Nitro-containing carbon chain polymer, polymer binder, polymer film and application thereof

Abstract

The invention relates to a nitro-containing carbon chain polymer, a polymer binder, a polymer film and application of the nitro-containing carbon chain polymer, the nitro-containing carbon chain polymer is prepared by Friedel-Crafts reaction of raw materials such as a nitrogen heterocyclic monomer, an aromatic monomer and a nitro-containing ketone monomer, and the nitro-containing carbon chain polymer contains nitro, so that free radicals can be quenched, and the nitro-containing carbon chain polymer can be used as a polymer binder. The free radical resistance of the polymer is improved, so that the damage of hydroxyl radicals to the polymer is relieved, and the stability of the polymer is improved. The ion exchange membrane or ionomer adhesive prepared from the nitro-containing carbon chain polymer has excellent free radical resistance.

Description

Technical Field

[0001] The invention relates to the technical field of polymer functional materials, and in particular to a class of nitro-containing carbon chain polymers, polymer binders and polymer films and applications thereof. Background Art

[0002] Ion exchange membranes and ionomers are the core basic materials for electrochemical energy devices such as water electrolysis to produce hydrogen, fuel cells, flow batteries, metal-air batteries, and carbon dioxide reduction. However, free radicals are easily generated during operation. Free radicals will attack the membrane or ionomer, causing material degradation and further leading to equipment failure.

[0003] In order to solve the above problems, people have adopted the method of adding free radical scavengers, such as cerium dioxide particles. However, these added particles will reduce the uniformity of the membrane and there is also a loss problem. Especially for anion exchange membranes, it has been proven that adding cerium dioxide does not improve the membrane's anti-free radical performance. Therefore, the development of a new free radical scavenging method to give polymers anti-free radical properties is a problem that needs to be solved. Summary of the invention

[0004] The purpose of the present invention is to overcome the above technical deficiencies, provide a class of nitro carbon chain polymers, polymer binders and polymer films and their applications, and solve the technical problem of insufficient free radical resistance in the prior art.

[0005] In order to achieve the above technical purpose, the technical solution provided by the present invention is: Aiming at the problem that the existing ion exchange membranes and / or ionomers, especially the anion exchange membranes, have low free radical resistance, the present invention provides a class of nitro carbon chain polymers, polymer binders and polymer films with good free radical resistance stability and their applications. The present invention introduces a nitrobenzene-containing structure into the polymer molecule, so that the polymer has intrinsic free radical resistance.

[0006] In a first aspect, the present invention provides a type of nitro-containing carbon chain polymer, comprising a structural unit shown in the following general formula I:

[0007] I Among them, a is any natural number ≥ 0, and b is any natural number ≥ 1; A 1 , A 2 are aryl groups, each independently selected from at least one of the groups represented by the following structural formula:

[0008] Among them, m 1 、m 2 、m 3 、m4 、m 5 、m 6 、m 7 Each is independently any natural number less than or equal to 20; R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 22 , R 23 , R 24 , R 25 , R 26 Any one independently selected from hydrogen, methyl, deuterated methyl, ethyl, propyl, butyl, fluorine, chlorine, bromine, trifluoromethyl, hydroxyl, methoxy, ethoxy, amino, methylamino, dimethylamino, ethylamino, diethylamino, sulfonic acid, and nitro; G 1 , G 2 , G 3 , G 4 , G 5 , G 6 , G 7 , G 8 , G 9 , G 10 , G 11 , G 12 , G 13 , G 14 , G 15 Independently selected from O, S, CR 27 , CR 28 R 29 NR 30 Any one of R 27 , R 28 , R 29 , R 30 Any one independently selected from hydrogen, methyl, deuterated methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl; Q is a nitrogen heterocycle, and Q is selected from at least one of the groups shown in the following structural formula: ; R 1 , R 2 , R 3 independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopropyl, isopropyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl or N,N,N-trimethylpentylammonium; B is a nitro-containing aromatic group, selected from at least one of the groups shown in the following structural formula:

[0009] R 31 is any one of hydrogen, methyl, ethyl, propyl, acyl, trifluoromethyl, Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 M is independently selected from any one of hydrogen, fluorine, chlorine, bromine, iodine, nitro, hydroxyl, methyl, ethyl, acyl, trifluoromethyl, and phenyl; 1 、M 2 Independently selected from O, NR 12 Any one of R 12 Any one selected from H, methyl, ethyl, propyl, butyl, pentyl and hexyl.

[0010] In a second aspect, the present invention provides a method for preparing a nitro-containing carbon chain polymer, comprising the following steps: In the presence of an acid catalyst, a nitrogen heterocyclic monomer, an aromatic hydrocarbon monomer, a nitro-containing ketone monomer, and an aromatic crosslinking agent monomer undergo a Friedel-Crafts reaction to obtain a nitro-containing carbon chain polymer; wherein the molar ratio of the nitrogen heterocyclic monomer, the aromatic hydrocarbon monomer, the nitro-containing ketone monomer, and the aromatic crosslinking agent monomer is 1: (0.001-1.1): (0.001-1.1): (0-0.5); The nitrogen heterocyclic monomer is selected from at least one of the groups shown in the following structural formula: ; The aromatic hydrocarbon monomer is selected from at least one of the compounds shown in the following structural formula:

[0011] The nitro-containing ketone monomer is selected from at least one of the compounds shown in the following structural formula:

[0012] The aromatic crosslinking agent monomer is selected from at least one of the compounds shown in the following structural formula: ; R 32 It is any one of hydrogen, methyl, ethyl, propyl, butyl, pentyl and hexyl; o is any natural number ≥1.

[0013] Among them, R 1 -R 3 、m 1 -m 7 , R 13 -R 31 , G1 -G 15 , X and other groups are as defined in the first aspect of the specification.

[0014] Preferably, the acid catalyst is selected from at least one of trifluoromethanesulfonic acid, trifluoroacetic acid, concentrated sulfuric acid, trichloroacetic acid, methanesulfonic acid, pentafluoropropionic acid, heptafluorobutyric acid and perfluorosulfonic acid resin.

[0015] Preferably, the molar ratio of the acid catalyst to the nitrogen heterocyclic monomer is (0.01-20):1.

[0016] Preferably, the molar ratio of the nitrogen heterocyclic monomer, the aromatic hydrocarbon monomer and the nitro-containing ketone monomer is 1:(0.1-1.1):(0.1-1.1), including but not limited to 1:1.1:0.2, 1:1:0.1, 1:1:0.2, 1:1:0.3, 1:1:0.4, 1:0.9:0.2, 1:0.8:0.3, 1:0.2:0.8, etc.

[0017] In a third aspect, the present invention provides a type of quaternary ammonium salt polymer, the structure of which is different from that of a nitro carbon chain-containing polymer in that the nitrogen heterocycle is a quaternized nitrogen heterocycle of the following structure: ; R 4 , R 5 , R 6 , R 7 Methyl, deuterated methyl, ethyl, propyl, butyl, pentyl, hexyl, N,N,N-trimethylpentylammonium, heptyl, octyl, nonyl, decyl, -CH 2 CH 2 NH 2 、-CH 2 CH 2 OH, -CH 2 C(CH 2 OH) 2 (CH 2 Br), -CH 2 C(CH 2 OH) 3 , cyclopropyl, isopropyl, isobutyl, cyclopentyl, cyclohexyl, -CH 2 CH 2 CH 2 CH 2 CH 2 N(CH 3 ) 3 、-CH 2 CH 2 (OCH 2 CH 2 ) n OCH 3 、-CH2 CH 2 (OCH 2 CH 2 ) n OCH 2 CH 3 Any one of , where n is a natural number.

[0018] In a fourth aspect, the present invention provides a method for preparing a quaternary ammonium salt polymer, comprising the following steps: in the presence of base A or in the absence of base, the nitro-containing carbon chain polymer is subjected to a quaternization reaction with a monohalogenated compound, wherein the molar ratio of the monohalogenated compound to the N site in the nitro-containing carbon chain polymer is (0.5-5):1, to generate the quaternary ammonium salt polymer.

[0019] Preferably, the base A 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.

[0020] Preferably, the monohalogenated compound is selected from methyl iodide, deuterated methyl iodide, ethyl iodide, propyl iodide, butyl iodide, pentyl iodide, hexyl iodide, heptyl iodide, octane iodide, nonane iodide, decane iodide, methyl bromide, deuterated methyl bromide, ethyl bromide, propyl bromide, butyl bromide, pentyl bromide, hexyl bromide, heptyl bromide, octane iodide, nonane iodide, decane iodide, 2-bromoethylamine, 2-bromoethanol, cyclopropyl iodide, isopropyl iodide, isobutyl iodide, cyclopentyl iodide, cyclohexyl iodide and (5-bromopentyl)trimethylammonium bromide, BrCH 2 C(CH 2 OH) 3 BrCH 2 CH 2 (OCH 2 CH 2 ) r OCH 3 and BrCH 2 CH 2 (OCH 2 CH 2 ) r OCH 2 CH 3 At least one of , where r is a natural number, and 0≤r≤10.

[0021] In a fifth aspect, the present invention provides a class of N-site cross-linked quaternary ammonium polymers, wherein the structure of the quaternary ammonium polymer is different from that of the quaternary ammonium salt polymer in that the nitrogen sites of some nitrogen heterocycles are cross-linked by alkyl cross-linking structures, and the alkyl cross-linking structures are selected from the following structures: , Wherein, n1, n2, n3, n4, n5, n6, n7, n9, n10, n11, n12, n13 are all natural numbers not greater than 30, n8 is a natural number between 2 and 6, Ar 1 ,Ar 2 is at least one of phenyl, naphthyl, anthracenyl, furanyl, thienyl and pyridyl, R 8 , R 9 It is at least one of hydrogen, fluorine, chlorine, methyl, ethyl, propyl, hydroxide, methoxy, and hydroxymethyl.

[0022] In a sixth aspect, the present invention provides a method for preparing a class of N-site cross-linked quaternary ammonium polymers, comprising the following steps: In the presence of base B or in the absence of base, the nitro carbon chain polymer and the polyhalogenated compound undergo a quaternary ammonium crosslinking reaction, wherein the nitrogen sites participating in the quaternary ammonium crosslinking reaction account for 0.001 to 50% of all nitrogen sites. After the reaction is completed, a partially quaternary ammonium crosslinked intermediate polymer is obtained, and the remaining nitrogen sites of the intermediate polymer are subjected to a quaternary ammonium non-crosslinking reaction with a monohalogenated compound to obtain the N-site crosslinked quaternary ammonium polymer; Alternatively, the nitro carbon chain polymer and the monohalogenated compound are subjected to a quaternary ammonium non-crosslinking reaction in the presence of base B or in the absence of base, and the nitrogen sites participating in the quaternary ammonium non-crosslinking reaction account for 0.50 to 99.999% of all nitrogen sites. After the reaction is completed, a partially quaternary ammonium intermediate polymer is obtained, and the remaining nitrogen sites of the intermediate polymer are subjected to a quaternary ammonium crosslinking reaction with a polyhalogenated compound to obtain the N-site crosslinked quaternary ammonium polymer; Alternatively, in the presence of base B or in the absence of base, the nitro-containing carbon chain polymer is subjected to quaternization reaction with a polyhalogenated compound and a monohalogenated compound simultaneously, and the nitrogen sites participating in the quaternization cross-linking reaction account for 0.0001 to 50% of all nitrogen sites. After the reaction is completed, the N-site cross-linked quaternary ammonium polymer is obtained.

[0023] Preferably, the base B 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.

