An oxygen-containing fluorene polyarylpiperidine anion exchange membrane and a preparation method thereof

Abstract

The application belongs to the technical field of anion exchange membranes, and discloses an oxygen-containing fluorene polyarylpiperidine type anion exchange membrane and a preparation method thereof. A piperidine type trimonomer polymer with good alkali stability and mechanical properties is synthesized, the main chain structure of the polymer is controlled by controlling the feeding proportion of monomers, the polymer is reacted with iodomethane to obtain a quaternary ammonium polymer, and the quaternary ammonium polymer is used for casting a film. The prepared membrane has good dimensional stability and good ion conductivity, has good alkali stability and mechanical strength, and can be applied to alkaline fuel cells and alkaline water electrolysis.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of alkaline anion exchange membranes, and relates to an oxygen-containing fluorene polyaryl piperidine type anion exchange membrane and a preparation method thereof. BACKGROUND

[0002] With the overexploitation and large consumption of fossil energy, the crisis of energy shortage and environmental deterioration is increasingly prominent. Therefore, it is necessary and urgent to find clean and sustainable energy. At present, traditional clean energy such as wind energy, solar energy and tidal energy has been put into use in various industries. However, these clean energy is limited by natural conditions and cannot provide stable energy output, nor can it be directly used by people. Compared with traditional fossil energy and conventional clean energy, hydrogen energy is an ideal alternative energy. Hydrogen energy has the advantages of good combustion performance, high heat value, various storage forms and high utilization rate. Combining fuel cells and hydrogen energy can provide sustainable energy to the outside under the premise of green and pollution-free. In addition, hydrogen can be obtained by electrolysis of water, and only electrical energy is consumed in the whole process, and the purity of obtained hydrogen is as high as 99.99%. Fuel cells and water electrolysis ensure the advantages of pollution-free source and use process of hydrogen.

[0003] Anion exchange membrane is the core component of anion exchange membrane fuel cell and anion exchange membrane water electrolysis, and its performance determines the performance and service life of the fuel cell and the water electrolysis. Anion exchange membrane is usually prepared from a polymer containing cationic groups, which plays a role in transferring hydroxyl ions and separating materials of the anode and the cathode. According to the working requirements of fuel cells and water electrolysis, the anion exchange membrane not only needs to have excellent ability to transfer hydroxyl ions, but also needs to maintain stable performance in alkaline environment. At present, by learning from the successful experience of proton exchange membrane, similar engineering plastics such as polyether sulfone and polyether ether ketone are usually used as the main chain of anion exchange membrane, but these polymers will degrade in alkaline environment, resulting in the decrease of ion conductivity of anion exchange membrane and the loss of mechanical strength. At the same time, the problems such as low monomer reactivity, poor dimensional stability and high synthesis price further limit the commercialization of anion exchange membrane. It is pointed out in the paper “Comb-shaped ether-free poly(biphenyl indole)based alkaline membrane” by Wang Kai-feng et al. that aromatic polymers containing ether bonds, such as polysulfone, are synthesized from typical copolymers of dihalides and dihydroxy monomers, and are most commonly used as the polymer backbone of alkaline membranes because of their advantages of easy functionalization and good mechanical properties. However, due to the presence of ether bonds, the stability of these polymer backbones in alkaline environment is poor, especially when quaternary ammonium is connected to the polymer backbone through a benzyl group. Therefore, it is one of the current focuses to find a polymer with good alkaline stability and high electrical conductivity. SUMMARY

[0004] The present application aims to improve the dimensional stability, alkaline stability and hydroxyl ion transfer performance of the basic anion exchange membrane, improve the reaction activity, and reduce the preparation cost. A preparation method of an oxygen-containing fluorene polyaryl piperidine type anion exchange membrane with low catalyst dosage is provided, so that there is no strong electron-withdrawing group and benzyl ammonium group in the main chain, a piperidine type trimonomer polymer with good alkaline stability and mechanical properties is synthesized, the main chain structure of the polymer is controlled by controlling the feeding ratio of the monomers, then the quaternary ammonium polymer is obtained by reacting the polymer with iodomethane, and the quaternary ammonium polymer is used for casting film. The prepared membrane has good dimensional stability and good ion conductivity, and can be used in alkaline fuel cells and water electrolysis.

