main chain: Under a nitrogen atmosphere, m-terphenyl (1.16 g, 5 mmol) and N-methyl-4-piperidone (0.68 g, 6 mmol) were added to 5 mL of dichloromethane and stirred at 0°C for 10 min. After complete dissolution, 0.45 mL of TFA and 4 mL of TFSA were added dropwise in sequence. After reacting for 4 h, the obtained viscous solution was poured into a 1 mol / L NaOH solution. After stirring and soaking for 15 min, the precipitated block polymer solid was taken out, cut into pieces, and fully soaked and washed three times with deionized water. It was vacuum dried at 60°C for 24 h to obtain PmTP.

[0113] 2) Synthesis of double bond functionalized main chain: (1.2 g, 3.5 mmol) PmTP was added to 20 mL DMF and stirred at 60 °C for 30 min. Then, an excess of 6-bromo-1-hexene (21 mmol, 3.42 g) and 0.01386 g of inhibitor (HQ) hydroquinone (mass fraction of 3‰) were added, and the reaction was carried out at 60 °C for 48 h. The product was then extracted with butyl acetate, the precipitate was centrifuged, and the solid product was collected and dried under vacuum at 60 °C for 4 h to obtain a double bond functionalized aromatic piperidine polymer main chain QPmTP.

[0114] 3) Synthesis of dicationic crosslinker QDMP: 4-methylpiperidine (MP, 1.0 g, 10 mmol), Na2CO3 (1.59 g, 15 mmol) and acetonitrile (8 mL) were stirred and mixed at 70°C, and then acetonitrile (8 mL) and 1,6-dibromohexane (1.22 g, 5 mmol) were mixed and added dropwise to the above solution. The reaction was stirred at 70°C for 48 h. The resulting solution was poured into deionized water and extracted with butyl acetate. The organic phase was collected, dried over MgSO4, and concentrated on a rotary evaporator to obtain a yellow DMP liquid. Excess 6-bromo-1-hexene (22.5 mmol, 3.67 g) was dissolved in 15 mL of tetrahydrofuran, and 0.01101 g of inhibitor hydroquinone (mass fraction of 3‰) was added to obtain a reaction solution; DMP (2.5 mmol, 0.70 g) was dissolved in 8 mL of acetonitrile and added dropwise to the above reaction solution, and the mixture was reacted at 60°C for 24 h. After the reaction was completed, the mixture was precipitated and washed in ether, and vacuum dried for 24 h to obtain a light pink QDMP powder.

[0115] 4) Preparation of polycationic photo-crosslinked polyaryl piperidine anion exchange membrane: In a light-proof environment, 0.5g QPmTP and 0.158g crosslinker QDMP were added to 5mL DMF (the amount of QDMP was calculated based on the designed crosslinker molar dose of 60%), and the mixture was stirred for 1h until it was completely dissolved to obtain a mixed solution. Then, 3% of the mass fraction of 1173 photoinitiator was dissolved in 3mL DMF and added dropwise to the above mixed solution, stirred for 2h, and then dropped into a PTFE mold, placed in a 60°C oven and dried in a vacuum for 1h away from light, and finally placed in a UV curing instrument for curing for 40s to obtain a light yellow film. The prepared membrane was then immersed in a 1M NaOH solution for 48h to obtain an OH-type membrane, which was washed 3 times with deionized water to obtain a polycationic photo-crosslinked polyaryl piperidine anion exchange membrane, denoted as QPmTP-QDMP-60%, with the following structure:

[0116]

[0117] Example 9

[0118] 1) Synthesis of the main chain: Under a nitrogen atmosphere, p-quaterphenyl (1.53 g, 5 mmol) and N-methyl-4-piperidone (0.68 g, 6 mmol) were added to 5 mL of dichloromethane and stirred at 0°C for 10 min. After complete dissolution, 0.45 mL of TFA and 4 mL of TFSA were added dropwise in sequence. After reacting for 4 h, the obtained viscous solution was poured into a 1 mol / L NaOH solution. After stirring and soaking for 15 min, the precipitated block polymer solid was taken out, cut into pieces, and fully soaked and washed three times with deionized water. It was vacuum dried at 60°C for 24 h to obtain PQuP.

[0119] 2) Synthesis of double bond functionalized main chain: PQuP (1.2 g, 2.9 mmol) was added to 20 mL of cyclohexane sulfone, and the mixture was stirred at 60 °C for 30 min. Then, an excess of 6-bromo-1-hexene (20.3 mmol, 3.31 g) and 0.01353 g of inhibitor BHT (mass fraction of 3‰) were added, and the mixture was reacted at 60 °C for 48 h. The product was then extracted with ethyl acetate, the precipitate was centrifuged, and the solid product was collected and dried under vacuum at 60 °C for 4 h to obtain a double bond functionalized aryl piperidine polymer main chain QPQuP.

