Nitrogen-containing heterocyclic polymer, polymer film, and their applications

Abstract

The present invention discloses a nitrogen-containing heterocyclic polymer, a polymer film containing a structural unit of the following general formula, and its applications. JPEG2025523669000025.jpg19170 The nitrogen-containing heterocycle in the nitrogen-containing heterocyclic polymer has a large steric hindrance and an electron-donating group, further improving the stability of the material. The nitrogen-containing heterocyclic polymer can be formed into a film by a general industrial method such as a coating method. The produced polymer film has advantages such as being large-scale, thin in thickness, high in strength, and excellent in ionic conductivity, and can be used in fields such as fuel cells, hydrogen production by water electrolysis, metal-air batteries, flow batteries, carbon dioxide reduction, supercapacitors, electrodialysis, water treatment, membrane humidification, nickel-metal hydride batteries, zinc-manganese batteries, acid separation, and lithium extraction from salt lakes.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer functional materials, and particularly relates to nitrogen-containing heterocyclic polymers, polymer films and their applications.

Background Art

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

[0003] In recent years, in order to solve the problem of skeletal stability, it has been proposed to use a carbon chain as the polymer backbone. In addition, various quaternary ammonium salt ions have also been developed as anion exchange groups. However, most quaternary ammonium salt ions do not have high stability. In recent years, it has been discovered that N-methylpiperidinyl quaternary ammonium salt ions have good stability. However, N-methylpiperidinyl quaternary ammonium salt ions are usually stable only in medium-concentration alkaline solutions or at room temperature. For example, Jannasch et al. reported that the linear poly(aryl N-methylpiperidine) electrolyte in 2M aqueous sodium hydroxide solution can exist stably at 60°C for 15 days, but cation decomposition occurs at 5% within 15 days at 90°C (Reference: Jannasch P., et al., Adv. Funct. Mater. 2017, 1702758; DOI: 10.1002 / adfm.201702758). Hu et al. reported that the branched poly(aryl N-methylpiperidine) electrolyte can exist stably at 80°C for 1500 hours in 1M aqueous potassium hydroxide solution, but cation decomposition occurs at 17% within 1500 hours at 80°C in 3M aqueous potassium hydroxide solution (Reference: Hu X., et al., Angew. Chem. Int. Ed. 2022, 61, e202114892; DOI: 10.1002 / anie.202114892). Cross-linked poly(aryl N-methylpiperidine) electrolyte has also been reported in Chinese Patent CN202011577765.3. When immersed in 4M aqueous sodium hydroxide solution at 80°C for 10 days, cation decomposition occurred at 4.6%. Therefore, in order to further develop a new ion exchange membrane with excellent comprehensive properties, especially excellent alkali stability, it is very necessary to explore new quaternary ammonium salt ions.

Summary of the Invention

Problems to be Solved by the Invention

[0004] In order to solve the problems existing in the above prior art, the present invention provides a nitrogen-containing heterocyclic polymer, a polymer film, and its applications. The nitrogen-containing heterocyclic ring in the nitrogen-containing heterocyclic polymer has a large steric hindrance and an electron-donating group, further improving the stability of the material. The polymer film has the advantages of large size, thin thickness, high stability, and high ionic conductivity, and can be used in many fields.

Means for Solving the Problems

[0005] In order to achieve the above object, the present invention adopts the following technical means.

[0006] In a nitrogen-containing heterocyclic polymer containing a structural unit of the following general formula, JPEG2025523669000002.jpg18170Here, R1 and R2 are each hydrogen, a methyl group, an ethyl group, a trifluoromethyl group, a pyridyl group, a phenyl group, an o-methylphenyl group, an m-methylphenyl group, a p-methylphenyl group, or a mesitylene group, a is any integer of 1 or more, b is any integer of 0 or more, and generally within 10 million.

[0007] A is a group selected from the following structural formulas, JPEG2025523669000003.jpg74170B is a nitrogen-containing heterocyclic ring selected from the following structural formulas, JPEG2025523669000004.jpg20170Here, R3 is hydrogen, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopropyl group, an isopropyl group, an isobutyl group, a t-butyl group, a cyclopentyl group, a cyclohexyl group, or an N,N,N-trimethylpentaammonium group.

[0008] When both A and B are selected from multiple types, the combination of A and B in A and B is random, and the arrangement methods of different combinations are also random.

[0009] In addition, the nitrogen-containing heterocyclic polymer produced by the following method is In the presence of an acid catalyst, a Friedel-Crafts reaction occurs between the nitrogen-containing heterocyclic monomer C and the aromatic hydrocarbon monomer D, and the molar ratio of the nitrogen-containing heterocyclic monomer to the aromatic hydrocarbon monomer C is 0.5 to 1.5:1, and the nitrogen-containing heterocyclic polymer is obtained.

[0010] In addition, the nitrogen-containing heterocyclic polymer produced by the following method is In the presence of an acid catalyst, the nitrogen-containing heterocyclic monomer C, the aromatic hydrocarbon monomer D, and the ketone monomer E undergo a Friedel-Crafts reaction, and the molar ratio of the nitrogen-containing heterocyclic monomer C, the ketone monomer E, and the aromatic hydrocarbon monomer D is 0.2 to 0.999:0.001 to 0.8:1, and the nitrogen-containing heterocyclic polymer is obtained. The ketone monomer E is one or more combinations selected from the group consisting of the following structures: JPEG2025523669000005.jpg24170 Here, R1 and R2 are each hydrogen, a methyl group, an ethyl group, a trifluoromethyl group, a pyridyl group, a phenyl group, an o-methylphenyl group, an m-methylphenyl group, a p-methylphenyl group, or a mesitylene group.

[0011] In addition, the nitrogen-containing heterocyclic polymer produced by the following method is In the presence of an acid catalyst, the nitrogen-containing heterocyclic monomer C, the aromatic hydrocarbon monomer D, and the aromatic crosslinking agent monomer F undergo a Friedel-Crafts reaction, and the molar ratio of the nitrogen-containing heterocyclic monomer C, the aromatic hydrocarbon monomer D, and the aromatic crosslinking agent monomer F is 1:0.8 to 1.2:0.001 to 0.3, and the nitrogen-containing heterocyclic polymer is obtained. The aromatic crosslinking agent monomer F is one of triphenylmethane, 1,3,5-triphenylbenzene, 9,9'-spirobifluorene, tetraphenylethylene, tetraphenylmethane, hexaphenylbenzene, or a combination of multiple types.

[0012] JPEG2025523669000006.jpg Before 20170, the aromatic hydrocarbon monomer D is one or a combination of benzene, biphenyl, 4,4-dimethylbiphenyl, fluorene, 9,9-dimethylfluorene, p-terphenyl, m-terphenyl, o-terphenyl, diphenylmethane, 1,2-diphenylethane, 1,3-diphenylpropane, para-xylene dimer, 2,2-bis(3,4-dimethylphenyl)hexafluoropropane, 2,3-dimethyl-2,3-diphenylbutane, 1,2-di(1-naphthyl)ethane.

[0013] The acid catalyst is one or a combination of trifluoromethanesulfonic acid, trifluoroacetic acid, acetic acid, trichloroacetic acid, methylsulfonic acid, pentafluoropropionic acid, heptafluorobutyric acid, and perfluorosulfonic acid resin.

[0014] A quaternary ammonium salt polymer, and the quaternarization structural formula of the nitrogen site of the nitrogen-containing heterocyclic ring in the general formula of its structure is JPEG2025523669000007.jpg Selected from 18170, and R4 is any one of methyl, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, cyclopropyl group, isopropyl group, isobutyl group, t-butyl group, cyclopentyl group, cyclohexyl group, and N,N,N-trimethylpentaammonium.

[0015] In the method for producing a quaternary ammonium salt polymer, In the presence of an alkali, a nitrogen-containing heterocyclic ring polymer and a monohalide are subjected to a quaternarization reaction, and the molar ratio of the monohalide to the N site is 1 to 20:1, and the quaternary ammonium salt polymer is obtained. The monohalide is one or a combination of several of iodomethane, iodoethane, iodopropane, iodobutane, iodopentane, iodohexane, iodoheptane, iodoctane, iodononane, iododecane, bromomethane, bromoethane, bromopropane, bromobutane, bromopentane, bromohexane, bromoheptane, bromooctane, bromononane, bromodecane, 2-bromoethylamine, 2-bromoethanol, cyclopropyl iodide, isopropyl iodide, isobutyl iodide, cyclopentyl iodide, cyclohexyl iodide, and (5-bromopentyl) trimethylammonium bromide, The alkali is one or a combination of several 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.

[0016] A quaternized crosslinked polymer produced by the following method, A nitrogen-containing heterocyclic polymer and a polyhalide are subjected to a quaternized crosslinking reaction under alkaline or non-alkaline conditions, and the nitrogen sites involved in the quaternized crosslinking reaction account for 0.001 to 10% of all nitrogen sites. After the reaction is completed, some quaternized crosslinked intermediate polymers are obtained, and the remaining nitrogen sites of the intermediate polymers are subjected to a quaternized non-crosslinking reaction with a monohalide to obtain the quaternized crosslinked polymer, or Or a nitrogen-containing heterocyclic polymer and a monohalide are subjected to a quaternized non-crosslinking reaction under alkaline or non-alkaline conditions, and the nitrogen sites involved in the quaternized non-crosslinking reaction account for 0.90 to 99.999% of all nitrogen sites. After the reaction is completed, some quaternized intermediate polymers are obtained, and the remaining nitrogen sites of the intermediate polymers are subjected to a quaternized crosslinking reaction with a polyhalide to obtain the quaternized crosslinked polymer, Alternatively, a nitrogen-containing heterocyclic polymer, a polyhalide, and a monohalide are simultaneously subjected to a quaternization reaction under alkaline or non-alkaline conditions, and the nitrogen sites involved in the quaternization cross-linking reaction account for 0.001 to 10% of all nitrogen sites. After the reaction is completed, the quaternized cross-linked polymer is obtained. The polyhalide is one or several combinations selected from the following structures: JPEG2025523669000008.jpg26170Here, Y is F, Cl, Br, or I, and n is an integer from 0 to 12. The monohalide is one or several combinations of iodomethane, iodoethane, iodopropane, iodobutane, iodopentane, iodohexane, iodoheptane, iodoctane, iodononane, iododecane, bromomethane, bromoethane, bromopropane, bromobutane, bromopentane, bromohexane, bromoheptane, bromooctane, bromononane, bromodecane, cyclopropyl iodide, isopropyl iodide, isobutyl iodide, cyclopentyl iodide, cyclohexyl iodide, and (5-bromopentyl) trimethylammonium bromide. The alkali is one or several combinations 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.