[0005] The technical scheme of the present application is as follows:

[0006] An oxygen-containing fluorene polyaryl piperidine type anion exchange membrane has the following structure:

[0007]

[0008] The structure of Ar is as follows:

[0009]

[0010] Wherein x=0.15-0.35.

[0011] A preparation method of an oxygen-containing fluorene polyaryl piperidine type anion exchange membrane, the steps are as follows:

[0012] (1) Synthesis of oxygen-containing fluorene polyaryl piperidine type trimonomer polymer: dissolve oxygen fluorene in dichloromethane, after dissolving, add N-methyl-4 piperidone and aryl monomer, drop trifluoroacetic acid and trifluoromethanesulfonic acid under ice bath, remove the ice bath after 30 min, react at room temperature for 3 hours to obtain a black viscous solution, then pour the solution into solvent A for precipitation, finally wash with deionized water until neutral, dry to obtain the trimonomer polymer;

[0013] The molar concentration of N-methyl-4 piperidone in dichloromethane is 1-1.3 mol / L;

[0014] The molar ratio of N-methyl-4 piperidone: oxygen fluorene: aryl monomer is 1:0-0.35:1-0.65;

[0015] The molar ratio of N-methyl-4 piperidone to trifluoromethanesulfonic acid is 1:6-9;

[0016] The molar ratio of N-methyl-4 piperidone to trifluoroacetic acid is 1:0.8-1;

[0017] The solvent A is methanol, ethanol, water;

[0018] (2) Quaternary ammonium polymer preparation: the trimer polymer is dissolved in solvent B, potassium carbonate is added after dissolution, iodomethane is added after stirring uniformly, and the reaction is carried out at 40℃ for a period of time in the dark; the solution after the reaction is finished is centrifuged, and after removing the potassium carbonate, it is poured into solvent C to precipitate, and finally washed with solvent C, filtered and dried to obtain the quaternary ammonium polymer;

[0019] The molar ratio of the trimer polymer: iodomethane: potassium carbonate is 1:2:1-1.5;

[0020] The solvent B is N-methylpyrrolidone or dimethyl sulfoxide;

[0021] The mass concentration of the trimer polymer in the solvent B is 0.03-0.05 g / mL;

[0022] The precipitating agent C is acetone, ethyl acetate or diethyl ether;

[0023] The light-proof reaction time is 36-48 h;

[0024] (3) Preparation of anion exchange membrane containing oxygen fluorene polyaryl piperidine: the quaternary ammonium polymer is dissolved in solvent D, and after dissolution, the casting solution is obtained by removing impurities by centrifugation; the casting solution is cast on a glass plate, and dried at a certain temperature to form a film; the film is soaked in 1 mol / L potassium hydroxide solution for 24-48 h, and then soaked in deionized water until neutral, to obtain an anion exchange membrane containing oxygen fluorene polyaryl piperidine;

[0025] The solvent D is N-methylpyrrolidone, dimethyl sulfoxide or N,N dimethylformamide;

[0026] The mass concentration of the casting solution is 0.015-0.025 g / mL;

[0027] The drying temperature of the film formed by the casting method is 60-80℃, and the time is 24 hours.

[0028] The drying condition in step (1) is: temperature is 60-70℃, and time is 24-36 hours.

[0029] The drying condition in step (2) is: temperature is 60-70℃, and time is more than 24 hours.

[0030] The beneficial effects of the present application are:

[0031] (1) By using high-activity reaction monomers, the reaction activity can be improved, the catalyst usage can be reduced, and the cost can be reduced.

[0032] (2) The introduction of oxygen fluorene monomers can effectively control the water absorption performance of the polymer, improve the electrical conductivity, and maintain excellent mechanical properties.

