An arylpiperidine type anion exchange membrane containing electron-rich branched monomers, a preparation method and applications thereof

Abstract

The application belongs to the technical field of basic anion exchange membranes, and discloses an arylpiperidine type anion exchange membrane containing an electron-rich branched monomer, a preparation method and application thereof. The branched monomer is first introduced to copolymerize with arylpiperidine, then the polymer is directly quaternized by taking the piperidine ring of N-methyl-4-piperidone as a grafting site to obtain a membrane material and prepare a membrane. The branched monomer can play a role in enriching ion clusters, can improve the ion conductivity of the polymer, and contains the branched monomer rich in Π electrons, can enhance the Π-Π conjugation of the polymer, can reduce the swelling rate of the polymer, and can be applied to basic fuel cells and basic water electrolysis.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of basic anion exchange membranes, and relates to an arylpiperidine type anion exchange membrane containing an electron-rich branched monomer, a preparation method and application thereof. BACKGROUND

[0002] Proton exchange membrane fuel cells (PEMFC) and proton exchange membrane water electrolysis (PEMWE) use noble metal catalysts, resulting in high device costs, while anion exchange membrane fuel cells (AEMFC) and anion exchange membrane water electrolysis for hydrogen production (AEMWE) can use non-noble metal catalysts, greatly reducing the cost of the device. However, as of now, the alkaline stability and cell performance of AEMFC and AEMWE still need to be further improved.

[0003] The key component of AEMFC and AEMWE is the membrane electrode, which is composed of a catalyst, an ion polymer and a membrane. The membrane material is crucial in the membrane electrode, and the membrane plays an important role in transferring hydroxyl ions, which is directly related to the performance of the cell. In addition to the need for high conductivity, the polymer also needs to have a low swelling rate and good alkaline stability to ensure the stability of the cell. Lin et al. reported in Alkaline polymer electrolyte fuel cells stably working at 80℃ that a non-oxygen main chain polymer QAPPT was developed. The polymer exhibits good alkaline stability due to the absence of aryl ether bonds, and the cation retention rate is more than 80% after immersion in 8M NaOH for 10 days. Although significant progress has been made in this field, the swelling rate and conductivity of the membrane material need to be further optimized. The introduction of an electron-rich branched monomer into the arylpiperidine polymer not only increases the polymerization activity of the polymer by utilizing the rich Π electrons in the monomer to increase the molecular weight of the polymer, but also forms a branched structure that can reduce the swelling rate of the polymer, which is conducive to the long-term stable operation of the cell. Therefore, the study of electron-rich branched monomer arylpiperidine copolymer is of great significance for the structural design and optimization of AEMWE membrane materials. SUMMARY

[0004] The present application aims to reduce the swelling rate of basic anion exchange membrane, because the introduced branched monomer has rich Pi electrons, which can increase the reaction activity of aromatic ketone polymerization of super acid, can improve the molecular weight of the polymer, the high molecular weight polymer is beneficial to improve the alkali stability of the polymer, at the same time, the branched monomer structure contains multiple benzene ring structure, which can increase the Pi-Pi conjugation effect in the polymer, the Pi-Pi conjugation effect in the polymer is also beneficial to reduce the swelling rate of the polymer, the introduction of branched monomer to form branched center can also promote the microphase separation of the polymer to enrich ion clusters and improve the conductivity of the polymer, so that the aromatic piperidine polymer with high conductivity, low swelling rate and good alkali stability is formed, so the research of introducing electron-rich branched monomer into aromatic piperidine polymer to enhance Pi-Pi conjugation effect and form branched polymer has important significance for developing high-performance membrane material suitable for basic fuel cell and water electrolysis hydrogen production.

[0005] The technical scheme of the present application:

[0006] An aromatic piperidine type anion exchange membrane containing electron-rich branched monomer, the structure is as follows:

[0007]

[0008]

[0009] Among them, the structure of the electron-rich branched monomer is as follows:

[0010]

[0011] The branched unit structure of the aromatic piperidine type polymer containing electron-rich branched monomer is as follows:

[0012]

[0013] Among them, M - is I - , Br - , Cl - , OH - or HCO3 - ;

[0014] Among them, n=0.01~0.99, the multi-monomer polymer is copolymerized by replacing one or two of the following aryl structures:

[0015]

[0016] A preparation method of an aromatic piperidine type anion exchange membrane containing electron-rich branched monomer, the steps are as follows:

