Polymer with nitrogen heterocyclic ring hung on side chain, ion exchange membrane and application of polymer and ion exchange membrane

Abstract

The invention discloses a polymer with nitrogen heterocycle suspended on a side chain, an ion exchange membrane and application thereof, and an alkyl chain is connected with a carbon atom on the nitrogen heterocycle. The carbon-carbon connected structure has high alkaline stability. According to the structure of # imgabs0, the nitrogen heterocyclic ring is far away from the aryl group of the main chain, and the electron withdrawing effect of the aryl group is reduced, so that the alkaline stability of the nitrogen heterocyclic ring is further improved, and the alkaline stability of the whole polymer is improved. In addition, the side chain suspension is beneficial to improving the degree of freedom of the nitrogen heterocyclic ring, so that the ionic conductivity of the polymer is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer functional materials, and specifically relates to a class of polymers with nitrogen heterocycles suspended on the side chains, a class of ion exchange membranes and their applications. Background Art

[0002] Fuel cells, hydrogen production by electrolysis of water, metal-air batteries, flow batteries, carbon dioxide reduction, supercapacitors, acid separation, lithium extraction from salt lakes, etc. rely on functional polymer thin film materials. The essence of this type of thin film lies in the selective permeability to ions. However, at present, such thin films are still very lacking, especially ion exchange membranes with high stability and high selectivity suitable for strong acid and strong base environments. The ion exchange membrane is composed of a polymer containing ionic groups inside, and its stability is determined by the polymer chain backbone and the ionic groups on the backbone.

[0003] In 2017, Jannasch invented a polyaromatic piperidine anion exchange membrane (AEM). In 2022, we invented a polyaromatic quinine anion exchange membrane. Both have good alkaline stability. However, in the above two AEMs, the piperidine ring or the quinine ring is directly connected to the aromatic hydrocarbon. Due to the electron-withdrawing effect of the aromatic ring, it is not conducive to the long-term stability of the AEM. In addition, the direct connection of the piperidine ring or the quinine ring to the aromatic hydrocarbon makes the degree of freedom of movement of the piperidine ring or the quinine ring very small, which is not conducive to the free movement of ions, and thus not conducive to the improvement of ionic conductivity. Summary of the Invention

[0004] Based on the above prior art, the present invention provides a class of polymers with nitrogen heterocycles suspended on the side chains, a class of ion exchange membranes and their applications. The polymers of the present invention do not directly connect the piperidine or quinine ring to the aromatic hydrocarbon, which is beneficial to improving the stability, mechanical properties and ionic conductivity of the polymer. Preparing the polymer of the present invention into an ion exchange membrane can be used in the fields of fuel cells, hydrogen production by electrolysis of water, metal-air batteries, flow batteries, carbon dioxide reduction, supercapacitors, nickel-metal hydride batteries, zinc-manganese batteries, acid separation, lithium extraction from salt lakes, electrodialysis, water treatment and membrane humidification, etc.

[0005] The technical solution adopted to achieve the above object of the present invention is as follows:

[0006] A class of polymers I with nitrogen heterocycles suspended on the side chains, comprising structural units of the following general formula:

[0007]

[0008] Among them, A is an aryl group, B is -(CH2) n - or -(CF2) n -, and n is a natural number;

[0009] C is One or more of;

[0010] E is any one of hydrogen, methyl, deuterated methyl, ethyl, propyl, butyl, pentyl, hexyl, N,N,N-trimethylpentylammonium, heptyl, octyl, nonyl, decyl, -CH2CH2NH2, -CH2CH2OH, -CH2C(CH2OH)2CH2Br, -CH2C(CH2OH)3, cyclopropyl, isopropyl, isobutyl, cyclopentyl, cyclohexyl, -CH2CH2CH2CH2CH2N(CH3)3, -CH2CH2(OCH2CH2) m OCH3, -CH2CH2(OCH2CH2) m OCH2CH3, where m is a natural number and 1 ≤ m ≤ 10;

[0011] D is any one or more of;

[0012] R0, R1, G1 are any one of hydrogen, methyl, bromomethyl, chloromethyl, ethyl, propyl, acetyl, trifluoromethyl, pyridyl, phenyl, fluorophenyl, o-tolyl, m-tolyl, p-tolyl or mesityl;

[0013] a is any integer greater than or equal to 1; b and c are both natural numbers.

[0014] A preparation method of a polymer I with a piperidyl group hanging on the side chain, comprising the following steps:

[0015] In the presence of an acid catalyst, an azacyclic monomer and an aromatic monomer undergo a Friedel-Crafts reaction to obtain the polymer I with an azacyclic group hanging on the side chain;

[0016] Or in the presence of an acid catalyst, an azacyclic monomer, an aromatic monomer and an aromatic crosslinking monomer undergo a Friedel-Crafts reaction to obtain the polymer I with an azacyclic group hanging on the side chain;

[0017] Or in the presence of an acid catalyst, an azacyclic monomer, an aromatic monomer, an aromatic crosslinking monomer and a ketone monomer undergo a Friedel-Crafts reaction to obtain the polymer I with an azacyclic group hanging on the side chain;

[0018] Wherein, the molar ratio of the azacyclic monomer to the aromatic monomer is 0.5 - 2:1, and the molar amount of the aromatic crosslinking monomer or the ketone monomer to the azacyclic monomer is 0.5:1;

[0019] The general structural formula of the azacyclic monomer is:

[0020]

[0021] Wherein, B is -(CH2) n - or -(CF2) n -, n is a natural number;

[0022] C is a nitrogen heterocycle or one or more of them;

[0023] E is hydrogen, methyl, deuterated methyl, ethyl, propyl, butyl, pentyl, hexyl, N,N,N-trimethylpentylammonium, heptyl, octyl, nonyl, decyl, -CH2CH2NH2, -CH2CH2OH, -CH2C(CH2OH)2(CH2Br), -CH2C(CH2OH)3, cyclopropyl, isopropyl, isobutyl, cyclopentyl, cyclohexyl, -CH2CH2CH2CH2CH2N(CH3)3, -CH2CH2(OCH2CH2) m OCH3, -CH2CH2(OCH2CH2) m OCH2CH3, where m is a natural number and 1 ≤ m ≤ 10;

[0024] The aromatic monomer is selected from at least one of the compounds represented by the following structural formulas;

[0025]

[0026] wherein, n is a natural number and 0 ≤ n ≤ 10, and R2 and R3 are any one of a hydrogen atom, methyl, ethyl, propyl or butyl;

[0027] The aromatic crosslinking monomer is selected from at least one of the compounds represented by the following structural formulas;

[0028]

[0029] wherein, R4, R5 and R6 are any one of a hydrogen atom, methyl, ethyl, propyl or butyl respectively;

[0030] The ketone monomer is selected from at least one of the compounds represented by the following structural formulas:

[0031]

[0032] wherein, R0, R1 and G1 are any one of hydrogen, methyl, bromomethyl, chloromethyl, ethyl, acetyl, trifluoromethyl, pyridyl, phenyl, fluorophenyl, o-tolyl, m-tolyl, p-tolyl or mesityl; G1 is any one of a hydrogen atom, methyl, ethyl, propyl or butyl;

[0033] The acid catalyst is selected from at least one of trifluoromethanesulfonic acid, trifluoroacetic acid, acetic acid, trichloroacetic acid, methanesulfonic acid, pentafluoropropionic acid, heptafluorobutyric acid and perfluorosulfonic acid resin.

