Highly alkali-resistant polyarylenealkylene piperidine cationic polymer with a branched structure, its preparation method and application

Abstract

The present invention relates to the technical field of cationic polymers, in particular to a highly alkali-resistant polyarylenealkylene piperidine cationic polymer with a branched structure, its preparation method and application, including one or more of a central unit, a linear unit L1 and a linear unit L2. The central unit includes one or more of an MA unit, a piperidinium cation unit m-DMP and a CA unit. The linear unit L1 includes a piperidinium cation unit m-DMP and a BA unit. The linear unit L2 includes a BA unit and a CA unit. By adopting the above steps, the present invention enhances the intermolecular interaction force between polymer molecular chains and increases the polymer molecular weight through a branching strategy, so that the water absorption and swelling of the prepared anion exchange membrane are inhibited, and thus outstanding conductivity and mechanical properties are exhibited. At the same time, the piperidinium cation is linked to the polymer backbone with a branched structure through a flexible spacer, so that the prepared anion exchange membrane has outstanding alkali resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of cationic polymers, and particularly to a highly alkali-resistant poly(arylenealkylene piperidine) cationic polymer with a branched structure, a preparation method thereof, and an application thereof. Background Art

[0002] The efficient development and utilization of hydrogen energy are important means to solve the current environmental problems and energy crises. Anion exchange membrane water electrolysis (AEMWE) and anion exchange membrane fuel cells (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. Piperidine cations have received extensive attention due to their outstanding alkali resistance and easy linkage to the polyaromatic main chain. Among them, poly(aryl-piperidinium salt) cationic polymers in which the 4-position of the piperidine cation is linked to an aryl unit have been extensively studied due to their simple synthesis and excellent performance, and small-scale commercialization has been achieved. On the other hand, since the piperidine ring is directly linked to the aryl unit, the alkali stability of the piperidine cation is reduced (ChemSusChem 2024, e202301656).

[0003] In addition, there has always been a trade-off dilemma between conductivity and water absorption swelling in polymer electrolytes used in AEMWE and AEMFC. When the polymer electrolyte has a high ion exchange capacity, its ionic conductivity increases, leading to an improvement in device efficiency. However, a high ion exchange capacity causes the polymer electrolyte to absorb water and swell excessively 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 pose safety problems. Therefore, how to solve this trade-off dilemma is an important part of the research on polymer electrolytes. Summary of the Invention

[0004] The object of the present invention is to provide a highly alkali-resistant poly(arylenealkylene piperidine) cationic polymer with a branched structure, a preparation method thereof, and an application thereof. When applied to an anion exchange membrane and a catalyst layer binder, the mechanical and chemical stabilities of the anion exchange membrane and the catalyst layer binder are improved.

[0005] To achieve the above object, the present invention provides a highly alkali-resistant poly(arylenealkylene piperidine) cationic polymer with a branched structure, including one or more of a central unit, a linear unit L1, and a linear unit L2. The central unit includes one or more of an MA unit, a piperidine cation unit m-DMP, and a CA unit. The linear unit L1 includes a piperidine cation unit m-DMP and a BA unit. The linear unit L2 includes a BA unit and a CA unit;

[0006] The structural formula of the piperidinium cation unit m-DMP is wherein, R 1 and R 2 are independently selected from hydrocarbon groups having 1 to 20 carbon atoms, or R 1 and R 2 are connected to each other to form a cycloalkyl group composed of 4 to 7 carbon atoms, and the counterion A - is selected from one or more of halide ions, methyl sulfate ions, hydroxide ions or bicarbonate ions.

[0007] Preferably, the MA unit includes 2 to 6 aromatic rings and is 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 includes one or more of the following, wherein, R 3 and R 4 are independently selected from hydrocarbon groups having 1 to 20 carbon atoms, or R 3 and R 4 are connected to each other to form a cycloalkyl group composed of 4 to 7 carbon atoms; each R 5 is independently selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a fully or partially fluorinated alkyl group having 1 to 6 carbon atoms;

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

[0013] Preferably, the cations of nitrogen-containing heterocycles include one or more of partially or fully substituted pyrazole, pyrrole, piperidine, imidazole and quinine cations and have the following structures:

[0014]

[0015] wherein, R 61 -R 610 are independently selected from hydrocarbon groups having 1 to 20 carbon atoms, and the counterion A -Selected from one or more of halogen ions, methyl sulfate ions, hydroxide ions or bicarbonate ions.

[0016] Preferably, the central unit is connected to the linear unit L1. The central unit includes an MA unit and a piperidine cation unit m-DMP, and its structural formula is shown as follows.

[0017]

[0018] Preferably, the linear unit L1 is connected to the central unit and the linear unit L2. The central unit includes an MA unit, a piperidine cation unit m-DMP and a CA unit, and its structure is shown as follows.

[0019]

[0020] The preparation method of the above-mentioned highly alkali-resistant polyarylenealkylene piperidine cation polymer with a branched structure includes the following steps.

[0021] S1. Dissolve or disperse the raw materials MA', 1-R 7 piperidine-3-carbaldehyde or its salt or hydrate and BA' in a first organic solvent, and carry out a polycondensation reaction under the catalysis of an organic strong acid. React at -20 - 100 °C for 0.1 - 200 h to obtain a polyaromatic polymer precursor solution or dispersion containing a piperidine structure.

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

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

[0024]

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

[0026] S2. Slowly drop the polyaromatic polymer precursor solution or dispersion containing a piperidine structure obtained in S1 into a first precipitant, filter after precipitation to obtain a fibrous polymer, wash it thoroughly and then dry it to obtain a polyaromatic polymer precursor containing a piperidine structure.

[0027] S3. Disperse or dissolve the polyaromatic polymer precursor containing a piperidine structure obtained in S2 in a second organic solvent, add an ionizing reagent, and carry out an ionization reaction at 0 - 100 °C for 0.1 - 200 h to obtain a highly alkali-resistant polyarylenealkylene piperidine cation polymer solution or dispersion with a branched structure.