[0024] Preferably, the monohalogenated compound is selected from methyl iodide, deuterated methyl iodide, ethyl iodide, propyl iodide, butyl iodide, pentyl iodide, hexyl iodide, heptyl iodide, octane iodide, nonane iodide, decane iodide, methyl bromide, deuterated methyl bromide, ethyl bromide, propyl bromide, butyl bromide, pentyl bromide, hexyl bromide, heptyl bromide, octane iodide, nonane iodide, decane iodide, 2-bromoethylamine, 2-bromoethanol, cyclopropyl iodide, isopropyl iodide, isobutyl iodide, cyclopentyl iodide, cyclohexyl iodide and (5-bromopentyl)trimethylammonium bromide, BrCH 2 C(CH 2 OH) 3 BrCH 2 CH 2 (OCH 2 CH 2 ) r OCH 3 and BrCH 2 CH 2 (OCH 2 CH 2 ) r OCH 2 CH 3 At least one of , where r is a natural number, and 0≤r≤10.

[0025] Preferably, the polyhalogenated compound is selected from one or more of the following structures: ; Among them, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , X 8 , X 9 , X 10 , X 11 , X 12 , X 13 , X 14 、X1 5 , X 16 , X 17 is F, Cl, Br, I or hydroxyl.

[0026] In a seventh aspect, the present invention provides a polymer adhesive prepared by the following method: At least one of the quaternary ammonium salt polymer described in the third aspect and the N-site cross-linked quaternary ammonium polymer described in the fifth aspect is uniformly dispersed in a solvent to obtain a polymer adhesive.

[0027] Preferably, the solvent is one of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, methanol, ethanol, propanol, isopropanol, butanol, isobutanol and water, or a combination of multiple thereof.

[0028] Preferably, the mass concentration of the polymer binder is 0.01% to 80%.

[0029] In an eighth aspect, the present invention provides a polymer film prepared by the following method: At least one of the nitro carbon chain polymer described in the first aspect, the quaternary ammonium salt polymer described in the third aspect, and the N-site cross-linked quaternary ammonium polymer described in the fifth aspect is dissolved in an organic solvent to obtain a polymer solution, and the polymer solution is cast or cast on a substrate and dried to obtain the polymer film.

[0030] Preferably, the mass concentration of the polymer solution is 0.01% to 80%, more preferably 4% to 10%.

[0031] Preferably, the organic solvent 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 multiple thereof; Preferably, 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.

[0032] In a ninth aspect, the present invention provides a proton exchange membrane prepared by the following method: The polymer film described in the eighth aspect is immersed in a phosphoric acid aqueous solution with a concentration of 0.1 to 20 mol / L and an immersion temperature of 0 to 90° C. After the immersion is completed, it is washed with pure water and dried to obtain the proton exchange membrane.

[0033] In the tenth aspect, the present invention provides an application of the polymer adhesive described in the seventh aspect, the polymer film described in the eighth aspect, or the proton exchange membrane described in the ninth aspect in fuel cells, hydrogen production by electrolysis of water, metal-air batteries, flow batteries, carbon dioxide reduction, supercapacitors, nickel-hydrogen batteries, zinc-manganese batteries, acid separation, lithium extraction from salt lakes, electrodialysis, water treatment, and membrane humidification.

[0034] Compared with the prior art, the beneficial effects of the present invention include: The present invention uses nitrogen heterocyclic monomers, aromatic hydrocarbon monomers, nitro-containing ketone monomers and other raw materials to undergo Friedel-Crafts reaction to prepare a type of nitro-containing carbon chain polymer, the benzene ring of the polymer contains nitro, and the nitrobenzene structure can improve the oxidation electrode potential of the polymer through charge transfer interaction, which is conducive to quenching free radicals and improving the anti-free radical performance of the polymer, thereby alleviating the damage of free radicals to the polymer and improving the stability of the polymer. Then, the polymer is used to prepare a polymer adhesive and an ion exchange membrane, the polymer adhesive has strong adhesion, and the ion exchange membrane has good anti-free radical stability, high tensile strength and high proton conductivity. DETAILED DESCRIPTION

[0035] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0036] Example 1 1. A method for preparing a nitro-containing carbon chain polymer P1a, comprising the following steps: 2.303 g (10 mmol) of p-terphenyl (CAS No.: 92-94-4), 0.186 g (1 mmol) of 2,2'-dihydroxybiphenyl (CAS No.: 1806-29-7), 1.616 g (10 mmol) of 3-quinuclidinone hydrochloride (CAS No.: 1193-65-3) and 0.540 g (2 mmol) of 2,7-dinitro-9-fluorenone (CAS No.: 31551-45-8) were dissolved in 100 mL of dichloromethane, stirred at -5°C, and 5 mL of trifluoromethanesulfonic acid was slowly added dropwise. After the addition was completed, stirring was continued for 48 hours to obtain a viscous solution, which was washed with 80 mL of pure water in turn and dried at 100°C for 10 hours to obtain 4.612 g of a light yellow nitro-containing carbon chain polymer P1a.

[0037] 1 HNMR (600 MHz, DMSO-d 6 , ppm) δH =1.71-1.90,3.06-3.16, 3.41, 4.20,7.20-7.51, 8.02, 8.22, 8.29, 8.98.

[0038] 2. A method for preparing a quaternized polymer P1b, comprising the following steps: 1.5 g of polymer P1a, 1.42 g (10 mmol) of iodomethane and 1.382 g (10 mmol) of potassium carbonate were dissolved in 12 mL of dimethyl sulfoxide and stirred at 25°C for 10 hours. After the reaction was completed, the obtained product was washed three times with 50 mL of pure water and dried at 100°C for 10 hours to obtain 1.8 g of light yellow powdered quaternized polymer P1b.

[0039] 1 HNMR (600 MHz, DMSO-d 6 , ppm)δH =1.75-2.02, 3.13, 3.21-3.41, 3.50,4.42, 7.14-7.73, 8.02, 8.23, 8.41, 8.98.

[0040]

[0041] In the formula, A represents In any one of the groups, x and y represent only arbitrary natural numbers.

[0042] 3. 100 mg of polymer P1a and 20 mL of dimethyl sulfoxide were mixed evenly to obtain a polymer solution. The polymer solution was coated on a glass plate and dried at 100°C for 15 hours. The obtained polymer film was immersed in a 1M phosphoric acid aqueous solution at room temperature for 10 hours. The film was taken out and washed three times with pure water. It was dried in an oven at 100°C under nitrogen protection for 5 hours to obtain a proton exchange membrane F1a. The tensile strength of F1a was 46.5 MPa. At 160°C, the proton conductivity of F1a (tested in pure water using the two-electrode method) was 96.5 mS / cm.

[0043] The proton exchange membrane F1a was immersed in Fenton's reagent at 80°C for 600 hours, then taken out and dried, immersed in 1M phosphoric acid aqueous solution at room temperature for 10 hours, and the film was washed three times with pure water and dried in an oven at 100°C under nitrogen protection. The tensile strength of the recovered membrane in the dry state at room temperature was 43.6 MPa. At 160°C, the proton conductivity of the recovered F1a was 97.3 mS / cm. This shows that the proton exchange membrane has good anti-free radical stability.

[0044] 4. Take 100 mg of polymer P1b and dissolve it in 20 mL of dimethyl sulfoxide to obtain a polymer solution. The polymer solution is coated on a glass plate, and the glass plate is dried at 120°C for 20 hours to obtain an anion exchange membrane F1b. F1b is immersed in a 1M NaOH aqueous solution at room temperature for 5 hours, and the film is taken out and washed with pure water, and dried in a 60°C oven under nitrogen protection for 10 hours to obtain an alkaline anion exchange membrane F1c. The tensile strength of F1c is 52.3 MPa. At 80°C, the conductivity of F1c is 151.7 mS / cm.

[0045] F1c was immersed in 10M NaOH aqueous solution at 80℃ for 50 days, and there was no degradation. F1c was immersed in Fenton reagent at 80℃ for 600 hours, and it was completely intact, with a mass reduction efficiency of 6%. This shows that the membrane has excellent anti-free radical stability. F1c was used for water electrolysis, with 8M KOH solution as the electrolyte and pure nickel foam as the cathode and anode. At 80℃ and 2V, the current density was 0.89 A / cm 2 . After 1000 hours of continuous operation at this voltage, the current density dropped by less than 0.5%. This indicates that F1c has excellent anti-free radical stability. When F1c is used as a diaphragm in an alkaline fuel cell, the maximum power density of the battery is 2.61 W / cm at 80°C and 2 atmospheres with hydrogen and oxygen injection. 2 .

[0046] Example 2 1. A method for preparing a nitro-containing carbon chain polymer P2a, comprising the following steps: 2.303g (10mmol) of p-terphenyl (CAS No.: 92-94-4), 1.616g (10mmol) of 3-quinuclidinone hydrochloride (CAS No.: 1193-65-3) and 0.54g (2mmol) of 2,7-dinitro-9-fluorenone (CAS No.: 31551-45-8) were dissolved in 100mL of dichloromethane, stirred at -5°C, and 5mL of trifluoromethanesulfonic acid was slowly added dropwise. After the addition was completed, stirring was continued for 48 hours to obtain a viscous solution, which was washed with 80mL of pure water in turn and dried at 100°C for 10 hours to obtain 4.4g of a light yellow nitro-containing carbon chain polymer P2a.

[0047] 1 HNMR (600 MHz, DMSO-d 6 , ppm) δH = 1.74-1.91, 3.08-3.17, 3.42, 4.24, 7.23-7.58, 8.25, 8.36.

[0048] 2. A method for preparing a quaternized polymer P2b, comprising the following steps: 1.5 g of polymer P2a, 1.42 g (10 mmol) of iodomethane and 1.382 g (10 mmol) of potassium carbonate were dissolved in 12 mL of dimethyl sulfoxide and stirred at 25°C for 10 hours. After the reaction was completed, the obtained product was washed three times with 50 mL of pure water and dried at 100°C for 10 hours to obtain 1.68 g of light yellow powdered quaternized polymer P2b.

[0049] 1 HNMR (600 MHz, DMSO-d 6 , ppm) δH =1.76-2.03, 3.13, 3.22-3.42, 3.50,4.43, 7.15-7.72, 8.25, 8.43.

[0050]

[0051] In the formula, A represents Group, x, y represent only arbitrary natural numbers.

[0052] 3. 100 mg of polymer P2a and 20 mL of dimethyl sulfoxide were mixed evenly to obtain a polymer solution, the polymer solution was coated on a glass plate, and dried at 100°C for 15 hours. The obtained polymer film was immersed in a 1M phosphoric acid aqueous solution at room temperature for 10 hours, and the film was taken out and washed three times with pure water, and dried in an oven at 100°C under nitrogen protection for 5 hours to obtain a proton exchange membrane F2a, the tensile strength of F2a was 41.5 MPa. At 160°C, the proton conductivity of F2a was 90.1 mS / cm.

[0053] The proton exchange membrane F2a was soaked in Fenton's reagent at 80°C for 600 hours, then taken out and dried, and then soaked in 1M phosphoric acid aqueous solution at room temperature for 10 hours. The film was taken out and washed three times with pure water, and dried in an oven at 100°C under nitrogen protection. The tensile strength of the recovered membrane was 38.5 MPa. At 160°C, the proton conductivity of the recovered F2a was 91.2 mS / cm. This shows that the proton exchange membrane has good anti-free radical stability.

[0054] 4. Take 100 mg of polymer P2b and dissolve it in 20 mL of dimethyl sulfoxide to obtain a polymer solution. The polymer solution is coated on a glass plate, and the glass plate is dried at 120°C for 20 hours to obtain an anion exchange membrane F2b. F2b is immersed in a 1M NaOH aqueous solution at room temperature for 5 hours, and the film is taken out and washed with pure water, and dried in a 60°C oven under nitrogen protection for 10 hours to obtain an alkaline anion exchange membrane F2c. The tensile strength of F2c is 48.3 MPa. At 80°C, the conductivity of F2c is 149.5mS / cm.

