WO2020238732A1 - Heterocyclic ammonium polybenzimidazole and anion exchange membrane, and preparation method and application thereof - Google Patents

Heterocyclic ammonium polybenzimidazole and anion exchange membrane, and preparation method and application thereof Download PDF

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WO2020238732A1
WO2020238732A1 PCT/CN2020/091453 CN2020091453W WO2020238732A1 WO 2020238732 A1 WO2020238732 A1 WO 2020238732A1 CN 2020091453 W CN2020091453 W CN 2020091453W WO 2020238732 A1 WO2020238732 A1 WO 2020238732A1
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polybenzimidazole
heterocyclic ammonium
ammonium ion
membrane
exchange membrane
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朱秀玲
刘品阳
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大连理工大学
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/18—Polybenzimidazoles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/428—Membrane capacitive deionization
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/422—Electrodialysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/12—Macromolecular compounds
    • B01J41/13—Macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/08—Seawater, e.g. for desalination
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the invention relates to a heterocyclic ammonium ion polybenzimidazole and an anion exchange membrane and its preparation method and application, belonging to the technical field of polymer electrolytes and ion exchange membranes.
  • polybenzimidazole exhibits excellent mechanical stability, heat resistance and alkali resistance. It has attracted the attention of more and more researchers. It is used in ionic membranes for fuel cells and energy storage batteries. Applications in other fields have attracted attention.
  • polybenzimidazole is mostly used for high-temperature proton membranes.
  • the patent [Wang Lei et al., Patent Publication No.: CN 106684415 A] discloses the preparation of a PBI-doped phosphoric acid high-temperature proton membrane.
  • the patent [Lu Jinbo, etc., Patent Publication No. : CN 107887626 A] discloses a cross-linked composite high-temperature proton membrane and its preparation method.
  • the patent [Yan Xiaoming et al., Patent Publication No.: CN 107674417 A] discloses a non-ionic hydrophilic side chain polybenzo Imidazole and its preparation method. However, there are few published documents about using polybenzimidazole for basic anion exchange membranes.
  • the patent [Zhu Xiuling et al., Patent Publication No.: CN 108623806 A] discloses a polybenzimidazole with pendant amino groups and its anion exchange membrane And preparation method.
  • the present invention provides a heterocyclic ring with good mechanical properties, high alkali resistance and good dimensional stability.
  • a heterocyclic ammonium ion polybenzimidazole having the following structure:
  • n 0 ⁇ 0.8;
  • Z is Cl -, Br -, or OH - ions, preferably OH - ions;
  • A is a single bond, methylene -CH 2 -, ether bond -O- or carbonyl -CO-, preferably A is a single bond or methylene -CH 2 -;
  • X takes the following structure: Wherein 2 ⁇ n' ⁇ 18, preferably X is 2 ⁇ n' ⁇ 8;
  • Y has the following structure:
  • Y is (a), (c), (e) and (f);
  • the present invention provides a preparation method of the above heterocyclic ammonium ion polybenzimidazole, which comprises the following steps:
  • the polybenzimidazole is synthesized from tetraamine monomer (II) and diacid monomer (III) through solution polycondensation.
  • A is a single bond or methylene -CH 2 -;
  • the structure of the diacid monomer (III) is as follows:
  • X takes the following structure: Wherein 2 ⁇ n' ⁇ 18, preferably X is 2 ⁇ n' ⁇ 8;
  • Y has the following structure:
  • Y is (a), (c), (e) and (f);
  • Step 2-1 synthesis of heterocyclic ammonium ion polybenzimidazole (1)
  • a certain amount of polybenzimidazole is heated and dissolved in solvent 2 to obtain a solution with a mass volume ratio of 0.5-10%.
  • Dibromopentane and basic compound 2 are added and reacted at 30-150°C for 8-100 hours.
  • the precipitating agent 1 is poured into, filtered, the filter cake is washed 3 times with deionized water, and the product is dried to obtain heterocyclic ammonium ion polybenzimidazole (1).
  • a certain amount of polybenzimidazole is heated and dissolved in solvent 2 to obtain a 0.5-10 wt% solution, and M'is added to react at 30-150°C for 8-100 hours. After the reaction is over, the precipitant 1 is poured into it, filtered, the filter cake is washed with deionized water three times, and the product is dried to obtain heterocyclic ammonium ion polybenzimidazole (2).
  • Z is an OH - ion;
  • A is a single bond or methylene -CH 2 -; in X, n is 2 ⁇ n' ⁇ 8; Y is selected from (a), (c), (e) or (f).
  • the solvent 1 is toluene, methanol, ethanol, dichloromethane, tetrahydrofuran, acetonitrile, acetone, ethyl acetate, N,N-dimethylacetamide, dimethylsulfoxide, One or a mixture of N,N-dimethylformamide and N-methylpyrrolidone;
  • the solvent 2 is one or more of toluene, dichloromethane, chloroform, N,N-dimethylacetamide, dimethylsulfoxide, N,N-dimethylformamide, and N-methylpyrrolidone Mixture of species
  • the molar ratio of polybenzimidazole to dibromopentane in step 2-1 is 0.1-1:1, preferably 0.4-1:1;
  • step 2-2 the molar ratio of piperidine to dihaloalkane P-(CH 2 ) m -P is 0.05-1:1, preferably 0.1-0.5:1;
  • the molar ratio of bisimidazole to M' is 0.1-1:1.
  • a method for preparing heterocyclic ammonium ion polybenzimidazole and its anion exchange membrane characterized in that the precipitating agent 1 is methanol, ethanol, ether, ethyl acetate, dichloromethane, tetrahydrofuran, acetone and water. kind or a mixture of several.
  • the basic compound 2 is selected from one or more of sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydride, and lithium hydride.
  • the viscosity average molecular weight of the polybenzimidazole is 10,000-450,000 g/mol, and the degree of polymerization n is 20-1200.
  • the present invention provides a method for preparing a heterocyclic ammonium ion polybenzimidazole anion exchange membrane.
  • the heterocyclic ammonium ion polybenzimidazole (1) or heterocyclic ammonium ion polybenzimidazole (2) is heated in a solvent 3. Dissolve and prepare a 1-15 wt% solution, filter, cast the filtrate on a clean plate, and then transfer it to an oven to dry.
  • the solvent 3 is selected from toluene, methanol, ethanol, dichloromethane, tetrahydrofuran, acetonitrile, acetone, ethyl acetate, N,N-dimethylacetamide, dimethylsulfoxide , N,N-dimethylformamide, N-methylpyrrolidone or a mixture of several.
  • the present invention provides the application of the heterocyclic ammonium ion polybenzimidazole as an electrolyte in fuel cells, flow batteries, water electrolysis, electrodialysis and membrane separation.
