High-alkali-resistance polyarylene alkylene piperidine cationic polymer as well as preparation method and application thereof

Abstract

The invention relates to the technical field of cationic polymers, in particular to a high-alkali-resistance polyarylene alkylene piperidine cationic polymer as well as a preparation method and application thereof. The preparation method of the high alkali resistance poly (arylene alkylene piperidine) cationic polymer comprises the following steps: carrying out catalytic polycondensation on 1-R6-3-piperidine formaldehyde or salt or hydrate thereof and an aromatic compound to obtain a polymer with a piperidine structure; and further performing ionization reaction to obtain the polyarylene alkylene piperidine cationic polymer. The anion exchange membrane prepared based on the piperidine cationic polymer has ultrahigh alkali resistance and excellent mechanical properties and ionic conductivity, and can be used in the electrochemical energy conversion fields of fuel cells, water electrolysis hydrogen production, carbon dioxide electroreduction, flow batteries and the like, and the separation fields of electrodialysis, water treatment and the like.

Description

Technical Field

[0001] The invention relates to the technical field of cationic polymers, and in particular to a highly alkali-resistant polyarylene alkylene piperidine cationic polymer and a preparation method and application thereof. Background Art

[0002] In recent years, anion exchange membrane fuel cells (AEMFC) and water electrolysis (AEMWE) in alkaline operating environments have received a lot of attention from academia and industry due to their low operating costs and electrochemical conversion efficiency comparable to that of acidic systems. However, the alkaline operating environment causes the functional cations of the polymer electrolyte in the AEMWE and AEMFC devices to degrade during long-term operation. Polymer electrolytes are cationic polymers that are mainly used in anion exchange membranes (AEM) and catalyst layer binders. When their functional cations degrade in alkaline solutions, they will directly lead to performance degradation of AEMFC and AEMWE. At present, the main reason restricting the commercialization of AEMFC and AEMWE is that their performance decays too quickly during device operation. Therefore, it is crucial to develop polymer electrolytes with outstanding alkaline stability to improve the operating stability of AEMFC and AEMWE.

[0003] After a lot of efforts by researchers, polyaryl piperidine salt polymers are currently the most promising polymer electrolytes for alkaline electrochemical conversion devices. However, when the piperidine ring is directly connected to the aromatic unit, the Hofmann elimination degradation pathway of the piperidine cationic group is activated under high alkali concentration conditions, which weakens its alkali resistance to a certain extent (Chemistry and Sustainable Chemistry (ChemSusChem) 2024, e202301656). Therefore, it is an urgent problem to be solved in the prior art to improve the alkali resistance of piperidine cationic polymer electrolytes through structural design and maintain their other advantages. Summary of the invention

[0004] The purpose of the present invention is to provide a highly alkali-resistant polyarylene alkylene piperidine cationic polymer and a preparation method and application thereof, so as to improve the alkali resistance and mechanical strength of the polyarylene alkylene piperidine cationic polymer and ensure its excellent electrochemical properties.

[0005] To achieve the above object, the present invention provides a highly alkali-resistant polyarylene alkylene piperidine cationic polymer, characterized in that the polyarylene alkylene piperidine cationic polymer comprises structural units:

[0006]

[0007] Among them, R 1 is selected from H atoms, hydrocarbon groups containing 1 to 20 carbon atoms, or R 1Connected to form a cycloalkyl group consisting of 4 to 10 carbon atoms; counterion A - One or more selected from halide ions, methyl sulfate ions, hydroxide ions or bicarbonate ions;

[0008] The Ar' fragment is selected from one or more of the following structures,

[0009]

[0010] Preferably, the polyarylene alkylene piperidine cationic polymer may contain one or more of the following structural units in addition to the above structural units:

[0011]

[0012] Wherein, k = 0 or 1; x = 0-12;

[0013] R 2 Independently selected hydrogen atoms or hydrocarbon groups with 1-20 carbon atoms, fully or partially fluorinated alkyl groups with 1-6 carbon atoms;

[0014] Q' is selected from H atoms, -N + (R 5 )3 and one or more of the cations containing nitrogen heterocycles, counter anions A - selected from halide ions, methyl sulfate ions, hydroxide ions or bicarbonate ions;

[0015] R 3 and R 4 Each independently selected H atom, a hydrocarbon group having 1 to 20 carbon atoms, or an independent R 3 are linked to each other to form a cycloalkyl group consisting of 4 to 10 carbon atoms, or independently R 4 They are linked to each other to form a cycloalkyl group consisting of 4 to 10 carbon atoms;

[0016] More preferably, -N + (R 5 )3, each R 5 Independently selected from hydrocarbon groups having 1 to 20 carbon atoms;

[0017] The nitrogen-containing heterocyclic cation comprises one or more of partially or completely substituted pyrazole, pyrrole, piperidine, imidazole and quinine cations, and has the following structural formula:

[0018]

[0019] Among them, R 501 –R 510 independently selected from hydrocarbon groups having 1 to 20 carbon atoms, counter ion A -One or more selected from halide ions, methyl sulfate ions, hydroxide ions or bicarbonate ions.

[0020] The present invention also provides a method for preparing a highly alkali-resistant polyarylene alkylene piperidine cationic polymer, comprising the following steps:

[0021] S1, 1-R 6 -3-piperidinecarboxaldehyde or its salt or hydrate and an aromatic compound are mixed to obtain a polymer monomer system, and the system is placed in a first organic solvent, and an organic strong acid is added to perform catalytic polycondensation, and the system is reacted at -20-100° C. for 0.01-100 hours to obtain a polymer dispersion having a piperidine structure;

[0022] In S1, the aromatic compound is one or more of the following structures,

[0023]

[0024] S2, slowly dropping the polymer dispersion having a piperidine structure in S1 into the first precipitant, filtering, washing and vacuum drying to obtain a polymer powder having a piperidine structure;

[0025] S3, dissolving the polymer powder having a piperidine structure in S2 in a second organic solvent, adding an ionizing agent, and performing an ionization reaction at 0-100° C. for 0.1-100 h to obtain a cationic polymer solution;

[0026] S4. Slowly add the cationic polymer solution in S3 into the second precipitant, filter and dry to obtain polyarylene alkylene piperidine cationic polymer powder.

[0027] Preferably, in S1, 1-R 6 The structural formula of 3-piperidinecarboxaldehyde is shown below:

[0028]

[0029] Among them, R 6 One or more selected from H atoms and hydrocarbon groups containing 1 to 20 carbon atoms.

