High-alkali-resistance polyarylene alkylene piperidine cationic polymer with branched structure as well as preparation method and application of high-alkali-resistance polyarylene alkylene piperidine cationic polymer

Abstract

The invention relates to the technical field of cationic polymers, in particular to a high-alkali-resistance polyarylene alkylene piperidine cationic polymer with a branched structure as well as a preparation method and application of the high-alkali-resistance polyarylene alkylene piperidine cationic polymer with the branched structure, and the high-alkali-resistance polyarylene alkylene piperidine cationic polymer comprises one or more of a central unit, a linear unit L1 and a linear unit L2, the central unit comprises one or more of an MA unit, a piperidine cation unit m-DMP and a CA unit, the linear unit L1 comprises the piperidine cation unit m-DMP and a BA unit, and the linear unit L2 comprises a BA unit and a CA unit. By adopting the steps, the interaction force between polymer molecular chains is enhanced and the polymer molecular weight is increased through a branching strategy, so that the water absorption swelling of the prepared anion exchange membrane is inhibited, and the anion exchange membrane shows outstanding conductivity and mechanical properties; meanwhile, piperidine cations are linked to a polymer skeleton with a branched structure through a flexible spacer, so that the prepared anion exchange membrane has outstanding alkali resistance.

Description

Technical Field

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

[0002] The efficient development and utilization of hydrogen energy is an important means to solve the current environmental problems and energy crisis. Anion exchange membrane water electrolysis (AEMWE) and anion exchange membrane fuel cell (AEMFC) have the advantages of low cost and high efficiency, and are important means for the development and utilization of green hydrogen. However, the alkaline operating environment of AEMFC and AEMWE poses new challenges to the stability of polymer electrolytes, especially to the cationic functional groups in polymer electrolytes. Piperidinium cations have received extensive attention due to their outstanding alkaline resistance and easy linking to polyaromatic backbone chains. Among them, poly (aryl-piperidinium salt) cationic polymers in which piperidinium cations are linked to aromatic units at the 4th position have been extensively studied due to their simple synthesis and excellent performance, and have achieved small-scale commercialization. On the other hand, due to the direct linking of the piperidine ring to the aromatic unit, the alkaline stability of the piperidinium cation is reduced (ChemSusChem 2024, e202301656).

[0003] In addition, the polymer electrolytes used in AEMWE and AEMFC have always faced a trade-off between conductivity and water absorption and swelling. When the polymer electrolyte has a higher ion exchange capacity, its ion conductivity increases, leading to an increase in device efficiency. However, the higher ion exchange capacity causes the polymer electrolyte to absorb water excessively and swell at high temperatures, resulting in a decrease in mechanical properties, which will lead to the inability to ensure the stable operation of AEMFC and AEMWE, and even safety issues. Therefore, how to solve this trade-off dilemma is an important part of polymer electrolyte research. Summary of the invention

[0004] The purpose of the present invention is to provide a highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure and a preparation method and application thereof, which can improve the mechanical and chemical stability of anion exchange membranes and catalyst layer binders when applied to anion exchange membranes and catalyst layer binders.

[0005] To achieve the above object, the present invention provides a highly alkali-resistant polyarylene alkylene piperidine cationic polymer having a branched structure, comprising one or more of a central unit, a linear unit L1 and a linear unit L2, wherein the central unit comprises one or more of a MA unit, a piperidine cationic unit m-DMP and a CA unit, the linear unit L1 comprises a piperidine cationic unit m-DMP and a BA unit, and the linear unit L2 comprises a BA unit and a CA unit;

[0006] The structural formula of the piperidinium cation unit m-DMP is Among them, R 1 and R 2 independently selected from hydrocarbon groups having 1 to 20 carbon atoms, or R 1 and R 2 Connected to form a cycloalkyl group consisting of 4 to 7 carbon atoms, the counterion A - One or more selected from halide ions, methyl sulfate ions, hydroxide ions or bicarbonate ions.

[0007] Preferably, the MA unit comprises 2-6 aromatic rings, independently selected from one or more of the following structures,

[0008]

[0009] Preferably, the BA unit is independently selected from one or more of the following structures:

[0010]

[0011] Preferably, the CA unit comprises One or more of the following, where R 3 and R 4 independently selected from hydrocarbon groups having 1 to 20 carbon atoms, or R 3 and R 4 are connected to form a cycloalkyl group consisting of 4 to 7 carbon atoms; each R 5 Independently selected from hydrogen atoms, hydrocarbon groups with 1 to 20 carbon atoms, and fully or partially fluorinated alkyl groups with 1 to 6 carbon atoms;

[0012] k=0 or 1;x=0-12;Q is selected from H atom, -N + (R 6 )3 and one or more of a nitrogen-containing heterocyclic cation; -N + (R 6 )3, each R 6 Independently selected from hydrocarbon groups having 1 to 20 carbon atoms.

[0013] Preferably, the nitrogen-containing heterocyclic cation comprises one or more of a partially or completely substituted pyrazole, pyrrole, piperidine, imidazole and quinine cation, having the following structure:

[0014]

[0015] Among them, R 61 -R 610 independently selected from hydrocarbon groups having 1 to 20 carbon atoms, the counterion A -One or more selected from halide ions, methyl sulfate ions, hydroxide ions or bicarbonate ions.

[0016] Preferably, the central unit is connected to the linear unit L1, and the central unit includes a MA unit and a piperidinium cationic unit m-DMP, and its structural formula is shown below:

[0017]

[0018] Preferably, the linear unit L1 is connected to the central unit and the linear unit L2, and the central unit includes a MA unit, a piperidinium cationic unit m-DMP and a CA unit, and its structure is shown below:

[0019]

[0020] The method for preparing the above-mentioned highly alkali-resistant polyarylene alkylene piperidine cationic polymer having a branched structure comprises the following steps:

[0021] S1, raw materials MA', 1-R 7 Piperidine-3-carboxaldehyde or its salt or hydrate and BA' are mixed and dissolved or dispersed in a first organic solvent, and polycondensed under the catalysis of an organic strong acid, and reacted at -20-100° C. for 0.1-200 hours to obtain a polyaromatic polymer precursor solution or dispersion containing a piperidine structure;

[0022] Preferably, in S1, 1-R 7 The molar ratio of piperidine-3-carboxaldehyde or its salt or hydrate to the organic strong acid is 1:(1-20).