[0017] Step one: first dissolve p-terphenyl in solvent dichloromethane, stir for 10 min, then add N-methyl-4-piperidone and the third monomer A to obtain a mixed solution;

[0018] The molar concentration of N-methyl-4-piperidone in dichloromethane is 1-1.2 mol / L;

[0019] The molar ratio of N-methyl-4-piperidone: the third monomer A: p-terphenyl is 1.1:0.01-0.5:0.5-0.99;

[0020] The monomer A is 9,10-benzophenanthrene, corannulene, hexaphenylbenzene, spiro[fluorene-9,9'-xanthene], spiro[9H-fluorene-9,9'-[9H]thioxanthene], 5λ4-5,5'-spirobis[2-benzothiophene](9CI)(CAS No.: 144190-64-7), 1,3,6,8-tetraphenylpyrene, 2,3,6,7,10,11-hexaphenyltriphenylene, 1,3-dithiazole, 2-(4,5-diphenyl-1,3-dithiol-2-ylidene)-4,5-diphenyl(CAS No.: 23780-79-2);

[0021] Step two: add trifluoroacetic acid and triflic acid to the mixed solution obtained in step one under ice bath condition, remove the ice bath after 1 h, react at room temperature for 2-3 h, then add the mixed solution to solvent B to precipitate, finally wash with water until neutral, and dry in an oven to obtain a trimonomer polymer;

[0022] The molar ratio of p-terphenyl to triflic acid is 1:5-9;

[0023] The molar ratio of p-terphenyl to trifluoroacetic acid is 1:1;

[0024] The solvent B is methanol, ethanol or water;

[0025] Step three: dissolve the trimonomer polymer in solvent C, add potassium carbonate after dissolution, stir uniformly, then add iodomethane, and react in the dark at 40°C for a period of time; centrifuge the solution after the reaction is completed, remove the potassium carbonate, pour into solvent D to precipitate, finally wash with solvent D, filter and dry to obtain a quaternary ammonium polymer;

[0026] The molar ratio of the trimonomer polymer: iodomethane: potassium carbonate is 1:1.2-1.5:1-1.5;

[0027] The solvent C is N-methylpyrrolidone or dimethyl sulfoxide;

[0028] The mass concentration of the trimonomer polymer in solvent C is 0.03-0.05 g / mL;

[0029] The precipitation agent D is acetone, ethyl acetate or diethyl ether;

[0030] The light-avoiding reaction time is 36-48h;

[0031] Step four: preparation of the polyaryl piperidine type anion exchange membrane: dissolve the quaternary ammonium polymer in solvent E, remove impurities by centrifugation after dissolution to obtain a casting solution; then cast the casting solution on a glass plate and dry into a film at a certain temperature; immerse the film in 1 mol / L potassium hydroxide solution for 24-48h, and immerse in deionized water until neutral, to obtain the aryl piperidine type anion exchange membrane;

[0032] The solvent E is N-methyl pyrrolidone or dimethyl sulfoxide;

[0033] The mass concentration of the casting solution is 0.015-0.025g / mL;

[0034] The drying temperature of the film formed by the casting method is 60-80℃, and the time is 24 hours.

[0035] The beneficial effects of the present application are:

[0036] (1) By introducing branched monomers rich in Π electrons, the polymerization activity of aryl ketone is greatly improved, the molecular weight of the polymer is increased, which is beneficial to reduce the swelling rate and enhance the stability.

[0037] (2) The introduction of branched monomers containing rich Π electrons can enhance the Π-Π conjugation of the polymer and reduce the swelling rate of the polymer.

[0038] (3) The branched monomers introduced can play the role of enriching ion clusters, which can improve the ion conductivity of the polymer. DETAILED DESCRIPTION

[0039] The specific embodiments of the present application will be further described below in combination with the technical solutions.

[0040] Example 1

[0041] Synthesis of 9,10-benzenophenanthrene containing polyarylpiperidine type termonomer polymer: 2.187 g (9.5 mmol) of p-terphenyl was added to a 25 mL three-necked flask, then 5 mL of dichloromethane solution was added, followed by 1.35 ml (11 mmol) of N-methyl-4-piperidone and 0.114 g (0.5 mmol) of 9,10-benzenophenanthrene, after mechanical stirring for a period of time, 0.75 mL (9.8 mmol) of trifluoroacetic acid, 8 mL (90 mmol) of trifluoromethanesulfonic acid was slowly added under ice bath condition, after 60 min, the ice bath was removed and the reaction system temperature gradually rose to room temperature. When the reaction solution became very viscous, the reaction solution was poured into methanol to precipitate the crude polymer, then washed with deionized water until neutral, dried at 60°C for 24 h to obtain the termonomer polymer material.