  • the present invention provides the application of the above heterocyclic ammonium ion polybenzimidazole anion exchange membrane in fuel cells, flow batteries, water electrolysis, electrodialysis and membrane separation related fields.
  • Another object of the present invention is to claim the application of the above-mentioned heterocyclic ammonium ion polybenzimidazole anion exchange membrane in fuel cells, flow batteries, electrolysis and electrodialysis, and seawater desalination plasma membranes.
  • the present invention has the following advantages: the heterocyclic ammonium ion polybenzimidazole and the anion exchange membrane and preparation method thereof prepared according to the present invention have good film forming properties, high ion conductivity, and membrane toughness. With high alkali resistance and stability, it is widely used in fuel cells, flow batteries, electrolysis and electrodialysis, and plasma membranes related to seawater desalination.
  • Ion exchange capacity test method Take 3 parts of monoammonium ion polybenzimidazole 0.1g, soak them in 100ml, 1M NaOH for 24h, and then soak in 100ml deionized water for 24h and wash with water until neutral, vacuum Dry in an oven at 60 degrees, and soak them in 0.02002M HCl for 24 hours. Add a few drops of phenolphthalein and titrate with 0.0182M NaOH to turn pink. Record the amount of NaOH needed. Subtract the moles of NaOH from the moles of HCl and divide by 0.1 (g) to get the IEC.
  • the electrochemical workstation used is produced by Shanghai Chenhua Instrument Co., Ltd., model: chi660c.
  • NMR test The NMR spectrometer used is produced by Varian Company, the model is BrukerAvance II 400, 400MHZ. In the NMR spectrum, D 2 O was used as the solvent for both salts and DMSO-d6 was used as the solvent for the polymer after grafting.
  • Table 1 shows the chemical structure of heterocyclic ammonium ion polybenzimidazole used in the examples.
  • the product is poured into a large amount of deionized water, and excess NaHCO 3 is added, and the mixture is stirred overnight. Filter and wash the polymer with deionized water until neutral. The product is dried to obtain polybenzimidazole.
  • the polymer product (1) was dissolved in DMSO to prepare a 4 wt% solution, vacuumed for 0.5 h, filtered, and the filtrate was cast on a clean flat plate to spread a film, and then transferred to an oven at 60°C for drying.
  • the prepared membrane was immersed in a 1M NaOH solution for 24 hours, taken out and soaked in water for 24 hours, taken out and dried to obtain a diammonium ion PBI anion membrane.
  • the OH - conductivity of the bisammonium PBI anion membrane at 80°C is 42mS/cm, and the ionic membrane has good toughness. After being soaked in a 1M KOH solution at 80°C for 1000h, the OH - ion conductivity remains 85%.
  • the product is poured into a large amount of deionized water, and excess NaHCO 3 is added, and the mixture is stirred overnight. Filter and wash the polymer with deionized water until neutral. The product is dried to obtain polybenzimidazole.
  • the polymer product (1) was dissolved in DMSO to prepare a 4 wt% solution, vacuumed for 0.5 h, filtered, and the filtrate was cast on a clean flat plate to spread a film, and then transferred to an oven at 60°C for drying.
  • the prepared membrane was immersed in a 1M NaOH solution for 24 hours, taken out and soaked in water for 24 hours, taken out and dried to obtain a diammonium ion PBI anion membrane.
  • the OH - conductivity of the diammonium PBI anion membrane at 80°C is 40mS/cm, and the ionic membrane has good toughness. After immersing in a 1M KOH solution at 80°C for 1400h, the OH - ion conductivity remains 85%.
  • the above product (1) was dissolved in chloroform to prepare a 10 wt% solution, vacuumed for 0.5 h, filtered, and the filtrate was cast on a clean flat plate to spread a film, and then transferred to an oven at 60°C for drying.
  • the prepared membrane was immersed in a 1M NaOH solution for 24 hours, taken out and soaked in water for 24 hours, taken out and dried to obtain a diammonium ion PBI anion membrane.
  • the OH - conductivity of the diammonium ion PBI anion membrane at 80°C is 45mS/cm, and the ionic membrane has good toughness. After immersing in a 1M KOH solution at 80°C for 1300h, the OH - ion conductivity remains 87%.
  • the synthesis of the main chain polybenzimidazole is the same as in Example 2, wherein the oxalic acid and terephthalic acid are replaced with pimelic acid and diphenyl ether diacid.
  • the above-mentioned product (1) was dissolved in dimethyl sulfoxide (DMSO) to prepare a 6 wt% solution, vacuumed for 0.5 h, filtered, and the filtrate was cast on a clean plate to spread a film, and then transferred to an oven at 60°C for drying.
  • the prepared membrane was immersed in a 1M NaOH solution for 24 hours, taken out and soaked in water for 24 hours, taken out and dried to obtain a diammonium ion PBI anion membrane.
  • the OH - conductivity of the diammonium PBI anion membrane at 80°C is 42mS/cm, and the ionic membrane has good toughness. After being immersed in a 1M KOH solution at 80°C for 1300h, the OH - ion conductivity remains 85%.
  • the synthesis of the main chain polybenzimidazole is the same as in Example 2, wherein the oxalic acid and terephthalic acid are replaced with adipic acid and diphenylmethanedioic acid.
  • the above product (2) was dissolved in N-methylpyrrolidone (NMP) to prepare a 4wt% solution, vacuumed for 0.5h, filtered, and the filtrate was cast on a clean flat plate and then transferred to an oven at 60°C for drying.
  • NMP N-methylpyrrolidone
  • the prepared membrane was immersed in a 1M NaOH solution for 24 hours, taken out and soaked in water for 24 hours, taken out and dried to obtain a diammonium ion PBI anion membrane.
  • the OH - conductivity of the diammonium ion PBI anion membrane at 80°C is 40mS/cm, and the ionic membrane has good toughness. After immersing in a 1M KOH solution at 80°C for 1200h, the OH - ion conductivity remains 85%.
  • the above product (1) was dissolved in NMP to prepare a 6 wt% solution, vacuumed for 0.5 h, filtered, and the filtrate was cast on a clean flat plate to spread a film, and then transferred to an oven at 60° C. for drying.
  • the prepared membrane was immersed in a 1M NaOH solution for 24 hours, taken out and soaked in water for 24 hours, taken out and dried to obtain a diammonium ion PBI anion membrane.
  • the OH - conductivity of the bisammonium PBI anion membrane at 80°C is 42mS/cm, and the ionic membrane has good toughness. After immersing in 1M KOH solution at 80°C for 1350h, the OH - ion conductivity remains 86%.
  • the synthesis of the main chain polybenzimidazole is the same as in Example 1, wherein the succinic acid and the biphthalic acid are replaced with malonic acid and diphenyl ether diacid.