[0033] (3) By adjusting the ratio of fluorene monomers to aryl monomers, the rigidity of the polymer can be increased, thereby increasing its mechanical strength. Detailed Implementation

[0034] The present invention will be further described in detail below with reference to specific implementation examples, but the implementation of the present invention is not limited thereto.

[0035] Example 1

[0036] Synthesis of ether-piperidine-containing polymers: 1.38 g (6 mmol) of p-terphenyl was added to a 50 mL three-necked flask, followed by 6.5 mL of dichloromethane solution, then 0.905 g (8 mmol) of N-methyl-4-piperidinone and 0.34 g (2 mmol) of oxyfluorene. After mechanical stirring for a period of time, 0.6 mL (8 mmol) of trifluoroacetic acid and 4.32 mL (48 mmol) of trifluoromethanesulfonic acid were slowly added under ice bath conditions. After 30 min, the ice bath was removed, and the reaction system temperature was gradually raised to room temperature. When the reaction solution became highly viscous, the reaction solution was poured into methanol to precipitate the crude polymer, which was then washed with deionized water until neutral and dried at 60 °C for 24 h to obtain the three-monomer polymer material.

[0037] Preparation of quaternized anion exchange membrane: 1 g (2.92 mmol) of polymer material was weighed and added to a 50 mL single-necked flask, followed by 20 mL of DMSO. After dissolution, 0.605 g (4.39 mmol) of potassium carbonate and 0.829 g (5.84 mmol) of iodomethane were added. The mixture was reacted at 40 °C in the dark for approximately 48 h. After the reaction, the resulting solution was poured into ethyl acetate to precipitate a solid powder product. After filtration and drying, the product was washed repeatedly with deionized water to remove unreacted salts. The product was then dried at 60 °C for 24 h to obtain the quaternized polymer. 0.08 g of the quaternized polymer was weighed and dissolved in 5 mL of DMSO. The casting solution was centrifuged and cast into a glass mold. The membrane was dried at 60 °C for 48 h to obtain the polymer membrane. The polymer membrane was then immersed in a 1 mol / L KOH solution at room temperature for 24 h, followed by repeated washing and immersion in deionized water for 24 h until neutral to obtain the oxygen-containing fluorene polyarylpiperidine anion exchange membrane.

[0038] Tests showed that the quaternized piperidine anion exchange membrane prepared in this embodiment had an ion conductivity of 134.21 mS / cm at 80°C. -1 The membrane exhibits a water absorption rate of 70%, a swelling degree of 23%, and after immersion in a 1 mol / L NaOH solution at 80℃ for 1000 h, the conductivity retention rate is greater than 90%, and the dry membrane tensile strength is 45.75 MPa. The membrane demonstrates good mechanical strength and alkaline stability. When assembled into an alkaline fuel cell for testing, the maximum output power at 80℃ is 1.2 W / cm². 2. In the alkaline electrolysis water cell, the current reached 1 A / cm2at 50 °C and 2 V voltage 2 .

[0039] The structure of the anion exchange membrane obtained in this example is as follows:

[0040]

[0041] Example 2

[0042] Synthesis of ether-containing piperidine-type polymer: 0.8 g (5.2 mmol) of biphenyl was added to a 50 mL three-necked flask, followed by 5 mL of dichloromethane solution, then 0.905 g (8 mmol) of N-methyl-4-piperidone and 0.47 g (2.8 mmol) of oxadiazole were added, and after mechanical stirring for a period of time, 0.6 mL (8 mmol) of trifluoroacetic acid and 4.32 mL (48 mmol) of triflic acid were slowly added under ice bath conditions. After 30 min, the ice bath was removed and the temperature of the reaction system gradually rose to room temperature. When the reaction solution became highly viscous, the reaction solution was poured into methanol to precipitate the crude polymer, which was then washed with deionized water until neutral and dried at 60 °C for 24 h to obtain a trimer polymer material.