[0028] S4. Slowly add the highly alkali-resistant poly(arylenealkylene piperidine) cationic polymer solution or dispersion with a branched structure obtained in S3 into a second precipitating agent. After precipitation, filter and dry the precipitate to obtain the highly alkali-resistant poly(arylenealkylene piperidine) cationic polymer with a branched structure.

[0029] The preparation method of the above-mentioned highly alkali-resistant poly(arylenealkylene piperidine) cationic polymer with a branched structure includes the following steps.

[0030] S1. Dissolve or disperse the raw materials MA', 1-R 7 piperidine-3-carbaldehyde or its salt or hydrate, BA' and compound CA'' in a first organic solvent, and carry out a polycondensation reaction under the catalysis of an organic strong acid.

[0031] React at -20 - 100 °C for 0.1 - 200 h to obtain a polyaromatic polymer precursor solution or dispersion containing a piperidine structure.

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

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

[0034]

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

[0036] S2. Slowly drop the polyaromatic polymer precursor solution or dispersion containing a piperidine structure obtained in S1 into a first precipitating agent. After precipitation, filter to obtain a fibrous polymer, wash it thoroughly and then dry it to obtain the polyaromatic polymer precursor containing a piperidine structure.

[0037] S3. Disperse or dissolve the polyaromatic polymer precursor containing a piperidine structure obtained in S2 in a second organic solvent, add an ionizing agent, and carry out an ionization reaction at 0 - 100 °C for 0.1 - 200 h to obtain a highly alkali-resistant poly(arylenealkylene piperidine) cationic polymer solution or dispersion with a branched structure.

[0038] S4. Slowly add the highly alkali-resistant poly(arylenealkylene piperidine) cationic polymer solution or dispersion with a branched structure obtained in S3 into a second precipitating agent. After precipitation, filter and dry the precipitate to obtain the highly alkali-resistant poly(arylenealkylene piperidine) cationic polymer with a branched structure.

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

[0044]

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

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

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

[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 organic strong acid includes one or more of trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoro-1-propane sulfonic acid, trifluoroacetic acid, perfluoropropionic acid, heptafluorobutyric acid or methanesulfonic acid.

[0051] Preferably, in S2, the first precipitating agent includes one or more of water, ethanol, methanol, and isopropanol.

[0052] Preferably, in S3, the ionizing reagent is one or more of dimethyl sulfate, halogenated hydrocarbons with 1-20 carbon atoms, N(R 14 )3, and nitrogen heterocycles. In N(R 14 )3, each R 14 is independently selected from hydrocarbon groups with 1-20 carbon atoms. The nitrogen heterocycle includes one or more of partially or fully 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 hydrocarbon groups with 1–20 carbon atoms.

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

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

[0057] The application of the above-mentioned highly alkali-resistant poly(arylenealkylene)piperidine cationic polymer with a branched structure. The highly alkali-resistant poly(arylenealkylene)piperidine cationic polymer with a branched structure is applied to the preparation of anion exchange membranes and catalyst layer binders.

[0058] Preferably, the method for preparing the anion exchange membrane is to dissolve or disperse the highly alkali-resistant poly(arylenealkylene)piperidine cationic polymer with a branched structure in a third organic solvent to obtain a solution or dispersion of the highly alkali-resistant poly(arylenealkylene)piperidine cationic polymer with a branched structure. Then, coat the solution or dispersion of the highly alkali-resistant poly(arylenealkylene)piperidine cationic polymer with a branched structure on a substrate, dry to remove the third organic solvent, and after demolding and washing, obtain the anion exchange membrane.

[0059] Preferably, the coating method is one of solution casting, spin coating, blade coating, casting, or dip coating. The method for removing the solvent is room temperature evaporation 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 a highly alkali-resistant poly(arylenealkylene)piperidinium cation polymer with a branched structure in a fourth organic solvent to obtain a solution or dispersion of the catalyst layer binder, and then mix the catalyst layer binder solution or dispersion with a catalyst uniformly to obtain a slurry using the highly alkali-resistant poly(arylenealkylene)piperidinium cation polymer with a branched structure as the catalyst layer binder.

[0062] Preferably, the fourth organic solvent is a low-boiling 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 poly(arylenealkylene)piperidinium cation polymer solution with 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 a polyfunctional monomer in 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, thus greatly improving the anti-swelling performance of the cationic polymer and ensuring the stable and safe operation of the device. In addition, the piperidinium cation is connected to the aryl group through a flexible spacer, thereby reducing the influence of the aromatic ring on the stability of the piperidinium cation and enhancing its alkali stability.

[0066] Therefore, the present invention uses the highly alkali-resistant poly(arylenealkylene)piperidinium cation polymer with the above structure, and its beneficial effects are as follows:

[0067] 1. The preparation method of the highly alkali-resistant cationic polymer with a branched structure provided by the present invention is simple in operation and mild in reaction conditions, which is beneficial to large-scale 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 under a high ion exchange capacity, and shows excellent physical stability when applied to the preparation of anion exchange membranes and slurries for catalyst layer bonding;

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

[0070] 4. The highly alkaline-resistant poly(arylenealkylene)piperidinium 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 alkaline-resistant poly(arylenealkylene)piperidinium cationic polymer with a branched structure can also be used as a catalyst binder material in the catalyst layers of fuel cells and water electrolysis.

[0071] The technical solution of the present invention will be further described in detail below with reference to the drawings and examples. Description of the Drawings

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

[0073] Figure 2 It is a graph showing the change of water absorption rate of the anion exchange membranes in Application Example 1 and Comparative Example 1 of the present invention with temperature;

[0074] Figure 3 It is a graph showing the change of swelling ratio of Anion Exchange Membrane 1 in Application Example 1 and the anion exchange membrane in Comparative Example 1 of the present invention with temperature;

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

[0076] Figure 5 It is an electrochemical performance diagram of the catalyst binder prepared in Application Example 1 and Anion Exchange Membrane 1 of the present invention. Detailed Embodiments

[0077] The present invention will be further described below with reference to the drawings and examples. Unless otherwise defined, the technical terms or scientific terms used in the present invention should have the ordinary meaning understood by those of ordinary skill in the field to which the present invention belongs. The features mentioned above in the present invention or the features mentioned in the specific examples can be combined arbitrarily. These specific examples are only used to illustrate the present invention and do not 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 a polycondensation reaction was carried out 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 drop the polyaromatic polymer precursor dispersion containing a piperidine structure obtained in S1 into a 1:1 (v / v) mixed solution of methanol and water. After precipitation, filter to obtain a white fibrous polymer, filter, wash thoroughly, and then dry under vacuum to obtain 0.45 g of the polyaromatic polymer precursor containing a piperidine structure.