[0055] F2c was immersed in 10M NaOH aqueous solution at 80℃ for 50 days, and there was no degradation. F2c was immersed in Fenton reagent at 80℃ for 600 hours, and it was completely intact, with a mass reduction efficiency of 5%. This shows that the membrane has excellent anti-free radical stability. F2c was used for water electrolysis, with 8M KOH solution as the electrolyte and pure nickel foam as the cathode and anode. At 80℃ and 2V, the current density was 0.81 A / cm 2 . The current density dropped by less than 0.6% after continuous operation for 1000 hours at this voltage. This indicates that F2c has excellent anti-free radical stability. When F2c is used as a diaphragm in an alkaline fuel cell, the maximum power density of the battery is 2.52 W / cm at 80°C and 2 atmospheres with hydrogen and oxygen injection. 2 .

[0056] Example 3 1. A method for preparing a nitro-containing carbon chain polymer P3a, comprising the following steps: 3.04g (10mmol) of p-quaterphenyl (CAS No.: 135-70-6), 1.1316g (10mmol) of N-methyl-4-piperidone (CAS No.: 1445-73-4) and 0.3283g (2mmol) of p-nitroacetophenone (CAS No.: 100-19-6) were dissolved in 100mL of dichloromethane, stirred at -5°C, and 5mL of trifluoromethanesulfonic acid was slowly added dropwise. After the addition was completed, stirring was continued for 52 hours to obtain a viscous solution, which was washed with 80mL of pure water in turn and dried at 100°C for 10 hours to obtain 5.2g of a light yellow nitro-containing carbon chain polymer P3a.

[0057] 1 HNMR (600 MHz, DMSO-d 6 , ppm)δH =2.67, 2.68-2.94, 3.22, 3.34-3.69,7.21-7.59, 8.19-8.21.

[0058] 2. A method for preparing a quaternized polymer P3b, comprising the following steps: 1.5 g of polymer P3a, 1.42 g (10 mmol) of iodomethane and 1.382 g (10 mmol) of potassium carbonate were dissolved in 12 mL of dimethyl sulfoxide and stirred at 25°C for 10 hours. After the reaction was completed, the obtained product was washed three times with 50 mL of pure water and dried at 100°C for 10 hours to obtain 1.79 g of light yellow powdered quaternized polymer P3b.

[0059] 1 HNMR (600 MHz, DMSO-d 6, ppm)δH =2.67, 2.75-2.98, 3.24, 3.38-3.74,7.14-7.78, 8.19-8.21.

[0060]

[0061] In the formula, A represents Group, x, y represent only arbitrary natural numbers.

[0062] 3. 100 mg of polymer P3a and 20 mL of dimethyl sulfoxide were mixed evenly to obtain a polymer solution, the polymer solution was coated on a glass plate, and dried at 100°C for 15 hours. The obtained polymer film was immersed in a 1M phosphoric acid aqueous solution at room temperature for 10 hours, and the film was taken out and washed three times with pure water, and dried in an oven at 100°C under nitrogen protection for 5 hours to obtain a proton exchange membrane F3a, the tensile strength of F3a was 42.6 MPa. At 160°C, the proton conductivity of F3a was 89.3 mS / cm.

[0063] The proton exchange membrane F3a was immersed in Fenton's reagent at 80°C for 600 hours, then taken out for drying, immersed in 1M phosphoric acid aqueous solution at room temperature for 10 hours, and the film was taken out and washed three times with pure water, and dried in an oven at 100°C under nitrogen protection. The tensile strength of the recovered membrane was 41.2MPa. At 160°C, the proton conductivity of the recovered F3a was 88.7mS / cm. This shows that the proton exchange membrane has good anti-free radical stability.

[0064] 4. Take 100 mg of polymer P3b and dissolve it in 20 mL of dimethyl sulfoxide to obtain a polymer solution. The polymer solution is coated on a glass plate, and the glass plate is dried at 120°C for 20 hours to obtain an anion exchange membrane F3b. F3b is immersed in a 1M NaOH aqueous solution at room temperature for 5 hours, and the film is taken out and washed with pure water, and dried in a 60°C oven under nitrogen protection for 10 hours to obtain an alkaline anion exchange membrane F3c. The tensile strength of F3c is 50.4 MPa. At 80°C, the conductivity of F3c is 148.2 mS / cm.

[0065] F3c was immersed in 10M NaOH aqueous solution at 80℃ for 50 days, and there was no degradation. F3c was immersed in Fenton reagent at 80℃ for 600 hours, and it was completely intact, with a mass reduction efficiency of 5.1%. This shows that the membrane has excellent anti-free radical stability. F3c was used for water electrolysis, with 8M KOH solution as the electrolyte and pure nickel foam as the cathode and anode. At 80℃ and 2V, the current density was 0.82A / cm 2 When F3c is used as a membrane in an alkaline fuel cell, the maximum power density of the cell is 2.74 W / cm at 80°C and 2 atmospheres with hydrogen and oxygen injected.2 .

[0066] Example 4 1. A method for preparing a nitro-containing carbon chain polymer P4a, comprising the following steps: 2.303g (10mmol) of p-terphenyl (CAS No.: 92-94-4), 1.616g (10mmol) of 3-quinuclidinone hydrochloride (CAS No.: 1193-65-3) and 0.366g (2mmol) of 4-fluoro-3-nitroacetophenone (CAS No.: 400-93-1) were dissolved in 100mL of dichloromethane, stirred at -5°C, and 5mL of trifluoromethanesulfonic acid was slowly added dropwise. After the addition was completed, stirring was continued for 48 hours to obtain a viscous solution, which was washed with 80mL of pure water in turn and dried at 100°C for 10 hours to obtain 4.15g of a light yellow nitro-containing carbon chain polymer P4a.

[0067] 1 HNMR (600 MHz, DMSO-d 6 , ppm) δH = 1.74-1.91, 2.64, 3.08-3.17, 3.42, 4.24, 7.23-7.58, 8.34-8.36, 8.42-8.44, 8.62.

[0068] 2. A method for preparing a quaternized polymer P4b, comprising the following steps: 1.5 g of polymer P4a, 1.42 g (10 mmol) of iodomethane and 1.382 g (10 mmol) of potassium carbonate were dissolved in 12 mL of dimethyl sulfoxide and stirred at 25°C for 10 hours. After the reaction was completed, the obtained product was washed three times with 50 mL of pure water and dried at 100°C for 10 hours to obtain 1.63 g of light yellow powdered quaternized polymer P4b.

[0069] 1 HNMR (600 MHz, DMSO-d 6 , ppm)δH = 1.76-2.03, 2.64, 3.13, 3.22-3.42, 3.50, 4.43, 7.15-7.72, 8.34-8.36, 8.42-8.44, 8.62.

[0070]

[0071] In the formula, A represents Group, x, y represent only arbitrary natural numbers.

[0072] 3. 100 mg of polymer P4a and 20 mL of dimethyl sulfoxide were mixed evenly to obtain a polymer solution, the polymer solution was coated on a glass plate, and dried at 100°C for 15 hours. The obtained polymer film was immersed in a 1M phosphoric acid aqueous solution at room temperature for 10 hours, and the film was taken out and washed three times with pure water, and dried in an oven at 100°C under nitrogen protection for 5 hours to obtain a proton exchange membrane F4a, the tensile strength of F4a was 40.3 MPa. At 160°C, the proton conductivity of F4a was 92.6 mS / cm.

[0073] The proton exchange membrane F4a was immersed in Fenton's reagent at 80°C for 600 hours, then taken out and dried, and immersed in 1M phosphoric acid aqueous solution at room temperature for 10 hours. The film was taken out and washed three times with pure water, and dried in an oven at 100°C under nitrogen protection. The tensile strength of the recovered membrane was 37.8MPa. At 160°C, the proton conductivity of the recovered F4a was 92.2mS / cm. This shows that the proton exchange membrane has good anti-free radical stability.

[0074] 4. Take 100 mg of polymer P4b and dissolve it in 20 mL of dimethyl sulfoxide to obtain a polymer solution. The polymer solution is coated on a glass plate, and the glass plate is dried at 120°C for 20 hours to obtain an anion exchange membrane F4b. F4b is immersed in a 1M NaOH aqueous solution at room temperature for 5 hours, and the film is taken out and washed with pure water, and dried in a 60°C oven under nitrogen protection for 10 hours to obtain an alkaline anion exchange membrane F4c. The tensile strength of F4c is 50.5 MPa. At 80°C, the conductivity of F4c is 150.6 mS / cm.

[0075] F4c was immersed in 10M NaOH aqueous solution at 80℃ for 50 days, and there was no degradation. F4c was immersed in Fenton reagent at 80℃ for 600 hours, and it was completely intact, with a mass reduction efficiency of 5.9%. This shows that the membrane has excellent anti-free radical stability. F4c was used for water electrolysis, with 8M KOH solution as the electrolyte and pure nickel foam as the cathode and anode. At 80℃ and 2V, the current density was 0.91A / cm 2 When F4c is used as a membrane in an alkaline fuel cell, the maximum power density of the cell is 2.62 W / cm at 80°C and 2 atmospheres with hydrogen and oxygen injection. 2 .

[0076] Example 5 (Adhesive) 1. A method for preparing a nitro-containing carbon chain polymer P5a, comprising the following steps: 1.542g (10mmol) biphenyl (CAS No.: 92-52-4), 1.616g (10mmol) 3-quinuclidine hydrochloride (CAS No.: 1193-65-3) and 0.366g (2mmol) 4-fluoro-3-nitroacetophenone (CAS No.: 400-93-1) were dissolved in 100mL dichloromethane, stirred at -5°C, and 5mL trifluoromethanesulfonic acid was slowly added dropwise. After the addition was completed, stirring was continued for 48 hours to obtain a viscous solution, which was washed with 80mL pure water in turn and dried at 100°C for 10 hours to obtain 3.65g of a light yellow nitro-containing carbon chain polymer P5a.

[0077] 1 HNMR (600 MHz, DMSO-d 6 , ppm) δH = 1.74-1.91, 3.08-3.17, 3.42, 4.24, 7.23-7.58, 8.34-8.36, 8.42-8.44, 8.62.

[0078] 2. A method for preparing a quaternized polymer P5b, comprising the following steps: 1.5 g of polymer P5a, 1.42 g (10 mmol) of iodomethane and 1.382 g (10 mmol) of potassium carbonate were dissolved in 12 mL of dimethyl sulfoxide and stirred at 25°C for 10 hours. After the reaction was completed, the obtained product was washed three times with 50 mL of pure water and dried at 100°C for 10 hours to obtain 1.73 g of light yellow powdered quaternized polymer P5b.

[0079] 1 HNMR (600 MHz, DMSO-d 6 , ppm)δH = 1.76-2.03, 3.13, 3.22-3.42, 3.50, 4.43, 7.15-7.72, 8.34-8.36, 8.42-8.44, 8.62.

[0080]

[0081] In the formula, A represents Group, x, y represent only arbitrary natural numbers.

[0082] 3. Take 100 mg of polymer P5b and dissolve it in a mixed solution of 0.5 mL of dimethyl sulfoxide and 2 mL of ethanol. After dissolution, filtration and centrifugation, an ionomer solution, i.e., an adhesive solution, is obtained. The adhesive and nickel-iron catalyst powder are configured into a slurry and sprayed on a nickel foam electrode. The nickel foam electrode is immersed in Fenton's reagent at 80°C for 600 hours, and no catalyst shedding is observed, indicating that the adhesive has good anti-free radical properties.

[0083] Example 6 1. A method for preparing a nitro-containing carbon chain polymer P6a, comprising the following steps: 2.303g (10mmol) of p-terphenyl (CAS No.: 92-94-4), 1.616g (10mmol) of 3-quinuclidinone hydrochloride (CAS No.: 1193-65-3), 0.540g (2mmol) of 2,7-dinitro-9-fluorenone (CAS No.: 31551-45-8) and 0.307g (1mmol) of triphenylbenzene (CAS No.: 612-71-5) were dissolved in 100mL of dichloromethane, stirred at -5°C, and 5mL of trifluoromethanesulfonic acid was slowly added dropwise. After the addition was completed, stirring was continued for 45 hours to obtain a viscous solution, which was washed with 80mL of pure water in turn and dried at 100°C for 10 hours to obtain 4.52g of a light yellow nitro-containing carbon chain polymer P6a.