[0030] More preferably, in S1, 1-R 6 -3-Piperidinecarboxaldehyde or its salt or hydrate includes 1-R 6 -3-Piperidinecarboxaldehyde, 1-R 6 -3-Piperidinecarboxaldehyde hydrochloride, 1-R 6 -3-Piperidinecarboxaldehyde hydrofluoride, 1-R 6 -3-Piperidinecarboxaldehyde hydrobromide, 1-R 6 -3-Piperidinecarboxaldehyde hydroiodide, 1-R 6 -3-Piperidinecarboxaldehyde trifluoroacetate, 1-R6 -3-Piperidinecarboxaldehyde acetate, 1-R 6 -3-Piperidinecarboxaldehyde trifluoromethanesulfonate, 1-R 6 -3-Piperidinecarboxaldehyde methanesulfonate, 1-R 6 -3-Piperidinecarboxaldehyde sulfate, 1-R 6 -3-Piperidinecarboxaldehyde nitrate, 1-R 6 -3-Piperidinecarboxaldehyde tetrafluoroborate, 1-R 6 -3-Piperidinecarboxaldehyde hexafluorophosphate, 1-R 6 -3-Piperidinecarboxaldehyde formate, 1-R 6 -3-Piperidinecarboxaldehyde benzenesulfonate, 1-R 6 -3-Piperidinecarboxaldehyde toluate, 1-R 6 -3-Piperidinecarboxaldehyde perchlorate, 1-R 6 -3-piperidinylcarboxaldehyde benzoate and one or more of its hydrates.

[0031] Preferably, in S1, the polymer monomer system further includes a carbonyl-containing compound, and the carbonyl-containing compound is one or more of the following structures:

[0032]

[0033] Wherein, k is 0 or 1, x=0-12;

[0034] Q is selected from one or more of H atoms and halogen atoms;

[0035] R 7 One or more selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a fully or partially fluorinated alkyl group having 1 to 6 carbon atoms;

[0036] R 8 and R 9 Independently selected from H atoms or hydrocarbon groups containing 1-20 carbon atoms.

[0037] Preferably, in S1, 1-R 6 The molar ratio of 3-piperidinecarboxaldehyde or its salt or hydrate to the organic strong acid is 1:(1-20).

[0038] Preferably, in S1, 1-R 6 The molar ratio of 3-piperidinecarboxaldehyde or its salt or hydrate to the carbonyl-containing compound and the organic strong acid is 1:(1-20).

[0039] Preferably, in S1, the first organic solvent is one or more of dichloromethane, chloroform, carbon tetrachloride, dichloroethane, nitromethane, and nitrobenzene;

[0040] The strong organic acid is at least one of methanesulfonic acid, trifluoromethanesulfonic acid and trifluoroacetic acid.

[0041] Preferably, in S2, the first precipitant is one or more of water, ethanol, methanol and isopropanol.

[0042] Preferably, in S3, the second organic solvent is at least one of the polar aprotic solvents dimethyl sulfoxide, N-methylpyrrolidone, N,N-dimethylacetamide and N,N-dimethylformamide.

[0043] Preferably, in S3, the ionizing agent is dimethyl sulfate or a halogenated hydrocarbon having 1 to 20 carbon atoms, the structure of which is

[0044] Among them, R 101 , R 102 , R 103 and R 104 They are independently selected from hydrogen, halogen, a hydrocarbon group or a halogenated hydrocarbon group having 1 to 20 carbon atoms, or an aryl group or a halogenated aryl group having 1 to 20 carbon atoms, and the halogenated hydrocarbon group or the halogenated aryl group contains at least one halogen atom.

[0045] Preferably, the molar ratio of the piperidine group in the polymer having a piperidine structure to the ionizing agent is 1:(1-10).

[0046] Preferably, one or more of potassium carbonate, potassium hydroxide, sodium carbonate, sodium bicarbonate and sodium hydroxide can be added to S3.

[0047] Preferably, in S4, the second precipitant is one or more of water, acetone, ether, toluene, ethyl acetate and petroleum ether.

[0048] Preferably, the prepared polyarylene alkylene piperidine cationic polymer powder is immersed in a solution containing other types of counter ions to perform ion exchange, thereby obtaining a cationic polymer containing other types of counter ions.

[0049] More preferably, the other type of counterion is different from the counterion A. - At least one of hydroxide ions, carbonate ions, bicarbonate ions, sulfate ions, and halogen ions;

[0050] More preferably, the solution containing other types of counter ions has a concentration of 0.01-10 mol / L.

[0051] The above-mentioned highly alkali-resistant polyarylene alkylene piperidine cationic polymer is used in anion exchange membrane or catalyst layer binder.

[0052] Preferably, the preparation method of the anion exchange membrane is to dissolve the highly alkali-resistant polyarylene alkylene piperidine cationic polymer in a third organic solvent to obtain a cationic polymer solution, coat the polymer solution on a substrate, dry to remove the third organic solvent, and obtain the anion exchange membrane after stripping and washing.

[0053] Preferably, the coating method is one of solution casting, spin coating, scraping, casting or dipping, and the method for removing the solvent is volatilization at room temperature or heating and drying at 30-100°C.

[0054] Preferably, the third organic solvent is a polar aprotic solvent, specifically one or more of dimethyl sulfoxide, N-methylpyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide.

[0055] Preferably, the preparation method of the catalyst layer binder is to dissolve or disperse the highly alkali-resistant polyarylene alkylene piperidine cationic polymer in a fourth organic solvent to obtain a solution or dispersion of the catalyst layer binder, and mix the catalyst layer binder solution or dispersion with the catalyst to obtain a slurry of the cationic polymer as the catalyst layer binder.

[0056] Preferably, the fourth organic solvent is a low boiling point solvent, more preferably at least one of water, methanol, ethanol, n-propanol, isopropanol and n-butanol.

[0057] Preferably, the concentration of the polyarylene alkylene piperidine cationic polymer is between 1-99 wt %, more preferably between 1-75 wt %, and further preferably between 1-40 wt %.

[0058] The mechanism of the present invention is:

[0059] By connecting the piperidinium cation to the phenyl group through an alkyl spacer, the number of β-hydrogen atoms on the piperidinium ring is reduced from 4 to 3. In addition, the degree to which the β-hydrogen on the piperidinium ring is affected by the electron-withdrawing effect of the benzene ring is reduced, thereby greatly reducing the probability of Hofmann elimination of the piperidinium cation in the polymer and greatly improving the alkali stability of the piperidinium cation-containing polymer. In addition, due to the high activity of the aldehyde group, the polymerization reaction is easier to occur, thereby increasing the molecular weight of the ionomer, which will improve the mechanical properties of the highly alkali-resistant polyarylene alkylene piperidinium cation polymer.