[0017] A polymer flat film produced by the following method: Dissolve any one or more of a nitrogen-containing heterocyclic polymer, a quaternary ammonium salt polymer, and a quaternized cross-linked polymer in an organic solvent to obtain a polymer solution, or Alternatively, dissolve at least one of a nitrogen-containing heterocyclic polymer and an intermediate polymer together with a monohalide and / or a polyhalide in an organic solvent to obtain a polymer solution. Cast or mold the polymer solution onto a substrate and dry it 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 base material is a glass plate, a copper plate, an iron plate, 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.

[0018] A polymer hollow fiber membrane produced by the following method, dissolving one or more of a nitrogen-containing heterocyclic polymer, a quaternary ammonium salt polymer, and a quaternized crosslinked polymer in an organic solvent to obtain a polymer solution, or dissolving at least one of a nitrogen-containing heterocyclic polymer and an intermediate polymer together with a monohalide and / or a polyhalide in an organic solvent to obtain a polymer solution, immersing a hollow fiber base film in the polymer solution, taking it out after the immersion is completed, and drying it to obtain the polymer hollow fiber membrane, or manufacturing the polymer hollow fiber membrane by a dry-wet spinning method using the polymer solution, 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 contains any one of a ceramic hollow fiber membrane, a polytetrafluoroethylene hollow fiber membrane, a polyvinylidene fluoride hollow fiber membrane, a polyethylene terephthalate base 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.

[0019] A proton exchange film produced by the following method, Immerse a polymer flat film and a polymer hollow fiber membrane in an aqueous phosphoric acid solution respectively, where the concentration of the aqueous phosphoric acid solution is 0.1 - 20 M and the immersion temperature is 0 - 90 °C, to obtain a proton exchange film.

[0020] An anion exchange film produced by the following method, Immerse a polymer flat film or a polymer hollow fiber membrane 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 the immersion is completed, wash with pure water to obtain an anion exchange film. The hydroxide is one or some combinations of lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, and ammonium hydroxide. The bromide is one or some combinations of sodium bromide, potassium bromide, cesium bromide, ammonium bromide, magnesium bromide, and calcium bromide. The chloride is one or some combinations of sodium chloride, potassium chloride, cesium chloride, ammonium chloride, magnesium chloride, and calcium chloride. The fluoride is one or some combinations of sodium fluoride, potassium fluoride, cesium fluoride, ammonium fluoride, magnesium fluoride, and calcium fluoride. The nitrate is one or some combinations of sodium nitrate, potassium nitrate, cesium nitrate, ammonium nitrate, magnesium nitrate, and calcium nitrate. The bicarbonate is one or some combinations of sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, ammonium bicarbonate, magnesium bicarbonate, and calcium bicarbonate.

[0021] Provided are the applications of a polymer flat film, a polymer hollow fiber membrane, a proton exchange film, and an anion exchange film in an alkaline fuel cell, alkaline water electrolysis hydrogen production, a metal-air battery, a flow battery, carbon dioxide reduction, a supercapacitor, a nickel-hydrogen battery, a zinc-manganese battery, acid separation, lithium extraction from a salt lake, electrodialysis, water treatment, and membrane humidification, respectively.

Advantages of the Invention

[0022] Compared with the prior art, the advantages and beneficial effects of the present invention are as follows.

[0023] 1. The nitrogen-containing heterocycle in the nitrogen-containing heterocyclic polymer of the present invention has a large steric hindrance and an electron-donating group compared with the reported N-piperidine ring. These groups function as ion exchange groups, and the groups after exchange have high stability in various environments.

[0024] 2. The present invention uses 3-quinuclidinone, N-alkyl-3-methyl-4-piperidone, and 8-alkyl-8-azabicyclo[3.2.1]octan-3-one for the first time as monomers for manufacturing an ion exchange membrane. Such monomers are inexpensive, easily available, and easy to store.

[0025] 3. The nitrogen-containing heterocyclic polymer of the present invention has a simple manufacturing method, mild conditions, easy operation, low manufacturing cost, and can be used for large-scale industrial production.

[0026] 4. The nitrogen-containing heterocyclic polymer of the present invention can be formed into a film by a general industrial method such as a coating method. The manufactured polymer film has advantages such as being large-scale, thin in thickness, high in mechanical strength, good in stability, and excellent in ion conductivity, and can be used in fields such as fuel cells, hydrogen production by water electrolysis, metal-air batteries, flow batteries, carbon dioxide reduction, supercapacitors, electrodialysis, water treatment, membrane humidification, nickel-hydrogen batteries, zinc-manganese batteries, acid separation, and lithium extraction from salt lakes.

Modes for Carrying Out the Invention

[0027] Hereinafter, the present invention will be described in more detail with specific examples, but these examples do not limit the protection scope of the present invention in any way.

[0028] <Example 1> (1) 2.303 g (10 mmol) of p - terphenyl (CAS No. 92 - 94 - 4) and 1.616 g (10 mmol) of 3 - quinuclidinone hydrochloride (CAS No. 1193 - 65 - 3) were dissolved in 100 mL of dichloromethane. While stirring at - 5°C, 5 mL of trifluoromethanesulfonic acid and 1 mL of trifluoroacetic acid were slowly added dropwise. After the addition was completed, stirring was continued at 0°C for 72 hours to obtain a viscous solution. The viscous solution was washed with 60 mL of pure water and dried at 90°C for 30 hours to obtain 3.21 g of a pale yellow powdery nitrogen - containing heterocyclic polymer P1a. The yield was 90%.

[0029] 1 HNMR (600 MHz, DMSO - d6, ppm) δH = 7.78 - 7.52 (12H), 4.34 (2H), 3.51 (1H), 3.21 (2H), 3.13 (2H), 1.99 (2H), 1.79 (2H).

[0030] (2) 1.78 g of polymer P1a, 1.42 g (10 mmol) of iodomethane and 1.382 g (10 mmol) of potassium carbonate were dissolved in 10 mL of dimethyl sulfoxide and stirred at 25°C for 10 hours for a reaction. After the reaction was completed, the obtained product was washed 3 times with 60 mL of pure water and dried at 90°C for 30 hours to obtain 2.2 g of a pale yellow powdery quaternary ammonium salt polymer P1b. The yield was 89%. 1 HNMR (600 MHz, DMSO - d6, ppm) δH = 7.75 - 7.50 (12H), 4.49 (2H), 3.52 (1H), 3.44 (2H), 3.29 (2H), 3.18 (3H), 2.05 (2H), 1.85 (2H). JPEG2025523669000009.jpg23170

[0031] (3) 100 mg of polymer P1a was taken out and dissolved in 20 mL of dimethyl sulfoxide to obtain a polymer solution. After that, the polymer solution was applied onto a glass plate, and the glass plate was baked at 100 °C for 15 hours to obtain a polymer flat film F1a. F1a had a thickness of 15 μm, a tensile strength of 15 MPa, and a Young's modulus of 265 MPa. F1a was used for nanofiltration separation of aluminum oxide waste acid. A waste liquid with a sulfuric acid concentration of 150 g / L and an aluminum ion concentration of 20 g / L was used as the mother liquor, and filtration was carried out at 3 atm and room temperature. The sulfuric acid concentration in the filtrate was increased to 200 g / L, and the aluminum ion concentration was decreased to 8 g / L. F1a was used for diffusion dialysis of aluminum oxide waste acid. At room temperature, the sulfuric acid concentration in the dialysate was 130 g / L, and the aluminum ion concentration was 0.5 g / L.

[0032] (4) F1a was immersed in a 1 M aqueous phosphoric acid 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 gas protection to obtain a proton exchange film F1b with a tensile strength of 13 MPa and a Young's modulus of 265 MPa. At 160 °C, the proton conductivity of F1b was 62 mS / cm, and at 180 °C, the proton conductivity of F1b was 102 mS / cm.

[0033] (5) 100 mg of polymer P1b, which is a quaternary ammonium salt polymer, was taken out and dissolved in 20 mL of N-methylpyrrolidone to obtain a polymer solution. After that, the polymer solution was applied onto a glass plate, and the glass plate was baked at 120 °C for 20 hours to obtain an iodine ion exchange membrane F1c. F1c had a tensile strength of 16 MPa and a Young's modulus of 235 MPa. At 80 °C, the conductivity of F1c was 80 mS / cm.

[0034] (6) F1c was immersed in a 1 M aqueous NaCl solution at room temperature for 5 hours. After taking out the film, it was washed three times with pure water and then dried in an oven at 100 °C for 5 hours under nitrogen gas protection to obtain a chloride ion exchange membrane F1d with a tensile strength of 15 MPa and a Young's modulus of 221 MPa. At 80 °C, the conductivity of F1d was 105 mS / cm. F1d was used for lithium extraction from a salt lake by diffusion dialysis. The lithium ion concentration in the mother liquor was 6 g / L, and the magnesium ion concentration was 120 g / L. At room temperature, the lithium ion concentration in the dialysate was 5.8 g / L, and the magnesium ion concentration was 0.8 g / L.

[0035] (7) F1c was immersed in a 1 M aqueous NaBr solution at room temperature for 5 hours. After taking out the film, it was washed three times with pure water and then dried in an oven at 120 °C for 5 hours under nitrogen gas protection to obtain a bromide ion exchange film F1e with a tensile strength of 16 MPa and a Young's modulus of 256 MPa. At 80 °C, the conductivity of F1e was 98 mS / cm. When F1e was used in an all-vanadium flow battery, the vanadium ion permeability was 5×10 -10 cm 2 / s. At 80 °C, when F1e was immersed in a solution of 1.5 M VO 2+ / 3 M H2SO4 for 30 days, the decrease in conductivity was only 2%, and the all-vanadium flow battery was assembled with a Coulomb efficiency of 98.5%.

[0036] (8) F1c was immersed in a 1 M aqueous NaHCO3 solution at room temperature for 5 hours. After taking out the film, it was washed three times with pure water and then dried in an oven at 60 °C for 10 hours under nitrogen gas protection to obtain a bicarbonate ion exchange film F1f with a tensile strength of 13 MPa and a Young's modulus of 265 MPa. At 80 °C, the conductivity of F1f was 54 mS / cm.