[0081] S3. Dissolve the polyaromatic polymer precursor containing a piperidine structure obtained in S2 in 10 mL of N-methylpyrrolidone. After adding 0.50 mL of methyl iodide and 0.3 g of potassium carbonate, carry out an ionization reaction at room temperature for 72 h to obtain a highly alkali-resistant poly(arylenealkylene)piperidine cationic polymer solution with a branched structure.

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

[0083]

[0084] Application Example 1

[0085] a. Preparation of an anion exchange membrane

[0086] Dissolve the highly alkali-resistant poly(arylenealkylene)piperidine cationic polymer PTP-DMP-Tri-3% with a branched structure prepared in Example 1 in 4 mL of dimethyl sulfoxide to obtain a highly alkali-resistant poly(arylenealkylene)piperidine cationic polymer solution with a mass fraction of about 10%. Use the casting method to coat the highly alkali-resistant poly(arylenealkylene)piperidine cationic polymer solution with a branched structure on a clean glass plate. Place the glass plate in a blast drying oven at 80 °C for 24 h to remove dimethyl sulfoxide. After the temperature drops to room temperature, take out the glass plate, place it in deionized water to remove the membrane, and then wash it thoroughly with deionized water to obtain an anion exchange membrane I with a counter ion of I - -.

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

[0088] Place the anion exchange membrane I with a counter ion of I - in a 1 mol / L NaOH solution and soak it for 48 h. Then wash the anion exchange membrane I thoroughly with deionized water to obtain an anion exchange membrane I with a counter ion of OH - -. Place the anion exchange membrane I with a counter ion of I -The anion exchange membrane was immersed in 2 mol / L NaCl solution for 24 h, and then the anion exchange membrane was thoroughly washed with deionized water to obtain an anion exchange membrane with Cl as the counter ion. - The anion exchange membrane 1.

[0089] c. Preparation of the 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 2 mol / L NaOH solution for 48 h, and then thoroughly washed with deionized water and filtered to obtain a highly alkaline poly(arylenealkylene)piperidine cationic polymer with a branched structure and OH as the counter ion. - The highly alkaline poly(arylenealkylene)piperidine cationic polymer with a branched structure.

[0091] The prepared highly alkaline poly(arylenealkylene)piperidine cationic polymer with a branched structure and OH as the counter ion - was dissolved in a mixed solvent of isopropanol and water at a solid content of 2 wt%, and a metal catalyst was added and mixed to prepare a slurry of the catalyst layer binder that was uniformly dispersed, that is, a slurry of the catalyst layer binder of the highly alkaline poly(arylenealkylene)piperidine cationic polymer with a branched structure and OH as the counter ion. - The slurry of the catalyst layer binder of the highly alkaline poly(arylenealkylene)piperidine cationic polymer with a branched structure.

[0092] Comparative Example 1

[0093] S1. A polymerization mixture composed 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 for catalytic polycondensation reaction. The reaction was carried out at 25 °C for 10 h to obtain a dispersion of a polymer with a piperidine structure in a viscous state.

[0094] S2. The dispersion of the polymer with a piperidine structure in S1 was slowly dropped into a 1:1 (v / v) mixed solution of methanol and water to obtain a light yellow fibrous polymer, which was filtered, thoroughly washed, and vacuum dried to obtain 0.43 g of a white fibrous polymer powder with a piperidine structure.

[0095] S3. The polymer powder with a piperidine structure in S2 was dissolved in 5 mL of N-methylpyrrolidone. After adding 0.50 mL of methyl iodide and 0.3 g of potassium carbonate, an ionization reaction was carried out at room temperature for 72 h to obtain a cationic polymer solution.

[0096] S4. Slowly add the cationic polymer solution in S3 into diethyl ether, filter and dry to obtain 0.45 g of highly alkali-resistant cationic polymer PTP-DMP powder. Prepare an anion exchange membrane from the PTP-DMP powder, with the counterion being I - . And it can be exchanged to OH - or other counterions (such as Cl - ). After replacement, the structure is as shown below, and the counterion of the PTP-DMP membrane is OH - .

[0097]

[0098] Test Example 1

[0099] Perform the following tests on the anion exchange membrane 1 with different counterions and the catalyst layer binder in Application Example 1 to characterize their basic properties and compare with the PTP-DMP membrane in Comparative Example 1

[0100] a. Conductivity test

[0101] Determine by the four-electrode AC impedance method. Cut both the anion exchange membrane 1 with the counterion being OH - and the PTP-DMP anion exchange membrane into 1 cm × 5 cm splines, then clamp them on the fixture and place them in a water tank filled with pure water. Install the electrodes, connect the electrochemical workstation, and in the constant current mode (0.1 mA), the scanning frequency range is 1 MHz - 100 Hz. On the Bode curve, find the frequency range where the impedance is stable, and then read the resistance R of the anion exchange membrane 1 with the counterion being OH - and the PTP-DMP anion exchange membrane on the corresponding curve

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

[0103]

[0104] where 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 detected at different temperatures, obtain the curve of the hydroxide ion conductivity of the anion exchange membrane changing with temperature, as shown in Figure 1 . As can be seen from Figure 1 , at 80 °C, the OH - conductivity of the anion exchange membrane 1 with a branched structure and the counterion being OH - reaches 188 mS·cm -1conductivity of the anion exchange membrane PTP-DMP membrane without a branched structure is only 162 mS·cm - -1 .