[0060] Therefore, the present invention adopts the above technical solution, and its beneficial effects are:

[0061] 1. A highly alkali-resistant polyarylene alkylene piperidine cationic polymer provided by the present invention has ultra-high alkali stability. The piperidine cation is connected to the aryl group through a flexible spacer, so that its alkali stability is greatly increased. It is applied to anion exchange membranes or catalyst layer bonding materials to exhibit outstanding alkali stability;

[0062] 2. The preparation method of the highly alkali-resistant polyarylene alkylene piperidine cationic polymer provided by the invention is simple to operate, has mild reaction conditions, and is suitable for large-scale production;

[0063] 3. The aldehyde monomers used in the preparation method of the highly alkali-resistant polyarylene alkylene piperidine cationic polymer provided by the present invention have high reactivity, so that the synthesis efficiency of the high molecular weight polyarylene alkylene piperidine cationic polymer is improved;

[0064] 4. The cationic polymer prepared by the present invention can be used as a diaphragm material in many fields such as fuel cells and water electrolysis. At the same time, the cationic polymer can also be used as a catalyst binder material in the catalyst layer of fuel cells and water electrolysis;

[0065] 5. The anion exchange membrane prepared based on the piperidine cationic polymer provided by the present invention has ultra-high alkali resistance and excellent mechanical properties and ion conductivity, and can be used in electrochemical energy conversion fields such as fuel cells, water electrolysis to produce hydrogen, carbon dioxide electroreduction, liquid flow batteries, and separation fields such as electrodialysis and water treatment.

[0066] The technical solution of the present invention is further described in detail below through the accompanying drawings and embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0067] Figure 1 is the hydrogen nuclear magnetic resonance spectrum of PBMP in Test Example 1 of the present invention;

[0068] Figure 2 is the NMR spectra of PBMP and the traditional cationic polymer PBP before and after alkaline hydrolysis in Test Example 1 of the present invention;

[0069] Figure 3 is a curve diagram showing the change of the hydroxyl ion conductivity of the anion exchange membrane 2 with the temperature in Application Example 2 of the present invention;

[0070] Figure 4 is a curve diagram showing the change of water absorption rate of anion exchange membrane 2 with temperature in Application Example 2 of the present invention;

[0071] Figure 5 is a curve diagram showing the change of swelling rate of anion exchange membrane 2 with temperature in Application Example 2 of the present invention;

[0072] Figure 6 This is a graph of the electrochemical performance of the catalyst layer binder and anion exchange membrane 2 prepared from the polyarylene alkylene piperidine cationic polymer in Example 2 of the present invention. DETAILED DESCRIPTION

[0073] The present invention is further described below in conjunction with the accompanying drawings and embodiments. Unless otherwise defined, the technical terms or scientific terms used in the present invention should be the common meanings understood by people with ordinary skills in the field to which the present invention belongs. The above-mentioned features or features mentioned in the specific examples mentioned in the present invention can be combined arbitrarily, and these specific embodiments are only used to illustrate the present invention and are not used to limit the scope of the present invention.

[0074] Example 1

[0075] S1. A polymerization mixture consisting of 3-piperidinecarboxaldehyde hydrochloride (0.17 g, 1.16 mmol) and biphenyl (0.16 g, 1.05 mmol) was placed in dichloromethane (1.7 mL), and trifluoromethanesulfonic acid (2.5 mL) was added to carry out a catalytic polycondensation reaction. The reaction was carried out at 22°C for 10 h to obtain a viscous dispersion of a polymer having a piperidine structure.

[0076] S2. Slowly drop the dispersion of the polymer with a piperidine structure in S1 into a 1:1 (v / v) mixed solution of methanol and water, filter the obtained light yellow fibrous polymer, wash it thoroughly, and vacuum dry it to obtain 0.25 g of white fibrous polymer powder with a piperidine structure.

[0077] S3. The polymer powder having a piperidine structure in S2 was dissolved in 3 mL of N-methylpyrrolidone, 0.26 mL of iodomethane and 0.15 g of potassium carbonate were added, and an ionization reaction was carried out at room temperature for 72 h to obtain a cationic polymer solution.

[0078] S4, slowly add the cationic polymer solution in S3 into diethyl ether, filter and dry, and obtain 0.29 g of counter ion I - The highly alkali-resistant polyarylene alkylene piperidine cationic polymer powder has the following structure:

[0079]

[0080] Application Example 1

[0081] a. Preparation of anion exchange membrane

[0082] The highly alkali-resistant polyarylene alkylene piperidine cationic polymer powder prepared in Example 1 was dissolved in 3 mL of dimethyl sulfoxide to obtain a polyarylene alkylene piperidine cationic polymer solution with a mass fraction of about 10%. The polyarylene alkylene piperidine cationic polymer solution was coated on a clean glass plate by a casting method, and the glass plate was placed in a blast drying oven at 80°C for 24 hours to remove dimethyl sulfoxide. After the temperature dropped to room temperature, the glass plate was taken out, placed in deionized water for demolding, and then fully washed with deionized water to obtain a glass plate with a counter ion of I - Anion exchange membrane 1.

[0083] b. Replace the counter ions in anion exchange membrane 1

[0084] The counter ion prepared in a is I - The anions in the anion exchange membrane 1 are exchanged as needed, and the counter ions are I - The anion exchange membrane was immersed in a 2 mol / L NaCl solution for 24 h, and then the membrane was fully washed with deionized water to obtain a counter ion of Cl - Anion exchange membrane 1.

[0085] c. Preparation of catalyst layer binder

[0086] The counter ions in the polyarylene alkylene piperidine cationic polymer prepared in Example 1 were ion exchanged as needed. The polyarylene alkylene piperidine cationic polymer powder prepared in Example 1 was immersed in a 2 mol / L NaOH solution for 48 h, and then fully washed with deionized water. The counter ions were OH and NH4OH. - Poly(arylene alkylene piperidinium) cationic polymers.

[0087] The counter ion is OH - The polyarylene alkylene piperidine cationic polymer is dissolved in a mixed solvent of isopropanol and water with a solid content of 2 wt %, and mixed with a metal catalyst to prepare a uniformly dispersed slurry, that is, a slurry of a catalyst layer binder based on the polyarylene alkylene piperidine cationic polymer in Example 1.

[0088] Test Example 1

[0089] a. H NMR

[0090] The counter ion in the highly alkali-resistant polyarylene alkylene piperidine cationic polymer of the structure shown in formula (1) is changed to obtain a counter ion of Cl - The highly alkali-resistant polyarylene alkylene piperidine cationic polymer PBMP was tested using DMSO-d6 as a solvent under an Agilent 600MHz nuclear magnetic resonance spectrometer. The results are as follows Figure 1 As shown, it can be seen that PBMP was successfully prepared.