[0023] The polyaromatic polymer precursor containing piperidine structure has the following structural formula:

[0024]

[0025] Among them, the MA unit is a polysubstituted aromatic unit, the BA unit is a disubstituted aromatic unit, and R 8 Independently selected from H atoms or hydrocarbon groups with 1-20 carbon atoms.

[0026] S2, slowly dropping the piperidine structure-containing polyaromatic polymer precursor solution or dispersion obtained in S1 into a precipitant 1, filtering after precipitation to obtain a fibrous polymer, fully washing and drying to obtain a piperidine structure-containing polyaromatic polymer precursor;

[0027] S3, dispersing or dissolving the polyaromatic polymer precursor containing piperidine structure obtained in S2 in a second organic solvent, adding an ionizing agent, and performing an ionization reaction at 0-100° C. for 0.1-200 h to obtain a highly alkali-resistant polyarylene alkylene piperidine cationic polymer solution or dispersion having a branched structure;

[0028] S4, slowly adding the highly alkali-resistant polyarylene alkylene piperidine cationic polymer solution or dispersion having a branched structure obtained in S3 into the second precipitant, filtering and drying the precipitate after precipitation, to obtain a highly alkali-resistant polyarylene alkylene piperidine cationic polymer having a branched structure.

[0029] The method for preparing the above-mentioned highly alkali-resistant polyarylene alkylene piperidine cationic polymer having a branched structure comprises the following steps:

[0030] S1, raw materials MA', 1-R 7 Piperidine-3-carboxaldehyde or its salt or hydrate, BA' and compound CA" are dissolved or dispersed in a first organic solvent, and a polycondensation reaction is carried out under the catalysis of an organic strong acid.

[0031] The reaction is carried out at -20-100° C. for 0.1-200 hours to obtain a polyaromatic polymer precursor solution or dispersion containing a piperidine structure;

[0032] Preferably, in S1, the aldehyde-containing compound and 1-R 7 The molar ratio of the mixture of piperidine-3-carboxaldehyde or its salt or hydrate to the organic strong acid is 1:(1-20).

[0033] The polyaromatic polymer precursor containing piperidine structure has the following structural formula:

[0034]

[0035] Among them, the MA unit is a polysubstituted aromatic unit, the BA unit is a disubstituted aromatic unit, and R 8 Independently selected from H atoms or hydrocarbon groups with 1-20 carbon atoms.

[0036] S2, slowly dropping the piperidine structure-containing polyaromatic polymer precursor solution or dispersion obtained in S1 into a precipitant 1, filtering after precipitation to obtain a fibrous polymer, fully washing and drying to obtain a piperidine structure-containing polyaromatic polymer precursor;

[0037] S3, dispersing or dissolving the polyaromatic polymer precursor containing piperidine structure obtained in S2 in a second organic solvent, adding an ionizing agent, and performing an ionization reaction at 0-100° C. for 0.1-200 h to obtain a highly alkali-resistant polyarylene alkylene piperidine cationic polymer solution or dispersion having a branched structure;

[0038] S4, slowly adding the highly alkali-resistant polyarylene alkylene piperidine cationic polymer solution or dispersion having a branched structure obtained in S3 into the second precipitant, filtering and drying the precipitate after precipitation, to obtain a highly alkali-resistant polyarylene alkylene piperidine cationic polymer having a branched structure.

[0039] Preferably, in S1, MA' is an aromatic compound containing 2 to 6 aromatic rings, independently selected from one or more of the following structures,

[0040]

[0041] BA' has one or more of the following structures,

[0042]

[0043] 1-R 7 Piperidine-3-carboxaldehyde is One or more selected from the following structures

[0044]

[0045] Preferably, compound CA" is One or more of the following, where R 9 independently selected from H atoms or hydrocarbon groups containing 1-20 carbon atoms; k = 0 or 1; x = 0-12; each R 10 Q" is independently selected from a hydrogen atom or a hydrocarbon group with 1-20 carbon atoms, or a fully or partially fluorinated alkyl group with 1-6 carbon atoms; Q" is selected from one or more of a H atom and a halogen atom.

[0046] Preferably, the CA' unit is One or more of;

[0047] Among them, R 11 and R 12 are independently selected from H atoms or hydrocarbon groups with 1 to 20 carbon atoms; each R 13 Independently selected from hydrogen atoms or hydrocarbon groups with 1-20 carbon atoms, fully or partially fluorinated alkyl groups with 1-6 carbon atoms; k=0 or 1; x=0-12; Q' is selected from one or more of H atoms or halogen atoms.

[0048] Preferably, in S1, the molar ratio of MA' to BA' is 0.001-0.3.

[0049] Preferably, in S1, the first organic solvent includes one or more of dichloromethane, chloroform, carbon tetrachloride, dichloroethane, nitromethane or nitrobenzene.

[0050] Preferably, in S1, the strong organic acid includes one or more of trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoro-1-propanesulfonic acid, trifluoroacetic acid, perfluoropropionic acid, heptafluorobutyric acid or methanesulfonic acid.

[0051] Preferably, in S2, the precipitant 1 comprises one or more of water, ethanol, methanol and isopropanol.

[0052] Preferably, in S3, the ionizing agent is dimethyl sulfate, a halogenated hydrocarbon having 1 to 20 carbon atoms, N(R 14 )3 and one or more of nitrogen heterocyclic rings, N(R 14 )3, each R 14 Independently selected from hydrocarbon groups with carbon atoms between 1 and 20, the nitrogen heterocyclic ring contains one or more of partially or completely substituted pyrazole, pyrrole, piperidine, imidazole and quinine, and the structure is as follows:

[0053]

[0054] Among them, R 141 –R 1410 Each substituent is independently selected from a hydrocarbon group having 1 to 20 carbon atoms.

[0055] Preferably, in S3, the second organic solvent includes one or more of the polar aprotic solvents dimethyl sulfoxide, N-methylpyrrolidone, N,N-dimethylacetamide and N,N-dimethylformamide.

[0056] Preferably, in S4, the second precipitant comprises one or more of water, acetone, ether, toluene, ethyl acetate or petroleum ether.

[0057] The application of the highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure is used to prepare anion exchange membranes and catalyst layer binders.