[0037] (9) F1c was immersed in a 1 M aqueous NaNO3 solution at room temperature for 5 hours. After taking out the film, it was washed three times with pure water and then dried in an oven at 60 °C for 10 hours under nitrogen gas protection to obtain a nitrate ion exchange film F1g with a tensile strength of 19 MPa and a Young's modulus of 268 MPa. At 80 °C, the conductivity of F1g was 51 mS / cm.

[0038] (10) F1c was immersed in a 1 M aqueous NaOH solution at room temperature for 5 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 gas protection to obtain an alkaline anion exchange film F1h with a tensile strength of 19 MPa and a Young's modulus of 278 MPa. At 80 °C, the conductivity of F1h was 125 mS / cm. F1h was used as a separator for an alkaline fuel cell and immersed in a 10 M aqueous NaOH solution for 30 days, but no decomposition occurred. At 80 °C, the water absorption rate of F1h was 2% and the water swelling rate was 3%. When F1h was used as a separator for an alkaline fuel cell at 80 °C and 2 atm, the cell output density was 1.8 W / cm 2 It was.

[0039] <Example 2> (1) 2.303 g (10 mmol) of p-terphenyl (CAS No. 92-94-4, reagent of Aladdin) and 1.272 g (10 mmol) of N-methyl-3-methyl-4-piperidone (CAS No. 4629-80-5, reagent of Aladdin) were dissolved in 120 mL of dichloromethane. While stirring at 0 °C, 5 mL of trifluoromethanesulfonic acid and 2 mL of trifluoroacetic acid were slowly added dropwise. After the addition was completed, stirring was continued at 0 °C for 72 hours to obtain a viscous solution. The viscous solution was washed with 60 mL of pure water and dried at 90 °C for 30 hours to obtain 3.12 g of a pale yellow powder of nitrogen-containing heterocyclic polymer P2a. The yield was 92%.

[0040] 1 HNMR (600 MHz, DMSO-d6, ppm) δH = 7.76 - 7.53 (12H), 3.61 (2H), 3.47 (1H), 3.26 (2H), 3.12 (2H), 3.02 (3H), 1.05 (3H).

[0041] (2) 1.698 g of nitrogen-containing heterocyclic polymer P2a, 1.42 g (10 mmol) of iodomethane, and 1.382 g (10 mmol) of potassium carbonate were dissolved in 9 mL of dimethyl sulfoxide and stirred at 40 °C for 10 h. After the reaction was completed, the resulting product was washed three times with 20 mL of pure water and dried at 90 °C for 30 h to obtain 2.12 g of a pale yellow powdery quaternary ammonium salt polymer P2b. The yield was 88%. 1 HNMR(600MHz,DMSO-d6,ppm) δH=7.73 - 7.52(12H), 3.72(2H), 3.52(1H), 3.31(2H), 3.19(2H), 3.08(6H), 1.12(3H). JPEG2025523669000010.jpg25170

[0042] (3) 100 mg of nitrogen-containing heterocyclic polymer P2a was taken out and dissolved in 20 mL of dimethyl sulfoxide to obtain a polymer solution. Then the polymer solution was applied onto a glass plate, and the glass plate was baked in an oven at 100 °C for 20 h to obtain a polymer flat film F2a. F2a had a thickness of 16 μm, a tensile strength of 21 MPa, and a Young's modulus of 289 MPa. F2a was used for nanofiltration separation of aluminum oxide waste acid. Using 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, filtration was carried out at 3 atm and room temperature. The sulfuric acid concentration in the filtrate increased to 198 g / L, and the aluminum ion concentration decreased to 9 g / L. F2a was used for diffusion dialysis of aluminum oxide waste acid. At room temperature, the sulfuric acid concentration in the dialysate was 135 g / L, and the aluminum ion concentration was 0.4 g / L.

[0043] (4) F2a was immersed in 1 M aqueous phosphoric acid solution at room temperature for 6 h. After taking out the film, it was washed three times with pure water and dried in an oven at 80 °C for 6 h under nitrogen gas protection to obtain a proton exchange film F2b with a tensile strength of 18 MPa and a Young's modulus of 285 MPa. At 160 °C, the proton conductivity of F2b was 66 mS / cm, and at 180 °C, the proton conductivity of F2b was 110 mS / cm.

[0044] (5) 100 mg of polymer P2b was taken out and dissolved in 20 mL of N-methylpyrrolidone to obtain a polymer solution. After that, the polymer solution was applied onto a glass plate and dried in an oven at 120 °C for 20 hours to obtain an iodine ion-exchange film F2c. The tensile strength of F2c was 22 MPa and the Young's modulus was 279 MPa. At 80 °C, the conductivity of F2c was 82 mS / cm.

[0045] (6) F2c was immersed in a 1 M aqueous NaCl 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 80 °C for 6 hours under nitrogen gas protection to obtain a chlorine ion-exchange film F2d with a tensile strength of 25 MPa and a Young's modulus of 305 MPa. At 80 °C, the conductivity of F2d was 102 mS / cm. F2d was used for lithium extraction from a salt lake by diffusion dialysis. The lithium ion concentration in the mother liquor was 6 g / L and the magnesium ion concentration was 120 g / L. At room temperature, the lithium ion concentration in the dialysis solution was 5.6 g / L and the magnesium ion concentration was 0.6 g / L.

[0046] (7) F2c was immersed in a 1 M aqueous NaBr 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 80 °C for 5 hours under nitrogen gas protection to obtain a bromine ion-exchange film F2e with a tensile strength of 23 MPa and a Young's modulus of 301 MPa. At 80 °C, the conductivity of F2e was 101 mS / cm. When F2e was used in an all-vanadium flow battery, the vanadium ion permeability was 4×10 -10 cm 2 / s. At 80 °C, when F2e was immersed in a solution of 1.5 M VO 2+ / 3 M H2SO4 for 30 days, the decrease in conductivity was only 1%, and the all-vanadium flow battery was assembled with a Coulomb efficiency of 98.2%.

[0047] (8) F2c was immersed in a 1 M aqueous NaHCO3 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 60 °C for 5 hours under nitrogen gas protection to obtain a bicarbonate ion-exchange film F2f with a tensile strength of 19 MPa and a Young's modulus of 279 MPa. At 80 °C, the conductivity of F2f was 61 mS / cm.

[0048] (9) F2c was immersed in a 1 M aqueous solution of NaNO3 at room temperature for 5 hours. After taking out the film, it was washed three times with pure water and then dried in an oven at 60 °C for 5 hours under nitrogen gas protection to obtain a nitrate ion exchange film F2g with a tensile strength of 18 MPa and a Young's modulus of 298 MPa. At 80 °C, the conductivity of F2g was 54 mS / cm.

[0049] (10) F2c was immersed in a 1 M aqueous solution of NaOH at room temperature for 5 hours. After taking out the film, it was washed with pure water and then dried in an oven at 60 °C for 5 hours under nitrogen gas protection to obtain an alkaline anion exchange film F2h with a tensile strength of 21 MPa and a Young's modulus of 312 MPa. At 80 °C, the conductivity of F2h was 120 mS / cm. F2h was used as a separator for an alkaline fuel cell and immersed in a 10 M aqueous solution of NaOH for 30 days, but no decomposition was observed. At 80 °C, the water absorption rate of F2h was 10% and the water swelling rate was 9%. When F2h was used as a separator for an alkaline fuel cell at 80 °C and 2 atm, the cell output density was 1.5 W / cm 2 was obtained.

[0050] <Example 3> (1) 2.303 g (10 mmol) of p - terphenyl (CAS No. 92 - 94 - 4) and 1.392 g (10 mmol) of 8 - alkyl - 8 - azabicyclo[3.2.1]octan - 3 - one (CAS No. 532 - 24 - 1) were dissolved in 200 mL of dichloromethane. While stirring at 0 °C, 5 mL of trifluoromethanesulfonic acid and 1 mL of trifluoroacetic acid were slowly added dropwise. After the addition was complete, the temperature was raised to 30 °C and stirring was continued for 25 hours to obtain a viscous solution. The viscous solution was successively washed with 60 mL of pure water and vacuum - dried at 90 °C for 30 hours to obtain 3.21 g of a pale - yellow powdery nitrogen - containing heterocyclic polymer P3a. The yield was 91%.

[0051] 1HNMR (600 MHz, DMSO-d6, ppm) δH = 7.74 - 7.35 (12H), 3.38 (2H), 3.15 (2H), 2.85 (2H), 2.53 (3H), 1.92 (2H), 1.57 (2H).

[0052] (2) 1.758 g of nitrogen-containing heterocyclic polymer P3a and 2.84 g (20 mmol) of iodomethane were dissolved in 10 mL of dimethyl sulfoxide, and stirred and reacted at 60 °C for 10 hours. After the reaction was completed, the obtained product was washed three times with 20 mL of pure water and dried at 90 °C for 30 hours to obtain 2.23 g of a pale yellow powdery quaternary ammonium salt polymer P3b. The yield was 90%.

[0053] 1 HNMR (600 MHz, DMSO-d6, ppm) δH = 7.81 - 7.52 (12H), 3.45 (2H), 3.22 (2H), 2.89 (2H), 2.67 (6H), 1.98 (2H), 1.68 (2H). JPEG2025523669000011.jpg23170

[0054] (3) 100 mg of nitrogen-containing heterocyclic polymer P3a was taken out and dissolved in 20 mL of N-methylpyrrolidone to obtain a polymer solution. Then, the polymer solution was coated on a glass plate and baked at 100 °C for 20 hours to obtain a polymer flat film F3a. F3a had a thickness of 14 μm, a tensile strength of 25 MPa, and a Young's modulus of 316 MPa. F3a was used for nanofiltration separation of aluminum oxide waste acid. Using 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, filtration was carried out at 3 atm and room temperature. The sulfuric acid concentration in the filtrate was increased to 185 g / L, and the aluminum ion concentration was decreased to 10 g / L. F3a was used for diffusion dialysis of aluminum oxide waste acid. At room temperature, the sulfuric acid concentration in the dialysis solution was 138 g / L, and the aluminum ion concentration was 0.6 g / L.

[0055] (4) F3a was immersed in a 1 M aqueous phosphoric acid solution at room temperature for 6 hours. After taking out the film, it was washed three times with pure water and then dried in an oven at 80 °C for 6 hours under nitrogen gas protection to obtain a proton exchange film F3b with a tensile strength of 21 MPa and a Young's modulus of 286 MPa. At 160 °C, the proton conductivity of F3b was 54 mS / cm, and at 180 °C, the proton conductivity of F3b was 98 mS / cm.