[0043] Preparation of quaternized anion exchange membrane: 1 g (3.51 mmol) of polymer material was weighed into a 50 mL single-necked flask, followed by 20 mL of DMSO, and after dissolution, 0.726 g (5.27 mmol) of potassium carbonate and 0.99 g (7 mmol) of iodomethane were added. The reaction was carried out at 40 °C for about 48 h in the dark. After the reaction was completed, the obtained solution was poured into ethyl acetate to precipitate the solid powder product, which was filtered and dried, and then washed with deionized water several times to remove unreacted salt. The quaternized polymer was dried at 60 °C for 24 h. 0.1 g of the quaternized polymer was dissolved in 5 mL of DMSO, centrifuged, and then cast into a glass mold. The polymer membrane was dried at 60 °C for 48 h, and then soaked in a 1 mol / L KOH solution at room temperature for 24 h. The polymer membrane was then repeatedly washed and soaked in deionized water for 24 h until neutral, to obtain an oxadiazole-containing polyarylpiperidine-type anion exchange membrane.

[0044] Tests showed that the quaternized piperidine-type anion exchange membrane prepared in this example had an ionic conductivity of 121 mS cm -1 at 80 °C, a water absorption of 135%, a swelling degree of 33%, a conductivity retention rate of more than 88% after being soaked in a 1 mol / L NaOH solution at 80 °C for 1000 h, and a dry film tensile strength of 32 MPa. The membrane showed good mechanical strength and alkaline stability. When the membrane was assembled into an alkaline fuel cell and tested, the maximum output power was 0.7 W / cm 2Tests were conducted in an alkaline water electrolysis battery, and at 50°C and 2V, the current reached 0.8A / cm². 2 .

[0045] The structure of the anion exchange membrane obtained in this example is as follows:

[0046]

[0047] Example 3

[0048] Synthesis of ether-piperidine-containing polymers: 1.17 g (6 mmol) of 9,9-dimethylfluorene was added to a 50 mL three-necked flask, followed by 6 mL of dichloromethane solution, then 0.905 g (8 mmol) of N-methyl-4-piperidinone and 0.34 g (2 mmol) of oxyfluorene. After mechanical stirring for a period of time, 0.6 mL (8 mmol) of trifluoroacetic acid and 5.4 mL (60 mmol) of trifluoromethanesulfonic acid were slowly added under ice bath conditions. After 30 min, the ice bath was removed, and the reaction system temperature was gradually raised to room temperature. When the reaction solution became highly viscous, the reaction solution was poured into methanol to precipitate the crude polymer, which was then washed with deionized water until neutral and dried at 60 °C for 24 h to obtain the three-monomer polymer material.

[0049] Preparation of quaternized anion exchange membrane: 1 g (3.17 mmol) of polymer material was weighed and added to a 50 mL single-necked flask, followed by 20 mL of DMSO. After dissolution, 0.656 g (4.755 mmol) of potassium carbonate and 0.9 g (6.34 mmol) of iodomethane were added. The mixture was reacted at 40 °C in the dark for approximately 48 h. After the reaction, the resulting solution was poured into ethyl acetate to precipitate a solid powder product. The product was filtered, dried, and washed repeatedly with deionized water to remove unreacted salts. The product was then dried at 60 °C for 24 h to obtain the quaternized polymer. 0.08 g of the quaternized polymer was weighed and dissolved in 5 mL of DMSO. The casting solution was centrifuged and cast into a glass mold. The membrane was dried at 60 °C for 48 h to obtain the polymer membrane. The polymer membrane was then immersed in a 1 mol / L KOH solution at room temperature for 24 h, followed by repeated washing and immersion in deionized water for 24 h until neutral to obtain the oxygen-containing fluorene polyarylpiperidine anion exchange membrane.