  • the above product (1) was dissolved in N,N-dimethylacetamide (DMAc) to prepare a 10wt% solution, vacuumed for 0.5h, filtered, and the filtrate was cast on a clean flat plate and then transferred to an oven at 60°C for drying.
  • the prepared membrane was immersed in a 1M NaOH solution for 24 hours, taken out and soaked in water for 24 hours, taken out and dried to obtain a diammonium ion PBI anion membrane.
  • the OH - conductivity of the diammonium ion PBI anion membrane at 80°C is 40mS/cm, and the ionic membrane has good toughness. After immersing in a 1M KOH solution at 80°C for 1400h, the OH - ion conductivity remains 84%.
  • the synthesis of the main chain polybenzimidazole is the same as in Example 2, wherein the oxalic acid and terephthalic acid are replaced with suberic acid and terephthalic acid.
  • the above product (1) was dissolved in DMAc to prepare a 12 wt% solution, vacuumed for 0.5 h, filtered, and the filtrate was cast on a clean flat plate to spread a film, and then transferred to an oven at 60°C for drying.
  • the prepared membrane was immersed in a 1M NaOH solution for 24 hours, taken out and soaked in water for 24 hours, taken out and dried to obtain a diammonium ion PBI anion membrane.
  • the OH - conductivity of the diammonium ion PBI anion membrane at 80°C is 50mS/cm, and the ionic membrane has good toughness. After being soaked in a 1M KOH solution at 80°C for 1300h, the OH - ion conductivity remains 87%.
  • the synthesis of the main chain polybenzimidazole is the same as in Example 2, wherein the oxalic acid and terephthalic acid are replaced with diphenyl ether diacid.
  • the above-mentioned product (1) was dissolved in DMSO to prepare a 10 wt% solution, vacuumed for 0.5 h, filtered, and the filtrate was cast on a clean flat plate to spread a film, and then transferred to an oven at 60°C for drying.
  • the prepared membrane was immersed in a 1M NaOH solution for 24 hours, taken out and soaked in water for 24 hours, taken out and dried to obtain a diammonium ion PBI anion membrane.
  • the OH - conductivity of the bisammonium PBI anion membrane at 80°C is 45mS/cm, and the ionic membrane has good toughness. After immersing in a 1M KOH solution at 80°C for 1200h, the OH - ion conductivity remains 86%.
  • Figure 1 is the hydrogen nuclear magnetic spectrum of the main chain spirocyclic benzimidazole anion exchange membrane, the solvent is DMSO-d6, and the frequency of the nuclear magnetic instrument is 400MHz.
  • the frequency of the nuclear magnetic instrument is 400MHz.
  • the main chain imidazole NH was successfully cyclized into a spiro ring structure.
  • the chemical shifts at 3.51 ppm and 2.41 ppm are characteristic peaks of trace water molecules and solvent DMSO molecules.
  • the chemical shifts of 8.30 and 7.36 ppm are the characteristic peaks of H2 and H1 on the benzene ring of diphenyl ether in the polymer structural unit.
  • the chemical shifts at 7.91 ppm, 7.73 ppm, and 7.64 ppm are the characteristic peaks of H3, H4, and H5 of the benzene ring connected to the tetraamine of the polymer structural unit.
  • the chemical shift at 4.40 ppm is the characteristic peak of H6 on CH 2 which is directly connected to the N positive ion in the spiro ring
  • the chemical shift of 1.79 ppm is the characteristic peak of H7 on the N positive ion meta-position-CH 2 in the spiro ring.
  • the synthesis of the main chain polybenzimidazole is the same as in Example 2, wherein the oxalic acid and terephthalic acid are replaced with isophthalic acid.
  • the above product (1) was dissolved in NMP to prepare a 10 wt% solution, vacuumed for 0.5 h, filtered, and the filtrate was cast on a clean flat plate to spread a film, and then transferred to an oven at 60°C for drying.
  • the prepared membrane was immersed in a 1M NaOH solution for 24 hours, taken out and soaked in water for 24 hours, taken out and dried to obtain a diammonium ion PBI anion membrane.
  • the OH - conductivity of the diammonium PBI anion membrane at 80°C is 40mS/cm, and the ionic membrane has good toughness. After immersing in a 1M KOH solution at 80°C for 1300h, the OH - ion conductivity remains 84%.

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Abstract

A heterocyclic ammonium polybenzimidazole, an anion exchange membrane, and a preparation method and an application thereof, in the technical field of polyelectrolyte and ion exchange membranes. First, synthesizing a halogenated spirocyclic ammonium salt, then attracting halogenated spirocyclic ammonium onto a polybenzimidazole molecule chain by means of a grafting reaction, synthesizing heterocyclic ammonium polybenzimidazole, then undergoing alkali ion exchange, preparing a heterocyclic ammonium polybenzimidazole anion exchange membrane. Heterocyclic ammonium polybenzimidazole and an anion exchange membrane prepared according to the present method have good polymer membrane forming, high ion conductivity, significantly improved mechanical functionality and alkali resistance stability, and good dimensional stability, and can be broadly used in ion exchange membrane fields such as fuel cells, flow batteries, electrolysis and electrodialysis, and desalination.

Description

一种杂环铵离子聚苯并咪唑及阴离子交换膜其制备方法和应用Heterocyclic ammonium ion polybenzimidazole and anion exchange membrane and its preparation method and application 技术领域Technical field
本发明涉及一种杂环铵离子聚苯并咪唑及阴离子交换膜其制备方法和应用，属于高分子电解质及离子交换膜技术领域。The invention relates to a heterocyclic ammonium ion polybenzimidazole and an anion exchange membrane and its preparation method and application, belonging to the technical field of polymer electrolytes and ion exchange membranes.
背景技术Background technique
近年来，能源危机、资源枯竭引发了各行业及民生对清洁能源的迫切需求，世界各国加倍重视清洁能源的开发。燃料电池因其绿色环保、能量转化率高等一系列优点得到越来越多的科研人员的关注，同时燃料电池也取得了一系列长足的进步。碱性阴离子交换膜燃料电池作为燃料电池的一种，有无需贵金属作催化剂、水管理简单等优点，同时也面临离子传导率不高、耐碱稳定性不好的挑战，这也是本发明着力提高的地方。In recent years, the energy crisis and resource depletion have triggered an urgent need for clean energy in various industries and people's livelihoods. Countries around the world have paid more attention to the development of clean energy. Fuel cells have attracted more and more attention of scientific researchers due to their green environmental protection and high energy conversion rate. At the same time, fuel cells have also made a series of considerable progress. Alkaline anion exchange membrane fuel cell, as a kind of fuel cell, has the advantages of not requiring precious metals as catalysts and simple water management. At the same time, it also faces the challenges of low ion conductivity and poor alkali resistance stability. This is also the focus of the present invention. The place.