[0056] (5) 100 mg of polymer P3b was taken out and dissolved in 20 mL of N-methylpyrrolidone to obtain a polymer solution. After the polymer solution was applied onto a glass plate and the glass plate was dried in an oven at 80 °C for 5 hours, the temperature was raised to 120 °C and baking was continued for 20 hours to obtain an iodine ion exchange film F3c. F3c had a tensile strength of 22 MPa and a Young's modulus of 305 MPa. At 80 °C, the conductivity of F3c was 79 mS / cm.

[0057] (6) F3c was immersed in a 1 M aqueous NaCl solution at room temperature for 5 hours. After taking out the film, it was washed three times with pure water and then dried in an oven at 80 °C for 6 hours under nitrogen gas protection to obtain a chlorine ion exchange film F3d with a tensile strength of 26 MPa and a Young's modulus of 336 MPa. At 80 °C, the conductivity of F3d was 101 mS / cm. F3d was used for lithium extraction from a salt lake by diffusion dialysis. The lithium ion concentration in the mother liquor was 6 g / L and the magnesium ion concentration was 120 g / L. At room temperature, the lithium ion concentration in the dialysate was 5.7 g / L and the magnesium ion concentration was 1.1 g / L.

[0058] (7) F3c was immersed in a 1 M aqueous NaBr solution at room temperature for 5 hours. After taking out the film, it was washed three times with pure water and then dried in an oven at 80 °C for 5 hours under nitrogen gas protection to obtain a bromine ion exchange film F3e with a tensile strength of 25 MPa and a Young's modulus of 328 MPa. At 80 °C, the conductivity of F3f was 96 mS / cm. When F3e was used in an all-vanadium flow battery, the vanadium ion permeability was 3×10 -10 cm 2 / s, and at 80 °C, when F3e was in a 1.5 M VO 2+When immersed in a 3M H2SO4 solution for 30 days, the decrease in conductivity was only 2%, and all vanadium flow batteries were assembled with a Coulomb efficiency of 97.5%.

[0059] (8) F3c was immersed in a 1M aqueous NaHCO3 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 60°C for 5 hours under nitrogen gas protection to obtain a bicarbonate ion exchange film F3f with a tensile strength of 22 MPa and a Young's modulus of 288 MPa. At 80°C, the conductivity of F3f was 66 mS / cm.

[0060] (9) F3c was immersed in a 1M aqueous NaNO3 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 60°C for 5 hours under nitrogen gas protection to obtain a nitrate ion exchange film F3g with a tensile strength of 20 MPa and a Young's modulus of 273 MPa. At 80°C, the conductivity of F3g was 56 mS / cm.

[0061] (10) F3c was immersed in a 1M aqueous NaOH solution at room temperature for 5 hours. After taking out the film, it was washed with pure water and dried in an oven at 60°C for 5 hours under nitrogen gas protection to obtain an alkaline anion exchange film F3h with a tensile strength of 25 MPa and a Young's modulus of 356 MPa. At 80°C, the conductivity of F3h was 112 mS / cm. Using F3h as the separator of an alkaline fuel cell and immersing it in a 3M aqueous NaOH solution for 30 days, no decomposition occurred. At 80°C, the water absorption rate of F3h was 6% and the water swelling rate was 4%. When F3h was used as the separator of an alkaline fuel cell at 80°C and 2 atmospheres, the battery output density was 1.3 W / cm 2 was obtained.

[0062] <Example 4> (1) Dissolve 2.234 g (9.7 mmol) of p - terphenyl (CAS No. 92 - 94 - 4), 0.046 g (0.2 mmol) of 1,3,5 - triphenylbenzene (CAS No. 612 - 71 - 5), and 1.616 g (10 mmol) of 3 - quinuclidinone hydrochloride (CAS No. 1193 - 65 - 3) in 120 mL of dichloromethane. While stirring at 0 °C, slowly dropwise add 20 mL of trifluoromethanesulfonic acid and 10 mL of trifluoroacetic acid. After the addition is complete, continue stirring for 72 hours to obtain a viscous solution. Wash the viscous solution successively with 100 mL of pure water, 20 mL of NaOH aqueous solution (1 M), and 20 mL of pure water, and dry at 100 °C for 30 hours to obtain 3.12 g of a pale yellow powdery nitrogen - containing heterocyclic polymer P4a. The yield is 93%.

[0063] 1 HNMR(600MHz,DMSO - d6,ppm) δH = 7.86 - 7.56(13H), 4.32(2H), 3.53(1H), 3.21 - 3.13(4H), 2.14 - 1.68(4H).

[0064] (2) Dissolve 1.676 g of the nitrogen - containing heterocyclic polymer P4a and 2.84 g (20 mmol) of iodomethane in 10 mL of dimethyl sulfoxide, and carry out a stirring reaction at 60 °C for 10 hours. After the reaction is complete, wash the obtained product 3 times with 20 mL of pure water, and dry at 100 °C for 30 hours to obtain 2.12 g of a pale yellow powdery quaternary ammonium salt polymer P4b. The yield is 89%.

[0065] 1 HNMR(600MHz,DMSO - d6,ppm) δH = 7.83 - 7.65(13H), 4.52(2H), 3.58(1H), 3.56 - 3.35(4H), 3.21(3H), 2.21 - 1.91(4H). JPEG2025523669000012.jpg127170

[0066] (3) 100 mg of the nitrogen-containing heterocyclic polymer P4a was taken out and dissolved in 20 mL of dimethyl sulfoxide to obtain a polymer solution. After that, the polymer solution was applied onto a glass plate, and the glass plate was dried in an oven at 120 °C for 15 hours to obtain a polymer flat film F4a. F4a had a thickness of 15 μm, a tensile strength of 38 MPa, and a Young's modulus of 689 MPa. F4a was used for nanofiltration separation of aluminum oxide waste acid. A waste liquid with a sulfuric acid concentration of 150 g / L and an aluminum ion concentration of 20 g / L was used as the mother liquor, and filtration was carried out at 3 atm and room temperature. The sulfuric acid concentration in the filtrate was increased to 190 g / L, and the aluminum ion concentration was decreased to 12 g / L. F4a was used for diffusion dialysis of aluminum oxide waste acid. At room temperature, the sulfuric acid concentration in the dialysis solution was 132 g / L, and the aluminum ion concentration was 0.7 g / L.

[0067] (4) F4a was immersed in a 1 M aqueous phosphoric acid solution at room temperature for 5 hours. After taking out the film, it was washed three times with pure water and then dried in an oven at 100 °C for 5 hours under nitrogen gas protection to obtain a proton exchange film F4b with a tensile strength of 35 MPa and a Young's modulus of 578 MPa. At 160 °C, the proton conductivity of F4b was 65 mS / cm, and at 180 °C, the proton conductivity of F4b was 117 mS / cm.

[0068] (5) 100 mg of the polymer P4b was taken out and dissolved in 20 mL of N,N-dimethylacetamide to obtain a polymer solution. After that, the polymer solution was applied onto a glass plate, dried in an oven at 80 °C for 5 hours, and then heated to 120 °C and baked continuously for 20 hours to obtain an iodine ion exchange film F4c. F4c had a tensile strength of 36 MPa and a Young's modulus of 625 MPa. At 80 °C, the conductivity of F4c was 75 mS / cm.

[0069] (6) F4c was immersed in a 1 M aqueous NaCl solution at room temperature for 5 hours. After taking out the film, it was washed three times with pure water and then dried in an oven at 60 °C for 5 hours under nitrogen gas protection to obtain a chloride ion exchange film F4d with a tensile strength of 39 MPa and a Young's modulus of 695 MPa. At 80 °C, the conductivity of F4d was 118 mS / cm. F4d 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 120 g / L. At room temperature, the lithium ion concentration in the dialysis solution was 5.3 g / L and the magnesium ion concentration was 1.2 g / L.

[0070] (7) F4c was immersed in a 1 M aqueous NaBr solution at room temperature for 5 hours. After taking out the film, it was washed three times with pure water and then dried in an oven at 100 °C for 5 hours under nitrogen gas protection to obtain a bromide ion exchange film F4e with a tensile strength of 37 MPa and a Young's modulus of 632 MPa. At 80 °C, the conductivity of F4e was 95 mS / cm. When F4e was used in an all-vanadium flow battery, the vanadium ion permeability was 3×10 -10 cm 2 / s. At 80 °C, when F4e was immersed in a solution of 1.5 M VO 2+ / 3 M H2SO4 for 30 days, the decrease in conductivity was only 1%, and the all-vanadium flow battery was assembled with a Coulomb efficiency of 99.2%.

[0071] (8) F4c was immersed in a 1 M aqueous NaHCO3 solution at room temperature for 5 hours. After taking out the film, it was washed three times with pure water and then dried in an oven at 100 °C for 5 hours under nitrogen gas protection to obtain a bicarbonate ion exchange film F4f with a tensile strength of 35 MPa and a Young's modulus of 526 MPa. At 80 °C, the conductivity of F4f was 58 mS / cm.

[0072] (9) F4c was immersed in a 1 M aqueous NaNO3 solution at room temperature for 5 hours. After taking out the film, it was washed three times with pure water and then dried in an oven at 100 °C for 5 hours under nitrogen gas protection to obtain a nitrate ion exchange film F4g with a tensile strength of 33 MPa and a Young's modulus of 498 MPa. At 80 °C, the conductivity of F4g was 50 mS / cm.

[0073] (10) F4c was immersed in a 1 M aqueous NaOH solution at room temperature for 5 hours. After taking out the film, it was washed with pure water and dried in an oven at 100 °C for 5 hours under nitrogen gas protection, obtaining an alkaline anion exchange film F4h with a tensile strength of 41 MPa and a Young's modulus of 725 MPa. At 80 °C, the conductivity of F4h was 120 mS / cm. Using F4h as the electrolyte of an alkaline fuel cell and immersing it in a 10 M aqueous NaOH solution for 30 days, no decomposition occurred. At 80 °C, the water absorption rate of F4h was 4% and the water swelling rate was 3%. When F4h was used as the separator of an alkaline fuel cell at 80 °C and 2 atm, the cell output density was 1.7 W / cm 2 It was.