[0050] Tests showed that the quaternized piperidine anion exchange membrane prepared in this embodiment has an ion conductivity of 10⁶ mS / cm at 80°C. -1 The membrane exhibits a water absorption rate of 62%, a swelling degree of 19%, and after immersion in a 1 mol / L NaOH solution at 80℃ for 1000 h, a conductivity retention rate greater than 85%, and a dry membrane tensile strength of 47 MPa. The membrane demonstrates good mechanical strength and alkaline stability. When assembled into an alkaline fuel cell for testing, the maximum output power at 80℃ was 0.6 W / cm². 2. The test was carried out in an alkaline electrolysis water cell, and the current reached 0.7 A / cm2at 50 °C and 2 V voltage 2 .

[0051] The structure of the anion exchange membrane obtained in this example is as follows:

[0052]

[0053] Example 4

[0054] Synthesis of ether-containing piperidine-type polymer: 1.14 g (6.8 mmol) of diphenylmethane was added to a 50 mL three-necked flask, followed by 6.5 mL of dichloromethane solution, then 0.905 g (8 mmol) of N-methyl-4-piperidone and 0.2 g (1.2 mmol) of oxadiazole were added, and after mechanical stirring for a period of time, 0.6 mL (8 mmol) of trifluoroacetic acid and 4.32 mL (48 mmol) of triflic acid were slowly added under ice bath conditions. After 30 min, the ice bath was removed and the temperature of the reaction system gradually rose to room temperature. When the reaction solution became highly viscous, the reaction solution was poured into methanol to precipitate the crude polymer, which was then washed with deionized water until neutral and dried at 60 °C for 24 h to obtain a trimer polymer material.

[0055] Preparation of quaternary ammonium anion exchange membrane: 1 g (3.38 mmol) of polymer material was weighed into a 50 mL single-necked flask, followed by 20 mL of DMSO, and after dissolution, 0.7 g (5.07 mmol) of potassium carbonate and 0.9538 g (6.72 mmol) of iodomethane were added. The reaction was carried out at 40 °C for about 48 h in the dark. After the reaction was completed, the obtained solution was poured into ethyl acetate to precipitate the solid powder product, which was filtered and dried, and then washed with deionized water several times to remove unreacted salt. The quaternary ammonium polymer was obtained by drying at 60 °C for 24 h. 0.08 g of the quaternary ammonium polymer was dissolved in 5 mL of DMSO, and the casting solution was centrifuged and cast into a glass mold. The polymer membrane was dried at 60 °C for 48 h, and then soaked in a 1 mol / L KOH solution at room temperature for 24 h. The membrane was then repeatedly washed and soaked in deionized water for 24 h until neutral, to obtain an oxadiazole-containing polyarylpiperidine-type anion exchange membrane.

[0056] Tests showed that the quaternary ammonium piperidine-type anion exchange membrane prepared in this example had an ionic conductivity of 126 mS cm -1 , a water absorption of 124%, a swelling degree of 31%, a conductivity retention rate of more than 91% after soaking in a 1 mol / L NaOH solution at 80 °C for 1000 h, and a dry film tensile strength of 26.5 MPa. The membrane showed good mechanical strength and alkaline stability. The membrane was assembled into an alkaline fuel cell and tested, and the maximum output power was 0.75 W / cm 2. The test was carried out in an alkaline electrolysis water cell, and the current reached 0.82 A / cm2at 50°C and 2V voltage 2 .

[0057] The structure of the anion exchange membrane obtained in this example is as follows:

[0058]

[0059] Example 5

[0060] Synthesis of ether-containing piperidine-type polymer: 1.09 g (6 mmol) of 1,2-diphenyl ethane was added to a 50 mL three-necked flask, then 6 mL of dichloromethane solution was added, followed by 0.905 g (8 mmol) of N-methyl-4-piperidone and 0.34 g (2 mmol) of oxadiazole. After mechanical stirring for a period of time, 0.6 mL (8 mmol) of trifluoroacetic acid and 4.32 mL (48 mmol) of triflic acid were slowly added under ice bath conditions. After 30 min, the ice bath was removed and the temperature of the reaction system gradually rose to room temperature. When the reaction solution became highly viscous, the reaction solution was poured into methanol to precipitate the crude polymer, which was then washed with deionized water until neutral and dried at 60°C for 24 h to obtain a trimer polymer material.