聚苯并咪唑作为一种优异的特种工程塑料，表现出优异的机械稳定性、耐热性及耐碱性，吸引了越来越多科研人员的关注，在燃料电池、储能电池用离子膜等领域应用受到关注。目前，聚苯并咪唑多用于高温质子膜，专利[Wang Lei等，专利公开号：CN 106684415 A]公开了一种PBI掺杂磷酸的高温质子膜的制备，专利[路金波等，专利公开号：CN 107887626 A]公开了一种交联复合型高温质子膜及其制备方法，专利[焉晓明等，专利公开号：CN 107674417 A]公开了一种非离子型亲水侧链聚苯并咪唑及其制备方法。然而，将聚苯并咪唑用于碱性阴离子交换膜的公开文献较少，专利[朱秀玲等，专利公开号：CN 108623806 A]公开了一种带侧胺基的聚苯咪唑及其阴离子交换膜及制备方法。As an excellent special engineering plastic, polybenzimidazole exhibits excellent mechanical stability, heat resistance and alkali resistance. It has attracted the attention of more and more researchers. It is used in ionic membranes for fuel cells and energy storage batteries. Applications in other fields have attracted attention. Currently, polybenzimidazole is mostly used for high-temperature proton membranes. The patent [Wang Lei et al., Patent Publication No.: CN 106684415 A] discloses the preparation of a PBI-doped phosphoric acid high-temperature proton membrane. The patent [Lu Jinbo, etc., Patent Publication No. : CN 107887626 A] discloses a cross-linked composite high-temperature proton membrane and its preparation method. The patent [Yan Xiaoming et al., Patent Publication No.: CN 107674417 A] discloses a non-ionic hydrophilic side chain polybenzo Imidazole and its preparation method. However, there are few published documents about using polybenzimidazole for basic anion exchange membranes. The patent [Zhu Xiuling et al., Patent Publication No.: CN 108623806 A] discloses a polybenzimidazole with pendant amino groups and its anion exchange membrane And preparation method.
发明内容Summary of the invention
针对目前碱性阴离子树脂及其离子交换膜存在离子传导率不高、耐碱稳定性不好的问题，本发明提供了一种具有机械性能好、耐碱性高和尺寸稳定性好的杂环铵离子聚苯并咪唑及其阴离子交换膜及其制备方法。Aiming at the problems of low ion conductivity and poor alkali resistance stability in current basic anion resins and their ion exchange membranes, the present invention provides a heterocyclic ring with good mechanical properties, high alkali resistance and good dimensional stability. Ammonium ion polybenzimidazole and its anion exchange membrane and preparation method thereof.
本发明是采用以下技术方案实现的：The present invention is realized by adopting the following technical solutions:
一种杂环铵离子聚苯并咪唑，具有以下结构：A heterocyclic ammonium ion polybenzimidazole having the following structure:
Figure PCTCN2020091453-appb-000001
Figure PCTCN2020091453-appb-000001
其中，n＝0～0.8；Among them, n=0～0.8;
Z是Cl -,Br -,或OH -离子，优选是OH -离子； Z is Cl -, Br -, or OH - ions, preferably OH - ions;
A为单键、亚甲基-CH 2-，醚键-O-或羰基-CO-，优选A为单键或亚甲基-CH 2-； A is a single bond, methylene -CH 2 -, ether bond -O- or carbonyl -CO-, preferably A is a single bond or methylene -CH 2 -;
X取以下结构：
Figure PCTCN2020091453-appb-000002
其中2≤n’≤18，优选X为2≤n’≤8； X takes the following structure:
Figure PCTCN2020091453-appb-000002
Wherein 2≤n'≤18, preferably X is 2≤n'≤8;
Y具有以下结构：Y has the following structure:
Figure PCTCN2020091453-appb-000003
Figure PCTCN2020091453-appb-000003
优选Y是(a),(c),(e)和(f)；Preferably Y is (a), (c), (e) and (f);
本发明提供上述杂环铵离子聚苯并咪唑的制备方法，包含以下步骤：The present invention provides a preparation method of the above heterocyclic ammonium ion polybenzimidazole, which comprises the following steps:
步骤1，聚苯并咪唑的合成 Step 1. Synthesis of polybenzimidazole
所述聚苯并咪唑是由四胺单体(Ⅱ)和二酸单体(Ⅲ)通过溶液缩聚反应合成。The polybenzimidazole is synthesized from tetraamine monomer (II) and diacid monomer (III) through solution polycondensation.
所述四胺单体(Ⅱ)的结构如下：The structure of the tetraamine monomer (II) is as follows:
Figure PCTCN2020091453-appb-000004
Figure PCTCN2020091453-appb-000004
其中，A为单键或亚甲基-CH 2-； Wherein, A is a single bond or methylene -CH 2 -;
所述二酸单体(Ⅲ)的结构如下：The structure of the diacid monomer (III) is as follows:
HOOC-X-COOH和HOOC-Y-COOHHOOC-X-COOH and HOOC-Y-COOH
其中，X取以下结构：
Figure PCTCN2020091453-appb-000005
其中2≤n’≤18，优选X为2≤n’≤8； Among them, X takes the following structure:
Figure PCTCN2020091453-appb-000005
Wherein 2≤n'≤18, preferably X is 2≤n'≤8;
Y具有以下结构：Y has the following structure:
Figure PCTCN2020091453-appb-000006
Figure PCTCN2020091453-appb-000006
优选Y是(a),(c),(e)和(f)；Preferably Y is (a), (c), (e) and (f);
在带搅拌的反应器中加入多聚磷酸，在N 2保护下，加入四胺单体(Ⅱ)和等摩尔比的二酸单体(Ⅲ)HOOC-X-COOH和HOOC-Y-COOH，搅拌溶解，使单体Ⅱ和Ⅲ的总质量浓度为1-20wt％。升温到90～140℃搅拌反应0.5～10h，然后升温到140～160℃搅拌反应0.5～10h，升温到160～190℃反应8～30h。聚合反应结束，将产物倒入大量去离子水中，加入过量NaHCO 3，搅拌过夜。过滤，用去离子水洗聚合物直至中性。产物干燥，得到聚苯并咪唑。 Add polyphosphoric acid into a stirred reactor. Under the protection of N 2 , add tetraamine monomer (Ⅱ) and diacid monomer (Ⅲ) HOOC-X-COOH and HOOC-Y-COOH in equal molar ratio. Stir and dissolve so that the total mass concentration of monomers II and III is 1-20 wt%. The temperature is raised to 90-140°C and the reaction is stirred for 0.5-10h, then the temperature is raised to 140-160°C and the reaction is stirred for 0.5-10h, and the temperature is raised to 160-190°C for 8-30h. After the polymerization reaction is over, the product is poured into a large amount of deionized water, and excess NaHCO 3 is added, and the mixture is stirred overnight. Filter and wash the polymer with deionized water until neutral. The product is dried to obtain polybenzimidazole.