[0091] b. Alkali stability test

[0092] The PBMP obtained in a is mixed with the reported cationic polymer PBP (chemical structure as Figure 2 As shown) at 80℃, 8 mol L -1 After 360 hours of alkaline hydrolysis in NaOH aqueous solution, the NMR changes before and after (solvent: DMSO-d6) are as follows Figure 2As shown. It can be seen that after PBMP was alkaline hydrolyzed for 360 hours, the polyarylene alkylene piperidine cation was not degraded. In addition, Figure 2 No obvious chemical shift changes and new signal peaks were observed, which proves that PBMP has outstanding alkali stability. On the other hand, the traditional cationic polymer PBP, in which the fourth position of the piperidinium cation is directly connected to the aromatic ring, showed 16% ion loss after alkali treatment, and the main degradation mode was Hofmann degradation. It can be seen that the highly alkali-resistant polyarylene alkylene piperidinium cationic polymer provided by the present invention has outstanding alkali resistance.

[0093] Example 2

[0094] S1. A polymerization mixture consisting of 3-piperidinecarboxaldehyde hydrochloride (0.17 g, 1.16 mmol), biphenyl (0.3 g, 1.96 mmol) and trifluoroacetone (0.09 g, 0.86 mmol) was placed in dichloromethane (2.0 mL), and trifluoromethanesulfonic acid (3.0 mL) was added to carry out a catalytic polycondensation reaction. The reaction was carried out at 0°C for 10 h to obtain a viscous dispersion of a polymer having a piperidine structure.

[0095] S2. Slowly drop the dispersion of the polymer with a piperidine structure in S1 into a 1:1 (v / v) mixed solution of methanol and water to obtain a light yellow fibrous polymer. Filter, wash thoroughly, and vacuum dry to obtain 0.44 g of white fibrous polymer powder with a piperidine structure.

[0096] S3. The polymer powder having a piperidine structure in S2 was dissolved in 5 mL of N-methylpyrrolidone, 0.49 mL of iodomethane and 0.2 g of potassium carbonate were added, and an ionization reaction was carried out at room temperature for 72 h to obtain a cationic polymer PBMP-60 solution.

[0097] S4, slowly add the cationic polymer solution in S3 into diethyl ether, filter and dry, and obtain 0.50 g of highly alkali-resistant polyarylene alkylene piperidine cationic polymer PBMP-60 powder, the structure of which is shown below:

[0098]

[0099] Application Example 2

[0100] a. Preparation of anion exchange membrane

[0101] The highly alkali-resistant polyarylene alkylene piperidine cationic polymer powder prepared in Example 2 was dissolved in 5 mL of dimethyl sulfoxide to obtain a polyarylene alkylene piperidine cationic polymer solution with a mass fraction of about 10%. The polyarylene alkylene piperidine cationic polymer solution was coated on a clean glass plate by a casting method, and the glass plate was placed in a blast drying oven at 80°C for 24 hours to remove dimethyl sulfoxide. After the temperature dropped to room temperature, the glass plate was taken out, placed in deionized water for demolding, and then fully washed with deionized water to obtain a counter ion of I - Anion exchange membrane II.

[0102] b. Replace the counter ion with I - The counter ions in the anion exchange membrane II

[0103] The above counter ion is I - The anion exchange membrane II was placed in a 1 mol / L NaOH solution and soaked for 48 h, and then the anion exchange membrane II was fully washed with deionized water to obtain a counter ion of OH - Anion exchange membrane II.

[0104] c. Preparation of catalyst layer binder

[0105] The counter ions in the PBMP-60 prepared in Example 2 were ion exchanged as needed. The PBMP-60 powder prepared in Example 2 was immersed in a 2 mol / L NaOH solution for 48 h, and then washed thoroughly with deionized water. The counter ions were OH and ions were obtained by filtration. - Catalytic layer binder.

[0106] The counter ion prepared is OH - The catalyst layer binder is dissolved in a mixed solvent of isopropanol and water with a solid content of 2 wt %, and mixed with a metal catalyst to prepare a uniformly dispersed slurry to obtain a slurry of the catalyst layer binder based on PBMP-60 in Example 2.

[0107] Test Example 2

[0108] The following tests were performed on the anion exchange membrane 2 and the catalyst layer binder in Example 2 to characterize their basic properties.

[0109] (1) Hydroxide ion conductivity

[0110] The four-electrode electrochemical impedance spectroscopy was used to measure the -The anion exchange membrane was cut into 1 cm × 5 cm strips, then clamped on a fixture and placed in a tank filled with pure water. After the electrodes were installed, the electrochemical workstation was connected. In constant current mode (0.1 mA), the scanning frequency range was 1 MHz-100 Hz. On the Bode curve, the frequency range where the impedance was stable was found, and then the counter ion was read as OH on the corresponding curve. - The resistance R of anion exchange membrane II.

[0111] The hydroxide ion conductivity is calculated by the following formula:

[0112]

[0113] Among them, R is the counter ion OH - The resistance of the anion exchange membrane II, L is the distance between the electrodes (1.0 cm), W is the counter ion OH - The width of the anion exchange membrane II, d is the counter ion OH - The thickness of the anion exchange membrane II.

[0114] According to the hydroxyl ion conductivity detected at different temperatures, the counter ion is OH - The curve of the hydroxide ion conductivity of the anion exchange membrane II as a function of temperature is shown in Figure 3 As shown. Figure 3 It can be seen that at 80°C, the counter ion is OH - The hydroxide ion conductivity of the anion exchange membrane II reaches 182mS·cm -1 .

[0115] (2) Water absorption and swelling rate

[0116] The anion exchange membrane II was cut into strips of 1 cm × 8 cm and fully dried in an oven. The weight of the dried anion exchange membrane II was recorded as W. dry Then, the dried anion exchange membrane 2 was immersed in deionized water. The anion exchange membrane 2 was taken out every 12 hours, and the water on the surface of the anion exchange membrane 2 was wiped dry. The weight W of the anion exchange membrane 2 after immersion at different temperatures (30-80°C) was recorded. wet .

[0117] The water absorption (WU) is calculated by the following formula:

[0118]

[0119] According to the calculated water absorption rate detected at different temperatures, the water absorption rate of the anion exchange membrane 2 is plotted as a function of temperature, as shown in FIG. Figure 4 shown.

[0120] The swelling ratio (SR) is an important indicator to measure the dimensional stability of the membrane. It is measured by the length (L) of the dry and wet anion exchange membrane. dry ) and (L wet ) is calculated by the following formula:

[0121]

[0122] According to the swelling rates detected at different temperatures, the swelling rate curve of the anion exchange membrane 2 versus temperature is obtained, such as Figure 5 shown.

[0123] (3) Electrochemical performance

[0124] The PBMP-60 in Example 2 was used to prepare the catalyst layer binder and the anion exchange membrane 2, respectively. Pt / C was used as the cathode and anode catalysts. The Pt loading in the anode and cathode was 0.5 mg cm -2 , membrane electrode is prepared by catalyst coated membrane technology.