[0061] Preparation of quaternized anion exchange membrane: 1 g (3.27 mmol) of polymer material was weighed into a 50 mL single-necked flask, then 20 mL of DMSO was added, followed by 0.68 g (4.9 mmol) of potassium carbonate and 0.93 g (6.54 mmol) of iodomethane after dissolution. The reaction was carried out at 40°C for about 48 h in the dark. After the reaction was completed, the obtained solution was poured into ethyl acetate to precipitate the solid powder product. After filtration and drying, the unreacted salt was removed by washing with deionized water several times, and the quaternized polymer was dried at 60°C for 24 h. 0.08 g of the quaternized polymer was dissolved in 5 mL of DMSO, centrifuged, and then cast into a glass mold. The polymer membrane was dried at 60°C for 48 h, and then soaked in a 1 mol / L KOH solution at room temperature for 48 h. After repeated washing and soaking in deionized water for 48 h until neutral, the oxygen-containing oxadiazole-containing polyarylpiperidine-type anion exchange membrane was obtained.

[0062] Tests showed that the quaternized piperidine-type anion exchange membrane prepared in this example had an ionic conductivity of 130 mS cm -1 at 80°C, a water absorption of 140%, a swelling degree of 37%, a conductivity retention rate of more than 91% after soaking in a 1 mol / L NaOH solution at 80°C for 1000 h, a dry film tensile strength of 25.8 MPa, and the membrane exhibited good mechanical strength and alkaline stability. The membrane was assembled into an alkaline fuel cell and tested, and the maximum output power was 1 W / cm 2. The test was carried out in an alkaline electrolysis water cell, and the current reached 0.94 A / cm2at 50°C and 2V voltage 2 .

[0063] The structure of the anion exchange membrane obtained in this example is as follows:

[0064]

[0065] Example 6

[0066] Synthesis of ether-containing piperidine-type polymer: 1.17 g (6 mmol) of N-ethylcarbazole was added to a 50 mL three-necked flask, followed by 6.5 mL of dichloromethane solution, then 0.905 g (8 mmol) of N-methyl-4-piperidone and 0.34 g (2 mmol) of oxadiazole were added, and after mechanical stirring for a period of time, 0.6 mL (8 mmol) of trifluoroacetic acid was slowly added under ice bath conditions, and 5.4 mL (60 mmol) of triflic acid was added. After 30 min, the ice bath was removed, and the reaction system temperature gradually rose to room temperature. When the reaction solution became highly viscous, the reaction solution was poured into methanol to precipitate the crude polymer, which was then washed with deionized water until neutral, and dried at 60°C for 24 h to obtain a trimer polymer material.

[0067] Preparation of quaternary ammonium anion exchange membrane: 1 g (3.17 mmol) of polymer material was weighed into a 50 mL single-necked flask, followed by 20 mL of DMSO, and after dissolution, 0.656 g (4.75 mmol) of potassium carbonate and 0.9 g (6.34 mmol) of iodomethane were added. The reaction was carried out at 40°C for about 48 h in the dark, and after the reaction was completed, the obtained solution was poured into ethyl acetate to precipitate the solid powder product, which was filtered and dried, and then washed with deionized water several times to remove unreacted salt, and dried at 60°C for 24 h to obtain a quaternary ammonium polymer. 0.1 g of the quaternary ammonium polymer was dissolved in 5 mL of DMSO, and the casting solution was centrifuged and cast into a glass mold, and dried at 60°C for 48 h to obtain a polymer membrane. The polymer membrane was soaked in a 1 mol / L KOH solution at room temperature for 48 h, and then repeatedly washed and soaked in deionized water for 48 h until neutral, to obtain an oxadiazole-containing polyarylpiperidine-type anion exchange membrane.