[0120] 3) Synthesis of dicationic crosslinker QDMiM: 2-methylimidazole (MiM, 0.82 g, 10 mmol), K2CO3 (2 g, 15 mmol) and acetonitrile (8 mL) were stirred and mixed at 70°C, then acetonitrile (8 mL) and 1,6-dibromohexane (1.22 g, 5 mmol) were mixed and added dropwise to the above solution, and the reaction was stirred at 70°C for 48 h. The resulting solution was poured into deionized water and extracted with chloroform. The organic phase was collected, dried over MgSO4, and concentrated on a rotary evaporator to obtain DMiM. Excess 6-bromo-1-hexene (25 mmol, 4.08 g) was dissolved in 15 mL of acetonitrile, and 0.01224 g of inhibitor 2,6-di-tert-butyl-p-cresol BHT (mass fraction of 3‰) was added to obtain a reaction solution; then DMiP (2.5 mmol, 0.616 g) was dissolved in 8 mL of acetonitrile and added dropwise to the above reaction solution, and the reaction was carried out at 60°C for 24 h. After the reaction was completed, the mixture was precipitated and washed in ethyl acetate, and vacuum dried for 24 h to obtain QDMiM powder.

[0121] 4) Preparation of polycationic photo-crosslinked polyaryl piperidine anion exchange membrane: In a light-proof environment, 0.5g QPQuP and 0.042g crosslinker QDMiM were added to 5mL sulfolane (the amount of QDMiM was calculated based on the designed crosslinker molar dosage of 20%), stirred for 1h to completely dissolve, and a mixed solution was obtained. Then, 3% of ITX photoinitiator was dissolved in 3mL sulfolane and added dropwise to the mixed solution, stirred for 2h, and then dropped into a PTFE mold, placed in a 60°C oven and dried in a vacuum oven for 1h, and finally placed in a UV curing instrument for curing for 40s to obtain a light yellow film. The prepared membrane was then immersed in a 1M NaOH solution for 48h to obtain an OH-type membrane, which was washed 3 times with deionized water to obtain a polycationic photo-crosslinked polyaryl piperidine anion exchange membrane, denoted as QPQuP-QDMiM-20%, with the following structure:

[0122]

[0123] Comparative Example

[0124] The polyarylpiperidine membrane PBP prepared according to the literature (Olsson J S., et al, Adv. Funct. Mater. 2017, 1702758) has the following structure:

[0125] Total reflection infrared spectra of multi-cationic photocrosslinked polyarylpiperidine anion exchange membranes prepared with different contents of dicationic crosslinkers are shown in Figure 2 , it can be seen that 3403cm -1 The infrared absorption broad peak is the absorption vibration peak of water molecules, 1643cm -1The peaks at 1010cm can be attributed to the vibration absorption peak of the benzene ring skeleton and the stretching vibration peak of C=C. -1 The infrared absorption peak is the stretching vibration peak of CN on the piperidine salt, and the peak at 1456 cm -1 The characteristic absorption peak of quaternary ammonium salt (CH3-N) appears at 910 cm -1 The vibration absorption peak of the CH=CH2 group disappeared, indicating that the UV cross-linking was successful.

[0126] The OH- conductivity of multi-cationic photocrosslinked polyarylpiperidine anion exchange membranes prepared with different contents of dicationic crosslinkers is shown in Figure 3 It can be seen that the multi-cationic photo-crosslinked polyaryl piperidine anion exchange membrane prepared by the present invention has good ion conductivity.

[0127] The mechanical properties of multi-cationic photocrosslinked polyarylpiperidine anion exchange membranes prepared with different contents of dicationic crosslinkers are shown in Figure 4 It can be seen that the room temperature tensile strength of the multi-cationic photo-crosslinked polyaryl piperidine anion exchange membranes prepared in Examples 1 to 5 are all higher than 17 MPa, among which the multi-cationic photo-crosslinked polyaryl piperidine anion exchange membrane prepared in Example 4 has the highest tensile strength of 42.93 MPa.

[0128] The ion exchange capacity, water absorption rate and swelling degree of the multi-cationic photo-crosslinked polyaryl piperidine anion exchange membrane (AEM with different contents of dicationic crosslinking agent) prepared with different contents of dicationic crosslinking agent are shown in Table 1.

[0129] Table 1 Ion exchange capacity, water absorption and swelling degree of dicationic crosslinker AEM with different contents

[0130]

[0131] As can be seen from Table 1, the water absorption and swelling degree of the uncrosslinked film prepared in the comparative example are as high as 162% and 47%, while the water absorption and swelling degree of the polycationic photo-crosslinked polyaryl piperidine anion exchange membrane after ultraviolet light crosslinking are significantly reduced. Among them, the polycationic photo-crosslinked polyaryl piperidine anion exchange membrane prepared in Example 5 has a higher ion exchange capacity (1.914mmol / g), while maintaining a lower water absorption and swelling degree, which are 7.4% and 1.67% respectively. The water absorption and swelling of other crosslinked embodiments are greatly reduced compared with the comparative example. In addition, the water absorption and swelling of the membrane can reflect its dimensional stability. It can be seen from the above data that the polycationic photo-crosslinked polyaryl piperidine anion exchange membrane prepared by the present invention has good dimensional stability.

[0132] In summary, the multi-cationic photo-crosslinked polyaryl piperidine anion exchange membrane of the present invention has both good ionic conductivity and excellent dimensional stability, and can be formed by an energy-saving and environmentally friendly photocuring method, which greatly reduces the curing time and has good application prospects.