[0125] H2-O2 fuel cell test at 80 °C with a gas flow rate of 350 mL min -1 , the back pressure is 200 kPa, the relative humidity (RH) is 100%, and the electrochemical performance diagram of the catalyst layer binder prepared by PBMP-60 in Example 2 and the anion exchange membrane 2 is detected, as shown in FIG. Figure 6 shown.

[0126] In summary, at 80°C, the hydroxyl ion conductivity of anion exchange membrane II reaches 182 mS·cm -1 The anion exchange membrane II has moderate water absorption and swelling rate, and the maximum power density of the membrane electrode composed of PBMP-60 reaches 1.32W·cm -2 .

[0127] Example 3

[0128] S1. A polymerization mixture consisting of 3-piperidinecarboxaldehyde hydrochloride (0.21 g, 1.45 mmol) and p-terphenyl (0.3 g, 1.32 mmol) was placed in dichloromethane (1.3 mL), and trifluoromethanesulfonic acid (2.0 mL) was added to carry out a catalytic polycondensation reaction. The reaction was carried out at 22°C for 14 h to obtain a viscous dispersion of a polymer having a piperidine structure.

[0129] S2. Slowly drop the dispersion of the polymer with a piperidine structure in S1 into a 1:1 (v / v) mixed solution of methanol and water, filter the obtained light yellow fibrous polymer, wash it thoroughly, and vacuum dry it to obtain 0.42 g of white fibrous polymer powder with a piperidine structure.

[0130] S3. The polymer powder having a piperidine structure in S2 was dissolved in 4 mL of N-methylpyrrolidone, 0.50 mL of iodomethane and 0.2 g of potassium carbonate were added, and an ionization reaction was carried out at room temperature for 72 h to obtain a cationic polymer solution.

[0131] S4, slowly adding the cationic polymer solution in S3 into diethyl ether, filtering and drying, to obtain 0.55 g of highly alkali-resistant polyarylene alkylene piperidine cationic polymer powder, the structure of which is shown below:

[0132]

[0133] Application Example 3

[0134] a. Preparation of anion exchange membrane

[0135] The highly alkali-resistant polyarylene alkylene piperidine cationic polymer powder prepared in Example 3 was dissolved in 5.5 mL of dimethyl sulfoxide to obtain a cationic polymer solution with a mass fraction of about 10%. The polyarylene alkylene piperidine cationic polymer solution was coated on a clean glass plate by a casting method, and the glass plate was placed in a blast drying oven at 80°C for 24 hours to remove dimethyl sulfoxide. After the temperature dropped to room temperature, the glass plate was taken out, placed in deionized water for demolding, and then fully washed with deionized water to obtain a counter ion of I - Anion exchange membrane III.

[0136] b. Replace the counter ions in anion exchange membrane 3

[0137] The counter ion prepared in a is I - The anions in the anion exchange membrane 3 are exchanged as needed, and the counter ions are I - The anion exchange membrane was immersed in a 2 mol / L NaCl solution for 48 h and then washed thoroughly with deionized water to obtain a counter ion of Cl - Anion exchange membrane III.

[0138] c. Preparation of catalyst layer binder

[0139] The counter ions in the polyarylene alkylene piperidine cationic polymer prepared in Example 3 were ion exchanged as needed. The polyarylene alkylene piperidine cationic polymer powder prepared in Example 3 was immersed in a 2 mol / L NaOH solution for 48 h, and then washed with deionized water. The counter ions were OH and NH4OH. - Poly(arylene alkylene piperidinium) cationic polymers.

[0140] The counter ion prepared is OH -The polyarylene alkylene piperidine cationic polymer is dissolved in a mixed solvent of isopropanol and water with a solid content of 2 wt %, and mixed with a metal catalyst to prepare a uniformly dispersed slurry to obtain a slurry with the polyarylene alkylene piperidine cationic polymer in Example 3 as a catalyst layer binder.

[0141] Example 4

[0142] S1. A polymerization mixture consisting of 3-piperidinecarboxaldehyde hydrochloride (0.1 g, 0.72 mmol), p-terphenyl (0.3 g, 1.32 mmol) and p-cyanobenzaldehyde (0.1 g, 0.72 mmol) was placed in dichloromethane (0.9 mL), and trifluoromethanesulfonic acid (1.0 mL) was added to carry out a catalytic polycondensation reaction. The reaction was carried out at 0°C for 5 h to obtain a viscous dispersion of a polymer having a piperidine structure.

[0143] S2. Slowly drop the dispersion of the polymer with a piperidine structure in S1 into a 1:1 (v / v) mixed solution of methanol and water, filter the obtained light yellow fibrous polymer, wash it thoroughly, and vacuum dry it to obtain 0.34 g of white fibrous polymer powder with a piperidine structure.

[0144] S3. The polymer powder having a piperidine structure in S2 was dissolved in 4 mL of N-methylpyrrolidone, 0.18 mL of iodomethane and 0.12 g of potassium carbonate were added, and an ionization reaction was carried out at room temperature for 72 h to obtain a cationic polymer solution.

[0145] S4, slowly adding the cationic polymer solution in S3 into diethyl ether, filtering and drying, to obtain 0.36 g of highly alkali-resistant polyarylene alkylene piperidine cationic polymer powder, the structure of which is shown below:

[0146]

[0147] Application Example 4

[0148] a. Preparation of anion exchange membrane

[0149] The highly alkali-resistant polyarylene alkylene piperidine cationic polymer powder prepared in Example 4 was dissolved in 3 mL of dimethyl sulfoxide to obtain a cationic polymer solution with a mass fraction of about 10%. The polyarylene alkylene piperidine cationic polymer solution was coated on a clean glass plate by a casting method, and the glass plate was placed in a blast drying oven at 80°C for 24 hours to remove dimethyl sulfoxide. After the temperature dropped to room temperature, the glass plate was taken out, placed in deionized water for demolding, and then fully washed with deionized water to obtain a counter ion of I - Anion exchange membrane IV.

[0150] b. Replace the counter ions in anion exchange membrane 4

[0151] The counter ion prepared in a is I - The anions in the anion exchange membrane 4 are exchanged as needed, and the counter ions are I - The anion exchange membrane was immersed in a 2 mol / L NaCl solution for 48 h and then washed thoroughly with deionized water to obtain a counter ion of Cl - Anion exchange membrane IV.

[0152] Example 5

[0153] S1. A polymerization mixture consisting of 3-piperidinecarboxaldehyde hydrochloride (0.10 g, 0.73 mmol), p-terphenyl (0.3 g, 1.32 mmol) and 1-piperidin-3-one hydrochloride (0.10 g, 0.73 mmol) was placed in dichloromethane (4 mL), and trifluoromethanesulfonic acid (6.0 mL) was added to carry out a catalytic polycondensation reaction. The reaction was carried out at 0°C for 22 hours to obtain a viscous dispersion of a polymer having a piperidine structure.