[0106] b. Water absorption rate and swelling ratio

[0107] Cut the anion exchange membrane one and the anion exchange membrane PTP-DMP membrane into 1 cm × 8 cm splines respectively, dry them thoroughly in an oven, and record the weight of the dried anion exchange membrane as W dry Then soak the dried anion exchange membrane in deionized water. Take out the anion exchange membrane every 12 h, dry the water on the surface of the anion exchange membrane, and record the weight W of the anion exchange membrane after soaking at different temperatures (30–80 °C). wet The water absorption rate (WU) is calculated by the following formula

[0108]

[0109] According to the water absorption rates detected at different temperatures, obtain the water absorption rate vs. temperature curves of the two anion exchange membranes, as Figure 2 shown

[0110] The swelling ratio (SR) is an important index to measure the dimensional stability of the membrane, and is calculated from the lengths (L dry and L wet ) of the dry and wet anion exchange membranes, and is calculated by the following formula

[0111]

[0112] According to the swelling ratios detected at different temperatures, obtain the swelling ratio vs. temperature curves of the anion exchange membrane one with Cl - as the counterion and the PTP-DMP membrane with Cl - as the counterion, as Figure 3 shown

[0113] c. Mechanical property test

[0114] Use a CMT 4506 electronic universal testing machine to measure the tensile properties of the obtained anion exchange membrane one and the anion exchange membrane PTP-DMP membrane at a tensile speed of 5 mm min -1 . The anion exchange membrane one and the anion exchange membrane PTP-DMP membrane are both cut into dumbbell shapes, 40 mm × 10 mm × 0.03 mm (length × width × thickness). Set 3 parallel samples for each group of samples. The splines are balanced in the test environment for 24 hours before use. The test results are as Figure 4 shown

[0115] d. Electrochemical property test

[0116] The slurry for preparing the catalyst layer binder and the first anion exchange membrane were respectively prepared with PTP-DMP-Tri-3% in Example 1. Pt / C was used as the cathode and anode catalysts, and the Pt loading in the anode and cathode was 0.5 mg cm -2 . The membrane electrode was prepared by the catalyst coated membrane technology.

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

[0118] In summary, at 80 °C, the hydroxide ion conductivity of the first anion exchange membrane reached 188 mS·cm -1 , the first anion exchange membrane had a low water absorption rate and swelling rate and had good mechanical properties. The maximum power density of the membrane electrode composed of PTP-DMP-Tri-3% reached 1.32 W·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 a polycondensation reaction was carried out 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. The polyaromatic polymer precursor dispersion containing a piperidine structure obtained in S1 was slowly dropped into a 1:1 (v / v) mixed solution of methanol and water. After precipitation, filtration was carried out to obtain a light yellow fibrous polymer. After filtration and thorough washing, it was dried in vacuo to obtain 0.41 g of a polyaromatic polymer precursor containing a piperidine structure;

[0122] S3. The polyaromatic polymer precursor containing a piperidine structure obtained in S2 was dissolved in 4 mL of N-methylpyrrolidone. After adding 0.45 mL of methyl iodide and 0.2 g of potassium carbonate, an ionization reaction was carried out at room temperature for 72 h to obtain a highly alkali-resistant poly(arylenealkylene)piperidinium cation polymer solution with a branched structure;

[0123] S4. Slowly add the highly alkali-resistant poly(arylenealkylene)piperidinium cationic polymer solution with a branched structure obtained in S3 into diethyl ether. After precipitation, filter and dry the precipitate to obtain 0.43 g of the highly alkali-resistant poly(arylenealkylene)piperidinium cationic polymer with a branched structure, and the structure is as follows:

[0124] [[ID=5]]

[0125] Application Example 2

[0126] a. Prepare an anion exchange membrane

[0127] Dissolve the highly alkali-resistant poly(arylenealkylene)piperidinium cationic polymer with a branched structure prepared in Example 2 in 4 mL of dimethyl sulfoxide to obtain a highly alkali-resistant poly(arylenealkylene)piperidinium cationic polymer solution with a mass fraction of about 10%. Use the casting method to coat the highly alkali-resistant poly(arylenealkylene)piperidinium cationic polymer solution with a branched structure on a clean glass plate, and place the glass plate in a blast drying oven at 80 °C for 24 h to remove the solvent. After the temperature drops to room temperature, take out the glass plate, demold it in deionized water, and then wash it thoroughly with deionized water to obtain an anion exchange membrane II with a counter ion of I -

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

[0129] [[ID=20]]Ion exchange the anions in the anion exchange membrane II with a counter ion of I - prepared in a as needed. Immerse the anion exchange membrane II with a counter ion of I - in a 2 mol / L NaCl solution for 24 h, and then wash it thoroughly with deionized water to obtain an anion exchange membrane II with a counter ion of Cl -

[0130] c. Prepare a catalyst layer binder

[0131] Ion exchange the counter ions in the highly alkali-resistant poly(arylenealkylene)piperidinium cationic polymer with a branched structure prepared in Example 2 as needed. Immerse the powder of the highly alkali-resistant poly(arylenealkylene)piperidinium cationic polymer with a branched structure prepared in Example 2 in a 2 mol / L NaOH solution for 48 h, and then wash it thoroughly with deionized water. After suction filtration, obtain the highly alkali-resistant poly(arylenealkylene)piperidinium cationic polymer with a counter ion of OH -

[0132] The prepared highly alkali-resistant poly(arylenealkylene)piperidinium cationic polymer with a counter ion of OH - ​The highly alkali-resistant polyarylenealkylene 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 after mixing with a metal catalyst, a uniformly dispersed slurry is prepared, that is, a slurry of the catalytic layer binder based on the highly alkali-resistant polyarylenealkylene piperidine cationic polymer with a branched structure in Example 2.

[0133] Example 3

[0134] S1. Mix 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), disperse them in dichloromethane (4.0 mL), and carry out a polycondensation reaction under the catalysis of trifluoromethanesulfonic acid (4.5 mL). React at 25 °C for 24 h to obtain a viscous polyaromatic polymer precursor dispersion containing a piperidine structure.