[0034] A class of polymer II with a nitrogen heterocycle pendant on the side chain, comprising a structural unit of the following general formula:

[0035]

[0036] Wherein, A is an aryl group, and B is -(CH2) n - or -(CF2) n -, and n is a natural number;

[0037] G is one or more of ionic nitrogen heterocycles among them;

[0038] E is hydrogen, methyl, deuterated methyl, ethyl, propyl, butyl, pentyl, hexyl, N,N,N-trimethylpentylammonium, heptyl, octyl, nonyl, decyl, -CH2CH2NH2, -CH2CH2OH,

[0039] -CH2C(CH2OH)2(CH2Br), -CH2C(CH2OH)3, cyclopropyl, isopropyl, isobutyl, cyclopentyl, cyclohexyl, -CH2CH2CH2CH2CH2N(CH3)3, -CH2CH2(OCH2CH2) m OCH3, -CH2CH2(OCH2CH2) m OCH2CH3, where m is a natural number and 1 ≤ m ≤ 10;

[0040] D is any one or more of;

[0041] R0 and R1 are any one of hydrogen, methyl, bromomethyl, chloromethyl, ethyl, acetyl, trifluoromethyl, pyridyl, phenyl, fluorophenyl, o-tolyl, m-tolyl, p-tolyl and mesityl; G1 is any one of a hydrogen atom, methyl, ethyl, propyl or butyl;

[0042] a is any integer greater than or equal to 1; b and c are both any integers greater than or equal to 0.

[0043] A preparation method of a polymer II with a side-chain pendant nitrogen heterocycle, comprising the following steps:

[0044] Under the condition of the presence or absence of a base, a quaternization reaction is carried out between the polymer I and a monohalogenated compound, and the molar ratio of the monohalogenated compound to the N site of the polymer I is 1-5:1 to obtain the polymer II with a side-chain pendant nitrogen heterocycle;

[0045] The monohalogenated compound is selected from at least one of methyl iodide, deuterated methyl iodide, ethyl iodide, propyl iodide, butyl iodide, pentyl iodide, hexyl iodide, heptyl iodide, octyl iodide, nonyl iodide, decyl iodide, methyl bromide, deuterated methyl bromide, ethyl bromide, propyl bromide, butyl bromide, pentyl bromide, hexyl bromide, heptyl bromide, octyl bromide, nonyl bromide, decyl bromide, 2-bromoethylamine, 2-bromoethanol, cyclopropyl iodide, isopropyl iodide, isobutyl iodide, cyclopentyl iodide, cyclohexyl iodide, and (5-bromopentyl)trimethylammonium bromide, BrCH2C(CH2OH)2(CH2Br), BrCH2C(CH2OH)3, BrCH2CH2(OCH2CH2) r OCH3 and BrCH2CH2(OCH2CH2) r OCH2CH3, where r is a natural number and 0 ≤ r ≤ 10;

[0046] The base is selected from at least one of sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, calcium oxide, calcium hydroxide, trimethylamine, triethylamine, N,N-dimethylethylenediamine, and N,N-diisopropylethylamine.

[0047] Further, when C is 1 ≤ n ≤ 20; when C is 0 ≤ n ≤ 20.

[0048] A class of polymers III with piperidyl groups pendant on the side chain, comprising structural units of the following general formula:

[0049]

[0050] where A is an aryl group; B is -(CH2) r - or -(CF2) n -, r is a natural number and 1 ≤ r ≤ 10;

[0051] D is any one or more of;

[0052] R0, R1, and G1 are any one of hydrogen, methyl, bromomethyl, chloromethyl, ethyl, acetyl, trifluoromethyl, pyridyl, phenyl, fluorophenyl, o-tolyl, m-tolyl, p-tolyl, or mesityl;

[0053] a is any integer greater than or equal to 1, and b and c are both natural numbers.

[0054] A method for preparing a class of polymers III with piperidyl groups pendant on the side chain, comprising the following steps:

[0055] In the presence or absence of a base, polymer I is subjected to a quaternization reaction with 1,5-dihalopentane to form polymer III with piperidinyl groups pendant on the side chains;

[0056] The 1,5-dihalopentane is selected from at least one of 1,5-difluoropentane, 1,5-dichloropentane, 1,5-dibromopentane, and 1,5-diiodopentane;

[0057] The base is selected from at least one of sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, calcium oxide, calcium hydroxide, trimethylamine, triethylamine, N,N-dimethylethylenediamine, and N,N-diisopropylethylamine.

[0058] Furthermore, A is selected from groups having the following structural formula:

[0059]

[0060] wherein n is a natural number and 0 ≤ n ≤ 10, and R2 and R3 are each independently a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a butyl group.

[0061] A polymer flat film is prepared by the following method:

[0062] At least one of polymer I, polymer II, and polymer III is dissolved in an organic solvent to obtain a polymer solution, and the polymer solution is cast or spread on a substrate and dried to obtain the polymer flat film;

[0063] The organic solvent is one or a combination of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, chloroform, dichloromethane, toluene, ethylbenzene, xylene, and ethyl acetate;

[0064] The substrate is a glass plate, a copper sheet, an iron sheet, a ceramic plate, a polytetrafluoroethylene plate, a polyethylene terephthalate base film, a polyamide base film, a polytetrafluoroethylene base film, a polyethylene base film, a polypropylene base film, a carbon fiber base film, or a glass fiber base film.

[0065] A polymer hollow fiber membrane is prepared by the following method:

[0066] At least one of polymer I, polymer II, and polymer III is dissolved in an organic solvent to obtain a polymer solution, and a hollow fiber base membrane is immersed in the polymer solution. After immersion is completed, it is taken out and dried to obtain the polymer hollow fiber membrane; or the polymer solution is used to prepare a polymer hollow fiber membrane by a dry-wet spinning method;

[0067] The organic solvent described above is one of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, chloroform, dichloromethane, toluene, ethylbenzene, xylene, and ethyl acetate, or a combination of several of them;

[0068] The hollow fiber membrane described above is one of a ceramic hollow fiber membrane, a polytetrafluoroethylene hollow fiber membrane, a polyvinylidene fluoride hollow fiber membrane, a polyethylene terephthalate-based hollow fiber membrane, a polyamide hollow fiber membrane, a polyethylene hollow fiber membrane, a polypropylene hollow fiber membrane, a carbon fiber hollow fiber membrane, and a glass hollow fiber membrane.

[0069] A proton exchange membrane is prepared by the following method:

[0070] Soak a polymer flat film or a polymer hollow fiber membrane in an aqueous phosphoric acid solution with a concentration of 0.1 - 20 M and a soaking temperature of 0 - 90 °C. After soaking, wash with pure water and dry to obtain the proton exchange film described above.

[0071] An anion exchange membrane is prepared by the following method:

[0072] Soak a polymer flat film or a polymer hollow fiber membrane in an aqueous solution of hydroxide, bromide, chloride, fluoride, nitrate, or bicarbonate. After soaking, wash with pure water and dry to obtain the anion exchange film described above;

[0073] The hydroxide described above is one of lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, and ammonium hydroxide, or a combination of several of them;

[0074] The bromide selected from at least one of sodium bromide, potassium bromide, cesium bromide, ammonium bromide, magnesium bromide, and calcium bromide;

[0075] The chloride selected from at least one of sodium chloride, potassium chloride, cesium chloride, ammonium chloride, magnesium chloride, and calcium chloride;

[0076] The fluoride selected from at least one of sodium fluoride, potassium fluoride, cesium fluoride, ammonium fluoride, magnesium fluoride, and calcium fluoride;

[0077] The nitrate selected from at least one of sodium nitrate, potassium nitrate, cesium nitrate, ammonium nitrate, magnesium nitrate, and calcium nitrate;

[0078] The bicarbonate selected from at least one of sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, ammonium bicarbonate, magnesium bicarbonate, and calcium bicarbonate.

[0079] Applications of a polymer flat film, a polymer hollow fiber membrane, a proton exchange membrane, or an anion exchange membrane in fuel cells, hydrogen production by electrolyzing water, metal-air batteries, flow batteries, carbon dioxide reduction, supercapacitors, nickel-metal hydride batteries, zinc-manganese batteries, acid separation, lithium extraction from salt lakes, electrodialysis, water treatment, and membrane humidification.