[0084] 1 HNMR (600 MHz, DMSO-d 6 , ppm) δH = 1.74-1.91, 3.08-3.17, 3.42, 4.24, 7.23-7.79, 8.25, 8.36.

[0085] 2. A method for preparing a quaternized polymer P6b, comprising the following steps: 1.5 g of polymer P6a, 1.42 g (10 mmol) of iodomethane and 1.382 g (10 mmol) of potassium carbonate were dissolved in 12 mL of dimethyl sulfoxide and stirred at 25°C for 10 hours. After the reaction was completed, the obtained product was washed three times with 50 mL of pure water and dried at 100°C for 10 hours to obtain 1.59 g of light yellow powdered quaternized polymer P6b.

[0086] 1 HNMR (600 MHz, DMSO-d 6 , ppm)δH = 1.76-2.03, 3.13, 3.22-3.42, 3.50, 4.43, 7.15-7.81, 8.25, 8.43.

[0087]

[0088] In the formula, A represents Group, x, y represent only arbitrary natural numbers.

[0089] 3. 150 mg of polymer P6a and 20 mL of dimethyl sulfoxide were mixed evenly to obtain a polymer solution, the polymer solution was coated on a glass plate, and dried at 100°C for 15 hours. The obtained polymer film was immersed in a 1M phosphoric acid aqueous solution at room temperature for 10 hours, and the film was taken out and washed three times with pure water, and dried in an oven at 100°C under nitrogen protection for 5 hours to obtain a proton exchange membrane F6a, the tensile strength of F6a was 55.8 MPa. At 160°C, the proton conductivity of F6a was 99.2 mS / cm.

[0090] The proton exchange membrane F6a was immersed in Fenton's reagent at 80°C for 600 hours, then taken out for drying, immersed in 1M phosphoric acid aqueous solution at room temperature for 10 hours, and the film was taken out and washed three times with pure water, and dried in an oven at 100°C under nitrogen protection. The tensile strength of the recovered membrane was 54.9MPa. At 160°C, the proton conductivity of the recovered F6a was 97.6mS / cm. This shows that the proton exchange membrane has good anti-free radical stability.

[0091] 4. Take 100 mg of polymer P6b and dissolve it in 20 mL of dimethyl sulfoxide to obtain a polymer solution. The polymer solution is coated on a glass plate, and the glass plate is dried at 120°C for 20 hours to obtain an anion exchange membrane F6b. F6b is immersed in a 1M NaOH aqueous solution at room temperature for 5 hours, and the film is taken out and washed with pure water, and dried in a 60°C oven under nitrogen protection for 10 hours to obtain an alkaline anion exchange membrane F6c. The tensile strength of F6c is 55.2 MPa. At 80°C, the conductivity of F6c is 143.8 mS / cm.

[0092] F6c was immersed in 10M NaOH aqueous solution at 80℃ for 50 days, and there was no degradation. F6c was immersed in Fenton reagent at 80℃ for 800 hours, and it was completely intact, with a mass reduction efficiency of 4%. This shows that the membrane has excellent anti-free radical stability. F6c was used for water electrolysis, with 8M KOH solution as the electrolyte and pure nickel foam as the cathode and anode. At 80℃ and 2V, the current density was 0.85A / cm 2 When F6c is used as a membrane in an alkaline fuel cell, the maximum power density of the cell is 2.31 W / cm at 80°C and 2 atmospheres with hydrogen and oxygen injection. 2 .

[0093] Example 7 1. A method for preparing a nitro-containing carbon chain polymer P7a, comprising the following steps: 2.303g (10mmol) of p-terphenyl (CAS No.: 92-94-4), 1.616g (10mmol) of 3-quinuclidinone hydrochloride (CAS No.: 1193-65-3), 0.540g (2mmol) of 2,7-dinitro-9-fluorenone (CAS No.: 31551-45-8), and 0.328g (2mmol) of m-nitroacetophenone (CAS No.: 121-89-1) were dissolved in 100mL of dichloromethane, stirred at -5°C, and 5mL of trifluoromethanesulfonic acid was slowly added dropwise. After the addition was completed, stirring was continued for 48 hours to obtain a viscous solution, which was washed with 80 mL of pure water in turn and dried at 100°C for 10 hours to obtain 5.32g of a light yellow nitro carbon chain polymer P7a.

[0094] 1 HNMR (600 MHz, DMSO-d 6 , ppm) δH = 1.74-1.91, 2.63, 3.08-3.17, 3.42,4.24, 7.23-8.11, 8.25, 8.36,8.44, 8.63.

[0095] 2. A method for preparing the quaternized polymer P7b comprises the following steps: 1.5 g of polymer P7a, 1.42 g (10 mmol) of iodomethane and 1.382 g (10 mmol) of potassium carbonate were dissolved in 12 mL of dimethyl sulfoxide and stirred at 25°C for 10 hours. After the reaction was completed, the obtained product was washed three times with 50 mL of pure water and dried at 100°C for 10 hours to obtain 1.73 g of light yellow powdered quaternized polymer P7b.

[0096] 1 HNMR (600 MHz, DMSO-d 6 , ppm)δH = 1.76-2.03, 2.63, 3.13, 3.22-3.42, 3.50, 4.43, 7.15-8.14, 8.25, 8.43, 8.51, 8.71.

[0097] In the formula, A represents Group, x, y, z represent only arbitrary natural numbers.

[0098] 3. 100 mg of polymer P7a and 20 mL of dimethyl sulfoxide were mixed evenly to obtain a polymer solution, the polymer solution was coated on a glass plate, and dried at 100°C for 15 hours. The obtained polymer film was immersed in a 1M phosphoric acid aqueous solution at room temperature for 10 hours, and the film was taken out and washed three times with pure water, and dried in an oven at 100°C under nitrogen protection for 5 hours to obtain a proton exchange membrane F7a, the tensile strength of F7a was 54.6 MPa. At 160°C, the proton conductivity of F7a was 93.5 mS / cm.

[0099] The proton exchange membrane F7a was immersed in Fenton's reagent at 80°C for 800 hours, then taken out for drying, immersed in 1M phosphoric acid aqueous solution at room temperature for 10 hours, and the film was taken out and washed three times with pure water, and dried in an oven at 100°C under nitrogen protection. The tensile strength of the recovered membrane was 53.2MPa. At 160°C, the proton conductivity of the recovered F7a was 93.1mS / cm. This shows that the proton exchange membrane has good anti-free radical stability.

[0100] 4. Take 100 mg of polymer P7b and dissolve it in 20 mL of dimethyl sulfoxide to obtain a polymer solution. The polymer solution is coated on a glass plate, and the glass plate is dried at 120°C for 20 hours to obtain an anion exchange membrane F7b. F7b is immersed in a 1M NaOH aqueous solution at room temperature for 5 hours, and the film is taken out and washed with pure water, and dried in a 60°C oven under nitrogen protection for 10 hours to obtain an alkaline anion exchange membrane F7c. The tensile strength of F7c is 61.1 MPa. At 80°C, the conductivity of F7c is 146.7 mS / cm.

[0101] F7c was immersed in 10M NaOH aqueous solution at 80℃ for 50 days, and there was no degradation. F7c was immersed in Fenton reagent at 80℃ for 2000 hours, and it was completely intact, with a mass reduction efficiency of 1.6%. This shows that the membrane has excellent anti-free radical stability. F7c was used for water electrolysis, with 8M KOH solution as the electrolyte and pure nickel foam as the cathode and anode. At 80℃ and 2V, the current density was 0.83A / cm 2 When F7c is used as a membrane in an alkaline fuel cell, the maximum power density of the cell is 2.25 W / cm at 80°C and 2 atmospheres with hydrogen and oxygen injection. 2 .

[0102] Example 8 1. A method for preparing a nitro-containing carbon chain polymer P8a, comprising the following steps: 2.303g (10mmol) of p-terphenyl (CAS No.: 92-94-4), 1.616g (10mmol) of 3-quinuclidine hydrochloride (CAS No.: 1193-65-3) and 0.366g (2mmol) of m-nitroacetophenone (CAS No.: 121-89-1) were dissolved in 100mL of dichloromethane, stirred at -5°C, and 5mL of trifluoromethanesulfonic acid was slowly added dropwise. After the addition was completed, stirring was continued for 48 hours to obtain a viscous solution, which was washed with 80mL of pure water in turn and dried at 100°C for 10 hours to obtain 3.96g of a light yellow nitro carbon chain polymer P8a.

[0103] 1 HNMR (600 MHz, DMSO-d 6 , ppm) δH = 1.74-1.91, 2.64, 3.08-3.17, 3.42, 4.24, 7.23-7.58, 8.34-8.36, 8.42-8.44, 8.62.

[0104] 2. A method for preparing a quaternized polymer P8b, comprising the following steps: 1.5 g of polymer P8a, 1.42 g (10 mmol) of iodomethane and 1.382 g (10 mmol) of potassium carbonate were dissolved in 12 mL of dimethyl sulfoxide and stirred at 25°C for 10 hours. After the reaction was completed, the obtained product was washed three times with 50 mL of pure water and dried at 100°C for 10 hours to obtain 1.78 g of light yellow powdered quaternized polymer P8b.

[0105] 1 HNMR (600 MHz, DMSO-d 6 , ppm)δH = 1.76-2.03, 2.64, 3.13, 3.22-3.42, 3.50, 4.43, 7.15-7.72, 8.34-8.36, 8.42-8.44, 8.62.

[0106]

[0107] In the formula, A represents Group, x, y represent only arbitrary natural numbers.

[0108] 3. 100 mg of polymer P8a and 20 mL of dimethyl sulfoxide were mixed evenly to obtain a polymer solution, the polymer solution was coated on a glass plate, and dried at 100°C for 15 hours. The obtained polymer film was immersed in a 1M phosphoric acid aqueous solution at room temperature for 10 hours, and the film was taken out and washed three times with pure water, and dried in an oven at 100°C under nitrogen protection for 5 hours to obtain a proton exchange membrane F8a, the tensile strength of which was 41.5 MPa. At 160°C, the proton conductivity of F8a was 92.9 mS / cm.

[0109] The proton exchange membrane F8a was immersed in Fenton's reagent at 80°C for 1000 hours, then taken out for drying, immersed in 1M phosphoric acid aqueous solution at room temperature for 10 hours, and the film was washed three times with pure water and dried in an oven at 100°C under nitrogen protection. The tensile strength of the recovered membrane was 39.2MPa. At 160°C, the proton conductivity of the recovered F8a was 92.5mS / cm. This shows that the proton exchange membrane has good anti-free radical stability.

[0110] 4. Take 100 mg of polymer P8b and dissolve it in 20 mL of dimethyl sulfoxide to obtain a polymer solution. The polymer solution is coated on a glass plate, and the glass plate is dried at 120°C for 20 hours to obtain an anion exchange membrane F8b. F8b is immersed in a 1M NaOH aqueous solution at room temperature for 5 hours, and the film is taken out and washed with pure water, and dried in a 60°C oven under nitrogen protection for 10 hours to obtain an alkaline anion exchange membrane F8c. The tensile strength of F8c is 45.6 MPa. At 80°C, the conductivity of F8c is 146.3 mS / cm.

[0111] F8c was immersed in 10M NaOH aqueous solution at 80℃ for 50 days, and there was no degradation. F8c was immersed in Fenton reagent at 80℃ for 500 hours, and it was completely free of cracks, and the mass reduction efficiency was 5.8%. This shows that the membrane has excellent anti-free radical stability. F8c was used for water electrolysis, 8M KOH solution was the electrolyte, pure nickel foam was the cathode and anode, and the current density was 0.92A / cm at 2V at 80℃. 2 When F8c is used as a membrane in an alkaline fuel cell, the maximum power density of the cell is 2.48 W / cm at 80 °C and 2 atmospheres with hydrogen and oxygen injection. 2 .