[0154] S2. Slowly drop the dispersion of the polymer with a piperidine structure in S1 into a 1:1 (v / v) mixed solution of methanol and water, filter the obtained light yellow fibrous polymer, wash it thoroughly, and vacuum dry it to obtain 0.45 g of white fibrous polymer powder with a piperidine structure.

[0155] S3. The polymer powder having a piperidine structure in S2 was dissolved in 4 mL of N-methylpyrrolidone, 0.44 mL of iodomethane and 0.23 g of potassium carbonate were added, and an ionization reaction was carried out at room temperature for 72 h to obtain a cationic polymer solution.

[0156] S4, slowly adding the cationic polymer solution in S3 into diethyl ether, filtering and drying, to obtain 0.52 g of highly alkali-resistant polyarylene alkylene piperidine cationic polymer powder, the structure of which is shown below:

[0157]

[0158] Application Example 5

[0159] a. Preparation of anion exchange membrane

[0160] The highly alkali-resistant polyarylene alkylene piperidine cationic polymer powder prepared in Example 5 was dissolved in 5 mL of dimethyl sulfoxide to obtain a polyarylene alkylene piperidine cationic polymer solution with a mass fraction of about 10%. The polyarylene alkylene piperidine cationic polymer solution was coated on a clean glass plate by a casting method, and the glass plate was placed in a blast drying oven at 80°C for 24 hours to remove dimethyl sulfoxide. After the temperature dropped to room temperature, the glass plate was taken out, placed in deionized water for demolding, and then fully washed with deionized water to obtain a glass plate with a counter ion of I - Anion exchange membrane V.

[0161] b. Replace the counter ions in anion exchange membrane 5

[0162] The counter ion prepared in a is I - The anions in the anion exchange membrane 5 are exchanged as needed, and the counter ions are I - The anion exchange membrane was immersed in a 2 mol / L NaCl solution for 48 h and then washed thoroughly with deionized water to obtain a counter ion of Cl - Anion exchange membrane V.

[0163] Example 6

[0164] S1. A polymerization mixture consisting of 3-piperidinecarboxaldehyde hydrochloride (0.20 g, 1.43 mmol) and biphenyl (0.20 g, 1.32 mmol) was placed in dichloromethane (4.0 mL), and trifluoromethanesulfonic acid (5.2 mL) was added to carry out a catalytic polycondensation reaction. The reaction was carried out at 22°C for 2 h to obtain a viscous dispersion of a polymer having a piperidine structure.

[0165] S2. Slowly drop the dispersion of the polymer with a piperidine structure in S1 into a 1:1 (v / v) mixed solution of methanol and water, filter the obtained light yellow fibrous polymer, wash it thoroughly, and vacuum dry it to obtain 0.35 g of white fibrous polymer powder with a piperidine structure.

[0166] S3. The polymer powder with piperidine structure in S2 was dissolved in 4 mL of N-methylpyrrolidone, 0.015 mL of iodomethane and 0.2 g of potassium carbonate were added, and ionization reaction was carried out at room temperature for 72 h, and then 0.1 g of 1,6-dibromohexane was added to obtain a cationic polymer solution.

[0167] S4, slowly adding the cationic polymer solution in S3 into diethyl ether, filtering and drying, to obtain 0.44 g of highly alkali-resistant polyarylene alkylene piperidine cationic polymer powder, the structure of which is shown below:

[0168]

[0169] Application Example 6

[0170] a. Preparation of anion exchange membrane

[0171] The highly alkali-resistant polyarylene alkylene piperidine cationic polymer powder prepared in Example 6 was dissolved in 4 mL of dimethyl sulfoxide to obtain a polyarylene alkylene piperidine cationic polymer solution with a mass fraction of about 10%. The polyarylene alkylene piperidine cationic polymer solution was coated on a clean glass plate by a casting method, and the glass plate was placed in a blast drying oven at 80°C for 24 hours to remove dimethyl sulfoxide. After the temperature dropped to room temperature, the glass plate was taken out, placed in deionized water for demolding, and then fully washed with deionized water to obtain a counter ion of I - Anion exchange membrane VI.

[0172] b. Replace the counter ions in anion exchange membrane VI

[0173] The counter ion prepared in a is I - The anions in the anion exchange membrane VI are exchanged as needed, and the counter ions are I - The anion exchange membrane was immersed in a 2 mol / L NaCl solution for 48 h and then washed thoroughly with deionized water to obtain a counter ion of Cl - Anion exchange membrane VI.

[0174] Example 7

[0175] S1. A polymerization mixture consisting of 3-piperidinecarboxaldehyde hydrochloride (0.20 g, 1.43 mmol), spiro(cyclohexane-1,9'-fluorene) (0.16 g, 0.65 mmol) and 9,9-dimethylfluorene (0.13 g, 0.65 mmol) was placed in dichloromethane (3 mL), and trifluoromethanesulfonic acid (4.0 mL) was added to carry out a catalytic polycondensation reaction. The reaction was carried out at 22°C for 10 h to obtain a viscous dispersion of a polymer having a piperidine structure.

[0176] S2. Slowly drop the dispersion of the polymer with a piperidine structure in S1 into a 1:1 (v / v) mixed solution of methanol and water, filter the obtained light yellow fibrous polymer, wash it thoroughly, and vacuum dry it to obtain 0.43 g of white fibrous polymer powder with a piperidine structure.

[0177] S3. The polymer having a piperidine structure in S2 was dissolved in 5 mL of N-methylpyrrolidone, 0.013 mL of iodomethane and 0.2 g of potassium carbonate were added, and an ionization reaction was carried out at room temperature for 72 hours to obtain a cationic polymer solution.

[0178] S4, slowly adding the cationic polymer solution in S3 into diethyl ether, filtering and drying, to obtain 0.46 g of highly alkali-resistant polyarylene alkylene piperidine cationic polymer powder, the structure of which is shown below:

[0179]

[0180] Application Example 7

[0181] a. Replace the counter ions in the cationic polymer powder

[0182] The counter ion prepared in Example 7 is I - The highly alkali-resistant polyarylene alkylene piperidine cationic polymer powder is ion exchanged as needed, and the counter ion is I - The polyarylene alkylene piperidine cationic polymer powder was immersed in a 2 mol / L NaOH solution for 48 h, and then the powder was fully washed with deionized water. The counter ion OH was obtained by filtration. - Highly alkali-resistant polyarylene alkylene piperidine cationic polymer powder.