[0080] Compared with the prior art, the advantages and beneficial effects of the present invention are as follows:

[0081] 1. In the present invention, piperidine or quinuclidine is not directly connected to the aromatic hydrocarbon, so that the positive charge center is far from the benzene ring, which is beneficial to further improving the alkaline stability of the anion exchange membrane AEM.

[0082] 2. In the present invention, piperidine or quinuclidine is connected to the aryl through an alkyl chain. Compared with the case where piperidine or quinuclidine is directly connected to the aryl, the side chain is longer, which is beneficial to the entanglement between polymer chains, thereby improving the mechanical properties of the membrane.

[0083] 3. More alkyl chains in the present invention have hydrophobicity, which is beneficial to phase separation to construct ion channels, thereby improving the ionic conductivity of the AEM. Specific Embodiments

[0084] The present invention will be described in detail below with reference to specific embodiments, but these embodiments are not construed as limiting the protection scope of the present invention in any sense.

[0085] Example 1

[0086] 1. Add 2.232 g (10 mmol) of piperidinyl monomer 1 and 2.303 g (10 mmol) of p-terphenyl (CAS No.: 92-94-4) to 20 mL of dichloromethane solvent. After stirring evenly, slowly drop 1 mL of trifluoromethanesulfonic acid (TFSA) under an ice-water bath. After the addition is complete, continue stirring until the system becomes viscous. After the reaction, add 20 mL of 10 w% NaOH aqueous solution to the obtained product for neutralization, filter, wash the filter cake with ethanol first to remove unreacted small molecules, and then wash with water to remove excess alkali and salts to obtain 4.08 g of a pale yellow powdery polymer P1a.

[0087] 1 HNMR (600 MHz, DMSO-d6, ppm) δH = 7.38 - 7.15, 2.79, 2.69, 2.0, 1.56, 1.48, 1.40, 1.31, 1.25, 1.19.

[0088] 2. Dissolve 1.78 g of polymer P1a, 1.42 g (10 mmol) of methyl iodide, and 1.382 g (10 mmol) of potassium carbonate in 10 mL of dimethyl sulfoxide (DMSO), and stir the reaction at 25 °C for 10 hours. After the reaction is completed, wash the obtained product with ethanol and pure water multiple times. Finally, dry the obtained solid at 90 °C for 30 hours to obtain 2.2 g of pale yellow powdery polymer P1b.

[0089] 1 HNMR (600 MHz, DMSO-d6, ppm) δH = 7.38 - 7.15, 3.30, 3.27, 3.17, 1.77, 1.52, 1.48, 1.25, 1.20, 1.19.

[0090] 3. Dissolve 1.78 g of polymer P1a, 1.78 g (7.7 mmol) of 1,5-dibromopentane, and 1.382 g (10 mmol) of potassium carbonate in 10 mL of dimethyl sulfoxide (DMSO), and stir the reaction at 25 °C for 10 hours. After the reaction is completed, wash the obtained product with ethanol and pure water multiple times. Finally, dry the obtained solid at 90 °C for 30 hours to obtain 2.1 g of yellow powdery nitrogen-containing heterocyclic ionic polymer P1c.

[0091] 1 HNMR (600 MHz, DMSO-d6, ppm) δH = 7.38 - 7.15, 3.27, 3.22, 3.17, 1.77, 1.71, 1.60, 1.52, 1.48, 1.25, 1.20, 1.19.

[0092]

[0093] 5. Take 100 mg of polymer P1b and dissolve it in 5 mL of dimethyl sulfoxide to obtain a polymer solution. Coat the polymer solution on a glass plate and bake the glass plate at 100 °C for 15 hours to obtain a polymer flat film F1a. The thickness of F1a is 10 μm and the tensile strength is 42 MPa. Use F1a for nanofiltration separation of waste acid from aluminum oxidation: Use a waste liquid with a sulfuric acid concentration of 150 g / L and an aluminum ion concentration of 20 g / L as the mother liquor, and filter at 3 atmospheres and room temperature. In the filtrate, the sulfuric acid concentration is increased to 220 g / L and the aluminum ion concentration is decreased to 8 g / L. Use F1a for diffusion dialysis of waste acid from aluminum oxidation. At room temperature, in the dialysis liquid, the sulfuric acid concentration is 140 g / L and the aluminum ion concentration is 0.4 g / L.

[0094] 6. F1a was immersed in 1 M phosphoric acid aqueous solution at room temperature for 5 hours. After taking out the film, it was washed three times with pure water and dried in an oven at 100 °C for 5 hours under nitrogen protection to obtain a proton exchange membrane F1b. The tensile strength of F1b was 45 MPa. At 160 °C, the proton conductivity of F1b was 138 mS / cm; at 180 °C, the proton conductivity of F1b was 182 mS / cm. F1b was used as a separator in a fuel cell. At 150 °C and 2 atmospheres, hydrogen and oxygen were introduced, and the maximum power density of the cell was 1.6 W / cm 2 .

[0095] 7. 100 mg of polymer P1b was dissolved in 5 mL of N-methylpyrrolidone to obtain a polymer solution. The polymer solution was coated on a glass plate, and the glass plate was baked at 120 °C for 20 hours to obtain a polymer flat film F1c. The tensile strength of F1c was 42 MPa. At 80 °C, the conductivity of F1c was 98 mS / cm.

[0096] 8. F1c was immersed in 1 M NaCl aqueous solution at room temperature for 5 hours. After taking out the film, it was washed three times with pure water and dried in an oven at 100 °C for 5 hours under nitrogen protection to obtain a chloride ion exchange membrane F1d. The tensile strength of F1d was 41 MPa. At 80 °C, the conductivity of F1d was 140 mS / cm. F1d was used for extracting lithium from salt lakes by diffusion dialysis. The concentration of lithium ions in the mother liquor was 6 g / L, and the concentration of magnesium ions was 120 g / L. At room temperature, in the dialysate, the concentration of lithium ions was 5.8 g / L, and the concentration of magnesium ions was 0.8 g / L.

[0097] 9. F1c was immersed in 1 M NaBr aqueous solution at room temperature for 5 hours. After taking out the film, it was washed three times with pure water and dried in an oven at 120 °C for 5 hours under nitrogen protection to obtain a bromide ion exchange membrane F1d. The tensile strength of F1d was 42 MPa. At 80 °C, the conductivity of F1d was 137 mS / cm. F1d was used in a vanadium redox flow battery. The vanadium ion permeability was 4×10 -10 cm 2 / s. At 80 °C, F1d was immersed in 1.5 M VO 2+ / 3M H2SO4 solution for 30 days, and the conductivity only decreased by 1.8%. Assembled into a vanadium redox flow battery, the Coulomb efficiency was 99.1%.

[0098] 10. F1c was immersed in a 1 M NaOH aqueous solution at room temperature for 24 hours. After taking out the film, it was washed three times with pure water and dried in an oven at 120 °C for 5 hours under nitrogen protection to obtain the hydroxide exchange film F1e. The tensile strength of F1e was 46 MPa. At 80 °C, the conductivity of F1e was 188 mS / cm. F1e was immersed in a 5 M NaOH aqueous solution at 90 °C for 30 days without any degradation. At 80 °C, the water absorption rate of F1e was 32%, and the water swelling rate was 18%. F1e was used for water electrolysis with a 3 M KOH solution as the electrolyte, NiMo as the cathode, and NiFe as the anode. At 80 °C and 2 V, the current density was 1.96 A / cm 2 。

[0099] 11. 100 mg of polymer P1c was dissolved in 5 mL of dimethyl sulfoxide to obtain a polymer solution. The polymer solution was cast on a glass plate, and the glass plate was baked at 100 °C for 15 hours to obtain a polymer flat film F1f. The thickness of F1f was 12 μm, and the tensile strength was 45 MPa.