[0112] Example 9 1. A method for preparing a nitro-containing carbon chain polymer P9a, comprising the following steps: 2.303g (10mmol) of p-terphenyl (CAS No.: 92-94-4), 1.616g (10mmol) of 3-quinuclidinone hydrochloride (CAS No.: 1193-65-3), 0.54g (2mmol) of 2,7-dinitro-9-fluorenone (CAS No.: 31551-45-8) and 0.389g (2mmol) of 9,9-dimethylfluorene (CAS No.: 4569-45-3) were dissolved in 100mL of dichloromethane, stirred at -5°C, and 5mL of trifluoromethanesulfonic acid was slowly added dropwise. After the addition was completed, stirring was continued for 48 hours to obtain a viscous solution, which was washed with 80mL of pure water in turn and dried at 100°C for 10 hours to obtain 4.13g of a light yellow nitro-containing carbon chain polymer P9a.

[0113] 1 HNMR (600 MHz, DMSO-d 6 , ppm) δH = 1.44, 1.74-1.91, 3.08-3.17, 3.42, 4.24, 7.08-7.78, 8.25, 8.36.

[0114] 2. A method for preparing a quaternized polymer P9b, comprising the following steps: 1.5 g of polymer P9a, 1.42 g (10 mmol) of iodomethane and 1.382 g (10 mmol) of potassium carbonate were dissolved in 12 mL of dimethyl sulfoxide and stirred at 25°C for 10 hours. After the reaction was completed, the obtained product was washed three times with 50 mL of pure water and dried at 100°C for 10 hours to obtain 1.71 g of light yellow powdered quaternized polymer P9b.

[0115] 1 HNMR (600 MHz, DMSO-d 6 , ppm)δH = 1.44, 1.76-2.03, 3.13, 3.22-3.42, 3.50, 4.43, 7.05-7.84, 8.25, 8.36.

[0116]

[0117] In the formula, A represents Group, x, y represent only arbitrary natural numbers.

[0118] 3. 100 mg of polymer P9a and 20 mL of dimethyl sulfoxide were mixed evenly to obtain a polymer solution, the polymer solution was coated on a glass plate, and dried at 100°C for 15 hours. The obtained polymer film was immersed in a 1M phosphoric acid aqueous solution at room temperature for 10 hours, and the film was taken out and washed three times with pure water, and dried in an oven at 100°C under nitrogen protection for 5 hours to obtain a proton exchange membrane F9a, the tensile strength of F9a was 42.8 MPa. At 160°C, the proton conductivity of F9a was 96.5 mS / cm.

[0119] The proton exchange membrane F9a was soaked in Fenton's reagent at 80°C for 800 hours, then taken out and dried, and then soaked in 1M phosphoric acid aqueous solution at room temperature for 10 hours. The film was taken out and washed three times with pure water, and dried in an oven at 100°C under nitrogen protection. The tensile strength of the recovered membrane was 41.5MPa. At 160°C, the proton conductivity of the recovered F9a was 95.9mS / cm. This shows that the proton exchange membrane has good anti-free radical stability.

[0120] 4. Take 100 mg of polymer P9b and dissolve it in 20 mL of dimethyl sulfoxide to obtain a polymer solution. The polymer solution is coated on a glass plate, and the glass plate is dried at 120°C for 20 hours to obtain an anion exchange membrane F9b. F9b is immersed in a 1M NaOH aqueous solution at room temperature for 5 hours, and the film is taken out and washed with pure water, and dried in a 60°C oven under nitrogen protection for 10 hours to obtain an alkaline anion exchange membrane F9c. The tensile strength of F9c is 51.3 MPa. At 80°C, the conductivity of F9c is 152.6 mS / cm.

[0121] F9c was immersed in 10M NaOH aqueous solution at 80℃ for 50 days, and there was no degradation. F9c was immersed in Fenton reagent at 80℃ for 600 hours, and it was completely intact, with a mass reduction efficiency of 6.1%. This shows that the membrane has excellent anti-free radical stability. F9c was used for electrolysis of water, with 8M KOH solution as the electrolyte and pure nickel foam as the cathode and anode. At 80℃ and 2V, the current density was 0.93A / cm 2 When F9c was used as a membrane in an alkaline fuel cell, the maximum power density of the cell was 2.58 W / cm at 80°C and 2 atmospheres with hydrogen and oxygen injection. 2 .

[0122] Example 10 1. A method for preparing a nitro-containing carbon chain polymer P10a, comprising the following steps: 2.303 g (10 mmol) of p-terphenyl (CAS No.: 92-94-4), 1.616 g (10 mmol) of 3-quinuclidinone hydrochloride (CAS No.: 1193-65-3), 0.54 g (2 mmol) of 2,7-dinitro-9-fluorenone (CAS No.: 31551-45-8), 0.389 g (2 mmol) of 9,9-dimethylfluorene (CAS No.: 4569-45-3) and 0.307 g (1 mmol) of triphenylbenzene (CAS No.: 612-71-5) were dissolved in 100 mL of dichloromethane, stirred at -5°C, and 5 mL of trifluoromethanesulfonic acid was slowly added dropwise. After the addition was completed, stirring was continued for 52 hours to obtain a viscous solution, which was washed with 80 mL of pure water in sequence and dried at 100° C. for 10 hours to obtain 4.18 g of a light yellow nitro-containing carbon chain polymer P10a.

[0123] 1 HNMR (600 MHz, DMSO-d 6 , ppm) δH = 1.44, 1.74-1.91, 3.08-3.17, 3.42, 4.24, 7.09-7.92, 8.25, 8.36.

[0124] 2. A method for preparing a quaternary ammonium polymer P10b comprises the following steps: 1.5 g of polymer P10a, 1.42 g (10 mmol) of iodomethane and 1.382 g (10 mmol) of potassium carbonate were dissolved in 12 mL of dimethyl sulfoxide and stirred at 25°C for 10 hours. After the reaction was completed, the obtained product was washed three times with 50 mL of pure water and dried at 100°C for 10 hours to obtain 1.69 g of light yellow powdered quaternized polymer P10b.

[0125] 1 HNMR (600 MHz, DMSO-d 6 , ppm)δH = 1.44, 1.76-2.03, 3.13, 3.22-3.42, 3.50, 4.43, 7.05-7.98, 8.25, 8.36.

[0126] In the formula, A represents Group, x, y represent only arbitrary natural numbers.

[0127] 3. 100 mg of polymer P10a and 20 mL of dimethyl sulfoxide were mixed evenly to obtain a polymer solution, the polymer solution was coated on a glass plate, and dried at 100°C for 15 hours. The obtained polymer film was immersed in a 1M phosphoric acid aqueous solution at room temperature for 10 hours, and the film was taken out and washed three times with pure water, and dried in an oven at 100°C under nitrogen protection for 5 hours to obtain a proton exchange membrane F10a, the tensile strength of F10a was 41.2 MPa. At 160°C, the proton conductivity of F10a was 93.1 mS / cm.

[0128] The proton exchange membrane F10a was immersed in Fenton's reagent at 80°C for 1000 hours, then taken out for drying, immersed in 1M phosphoric acid aqueous solution at room temperature for 10 hours, and the film was taken out and washed three times with pure water, and dried in an oven at 100°C under nitrogen protection. The tensile strength of the recovered membrane was 40.5MPa. At 160°C, the proton conductivity of the recovered F10a was 92.8mS / cm. This shows that the proton exchange membrane has good anti-free radical stability.

[0129] 4. Take 100 mg of polymer P10b and dissolve it in 20 mL of dimethyl sulfoxide to obtain a polymer solution. The polymer solution is coated on a glass plate, and the glass plate is dried at 120°C for 20 hours to obtain an anion exchange membrane F10b. F10b is immersed in a 1M NaOH aqueous solution at room temperature for 5 hours, and the film is taken out and washed with pure water, and dried in a 60°C oven under nitrogen protection for 10 hours to obtain an alkaline anion exchange membrane F10c. The tensile strength of F10c is 49.1 MPa. At 80°C, the conductivity of F10c is 152.3 mS / cm.

[0130] F10c was immersed in 10M NaOH aqueous solution at 80℃ for 50 days, and there was no degradation. F10c was immersed in Fenton reagent at 80℃ for 600 hours, and it was completely intact, with a mass reduction efficiency of 5.7%. This shows that the membrane has excellent anti-free radical stability. F10c was used for water electrolysis, with 8M KOH solution as the electrolyte and pure nickel foam as the cathode and anode. At 80℃ and 2V, the current density was 0.86A / cm 2 When F10c is used as a membrane in an alkaline fuel cell, the maximum power density of the cell is 2.49 W / cm at 80°C and 2 atmospheres with hydrogen and oxygen injection. 2 .

[0131] Embodiment 11 1. A method for preparing a nitro-containing carbon chain polymer P11a, comprising the following steps: 1.542 g (10 mmol) of biphenyl (CAS No.: 92-52-4), 1.616 g (10 mmol) of 3-quinuclidinone hydrochloride (CAS No.: 1193-65-3) and 0.27 g (1 mmol) of 2,7-dinitro-9-fluorenone (CAS No.: 31551-45-8) were dissolved in 100 mL of dichloromethane and stirred at -5°C while slowly dropping 5 mL of trifluoromethanesulfonic acid. After the addition was completed, stirring was continued for 48 hours to obtain a viscous solution, which was washed with 80 mL of pure water in turn and dried at 100°C for 10 hours to obtain 3.73 g of a light yellow nitro-containing carbon chain polymer P11a.

[0132] 1 HNMR (600 MHz, DMSO-d 6 , ppm) δH = 1.50-2.21, 2.85-3. 21, 3.44, 4.257.25-7.53, 8.25, 8.36.

[0133] 2. A method for preparing a quaternized polymer P11b, comprising the following steps: 1.5 g of polymer P11a, 1.42 g (10 mmol) of iodomethane and 1.382 g (10 mmol) of potassium carbonate were dissolved in 12 mL of dimethyl sulfoxide and stirred at 25°C for 10 hours. After the reaction was completed, the obtained product was washed three times with 50 mL of pure water and dried at 100°C for 10 hours to obtain 1.76 g of light yellow powdered quaternized polymer P11b.

[0134] 1 HNMR (600 MHz, DMSO-d 6 , ppm)δH = 1.45-2.31, 3.14, 3.22-3.40, 3.51,4.43, 7.14-7.72, 8.25, 8.35-8.46.

[0135]

[0136] In the formula, A represents Group, x, y represent only arbitrary natural numbers.

[0137] 3. 100 mg of polymer P11b was dissolved in a mixed solution of 0.5 mL of dimethyl sulfoxide and 2 mL of ethanol. After dissolution, filtration and centrifugation, an ionomer solution, i.e., an adhesive solution, was obtained. The adhesive and nickel-iron catalyst powder were configured into a slurry and sprayed on a nickel foam electrode. The nickel foam electrode was immersed in Fenton's reagent at 80°C for 600 hours, and no catalyst shedding was observed, indicating that the adhesive has good anti-free radical properties.

[0138] Example 12 1. A method for preparing a nitro-containing carbon chain polymer P12a, comprising the following steps: 1.542 g (10 mmol) of biphenyl (CAS No.: 92-52-4), 1.616 g (10 mmol) of 3-quinuclidinone hydrochloride (CAS No.: 1193-65-3), 0.194 g (1 mmol) of 9,9-dimethylfluorene (CAS No.: 4569-45-3) and 0.54 g (2 mmol) of 2,7-dinitro-9-fluorenone (CAS No.: 31551-45-8) were dissolved in 100 mL of dichloromethane and stirred at -5°C while slowly dropping 5 mL of trifluoromethanesulfonic acid. After the addition was completed, stirring was continued for 48 hours to obtain a viscous solution, which was washed with 80 mL of pure water in turn and dried at 100°C for 10 hours to obtain 3.72 g of a light yellow nitro-containing carbon chain polymer P12a.