步骤2-1,杂环铵离子聚苯并咪唑(1)的合成Step 2-1, synthesis of heterocyclic ammonium ion polybenzimidazole (1)
将一定量聚苯并咪唑在溶剂2中加热溶解得到质量体积比浓度0.5～10％溶液，加入二溴戊烷和碱性化合物2，在30～150℃反应8～100h。反应结束，倒入沉淀剂1，过滤，滤饼用去离子水洗3次，产物干燥，得到杂环铵离子聚苯并咪唑(1)。A certain amount of polybenzimidazole is heated and dissolved in solvent 2 to obtain a solution with a mass volume ratio of 0.5-10%. Dibromopentane and basic compound 2 are added and reacted at 30-150°C for 8-100 hours. After the reaction is over, the precipitating agent 1 is poured into, filtered, the filter cake is washed 3 times with deionized water, and the product is dried to obtain heterocyclic ammonium ion polybenzimidazole (1).
步骤2-2,杂环铵离子聚苯并咪唑(2)的合成Step 2-2, Synthesis of heterocyclic ammonium ion polybenzimidazole (2)
将一定量哌啶加入到含二卤代烷P-(CH 2) m-P(P是Cl或Br原子，0＜m≤6的整数，优选2≤m≤3)的溶剂2中，升温到30～90℃搅拌反应6～72h。反应结束，过滤，干燥得到M’； Add a certain amount of piperidine to solvent 2 containing dihaloalkane P-(CH 2 ) m -P (P is Cl or Br atom, 0<m≤6 integer, preferably 2≤m≤3), and raise the temperature to 30 Stir the reaction at ~90°C for 6~72h. After the reaction is over, filter and dry to obtain M';
将一定量聚苯并咪唑在溶剂2中加热溶解得到0.5～10wt％溶液，加入M’，在30～150℃反应8～100h。反应结束，倒入沉淀剂1，过滤，滤饼用去离子水洗3次，产物干燥，得到杂环铵离子聚苯并咪唑(2)。A certain amount of polybenzimidazole is heated and dissolved in solvent 2 to obtain a 0.5-10 wt% solution, and M'is added to react at 30-150°C for 8-100 hours. After the reaction is over, the precipitant 1 is poured into it, filtered, the filter cake is washed with deionized water three times, and the product is dried to obtain heterocyclic ammonium ion polybenzimidazole (2).
进一步地，在上述技术方案中，Z是OH -离子；A为单键或亚甲基-CH 2-；X中n为2≤n’≤8；Y选自(a),(c),(e)或(f)。 Further, in the above technical solution, Z is an OH - ion; A is a single bond or methylene -CH 2 -; in X, n is 2≤n'≤8; Y is selected from (a), (c), (e) or (f).
进一步地，在上述技术方案中，所述溶剂1是甲苯、甲醇、乙醇、二氯甲烷、四氢呋喃、乙腈、丙酮、乙酸乙酯、N，N-二甲基乙酰胺、二甲基亚砜、N，N-二甲基甲酰胺、N-甲基吡咯烷酮中的一种或几种的混合物；Further, in the above technical solution, the solvent 1 is toluene, methanol, ethanol, dichloromethane, tetrahydrofuran, acetonitrile, acetone, ethyl acetate, N,N-dimethylacetamide, dimethylsulfoxide, One or a mixture of N,N-dimethylformamide and N-methylpyrrolidone;
所述溶剂2是甲苯、二氯甲烷、氯仿、N，N-二甲基乙酰胺、二甲基亚砜、N，N-二甲基甲酰胺、N-甲基吡咯烷酮中的一种或几种的混合物；The solvent 2 is one or more of toluene, dichloromethane, chloroform, N,N-dimethylacetamide, dimethylsulfoxide, N,N-dimethylformamide, and N-methylpyrrolidone Mixture of species
进一步地，在上述技术方案中，步骤2-1中聚苯并咪唑与二溴戊烷的摩尔比是0.1～1:1，优选是0.4～1:1；Further, in the above technical solution, the molar ratio of polybenzimidazole to dibromopentane in step 2-1 is 0.1-1:1, preferably 0.4-1:1;
进一步地，在上述技术方案中，步骤2-2中，哌啶与二卤烷烃P-(CH 2) m-P的摩尔比是0.05～1:1，优选为0.1～0.5:1；聚苯并咪唑与M’的摩尔比是0.1～1:1。 Further, in the above technical scheme, in step 2-2, the molar ratio of piperidine to dihaloalkane P-(CH 2 ) m -P is 0.05-1:1, preferably 0.1-0.5:1; The molar ratio of bisimidazole to M'is 0.1-1:1.
一种杂环铵离子聚苯并咪唑及其阴离子交换膜的制备方法，其特征在于，所述沉淀剂1是甲醇、乙醇、乙醚、乙酸乙酯、二氯甲烷、四氢呋喃、丙酮和水中的一种或几种的混合物。A method for preparing heterocyclic ammonium ion polybenzimidazole and its anion exchange membrane, characterized in that the precipitating agent 1 is methanol, ethanol, ether, ethyl acetate, dichloromethane, tetrahydrofuran, acetone and water. Kind or a mixture of several.
所述碱性化合物2选自碳酸氢钠、碳酸氢钾、碳酸钠、碳酸钾、碳酸铯，氢化钠、氢化锂中的一种或几种。The basic compound 2 is selected from one or more of sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydride, and lithium hydride.
进一步地，在上述技术方案中，聚苯并咪唑的粘均分子量为10,000～450,000g/mol，聚合度n为20～1200。Further, in the above technical solution, the viscosity average molecular weight of the polybenzimidazole is 10,000-450,000 g/mol, and the degree of polymerization n is 20-1200.
本发明提供一种杂环铵离子聚苯并咪唑阴离子交换膜的制备方法，将上述杂环铵离子聚苯并咪唑(1)或杂环铵离子聚苯并咪唑(2)在溶剂3中加热溶解配制1～15wt％溶液，过滤，将滤液浇铸在洁净平板上铺膜，转入烘箱干燥。将制得的膜，放入1M NaOH或1M KOH溶液中24～48h，取出后用水浸泡24h，取出烘干，得到杂环铵离子聚苯并咪唑阴离子交换膜(1)或杂环铵离子聚苯并咪唑阴离子交换膜(2)。The present invention provides a method for preparing a heterocyclic ammonium ion polybenzimidazole anion exchange membrane. The heterocyclic ammonium ion polybenzimidazole (1) or heterocyclic ammonium ion polybenzimidazole (2) is heated in a solvent 3. Dissolve and prepare a 1-15 wt% solution, filter, cast the filtrate on a clean plate, and then transfer it to an oven to dry. Put the prepared membrane in 1M NaOH or 1M KOH solution for 24 to 48 hours, take it out and soak it in water for 24 hours, take it out and dry it to obtain heterocyclic ammonium ion polybenzimidazole anion exchange membrane (1) or heterocyclic ammonium ion poly Benzimidazole anion exchange membrane (2).