[0100] 12. F1f was immersed in a 1 M NaOH aqueous solution at room temperature for 24 hours. After taking out the film, it was washed with pure water and dried in an oven at 60 °C for 10 hours under nitrogen protection to obtain the alkaline anion exchange film F1g. The tensile strength of F1g was 48 MPa. At 80 °C, the conductivity of F1g was 198 mS / cm. F1g was immersed in a 5 M NaOH aqueous solution at 90 °C for 30 days without any degradation. At 80 °C, the water absorption rate of F1g was 25%, and the water swelling rate was 15%. F1g was used as a separator in a fuel cell. At 80 °C and 2 atmospheres, with hydrogen and oxygen inlet, the maximum power density of the cell was 1.8 W / cm 2 。

[0101] Example 2

[0102] 1. 2.232 g (10 mmol) of piperidyl monomer 11, 1.388 g (9 mmol) of biphenyl (CAS No.: 92 - 52 - 4), and 0.204 g (0.67 mmol) of 1,3,5 - triphenylbenzene (CAS No.: 612 - 71 - 5) were added to 20 mL of dichloromethane solvent. After stirring evenly, 5 mL of trifluoromethanesulfonic acid (TFSA) was slowly dropped in under an ice - water bath. After the dropping was completed, stirring was continued until the system became viscous. After the reaction, an NaOH aqueous solution was added to the obtained product for neutralization, and then filtered. The filter cake was washed first with ethanol and then with water to obtain 3.37 g of a pale yellow powdery polymer P2a.

[0103] 2. Dissolve 1.78 g of polymer P2a, 1.42 g (10 mmol) of methyl iodide, and 1.382 g (10 mmol) of potassium carbonate in 10 mL of dimethyl sulfoxide (DMSO), stir and react at 25 °C for 10 hours. After the reaction is completed, wash the obtained product with pure water and ethanol multiple times. Finally, dry the obtained solid at 90 °C for 30 hours to obtain 2.14 g of pale yellow powdery polymer P2b.

[0104] 1 HNMR (600 MHz, DMSO-d6, ppm) δH = 7.38 - 7.15, 2.27, 1.99, 1.89, 1.56, 1.48, 1.31, 1.25, 1.19.

[0105]

[0106] 3. Take 100 mg of polymer P2b and dissolve it in 5 mL of dimethyl sulfoxide to obtain a polymer solution. Coat the polymer solution on a glass plate and bake the glass plate at 100 °C for 15 hours to obtain a polymer flat film F2a. The thickness of F2a is 16 μm and the tensile strength is 58 MPa. Use F2a for nanofiltration separation of waste acid from aluminum oxidation: Use a waste liquid with a sulfuric acid concentration of 150 g / L and an aluminum ion concentration of 20 g / L as the mother liquor, filter at 3 atmospheres and room temperature. In the filtrate, the sulfuric acid concentration is increased to 222 g / L and the aluminum ion concentration is reduced to 6 g / L. Use F2a for diffusion dialysis of waste acid from aluminum oxidation. At room temperature, in the dialysis solution, the sulfuric acid concentration is 142 g / L and the aluminum ion concentration is 0.5 g / L.

[0107] 4. Immerse F2a in 1 M phosphoric acid aqueous solution at room temperature for 5 hours. After taking out the film, wash it three times with pure water and dry it in an oven at 100 °C for 5 hours under nitrogen protection to obtain a proton exchange membrane F2b. The tensile strength of F2b is 53 MPa. At 160 °C, the proton conductivity of F2b is 129 mS / cm; at 180 °C, the proton conductivity of F2b is 153 mS / cm. Use F2b as a diaphragm for a fuel cell. At 150 °C and 2 atmospheres, hydrogen and oxygen are injected, and the maximum power density of the battery is 1.7 W / cm 2 .

[0108] 5. Take 100 mg of polymer P2b and dissolve it in 5 mL of N-methylpyrrolidone to obtain a polymer solution. Coat the polymer solution on a glass plate and bake the glass plate at 120 °C for 20 hours to obtain a polymer flat film F2c.

[0109] 6. F2c was immersed in a 1M NaCl aqueous solution at room temperature for 24 hours. After taking out the film, it was washed three times with pure water and dried in an oven at 100 °C for 5 hours under nitrogen protection to obtain a chloride ion exchange membrane F2d. The tensile strength of F2d was 53 MPa. F2d was used for lithium extraction from salt lakes by diffusion dialysis. The lithium ion concentration in the mother liquor was 6 g / L, and the magnesium ion concentration was 141 g / L. At room temperature, in the dialysate, the lithium ion concentration was 6.9 g / L, and the magnesium ion concentration was 0.5 g / L.

[0110] 7. F2c was immersed in a 1M NaOH aqueous solution at room temperature for 48 hours. After taking out the film, it was washed with pure water and dried in an oven at 60 °C for 10 hours under nitrogen protection to obtain an alkaline anion exchange membrane F2d. The tensile strength of F2d was 61 MPa. At 80 °C, the conductivity of F2d was 199 mS / cm. F2d was immersed in a 5M NaOH aqueous solution at 90 °C for 30 days without degradation. At 80 °C, the water absorption rate of F1g was 31%, and the water swelling rate was 12%. F2c was used as a separator for fuel cells. At 80 °C and 2 atmospheres, with hydrogen and oxygen injection, the maximum power density of the battery was 1.9 W / cm 2 . F2d was used for water electrolysis. A 3M KOH solution was used as the electrolyte, Pt / C was used as the cathode catalyst, and NiFe was used as the anode catalyst. At 80 °C and 2V, the current density was 5.6 A / cm 2 .

[0111] Example 3

[0112] 1. 2.072 g (10 mmol) of quinine-based monomer 2 and 2.303 g (10 mmol) of p-terphenyl (CAS No.: 92 - 94 - 4) were added to 30 mL of dichloromethane solvent. After stirring evenly, 2 mL of trifluoromethanesulfonic acid (TFSA) was slowly dropped in under an ice-water bath. After the dropping was completed, stirring was continued until the system became viscous. After the reaction, 30 mL of 10 w% NaOH aqueous solution was added to the obtained product for neutralization, and then filtered. The filter cake was first washed with ethanol to remove unreacted small molecules, and then washed with water to remove excess alkali and salts to obtain 4.21 g of a pale yellow powdery polymer P3a.

[0113] 1 HNMR (600 MHz, DMSO-d6, ppm) δH = 7.39 - 7.17, 3.3 - 3.1, 2.2 - 1.9.

[0114] 2. Dissolve 1.65 g of polymer P3a, 1.42 g (10 mmol) of methyl iodide, and 1.382 g (10 mmol) of potassium carbonate in 10 mL of dimethyl sulfoxide (DMSO), stir and react at 25 °C for 10 hours. After the reaction is completed, wash the obtained product with ethanol and pure water multiple times. Finally, dry the obtained solid at 100 °C for 20 hours to obtain 2.1 g of pale yellow powdery polymer P3b.

[0115] 1 HNMR (600 MHz, DMSO-d6, ppm) δH = 7.37 - 7.13, 3.60 - 3.31, 3.17, 2.21 - 1.65.

[0116]

[0117] 3. Take 100 mg of polymer P3a, dissolve it in 5 mL of dimethyl sulfoxide to obtain a polymer solution. Coat the polymer solution on a glass plate and bake the glass plate at 100 °C for 15 hours to obtain a polymer flat film F3a. The thickness of F3a is 15 μm and the tensile strength is 50 MPa.