[0139] 1 HNMR (600 MHz, DMSO-d 6 , ppm) δH =1.43, 1.73-1.90, 3.01-3.35, 3.50,4.30, 7.10-8.00, 8.18-8.48.

[0140] 2. A method for preparing a quaternized polymer P12b, comprising the following steps: 1.5 g of polymer P12a, 1.42 g (10 mmol) of iodomethane and 1.382 g (10 mmol) of potassium carbonate were dissolved in 12 mL of dimethyl sulfoxide and stirred at 25°C for 10 hours. After the reaction was completed, the obtained product was washed three times with 50 mL of pure water and dried at 100°C for 10 hours to obtain 1.77 g of light yellow powdered quaternized polymer P12b.

[0141] 1 HNMR (600 MHz, DMSO-d 6 , ppm)δH =1.44,1.77-2.03, 3.14, 3.22-3.40,3.51, 4.43, 7.14-7.72, 8.20-8.45.

[0142]

[0143] Where D 1 , D 2 express Group, x, y represent only arbitrary natural numbers.

[0144] 3. Take 100 mg of polymer P12b and dissolve it in a mixed solution of 0.5 mL of dimethyl sulfoxide and 2 mL of ethanol. After dissolution, filtration and centrifugation, an ionomer solution, i.e., an adhesive solution, is obtained. The adhesive and nickel-iron catalyst powder are configured into a slurry and sprayed on a nickel foam electrode. The nickel foam electrode is immersed in Fenton's reagent at 80°C for 600 hours, and no catalyst shedding is observed, indicating that the adhesive has good anti-free radical properties.

[0145] Embodiment 13 1. A method for preparing a nitro-containing carbon chain polymer P13a, comprising the following steps: 1.388 g (9 mmol) of biphenyl (CAS No.: 92-52-4), 1.616 g (10 mmol) of 3-quinuclidinone hydrochloride (CAS No.: 1193-65-3), 0.194 g (1 mmol) of 9,9-dimethylfluorene (CAS No.: 4569-45-3), 0.031 g (0.1 mmol) of 1,3,5-triphenylbenzene (CAS No.: 612-71-5) and 0.270 g (1 mmol) of 2,7-dinitro-9-fluorenone (CAS No.: 31551-45-8) were dissolved in 100 mL of dichloromethane and stirred at -5 °C while slowly adding 5 mL of trifluoromethanesulfonic acid dropwise. After the addition was completed, stirring was continued for 48 hours to obtain a viscous solution, which was washed with 80 mL of pure water in sequence and dried at 100° C. for 10 hours to obtain 3.22 g of a light yellow nitro-containing carbon chain polymer P13a.

[0146] 1 HNMR (600 MHz, DMSO-d 6 , ppm) δH = 1.44,1.73-1.90, 3.09-3.18, 3.44,4.25, 7.25-7.53, 8.26, 8.37.

[0147] 2. A method for preparing a quaternized polymer P13b, comprising the following steps: 1.5 g of polymer P13a, 1.42 g (10 mmol) of iodomethane and 1.382 g (10 mmol) of potassium carbonate were dissolved in 12 mL of dimethyl sulfoxide and stirred at 25°C for 10 hours. After the reaction was completed, the obtained product was washed three times with 50 mL of pure water and dried at 100°C for 10 hours to obtain 1.63 g of light yellow powdered quaternized polymer P13b.

[0148] 1 HNMR (600 MHz, DMSO-d 6, ppm)δH =1.44,1.77-2.03, 3.14, 3.22-3.40,3.51, 4.43, 7.14-7.72, 8.26, 8.37.

[0149]

[0150] In the formula, E 1 、E 2 、E 3 express Group, x, y represent only arbitrary natural numbers.

[0151] 100 mg of polymer P13b was dissolved in a mixed solution of 0.5 mL of dimethyl sulfoxide and 2 mL of ethanol. After dissolution, filtration and centrifugation, an ionomer solution, i.e., an adhesive solution, was obtained. The adhesive and nickel-iron catalyst powder were configured into a slurry and sprayed on a nickel foam electrode. The nickel foam electrode was immersed in Fenton's reagent at 80°C for 600 hours, and no catalyst shedding was observed, indicating that the adhesive has good anti-free radical properties. Example 14 1. A method for preparing a nitro-containing carbon chain polymer P14a, comprising the following steps: 1.542 g (10 mmol) of biphenyl (CAS No.: 92-52-4), 1.616 g (10 mmol) of 3-quinuclidinone hydrochloride (CAS No.: 1193-65-3), 0.168 g (1 mmol) of dibenzofuran (CAS No.: 132-64-9) and 0.54 g (2 mmol) of 2,7-dinitro-9-fluorenone (CAS No.: 31551-45-8) were dissolved in 100 mL of dichloromethane and stirred at -5°C while slowly dropping 5 mL of trifluoromethanesulfonic acid. After the addition was completed, stirring was continued for 46 hours to obtain a viscous solution, which was washed with 80 mL of pure water in turn and dried at 100°C for 10 hours to obtain 3.58 g of a light yellow nitro-containing carbon chain polymer P14a.

[0152] 1 HNMR (600 MHz, DMSO-d 6 , ppm) δH =1.75-1.95, 3.05-3.32, 3.54, 4.32, 7.12-8.05, 8.25-8.49.

[0153] 2. A method for preparing the quaternized polymer P14b comprises the following steps: 1.5 g of polymer P14a, 1.42 g (10 mmol) of iodomethane and 1.382 g (10 mmol) of potassium carbonate were dissolved in 12 mL of dimethyl sulfoxide and stirred at 25°C for 10 hours. After the reaction was completed, the obtained product was washed three times with 50 mL of pure water and dried at 100°C for 10 hours to obtain 1.81 g of light yellow powdered quaternized polymer P14b.

[0154] 1 HNMR (600 MHz, DMSO-d 6 , ppm)δH =1.76-2.02, 3.15, 3.23-3.41, 3.56,4.46, 7.11-7.73, 8.25-8.47.

[0155]

[0156] Where D 1 , D 2 express Group, x, y represent only arbitrary natural numbers.

[0157] 3. Take 100 mg of polymer P14b and dissolve it in a mixed solution of 0.3 mL of dimethyl sulfoxide and 2 mL of ethanol. After dissolution, filtration and centrifugation, an ionomer solution, i.e., an adhesive solution, is obtained. The adhesive and nickel-iron catalyst powder are configured into a slurry and sprayed on a nickel foam electrode. The nickel foam electrode is immersed in Fenton's reagent at 80°C for 600 hours, and no catalyst shedding is observed, indicating that the adhesive has good anti-free radical properties.

[0158] Embodiment 15 1. A method for preparing a nitro-containing carbon chain polymer P15a, comprising the following steps: 2.303g (10mmol) of p-terphenyl (CAS No.: 92-94-4), 1.616g (10mmol) of 3-quinuclidinone hydrochloride (CAS No.: 1193-65-3) and 0.384g (2mmol) of 4-nitrophthalimide (CAS No.: 89-40-7) were dissolved in 100mL of dichloromethane, stirred at -5°C, and 5mL of trifluoromethanesulfonic acid was slowly added dropwise. After the addition was completed, stirring was continued for 48 hours to obtain a viscous solution, which was washed with 80mL of pure water in turn and dried at 100°C for 10 hours to obtain 3.98g of a light yellow nitro-containing carbon chain polymer P15a.

[0159] 1 HNMR (600 MHz, DMSO-d 6, ppm) δH = 1.74-1.91, 3.08-3.17, 3.42, 4.24, 7.21-7.77, 8.45-8.61.

[0160] 2. A method for preparing the quaternized polymer P15b comprises the following steps: 1.5 g of polymer P15a, 1.42 g (10 mmol) of iodomethane and 1.382 g (10 mmol) of potassium carbonate were dissolved in 12 mL of dimethyl sulfoxide and stirred at 25°C for 10 hours. After the reaction was completed, the obtained product was washed three times with 50 mL of pure water and dried at 100°C for 10 hours to obtain 1.71 g of light yellow powdered quaternized polymer P15b.

[0161] 1 HNMR (600 MHz, DMSO-d 6 , ppm)δH = 1.76-2.03, 3.13, 3.22-3.50, 4.43, 7.15-7.78, 8.43-8.60.

[0162]

[0163] In the formula, A represents Group, x, y represent only arbitrary natural numbers.

[0164] 3. 100 mg of polymer P15a and 20 mL of dimethyl sulfoxide were mixed evenly to obtain a polymer solution, the polymer solution was coated on a glass plate, and dried at 100°C for 15 hours. The obtained polymer film was immersed in a 1M phosphoric acid aqueous solution at room temperature for 10 hours, and the film was taken out and washed three times with pure water, and dried in an oven at 100°C under nitrogen protection for 5 hours to obtain a proton exchange membrane F15a, the tensile strength of F15a was 42.5 MPa. At 160°C, the proton conductivity of F15a was 93.9 mS / cm.

[0165] The proton exchange membrane F15a was soaked in Fenton's reagent at 80°C for 1000 hours, then taken out for drying, and soaked in 1M phosphoric acid aqueous solution at room temperature for 10 hours. The film was taken out and washed three times with pure water, and dried in an oven at 100°C under nitrogen protection. The tensile strength of the recovered membrane was 40.2MPa. At 160°C, the proton conductivity of the recovered F15a was 92.1mS / cm. This shows that the proton exchange membrane has good anti-free radical stability.

[0166] 4. Take 100 mg of polymer P15b and dissolve it in 20 mL of dimethyl sulfoxide to obtain a polymer solution. The polymer solution is coated on a glass plate, and the glass plate is dried at 120°C for 20 hours to obtain an anion exchange membrane F15b. F15b is immersed in a 1M NaOH aqueous solution at room temperature for 5 hours, and the film is taken out and washed with pure water, and dried in a 60°C oven under nitrogen protection for 10 hours to obtain an alkaline anion exchange membrane F15c. The tensile strength of F15c is 44.6 MPa. At 80°C, the conductivity of F15c is 150.3 mS / cm.

[0167] F15c was immersed in 10M NaOH aqueous solution at 80℃ for 50 days, and there was no degradation. F15c was immersed in Fenton reagent at 80℃ for 500 hours, and it was completely intact, with a mass reduction efficiency of 4.8%. This shows that the membrane has excellent anti-free radical stability. F15c was used for water electrolysis, with 8M KOH solution as the electrolyte and pure nickel foam as the cathode and anode. At 80℃ and 2V, the current density was 0.94A / cm 2 When F15c is used as a membrane in an alkaline fuel cell, the maximum power density of the cell is 2.53 W / cm at 80 °C and 2 atmospheres with hydrogen and oxygen injection. 2 .

[0168] Example 16 1. A method for preparing a nitro-containing carbon chain polymer P16a, comprising the following steps: 2.303g (10mmol) of p-terphenyl (CAS No.: 92-94-4), 1.616g (10mmol) of 3-quinuclidinone hydrochloride (CAS No.: 1193-65-3) and 0.386g (2mmol) of 4-nitrophthalic anhydride (CAS No.: 5466-84-2) were dissolved in 100mL of dichloromethane, stirred at -5°C, and 5mL of trifluoromethanesulfonic acid was slowly added dropwise. After the addition was completed, stirring was continued for 48 hours to obtain a viscous solution, which was washed with 80mL of pure water in turn and dried at 100°C for 10 hours to obtain 3.95g of a light yellow nitro-containing carbon chain polymer P16a.

[0169] 1 HNMR (600 MHz, DMSO-d 6 , ppm) δH = 1.74-1.91, 3.08-3.17, 3.42, 4.24, 7.22-7.76, 8.40-8.62.

[0170] 2. A method for preparing a quaternized polymer P16b, comprising the following steps: 1.5 g of polymer P16a, 1.42 g (10 mmol) of iodomethane and 1.382 g (10 mmol) of potassium carbonate were dissolved in 12 mL of dimethyl sulfoxide and stirred at 25°C for 10 hours. After the reaction was completed, the obtained product was washed three times with 50 mL of pure water and dried at 100°C for 10 hours to obtain 1.77 g of light yellow powdered quaternized polymer P16b.