[0183] b. Preparation of catalyst layer binder

[0184] The counter ion prepared by a is OH - The highly alkali-resistant poly(arylene alkylene piperidinium) cationic polymer powder as the counter ion for OH - The prepared counter ion is OH - The cationic polymer is dissolved in a mixed solvent of isopropanol and water with a solid content of 2 wt %, and mixed with a metal catalyst to prepare a slurry of a uniformly dispersed catalyst layer binder, thereby obtaining a slurry of the cationic polymer based on Example 7 as a catalyst layer binder.

[0185] Example 8

[0186] S1. A polymerization mixture consisting of 3-piperidinecarboxaldehyde hydrochloride (0.19 g, 1.43 mmol) and bibenzyl (0.23 g, 1.29 mmol) was placed in dichloromethane (2 mL), and trifluoromethanesulfonic acid (4.0 mL) was added to carry out a catalytic polycondensation reaction. The reaction was carried out at 22° C. for 40 h to obtain a viscous dispersion of a piperidine structure polymer.

[0187] S2. Slowly drop the dispersion of the polymer with a piperidine structure in S1 into a 1:1 (v / v) mixed solution of methanol and water, filter the obtained light yellow fibrous polymer, wash it thoroughly, and vacuum dry it to obtain 0.37 g of white fibrous polymer powder with a piperidine structure.

[0188] S3. The polymer powder having a piperidine structure in S2 was dissolved in 5 mL of N-methylpyrrolidone, 0.19 mL of iodomethane and 0.21 g of potassium carbonate were added, and an ionization reaction was carried out at room temperature for 72 hours to obtain a cationic polymer solution.

[0189] S4, slowly adding the cationic polymer solution in S3 into diethyl ether, filtering and drying, to obtain 0.41 g of highly alkali-resistant polyarylene alkylene piperidine cationic polymer powder, the structure of which is shown below:

[0190]

[0191] Application Example 8

[0192] a. Replace the counter ions in the cationic polymer powder

[0193] The counter ion prepared in Example 8 is I - The highly alkali-resistant polyarylene alkylene piperidine cationic polymer powder is ion exchanged as needed, and the counter ion is I - The polyarylene alkylene piperidine cationic polymer powder was immersed in a 2 mol / L NaOH solution for 48 h, and then the powder was fully washed with deionized water. The counter ion OH was obtained by filtration. - Highly alkali-resistant polyarylene alkylene piperidine cationic polymer powder.

[0194] b. Preparation of catalyst layer binder

[0195] The counter ion prepared by a is OH - The highly alkali-resistant poly(arylene alkylene piperidinium) cationic polymer powder as the counter ion for OH - The prepared counter ion is OH - The cationic polymer is dissolved in a mixed solvent of isopropanol and water with a solid content of 2 wt %, and mixed with a metal catalyst to prepare a slurry of a uniformly dispersed catalyst layer binder, thereby obtaining a slurry of the cationic polymer based on Example 8 as a catalyst layer binder.

[0196] Example 9

[0197] S1. A polymerization mixture consisting of 3-piperidinecarboxaldehyde hydrochloride (0.39 g, 2.84 mmol), 9,9-dipropylfluorene (0.35 g, 1.29 mmol) and bibenzyl (0.23 g, 1.29 mmol) was placed in dichloromethane (5.0 mL), and trifluoromethanesulfonic acid (8.0 mL) was added to carry out a catalytic polycondensation reaction. The reaction was carried out at 22°C for 24 hours to obtain a viscous dispersion of a piperidine structure polymer.

[0198] S2. Slowly drop the dispersion of the polymer with a piperidine structure in S1 into a 1:1 (v / v) mixed solution of methanol and water, filter the obtained light yellow fibrous polymer, wash it thoroughly, and vacuum dry it to obtain 0.91 g of white fibrous polymer powder with a piperidine structure.

[0199] S3. The polymer powder having a piperidine structure in S2 was dissolved in 4 mL of N-methylpyrrolidone, 0.66 mL of iodomethane and 0.36 g of potassium carbonate were added, and an ionization reaction was carried out at room temperature for 72 h to obtain a cationic polymer solution.

[0200] S4, slowly adding the cationic polymer solution in S3 into diethyl ether, filtering and drying, to obtain 1.02 g of highly alkali-resistant polyarylene alkylene piperidine cationic polymer powder, the structure of which is shown below:

[0201]

[0202] Application Example 9

[0203] a. Replace the counter ions in the cationic polymer powder

[0204] The counter ion prepared in Example 9 is I - The highly alkali-resistant polyarylene alkylene piperidine cationic polymer powder is ion exchanged as needed, and the counter ion is I - The polyarylene alkylene piperidine cationic polymer powder was immersed in a 2 mol / L NaOH solution for 48 h, and then the powder was fully washed with deionized water. The counter ion OH was obtained by filtration. - Highly alkali-resistant polyarylene alkylene piperidine cationic polymer powder.

[0205] b. Preparation of catalyst layer binder

[0206] The counter ion prepared by a is OH - The highly alkali-resistant poly(arylene alkylene piperidinium) cationic polymer powder as the counter ion for OH - The prepared counter ion is OH - The cationic polymer was dissolved in a mixed solvent of isopropanol and water with a solid content of 2 wt %, and mixed with a metal catalyst to prepare a uniformly dispersed slurry, thereby obtaining a slurry based on the cationic polymer of Example 9 as a catalyst layer binder.

[0207] Example 10

[0208] S1. A polymerization mixture consisting of 3-piperidinecarboxaldehyde hydrochloride (0.13 g, 0.99 mmol), trifluoroacetophenone (0.03 g, 0.21 mmol), trifluoroacetone (0.02 g, 0.21 mmol) and spiro(cyclopentane-1,9'-fluorene) (0.31 g, 1.29 mmol) was placed in dichloromethane (8.0 mL), and trifluoromethanesulfonic acid (14.0 mL) was added to carry out a catalytic polycondensation reaction. The reaction was carried out at 22°C for 48 hours to obtain a viscous dispersion of a piperidine structure polymer.

[0209] S2. Slowly drop the dispersion of the polymer with a piperidine structure in S1 into a 1:1 (v / v) mixed solution of methanol and water, filter the obtained light yellow fibrous polymer, wash it thoroughly, and vacuum dry it to obtain 0.42 g of white fibrous polymer powder with a piperidine structure.

[0210] S3. The polymer powder having a piperidine structure in S2 was dissolved in 8 mL of N-methylpyrrolidone, 0.52 mL of iodomethane and 0.24 g of potassium carbonate were added, and an ionization reaction was carried out at room temperature for 72 h to obtain a cationic polymer solution.