[0135] S2. Slowly drop the polyaromatic polymer precursor dispersion containing a piperidine structure obtained in S1 into a 1:1 (v / v) mixed solution of methanol and water. After precipitation, filter to obtain a light yellow fibrous polymer. Filter, wash thoroughly, and then dry in vacuo to obtain 0.82 g of a white fibrous polyaromatic polymer precursor containing a piperidine structure.

[0136] S3. Dissolve the polyaromatic polymer precursor containing a piperidine structure obtained in S2 in 6 mL of N-methylpyrrolidone. Add 0.90 mL of methyl iodide and 0.4 g of potassium carbonate, and carry out an ionization reaction at room temperature for 72 h to obtain a solution of the highly alkali-resistant polyarylenealkylene piperidine cationic polymer with a branched structure.

[0137] S4. Slowly add the solution of the highly alkali-resistant polyarylenealkylene piperidine cationic polymer with a branched structure obtained in S3 to diethyl ether. After precipitation, filter and dry the precipitate to obtain 0.87 g of the highly alkali-resistant polyarylenealkylene piperidine cationic polymer with a branched structure. The structure is as follows:

[0138]

[0139] Application Example 3

[0140] Dissolve the highly alkali-resistant cationic polymer with a branched structure prepared in Example 3 in 7 mL of dimethyl sulfoxide to obtain a highly alkali-resistant polyarylenealkylene piperidine cationic polymer solution with a branched structure and a mass fraction of about 10%. Coating the highly alkali-resistant polyarylenealkylene piperidine cationic polymer solution with a branched structure on a clean glass plate by the casting method, and placing the glass plate in a blast drying oven at 80 °C for 24 h to remove the solvent. After the temperature drops to room temperature, take out the glass plate, demold it in deionized water, and then wash it thoroughly with deionized water to obtain an anion exchange membrane III with the counter ion I - of the anion exchange membrane III.

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

[0142] For the anion in the anion exchange membrane III with the counter ion I prepared in a - , perform ion exchange as needed. Immerse the anion exchange membrane III with the counter ion I - in a 2 mol / L NaCl solution for 24 h, and then wash the membrane thoroughly with deionized water to obtain an anion exchange membrane III with the counter ion Cl - of the anion exchange membrane III.

[0143] c. Prepare the catalyst layer binder

[0144] Perform ion exchange as needed for the counter ion in the highly alkali-resistant polyarylenealkylene piperidine cationic polymer with a branched structure prepared in Example 3. Immerse the highly alkali-resistant polyarylenealkylene piperidine cationic polymer powder with a branched structure prepared in Example 3 in a 2 mol / L NaOH solution for 48 h, and then wash it thoroughly with deionized water. After suction filtration, obtain a highly alkali-resistant polyarylenealkylene piperidine cationic polymer with a branched structure and the counter ion OH - .

[0145] Dissolve the prepared highly alkali-resistant polyarylenealkylene piperidine cationic polymer with a branched structure and the counter ion OH - in a mixed solvent of isopropanol and water with a solid content of 2 wt%, and mix it with a metal catalyst to prepare a uniformly dispersed slurry, that is, a slurry of the catalyst layer binder based on the highly alkali-resistant polyarylenealkylene piperidine cationic polymer with a branched structure in Example 3.

[0146] Example 4

[0147] S1. Disperse 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) in dichloromethane (3.0 mL), and carry out a polycondensation reaction under the catalysis of trifluoromethanesulfonic acid (2.5 mL). React at 25 °C for 48 h to obtain a viscous dispersion of a polyaromatic polymer precursor containing a piperidine structure.

[0148] S2. Slowly drop the dispersion of the polyaromatic polymer precursor containing a piperidine structure obtained in S1 into a 1:1 (v / v) mixed solution of methanol and water. After precipitation, filter to obtain a light yellow fibrous polymer. Filter, wash thoroughly, and then dry in vacuo to obtain 0.78 g of a white fibrous polyaromatic polymer precursor containing a piperidine structure.

[0149] S3. Dissolve the polyaromatic polymer precursor containing a piperidine structure obtained in S2 in 6 mL of N-methylpyrrolidone. Add 1.32 mL of methyl iodide and 0.9 g of potassium carbonate, and carry out an ionization reaction at room temperature for 72 h to obtain a highly alkali-resistant poly(arylenealkylene)piperidinium cationic polymer solution with a branched structure.

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

[0151]

[0152] Application Example 4

[0153] a. Preparation of an anion exchange membrane

[0154] Dissolve the highly alkali-resistant poly(arylenealkylene)piperidinium cationic polymer with a branched structure prepared in Example 4 in 9 mL of dimethyl sulfoxide to obtain a highly alkali-resistant poly(arylenealkylene)piperidinium cationic polymer solution with a mass fraction of about 10%. Use the casting method to coat the highly alkali-resistant poly(arylenealkylene)piperidinium cationic polymer solution with a branched structure on a clean glass plate, and place the glass plate in a blast drying oven at 80 °C for 24 h to remove the solvent. After the temperature drops to room temperature, take out the glass plate, place it in deionized water to remove the membrane, and then wash it thoroughly with deionized water to obtain an anion exchange membrane IV with I - as the counter ion.

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

[0156] The counter ion prepared in a is I - The anions in the anion exchange membrane 4 with counter ion I are ion-exchanged as needed, and the anion exchange membrane 4 with counter ion I - is immersed in 2 mol / L NaCl solution for 24 h, and then washed thoroughly with deionized water to obtain an anion exchange membrane 4 with counter ion Cl - .

[0157] c. Preparation of the catalyst layer binder

[0158] The highly alkali-resistant poly(arylenealkylene piperidine) cationic polymer powder with a branched structure prepared in Example 4 is ion-exchanged as needed. The poly(arylenealkylene piperidine) cationic polymer powder with a branched structure prepared in Example 4 is immersed in 2 mol / L NaOH solution for 48 h, and then washed thoroughly with deionized water. After suction filtration, a cationic polymer with counter ion OH - is obtained.