[0042] Preparation of quaternary ammonium anion exchange membrane: 2 g of termonomer polymer material was weighed into a 100 mL single-necked flask, then 50 mL of DMSO was added, after dissolution, 1.669 g of potassium carbonate and 2.28 g of iodomethane were added, and 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, then washed with deionized water several times to remove unreacted salt, and dried at 60°C for 24 h to obtain the quaternary ammonium polymer. 0.1 g of the quaternary ammonium polymer was weighed and dissolved in 4.5 mL of DMSO, the casting solution was centrifuged and cast in a glass mold, dried at 60°C for 48 h to obtain the polymer membrane. The polymer membrane was soaked in 1 mol / L KOH solution at room temperature for 48 h, then repeatedly washed and soaked in deionized water for 48 h until neutral, to obtain the quaternary ammonium piperidine type anion exchange membrane.

[0043] Test results show that the quaternary ammonium piperidine type anion exchange membrane prepared in this embodiment has an ionic conductivity of 145 mS cm -1 at 80°C, a water absorption rate of 50%, a swelling degree of 15%, a conductivity retention rate of 92% after soaking in 1 mol / L NaOH solution at 80°C for 2000 h, and a dry film tensile strength of 45 Mpa, indicating that the membrane has good mechanical strength and alkaline stability. When the membrane was assembled into an alkaline fuel cell, the maximum output power was 1.5 W / cm 2 at 80°C. 2 .

[0044] Example 2

[0045] Synthesis of the quaternized piperidinium anion exchange membrane: 1.842 g (8 mmol) of p-terphenyl was added to a 25 mL three-necked flask, then 5 mL of dichloromethane solution was added, followed by 1.35 ml (11 mmol) of N-methyl-4-piperidone and 0.276 g (1.5 mmol) of dibenzothiophene and 0.15 g (0.5 mmol) of coronene, after mechanical stirring for a period of time, 0.75 mL (9.8 mmol) of trifluoroacetic acid, 8 mL (90 mmol) of triflic acid was slowly added under ice bath condition, after 60 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, then washed with deionized water until neutral, and dried at 60°C for 24 h to obtain the tetramonomer polymer material.

[0046] Preparation of quaternary ammonium anion exchange membrane: 2 g of tetramonomer polymer material was weighed into a 100 mL single-necked flask, then 50 mL of DMSO was added, after dissolution, 1.669 g of potassium carbonate and 2.28 g of iodomethane were added, and 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, then washed with deionized water several times to remove unreacted salt, and dried at 60°C for 24 h to obtain the quaternary ammonium polymer. 0.1 g of the quaternary ammonium polymer was weighed and dissolved in 4.5 mL of DMSO, 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 1 mol / L KOH solution at room temperature for 48 h, then repeatedly washed and soaked in deionized water for 48 h until neutral, to obtain the quaternary ammonium piperidinium anion exchange membrane.

[0047] Test results show that the quaternary ammonium piperidinium anion exchange membrane prepared in this embodiment has an ionic conductivity of 152 mS cm -1 at 80°C, a water absorption of 40%, a swelling degree of 12%, a conductivity retention rate of 93% after soaking in 1 mol / L NaOH solution at 80°C for 2000 h, and a dry film tensile strength of 50 Mpa, indicating that the membrane has good mechanical strength and alkaline stability. The membrane was assembled into an alkaline fuel cell for testing, which had a maximum output power of 1.6 W / cm 2 at 80°C. 2

[0048] Example 3

[0049] ​Synthesis of hexa-phenylbenzene polyarylpiperidine type polymer: 2.072 g (9 mmol) of p-terphenyl was added to a 25 mL three-necked flask, followed by 5 mL of dichloromethane solution, then 1.35 ml (11 mmol) of N-methyl-4-piperidone and 0.535 g (1 mmol) of hexa-phenylbenzene were added, and after mechanical stirring for a period of time, 0.75 mL (9.8 mmol) of trifluoroacetic acid, 8 mL (90 mmol) of trifluoromethanesulfonic acid were slowly added under ice bath conditions, and after 60 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.