[0058] Preferably, the preparation method of the anion exchange membrane is to dissolve or disperse a highly alkali-resistant polyarylene alkylene piperidine cationic polymer having a branched structure in a third organic solvent to obtain a highly alkali-resistant polyarylene alkylene piperidine cationic polymer solution or dispersion having a branched structure, apply the highly alkali-resistant polyarylene alkylene piperidine cationic polymer solution or dispersion having a branched structure to a substrate, dry to remove the third organic solvent, and obtain the anion exchange membrane after stripping and washing.

[0059] 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 30-120°C.

[0060] 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.

[0061] Preferably, the preparation method of the catalyst layer binder is to dissolve or disperse the highly alkali-resistant polyarylene alkylene piperidine cationic polymer having a branched structure 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 with the highly alkali-resistant polyarylene alkylene piperidine cationic polymer having a branched structure as the catalyst layer binder.

[0062] Preferably, the fourth organic solvent is a low boiling point organic solvent, more preferably one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol or water.

[0063] Preferably, the concentration of the highly alkali-resistant polyarylene alkylene piperidine cationic polymer solution having a branched structure is 1-80 wt %, more preferably 1-75 wt %, and further preferably 1-40 wt %.

[0064] The mechanism of the present invention is as follows:

[0065] By adding multifunctional monomers to the organic strong acid catalyzed polycondensation reaction, the cationic polymer forms a branched structure, which greatly increases the molecular weight of the polymer and strengthens the entanglement between polymer chains, which greatly improves the swelling resistance of the cationic polymer, thereby ensuring the stability and safe operation of the device. In addition, the piperidinium cation is connected to the aromatic group through a flexible spacer, thereby reducing the influence of the aromatic ring on the stability of the piperidinium cation, thereby improving its alkali stability.

[0066] Therefore, the present invention adopts the highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure, and its beneficial effects are:

[0067] 1. The preparation method of the highly alkali-resistant cationic polymer with a branched structure provided by the present invention is simple to operate, has mild reaction conditions, and is conducive to expanding production;

[0068] 2. The highly alkali-resistant cationic polymer with a branched structure prepared by the present invention still has outstanding mechanical properties and anti-swelling properties at a high ion exchange capacity, and exhibits excellent physical stability when used in the preparation of slurry for bonding anion exchange membranes and catalyst layers;

[0069] 3. The highly alkali-resistant cationic polymer with a branched structure provided by the present invention enhances the interaction force between polymer molecular chains and increases the polymer molecular weight through a branching strategy. At the same time, the piperidine cation is linked to the polymer skeleton with a branched structure through a flexible spacer, so that the prepared anion exchange membrane has outstanding alkali resistance.

[0070] 4. The highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure prepared by the present invention can be used as a membrane material in many fields such as fuel cells and water electrolysis. At the same time, the highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure can also be used as a catalyst binder material in fuel cells and water electrolysis catalyst layers.

[0071] The technical solution of the present invention is further described in detail below through the accompanying drawings and embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0072] Figure 1 is a curve diagram showing the change of the hydroxide ion conductivity of the anion exchange membrane in Application Example 1 of the present invention and Comparative Example 1 with the temperature;

[0073] Figure 2 is a curve diagram showing the water absorption rate of the anion exchange membrane in Application Example 1 of the present invention and Comparative Example 1 as a function of temperature;

[0074] Figure 3 is a curve diagram showing the change in swelling rate of anion exchange membrane 1 in Application Example 1 of the present invention and anion exchange membrane in Comparative Example 1 as a function of temperature;

[0075] Figure 4 is a comparison diagram of the mechanical properties of the anion exchange membranes in Application Example 1 of the present invention and Comparative Example 1;

[0076] Figure 5 This is an electrochemical performance diagram of the catalyst layer binder and anion exchange membrane 1 prepared in Application Example 1 of the present invention. DETAILED DESCRIPTION

[0077] 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.

[0078] Example 1

[0079] S1. 1,3,5-triphenylbenzene (0.01 g, 0.04 mmol), 1-piperidine-3-carboxaldehyde hydrochloride (0.19 g, 1.43 mmol) and p-terphenyl (0.30 g, 1.32 mmol) were mixed and dispersed in dichloromethane (1.0 mL), and polycondensed under the catalysis of trifluoromethanesulfonic acid (2.0 mL). The reaction was carried out at 25° C. for 10 h to obtain a viscous polyaromatic polymer precursor dispersion containing a piperidine structure;

[0080] S2, slowly dropwise adding the polyaromatic polymer precursor dispersion containing piperidine structure obtained in S1 into a 1:1 (v / v) mixed solution of methanol and water, filtering after precipitation to obtain a white fibrous polymer, filtering, washing thoroughly and vacuum drying to obtain 0.45 g of polyaromatic polymer precursor containing piperidine structure;

[0081] S3, dissolving the polyaromatic polymer precursor containing piperidine structure obtained in S2 in 10 mL of N-methylpyrrolidone, adding 0.50 mL of methyl iodide and 0.3 g of potassium carbonate, and performing ionization reaction at room temperature for 72 h to obtain a highly alkali-resistant polyarylene alkylene piperidine cationic polymer solution having a branched structure;

[0082] S4. Slowly add the highly alkali-resistant polyarylene alkylene piperidine cationic polymer solution with a branched structure obtained in S3 into ether. After precipitation, filter and dry the precipitate to obtain 0.50 g of highly alkali-resistant polyarylene alkylene piperidine cationic polymer PTP-DMP-Tri-3% with a branched structure, the structure of which is shown in (1).

[0083]

[0084] Application Example 1

[0085] a. Preparation of anion exchange membrane

[0086] The highly alkali-resistant polyarylene alkylene piperidine cationic polymer PTP-DMP-Tri-3% with a branched structure prepared in Example 1 was dissolved in 4 mL of dimethyl sulfoxide to obtain a highly alkali-resistant polyarylene alkylene piperidine cationic polymer solution with a mass fraction of about 10%. The highly alkali-resistant polyarylene alkylene piperidine cationic polymer solution with a branched structure was coated on a clean glass plate by a casting method. The glass plate was placed in a blast drying oven at 80°C and dried 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 washed thoroughly with deionized water to obtain a counter ion of I - Anion exchange membrane 1.