[0074] <Example 5> (1) 2.303 g (10 mmol) of p - terphenyl (CAS No. 92 - 94 - 4), 0.808 g (5 mmol) of 3 - quinuclidinone hydrochloride (CAS No. 1193 - 65 - 3) and 0.636 g (5 mmol) of N - methyl - 3 - methyl - 4 - piperidone (CAS No. 4629 - 80 - 5) were dissolved in 150 mL of chloroform. While stirring at 0 °C, 5 mL of trifluoromethanesulfonic acid was slowly dropped. After the dropping was completed, stirring was continued for 30 hours to obtain a viscous solution. The viscous solution was successively washed with 60 mL of pure water and dried at 110 °C for 20 hours to obtain 2.958 g of a pale yellow powdery nitrogen - containing heterocyclic polymer P5a. Its yield was 87%.

[0075] 1 HNMR (600 MHz, DMSO - d6, ppm) δH = 7.71 - 7.36 (24H), 4.27 (2H), 3.59 - 3.45 (4H), 3.25 - 3.20 (4H), 3.14 - 3.04 (7H), 1.95 (2H), 1.76 (2H), 0.98 (3H).

[0076] (2) 1.693 g of nitrogen-containing heterocyclic polymer P5a, 1.42 g (10 mmol) of iodomethane, and 1.382 g (10 mmol) of potassium carbonate were dissolved in 10 mL of dimethyl sulfoxide, and stirred and reacted at 45 °C for 10 hours. After the reaction was completed, the resulting product was washed three times with 20 mL of pure water and dried at 110 °C for 20 hours to obtain 2.256 g of a pale yellow powdery quaternary ammonium salt polymer P5b. The yield was 94%.

[0077] 1 HNMR (600 MHz, DMSO-d6, ppm) δH = 7.74 - 7.43 (24H), 4.51 (2H), 3.70 (2H), 3.53 - 3.48 (2H), 3.41 - 3.31 (6H), 3.19 - 3.08 (11H), 2.06 (2H), 1.83 (2H), 1.13 (3H). JPEG2025523669000013.jpg51170 where x and y are the ratios of the two structural units, and x = y = 50%.

[0078] (3) 100 mg of polymer P5a was taken out and dissolved in 20 mL of dimethyl sulfoxide to obtain a polymer solution. Then, the polymer solution was applied onto a glass plate, and the glass plate was baked at 100 °C for 15 hours to obtain a polymer flat film F5a. F5a had a thickness of 13 μm, a tensile strength of 23 MPa, and a Young's modulus of 298 MPa. F5a was used for nanofiltration separation of aluminum oxide waste acid. Using 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, filtration was carried out at 3 atm and room temperature. The sulfuric acid concentration in the filtrate increased to 189 g / L, and the aluminum ion concentration decreased to 9 g / L. F5a was used for diffusion dialysis of aluminum oxide waste acid. At room temperature, the sulfuric acid concentration in the dialysis solution was 131 g / L, and the aluminum ion concentration was 0.6 g / L.

[0079] (4) F5a was immersed in a 1 M aqueous phosphoric acid solution at room temperature for 5 hours. After taking out the film, it was washed three times with pure water and then dried in an oven at 100 °C for 5 hours under nitrogen gas protection to obtain a proton exchange film F5b with a tensile strength of 20 MPa and a Young's modulus of 256 MPa. At 160 °C, the proton conductivity of F5b was 65 mS / cm, and at 180 °C, the proton conductivity of F5b was 115 mS / cm.

[0080] (5) 100 mg of polymer P5b was taken out and dissolved in 20 mL of N-methylpyrrolidone to obtain a polymer solution. Then the polymer solution was coated on a glass plate and the glass plate was dried in an oven at 90 °C for 5 hours to obtain an iodine ion exchange film F5c. F5c had a tensile strength of 19 MPa and a Young's modulus of 256 MPa. At 80 °C, the conductivity of F5c was 86 mS / cm.

[0081] (6) F5c was immersed in a 1 M aqueous NaCl solution at room temperature for 5 hours. After taking out the film, it was washed three times with pure water and then dried in an oven at 100 °C for 5 hours under nitrogen gas protection to obtain a chlorine ion exchange film F5d with a tensile strength of 21 MPa and a Young's modulus of 278 MPa. At 80 °C, the conductivity of F5d was 116 mS / cm. F5d 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 120 g / L. At room temperature, the lithium ion concentration in the dialysate was 4.9 g / L and the magnesium ion concentration was 1.2 g / L.

[0082] (7) F5c was immersed in a 1 M aqueous NaBr solution at room temperature for 5 hours. After taking out the film, it was washed three times with pure water and then dried in an oven at 100 °C for 5 hours under nitrogen gas protection to obtain a bromine ion exchange film F5e with a tensile strength of 22 MPa and a Young's modulus of 285 MPa. At 80 °C, the conductivity of F5e was 98 mS / cm. When F5e was used in an all-vanadium flow battery, the vanadium ion permeability was 4×10 -10 cm 2 / s, and at 80 °C, when F5e was in a 1.5 M VO 2+When immersed in a 3M H2SO4 solution for 30 days, the decrease in conductivity was only 3%, and the all-vanadium flow battery was assembled with a Coulomb efficiency of 98.2%.

[0083] (8) F5c was immersed in a 1M aqueous NaHCO3 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 gas protection to obtain a bicarbonate ion exchange film F5f with a tensile strength of 19 MPa and a Young's modulus of 252 MPa. At 80 °C, the conductivity of F5f was 54 mS / cm.

[0084] (9) F5c was immersed in a 1M aqueous NaNO3 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 gas protection to obtain a nitrate ion exchange film F5g with a tensile strength of 17 MPa and a Young's modulus of 231 MPa. At 80 °C, the conductivity of F5g was 61 mS / cm.

[0085] (10) F5c was immersed in a 1M aqueous NaOH solution at room temperature for 5 hours. After taking out the film, it was washed with pure water and dried in an oven at 100 °C for 5 hours under nitrogen gas protection to obtain an alkaline anion exchange film F5h with a tensile strength of 22 MPa and a Young's modulus of 267 MPa. At 80 °C, the conductivity of F5h was 130 mS / cm. F5h was used as a separator for an alkaline hydrogen fuel cell and immersed in a 10M aqueous NaOH solution for 15 days, but no decomposition occurred. At 80 °C, the water absorption rate of F5h was 3% and the water swelling rate was 4%. When F7h was used as a separator for an alkaline fuel cell at 80 °C and 2 atm, the cell output density was 1.7 W / cm 2 was obtained.

[0086] <Example 6> (1) 1.152 g (5 mmol) of p - terphenyl (CAS No. 92 - 94 - 4), 0.771 g (5 mmol) of biphenyl (CAS No. 92 - 52 - 4), and 1.616 g (10 mmol) of 3 - quinuclidinone hydrochloride (CAS No. 1193 - 65 - 3) were dissolved in 150 mL of dichloromethane. While stirring at 0 °C, 8 mL of trifluoromethanesulfonic acid and 1 mL of trifluoroacetic acid were slowly added dropwise. After the addition was complete, stirring was continued for 20 hours to obtain a viscous solution. The viscous solution was washed successively with 60 mL of pure water and dried at 110 °C for 20 hours to obtain 2.872 g of a pale yellow powdery nitrogen - containing heterocyclic polymer P6a. The yield was 96%.

[0087] 1 HNMR (600 MHz, DMSO - d6, ppm) δH = 7.71 - 7.48 (10H), 4.29 (2H), 3.46 (1H), 3.23 (2H), 3.16 (2H), 1.87 (2H), 1.76 (2H).

[0088] (2) 1.498 g of the nitrogen - containing heterocyclic polymer P6a, 1.42 g (10 mmol) of iodomethane, and 1.06 g (10 mmol) of sodium carbonate were dissolved in 10 mL of dimethyl sulfoxide. The mixture was stirred and reacted at 25 °C for 10 hours. After the reaction was complete, the resulting product was washed 3 times with 20 mL of pure water and dried at 110 °C for 20 hours to obtain 2.012 g of a pale yellow powdery quaternary ammonium salt polymer P6b. The yield was 91%. 1 HNMR (600 MHz, DMSO - d6, ppm) δH = 7.76 - 7.54 (10H), 4.45 (2H), 3.49 (1H), 3.47 (2H), 3.31 (2H), 3.13 (3H), 1.98 (2H), 1.82 (2H). JPEG2025523669000014.jpg53170In the formula, x and y are the ratios of the two structural units, and x = y = 50%.

[0089] (3) 100 mg of polymer P6a was taken out and dissolved in 20 mL of dimethyl sulfoxide to obtain a polymer solution. After that, the polymer solution was applied onto a glass plate, and the glass plate was baked at 100 °C for 15 hours to obtain a polymer flat film F6a. F6a had a thickness of 14 μm, a tensile strength of 25 MPa, and a Young's modulus of 326 MPa. F6a was used for the nanofiltration separation of aluminum oxide waste acid. Using 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, filtration was carried out at 3 atmospheres and room temperature. The sulfuric acid concentration in the filtrate was increased to 170 g / L, and the aluminum ion concentration was decreased to 15 g / L. F6a was used for the diffusion dialysis of aluminum oxide waste acid. At room temperature, the sulfuric acid concentration in the dialysate was 120 g / L, and the aluminum ion concentration was 0.9 g / L.

[0090] (4) F6a was immersed in a 1 M aqueous phosphoric acid solution at room temperature for 6 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 gas protection to obtain a proton exchange film F6b with a tensile strength of 21 MPa and a Young's modulus of 264 MPa. At 160 °C, the proton conductivity of F6b was 70 mS / cm, and at 180 °C, the proton conductivity of F6b was 118 mS / cm.

[0091] (5) 100 mg of quaternary ammonium salt polymer P6b was taken out and dissolved in 20 mL of N-methylpyrrolidone to obtain a polymer solution. After that, the P6b solution was applied onto a glass plate, and the glass plate was dried at 120 °C for 20 hours to obtain an iodine ion exchange film F6c. F6c had a tensile strength of 22 MPa and a Young's modulus of 282 MPa. At 80 °C, the conductivity of F6c was 89 mS / cm.

[0092] (6) F6c was immersed in a 1 M aqueous NaCl solution at room temperature for 5 hours. After taking out the film, it was washed three times with pure water and then dried in an oven at 100 °C for 5 hours under nitrogen gas protection, obtaining a chloride ion exchange film F6d with a tensile strength of 26 MPa and a Young's modulus of 326 MPa. At 80 °C, the conductivity of F6d was 105 mS / cm. F6d was used for lithium extraction from a salt lake by diffusion dialysis. The lithium ion concentration in the mother liquor was 6 g / L and the magnesium ion concentration was 120 g / L. At room temperature, the lithium ion concentration in the dialysate was 5.1 g / L and the magnesium ion concentration was 0.8 g / L.