[0171] 1 HNMR (600 MHz, DMSO-d 6 , ppm)δH = 1.76-2.03, 3.13, 3.22-3.50, 4.43, 7.15-7.79, 8.42-8.66.

[0172]

[0173] In the formula, A represents Group, x, y represent only arbitrary natural numbers.

[0174] 3. 100 mg of polymer P16a and 20 mL of dimethyl sulfoxide were mixed evenly to obtain a polymer solution, the polymer solution was coated on a glass plate, and dried at 100°C for 15 hours. The obtained polymer film was immersed in a 1M phosphoric acid aqueous solution at room temperature for 10 hours, and the film was taken out and washed three times with pure water, and dried in an oven at 100°C under nitrogen protection for 5 hours to obtain a proton exchange membrane F16a, the tensile strength of F16a was 43.5 MPa. At 160°C, the proton conductivity of F16a was 94.9 mS / cm.

[0175] The proton exchange membrane F16a was immersed in Fenton's reagent at 80°C for 1000 hours, then taken out for drying, immersed in 1M phosphoric acid aqueous solution at room temperature for 10 hours, and the film was taken out and washed three times with pure water, and dried in an oven at 100°C under nitrogen protection. The tensile strength of the recovered membrane was 39.6MPa. At 160°C, the proton conductivity of the recovered F16a was 90.4mS / cm. This shows that the proton exchange membrane has good anti-free radical stability.

[0176] 4. Take 100 mg of polymer P16b and dissolve it in 20 mL of dimethyl sulfoxide to obtain a polymer solution. The polymer solution is coated on a glass plate, and the glass plate is dried at 120°C for 20 hours to obtain an anion exchange membrane F16b. F16b is immersed in a 1M NaOH aqueous solution at room temperature for 5 hours, and the film is taken out and washed with pure water, and dried in a 60°C oven under nitrogen protection for 10 hours to obtain an alkaline anion exchange membrane F16c. The tensile strength of F16c is 46.6 MPa. At 80°C, the conductivity of F16c is 176.5 mS / cm.

[0177] F16c was immersed in 10M NaOH aqueous solution at 80℃ for 50 days, and there was no degradation. F16c was immersed in Fenton reagent at 80℃ for 500 hours, and it was completely intact, with a mass reduction efficiency of 4.4%. This shows that the membrane has excellent anti-free radical stability. F16c was used for water electrolysis, with 8M KOH solution as the electrolyte and pure nickel foam as the cathode and anode. At 80℃ and 2V, the current density was 0.96A / cm 2 .

[0178] Embodiment 17 1. A method for preparing a nitro-containing carbon chain polymer P17a, comprising the following steps: 2.303g (10mmol) of p-terphenyl (CAS No.: 92-94-4), 1.616g (10mmol) of 3-quinuclidinone hydrochloride (CAS No.: 1193-65-3) and 0.384g (2mmol) of 6-nitroindole-2,3-dione (CAS No.: 3433-54-3) were dissolved in 100mL of dichloromethane, stirred at -5°C, and 5mL of trifluoromethanesulfonic acid was slowly added dropwise. After the addition was completed, stirring was continued for 48 hours to obtain a viscous solution, which was washed with 80mL of pure water in turn and dried at 100°C for 10 hours to obtain 3.91g of a light yellow nitro-containing carbon chain polymer P17a.

[0179] 1 HNMR (600 MHz, DMSO-d 6 , ppm) δH = 1.74-1.91, 3.08-3.17, 3.42, 4.24, 7.23-7.58, 8.11-8.21, 8.40-8.52.

[0180] 2. A method for preparing the quaternized polymer P17b comprises the following steps: 1.5 g of polymer P17a, 1.42 g (10 mmol) of iodomethane and 1.382 g (10 mmol) of potassium carbonate were dissolved in 12 mL of dimethyl sulfoxide and stirred at 25°C for 10 hours. After the reaction was completed, the obtained product was washed three times with 50 mL of pure water and dried at 100°C for 10 hours to obtain 1.78 g of light yellow powdered quaternized polymer P17b.

[0181] 1 HNMR (600 MHz, DMSO-d 6 , ppm)δH = 1.76-2.03, 3.13, 3.22-3.51, 4.43, 7.25-7.72, 8.12-8.23, 8.41-8.55.

[0182]

[0183] In the formula, A represents Group, x, y represent only arbitrary natural numbers.

[0184] 3. 100 mg of polymer P17a and 20 mL of dimethyl sulfoxide were mixed evenly to obtain a polymer solution, the polymer solution was coated on a glass plate, and dried at 100°C for 15 hours. The obtained polymer film was immersed in a 1M phosphoric acid aqueous solution at room temperature for 10 hours, and the film was taken out and washed three times with pure water, and dried in an oven at 100°C under nitrogen protection for 5 hours to obtain a proton exchange membrane F17a, the tensile strength of F17a was 45.5 MPa. At 160°C, the proton conductivity of F17a was 94.4 mS / cm.

[0185] The proton exchange membrane F17a was soaked in Fenton's reagent at 80°C for 1000 hours, then taken out for drying, and soaked in 1M phosphoric acid aqueous solution at room temperature for 10 hours. The film was taken out and washed three times with pure water, and dried in an oven at 100°C under nitrogen protection. The tensile strength of the recovered membrane was 42.1MPa. At 160°C, the proton conductivity of the recovered F17a was 92.7mS / cm. This shows that the proton exchange membrane has good anti-free radical stability.

[0186] 4. Take 100 mg of polymer P17b and dissolve it in 20 mL of dimethyl sulfoxide to obtain a polymer solution. The polymer solution is coated on a glass plate, and the glass plate is dried at 120°C for 20 hours to obtain an anion exchange membrane F17b. F17b is immersed in a 1M NaOH aqueous solution at room temperature for 5 hours, and the film is taken out and washed with pure water, and dried in a 60°C oven under nitrogen protection for 10 hours to obtain an alkaline anion exchange membrane F17c. The tensile strength of F17c is 45.8 MPa. At 80°C, the conductivity of F17c is 177.5 mS / cm.

[0187] F17c was immersed in 10M NaOH aqueous solution at 80℃ for 50 days, and there was no degradation. F17c was immersed in Fenton's reagent at 80℃ for 500 hours, and it was completely intact, with a mass reduction efficiency of 4.1%. This shows that the membrane has excellent anti-free radical stability. F17c was used for water electrolysis, with 8M KOH solution as the electrolyte and pure nickel foam as the cathode and anode. At 80℃ and 2V, the current density was 0.98A / cm 2 When F17c is used as a membrane in an alkaline fuel cell, the maximum power density of the cell is 2.51 W / cm at 80°C and 2 atmospheres with hydrogen and oxygen injection. 2 .

[0188] Embodiment 18 1. A method for preparing a nitro-containing carbon chain polymer P18, comprising the following steps: 2.303g (10mmol) of p-terphenyl (CAS No.: 92-94-4) and 1.92g (10mmol) of 4-nitrophthalimide (CAS No.: 89-40-7) were dissolved in 100mL of dichloromethane, stirred at -5°C, and 5mL of trifluoromethanesulfonic acid was slowly added dropwise. After the addition was completed, stirring was continued for 60 hours to obtain a viscous solution, which was washed with 60 mL of pure water in turn and dried at 100°C for 10 hours to obtain 4.05g of a light yellow nitro-containing carbon chain polymer P18.

[0189] 1 HNMR (600 MHz, DMSO-d 6 , ppm) δH = 7.23-7.78, 8.46-8.60.

[0190]

[0191] In the formula, A represents group, x represents any positive integer.

[0192] 2. Mix 100 mg of polymer P18 and 20 mL of dimethylformamide evenly to obtain a polymer solution. Apply the polymer solution on a glass plate and bake at 100°C for 10 hours to obtain a film F18 with a tensile strength of 43.3 MPa. F18 was immersed in Fenton's reagent at 80°C for 500 hours without any cracks and the mass reduction rate was less than 1.6%. This indicates that the film has excellent anti-free radical stability. F18 was used for electrolysis of water, with 8M KOH solution as the electrolyte and pure nickel foam as the cathode and anode. At 80°C and 2V, the current density was 0.82A / cm 2 This indicates that the membrane can absorb alkali solution in an alkaline solution environment and serve as a diaphragm of an electrolytic cell.

[0193] Embodiment 19 1. A method for preparing a nitro-containing carbon chain polymer P19, comprising the following steps: 2.303g (10mmol) of p-terphenyl (CAS No.: 92-94-4) and 1.93g (10mmol) of 4-nitrophthalic anhydride (CAS No.: 5466-84-2) were dissolved in 100mL of dichloromethane, stirred at -5°C, and 5mL of trifluoromethanesulfonic acid was slowly added dropwise. After the addition was completed, stirring was continued for 60 hours to obtain a viscous solution, which was washed with 80 mL of pure water in turn and dried at 100°C for 10 hours to obtain 4.10g of a light yellow nitro-containing carbon chain polymer P19.

[0194] 1 HNMR (600 MHz, DMSO-d 6 , ppm) δH = 7.21-7.75, 8.39-8.61.

[0195]

[0196] In the formula, A represents group, x represents any positive integer.

[0197] 100 mg of polymer P19 and 20 mL of dimethyl sulfoxide were mixed evenly to obtain a polymer solution, which was coated on a glass plate and dried at 100 ° C for 15 hours to obtain a polymer film F19a with a tensile strength of 41.6 MPa. F19a was soaked in Fenton's reagent at 80 ° C for 500 hours and then taken out for drying. The mass loss rate was less than 2.2%, indicating that F19a had excellent anti-free radical oxidation stability. F19a was soaked in 1M phosphoric acid aqueous solution at room temperature to adsorb phosphoric acid. The film was taken out and washed three times with pure water, and dried in an oven at 100 ° C under nitrogen protection to obtain a proton exchange membrane. The proton conductivity of the proton exchange membrane at 160 ° C was 112.3 mS / cm.

[0198] Comparative Example 1 1. A method for preparing a poly(terphenyl-N,N'-dimethylpiperidinyl) anion exchange membrane, comprising the following steps: 2.303g (10mmol) of p-terphenyl (CAS No.: 92-94-4) and 1.132g (10mmol) of N-methyl-4-piperidinone (CAS No.: 1445-73-4) were dissolved in 100mL of dichloromethane, stirred at -5°C, and 5mL of trifluoromethanesulfonic acid was slowly added dropwise. After the addition was completed, stirring was continued for 48 hours to obtain a viscous solution, which was washed with 80mL of pure water in turn and dried at 100°C for 10 hours to obtain 3.92g of light yellow poly(terphenyl-N-methylpiperidinyl) polymer.

[0199] 1 HNMR (600 MHz, DMSO-d 6 , ppm)δH =2.67, 2.68-2.94, 3.34-3.69,7.21-7.59.

[0200] 2. Dissolve 1.5 g of polymer, 1.42 g (10 mmol) of iodomethane and 1.382 g (10 mmol) of potassium carbonate in 12 mL of dimethyl sulfoxide, and stir the mixture at 25 °C for 10 hours. After the reaction is completed, wash the obtained product three times with 50 mL of pure water and dry it at 100 °C for 10 hours to obtain 1.83 g of light yellow powdered poly(terphenyl-N,N'-dimethylpiperidinyl) polymer.

[0201] 1 HNMR (600 MHz, DMSO-d 6 , ppm)δH =2.75-2.98, 3.24, 3.38-3.74,7.14-7.78.

[0202]

[0203] 3. Take 100 mg of polymer and dissolve it in 20 mL of dimethyl sulfoxide to obtain a polymer solution, apply the polymer solution on a glass plate, and bake the glass plate at 120°C for 20 hours to obtain an anion exchange membrane. Soak it in Fenton's reagent at 80°C for 50 hours, and the mass reduction rate is 50%.