[0050] Preparation of quaternized anion exchange membrane: 2 g of polymer material was weighed into a 50 mL single-necked flask, followed by 40 mL of DMSO, and after dissolution, 1.62 g of potassium carbonate and 2.28 g of iodomethane were added, and 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, and dried at 60°C for 24 h to obtain a quaternized polymer. 0.1 g of the quaternized polymer was weighed and dissolved in 4.5 mL of DMSO, and the casting solution was centrifuged and cast into a glass mold, which was 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 a quaternized piperidine type anion exchange membrane.

[0051] Tests showed that the quaternized piperidine type anion exchange membrane prepared in this embodiment had an ionic conductivity of 155 mS cm -1 at 80°C, a water absorption rate of 54%, a swelling degree of 18%, a conductivity retention rate of 90% after being soaked in a 1 mol / L NaOH solution at 80°C for 2000 h, and a dry film tensile strength of 45 Mpa, indicating that the membrane exhibited good mechanical strength and alkaline stability. The membrane was assembled into an alkaline fuel cell for testing, which had a maximum output power of 1.7 W / cm 2 at 80°C. 2

[0052] Example 4

[0053] ​Synthesis of poly(9,9-dioctylfluorene-co-9,9-dioctyl-2,7-fluorene-9,9'-spiro[fluorene-9,9'-xanthene]) polymer: 1.727 g (7.5 mmol) of p-terphenyl was added to a 25 mL three-necked flask, followed by 5 mL of dichloromethane solution, then 1.35 ml (11 mmol) of N-methyl-4-piperidone and 0.831 g (2.5 mmol) of spiro[fluorene-9,9'-xanthene] were added, and after mechanical stirring for a period of time, 0.75 mL (9.8 mmol) of trifluoroacetic acid and 8 mL (90 mmol) of trifluoromethanesulfonic acid were slowly added under ice bath conditions, and after 60 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 the triblock polymer material.

[0054] Preparation of quaternized anion exchange membrane: 2 g of polymer material was weighed into a 50 mL single-necked flask, followed by 40 mL of DMSO, and after dissolution, 2 g of potassium carbonate and 1 ml of iodomethane were added, and 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, and dried at 60°C for 24 h to obtain the quaternized polymer. 0.1 g of the quaternized polymer was dissolved in 4.5 mL of DMSO, and the casting solution was centrifuged and cast into a glass mold, which was dried at 60°C for 48 h to obtain the polymer membrane. The polymer membrane was soaked in 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 the quaternized piperidine type anion exchange membrane.

[0055] Tests showed that the quaternized piperidine type anion exchange membrane prepared in this embodiment had an ionic conductivity of 150 mS cm -1 at 80°C, a water absorption rate of 52%, a swelling degree of 16%, a conductivity retention rate of 90% after being soaked in 1 mol / L NaOH solution at 80°C for 2000 h, and a dry film tensile strength of 55 Mpa, indicating that the membrane exhibited good mechanical strength and alkaline stability. When the membrane was assembled into an alkaline fuel cell, the maximum output power was 1.55 W / cm 2 at 80°C. 2 .

[0056] Example 5

[0057] Synthesis of polymeric material of spiro[9H-fluorene-9,9'-[9H]thianthrene] polyarylpiperidine type: 1.957 g (8.5 mmol) of p-terphenyl was added to a 25 mL three-necked flask, then 5 mL of dichloromethane solution was added, followed by 1.35 ml (11 mmol) of N-methyl-4-piperidone and 0.523 g (1.5 mmol) of spiro[9H-fluorene-9,9'-[9H]thianthrene], after mechanical stirring for a period of time, 0.75 mL (9.8 mmol) of trifluoroacetic acid, 8 mL (90 mmol) of trifluoromethanesulfonic acid were slowly added under ice bath conditions, after 60 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, then washed with deionized water until neutral, and dried at 60°C for 24 h to obtain a trimer polymer material.

[0058] Preparation of quaternized anion exchange membrane: 2 g of polymer material was weighed into a 50 mL single-necked flask, then 40 mL of DMSO was added, after dissolution, 2 g of potassium carbonate and 1 ml of iodomethane were added, and the reaction was carried out at 40°C for about 48 h in the dark. The obtained solution was poured into ethyl acetate to precipitate the solid powder product, which was filtered and dried, then washed with deionized water several times to remove unreacted salt, and dried at 60°C for 24 h to obtain a quaternized polymer. 0.1 g of the quaternized polymer was dissolved in 4.5 mL of DMSO, 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 1 mol / L KOH solution at room temperature for 48 h, then repeatedly washed and soaked in deionized water for 48 h until neutral, to obtain a quaternized piperidine type anion exchange membrane.