[0118] 4. Immerse F3a in 1 M phosphoric acid aqueous solution at room temperature for 12 hours. Take out the film and wash it three times with pure water, then dry it in an oven at 100 °C for 5 hours under nitrogen protection to obtain a proton exchange membrane F3b. The tensile strength of F3b is 46 MPa. At 160 °C, the proton conductivity of F3b is 145 mS / cm; at 180 °C, the proton conductivity of F3b is 176 mS / cm. Use F3b as a separator for fuel cells. At 150 °C and 2 atmospheres, hydrogen and oxygen are injected, and the maximum power density of the battery is 1.7 W / cm 2 。

[0119] 5. Take 100 mg of polymer P3b, dissolve it in 5 mL of N-methylpyrrolidone to obtain a polymer solution. Coat the polymer solution on a PET plastic substrate and bake it at 100 °C for 50 hours to obtain a polymer flat film F3c. The tensile strength of F3c is 43 MPa.

[0120] 6. Immerse F3c in 1 M NaCl aqueous solution at room temperature for 10 hours. Take out the film and wash it three times with pure water, then dry it in an oven at 100 °C for 5 hours under nitrogen protection to obtain a chloride ion exchange membrane F3d. The tensile strength of F3d is 48 MPa. At 80 °C, the conductivity of F3d is 186 mS / cm. Use F1d for lithium extraction from salt lakes by diffusion dialysis. The lithium ion concentration in the mother liquor is 6 g / L and the magnesium ion concentration is 120 g / L. At room temperature, in the dialysate, the lithium ion concentration is 5.9 g / L and the magnesium ion concentration is 0.7 g / L.

[0121] 7. F3c was immersed in a 1 M aqueous NaBr solution at room temperature for 10 hours. After taking out the film, it was washed three times with pure water and dried in an oven at 120 °C for 5 hours under nitrogen protection to obtain a bromide ion-exchange film F3d. The tensile strength of F3d was 41 MPa. At 80 °C, the conductivity of F3d was 179 mS / cm. F3d was used in a vanadium redox flow battery, and the vanadium ion permeability was 4×10 -10 cm 2 / s. At 80 °C, F3d was immersed in a 1.5 M VO 2+ / 3 M H2SO4 solution for 30 days, and the conductivity only decreased by 1.2%. Assembled into a vanadium redox flow battery, the Coulombic efficiency was 99.2%.

[0122] 8. F3c was immersed in a 1 M aqueous NaOH solution at room temperature for 24 hours. After taking out the film, it was washed three times with pure water and dried in an oven at 120 °C for 5 hours under nitrogen protection to obtain a hydroxide ion-exchange film F3e. The tensile strength of F3e was 48 MPa. At 80 °C, the conductivity of F3e was 232 mS / cm. F3e was immersed in an 11 M NaOH aqueous solution at 90 °C for 30 days without degradation. At 80 °C, the water absorption rate of F3e was 16%, and the water swelling rate was 3%. F3e was used for water electrolysis with a 6 M KOH solution as the electrolyte, NiMo as the cathode, and NiFe as the anode. At 80 °C and 2 V, the current density was 2.15 A / cm 2 . F3e was used as a separator in a fuel cell. At 80 °C and 2 atmospheres, with hydrogen and oxygen injection, the maximum power density of the battery was 1.85 W / cm 2 .

[0123] Example 4

[0124] 1. 2.072 g (10 mmol) of quinine-based monomer 2, 0.694 g (4.5 mmol) of biphenyl (CAS No.: 92-52-4), 1.036 g (4.5 mmol) of p-terphenyl (CAS No.: 92-94-4), and 0.153 g (0.6 mmol) of triptycene (CAS No.: 477-75-8) were added to 20 mL of chloroform solvent. After stirring evenly, 3 mL of trifluoromethanesulfonic acid (TFSA) and 0.5 mL of trifluoroacetic acid (TFA) were slowly dropped in an ice-water bath. After the dropping was completed, stirring was continued until the system became viscous. After the reaction was completed, a KOH aqueous solution was added to the obtained product for neutralization, and then filtered. The filter cake was first washed with ethanol and then with water to obtain 3.21 g of a pale yellow powdery polymer P4a.

[0125] 2. Dissolve 1.5 g of polymer P4a, 1.42 g (10 mmol) of methyl iodide, and 1.06 g (10 mmol) of sodium carbonate in 10 mL of N-methylpyrrolidone (NMP), and stir the reaction at 28 °C for 20 hours. After the reaction is completed, wash the obtained product with pure water and ethanol multiple times, and finally dry the obtained solid at 90 °C for 50 hours to obtain 2.18 g of polymer P4b in the form of a pale yellow powder.

[0126] 1 HNMR (600 MHz, DMSO-d6, ppm) δH = 7.37 - 7.13, 5.52 - 5.45, 3.61 - 3.32, 3.18, 2.23 - 1.69.

[0127]

[0128] 3. Take 150 mg of polymer P4b and dissolve it in 8 mL of dimethyl sulfoxide to obtain a polymer solution. Coat the polymer solution on a glass plate and bake the glass plate at 110 °C for 20 hours to obtain a polymer flat film F4a. Immerse F4a in 1 M NaOH aqueous solution at room temperature for 48 hours. After taking out the film, wash it with pure water and dry it in an oven at 60 °C under nitrogen protection for 10 hours to obtain an alkaline anion exchange membrane F4b. The tensile strength of F4b is 63 MPa. At 80 °C, the conductivity of F4b is 245 mS / cm. Immerse F4b in 13 M NaOH aqueous solution at 90 °C for 30 days, and there is no degradation phenomenon. At 80 °C, the water absorption rate of F1g is 25%, and the water swelling rate is 3%. Use F4b as a separator for fuel cells. At 80 °C and 2 atmospheres, with hydrogen and oxygen injection, the maximum power density of the battery is 1.95 W / cm 2 . Use F4b for water electrolysis. With 8 M KOH solution as the electrolyte, NiMo as the cathode catalyst, and NiFe as the anode catalyst. At 80 °C and 2 V, the current density is 2.3 A / cm 2 .

[0129] Example 5

[0130] 1. Add 2.072 g (10 mmol) of quinine-based monomer 3, 2.188 g (9.5 mmol) of p-terphenyl (CAS No.: 92-94-4), and 0.097 g (0.5 mmol) of 9,9-dimethylfluorene (CAS No.: 4569-45-3) into 25 mL of dichloromethane solvent. After stirring evenly, slowly drop 3 mL of trifluoromethanesulfonic acid (TFSA) under an ice-water bath. After the dropping is completed, continue stirring until the system becomes viscous. After the reaction is completed, add 30 mL of 10 w% NaOH aqueous solution to the obtained product for neutralization, filter, wash the filter cake first with ethanol to remove unreacted small molecules, and then wash with water to remove excess alkali and salts to obtain 4.05 g of a pale yellow powdery polymer P4a.

[0131] 1 HNMR (600 MHz, DMSO-d6, ppm) δH = 7.37 - 7.16, 4.37, 3.62, 3.41 - 3.16, 2.15 - 1.82, 1.45.

[0132] 2. Dissolve 1.5 g of polymer P5a, 1.42 g (10 mmol) of methyl iodide, and 1.382 g (10 mmol) of potassium carbonate in 10 mL of dimethyl sulfoxide (DMSO), stir and react at 25 °C for 10 hours. After the reaction is completed, wash the obtained product with ethanol and pure water multiple times, and finally dry the obtained solid at 100 °C for 20 hours to obtain 1.9 g of a pale yellow powdery polymer P5b.

[0133] 1 HNMR (600 MHz, DMSO-d6, ppm) δH = 7.39 - 7.13, 4.51, 3.66, 3.45 - 3.22, 3.18, 2.16 - 1.79, 1.46.

[0134]

[0135] 3. Take 100 mg of polymer P5a and dissolve it in 5 mL of dimethyl sulfoxide to obtain a polymer solution. Coat the polymer solution on a glass plate, and bake the glass plate at 100 °C for 15 hours to obtain a polymer flat film F5a. The thickness of F5a is 18 μm, and the tensile strength is 48 MPa.