[0087] b. Replace the counter ions in the anion exchange membrane in a.

[0088] The counter ion in a is I - The anion exchange membrane was immersed in a 1 mol / L NaOH solution for 48 h, and then the anion exchange membrane was fully washed with deionized water to obtain a counter ion of OH - The anion exchange membrane a. The counter ion in a is I -The anion exchange membrane was immersed in a 2 mol / L NaCl solution for 24 h, and then the anion exchange membrane was fully washed with deionized water to obtain a counter ion of Cl - Anion exchange membrane 1.

[0089] c. Preparation of catalyst layer binder

[0090] The counter ions in the PTP-DMP-Tri-3% prepared in Example 1 were ion exchanged as needed. The PTP-DMP-Tri-3% 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 filtered out and OH was obtained. - A highly alkali-resistant polyarylene alkylene piperidinium cationic polymer having a branched structure.

[0091] The counter ion prepared is OH - The highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure is dissolved in a mixed solvent of isopropanol and water at a solid content of 2 wt %, and a metal catalyst is added and mixed to prepare a slurry of a uniformly dispersed catalyst layer binder, that is, based on the counter ion OH - A slurry of a catalyst layer binder of a highly alkali-resistant polyarylene alkylene piperidine cationic polymer having a branched structure.

[0092] Comparative Example 1

[0093] S1. A polymerization mixture consisting of 1-piperidine-3-carboxaldehyde hydrochloride (0.19 g, 1.43 mmol) and p-terphenyl (0.3 g, 1.32 mmol) was placed in dichloromethane (1.0 mL), and trifluoromethanesulfonic acid (1.0 mL) was added to carry out a catalytic polycondensation reaction. The reaction was carried out at 25°C for 10 h to obtain a viscous dispersion of a polymer having a piperidine structure.

[0094] S2. Slowly add the dispersion of the polymer with a piperidine structure in S1 to 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 0.43 g of white fibrous polymer powder with a piperidine structure.

[0095] S3. The polymer powder having a piperidine structure in S2 was dissolved in 5 mL of N-methylpyrrolidone, 0.50 mL of iodomethane and 0.3 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.

[0096] S4, slowly adding the cationic polymer solution in S3 into diethyl ether, filtering and drying, obtaining 0.45 g of highly alkali-resistant cationic polymer PTP-DMP powder, and preparing anion exchange membrane from the PTP-DMP powder, wherein the counter ion is I - . And can be exchanged for OH as needed - or other counter ions (such as Cl - ), the structure after replacement is as follows, the counter ion is OH - PTP-DMP membrane.

[0097]

[0098] Test Example 1

[0099] The following tests were carried out on the anion exchange membrane 1 and the catalyst layer binder with different counter ions in Example 1 to characterize their basic performance and to compare them with the PTP-DMP membrane in Comparative Example 1.

[0100] a. Conductivity test

[0101] The four-electrode electrochemical impedance spectroscopy was used to measure the - The anion exchange membrane 1 and the anion exchange membrane PTP-DMP membrane were cut into 1cm×5cm strips, then clamped on a fixture and placed in a tank filled with pure water. The electrodes were installed and connected to the electrochemical workstation. In the constant current mode (0.1mA), the scanning frequency range was 1MHz–100Hz. 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 the anion exchange membrane A and the anion exchange membrane PTP-DMP membrane.

[0102] The hydroxide ion conductivity is calculated by the following formula:

[0103]

[0104] Wherein, R is the resistance of the anion exchange membrane, L is the distance between the electrodes (1.0 cm), W is the width of the anion exchange membrane, and d is the thickness of the anion exchange membrane.

[0105] According to the hydroxide ion conductivity obtained at different temperatures, a curve of the hydroxide ion conductivity of the anion exchange membrane changing with temperature is obtained, such as Figure 1 As shown. Figure 1 It can be seen that at 80°C, the counter ion with branched structure is OH - Anion exchange membrane OH - The conductivity reaches 188mS·cm -1, while the OH of the unbranched anion exchange membrane PTP-DMP membrane - The conductivity is only 162mS·cm -1 .

[0106] b. Water absorption and swelling rate

[0107] The anion exchange membrane 1 and the anion exchange membrane PTP-DMP membrane were cut into strips of 1 cm × 8 cm, and fully dried in an oven. The weight of the dried anion exchange membrane was recorded as W. dry Then, the dried anion exchange membrane was immersed in deionized water. The anion exchange membrane was taken out every 12 hours, the water on the surface of the anion exchange membrane was wiped dry, and the weight W of the anion exchange membrane after immersion at different temperatures (30–80°C) was recorded. wet The water absorption (WU) is calculated by the following formula:

[0108]

[0109] According to the calculated water absorption rates detected at different temperatures, the water absorption rate of the two anion exchange membranes versus temperature curves were obtained, as shown in Figure 2 shown.

[0110] 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.

[0111]

[0112] According to the swelling rate detected at different temperatures, the counter ion is Cl - Anion exchange membrane and Cl - The swelling rate of the PTP-DMP membrane as a counter ion changes with temperature, such as Figure 3 shown.

[0113] c. Mechanical properties test

[0114] CMT 4506 electronic universal testing machine was used to test the -1 The tensile properties of the obtained anion exchange membrane 1 and anion exchange membrane PTP-DMP membrane were measured at a tensile speed. Both the anion exchange membrane 1 and the anion exchange membrane PTP-DMP membrane were cut into dumbbell shapes, 40 mm × 10 mm × 0.03 mm (length × width × thickness). Three parallel samples were set for each group of samples. The samples were balanced in the test environment for 24 hours before use. The test results are shown in Figure 4 shown.

[0115] d. Electrochemical performance test

[0116] The PTP-DMP-Tri-3% in Example 1 was used to prepare the slurry of the catalyst layer binder and the anion exchange membrane 1, 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.

[0117] H2-O2 fuel cell test at 80 °C with a gas flow rate of 300 mL min -1 , the back pressure is 150 kPa, the relative humidity (RH) is 100%, and the electrochemical performance diagram of the catalyst layer binder slurry prepared by PTP-DMP-Tri-3% in Example 1 and the anion exchange membrane 1 is detected, as shown in FIG. Figure 5 shown.