[0059] Tests showed that the quaternized piperidine type anion exchange membrane prepared in this embodiment had an ionic conductivity of 156 mS cm -1 at 80°C, a water absorption of 48%, a swelling degree of 15%, a conductivity retention rate of 95% after soaking in 1 mol / L NaOH solution at 80°C for 2000 h, and a dry film tensile strength of 50 Mpa, indicating that the membrane had good mechanical strength and alkaline stability. The membrane was assembled into an alkaline fuel cell for testing, which had a maximum output power of 1.72 W / cm 2 at 80°C. In an alkaline electrolytic water battery test, the current reached 5.5 A / cm 2 at 80°C and 2V voltage.

[0060] Example 6

[0061] Synthesis of 5λ4-5,5'-spirobis(thiophene) (9Cl) containing polyarylpiperidine type polymer: 1.957 g (8.5 mmol) of p-terphenyl was added to a 25 mL three-necked flask, followed by 5 mL of dichloromethane solution, then 1.35 ml (11 mmol) of N-methyl-4-piperidone and 0.505 g (1.5 mmol) of 5λ4-5,5'-spirobis(thiophene) (9Cl) were added, after mechanical stirring for a period of time, 0.75 mL (9.8 mmol) of trifluoroacetic acid, 8 mL (90 mmol) of triflic acid were slowly added under ice bath conditions, after 60 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, then washed with deionized water until neutral, and dried at 60°C for 24 h to obtain a trimer polymer material.

[0062] Preparation of quaternized anion exchange membrane: 2 g of polymer material was weighed into a 50 mL single-necked flask, then 40 mL of DMSO was added, after dissolution, 2 g of potassium carbonate and 1 ml of iodomethane were added, and 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, then washed with deionized water several times to remove unreacted salt, and dried at 60°C for 24 h to obtain a quaternized polymer. 0.1 g of the quaternized polymer was dissolved in 4.5 mL of DMSO, 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, then repeatedly washed and soaked in deionized water for 48 h until neutral, to obtain a quaternized piperidine type anion exchange membrane.

[0063] Tests showed that the quaternized piperidine type anion exchange membrane prepared in this embodiment had an ionic conductivity of 165 mS cm-1 at 80°C -1 , a water absorption rate of 45%, a swelling degree of 13%, a conductivity retention rate of 95% after being soaked in a 1 mol / L NaOH solution at 80°C for 2000 h, and a dry film tensile strength of 50 Mpa, indicating that the membrane exhibited good mechanical strength and alkaline stability. When the membrane was assembled into an alkaline fuel cell, the maximum output power was 1.8 W / cm 2 at 80°C. When tested in an alkaline electrolytic water battery, the current reached 6 A / cm 2 at 80°C and 2 V voltage.

[0064] Example 7

[0065] Synthesis of 1,3,6,8-tetraphenylpyrene polyarylpiperidine type polymer: 1.957 g (8.5 mmol) of p-terphenyl was added to a 25 mL three-necked flask, then 5 mL of dichloromethane solution was added, followed by 1.35 ml (11 mmol) of N-methyl-4-piperidone and 0.760 g (1.5 mmol) of 1,3,6,8-tetraphenylpyrene, after mechanical stirring for a period of time, 0.75 mL (9.8 mmol) of trifluoroacetic acid, 8 mL (90 mmol) of trifluoromethanesulfonic acid was slowly added under ice bath condition, after 60 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, then washed with deionized water until neutral, and dried at 60°C for 24 h to obtain a trimer polymer material.

[0066] Preparation of quaternized anion exchange membrane: 2 g of polymer material was weighed into a 50 mL single-necked flask, then 40 mL of DMSO was added, after dissolution, 2 g of potassium carbonate and 1 ml of iodomethane were added, and the reaction was carried out at 40°C for about 48 h in the dark. The obtained solution was poured into ethyl acetate to precipitate the solid powder product, which was filtered and dried, then washed with deionized water several times to remove unreacted salt, and dried at 60°C for 24 h to obtain a quaternized polymer. 0.1 g of quaternized polymer was dissolved in 4.5 mL of DMSO, the casting solution was centrifuged and cast in a glass mold, and dried at 60°C for 48 h to obtain a polymer membrane. The polymer membrane was soaked in 1 mol / L KOH solution at room temperature for 48 h, then repeatedly washed and soaked in deionized water for 48 h until neutral, to obtain a quaternized piperidine type anion exchange membrane.