[0136] 4. F5a was immersed in a 1 M phosphoric acid aqueous solution at room temperature for 12 hours. After taking out the film, it was washed three times with pure water and dried in an oven at 100 °C for 5 hours under nitrogen protection to obtain a proton exchange membrane F5b. The tensile strength of F5b was 42 MPa. At 160 °C, the proton conductivity of F3b was 155 mS / cm; at 180 °C, the proton conductivity of F3b was 192 mS / cm. F5b was used as a separator in a fuel cell. At 150 °C and 2 atmospheres, with hydrogen and oxygen injection, the maximum power density of the cell was 1.73 W / cm 2 .

[0137] 5. 100 mg of polymer P5b was dissolved in 5 mL of dimethyl sulfoxide to obtain a polymer solution. The polymer solution was coated on a glass substrate and baked at 100 °C for 20 hours to obtain a polymer flat film F5c. F5c was immersed in a 1 M NaBr aqueous solution at room temperature for 10 hours. After taking out the film, it was washed three times with pure water and dried in an oven at 120 °C for 5 hours under nitrogen protection to obtain a bromide ion exchange membrane F5d. The tensile strength of F5d was 45 MPa. At 80 °C, the conductivity of F3d was 141 mS / cm. F5d was used in a vanadium redox flow battery, and the vanadium ion permeability was 3×10 -10 cm 2 / s. At 80 °C, F5d was immersed in a 1.5 M VO 2+ / 3 M H2SO4 solution for 30 days, and the conductivity only decreased by 0.8%. Assembled into a vanadium redox flow battery, the Coulomb efficiency was 99.6%.

[0138] 6. F5c was immersed in a 1 M NaOH aqueous solution at room temperature for 24 hours. After taking out the film, it was washed three times with pure water and dried in an oven at 120 °C for 10 hours under nitrogen protection to obtain a hydroxide ion exchange membrane F5e. The tensile strength of F5e was 58 MPa. At 80 °C, the conductivity of F5e was 245 mS / cm. F5e was immersed in a 13 M NaOH aqueous solution at 90 °C for 30 days without degradation. At 80 °C, the water absorption rate of F5e was 12%, and the water swelling rate was 2%. F5e was used for water electrolysis. With an 8 M KOH solution as the electrolyte, NiMo as the cathode, and NiFe as the anode, at 80 °C and 2 V, the current density was 2.52 A / cm 2 . F5e was used as a separator in a fuel cell. At 80 °C and 2 atmospheres, with hydrogen and oxygen injection, the maximum power density of the cell was 1.82 W / cm 2 .

[0139] Example 6

[0140] 1. Dissolve 1.968 g (9.5 mmol) of quinine-based monomer 2, 0.087 g (0.5 mmol) of 2,2,2-trifluoroacetophenone (CAS No.: 434-45-7), and 2.303 g (10 mmol) of p-terphenyl (CAS No.: 92-94-4) in 28 mL of chloroform solvent. After stirring evenly, slowly add 3 mL of trifluoromethanesulfonic acid (TFSA) under an ice-water bath. After the addition is complete, continue stirring until the system becomes viscous. After the reaction is completed, add 30 mL of 10 w% NaOH aqueous solution to the obtained product for neutralization, filter, wash the filter cake with ethanol first to remove unreacted small molecules, and then wash with water to remove excess alkali and salts to obtain 4.13 g of a pale yellow powdery polymer P6a.

[0141] 1 HNMR (600 MHz, DMSO-d6, ppm) δH = 7.41 - 7.16, 7.10 - 7.01, 3.31 - 3.12, 2.22 - 1.91.

[0142] 2. Dissolve 1.6 g of polymer P6a, 1.42 g (10 mmol) of methyl iodide, and 1.382 g (10 mmol) of potassium carbonate in 10 mL of dimethyl sulfoxide (DMSO), stir and react at 30 °C for 10 hours. After the reaction is completed, wash the obtained product with ethanol and pure water multiple times, and finally dry the obtained solid at 100 °C for 25 hours to obtain 2.0 g of a pale yellow powdery polymer P6b.

[0143] 1 HNMR (600 MHz, DMSO-d6, ppm) δH = 7.38 - 7.12, 7.09 - 6.98, 3.62 - 3.30, 3.18, 2.22 - 1.63.

[0144]

[0145] 3. Take 120 mg of polymer P6b and dissolve it in 10 mL of dimethyl sulfoxide to obtain a polymer solution. Coat the polymer solution on a PET plastic substrate and bake it at 80 °C for 60 hours to obtain a polymer flat film F6a. Immerse F6a in a 1 M NaOH aqueous solution at room temperature for 24 hours. After taking out the film, wash it three times with pure water and dry it in an oven at 120 °C under nitrogen protection for 5 hours to obtain a hydroxide exchange film F6b. The tensile strength of F6b is 56 MPa. At 80 °C, the conductivity of F6b is 243 mS / cm. Immerse F6b in a 13 M NaOH aqueous solution at 90 °C for 30 days, and there is no degradation phenomenon. At 80 °C, the water absorption rate of F6b is 12%, and the water swelling rate is 1%. Use F6b for water electrolysis, with an 8 M KOH solution as the electrolyte, NiMo as the cathode, and NiFe as the anode. At 80 °C and 2 V, the current density is 2.32 A / cm 2 . Use F6b as a separator for a fuel cell. At 80 °C and 2 atmospheres, with hydrogen and oxygen injection, the maximum power density of the cell is 1.76 W / cm 2 .

[0146] Example 7

[0147] 1. Add 1.968 g (9.5 mmol) of quinine-based monomer 4, 0.081 g (0.5 mmol) of 1-methylisatin (CAS No.: 2058-74-4), and 2.303 g (10 mmol) of p-terphenyl (CAS No.: 92-94-4) to 30 mL of dichloromethane solvent. After stirring evenly, slowly drop 2 mL of trifluoromethanesulfonic acid (TFSA) and 0.5 mL of trifluoroacetic acid (TFA) under an ice-water bath. After the dropping is completed, continue stirring until the system becomes viscous. After the reaction is completed, add 30 mL of 10 w% NaOH aqueous solution to the obtained product for neutralization, filter, wash the filter cake first with ethanol to remove unreacted small molecules, and then with water to remove excess alkali and salts to obtain 4.08 g of a pale yellow powdery polymer P7a.

[0148] 1 HNMR (600 MHz, DMSO-d6, ppm) δH = 7.37 - 7.15, 3.78, 3.32 - 3.13, 2.22 - 1.91.

[0149] 2. Dissolve 1.55 g of polymer P7a, 1.42 g (10 mmol) of methyl iodide, and 1.382 g (10 mmol) of potassium carbonate in 10 mL of dimethyl sulfoxide (DMSO), stir and react at 25 °C for 10 hours. After the reaction is completed, wash the obtained product with ethanol and pure water multiple times, and finally dry the obtained solid at 100 °C for 20 hours to obtain 1.96 g of a pale yellow powdery polymer P7b.

[0150] 1 HNMR (600 MHz, DMSO-d6, ppm) δH = 7.36 - 7.13, 3.78, 3.61 - 3.32, 3.16, 2.23 - 1.68.

[0151]

[0152] 3. Take 100 mg of polymer P7b, dissolve it in 5 mL of dimethyl sulfoxide to obtain a polymer solution. Coat the polymer solution on a glass plate, and bake the glass plate at 100 °C for 15 hours to obtain a polymer flat film F7a. Immerse F7a in 1 M NaOH aqueous solution at room temperature for 24 hours. After taking out the film, wash it three times with pure water, and dry it in an oven at 120 °C under nitrogen protection for 5 hours to obtain a hydroxide exchange film F7b. The tensile strength of F7b is 56 MPa. At 80 °C, the conductivity of F7b is 239 mS / cm. Immerse F7b in 13 M NaOH aqueous solution at 90 °C for 30 days, and there is no degradation phenomenon. At 80 °C, the water absorption rate of F7b is 26%, and the water swelling rate is 3%. Use F7b for water electrolysis, with 8 M KOH solution as the electrolyte, NiMo as the cathode, NiFe as the anode. At 80 °C and 2 V, the current density is 2.51 A / cm 2 . Use F7b as a diaphragm for a fuel cell. At 80 °C and 2 atmospheres, with hydrogen and oxygen injection, the maximum power density of the cell is 1.89 W / cm 2 .