[0118] In summary, at 80°C, the hydroxyl ion conductivity of anion exchange membrane 1 reaches 188 mS·cm -1 The anion exchange membrane has a lower water absorption rate and swelling rate and has good mechanical properties. The maximum power density of the membrane electrode composed of PTP-DMP-Tri-3% reaches 1.32W·cm -2 .

[0119] Example 2

[0120] S1. Tetraphenylmethane (0.02 g, 0.08 mmol), 1-piperidine-3-carboxaldehyde hydrochloride (0.19 g, 1.43 mmol) and p-terphenyl (0.30 g, 1.32 mmol) were mixed and dispersed in dichloromethane (1.5 mL), and polycondensed under the catalysis of trifluoromethanesulfonic acid (2.2 mL). The reaction was carried out at 25° C. for 15 h to obtain a viscous polyaromatic polymer precursor dispersion containing a piperidine structure;

[0121] S2, slowly dropwise adding the polyaromatic polymer precursor dispersion containing piperidine structure obtained in S1 into a 1:1 (v / v) mixed solution of methanol and water, filtering after precipitation to obtain a light yellow fibrous polymer, filtering, washing thoroughly and vacuum drying to obtain 0.41 g of polyaromatic polymer precursor containing piperidine structure;

[0122] S3, dissolving the piperidine structure-containing polyaromatic polymer precursor obtained in S2 in 4 mL of N-methylpyrrolidone, adding 0.45 mL of methyl iodide and 0.2 g of potassium carbonate, and performing an ionization reaction at room temperature for 72 h to obtain a highly alkali-resistant polyarylene alkylene piperidine cationic polymer solution having a branched structure;

[0123] S4, slowly adding the highly alkali-resistant polyarylene alkylene piperidine cationic polymer solution having a branched structure obtained in S3 into diethyl ether, filtering and drying the precipitate after precipitation, to obtain 0.43 g of a highly alkali-resistant polyarylene alkylene piperidine cationic polymer having a branched structure, the structure of which is shown below:

[0124]

[0125] Application Example 2

[0126] a. Preparation of anion exchange membrane

[0127] The highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure prepared in Example 2 was dissolved in 4 mL of dimethyl sulfoxide to obtain a polyarylene alkylene piperidine cationic polymer solution with a mass fraction of about 10% having a branched structure. The highly alkali-resistant polyarylene alkylene piperidine cationic polymer solution with a branched structure 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 the solvent. 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 II.

[0128] b. Replace the counter ions in the anion exchange membrane in a.

[0129] The counter ion prepared in a is I - The anions in the anion exchange membrane 2 are exchanged as needed, and the counter ions are I - The anion exchange membrane II was immersed in a 2 mol / L NaCl solution for 24 h and then washed thoroughly with deionized water to obtain a counter ion of Cl - Anion exchange membrane II.

[0130] c. Preparation of catalyst layer binder

[0131] The counter ions in the highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure prepared in Example 2 are subjected to ion exchange as required. The highly alkali-resistant polyarylene alkylene piperidine cationic polymer powder with a branched structure prepared in Example 2 is immersed in a 2 mol / L NaOH solution for 48 h, and then fully washed with deionized water. The counter ions are OH and OH. - A highly alkali-resistant polyarylene alkylene piperidinium cationic polymer having a branched structure.

[0132] The counter ion prepared is OH -The highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure is dissolved in a mixed solvent of isopropanol and water with a solid content of 2 wt %, and is mixed with a metal catalyst to prepare a uniformly dispersed slurry, i.e., a slurry of a catalyst layer binder based on the highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure in Example 2.

[0133] Example 3

[0134] S1. 1,3,5-triphenylbenzene (0.04 g, 0.14 mmol), 1-piperidine-3-carboxaldehyde hydrochloride (0.38 g, 2.86 mmol) and biphenyl (0.20 g, 1.32 mmol) were mixed and dispersed in dichloromethane (4.0 mL), and polycondensed under the catalysis of trifluoromethanesulfonic acid (4.5 mL). The reaction was carried out at 25° C. for 24 h to obtain a viscous polyaromatic polymer precursor dispersion containing a piperidine structure;

[0135] S2, slowly dropwise adding the polyaromatic polymer precursor dispersion containing piperidine structure obtained in S1 into a 1:1 (v / v) mixed solution of methanol and water, filtering after precipitation to obtain a light yellow fibrous polymer, filtering, fully washing and vacuum drying to obtain 0.82 g of a white fibrous polyaromatic polymer precursor containing piperidine structure;

[0136] S3, dissolving the polyaromatic polymer precursor containing piperidine structure obtained in S2 in 6 mL of N-methylpyrrolidone, adding 0.90 mL of methyl iodide and 0.4 g of potassium carbonate, and performing ionization reaction at room temperature for 72 h to obtain a highly alkali-resistant polyarylene alkylene piperidine cationic polymer solution having a branched structure;

[0137] S4, slowly adding the highly alkali-resistant polyarylene alkylene piperidine cationic polymer solution having a branched structure obtained in S3 into diethyl ether, filtering and drying the precipitate after precipitation, to obtain 0.87 g of a highly alkali-resistant polyarylene alkylene piperidine cationic polymer having a branched structure, the structure of which is shown below:

[0138]

[0139] Application Example 3

[0140] The highly alkali-resistant cationic polymer with a branched structure prepared in Example 3 was dissolved in 7 mL of dimethyl sulfoxide to obtain a highly alkali-resistant polyarylene alkylene piperidine cationic polymer solution with a mass fraction of about 10%. The highly alkali-resistant polyarylene alkylene piperidine cationic polymer solution with a branched structure 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 the solvent. 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.

[0141] b. Replace the counter ions in the anion exchange membrane in a.

[0142] 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 24 h, and then the membrane was fully washed with deionized water to obtain a counter ion of Cl - Anion exchange membrane III.

[0143] c. Preparation of catalyst layer binder

[0144] The counter ions in the highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure prepared in Example 3 were ion exchanged as needed. The highly alkali-resistant polyarylene alkylene piperidine cationic polymer powder with a branched structure prepared in Example 3 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. - A highly alkali-resistant polyarylene alkylene piperidinium cationic polymer having a branched structure.

[0145] The prepared counter ion is OH - The highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure 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, i.e., a slurry of a catalyst layer binder based on the highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure in Example 3.