[0067] Test results show that the quaternized piperidine type anion exchange membrane prepared in this embodiment has an ionic conductivity of 148 mS cm -1 at 80°C, a water absorption of 55%, a swelling degree of 17%, a conductivity retention rate of 92% after soaking in 1 mol / L NaOH solution at 80°C for 2000 h, and a dry film tensile strength of 45 Mpa, showing good mechanical strength and alkaline stability. The membrane was assembled into an alkaline fuel cell for testing, which had a maximum output power of 1.53 W / cm 2 at 80°C. In an alkaline electrolytic water battery test, the current reached 4.7 A / cm 2 at 80°C and 2V voltage.

[0068] Example 8

[0069] Synthesis of 2,3,6,7,10,11-hexaphenyltriphenylbenzene poly ( arylpiperidine) type polymer: 2.187 g (9.5 mmol) of p-terphenyl was added to a 25 mL three-necked flask, then 5 mL of dichloromethane solution was added, followed by 1.35 ml (11 mmol) of N-methyl-4-piperidone and 0.342 g (0.5 mmol) of 2,3,6,7,10,11-hexaphenyltriphenylbenzene, after mechanical stirring for a period of time, 0.75 mL (9.8 mmol) of trifluoroacetic acid, 8 mL (90 mmol) of trifluoromethanesulfonic acid was slowly added under ice bath condition, after 60 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, then washed with deionized water until neutral, and dried at 60 °C for 24 h to obtain the trimer polymer material.

[0070] Preparation of quaternary ammonium anion exchange membrane: 2 g of polymer material was weighed into a 50 mL single-necked flask, then 40 mL of DMSO was added, after dissolution, 2 g of potassium carbonate and 1 ml of iodomethane were added, and 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, then washed with deionized water several times to remove unreacted salt, and dried at 60 °C for 24 h to obtain the quaternary ammonium polymer. 0.1 g of the quaternary ammonium polymer was weighed and dissolved in 4.5 mL of DMSO, the casting solution was centrifuged and cast in a glass mold, and dried at 60 °C for 48 h to obtain the polymer membrane. The polymer membrane was soaked in 1 mol / L KOH solution at room temperature for 48 h, then repeatedly washed and soaked in deionized water for 48 h until neutral, to obtain the quaternary ammonium piperidine type anion exchange membrane.

[0071] Test results show that the quaternary ammonium piperidine type anion exchange membrane prepared in this embodiment has an ionic conductivity of 146 mS cm-1 at 80 °C -1 , a water absorption rate of 63%, a swelling degree of 20%, a conductivity retention rate of 92% after soaking in 1 mol / L NaOH solution at 80 °C for 2000 h, and a dry film tensile strength of 45 Mpa, indicating that the membrane has good mechanical strength and alkaline stability. The membrane was assembled into an alkaline fuel cell for testing, and the maximum output power was 1.51 W / cm 2 at 80 °C. In an alkaline electrolytic water cell, the current reached 5 A / cm 2 at 80 °C and 2 V voltage.

[0072] Example 9

[0073] Synthesis of polyarylpiperidine type polymer containing 1,3-dithiazole, 2-(4,5-diphenyl-1,3-dithiol-2-ylidene)-4,5-diphenyl (CAS No: 23780-79-2): 2.187 g (9.5 mmol) of p-terphenyl was added to a 25 mL three-necked flask, followed by 5 mL of dichloromethane solution, then 1.35 ml (11 mmol) of N-methyl-4-piperidone and 0.254 g (0.5 mmol) of 1,3-dithiazole, 2-(4,5-diphenyl-1,3-dithiol-2-ylidene)-4,5-diphenyl were added, and after mechanical stirring for a period of time, 0.75 mL (9.8 mmol) of trifluoroacetic acid, 8 mL (90 mmol) of trifluoromethanesulfonic acid were slowly added under ice bath conditions, and after 60 min, the ice bath was removed and the temperature of the reaction system was gradually increased 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.