[0093] (7) F6c was immersed in a 1 M aqueous NaBr solution at room temperature for 5 hours. After taking out the film, it was washed three times with pure water and then dried in an oven at 100 °C for 5 hours under nitrogen gas protection, obtaining a bromide ion exchange film F6e with a tensile strength of 24 MPa and a Young's modulus of 305 MPa. At 80 °C, the conductivity of F6e was 89 mS / cm. When F6e was used in an all-vanadium flow battery, the vanadium ion permeability was 3×10 -10 cm 2 / s. At 80 °C, when F6e was immersed in a solution of 1.5 M VO 2+ / 3 M H2SO4 for 30 days, the decrease in conductivity was only 2%, and the all-vanadium flow battery was assembled with a Coulomb efficiency of 97.6%.

[0094] (8) F6c was immersed in a 1 M aqueous NaHCO3 solution at room temperature for 5 hours. After taking out the film, it was washed three times with pure water and then dried in an oven at 100 °C for 5 hours under nitrogen gas protection, obtaining a bicarbonate ion exchange film F6f with a tensile strength of 21 MPa and a Young's modulus of 276 MPa. At 80 °C, the conductivity of F6f was 50 mS / cm.

[0095] (9) F6c was immersed in a 1 M aqueous NaNO3 solution at room temperature for 5 hours. After taking out the film, it was washed three times with pure water and then dried in an oven at 100 °C for 5 hours under nitrogen gas protection, obtaining a nitrate ion exchange film F6g with a tensile strength of 19 MPa and a Young's modulus of 253 MPa. At 80 °C, the conductivity of F6g was 42 mS / cm.

[0096] (10) F6c was immersed in 1 M aqueous NaOH solution at room temperature for 5 hours. After taking out the film, it was washed with pure water and dried in an oven at 100 °C for 5 hours under nitrogen gas protection, obtaining an alkaline anion exchange film F6h with a tensile strength of 23 MPa and a Young's modulus of 298 MPa. At 80 °C, the conductivity of F6h was 116 mS / cm. Using F6h as the separator of an alkaline hydrogen fuel cell and immersing it in 10 M aqueous NaOH solution for 20 days, no decomposition occurred. At 80 °C, the water absorption rate of F6h was 2% and the water swelling rate was 3%. When F6h was used as the separator of an alkaline fuel cell at 80 °C and 2 atm, the cell output density was 1.6 W / cm 2 It was.

[0097] <Example 7> (1) 2.303 g (10 mmol) of p - terphenyl (CAS No. 92 - 94 - 4), 0.808 g (5 mmol) of 3 - quinuclidinone hydrochloride (CAS No. 1193 - 65 - 3) and 0.871 g (5 mmol) of 2,2,2 - trifluoroacetophenone (CAS No. 434 - 45 - 7) were dissolved in 150 mL of chloroform. While stirring at 0 °C, 5 mL of trifluoromethanesulfonic acid was slowly added dropwise. After the addition was completed, stirring was continued for 25 hours to obtain a viscous solution. The viscous solution was successively washed with 60 mL of pure water and dried at 110 °C for 20 hours to obtain 3.32 g of a pale yellow powdery nitrogen - containing heterocyclic polymer P7a. Its yield was 91%.

[0098] 1 HNMR (600 MHz, DMSO - d6, ppm) δH = 7.76 - 7.45 (29H), 4.31 (2H), 3.46 (1H), 3.18 (2H), 3.10 (2H), 1.96 (2H), 1.72 (2H).

[0099] (2) 1.817 g of nitrogen-containing heterocyclic polymer P7a, 1.42 g (10 mmol) of iodomethane, and 1.01 g (10 mmol) of triethylamine were dissolved in 10 mL of N-methylpyrrolidone and stirred at 25 °C for 10 hours for a reaction. After the reaction was completed, the obtained product was washed three times with 20 mL of pure water and dried at 110 °C for 20 hours to obtain 1.985 g of a pale yellow powdery quaternary ammonium salt polymer P7b. The yield was 92%.

[0100] 1 HNMR (600 MHz, DMSO-d6, ppm) δH = 7.78 - 7.51 (29H), 4.52 (2H), 3.46 - 3.39 (3H), 3.26 (2H), 3.16 (3H), 2.01 (2H), 1.78 (2H). JPEG2025523669000015.jpg50170In the formula, x and y are the ratios of the two structural units, and x = y = 50%.

[0101] (3) 100 mg of polymer P7a was taken out and dissolved in 20 mL of dimethyl sulfoxide to obtain a polymer solution. Then, the polymer solution was applied onto a glass plate, and the glass plate was dried in an oven at 150 °C for 6 hours to obtain a polymer flat film F7a. F7a had a thickness of 17 μm, a tensile strength of 41 MPa, and a Young's modulus of 825 MPa. F7a was used for the nanofiltration separation of aluminum oxide waste acid. A waste liquid with a sulfuric acid concentration of 150 g / L and an aluminum ion concentration of 20 g / L was used as the mother liquor and filtered at 3 atm and room temperature. The sulfuric acid concentration in the filtrate was increased to 165 g / L, and the aluminum ion concentration was decreased to 15 g / L. F7a was used for the diffusion dialysis of aluminum oxide waste acid. At room temperature, the sulfuric acid concentration in the dialysate was 135 g / L, and the aluminum ion concentration was 0.8 g / L.

[0102] (4) F7a was immersed in 1 M aqueous phosphoric acid solution at room temperature for 5 hours. After taking out the film, it was washed three times with pure water and then dried in an oven at 100 °C for 5 hours under nitrogen gas protection to obtain a proton exchange film F7b with a tensile strength of 35 MPa and a Young's modulus of 716 MPa. At 160 °C, the proton conductivity of F7b is 45 mS / cm, and at 180 °C, the proton conductivity of F7b is 98 mS / cm.

[0103] (5) 100 mg of the quaternary ammonium salt polymer P7b was taken out and dissolved in 20 mL of N-methylpyrrolidone to obtain a polymer solution. Then, the P7b solution was applied onto a glass plate, and the glass plate was dried at 120 °C for 10 hours to obtain an iodine ion exchange film F7c. F7c had a tensile strength of 43 MPa and a Young's modulus of 895 MPa. At 80 °C, the conductivity of F7c was 68 mS / cm.

[0104] (6) F7c was immersed in 1 M aqueous NaCl solution at room temperature for 5 hours. After taking out the film, it was washed three times with pure water and then dried in an oven at 100 °C for 5 hours under nitrogen gas protection to obtain a chlorine ion exchange film F7d with a tensile strength of 45 MPa and a Young's modulus of 856 MPa. At 80 °C, the conductivity of F7d was 95 mS / cm. F7d 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 120 g / L. At room temperature, the lithium ion concentration in the dialysate was 4.5 g / L, and the magnesium ion concentration was 1.5 g / L.

[0105] (7) F7c was immersed in 1 M aqueous NaBr solution at room temperature for 5 hours. After taking out the film, it was washed three times with pure water and then dried in an oven at 100 °C for 5 hours under nitrogen gas protection to obtain a bromine ion exchange film F7e with a tensile strength of 46 MPa and a Young's modulus of 879 MPa. At 80 °C, the conductivity of F7e was 76 mS / cm. When F7e was used in an all-vanadium flow battery, the vanadium ion permeability was 1×10 -10 cm 2 / s, and at 80 °C, when F7e was in 1.5 M VO 2+When immersed in a 3M H2SO4 solution for 30 days, the decrease in conductivity was only 4%, and all vanadium flow batteries were assembled with a Coulomb efficiency of 96.8%.

[0106] (8) F7c was immersed in a 1M aqueous NaHCO3 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 gas protection to obtain a bicarbonate ion exchange film F7f with a tensile strength of 42 MPa and a Young's modulus of 810 MPa. At 80 °C, the conductivity of F7f was 38 mS / cm.

[0107] (9) F7c was immersed in a 1M aqueous NaNO3 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 gas protection to obtain a nitrate ion exchange film F7g with a tensile strength of 38 MPa and a Young's modulus of 726 MPa. At 80 °C, the conductivity of F7g was 50 mS / cm.

[0108] (10) F7c was immersed in a 1M aqueous NaOH solution at room temperature for 5 hours. After taking out the film, it was washed with pure water and dried in an oven at 100 °C for 5 hours under nitrogen gas protection to obtain F7h with a tensile strength of 43 MPa and a Young's modulus of 856 MPa. At 80 °C, the conductivity of F7h was 102 mS / cm. It was immersed in a 10M aqueous NaOH solution for 20 days, but no decomposition occurred. At 80 °C, the water absorption rate of F7h was 6% and the water swelling rate was 5%. When F7h was used as a separator for an alkaline hydrogen fuel cell, at 80 °C and 2 atm, the cell output density was 1.1 W / cm 2 It was.

[0109] <Example 8> (1) 1.78 g of nitrogen-containing heterocyclic polymer P1a, 0.639 g (4.5 mmol) of iodomethane, 0.061 g (0.25 mmol) of 1,6-dibromohexane (CAS: 629-03-8), and 1.382 g (10 mmol) of potassium carbonate were dissolved in 100 mL of dimethyl sulfoxide and stirred at 10 °C for 10 hours for a reaction. After the reaction was completed, the obtained product was washed successively three times with 20 mL of pure water and 20 mL of dichloromethane, and dried at 100 °C for 30 hours to obtain 2.10 g of a pale yellow powdery quaternized crosslinked polymer P8a. The yield was 85%.

[0110] 1 HNMR(600MHz,DMSO-d 6, ppm) δH = 7.73 - 7.52 (12H), 4.38 (2H), 3.57 (1H), 3.41 (2H), 3.23 - 3.15 (5H), 2.12 (2H), 1.87 (2H), 1.72 (0.2H), 1.25 (0.2H). JPEG2025523669000016.jpg39170 where x1, x2, y1, and y2 are the ratios of each structural unit, and x1 + x2 = 90%, y1 + y2 = 10%.