[0146] Example 4

[0147] S1. 1,3,5-triphenylbenzene (0.03 g, 0.12 mmol), spirofluorene (0.03 g, 0.12 mmol), 1-piperidine-3-carboxaldehyde hydrochloride (0.39 g, 2.30 mmol), and biphenyl (0.40 g, 2.60 mmol) were mixed and dispersed in dichloromethane (3.0 mL), and polycondensed under the catalysis of trifluoromethanesulfonic acid (2.5 mL). The reaction was carried out at 25° C. for 48 h to obtain a viscous polyaromatic polymer precursor dispersion containing a piperidine structure;

[0148] S2, slowly dropwise adding the polyaromatic polymer precursor dispersion containing piperidine structure obtained in S1 into a 1:1 (v / v) mixed solution of methanol and water, filtering to obtain a light yellow fibrous polymer after precipitation, filtering, washing thoroughly and vacuum drying to obtain 0.78 g of a white fibrous polyaromatic polymer precursor containing piperidine structure;

[0149] S3, dissolving the polyaromatic polymer precursor containing piperidine structure obtained in S2 in 6 mL of N-methylpyrrolidone, adding 1.32 mL of methyl iodide and 0.9 g of potassium carbonate, and performing ionization reaction at room temperature for 72 h to obtain a highly alkali-resistant polyarylene alkylene piperidine cationic polymer solution having a branched structure;

[0150] S4. Slowly add the highly alkali-resistant polyarylene alkylene piperidine cationic polymer solution with a branched structure obtained in S3 into ether. After precipitation, filter and dry the precipitate to obtain 0.85 g of highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure, the structure of which is shown in (4).

[0151]

[0152] Application Example 4

[0153] a. Preparation of anion exchange membrane

[0154] The highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure prepared in Example 4 was dissolved in 9 mL of dimethyl sulfoxide to obtain a highly alkali-resistant polyarylene alkylene piperidine cationic polymer solution with a mass fraction of about 10%. The highly alkali-resistant polyarylene alkylene piperidine cationic polymer solution with a branched structure 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 the solvent. 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.

[0155] b. Replace the counter ions in the anion exchange membrane in a.

[0156] 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 24 h and then washed thoroughly with deionized water to obtain a counter ion of Cl - Anion exchange membrane IV.

[0157] c. Preparation of catalyst layer binder

[0158] The high alkali resistance with branched structure prepared in Example 4 is subjected to ion exchange as required. The high alkali resistance polyarylene alkylene piperidine cationic polymer powder with branched structure prepared in Example 4 is immersed in 2 mol / L NaOH solution for 48 h, and then fully washed with deionized water. After suction filtration, the counter ion is OH - of cationic polymers.

[0159] The counter ion prepared 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 uniformly dispersed slurry, that is, a slurry of the catalyst layer binder based on the cationic polymer in Example 4.

[0160] Example 5

[0161] S1. Triphenylmethane (0.02 g, 0.08 mmol), 1-piperidine-3-carboxaldehyde hydrochloride (0.10 g, 0.72 mmol), 1-piperidin-3-one hydrochloride (0.09 g, 0.72 mmol) and p-terphenyl (0.30 g, 1.32 mmol) were mixed and dispersed in dichloromethane (1.5 mL), and polycondensed under the catalysis of trifluoromethanesulfonic acid (2.5 mL). The reaction was carried out at 25° C. for 48 h to obtain a viscous polyaromatic polymer precursor dispersion containing a piperidine structure;

[0162] S2, slowly dropwise adding the polyaromatic polymer precursor dispersion containing piperidine structure obtained in S1 into a 1:1 (v / v) mixed solution of methanol and water, filtering after precipitation to obtain a light yellow fibrous polymer, filtering, fully washing and vacuum drying to obtain 0.46 g of a white fibrous polyaromatic polymer precursor containing piperidine structure;

[0163] S3, dissolving the piperidine structure-containing polyaromatic polymer precursor obtained in S2 in 6 mL of N-methylpyrrolidone, adding 0.40 mL of methyl iodide and 0.3 g of potassium carbonate, and performing an ionization reaction at room temperature for 72 h to obtain a highly alkali-resistant polyarylene alkylene piperidine cationic polymer solution having a branched structure;

[0164] S4. Slowly add the highly alkali-resistant polyarylene alkylene piperidine cationic polymer solution with a branched structure obtained in S3 into ether. After precipitation, filter and dry the precipitate to obtain 0.50 g of highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure, the structure of which is shown in (5).

[0165]

[0166] Application Example 5

[0167] a. Preparation of anion exchange membrane

[0168] The highly alkali-resistant cationic polymer with a branched structure prepared in Example 5 was dissolved in 5 mL of dimethyl sulfoxide to obtain a highly alkali-resistant polyarylene alkylene piperidine cationic polymer solution with a mass fraction of about 10%. The highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure 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 the solvent. 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 solution with a counter ion of I - Anion exchange membrane V.

[0169] b. Replace the counter ions in the anion exchange membrane in a.

[0170] 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 24 h and then washed thoroughly with deionized water to obtain a counter ion of Cl - Anion exchange membrane V.

[0171] c. Preparation of catalyst layer binder

[0172] The counter ions in the highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure prepared in Example 5 are subjected to ion exchange as needed. The highly alkali-resistant polyarylene alkylene piperidine cationic polymer powder with a branched structure prepared in Example 5 is immersed in a 2 mol / L NaOH solution for 48 h, and then fully washed with deionized water. The counter ions are OH and NH. - A highly alkali-resistant polyarylene alkylene piperidinium cationic polymer having a branched structure.

[0173] The counter ion prepared is OH -The highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure 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, i.e., a slurry of a catalyst layer binder based on the highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure in Example 5.