[0074] Preparation of quaternized anion exchange membrane: 2 g of polymer material was weighed into a 50 mL single-necked flask, followed by 40 mL of DMSO, and after dissolution, 2 g of potassium carbonate and 1 ml of iodomethane were added, and 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, and dried at 60°C for 24 h to obtain a quaternized polymer. 0.1 g of the quaternized polymer was weighed and dissolved in 4.5 mL of DMSO, and the casting solution was centrifuged and cast into a glass mold, which was 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 a quaternized piperidine type anion exchange membrane.

[0075] Tests showed that the quaternized piperidine type anion exchange membrane prepared in this embodiment had an ionic conductivity of 153 mS cm-1 at 80°C, a water absorption of 57%, a swelling degree of 18%, a conductivity retention rate of 88% after being soaked in a 1 mol / L NaOH solution at 80°C for 2000 h, and a dry film tensile strength of 40 Mpa, indicating that the membrane exhibited good mechanical strength and basic stability. When the membrane was assembled into a basic fuel cell, the maximum output power was 1.65 W / cm -1 at 80°C. 2 When the membrane was tested in an alkaline electrolytic water battery, the current reached 5.5 A / cm 2 at 80°C and a voltage of 2V.

[0076] Comparative Example 1

[0077] Synthesis of poly(p-phenylenevinylene) polymer: 2.303 g (10 mmol) of p-phenylenevinylene was added to a 25 mL three-necked flask, then 5 mL of dichloromethane solution was added, followed by 1.35 ml (11 mmol) of N-methyl-4-piperidone, and after mechanical stirring for a period of time, 0.75 mL (9.8 mmol) of trifluoroacetic acid, 8 mL (90 mmol) of trifluoromethanesulfonic acid were slowly added under ice bath conditions, and after 60 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 the trimer polymer material.

[0078] Preparation of quaternary ammonium anion exchange membrane: 2 g of polymer material was weighed into a 50 mL single-necked flask, then 40 mL of DMSO was added, and after dissolution, 2 g of potassium carbonate and 1 ml of iodomethane were added, and 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, and dried at 60°C for 24 h to obtain the 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, which was dried at 60°C for 48 h to obtain the polymer membrane. The polymer membrane was soaked in 1 mol / L KOH solution at room temperature for 48 h, then repeatedly washed and soaked in deionized water for 48 h until neutral, to obtain the quaternary ammonium piperidine type anion exchange membrane.

[0079] Tests showed that the quaternary ammonium piperidine type anion exchange membrane prepared in this embodiment had an ionic conductivity of 120 mS cm -1 at 80°C, a water absorption rate of 70%, and a swelling degree of 23%. When the membrane was assembled into an alkaline fuel cell and tested, the maximum output power was 1.1 W / cm 2 at 80°C. When tested in an alkaline electrolytic water battery, the current reached 2.5 A / cm 2 at 80°C and 2V voltage.

[0080] Comparative Example 2

[0081] Synthesis of triphenylmethane polyaryl piperidine type polymer: 2.187 g (9.5 mmol) of p-terphenyl was added to a 25 mL three-necked flask, then 5 mL of dichloromethane solution was added, followed by 1.35 ml (11 mmol) of N-methyl-4-piperidone and 0.122 g (0.5 mmol) of triphenylmethane, after mechanical stirring for a period of time, 0.75 mL (9.8 mmol) of trifluoroacetic acid, 8 mL (90 mmol) of trifluoromethanesulfonic acid was slowly added under ice bath condition, after 60 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, then washed with deionized water until neutral, and dried at 60°C for 24 h to obtain a trimer polymer material.

[0082] Preparation of quaternary ammonium anion exchange membrane: 2 g of polymer material was weighed into a 50 mL single-necked flask, then 40 mL of DMSO was added, after dissolution, 2 g of potassium carbonate and 1 ml of iodomethane were added, and the reaction was carried out at 40°C for about 48 h in the dark. The obtained solution was poured into ethyl acetate to precipitate the solid powder product, which was filtered and dried, 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 quaternary ammonium polymer was dissolved in 4.5 mL of DMSO, the casting solution was centrifuged and cast in a glass mold, and dried at 60°C for 48 h to obtain a polymer membrane. The polymer membrane was soaked in 1 mol / L KOH solution at room temperature for 48 h, then washed and soaked in deionized water for 48 h until neutral, to obtain a quaternary ammonium piperidine type anion exchange membrane.