[0111] (2) 100 mg of the quaternized crosslinked polymer P8a was taken out, dissolved in 20 mL of N-methylpyrrolidone to obtain a polymer solution, and then the polymer solution was applied onto a glass plate. The glass plate was dried in an oven at 150 °C for 20 hours to obtain a polymer flat film F8a with a tensile strength of 45 MPa and a Young's modulus of 836 MPa.

[0112] (3) F8a was immersed in a 1 M aqueous NaOH solution at room temperature for 5 hours. After taking out the film, it was washed with pure water and dried in an oven at 100 °C for 8 hours under nitrogen gas protection to obtain an alkaline anion exchange film F8b with a tensile strength of 43 MPa and a Young's modulus of 795 MPa. At 80 °C, the conductivity of F8b was 116 mS / cm. F8b was used as a separator for an alkaline hydrogen fuel cell and immersed in a 10 M aqueous NaOH solution for 20 days, but no decomposition occurred. At 80 °C, the water absorption rate of F8b was 5% and the water swelling rate was 3%. When F8b was used as a separator for an alkaline hydrogen fuel cell at 80 °C and 2 atm, the cell output density was 1.9 W / cm 2 It was.

[0113] <Example 9>

[0114] (1) 1.78 g of a nitrogen-containing heterocyclic polymer P1a, 0.426 g (3 mmol) of iodomethane, and 0.101 g (1 mmol) of triethylamine were dissolved in 60 mL of dimethyl sulfoxide and stirred at 25 °C for 10 hours for a reaction. After the reaction was completed, the obtained product was washed 3 times with 20 mL of pure water and 20 mL of diethyl ether and dried at 100 °C for 30 hours to obtain 2.12 g of a powder P9a of a partially quaternized polymer. The yield was 96%. (2) 441 mg of P9a and 48 mg (0.2 mmol) of 1,6-dibromohexane (CAS: 629-03-8) were dissolved in 100 mL of N,N-dimethylformamide to prepare a homogeneous solution. The homogeneous solution was applied onto a glass plate, and the glass plate was dried at 130 °C for 20 hours to obtain a polymer flat film F9a. F9a had a tensile strength of 39 MPa and a Young's modulus of 756 Mpa

[0115] (3) F9a was immersed in a 1 M aqueous NaOH solution at room temperature for 5 hours. After taking out the film, it was washed with pure water and dried in an oven at 120 °C for 8 hours under nitrogen gas protection to obtain an alkaline anion exchange film F9b with a tensile strength of 41 MPa and a Young's modulus of 829 MPa. At 80 °C, the conductivity of F9b was 142 mS / cm. F9b was used as a separator for an alkaline hydrogen fuel cell and immersed in a 10 M aqueous NaOH solution for 15 days, but no decomposition occurred. At 80 °C, the water absorption rate of F9b was 8% and the water swelling rate was 6%. When F9b was used as a separator for an alkaline hydrogen fuel cell at 80 °C and 2 atm, the cell output density was 1.8 W / cm 2 It was.

[0116] <Example 10>

[0117] (1) 2.533 g (11 mmol) of p-terphenyl (CAS No. 92-94-4), 1.616 g (10 mmol) of 3-quinuclidinone hydrochloride (CAS No. 1193-65-3), and 0.056 g (0.5 mmol) of 1,4-cyclohexanedione (CAS No. 637-88-7) were dissolved in 150 mL of dichloromethane. While stirring at 0 °C, 3 mL of trifluoromethanesulfonic acid and 1 mL of trifluoroacetic acid were slowly added dropwise. After the addition was complete, stirring was continued for 30 hours to obtain a viscous solution. The viscous solution was successively washed with 60 mL of pure water and dried at 110 °C for 30 hours to obtain 3.212 g of a pale yellow powdery nitrogen-containing heterocyclic polymer P10a. The yield was 88%.

[0118] 1 HNMR (600 MHz, DMSO-d6, ppm) δH = 7.75 - 7.63 (13H), 4.35 (2H), 3.57 (1H), 3.25 (2H), 3.17 (2H), 2.12 - 1.95 (2.2H), 1.82 (2H).

[0119] (2) 1.822 g of P10a, 1.42 g (10 mmol) of iodomethane, and 0.101 g (1 mmol) of triethylamine were dissolved in 10 mL of dimethyl sulfoxide, and the mixture was stirred and reacted at 45 °C for 10 hours. After the reaction was completed, the obtained product was washed three times with 20 mL of pure water and dried at 100 °C for 30 hours to obtain 2.056 g of a pale yellow powdery quaternary ammonium salt polymer P10b. The yield was 90%.

[0120] 1 HNMR (600 MHz, DMSO-d6, ppm) δH = 7.76 - 7.65 (13H), 4.54 (2H), 3.62 (1H), 3.49 (2H), 3.35 (2H), 3.22 (3H), 2.12 - 1.97 (2.2H), 1.89 (2H). JPEG2025523669000017.jpg69170

[0121] (3) 100 mg of the nitrogen-containing heterocyclic polymer P10a was taken out and dissolved in 20 mL of dimethyl sulfoxide to obtain a polymer solution. Then, the polymer solution was applied onto a glass plate, and the glass plate was dried in an oven at 120 °C for 8 hours to obtain a polymer flat film F10a. F10a had a thickness of 14 μm, a tensile strength of 39 MPa, and a Young's modulus of 868 MPa.

[0122] (4) F10a was immersed in a 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 10 hours under nitrogen gas protection to obtain a proton exchange film F10b with a tensile strength of 35 MPa and a Young's modulus of 685 MPa. At 160 °C, the proton conductivity of F10b was 61 mS / cm, and at 180 °C, the proton conductivity of F10b was 120 mS / cm.

[0123] (5) 100 mg of quaternary ammonium salt polymer P10b was taken out and dissolved in 20 mL of N,N-dimethylacetamide to obtain a polymer solution. After the polymer solution was applied onto a glass plate and the glass plate was dried in an oven at 80 °C for 5 hours, the temperature was raised to 120 °C and baking was continued for 20 hours to obtain film F10c. F4d had a tensile strength of 35 MPa and a Young's modulus of 698 MPa. F10c was immersed in 1 M aqueous NaOH solution at room temperature for 6 hours. After the film was taken out, it was washed with pure water and dried in an oven at 100 °C for 5 hours under nitrogen gas protection to obtain an alkaline anion exchange film F10d with a tensile strength of 37 MPa and a Young's modulus of 726 MPa. At 25 °C, the conductivity of F10d was 72 mS / cm, and at 80 °C, the conductivity of F10d was 130 mS / cm. F10d was used as a separator for an alkaline hydrogen fuel cell and immersed in 10 M aqueous NaOH solution for 30 days, but no decomposition occurred. At 80 °C, the water absorption rate of F10d was 8% and the water swelling rate was 5%. When F10d was used as a separator for an alkaline hydrogen fuel cell at 80 °C and 2 atm, the cell output density was 1.4 W / cm 2 It was.

[0124] <Example 11> (1) 100 mg of nitrogen-containing heterocyclic polymer P1a was taken out and dissolved in 200 mL of dimethyl sulfoxide to obtain a polymer solution. A bundle of polyvinylidene fluoride (PVDF) hollow fiber membranes was immersed in the polymer solution for 10 hours. After taken out, it was dried at 150 °C for 10 hours to obtain polymer hollow fiber membrane F11a. F11a was used for nanofiltration separation of aluminum oxide waste acid. A waste liquid with a sulfuric acid concentration of 150 g / L and an aluminum ion concentration of 20 g / L was used as the mother liquor and filtered at 10 atm and room temperature. The sulfuric acid concentration in the filtrate was increased to 180 g / L and the aluminum ion concentration was decreased to 12 g / L. Hollow fiber membrane F11a was used for diffusion dialysis of aluminum oxide waste acid. At room temperature, the sulfuric acid concentration in the dialysis solution was 135 g / L and the aluminum ion concentration was 0.9 g / L.

[0125] (2) 100 mg of quaternary ammonium salt polymer P1b was taken out and dissolved in 200 mL of N-methylpyrrolidone to obtain a polymer solution. A bundle of polyvinylidene fluoride (PVDF) hollow fiber membranes was immersed in the polymer solution for 10 hours, taken out, and then dried at 80 °C for 20 hours to obtain polymer hollow fiber membrane F11b. F11b 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 120 g / L. At room temperature, the lithium ion concentration in the dialysate was 5.2 g / L, and the magnesium ion concentration was 1.1 g / L.

[0126] <Example 12> (1) 1000 mg of nitrogen-containing heterocyclic polymer P4a was taken out and dissolved in 200 mL of dimethyl sulfoxide to obtain a polymer solution. Then, a polymer hollow fiber membrane F12a was produced from the polymer solution by a dry-wet spinning process (extruding the solution of polymer P4a from the gap of an annular spinning head and injecting a toluene core liquid into the insertion tube of the spinning head after a certain time to solidify it). F12a was used for nanofiltration separation of aluminum oxide waste acid. A waste liquid with a sulfuric acid concentration of 150 g / L and an aluminum ion concentration of 20 g / L was used as the mother liquor and filtered at 6 atm and room temperature. The sulfuric acid concentration in the filtrate was increased to 185 g / L, and the aluminum ion concentration was decreased to 13 g / L. The polymer hollow fiber membrane F12a was used for diffusion dialysis of aluminum oxide waste acid. At room temperature, the sulfuric acid concentration in the dialysate was 138 g / L, and the aluminum ion concentration was 0.7 g / L.

[0127] (2) 1000 mg of quaternary ammonium salt polymer P4b was taken out and dissolved in 200 mL of N-methylpyrrolidone to obtain a polymer solution. Then, a polymer hollow fiber membrane F12b was produced from the polymer solution by a dry-wet spinning process (extruding the solution of the polymer from the gap of an annular spinning head and injecting a toluene core liquid into the insertion tube of the spinning head after a certain time to solidify it). F12b 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 120 g / L. At room temperature, the lithium ion concentration in the dialysate was 5.5 g / L, and the magnesium ion concentration was 0.8 g / L.

[0128] <Example 13> (1) 1.78 g of nitrogen-containing heterocyclic polymer P1a, 0.426 g (3 mmol) of iodomethane, and 0.101 g (1 mmol) of triethylamine were dissolved in 10 mL of dimethyl sulfoxide, uniformly stirred at 25°C, and the resulting mixture was applied onto a glass plate. The glass plate was dried in an oven at 120°C for 30 hours. The obtained film was successively immersed in dichloromethane and pure water, and then dried in an oven at 100°C for 10 hours to obtain a polymer flat film F13a with a tensile strength of 21 MPa and a Young's modulus of 365 MPa.