[0174] Example 6

[0175] S1. Tripterygium (0.02 g, 0.08 mmol), 1-piperidine-3-carboxaldehyde hydrochloride (0.10 g, 0.72 mmol), 7-bromo-1,1,1-trifluoro-2-heptanone (0.18 g, 0.72 mmol) and fluorene (0.30 g, 1.32 mmol) were mixed and dispersed in dichloromethane (2.0 mL), and polycondensed under the catalysis of trifluoromethanesulfonic acid (2.0 mL). The reaction was carried out at 25° C. for 4 h to obtain a viscous polyaromatic polymer precursor dispersion containing a piperidine structure;

[0176] S2, slowly dropwise adding the polyaromatic polymer precursor dispersion containing piperidine structure obtained in S1 into a 1:1 (v / v) mixed solution of methanol and water, filtering after precipitation to obtain a light yellow fibrous polymer, filtering, fully washing and vacuum drying to obtain 0.55 g of a white fibrous polyaromatic polymer precursor containing piperidine structure;

[0177] S3, dissolving the polyaromatic polymer precursor containing piperidine structure obtained in S2 in 6 mL of N-methylpyrrolidone, adding 0.20 mL of iodomethane and 2.4 mL of trimethylamine solution (4.2 mol L -1 ethanol solution) and 0.2 g potassium carbonate, and then ionization reaction was carried out at room temperature for 72 h to obtain a highly alkali-resistant polyarylene alkylene piperidine cationic polymer solution having a branched structure;

[0178] S4. Slowly add the highly alkali-resistant polyarylene alkylene piperidine cationic polymer solution with a branched structure obtained in S3 into ether. After precipitation, filter and dry the precipitate to obtain 0.62 g of highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure, the structure of which is shown in (6).

[0179]

[0180] Application Example 6

[0181] a. Preparation of anion exchange membrane

[0182] The highly alkali-resistant cationic polymer with a branched structure prepared in Example 6 was dissolved in 6 mL of dimethyl sulfoxide to obtain a highly alkali-resistant polyarylene alkylene piperidine cationic polymer solution with a mass fraction of about 10%. The highly alkali-resistant polyarylene alkylene piperidine cationic polymer solution with a branched structure 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 the solvent. 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.

[0183] b. Replace the counter ions in the anion exchange membrane in a.

[0184] 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 24 h, and then the membrane was fully washed with deionized water to obtain a counter ion of Cl - Anion exchange membrane VI.

[0185] c. Preparation of catalyst layer binder

[0186] The counter ions in the highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure prepared in Example 6 are subjected to ion exchange as needed. The highly alkali-resistant polyarylene alkylene piperidine cationic polymer powder with a branched structure prepared in Example 6 is immersed in a 2 mol / L NaOH solution for 48 h, and then fully washed with deionized water. The counter ions are OH and NH. - A highly alkali-resistant polyarylene alkylene piperidinium cationic polymer having a branched structure.

[0187] The counter ion prepared is OH - The highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure 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, i.e., a slurry of a catalyst layer binder based on the highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure in Example 6.

[0188] Example 7

[0189] S1, spirofluorene (0.02 g, 0.08 mmol), 1-piperidine-3-carboxaldehyde hydrochloride (0.19 g, 1.43 mmol), and spiro(cyclohexane-1,9'-fluorene) (0.32 g, 1.29 mmol) were mixed and dispersed in dichloromethane (1.2 mL), and polycondensed under the catalysis of trifluoromethanesulfonic acid (1.2 mL), and reacted at 25° C. for 48 h to obtain a viscous polyaromatic polymer precursor dispersion containing a piperidine structure;

[0190] S2, slowly dropwise adding the polyaromatic polymer precursor dispersion containing piperidine structure obtained in S1 into a 1:1 (v / v) mixed solution of methanol and water, filtering after precipitation to obtain a light yellow fibrous polymer, filtering, fully washing and vacuum drying to obtain 0.41 g of a white fibrous polyaromatic polymer precursor containing piperidine structure;

[0191] S3, dissolving the polyaromatic polymer precursor containing piperidine structure obtained in S2 in 4 mL of N-methylpyrrolidone, adding 0.70 mL of methyl iodide and 0.5 g of potassium carbonate, and performing ionization reaction at room temperature for 72 h to obtain a highly alkali-resistant polyarylene alkylene piperidine cationic polymer solution having a branched structure;

[0192] S4. Slowly add the highly alkali-resistant polyarylene alkylene piperidine cationic polymer solution with a branched structure obtained in S3 into ether. After precipitation, filter and dry the precipitate to obtain 0.47 g of highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure, the structure of which is shown in (7).

[0193]

[0194] Application Example 7

[0195] Preparation of catalyst layer binder

[0196] The counter ions in the highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure prepared in Example 7 were ion exchanged as needed. The highly alkali-resistant polyarylene alkylene piperidine cationic polymer powder with a branched structure prepared in Example 7 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. - of cationic polymers.

[0197] The counter ion prepared 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 uniformly dispersed slurry, i.e., a slurry of a catalyst layer binder based on the highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure in Example 7.

[0198] Example 8

[0199] S1, phenanthrene (0.02 g, 0.08 mmol), 1-piperidine-3-carboxaldehyde hydrochloride (0.19 g, 1.43 mmol), and 9,9-dimethylfluorene (0.32 g, 1.29 mmol) were mixed and dispersed in dichloromethane (1.2 mL), and polycondensed under the catalysis of trifluoromethanesulfonic acid (1.2 mL), and reacted at 25° C. for 48 h to obtain a viscous polyaromatic polymer precursor dispersion containing a piperidine structure;

[0200] S2, slowly dropwise adding the polyaromatic polymer precursor dispersion containing piperidine structure obtained in S1 into a 1:1 (v / v) mixed solution of methanol and water, filtering after precipitation to obtain a light yellow fibrous polymer, filtering, fully washing and vacuum drying to obtain 0.41 g of a white fibrous polyaromatic polymer precursor containing piperidine structure;

[0201] S3, dissolving the polyaromatic polymer precursor containing piperidine structure obtained in S2 in 4 mL of N-methylpyrrolidone, adding 3.0 mL of 1,5-diiodopentane and 0.5 g of potassium carbonate, and performing ionization reaction at room temperature for 72 h to obtain a highly alkali-resistant polyarylene alkylene piperidine cationic polymer solution having a branched structure;

[0202] S4. Slowly add the highly alkali-resistant polyarylene alkylene piperidine cationic polymer solution with a branched structure obtained in S3 into ether. After precipitation, filter and dry the precipitate to obtain 0.55 g of highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure, the structure of which is shown in (8).

[0203]

[0204] Application Example 8

[0205] Preparation of catalyst layer binder

[0206] The counter ions in the highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure prepared in Example 8 were subjected to ion exchange as needed. The highly alkali-resistant polyarylene alkylene piperidine cationic polymer powder with a branched structure prepared in Example 8 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. - of cationic polymers.