[0068] Tests showed that the quaternary ammonium piperidine-type anion exchange membrane prepared in this example had an ionic conductivity of 110 mS cm -1 at 80°C, a water absorption of 62%, a swelling degree of 15.5%, a conductivity retention rate of more than 87% after being soaked in a 1 mol / L NaOH solution at 80°C for 1000 h, a dry film tensile strength of 39.47 MPa, and the membrane exhibited good mechanical strength and alkaline stability. The membrane was assembled into an alkaline fuel cell for testing, and the maximum output power was 0.73 W / cm 2In an alkaline electrolysis water cell, a current of 0.86 A / cm2was reached at 50°C at a voltage of 2 V 2 .

[0069] The structure of the anion exchange membrane obtained in this example is as follows:

[0070]

Claims

1. An anion exchange membrane of the oxy-dibenzofulvene polyarylpiperidine type, characterized in that, The structure of the oxygen-containing fluorene polyarylpiperidine type anion exchange membrane is as follows: ； The structure of Ar is as follows: ； x=0.15~0.35； The preparation method of the oxygen-containing fluorene polyarylpiperidine type anion exchange membrane comprises the following steps: (1) Synthesis of oxygen-containing fluorene polyarylpiperidine type trimonomer polymer: oxygen fluorene is dissolved in dichloromethane, N-methyl-4 piperidone and aryl monomer are added after dissolution, trifluoroacetic acid and trifluoromethanesulfonic acid are added dropwise under ice bath, the ice bath is removed after 30 min, a black viscous solution is obtained after reacting at room temperature for 3 hours, then the solution is poured into solvent A for precipitation, finally, the obtained product is washed with deionized water until neutral, and dried to obtain the trimonomer polymer; The molar concentration of the N-methyl-4 piperidone in dichloromethane is 1-1.3 mol / L; The molar ratio of the N-methyl-4 piperidone, oxygen fluorene and aryl monomer is 1:0-0.35:1-0.65; The molar ratio of the N-methyl-4 piperidone and trifluoromethanesulfonic acid is 1:6-9; The molar ratio of the N-methyl-4 piperidone and trifluoroacetic acid is 1:0.8-1; The solvent A is methanol, ethanol or water; (2) Preparation of quaternary ammonium polymer: the trimonomer polymer is dissolved in solvent B, potassium carbonate is added after dissolution, iodomethane is added after stirring uniformly, and the reaction is carried out at 40 °C for a period of time in the dark; the solution after the reaction is centrifuged, the potassium carbonate is removed, and then poured into solvent C for precipitation, finally, the obtained product is washed, filtered and dried to obtain the quaternary ammonium polymer; The molar ratio of the trimonomer polymer, iodomethane and potassium carbonate is 1:2:1-1.5; The solvent B is N-methyl pyrrolidone or dimethyl sulfoxide; The mass concentration of the trimonomer polymer in the solvent B is 0.03-0.05 g / mL; The precipitation agent C is acetone, ethyl acetate or diethyl ether; The light-proof reaction time is 36-48 h; (3) Preparation of the oxygen-containing fluorene polyarylpiperidine type anion exchange membrane: the quaternary ammonium polymer is dissolved in solvent D, the casting solution is obtained after removing impurities by centrifugation after dissolution; the casting solution is cast on a glass plate, and dried at a certain temperature to form a film; the film is soaked in 1 mol / L potassium hydroxide solution for 24-48 h, and then soaked in deionized water until neutral, to obtain the oxygen-containing fluorene polyarylpiperidine type anion exchange membrane; The solvent D is N-methyl pyrrolidone, dimethyl sulfoxide or N,N dimethylformamide; The mass concentration of the casting solution is 0.015-0.025 g / mL; The drying temperature of the film formed by the casting method is 60-80 °C, and the time is 24 hours.

2. The oxylfluorene polyarylpiperidine anion exchange membrane according to claim 1, characterized in that, The drying conditions in step (1) are as follows: the temperature is 60-70 °C, and the time is 24-36 hours.

3. The oxylfluorene polyarylpiperidine anion exchange membrane of claim 2, wherein, The drying conditions in step (2) are as follows: the temperature is 60-70 °C, and the time is more than 24 hours.

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