进一步地，在上述技术方案中，所述溶剂3选自甲苯、甲醇、乙醇、二氯甲烷、四氢呋喃、乙腈、丙酮、乙酸乙酯、N，N-二甲基乙酰胺、二甲基亚砜、N，N-二甲基甲酰胺、N-甲基吡咯烷酮中的一种或几种的混合物。Further, in the above technical solution, the solvent 3 is selected from toluene, methanol, ethanol, dichloromethane, tetrahydrofuran, acetonitrile, acetone, ethyl acetate, N,N-dimethylacetamide, dimethylsulfoxide , N,N-dimethylformamide, N-methylpyrrolidone or a mixture of several.
本发明提供上述杂环铵离子聚苯并咪唑作为电解质在燃料电池、液流电池、水电解、电渗析及膜分离中的的应用。The present invention provides the application of the heterocyclic ammonium ion polybenzimidazole as an electrolyte in fuel cells, flow batteries, water electrolysis, electrodialysis and membrane separation.
本发明提供上述杂环铵离子聚苯并咪唑阴离子交换膜在燃料电池、液流电池、水电解、电渗析及膜分离相关领域的应用。The present invention provides the application of the above heterocyclic ammonium ion polybenzimidazole anion exchange membrane in fuel cells, flow batteries, water electrolysis, electrodialysis and membrane separation related fields.
本发明的另一目的是请求保护上述一种杂环铵离子聚苯并咪唑阴离子交换膜在燃料电池、液流电池、电解及电渗析、海水淡化等离子膜相关领域的应用。Another object of the present invention is to claim the application of the above-mentioned heterocyclic ammonium ion polybenzimidazole anion exchange membrane in fuel cells, flow batteries, electrolysis and electrodialysis, and seawater desalination plasma membranes.
与现有技术相比，本发明具有以下益处：按照本发明制备的杂环铵离子聚苯并咪唑及其阴离子交换膜及其制备方法，聚合物成膜性好，离子传导率高，膜韧性和耐碱稳定性高，在燃料电池、液流电池、电解及电渗析、海水淡化等离子膜相关领域有广泛应用。Compared with the prior art, the present invention has the following advantages: the heterocyclic ammonium ion polybenzimidazole and the anion exchange membrane and preparation method thereof prepared according to the present invention have good film forming properties, high ion conductivity, and membrane toughness. With high alkali resistance and stability, it is widely used in fuel cells, flow batteries, electrolysis and electrodialysis, and plasma membranes related to seawater desalination.
附图说明Description of the drawings
图1为实施例9制备得到的主链螺环铵PBI阴离子交换膜的氢核磁谱图。1 is a hydrogen nuclear magnetic spectrum of the main chain spirocyclic ammonium PBI anion exchange membrane prepared in Example 9.
具体实施方式Detailed ways
以下通过实施例进一步说明详细本发明一种杂环铵离子聚苯并咪唑阴离子交换膜及其制备方法及应用，但不用于限制本发明的保护范围，如无特殊说明，本发明所涉及化学试剂及药品均市售可得，如无特殊说明，所涉及的方法均是常规方法。The following examples further illustrate a heterocyclic ammonium ion polybenzimidazole anion exchange membrane of the present invention and its preparation method and application, but are not used to limit the scope of protection of the present invention. Unless otherwise specified, the chemical reagents involved in the present invention And drugs are commercially available, unless otherwise specified, the methods involved are conventional methods.
实施例所涉及的测试方法：Test methods involved in the embodiment:
离子交换容量(IEC)测试方法：取3份单铵离子聚苯并咪唑0.1g左右，分别浸泡在100ml，1M的NaOH中24h，再分别用100ml去离子水浸泡24h并水洗至中性，真空烘箱60度烘干，分别将其浸泡到0.02002M的HCl中24h。加入几滴酚酞，用0.0182M的NaOH滴定变成粉红色，记录所需NaOH的用量。用HCl摩尔数减去NaOH摩尔数再除以0.1(g)，即为IEC。Ion exchange capacity (IEC) test method: Take 3 parts of monoammonium ion polybenzimidazole 0.1g, soak them in 100ml, 1M NaOH for 24h, and then soak in 100ml deionized water for 24h and wash with water until neutral, vacuum Dry in an oven at 60 degrees, and soak them in 0.02002M HCl for 24 hours. Add a few drops of phenolphthalein and titrate with 0.0182M NaOH to turn pink. Record the amount of NaOH needed. Subtract the moles of NaOH from the moles of HCl and divide by 0.1 (g) to get the IEC.
实施例所涉及的测试仪器：Test equipment involved in the embodiment:
导电率测试：所用电化学工作站由上海辰华仪器有限公司出产，型号：chi660c。Conductivity test: The electrochemical workstation used is produced by Shanghai Chenhua Instrument Co., Ltd., model: chi660c.
核磁测试：所用核磁共振波谱仪是美国瓦里安公司出产，型号是BrukerAvance II 400，400MHZ。核磁谱图中，两种盐都是用D 2O做为溶剂，接枝后聚合物用的是DMSO-d6做为溶剂。 NMR test: The NMR spectrometer used is produced by Varian Company, the model is BrukerAvance II 400, 400MHZ. In the NMR spectrum, D 2 O was used as the solvent for both salts and DMSO-d6 was used as the solvent for the polymer after grafting.
表1 是实施例中采用的杂环铵离子聚苯并咪唑的化学结构。Table 1 shows the chemical structure of heterocyclic ammonium ion polybenzimidazole used in the examples.