[0207] The counter ion prepared 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 uniformly dispersed slurry, i.e., a slurry of a catalyst layer binder based on the highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure in Example 8.

[0208] Therefore, the highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure adopted in the present invention can be used as a membrane material in many fields such as fuel cells and water electrolysis. At the same time, the highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure can also be used as a catalyst binder material in fuel cells and water electrolysis catalyst layers.

[0209] 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 having a branched structure, characterized in that: It includes one or more of a central unit, a linear unit L1 and a linear unit L2, wherein the central unit includes one or more of a MA unit, a piperidinium cationic unit m-DMP and a CA unit, the linear unit L1 includes a piperidinium cationic unit m-DMP and a BA unit, and the linear unit L2 includes a BA unit and a CA unit; The structural formula of the piperidinium cation unit m-DMP is Among them, R 1 and R 2 independently selected from hydrocarbon groups having 1 to 20 carbon atoms, or R 1 and R 2 Connected to form a cycloalkyl group consisting of 4 to 7 carbon atoms, the counterion A - One or more selected from halide ions, methyl sulfate ions, hydroxide ions or bicarbonate ions.

2. The highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure according to claim 1, characterized in that: The MA unit includes 2-6 aromatic rings, independently selected from one or more of the following structures, 3. The highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure according to claim 2, characterized in that: The BA units are independently selected from one or more of the following structures:

4. The highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure according to claim 3, characterized in that: CA unit includes One or more of the following, where R 3 and R 4 independently selected from hydrocarbon groups having 1 to 20 carbon atoms, or R 3 and R 4 They are linked to each other to form a cycloalkyl group consisting of 4 to 7 carbon atoms; Each R 5 Independently selected from hydrogen atoms, hydrocarbon groups with 1 to 20 carbon atoms, and fully or partially fluorinated alkyl groups with 1 to 6 carbon atoms; k = 0 or 1; x = 0-12; Q is selected from H atoms, -N + (R 6 )3 or one or more of nitrogen-containing heterocyclic cations; -N + (R 6 )3, each R 6 Independently selected from hydrocarbon groups having 1 to 20 carbon atoms.

5. The highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure according to claim 4, characterized in that: The nitrogen-containing heterocyclic cation comprises one or more of a partially or completely substituted pyrazole, pyrrole, piperidine, imidazole and quinine cation, and has the following structure: Among them, R 61 -R 610 independently selected from hydrocarbon groups having 1 to 20 carbon atoms, the counterion A - One or more selected from halide ions, methyl sulfate ions, hydroxide ions or bicarbonate ions.

6. The highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure according to claim 1, characterized in that: The central unit is connected to the linear unit L1, and the central unit includes a MA unit and a piperidinium cationic unit m-DMP, and its structural formula is shown below:

7. The highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure according to claim 1, characterized in that: The linear unit L1 is connected to the central unit and the linear unit L2. The central unit includes a MA unit, a piperidinium cationic unit m-DMP and a CA unit. Its structure is shown below.

8. A method for preparing a highly alkali-resistant polyarylene alkylene piperidine cationic polymer having a branched structure according to claim 6, characterized in that: The following steps are included: S1, raw materials MA', 1-R 7 Piperidine-3-carboxaldehyde or its salt or hydrate and BA' are mixed and dissolved or dispersed in a first organic solvent, and polycondensed under the catalysis of an organic strong acid, and reacted at -20-100° C. for 0.1-200 hours to obtain a polyaromatic polymer precursor solution or dispersion containing a piperidine structure; S2, slowly dropping the piperidine structure-containing polyaromatic polymer precursor solution or dispersion obtained in S1 into a precipitant 1, filtering after precipitation to obtain a fibrous polymer, fully washing and drying to obtain a piperidine structure-containing polyaromatic polymer precursor; S3, dispersing or dissolving the polyaromatic polymer precursor containing piperidine structure obtained in S2 in a second organic solvent, adding an ionizing agent, and performing an ionization reaction at 0-100° C. for 0.1-200 h to obtain a highly alkali-resistant polyarylene alkylene piperidine cationic polymer solution or dispersion having a branched structure; S4, slowly adding the highly alkali-resistant polyarylene alkylene piperidine cationic polymer solution or dispersion having a branched structure obtained in S3 into the second precipitant, filtering and drying the precipitate after precipitation, to obtain a highly alkali-resistant polyarylene alkylene piperidine cationic polymer having a branched structure.

9. A method for preparing a highly alkali-resistant polyarylene alkylene piperidine cationic polymer having a branched structure according to claim 7, characterized in that: The following steps are included: S1, raw materials MA', 1-R 7 Piperidine-3-carboxaldehyde or its salt or hydrate, BA' and compound CA" are dissolved or dispersed in a first organic solvent, and subjected to polycondensation reaction under the catalysis of a strong organic acid at -20°C to 100°C for 0.1 to 200 hours to obtain a polyaromatic polymer precursor solution or dispersion containing a piperidine structure; S2, slowly dropping the piperidine structure-containing polyaromatic polymer precursor solution or dispersion obtained in S1 into a precipitant 1, filtering after precipitation to obtain a fibrous polymer, fully washing and drying to obtain a piperidine structure-containing polyaromatic polymer precursor; S3, dispersing or dissolving the polyaromatic polymer precursor containing piperidine structure obtained in S2 in a second organic solvent, adding an ionizing agent, and performing an ionization reaction at 0-100° C. for 0.1-200 h to obtain a highly alkali-resistant polyarylene alkylene piperidine cationic polymer solution or dispersion having a branched structure; S4, slowly adding the highly alkali-resistant polyarylene alkylene piperidine cationic polymer solution or dispersion having a branched structure obtained in S3 into the second precipitant, filtering and drying the precipitate after precipitation, to obtain a highly alkali-resistant polyarylene alkylene piperidine cationic polymer having a branched structure.

10. An application of a highly alkali-resistant polyarylene alkylene piperidine cationic polymer having a branched structure according to any one of claims 6 to 7, characterized in that: The highly alkali-resistant polyarylene alkylene piperidine cationic polymer with a branched structure is used for preparing anion exchange membranes and catalyst layer binders.

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