[0204] Compared with the above examples, the mass loss of the anion exchange membrane of Comparative Example 1 when immersed in Fenton's reagent is large, indicating that the oxidation stability of the membrane is very poor without the addition of nitro compounds. Therefore, the present invention introduces nitro groups into the polymer structure by using nitro-containing ketones, and cooperates with other monomer structures to effectively enhance the antioxidant properties of the obtained product.

[0205] Comparative Example 2 100 mg of poly(terphenyl-N-methylquinic acid) polymer was dissolved in 20 mL of dimethyl sulfoxide 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 an anion exchange membrane.

[0206] It was immersed in Fenton's reagent at 80°C for 200 hours. Compared with the above examples, the mass reduction rate of the anion exchange membrane in Comparative Example 2 in Fenton's reagent was 11%, indicating that the oxidation stability of the membrane was worse without the addition of nitro compounds. Therefore, the present invention introduces nitro groups into the polymer structure by using nitro-containing ketones, and cooperates with other monomer structures to effectively enhance the antioxidant properties of the obtained product. The structural formula of the poly (terphenyl-N-methylquinine) polymer is:

[0207] The specific implementation of the present invention described above does not constitute a limitation on the protection scope of the present invention. Any other corresponding changes and modifications made based on the technical concept of the present invention should be included in the protection scope of the claims of the present invention.

Claims

1. A type of nitro-containing carbon chain polymer, characterized in that: It includes the structural unit shown in the following general formula I: I Wherein, a is any natural number ≥ 0, and b is any natural number ≥ 1; A1 and A2 are aromatic groups, each independently selected from at least one of the groups represented by the following structural formula: Among them, m1, m2, m3, m4, m5, m6, and m7 are each independently any natural number less than or equal to 20; R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 22 , R 23 , R 24 , R 25 , R 26 Any one independently selected from hydrogen, methyl, deuterated methyl, ethyl, propyl, butyl, fluorine, chlorine, bromine, trifluoromethyl, hydroxyl, methoxy, ethoxy, amino, methylamino, dimethylamino, ethylamino, diethylamino, sulfonic acid, and nitro; G1, G2, G3, G4, G5, G6, G7, G8, G9, G 10 , G 11 , G 12 , G 13 , G 14 , G 15 Independently selected from O, S, CR 27 , CR 28 R 29 NR 30 Any one of R 27 , R 28 , R 29 , R 30 Any one independently selected from hydrogen, methyl, deuterated methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl; Q is a nitrogen heterocycle, and Q is selected from at least one of the groups shown in the following structural formula: ； R1, R2, R3 are independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopropyl, isopropyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl or N,N,N-trimethylpentylammonium; B is a nitro-containing aromatic group, selected from at least one of the groups shown in the following structural formula: R 31 is any one of hydrogen, methyl, ethyl, propyl, acyl, and trifluoromethyl; Y1, Y2, Y3, Y4, Y5, Y6, and Y7 are independently selected from any one of hydrogen, fluorine, chlorine, bromine, iodine, nitro, hydroxyl, methyl, ethyl, acyl, trifluoromethyl, and phenyl; M1 and M2 are independently selected from any one of O, NR 12 Any one of R 12 Any one selected from H, methyl, ethyl, propyl, butyl, pentyl and hexyl.

2. The method for preparing a nitro-containing carbon chain polymer according to claim 1, characterized in that: The steps include: In the presence of an acid catalyst, a nitrogen heterocyclic monomer, an aromatic hydrocarbon monomer, a nitro-containing ketone monomer, and an aromatic crosslinking agent monomer undergo a Friedel-Crafts reaction to obtain a nitro-containing carbon chain polymer; wherein the molar ratio of the nitrogen heterocyclic monomer, the aromatic hydrocarbon monomer, the nitro-containing ketone monomer, and the aromatic crosslinking agent monomer is 1: (0.001-1.1): (0.001-1.1): (0-0.5); The nitrogen heterocyclic monomer is selected from at least one of the groups shown in the following structural formula: ； The aromatic hydrocarbon monomer is selected from at least one of the compounds shown in the following structural formula: The nitro-containing ketone monomer is selected from at least one of the compounds shown in the following structural formula: The aromatic crosslinking agent monomer is selected from at least one of the compounds shown in the following structural formula: ； R 32 It is any one of hydrogen, methyl, ethyl, propyl, butyl, pentyl and hexyl; o is any natural number ≥1.

3. The method for preparing a nitro-containing carbon chain polymer according to claim 2, characterized in that: The acid catalyst is selected from at least one of trifluoromethanesulfonic acid, trifluoroacetic acid, concentrated sulfuric acid, trichloroacetic acid, methanesulfonic acid, pentafluoropropionic acid, heptafluorobutyric acid and perfluorosulfonic acid resin; The molar ratio of the acid catalyst to the nitrogen heterocyclic monomer is (0.01-20): 1; The molar ratio of the nitrogen heterocyclic monomer, the aromatic hydrocarbon monomer and the nitro-containing ketone monomer is 1:(0.1-1.1):(0.1-1.1).

4. A quaternary ammonium salt polymer, characterized in that: The structure of the quaternary ammonium salt polymer is different from the structure of the nitro carbon chain polymer according to claim 1 in that the nitrogen heterocycle is a quaternized nitrogen heterocycle with the following structure: ； R4, R5, R6, and R7 are 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) n OCH3, -CH2CH2(OCH2CH2) n Any one of OCH2CH3, wherein n is a natural number.

5. A method for preparing a quaternary ammonium salt polymer as claimed in claim 4, characterized in that: The method comprises the following steps: in the presence of base A or in the absence of base, the nitro-containing carbon chain polymer is subjected to quaternization reaction with a monohalogenated compound, wherein the molar ratio of the monohalogenated compound to the N site in the nitro-containing carbon chain polymer is (0.5-5):1, to generate the quaternary ammonium salt polymer.

6. The method for preparing a quaternary ammonium salt polymer according to claim 5, wherein: The base A is one or more 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; The monohalogenated compound is selected from methyl iodide, deuterated methyl iodide, ethyl iodide, propyl iodide, butyl iodide, pentane iodide, hexane iodide, heptane iodide, octane iodide, nonane iodide, decane iodide, methyl bromide, deuterated methyl bromide, ethyl bromide, propyl bromide, butyl bromide, pentane bromide, hexane bromide, heptane bromide, octane bromide, nonane bromide, decane bromide, 2-bromoethylamine, 2-bromoethanol, cyclopropyl iodide, isopropyl iodide, isobutyl iodide, cyclopentyl iodide, cyclohexyl iodide and (5-bromopentyl)trimethylammonium bromide, BrCH2C(CH2OH)3, BrCH2CH2(OCH2CH2) r OCH3 and BrCH2CH2 (OCH2CH2) r At least one of OCH2CH3, wherein r is a natural number, and 0≤r≤10.

7. A type of N-site cross-linked quaternary ammonium polymer, characterized in that: The structure of the quaternary ammonium polymer is different from the quaternary ammonium salt polymer according to claim 4 in that the nitrogen sites of some nitrogen heterocycles are cross-linked by alkyl cross-linking structures, and the alkyl cross-linking structures are selected from the following structures: ， Among them, n1, n2, n3, n4, n5, n6, n7, n9, n10, n11, n12, and n13 are all natural numbers not greater than 30, n8 is a natural number from 2 to 6, Ar1 and Ar2 are at least one of phenyl, naphthyl, anthracenyl, furanyl, thienyl, and pyridyl, and R8 and R9 are at least one of hydrogen, fluorine, chlorine, methyl, ethyl, propyl, hydroxide, methoxy, and hydroxymethyl.

8. A method for preparing the N-site cross-linked quaternary ammonium polymer as claimed in claim 7, characterized in that: The steps include: In the presence of base B or in the absence of base, the nitro carbon chain polymer and the polyhalogenated compound undergo a quaternary ammonium crosslinking reaction, wherein the nitrogen sites participating in the quaternary ammonium crosslinking reaction account for 0.001 to 50% of all nitrogen sites. After the reaction is completed, a partially quaternary ammonium crosslinked intermediate polymer is obtained, and the remaining nitrogen sites of the intermediate polymer are subjected to a quaternary ammonium non-crosslinking reaction with a monohalogenated compound to obtain the N-site crosslinked quaternary ammonium polymer; Alternatively, the nitro carbon chain polymer and the monohalogenated compound are subjected to a quaternary ammonium non-crosslinking reaction in the presence of base B or in the absence of base, and the nitrogen sites participating in the quaternary ammonium non-crosslinking reaction account for 0.50 to 99.999% of all nitrogen sites. After the reaction is completed, a partially quaternary ammonium intermediate polymer is obtained, and the remaining nitrogen sites of the intermediate polymer are subjected to a quaternary ammonium crosslinking reaction with a polyhalogenated compound to obtain the N-site crosslinked quaternary ammonium polymer; Alternatively, in the presence of base B or in the absence of base, the nitro-containing carbon chain polymer is subjected to quaternization reaction with a polyhalogenated compound and a monohalogenated compound simultaneously, and the nitrogen sites participating in the quaternization cross-linking reaction account for 0.0001 to 50% of all nitrogen sites. After the reaction is completed, the N-site cross-linked quaternary ammonium polymer is obtained.

9. The method for preparing the N-site cross-linked quaternary ammonium polymer according to claim 8, characterized in that: The base B 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; The monohalogenated compound is selected from methyl iodide, deuterated methyl iodide, ethyl iodide, propyl iodide, butyl iodide, pentane iodide, hexane iodide, heptane iodide, octane iodide, nonane iodide, decane iodide, methyl bromide, deuterated methyl bromide, ethyl bromide, propyl bromide, butyl bromide, pentane bromide, hexane bromide, heptane bromide, octane bromide, nonane bromide, decane bromide, 2-bromoethylamine, 2-bromoethanol, cyclopropyl iodide, isopropyl iodide, isobutyl iodide, cyclopentyl iodide, cyclohexyl iodide and (5-bromopentyl)trimethylammonium bromide, BrCH2C(CH2OH)3, BrCH2CH2(OCH2CH2) r OCH3 and BrCH2CH2 (OCH2CH2) r At least one of OCH2CH3, wherein r is a natural number, and 0≤r≤10; The polyhalogenated compound is selected from one or more of the following structures: ； Among them, X1, X2, X3, X4, X5, X6, X7, X8, X9, X 10 , X 11 , X 12 , X 13 , X 14 , X15, X 16 , X 17 is F, Cl, Br, I or hydroxyl.

10. A polymer adhesive, characterized in that: Prepared by the following method: Uniformly dispersing at least one of the quaternary ammonium salt polymer according to claim 4 and the N-site cross-linked quaternary ammonium polymer according to claim 7 in a solvent to obtain a polymer adhesive; The mass concentration of the polymer adhesive is 0.01% to 80%.

11. A polymer film, characterized in that: Prepared by the following method: At least one of the nitro carbon chain polymer described in claim 1, the quaternary ammonium salt polymer described in claim 4, and the N-site cross-linked quaternary ammonium polymer described in claim 7 is dissolved in an organic solvent to obtain a polymer solution with a mass concentration of 0.01% to 80%, and the polymer solution is cast or cast on a substrate and dried to obtain the polymer film.

12. A proton exchange membrane, characterized in that: Prepared by the following method: The polymer film of claim 11 is immersed in a phosphoric acid aqueous solution with a concentration of 0.1 to 20 mol / L and an immersion temperature of 0 to 90° C. After the immersion is completed, it is washed with pure water and dried to obtain the proton exchange membrane.

13. An application of the polymer adhesive according to claim 10, the polymer film according to claim 11 or the proton exchange membrane according to claim 12 in fuel cells, hydrogen production by electrolysis of water, metal-air batteries, flow batteries, carbon dioxide reduction, supercapacitors, nickel-hydrogen batteries, zinc-manganese batteries, acid separation, lithium extraction from salt lakes, electrodialysis, water treatment, and membrane humidification.

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