[0153] Example 8

[0154] 1. Add 2.212 g (10 mmol) of quinine-based monomer 5 and 2.303 g (10 mmol) of p-terphenyl (CAS No.: 92 - 94 - 4) to 40 mL of dichloromethane solvent. After stirring evenly, slowly drop 2 mL of trifluoromethanesulfonic acid (TFSA) under an ice-water bath. After the addition is complete, continue stirring until the system becomes viscous. After the reaction is completed, add 30 mL of 10 w% NaOH aqueous solution to the obtained product for neutralization, filter, wash the filter cake first with ethanol to remove unreacted small molecules, and then wash it with water to remove excess alkali and salts to obtain 4.32 g of a pale yellow powdery polymer P8a.

[0155] 1 HNMR (600 MHz, DMSO-d6, ppm) δH = 7.37 - 7.16, 4.36, 3.63, 3.42 - 3.17, 2.13 - 1.80.

[0156] 2. Dissolve 1.80 g of polymer P8a, 1.42 g (10 mmol) of methyl iodide, and 1.382 g (10 mmol) of potassium carbonate in 10 mL of dimethyl sulfoxide (DMSO), and stir the reaction at 25 °C for 10 hours. After the reaction is completed, wash the obtained product with ethanol and pure water multiple times. Finally, dry the obtained solid at 100 °C for 20 hours to obtain 2.2 g of a pale yellow powdery polymer P8b.

[0157] 1 HNMR (600 MHz, DMSO-d6, ppm) δH = 7.37 - 7.13, 4.50, 3.67, 3.44 - 3.21, 3.18, 2.15 - 1.80.

[0158]

[0159] 3. Take 100 mg of polymer P8b and dissolve it in 5 mL of dimethyl sulfoxide to obtain a polymer solution. Coat the polymer solution on a glass plate and bake the glass plate at 100 °C for 15 hours to obtain a polymer flat film F8a. Immerse F8a in a 1 M aqueous NaOH solution at room temperature for 24 hours. After taking out the film, wash it three times with pure water and dry it in an oven at 120 °C under nitrogen protection for 5 hours to obtain a hydroxide exchange film F8b. The tensile strength of F8b is 60 MPa. At 80 °C, the conductivity of F8b is 251 mS / cm. Immerse F8b in a 13 M aqueous NaOH solution at 90 °C for 30 days, and there is no degradation phenomenon. At 80 °C, the water absorption rate of F8b is 21%, and the water swelling rate is 1.5%. Use F8b for water electrolysis, with a 10 M KOH solution as the electrolyte, NiMo as the cathode, and NiFe as the anode. At 80 °C and 2 V, the current density is 2.62 A / cm 2 . Use F8b as a separator for a fuel cell. At 80 °C and 2 atmospheres, with hydrogen and oxygen injection, the maximum power density of the cell is 1.91 W / cm 2 .

Claims

1. A class of polymers I with azacycles suspended on the side chain, characterized in that It contains a structural unit with the following general formula: wherein, A is an aryl group, B is -(CH2) n - or -(CF2) n -, and n is a natural number; C is one or more of; E is any one of hydrogen, methyl, deuterated methyl, ethyl, propyl, butyl, pentyl, hexyl, N,N,N-trimethylpentylammonium, heptyl, octyl, nonyl, decyl, -CH2CH2NH2, -CH2CH2OH, -CH2C(CH2OH)2CH2Br, -CH2C(CH2OH)3, cyclopropyl, isopropyl, isobutyl, cyclopentyl, cyclohexyl, -CH2CH2CH2CH2CH2N(CH3)3, -CH2CH2(OCH2CH2) m OCH3, -CH2CH2(OCH2CH2) m OCH2CH3, where m is a natural number and 1 ≤ m ≤ 10; D is any one or more of; R0, R1, and G1 are any one of hydrogen, methyl, bromomethyl, chloromethyl, ethyl, propyl, acetyl, trifluoromethyl, pyridyl, phenyl, fluorophenyl, o-tolyl, m-tolyl, p-tolyl, or mesityl; a is any integer greater than or equal to 1; b and c are both natural numbers.

2. A method for preparing the polymer I with a piperidyl group pendant on the side chain as described in claim 1, characterized in that It includes the following steps: In the presence of an acid catalyst, the azacycle monomer and the aromatic monomer undergo a Friedel-Crafts reaction to obtain the polymer I with azacycles pendant on the side chain; Or in the presence of an acid catalyst, the azacycle monomer, the aromatic monomer, and the aromatic crosslinking agent monomer undergo a Friedel-Crafts reaction to obtain the polymer I with azacycles pendant on the side chain; Or in the presence of an acid catalyst, the azacycle monomer, the aromatic monomer, the aromatic crosslinking agent monomer, and the ketone monomer undergo a Friedel-Crafts reaction to obtain the polymer I with azacycles pendant on the side chain; The structural general formula of the azacycle monomer is: wherein, B is -(CH2) n - or -(CF2) n -, and n is a natural number; C is a nitrogen heterocycle or one or more of them; E is any one of hydrogen, methyl, deuterated methyl, ethyl, propyl, butyl, pentyl, hexyl, N,N,N-trimethylpentylammonium, heptyl, octyl, nonyl, decyl, -CH2CH2NH2, -CH2CH2OH, -CH2C(CH2OH)2(CH2Br), -CH2C(CH2OH)3, cyclopropyl, isopropyl, isobutyl, cyclopentyl, cyclohexyl, -CH2CH2CH2CH2CH2N(CH3)3, -CH2CH2(OCH2CH2) m OCH3, -CH2CH2(OCH2CH2) m OCH2CH3, where m is a natural number and 1 ≤ m ≤ 10; The aromatic monomer is selected from at least one of the compounds represented by the following structural formulas; Wherein, n is a natural number, and 0 ≤ n ≤ 10, and R2 and R3 are any one of a hydrogen atom, methyl, ethyl, propyl, or butyl; The aromatic crosslinking agent monomer is selected from at least one of the compounds represented by the following structural formulas; Wherein, R4, R5, and R6 are respectively any one of a hydrogen atom, methyl, ethyl, propyl, or butyl; The ketone monomer is selected from at least one of the compounds represented by the following structural formulas: Wherein, R0, R1, and G1 are any one of hydrogen, methyl, bromomethyl, chloromethyl, ethyl, acetyl, trifluoromethyl, pyridyl, phenyl, fluorophenyl, o-tolyl, m-tolyl, p-tolyl, or mesityl; G1 is any one of a hydrogen atom, methyl, ethyl, propyl, or butyl; The acid catalyst is selected from at least one of trifluoromethanesulfonic acid, trifluoroacetic acid, acetic acid, trichloroacetic acid, methanesulfonic acid, pentafluoropropionic acid, heptafluorobutyric acid, and perfluorosulfonic acid resin.

3. A class of polymers II with azacycles suspended on the side chains, characterized in that It contains a structural unit with the following general formula: wherein, A is an aryl group, and B is -(CH2) n - or -(CF2) n -, and n is a natural number; G is an ionic nitrogen heterocycle or one or more of them; E is any one of hydrogen, methyl, deuterated methyl, ethyl, propyl, butyl, pentyl, hexyl, N,N,N-trimethylpentylammonium, heptyl, octyl, nonyl, decyl, -CH2CH2NH2, -CH2CH2OH, -CH2C(CH2OH)2(CH2Br), -CH2C(CH2OH)3, cyclopropyl, isopropyl, isobutyl, cyclopentyl, cyclohexyl, -CH2CH2CH2CH2CH2N(CH3)3, -CH2CH2(OCH2CH2) m OCH3, -CH2CH2(OCH2CH2) m OCH2CH3, where m is a natural number and 1 ≤ m ≤ 10; D is any one or more of; R0 and R1 are any one of hydrogen, methyl, bromomethyl, chloromethyl, ethyl, acetyl, trifluoromethyl, pyridyl, phenyl, fluorophenyl, o-tolyl, m-tolyl, p-tolyl, and mesityl; G1 is any one of a hydrogen atom, methyl, ethyl, propyl, or butyl; a is any integer greater than or equal to 1; b and c are both any integers greater than or equal to 0.