[0133] The above are only preferred specific implementations of the present application, but the protection scope of the present application is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed in the present application should be included in the protection scope of the present application. Therefore, the protection scope of the present application should be based on the protection scope of the claims.

Claims

1. A multi-cation photo-crosslinked polyarylpiperidine anion exchange membrane, characterized in that: The structure of the multi-cationic photo-crosslinked polyaryl piperidine anion exchange membrane is as follows: Wherein, Ar is any one of the following monomers: R is any of the following structures: X represents the molar content of the double-bond functionalized dicationic crosslinking agent, and the value is 20 to 80%.

2. The multi-cation photo-crosslinked polyarylpiperidine anion exchange membrane according to claim 1, characterized in that: The value of X is 20%, 40%, 60% or 80%.

3. A method for preparing the multi-cationic photo-crosslinked polyarylpiperidine anion exchange membrane according to any one of claims 1 to 2, characterized in that: The following steps are involved: In a nitrogen atmosphere, a benzene ring-containing aromatic monomer and a piperidone monomer are dissolved in dichloromethane, and a viscous liquid is obtained after a low-temperature reaction, and an aromatic piperidine polymer is obtained by precipitation and washing; The polyaryl piperidine polymer is dissolved in solvent A, stirred and reacted at 50-90° C. for 15-45 minutes, then an excess of 6-bromo-1-hexene and an excess of a polymerization inhibitor are added, reacted at 50-90° C. for 24-48 hours, then the product is extracted with ethyl acetate, the precipitate is centrifuged and dried to obtain a double-bond functionalized polyaryl piperidine; In a light-proof environment, the double-bond functionalized polyaryl piperidine and the cross-linking agent are added to the solvent A, stirred evenly to obtain a mixed solution, and then the photoinitiator is dissolved in the solvent A and then added dropwise to the mixed solution, stirred evenly, and then dropped into a mold, vacuum dried, and photocured to obtain a light yellow film, and then the light yellow film is immersed in a NaOH solution to obtain an OH-type membrane, and washed to obtain a multi-cationic photo-cross-linked polyaryl piperidine anion exchange membrane.

4. The method for preparing a multi-cationic photo-crosslinked polyarylpiperidine anion exchange membrane according to claim 3, characterized in that: The solvent A is at least one of N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylacetamide, N,N-dimethylformamide and sulfolane.

5. The method for preparing a multi-cationic photo-crosslinked polyarylpiperidine anion exchange membrane according to claim 3, characterized in that: The molar ratio of the polyaryl piperidine to the 6-bromo-1-hexene is 1:(1.5-20); the molar ratio of the cross-linking agent to the 6-bromo-1-hexene is 1:(5-20).

6. The method for preparing a multi-cationic photo-crosslinked polyarylpiperidine anion exchange membrane according to claim 3, characterized in that: The polymerization inhibitor is at least one of hydroquinone, 4-methoxyphenol and 2,6-di-tert-butyl-p-cresol; The photoinitiator is at least one of TPO, 184, 1173, 819, ITX and 907.

7. The method for preparing a multi-cationic photo-crosslinked polyarylpiperidine anion exchange membrane according to claim 3, characterized in that: The cross-linking agent is a double-bond functionalized dicationic cross-linking agent, and the preparation method is as follows: 1,6-dibromohexane and a secondary amine compound are dissolved in acetonitrile, and an alkaline reagent B is added, and the reaction is carried out at 50 to 80° C. for 24 to 48 hours. After the reaction is completed, water is added, and the mixture is extracted with a solvent C, and then anhydrous magnesium sulfate is added for drying. Finally, the solvent is evaporated and concentrated to obtain a cross-linking agent containing a tertiary amine group. 6-bromo-1-hexene and the cross-linking agent containing tertiary amine group or N 1 ,N 1 ,N 6 ,N 6 -Tetramethyl-1,6-hexanediamine is dissolved in solvent D, an inhibitor is added, and the reaction is stirred at 50-90°C for 24-48 hours. After the reaction is completed, the product is extracted and washed with solvent E, and the solid product is vacuum dried to obtain a double-bond functionalized dicationic crosslinker.

8. The method for preparing a multi-cationic photo-crosslinked polyarylpiperidine anion exchange membrane according to claim 7, characterized in that: The secondary amine compound is piperidine, 4-methylpiperidine or 2-methylimidazole.

9. The method for preparing a multi-cationic photo-crosslinked polyarylpiperidine anion exchange membrane according to claim 7, characterized in that: The alkaline reagent B is one of sodium carbonate and potassium carbonate; The solvent C is at least one of ethyl acetate, butyl acetate and chloroform; The solvent D is at least one of methanol, ethanol, acetonitrile and tetrahydrofuran; The solvent E is at least one of petroleum ether, ethyl ether and ethyl acetate.

10. Use of the multi-cationic photo-crosslinked polyaryl piperidine anion exchange membrane according to any one of claims 1 to 2 in the preparation of an alkaline anion exchange membrane fuel cell.

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