表1Table 1
Figure PCTCN2020091453-appb-000007
Figure PCTCN2020091453-appb-000007
Figure PCTCN2020091453-appb-000008
Figure PCTCN2020091453-appb-000008
实施例1Example 1
在带搅拌的反应器中加入多聚磷酸，在N 2保护下，加入联苯四胺甲烷(A取亚甲基-CH 2-)和丁二酸和联苯二酸(丁二酸和联苯二酸的总摩尔数等于联苯四胺甲烷的摩尔数)，加热搅拌溶解，使单体浓度为10wt％。升温到110℃搅拌反应5h，140℃反应0.5h，然后升温到180℃反应8h，直至体系粘度不再增加。聚合结束，将产物倒入大量去离子水中，加入过量NaHCO 3，搅拌过夜。过滤，用去离子水洗聚合物直至中性。产物干燥，得到聚苯并咪唑。 Add polyphosphoric acid in a stirred reactor, under the protection of N 2 , add biphenyltetramine methane (A is methylene -CH 2 -) and succinic acid and biphthalic acid (succinic acid and biphthalic acid) The total number of moles of phthalic acid is equal to the number of moles of benzhydryl methane), heated and stirred to dissolve, so that the monomer concentration is 10 wt%. The temperature was raised to 110°C and stirred for 5 hours, 140°C was reacted for 0.5 hours, and then the temperature was raised to 180°C for 8 hours, until the viscosity of the system no longer increased. After the polymerization is over, the product is poured into a large amount of deionized water, and excess NaHCO 3 is added, and the mixture is stirred overnight. Filter and wash the polymer with deionized water until neutral. The product is dried to obtain polybenzimidazole.
将10mol合成的聚苯并咪唑在DMSO中加热溶解得到5wt％溶液，加入12mol二溴戊烷，在50℃反应30h。反应结束，倒入大量乙醇中，过滤，滤饼用去离子水洗3次，产物干燥，得到聚合产物(1)。10 mol of synthesized polybenzimidazole was heated and dissolved in DMSO to obtain a 5 wt% solution, 12 mol of dibromopentane was added, and the reaction was carried out at 50° C. for 30 hours. After the reaction is completed, it is poured into a large amount of ethanol, filtered, the filter cake is washed with deionized water three times, and the product is dried to obtain a polymer product (1).
将上述聚合产物(1)溶解在DMSO中配制4wt％溶液，抽真空0.5h，过滤，将滤液浇铸在洁净平板上铺膜，转入60℃烘箱干燥。将制得的膜，浸入1M NaOH溶液中24h，取出后用水浸泡24h，取出烘干，得到双铵离子PBI阴离子膜。The polymer product (1) was dissolved in DMSO to prepare a 4 wt% solution, vacuumed for 0.5 h, filtered, and the filtrate was cast on a clean flat plate to spread a film, and then transferred to an oven at 60°C for drying. The prepared membrane was immersed in a 1M NaOH solution for 24 hours, taken out and soaked in water for 24 hours, taken out and dried to obtain a diammonium ion PBI anion membrane.
经测试，80℃时该双铵离子PBI阴离子膜的OH -传导率为42mS/cm，该离子膜韧性好，在80℃1M的KOH溶液中浸泡1000h后，OH -离子传导率保持85％。 After testing, the OH - conductivity of the bisammonium PBI anion membrane at 80°C is 42mS/cm, and the ionic membrane has good toughness. After being soaked in a 1M KOH solution at 80°C for 1000h, the OH - ion conductivity remains 85%.
实施例2Example 2
在带搅拌的反应器中加入多聚磷酸，在N 2保护下，加入联苯四胺和乙二酸和对苯二酸(乙二酸和对苯二酸的总摩尔数等于联苯四胺甲烷的摩尔数)，加热搅拌溶解，使单体浓度为10wt％。升温到120℃搅拌反应10h，145℃反应2h，然后升温到180℃反应20h，直至体系粘度不再增加。聚合结束，将产物倒入大量去离子水中，加入过量NaHCO 3，搅拌过夜。过滤，用去离子水洗聚合物直至中性。产物干燥，得到聚苯并咪唑。 Add polyphosphoric acid in a stirred reactor, under the protection of N 2 , add benztetramine, oxalic acid and terephthalic acid (the total number of moles of oxalic acid and terephthalic acid is equal to benztetramine The number of moles of methane), heating and stirring to dissolve, so that the monomer concentration is 10wt%. The temperature was raised to 120°C and stirred for 10h, 145°C was reacted for 2h, and then the temperature was raised to 180°C for 20h, until the viscosity of the system no longer increased. After the polymerization is over, the product is poured into a large amount of deionized water, and excess NaHCO 3 is added, and the mixture is stirred overnight. Filter and wash the polymer with deionized water until neutral. The product is dried to obtain polybenzimidazole.
将10mol合成的聚苯并咪唑在DMSO中加热溶解得到5wt％溶液，加入10mol二溴戊烷，在50℃反应30h。反应结束，倒入大量乙醇中，过滤，滤饼用去离子水洗3次，产物干燥，得到聚合产物(1)。10 mol of the synthesized polybenzimidazole was heated and dissolved in DMSO to obtain a 5 wt% solution, 10 mol of dibromopentane was added, and the reaction was carried out at 50° C. for 30 hours. After the reaction is completed, it is poured into a large amount of ethanol, filtered, the filter cake is washed with deionized water three times, and the product is dried to obtain a polymer product (1).
将上述聚合产物(1)溶解在DMSO中配制4wt％溶液，抽真空0.5h，过滤，将滤液浇铸在洁净平板上铺膜，转入60℃烘箱干燥。将制得的膜，浸入1M NaOH溶液中24h，取出后用水浸泡24h，取出烘干，得到双铵离子PBI阴离子膜。The polymer product (1) was dissolved in DMSO to prepare a 4 wt% solution, vacuumed for 0.5 h, filtered, and the filtrate was cast on a clean flat plate to spread a film, and then transferred to an oven at 60°C for drying. The prepared membrane was immersed in a 1M NaOH solution for 24 hours, taken out and soaked in water for 24 hours, taken out and dried to obtain a diammonium ion PBI anion membrane.
经测试，80℃时该双铵离子PBI阴离子膜的OH -传导率为40mS/cm，该离子膜韧性好，在80℃1M的KOH溶液中浸泡1400h后，OH -离子传导率保持85％。 After testing, the OH - conductivity of the diammonium PBI anion membrane at 80°C is 40mS/cm, and the ionic membrane has good toughness. After immersing in a 1M KOH solution at 80°C for 1400h, the OH - ion conductivity remains 85%.
实施例3Example 3
主链聚苯并咪唑的合成同实施例2。The synthesis of main chain polybenzimidazole is the same as in Example 2.
将10mol聚苯并咪唑在氯仿中加热溶解得到12wt％溶液，加入10mol二溴戊烷，在40℃反应15h。反应结束，倒入大量乙醇中，过滤，滤饼用去离子水洗3次，产物干燥，得到产物(1)。10mol of polybenzimidazole was heated and dissolved in chloroform to obtain a 12wt% solution, 10mol of dibromopentane was added, and the reaction was carried out at 40°C for 15h. After the reaction is completed, it is poured into a large amount of ethanol, filtered, the filter cake is washed with deionized water three times, and the product is dried to obtain the product (1).