[0083] Test results show that the quaternary ammonium piperidine type anion exchange membrane prepared in this embodiment has an ionic conductivity of 125 mS cm -1 at 80°C, a water absorption rate of 60%, a swelling degree of 21%, a conductivity retention rate of 85% after soaking in 1 mol / L NaOH solution at 80°C for 2000 h, and a dry film tensile strength of 37 Mpa, showing good mechanical strength and alkaline stability. The membrane was assembled into an alkaline fuel cell for testing, which had a maximum output power of 1.3 W / cm 2 at 80°C. In an alkaline electrolytic water battery test, the current reached 3.5 A / cm 2 at 80°C and 2V voltage.

Claims

1. An arylpiperidine type anion exchange membrane containing an electron-rich branched monomer, characterized by, The structure of the arylpiperidine type anion exchange membrane is as follows: 、 、 、 、 ； wherein M - is I - , Br - , Cl - , OH - or HCO3 - ; n = 0.01~0.

99.

2. The arylpiperidine anion exchange membrane according to claim 1, wherein The structure of the electron-rich branched monomer is as follows: 。 3. The arylpiperidine anion exchange membrane of claim 2, wherein, The branched unit structure of the arylpiperidine type polymer containing the electron-rich branched monomer is as follows: 。 4. The arylpiperidine anion exchange membrane of claim 3, wherein, The structure of the arylpiperidine type anion exchange membrane is as follows: 。 5. A method for producing an arylpiperidine type anion exchange membrane containing an electron-rich branched monomer, characterized by, The steps are as follows: Step one: first, p-terphenyl is dissolved in solvent dichloromethane, stirred for 10 min, then N-methyl-4-piperidone and the third monomer A are added to obtain a mixed solution; The monomer A is 9,10-benzo phenanthrene; corannulene; hexaphenylbenzene, spiro[fluorene-9,9'-oxanthrene]; spiro[9H-fluorene-9,9'-[9H]thioxanthene]; 1,3,6,8-tetraphenylpyrene; 2,3,6,7,10,11-hexaphenyltriphenylene; Step two: trifluoroacetic acid, triflic acid is added to the mixed solution obtained in step one under ice bath condition, after 1 h, the ice bath is removed, and the reaction is carried out at room temperature for 2-3 h, then the mixed solution is added to solvent B for precipitation, finally washed with water until neutral, and oven dried to obtain a trimonomer polymer; The solvent B is methanol, ethanol or water; Step three: the trimonomer polymer is dissolved in solvent C, after dissolution, potassium carbonate is added, stirred uniformly, then methyl iodide is added, and the reaction is carried out at 40°C for a period of time in the dark; after the reaction is completed, the solution is centrifuged, the potassium carbonate is removed, and then poured into solvent D for precipitation, finally washed with solvent D, filtered and dried to obtain a quaternary ammonium polymer; The solvent C is N-methyl pyrrolidone or dimethyl sulfoxide; The solvent D is acetone, ethyl acetate or diethyl ether; Step four: preparation of the polyaryl piperidine type anion exchange membrane: the quaternary ammonium polymer is dissolved in solvent E, after dissolution, centrifuged to remove impurities to obtain a casting solution; then the casting solution is cast on a glass plate, 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 aryl piperidine type anion exchange membrane. The solvent E is N-methyl pyrrolidone or dimethyl sulfoxide.

6. The preparation method according to claim 5, wherein, in step one, the molar concentration of N-methyl-4-piperidone in dichloromethane is 1-1.2 mol / L; the molar ratio of N-methyl-4-piperidone: the third monomer A: p-terphenyl is 1.1:0.01-0.5:0.5-0.

99.

7. The preparation method according to claim 5, wherein, in step two, the molar ratio of p-terphenyl to triflic acid is 1:5-9; the molar ratio of p-terphenyl to trifluoroacetic acid is 1:

1.

8. The preparation method according to claim 5, wherein, in step three, the molar ratio of the trimonomer polymer: methyl iodide: potassium carbonate is 1:1.2-1.5:1-1.5; the mass concentration of the trimonomer polymer in solvent C is 0.03-0.05 g / mL; the time of the light-protected reaction is 36-48 h.

9. The preparation method according to claim 5, wherein, In step four, The mass concentration of the casting solution is 0.015-0.025 g / mL. The drying temperature for film formation is 60-80°C, and the time is 24 hours.

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