[0159] The prepared cationic polymer with counter ion OH - is dissolved in a mixed solvent of isopropanol and water at 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-piperidine-3-one hydrochloride (0.09 g, 0.72 mmol) and p-terphenyl (0.30 g, 1.32 mmol) are mixed and dispersed in dichloromethane (1.5 mL), and a polycondensation reaction is carried out under the catalysis of trifluoromethanesulfonic acid (2.5 mL). The reaction is carried out at 25 °C for 48 h to obtain a viscous dispersion of a polyaromatic polymer precursor containing a piperidine structure;

[0162] S2. The dispersion of the polyaromatic polymer precursor containing a piperidine structure obtained in S1 is slowly added dropwise to a 1:1 (v / v) mixed solution of methanol and water. After precipitation, the mixture is filtered to obtain a light yellow fibrous polymer, which is filtered, washed thoroughly and then dried in vacuo to obtain 0.46 g of a white fibrous polyaromatic polymer precursor containing a piperidine structure;

[0163] S3. The polyaromatic polymer precursor containing a piperidine structure obtained in S2 is dissolved in 6 mL of N-methylpyrrolidone. After adding 0.40 mL of methyl iodide and 0.3 g of potassium carbonate, an ionization reaction is carried out at room temperature for 72 h to obtain a solution of a highly alkali-resistant poly(arylenealkylene piperidine) cationic polymer with a branched structure;

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

[0165]

[0166] Application Example 5

[0167] a. Prepare an anion exchange membrane

[0168] Dissolve the highly alkali-resistant cationic polymer with a branched structure prepared in Example 5 in 5 mL of dimethyl sulfoxide to obtain a highly alkali-resistant poly(arylenealkylene)piperidinium cationic polymer solution with a branched structure having a mass fraction of about 10%. Use the casting method to coat the highly alkali-resistant poly(arylenealkylene)piperidinium cationic polymer solution with a branched structure on a clean glass plate, and place the glass plate in a forced-air drying oven at 80 °C for 24 h to remove the solvent. After the temperature drops to room temperature, take out the glass plate, demembrane it in deionized water, and then wash it thoroughly with deionized water to obtain an anion exchange membrane V with a counter ion of I - .

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

[0170] Perform ion exchange on the anions in the anion exchange membrane V with a counter ion of I - prepared in a as needed. Immerse the anion exchange membrane V with a counter ion of I - in a 2 mol / L NaCl solution for 24 h, and then wash it thoroughly with deionized water to obtain an anion exchange membrane V with a counter ion of Cl - .

[0171] c. Prepare a catalyst layer binder

[0172] Perform ion exchange on the counter ions in the highly alkali-resistant poly(arylenealkylene)piperidinium cationic polymer with a branched structure prepared in Example 5 as needed. Immerse the highly alkali-resistant poly(arylenealkylene)piperidinium cationic polymer powder prepared in Example 5 in a 2 mol / L NaOH solution for 48 h, and then wash it thoroughly with deionized water. After suction filtration, obtain a highly alkali-resistant poly(arylenealkylene)piperidinium cationic polymer with a counter ion of OH - .

[0173] The prepared highly alkali-resistant poly(arylenealkylene)piperidinium cationic polymer with a counter ion of OH -The highly alkali-resistant poly(arylenealkylene)piperidinium cationic polymer with a branched structure is dissolved in a mixed solvent of isopropanol and water at a solid content of 2 wt%, and mixed with a metal catalyst to prepare a uniformly dispersed slurry, that is, the slurry of the catalytic layer binder based on the highly alkali-resistant poly(arylenealkylene)piperidinium cationic polymer with a branched structure in Example 5.

[0174] Example 6

[0175] S1. Mix triphenylene (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), disperse them in dichloromethane (2.0 mL), and carry out a polycondensation reaction under the catalysis of trifluoromethanesulfonic acid (2.0 mL). React at 25 °C for 4 h to obtain a viscous dispersion of the polyaromatic polymer precursor containing a piperidine structure.

[0176] S2. Slowly drop the dispersion of the polyaromatic polymer precursor containing a piperidine structure obtained in S1 into a 1:1 (v / v) mixed solution of methanol and water. After precipitation, filter to obtain a light yellow fibrous polymer. Filter, wash thoroughly, and then dry in vacuo to obtain 0.55 g of a white fibrous polyaromatic polymer precursor containing a piperidine structure.

[0177] S3. Dissolve the polyaromatic polymer precursor containing a piperidine structure obtained in S2 in 6 mL of N-methylpyrrolidone, add 0.20 mL of methyl iodide, a solution of 2.4 mL of trimethylamine (4.2 mol L -1 ethanol solution), and 0.2 g of potassium carbonate, and carry out an ionization reaction at room temperature for 72 h to obtain a solution of the highly alkali-resistant poly(arylenealkylene)piperidinium cationic polymer with a branched structure.

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

[0179]

[0180] Application Example 6

[0181] a. Preparation of an anion exchange membrane

[0182] Dissolve the highly alkali-resistant cationic polymer with a branched structure prepared in Example 6 in 6 mL of dimethyl sulfoxide to obtain a highly alkali-resistant polyarylenealkylene piperidine cationic polymer solution with a branched structure and a mass fraction of about 10%. Coat the highly alkali-resistant polyarylenealkylene piperidine cationic polymer solution with a branched structure on a clean glass plate by the casting method, and place the glass plate in a blast drying oven at 80 °C for 24 h to remove the solvent. After the temperature drops to room temperature, take out the glass plate, demold it in deionized water, and then wash it thoroughly with deionized water to obtain an anion exchange membrane VI with a counter ion of I - of the anion exchange membrane VI.

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

[0184] For the anion in the anion exchange membrane VI with a counter ion of I prepared in a - perform ion exchange as needed. Immerse the anion exchange membrane VI with a counter ion of I - in a 2 mol / L NaCl solution for 24 h, and then wash the membrane thoroughly with deionized water to obtain an anion exchange membrane VI with a counter ion of Cl - of the anion exchange membrane VI.