[0211] S4, slowly adding the cationic polymer solution in S3 into diethyl ether, filtering and drying, to obtain 0.45 g of highly alkali-resistant polyarylene alkylene piperidine cationic polymer powder, the structure of which is shown below:

[0212]

[0213] Application Example 10

[0214] a. Replace the counter ions in the cationic polymer powder

[0215] The counter ion prepared in Example 10 is I - The highly alkali-resistant polyarylene alkylene piperidine cationic polymer powder is ion exchanged as needed, and the counter ion is I - The polyarylene alkylene piperidine cationic polymer powder was immersed in a 2 mol / L NaOH solution for 48 h, and then the powder was fully washed with deionized water. The counter ion OH was obtained by filtration. - Highly alkali-resistant polyarylene alkylene piperidine cationic polymer powder.

[0216] b. Preparation of catalyst layer binder

[0217] The counter ion prepared by a is OH - The highly alkali-resistant poly(arylene alkylene piperidinium) cationic polymer powder as the counter ion for OH - The prepared counter ion is OH -The cationic polymer was dissolved in a mixed solvent of isopropanol and water with a solid content of 2 wt %, and mixed with a metal catalyst to prepare a uniformly dispersed slurry, thereby obtaining a slurry based on the cationic polymer of Example 10 as a catalyst layer binder.

[0218] Therefore, the present invention adopts a highly alkali-resistant polyarylene alkylene piperidine cationic polymer with the above structure and its preparation method and application. The prepared cationic polymer can be used as a membrane material in many fields such as fuel cells and water electrolysis. At the same time, the cationic polymer can also be used as a catalyst binder material in fuel cells and water electrolysis catalyst layers.

[0219] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that they can still modify or replace the technical solution of the present invention with equivalents, and these modifications or equivalent replacements cannot cause the modified technical solution to deviate from the spirit and scope of the technical solution of the present invention.

Claims

1. A highly alkali-resistant polyarylene alkylene piperidine cationic polymer, characterized in that: The polyarylene alkylene piperidinium cationic polymer comprises the structural unit: Among them, R 1 is selected from H atoms, hydrocarbon groups containing 1 to 20 carbon atoms, or R 1 Connected to form a cycloalkyl group consisting of 4 to 10 carbon atoms; counterion A - One or more selected from halide ions, methyl sulfate ions, hydroxide ions or bicarbonate ions; The Ar' fragment is selected from one or more of the following structures, 2. A highly alkali-resistant polyarylene alkylene piperidine cationic polymer according to claim 1, characterized in that: The polyarylene alkylene piperidinium cationic polymer also includes one or more of the following structural units, Wherein, k = 0 or 1; x = 0-12; R 2 Independently selected hydrogen atoms or hydrocarbon groups with 1-20 carbon atoms, fully or partially fluorinated alkyl groups with 1-6 carbon atoms; Q' is selected from H atoms, -N + (R 5 )3 and one or more of the cations containing nitrogen heterocycles, counter anions A - selected from halide ions, methyl sulfate ions, hydroxide ions or bicarbonate ions; R 3 and R 4 Each independently selected H atom, a hydrocarbon group having 1 to 20 carbon atoms, or an independent R 3 are linked to each other to form a cycloalkyl group consisting of 4 to 10 carbon atoms, or independently R 4 They are linked to each other to form a cycloalkyl group consisting of 4 to 10 carbon atoms.

3. A method for preparing a highly alkali-resistant polyarylene alkylene piperidine cationic polymer according to any one of claims 1 to 2, characterized in that: The following steps are included: S1, 1-R 6 -3-piperidinecarboxaldehyde or its salt or hydrate and an aromatic compound are mixed to obtain a polymerization monomer system, and the system is placed in a first organic solvent, and an organic strong acid is added to perform catalytic polycondensation to obtain a polymer dispersion having a piperidine structure; S2, slowly dropping the polymer dispersion having a piperidine structure in S1 into the first precipitant, filtering, washing and drying to obtain a polymer powder having a piperidine structure; S3, dissolving the polymer powder having a piperidine structure in S2 in a second organic solvent, adding an ionizing agent, and performing an ionization reaction at 0-100° C. for 0.1-100 h to obtain a cationic polymer solution; S4. Slowly add the cationic polymer solution in S3 into the second precipitant, filter and dry to obtain polyarylene alkylene piperidine cationic polymer powder.

4. The method for preparing a highly alkali-resistant polyarylene alkylene piperidine cationic polymer according to claim 3, characterized in that: S1, 1-R 6 The structural formula of 3-piperidinecarboxaldehyde is shown below: Among them, R 6 One or more selected from H atoms and hydrocarbon groups containing 1 to 20 carbon atoms.

5. The method for preparing a highly alkali-resistant polyarylene alkylene piperidine cationic polymer according to claim 3, characterized in that: In S1, the polymerization monomer system also includes a carbonyl-containing compound, and the carbonyl-containing compound is one or more of the following structures: Wherein, k is 0 or 1, x=0-12; Q is selected from one or more of H atoms and halogen atoms; R 7 One or more selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a fully or partially fluorinated alkyl group having 1 to 6 carbon atoms; R 8 and R 9 Independently selected from H atoms or hydrocarbon groups containing 1-20 carbon atoms.

6. The method for preparing a highly alkali-resistant polyarylene alkylene piperidine cationic polymer according to claim 3, characterized in that: S1, 1-R 6 -The molar ratio of 3-piperidinecarboxaldehyde or its salt or hydrate to the organic strong acid is 1:(1-20).

7. The method for preparing a highly alkali-resistant polyarylene alkylene piperidine cationic polymer according to claim 5, characterized in that: S1, 1-R 6 The molar ratio of 3-piperidinecarboxaldehyde or its salt or hydrate to the carbonyl-containing compound and the organic strong acid is 1:(1-20).

8. The method for preparing a highly alkali-resistant polyarylene alkylene piperidine cationic polymer according to claim 3, characterized in that: In S3, the ionizing agent is dimethyl sulfate or a halogenated hydrocarbon having 1 to 20 carbon atoms, and its structure is Among them, R 101 , R 102 , R 103 and R 104 They are independently selected from hydrogen, halogen, a hydrocarbon group or a halogenated hydrocarbon group having 1 to 20 carbon atoms, or an aryl group or a halogenated aryl group having 1 to 20 carbon atoms, and the halogenated hydrocarbon group or the halogenated aryl group contains at least one halogen atom.

9. The method for preparing a highly alkali-resistant polyarylene alkylene piperidine cationic polymer according to claim 3, characterized in that: The polyarylene alkylene piperidine cationic polymer powder in S4 is immersed in a solution containing other types of counter ions to perform ion exchange, thereby obtaining a cationic polymer containing other types of counter ions.

10. An application of the highly alkali-resistant polyarylene alkylene piperidine cationic polymer according to any one of claims 1 to 2, characterized in that: The highly alkali-resistant polyarylene alkylene piperidine cationic polymer is used in anion exchange membrane or catalyst layer binder.

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