[0129] (2) F13a was immersed in a 1 M aqueous NaOH solution at room temperature for 5 hours to obtain an alkaline anion exchange film F13b with a tensile strength of 23 MPa and a Young's modulus of 426 MPa. At 80°C, the conductivity of F13b was 123 mS / cm. F13b was used as a separator for an alkaline hydrogen fuel cell and immersed in a 10 M aqueous NaOH solution for 15 days, but no decomposition occurred. At 80°C, the water absorption rate of F13b was 8% and the water swelling ratio was 6%. When F13b was used as a separator for an alkaline hydrogen fuel cell at 80°C and 2 atm, the cell output density was 1.5 W / cm 2 It was.

Claims

1. A nitrogen-containing heterocyclic polymer characterized by containing a structural unit of the following general formula: Here, R １ and R ２ are each a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group, a pyridyl group, a phenyl group, an o-methylphenyl group, an m-methylphenyl group, a p-methylphenyl group, or a mesitylene group, a is an integer of 1 or more, and b is an integer of 0 or more, A is a group selected from the following structural formulas: B is a nitrogen-containing heterocycle and is a group selected from the following structural formulas: Here, R ３ is hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopropyl, isopropyl, isobutyl, t-butyl, cyclopentyl, cyclohexyl, or N,N,N-trimethylpentamine; When A and B are both selected from a plurality of types, the combinations of A and B in A and B are random, and the arrangement methods of the different combinations are also random.

2. 2. The nitrogen-containing heterocyclic polymer according to claim 1, wherein a Friedel-Crafts reaction occurs between a nitrogen-containing heterocyclic monomer C and an aromatic hydrocarbon monomer D in the presence of an acid catalyst to obtain the nitrogen-containing heterocyclic polymer.

3. a Friedel-Crafts reaction of a nitrogen-containing heterocyclic monomer C, an aromatic hydrocarbon monomer D, and a ketone monomer E in the presence of an acid catalyst to obtain the nitrogen-containing heterocyclic polymer; The ketone monomer E is a combination of one or more selected from the group consisting of the following structures: Here, R １ and R ２ and each represent a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group, a pyridyl group, a phenyl group, an o-methylphenyl group, an m-methylphenyl group, a p-methylphenyl group, or a mesitylene group.

4. a Friedel-Crafts reaction occurs between the nitrogen-containing heterocyclic monomer C, the aromatic hydrocarbon monomer D, and the aromatic crosslinker monomer F in the presence of an acid catalyst to obtain the nitrogen-containing heterocyclic polymer; 2. The nitrogen-containing heterocyclic polymer according to claim 1, wherein the aromatic crosslinker monomer F is one or a combination of triphenylmethane, 1,3,5-triphenylbenzene, 9,9'-spirobifluorene, tetraphenylethylene, tetraphenylmethane, and hexaphenylbenzene.

5. The aromatic hydrocarbon monomer D is one or a combination of benzene, biphenyl, 4,4-dimethylbiphenyl, fluorene, 9,9-dimethylfluorene, p-terphenyl, m-terphenyl, o-terphenyl, diphenylmethane, 1,2-diphenylethane, 1,3-diphenylpropane, para-xylene dimer, 2,2-bis(3,4-dimethylphenyl)hexafluoropropane, 2,3-dimethyl-2,3-diphenylbutane, and 1,2-di(1-naphthyl)ethane; The nitrogen-containing heterocyclic polymer according to any one of claims 2 to 4, wherein the acid catalyst is one or a combination of several of trifluoromethanesulfonic acid, trifluoroacetic acid, acetic acid, trichloroacetic acid, methylsulfonic acid, pentafluoropropionic acid, heptafluorobutyric acid, and perfluorosulfonic acid resin.

6. A quaternary ammonium salt polymer, the general structural formula of which is a quaternized structural formula of the nitrogen moiety of the nitrogen-containing heterocycle: R ４ is any one of a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a cyclopropyl group, an isopropyl group, an isobutyl group, a t-butyl group, a cyclopentyl group, a cyclohexyl group, and an N,N,N-trimethylpentamine group.

7. 7. The method for producing a quaternary ammonium salt polymer according to claim 6, The method includes a step of subjecting the nitrogen-containing heterocyclic polymer according to claim 1 and a monohalide to a quaternary ammonium salt polymer under alkaline or alkaline-free conditions, wherein the molar ratio of the monohalide to the N moiety is 1 to 20:1, and the quaternary ammonium salt polymer is obtained; the monohalide is one or a combination of several of iodomethane, iodoethane, iodopropane, iodobutane, iodopentane, iodohexane, iodoheptane, iodooctane, iodononane, iododecane, bromomethane, bromoethane, bromopropane, bromobutane, bromopentane, bromohexane, bromoheptane, bromooctane, bromononane, bromodecane, 2-bromoethylamine, 2-bromoethyl alcohol, cyclopropyl iodine, isopropyl iodine, isobutyl iodine, cyclopentyl iodine, cyclohexyl iodine, and (5-bromopentyl)trimethylammonium bromide; The alkali is one or a combination 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. A quaternized crosslinked polymer produced by the following method: The nitrogen-containing heterocyclic polymer according to claim 1 is subjected to a quaternization crosslinking reaction with a polyhalide under alkaline or non-alkaline conditions, the nitrogen moieties participating in the quaternization crosslinking reaction occupying 0.001 to 10% of the total nitrogen moieties, and after the reaction is completed, a part of the quaternized crosslinked intermediate polymer is obtained, and the remaining nitrogen moieties of the intermediate polymer are subjected to a quaternization non-crosslinking reaction with a monohalide to obtain the quaternized crosslinked polymer; or Alternatively, the nitrogen-containing heterocyclic polymer according to claim 1 is subjected to a quaternization non-crosslinking reaction with a monohalide under alkaline or non-alkaline conditions, the nitrogen moieties participating in the quaternization non-crosslinking reaction occupying 0.90 to 99.999% of the total nitrogen moieties, and after the reaction is completed, a part of a quaternized intermediate polymer is obtained, and the remaining nitrogen moieties of the intermediate polymer are subjected to a quaternization crosslinking reaction with a polyhalide to obtain the quaternized crosslinked polymer; Alternatively, the nitrogen-containing heterocyclic polymer according to claim 1 is simultaneously subjected to a quaternization reaction with a polyhalide and a monohalide under alkaline or non-alkaline conditions, and the nitrogen moieties participating in the quaternization crosslinking reaction account for 0.001 to 10% of the total nitrogen moieties, and after the reaction is completed, the quaternized crosslinked polymer is obtained; The polyhalogen compound is one or a combination of several selected from the following structures: wherein Y is F, Cl, Br, or I, and n is an integer from 0 to 12; the monohalide is one or a combination of several of iodomethane, iodoethane, iodopropane, iodobutane, iodopentane, iodohexane, iodoheptane, iodooctane, iodononane, iododecane, bromomethane, bromoethane, bromopropane, bromobutane, bromopentane, bromohexane, bromoheptane, bromooctane, bromononane, bromodecane, cyclopropyl iodine, isopropyl iodine, isobutyl iodine, cyclopentyl iodine, cyclohexyl iodine, and (5-bromopentyl)trimethylammonium bromide; The alkali is one or a combination of sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate, 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.

9. A polymer flat membrane produced by the following method: A polymer solution is obtained by dissolving one or more of the nitrogen-containing heterocyclic polymer according to claim 1, the quaternary ammonium salt polymer according to claim 6, and the quaternized crosslinked polymer according to claim 8 in an organic solvent; or a method for producing a polymer solution by dissolving at least one of the nitrogen-containing heterocyclic polymer according to claim 1 and the intermediate polymer according to claim 8 in an organic solvent together with the monohalide and / or polyhalide according to claim 8; The polymer solution is cast or molded onto a substrate and dried to obtain the polymer flat membrane; 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; The polymer flat membrane is characterized in that the substrate is a glass plate, a copper plate, an iron plate, a ceramic plate, a polytetrafluoroethylene plate, a polyethylene terephthalate-based film, a polyamide-based film, a polytetrafluoroethylene-based film, a polyethylene-based film, a polypropylene-based film, a carbon fiber-based film, or a glass fiber-based film.

10. A polymer hollow fiber membrane produced by the following method: A polymer solution is obtained by dissolving one or more of the nitrogen-containing heterocyclic polymer according to claim 1, the quaternary ammonium salt polymer according to claim 6, and the quaternized crosslinked polymer according to claim 8 in an organic solvent; or a method for producing a polymer solution by dissolving at least one of the nitrogen-containing heterocyclic polymer according to claim 1 and the intermediate polymer according to claim 8 in an organic solvent together with the monohalide and / or polyhalide according to claim 8; The hollow fiber base film is immersed in a polymer solution, and after the 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; 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; The polymer hollow fiber membrane is characterized in that it includes any 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 produced by the following method: A proton exchange film, comprising: immersing the polymer flat membrane according to claim 9 and the polymer hollow fiber membrane according to claim 10 in an aqueous phosphoric acid solution having a concentration of 0.1 to 20 M and an immersion temperature of 0 to 90°C, thereby obtaining a proton exchange film.

12. An anion exchange film produced by the following method: The polymer flat membrane according to claim 9 or the polymer hollow fiber membrane according to claim 10 is immersed 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, and after the immersion is completed, the membrane is washed with pure water to obtain an anion exchange film; The hydroxide is one or a combination of lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, and ammonium hydroxide; the bromide is one or a combination of sodium bromide, potassium bromide, cesium bromide, ammonium bromide, magnesium bromide, and calcium bromide; the chloride is one or a combination of sodium chloride, potassium chloride, cesium chloride, ammonium chloride, magnesium chloride, and calcium chloride; the fluoride is one or a combination of sodium fluoride, potassium fluoride, cesium fluoride, ammonium fluoride, magnesium fluoride, and calcium fluoride; The nitrate is one or a combination of sodium nitrate, potassium nitrate, cesium nitrate, ammonium nitrate, magnesium nitrate, and calcium nitrate; The bicarbonate is one or a combination of sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, ammonium bicarbonate, magnesium bicarbonate, and calcium bicarbonate.

13. Applications of the polymer flat membrane according to claim 9, the polymer hollow fiber membrane according to claim 10, the proton exchange film according to claim 11, and the anion exchange film according to claim 12 in alkaline fuel cells, alkaline water electrolysis hydrogen production, 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, respectively.

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