[0185] c. Prepare the catalyst layer binder

[0186] Perform ion exchange on the counter ion in the highly alkali-resistant polyarylenealkylene piperidine cationic polymer with a branched structure prepared in Example 6 as needed. Immerse the highly alkali-resistant polyarylenealkylene piperidine cationic polymer powder with a branched structure prepared in Example 6 in a 2 mol / L NaOH solution for 48 h, and then wash it thoroughly with deionized water. After suction filtration, obtain a highly alkali-resistant polyarylenealkylene piperidine cationic polymer with a branched structure and a counter ion of OH - of the highly alkali-resistant polyarylenealkylene piperidine cationic polymer with a branched structure.

[0187] Dissolve the prepared highly alkali-resistant polyarylenealkylene piperidine cationic polymer with a branched structure and a counter ion of OH - in a mixed solvent of isopropanol and water at a solid content of 2 wt%, and mix it with a metal catalyst to prepare a uniformly dispersed slurry, that is, a slurry of the catalyst layer binder based on the highly alkali-resistant polyarylenealkylene piperidine cationic polymer with a branched structure in Example 6.

[0188] Example 7

[0189] S1. Mix fluorene (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), disperse the mixture in dichloromethane (1.2 mL), and carry out a polycondensation reaction under the catalysis of trifluoromethanesulfonic acid (1.2 mL). React at 25 °C for 48 h to obtain a viscous dispersion of a polyaromatic polymer precursor containing a piperidine structure.

[0190] S2. Slowly drip the polyaromatic polymer precursor dispersion containing a piperidine structure obtained in S1 into a 1:1 (v / v) mixed solution of methanol and water. After precipitation, filter to obtain a light yellow fibrous polymer. Filter, wash thoroughly, and then dry in vacuo to obtain 0.41 g of a white fibrous polyaromatic polymer precursor containing a piperidine structure.

[0191] S3. Dissolve the polyaromatic polymer precursor containing a piperidine structure obtained in S2 in 4 mL of N-methylpyrrolidone. Add 0.70 mL of methyl iodide and 0.5 g of potassium carbonate, and carry out an ionization reaction at room temperature for 72 h to obtain a highly alkali-resistant poly(arylenealkylene)piperidinium cationic polymer solution with a branched structure.

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

[0193]

[0194] Application Example 7

[0195] Preparation of a Catalyst Layer Binder

[0196] Carry out ion exchange on the counterions in the highly alkali-resistant poly(arylenealkylene)piperidinium cationic polymer with a branched structure prepared in Example 7 as needed. Immerse the powder of the highly alkali-resistant poly(arylenealkylene)piperidinium cationic polymer with a branched structure prepared in Example 7 in a 2 mol / L NaOH solution for 48 h, then wash thoroughly with deionized water, and obtain a cationic polymer with OH - as the counterion through suction filtration.

[0197] Dissolve the prepared cationic polymer with OH - as the counterion in a mixed solvent of isopropanol and water at a solid content of 2 wt%, and mix with a metal catalyst to prepare a uniformly dispersed slurry, that is, a slurry of a catalyst layer binder based on the highly alkali-resistant poly(arylenealkylene)piperidinium cationic polymer with a branched structure in Example 7.

[0198] Example 8

[0199] S1. Mix 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), disperse them in dichloromethane (1.2 mL), and carry out a polycondensation reaction under the catalysis of trifluoromethanesulfonic acid (1.2 mL). React at 25 °C for 48 h to obtain a viscous polyaromatic polymer precursor dispersion containing a piperidine structure.

[0200] S2. Slowly drop the polyaromatic polymer precursor dispersion containing a piperidine structure obtained in S1 into a 1:1 (v / v) mixed solution of methanol and water. After precipitation, filter to obtain a light yellow fibrous polymer. Filter, wash thoroughly, and then dry under vacuum to obtain 0.41 g of a white fibrous polyaromatic polymer precursor containing a piperidine structure.

[0201] S3. Dissolve the polyaromatic polymer precursor containing a piperidine structure obtained in S2 in 4 mL of N-methylpyrrolidone. Add 3.0 mL of 1,5-diiodopentane and 0.5 g of potassium carbonate, and then carry out an ionization reaction at room temperature for 72 h to obtain a highly alkali-resistant poly(arylenealkylene)piperidinium cation polymer solution with a branched structure.

[0202] S4. Slowly add the highly alkali-resistant poly(arylenealkylene)piperidinium cation polymer solution with a branched structure obtained in S3 into diethyl ether. After precipitation, filter and dry the precipitate to obtain 0.55 g of a highly alkali-resistant poly(arylenealkylene)piperidinium cation polymer with a branched structure, and the structure is as shown in (8).

[0203]

[0204] Application Example 8

[0205] Prepare a catalyst layer binder

[0206] Carry out ion exchange on the counterions in the highly alkali-resistant poly(arylenealkylene)piperidinium cation polymer with a branched structure prepared in Example 8 as needed. Immerse the powder of the highly alkali-resistant poly(arylenealkylene)piperidinium cation polymer with a branched structure prepared in Example 8 in a 2 mol / L NaOH solution for 48 h, then wash it thoroughly with deionized water, and obtain a cation polymer with counterions of OH - by suction filtration.

[0207] The prepared cation polymer with counterions of OH -The cationic polymer is dissolved in a mixed solvent of isopropanol and water at 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 highly alkali-resistant polyarylenealkylene piperidine cationic polymer with a branched structure in Example 8.

[0208] Therefore, the present invention adopts the highly alkali-resistant polyarylenealkylene piperidine cationic polymer with a branched structure having the above structure, which 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 polyarylenealkylene piperidine cationic polymer with a branched structure can also be used as a catalyst binder material in the catalyst layer of fuel cells and water electrolysis.