4. A method for preparing the polymer II with a nitrogen heterocycle pendant on the side chain as described in claim 3, characterized in that It includes the following steps: In the presence or absence of a base, the polymer I as claimed in claim 1 reacts with a monohalogenated compound to undergo a quaternization reaction, and the molar ratio of the monohalogenated compound to the N site in the polymer I is 1 - 5:1, to obtain the polymer II with azacycles pendant on the side chain; The monohalogenated compound is selected from methyl iodide, deuterated methyl iodide, ethyl iodide, propyl iodide, butyl iodide, pentyl iodide, hexyl iodide, heptyl iodide, octyl iodide, nonyl iodide, decyl iodide, methyl bromide, deuterated methyl bromide, ethyl bromide, propyl bromide, butyl bromide, pentyl bromide, hexyl bromide, heptyl bromide, octyl bromide, nonyl bromide, decyl bromide, 2-bromoethylamine, 2-bromoethanol, cyclopropyl iodide, isopropyl iodide, isobutyl iodide, cyclopentyl iodide, cyclohexyl iodide, and (5-bromopentyl)trimethylammonium bromide, BrCH2C(CH2OH)2(CH2Br), BrCH2C(CH2OH)3, BrCH2CH2(OCH2CH2) r OCH3, and BrCH2CH2(OCH2CH2) r OCH2CH3, where r is a natural number and 0 ≤ r ≤ 10; The base is selected from at least one of sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, calcium oxide, calcium hydroxide, trimethylamine, triethylamine, N,N-dimethylethylenediamine, and N,N-diisopropylethylamine.

5. The polymer I as claimed in claim 1 or the polymer II as claimed in claim 3, wherein: When C is , 1 ≤ n ≤ 20; when C is , 0 ≤ n ≤ 20.

6. A class of polymers III with piperidyl groups pendant on the side chain, characterized in that It contains a structural unit with the following general formula: Wherein, A is an aryl group; B is -(CH2) r - or -(CF2) n -, r is a natural number, and 1 ≤ r ≤ 10; D is any one or more of; R0, R1, and G1 are each independently selected from hydrogen, methyl, bromomethyl, chloromethyl, ethyl, acetyl, trifluoromethyl, pyridyl, phenyl, fluorophenyl, o-tolyl, m-tolyl, p-tolyl, or mesityl; a is any integer greater than or equal to 1, and b and c are both natural numbers.

7. A method for preparing the polymer III with a piperidyl group pendant on the side chain as described in claim 5, characterized in that It includes the following steps: Under the condition of the presence or absence of a base, quaternization reaction of the polymer I described in claim 1 with 1,5-dihalopentane is carried out to generate the polymer III with pendant piperidyl groups on the side chain; The 1,5-dihalopentane is selected from at least one of 1,5-difluoropentane, 1,5-dichloropentane, 1,5-dibromopentane, and 1,5-diiodopentane; The base is selected from at least one of sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, calcium oxide, calcium hydroxide, trimethylamine, triethylamine, N,N-dimethylethylenediamine, and N,N-diisopropylethylamine.

8. The polymer I according to claim 1, or the polymer II according to claim 3, or the polymer III according to claim 5, characterized in that: The A is selected from groups having the following structural formula: wherein, n is a natural number, and 0 ≤ n ≤ 10, and R2 and R3 are each independently selected from a hydrogen atom, methyl, ethyl, propyl, or butyl.

9. A polymer flat film, characterized in that It is prepared by the following method: At least one of the polymer I described in claim 1, the polymer II described in claim 3, and the polymer III of claim 5 is dissolved in an organic solvent to obtain a polymer solution, and the polymer solution is cast or spread on a substrate and dried to obtain the polymer flat film; The organic solvent is one or a combination of several of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, chloroform, dichloromethane, toluene, ethylbenzene, xylene, and ethyl acetate; The substrate is a glass plate, copper sheet, iron sheet, ceramic plate, polytetrafluoroethylene plate, polyethylene terephthalate base film, polyamide base film, polytetrafluoroethylene base film, polyethylene base film, polypropylene base film, carbon fiber base film, or glass fiber base film.

10. A polymer hollow fiber membrane, characterized in that It is prepared by the following method: At least one of the polymer I described in claim 1, the polymer II described in claim 3, and the polymer III of claim 6 is dissolved in an organic solvent to obtain a polymer solution. The hollow fiber base film is immersed in the polymer solution, and after immersion, it is taken out and dried to obtain the polymer hollow fiber membrane; or the polymer solution is used to prepare the polymer hollow fiber membrane by the dry-wet spinning method; The organic solvent is one or a combination of several of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, chloroform, dichloromethane, toluene, ethylbenzene, xylene, and ethyl acetate; The hollow fiber membrane described above is one of a ceramic hollow fiber membrane, a polytetrafluoroethylene hollow fiber membrane, a polyvinylidene fluoride hollow fiber membrane, a polyethylene terephthalate-based hollow fiber membrane, a polyamide hollow fiber membrane, a polyethylene hollow fiber membrane, a polypropylene hollow fiber membrane, a carbon fiber hollow fiber membrane, and a glass hollow fiber membrane.

11. A proton exchange membrane, characterized in that It is prepared by the following method: Soak the polymer flat film described in claim 7 or the polymer hollow fiber membrane described in claim 8 in an aqueous phosphoric acid solution with a concentration of 0.1 - 20 M and a soaking temperature of 0 - 90 °C. After soaking, wash with pure water and dry to obtain the proton exchange membrane described above.

12. An anion exchange membrane, characterized in that It is prepared by the following method: Soak the polymer flat film described in claim 7 or the polymer hollow fiber membrane described in claim 8 in an aqueous hydroxide solution, an aqueous bromide solution, an aqueous chloride solution, an aqueous fluoride solution, an aqueous nitrate solution, or an aqueous bicarbonate solution. After soaking, wash with pure water and dry to obtain the anion exchange membrane described above; The hydroxide described above is one of lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, and ammonium hydroxide, or a combination of several of them; The bromide described above is selected from at least one of sodium bromide, potassium bromide, cesium bromide, ammonium bromide, magnesium bromide, and calcium bromide; The chloride described above is selected from at least one of sodium chloride, potassium chloride, cesium chloride, ammonium chloride, magnesium chloride, and calcium chloride; The fluoride described above is selected from at least one of sodium fluoride, potassium fluoride, cesium fluoride, ammonium fluoride, magnesium fluoride, and calcium fluoride; The nitrate described above is selected from at least one of sodium nitrate, potassium nitrate, cesium nitrate, ammonium nitrate, magnesium nitrate, and calcium nitrate; The bicarbonate described above is selected from at least one of sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, ammonium bicarbonate, magnesium bicarbonate, and calcium bicarbonate.

13. Applications of the polymer flat film described in claim 9, the polymer hollow fiber membrane described in claim 10, the proton exchange membrane described in claim 11, or the anion exchange membrane described in claim 12 in fuel cells, hydrogen production by electrolysis of water, metal-air batteries, flow batteries, carbon dioxide reduction, supercapacitors, nickel-metal hydride batteries, zinc-manganese batteries, acid separation, lithium extraction from salt lakes, electrodialysis, water treatment, and membrane humidification.

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