[0209] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit them. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that they can still modify or equivalently replace the technical solutions of the present invention, and these modifications or equivalent replacements cannot make the modified technical solutions deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. A highly alkali-resistant polyarylenealkylene piperidine cationic polymer with a branched structure, characterized in that: comprising one or more of a central unit, linear unit L1, and linear unit L2, the central unit comprising one or more of an MA unit, a piperidinium cation unit m-DMP, and a CA unit, the linear unit L1 comprising a piperidinium cation unit m-DMP and a BA unit, and the linear unit L2 comprising a BA unit and a CA unit; The structural formula of the piperidinium cation unit m-DMP is wherein, R 1 and R 2 are independently selected from hydrocarbon groups having 1 to 20 carbon atoms, or R 1 and R 2 are connected to each other to form a cycloalkyl group composed of 4 to 7 carbon atoms, and the counterion A - is selected from one or more of halogen ions, methyl sulfate ions, hydroxide ions or bicarbonate ions; The MA unit comprises 2-6 aromatic rings, independently selected from one or more of the following structures, The BA unit is independently selected from one or more of the following structures: The CA unit includes one or more of the following, where R 3 and R 4 are independently selected from hydrocarbon groups having 1 to 20 carbon atoms, or R 3 and R 4 are connected to each other to form a cycloalkyl group composed of 4 to 7 carbon atoms; Each R 5 is independently 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; k = 0 or 1; x = 0-12; Q is selected from one or more of an H atom, -N + (R 6 )3 or a nitrogen-containing heterocyclic cation; -N + (R 6 )3, each R 6 is independently selected from hydrocarbon groups having 1 to 20 carbon atoms; The nitrogen-containing heterocyclic cation comprises one or more of partially or fully substituted pyrazole, pyrrole, piperidine, imidazole, and quinine cations, and has the following structure: wherein, R 61 -R 610 is independently selected from hydrocarbon groups having 1 to 20 carbon atoms, and the counter ion A - is selected from one or more of halide ions, methyl sulfate ions, hydroxide ions or hydrogen carbonate ions; The central unit of the highly alkali-resistant polyarylenealkylene piperidinium cation polymer having a branched structure is connected to the linear unit L1. The central unit comprises an MA unit and a piperidinium cation unit m-DMP, and its structural formula is as follows: The linear unit L1 of the highly alkali-resistant polyarylenealkylene piperidinium cation polymer having a branched structure is connected to the central unit and the linear unit L2. The central unit comprises an MA unit, a piperidinium cation unit m-DMP, and a CA unit, and its structure is as follows:

2. A method for preparing a highly alkali-resistant polyarylenealkylene piperidine cationic polymer with a branched structure according to claim 1, characterized in that: comprising the following steps, S1. Mix raw materials MA', 1-R 7 piperidine-3-carbaldehyde or its salt or hydrate and BA' and dissolve or disperse them in a first organic solvent, and carry out a polycondensation reaction under the catalysis of an organic strong acid, react at -20 - 100 °C for 0.1 - 200 h to obtain a polyaromatic polymer precursor solution or dispersion containing a piperidine structure; BA' has one or more of the following structures, 1-R 7 Piperidine-3-carbaldehyde is one or more selected from the following structures S2. Slowly drop the polyaromatic polymer precursor solution or dispersion containing a piperidine structure obtained in S1 into a first precipitant. After precipitation, filter to obtain a fibrous polymer. Wash it thoroughly and then dry it to obtain a polyaromatic polymer precursor containing a piperidine structure; S3. Disperse or dissolve the polyaromatic polymer precursor containing a piperidine structure obtained in S2 in a second organic solvent. After adding an ionizing reagent, carry out an ionization reaction at 0-100 °C for 0.1-200 h to obtain a solution or dispersion of a highly alkali-resistant polyarylenealkylene piperidinium cation polymer having a branched structure; S4. Slowly add the solution or dispersion of the highly alkali-resistant polyarylenealkylene piperidinium cation polymer having a branched structure obtained in S3 into a second precipitant. After precipitation, filter and dry the precipitate to obtain a highly alkali-resistant polyarylenealkylene piperidinium cation polymer having a branched structure.

3. A method for preparing a highly alkali-resistant polyarylenealkylene piperidinium cationic polymer with a branched structure according to claim 1, characterized in that: comprising the following steps, S1. Dissolve or disperse raw materials MA', 1-R 7 piperidine-3-carbaldehyde or its salt or hydrate, BA', and compound CA'' in a first organic solvent, and carry out a polycondensation reaction under the catalysis of an organic strong acid. React at -20°C to 100°C for 0.1 to 200 h to obtain a polyaromatic polymer precursor solution or dispersion containing a piperidine structure; 1-R 7 Piperidine-3-carbaldehyde is one or more selected from the following structures The compound CA” is one or more of Among them, R 9 is independently selected from an H atom or a hydrocarbon group having 1 to 20 carbon atoms; k = 0 or 1; x = 0 - 12; each R 10 is independently selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a fully or partially fluorinated alkyl group having 1 to 6 carbon atoms; Q'' is selected from one or more of an H atom and a halogen atom; S2. Slowly drop the polyaromatic polymer precursor solution or dispersion containing a piperidine structure obtained in S1 into a first precipitant. After precipitation, filter to obtain a fibrous polymer. Wash it thoroughly and then dry it to obtain a polyaromatic polymer precursor containing a piperidine structure; S3. Disperse or dissolve the polyaromatic polymer precursor containing a piperidine structure obtained in S2 in a second organic solvent. After adding an ionizing reagent, carry out an ionization reaction at 0-100 °C for 0.1-200 h to obtain a solution or dispersion of a highly alkali-resistant polyarylenealkylene piperidinium cation polymer having a branched structure; S4. Slowly add the solution or dispersion of the highly alkali-resistant polyarylenealkylene piperidinium cation polymer having a branched structure obtained in S3 into a second precipitant. After precipitation, filter and dry the precipitate to obtain a highly alkali-resistant polyarylenealkylene piperidinium cation polymer having a branched structure.

4. Use of the highly alkali-resistant polyarylenealkylene piperidine cationic polymer with a branched structure according to claim 1, characterized in that: The highly alkali-resistant polyarylenealkylene piperidine cationic polymer with a branched structure is applied to the preparation of anion exchange membranes and catalytic layer binders.

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