将上述产物(1)溶解在氯仿中配制10wt％溶液，抽真空0.5h，过滤，将滤液浇铸在洁净平板上铺膜，转入60℃烘箱干燥。将制得的膜，浸入1M NaOH溶液中24h，取出后用水浸泡24h，取出烘干，得到双铵离子PBI阴离子膜。The above product (1) was dissolved in chloroform to prepare a 10 wt% solution, vacuumed for 0.5 h, filtered, and the filtrate was cast on a clean flat plate to spread a film, and then transferred to an oven at 60°C for drying. The prepared membrane was immersed in a 1M NaOH solution for 24 hours, taken out and soaked in water for 24 hours, taken out and dried to obtain a diammonium ion PBI anion membrane.
经测试，80℃时该双铵离子PBI阴离子膜的OH -传导率为45mS/cm，该离子膜韧性好，在80℃1M的KOH溶液中浸泡1300h后，OH -离子传导率保持87％。 After testing, the OH - conductivity of the diammonium ion PBI anion membrane at 80°C is 45mS/cm, and the ionic membrane has good toughness. After immersing in a 1M KOH solution at 80°C for 1300h, the OH - ion conductivity remains 87%.
实施例4Example 4
主链聚苯并咪唑的合成同实施例2，其中，乙二酸和对苯二酸换成庚二酸和二苯醚二酸。The synthesis of the main chain polybenzimidazole is the same as in Example 2, wherein the oxalic acid and terephthalic acid are replaced with pimelic acid and diphenyl ether diacid.
将10mol聚苯并咪唑在DMSO中加热溶解得到7wt％溶液，加入30mol二溴戊烷，在50℃反应12h。反应结束，倒入大量乙醇中，过滤，滤饼用去离子水洗3次，产物干燥，得到产物(1)。10mol of polybenzimidazole was heated and dissolved in DMSO to obtain a 7wt% solution, 30mol of dibromopentane was added, and the reaction was carried out at 50°C for 12h. After the reaction is completed, it is poured into a large amount of ethanol, filtered, the filter cake is washed with deionized water three times, and the product is dried to obtain the product (1).
将上述产物(1)溶解在二甲基亚砜(DMSO)中配制6wt％溶液，抽真空0.5h，过滤，将滤液浇铸在洁净平板上铺膜，转入60℃烘箱干燥。将制得的膜，浸入1M NaOH溶液中24h，取出后用水浸泡24h，取出烘干，得到双铵离子PBI阴离子膜。The above-mentioned product (1) was dissolved in dimethyl sulfoxide (DMSO) to prepare a 6 wt% solution, vacuumed for 0.5 h, filtered, and the filtrate was cast on a clean plate to spread a film, and then transferred to an oven at 60°C for drying. The prepared membrane was immersed in a 1M NaOH solution for 24 hours, taken out and soaked in water for 24 hours, taken out and dried to obtain a diammonium ion PBI anion membrane.
经测试，80℃时该双铵离子PBI阴离子膜的OH -传导率为42mS/cm，该离子膜韧性好，在80℃1M的KOH溶液中浸泡1300h后，OH -离子传导率保持85％。 After testing, the OH - conductivity of the diammonium PBI anion membrane at 80°C is 42mS/cm, and the ionic membrane has good toughness. After being immersed in a 1M KOH solution at 80°C for 1300h, the OH - ion conductivity remains 85%.
实施例5Example 5
主链聚苯并咪唑的合成同实施例2，其中，乙二酸和对苯二酸换成己二酸和二苯甲烷二酸。The synthesis of the main chain polybenzimidazole is the same as in Example 2, wherein the oxalic acid and terephthalic acid are replaced with adipic acid and diphenylmethanedioic acid.
将10mol哌啶加入到40mol二溴乙烷的丙酮溶液中，升温到40℃搅拌反应20h。反应结束，过滤，干燥得到M’；将10mol聚苯并咪唑在DMSO中加热溶解得到7wt％溶液，加入20mol上述M’，在50℃反应15h。反应结束，倒入大量乙醇中。过滤，滤饼用去离子水洗3次，产物干燥，得到产物(2)。10 mol piperidine was added to 40 mol dibromoethane acetone solution, and the temperature was raised to 40° C. and the reaction was stirred for 20 hours. After the reaction is completed, filter and dry to obtain M'; heat and dissolve 10 mol of polybenzimidazole in DMSO to obtain a 7 wt% solution, add 20 mol of the above M', and react at 50°C for 15 hours. After the reaction is over, pour into a large amount of ethanol. After filtering, the filter cake was washed 3 times with deionized water, and the product was dried to obtain the product (2).
将上述产物(2)溶解在N-甲基吡咯烷酮(NMP)中配制4wt％溶液，抽真空0.5h，过滤，将滤液浇铸在洁净平板上铺膜，转入60℃烘箱干燥。将制得的膜，浸入1M NaOH溶液中24h，取出后用水浸泡24h，取出烘干，得到双铵离子PBI阴离子膜。The above product (2) was dissolved in N-methylpyrrolidone (NMP) to prepare a 4wt% solution, vacuumed for 0.5h, filtered, and the filtrate was cast on a clean flat plate and then transferred to an oven at 60°C for drying. The prepared membrane was immersed in a 1M NaOH solution for 24 hours, taken out and soaked in water for 24 hours, taken out and dried to obtain a diammonium ion PBI anion membrane.
经测试，80℃时该双铵离子PBI阴离子膜的OH -传导率为40mS/cm，该离子膜韧性好，在80℃1M的KOH溶液中浸泡1200h后，OH -离子传导率保持85％。 After testing, the OH - conductivity of the diammonium ion PBI anion membrane at 80°C is 40mS/cm, and the ionic membrane has good toughness. After immersing in a 1M KOH solution at 80°C for 1200h, the OH - ion conductivity remains 85%.
实施例6Example 6
主链聚苯并咪唑的合成同实施例1，其中，丁二酸和联苯二酸换成丁二酸和间苯二酸。The synthesis of the main chain polybenzimidazole is the same as in Example 1, wherein succinic acid and biphthalic acid are replaced with succinic acid and isophthalic acid.
将10mol合成的聚苯并咪唑在NMP中加热溶解得到15wt％溶液，加入10mol二溴戊烷，在35℃反应18h。反应结束，倒入大量甲醇中，过滤，滤饼用去离子水洗3次，产物干燥，得到产物(1)。10 mol of synthesized polybenzimidazole was heated and dissolved in NMP to obtain a 15 wt% solution, 10 mol of dibromopentane was added, and the reaction was carried out at 35° C. for 18 hours. After the reaction is completed, it is poured into a large amount of methanol, filtered, the filter cake is washed with deionized water three times, and the product is dried to obtain the product (1).
将上述产物(1)溶解在NMP中配制6wt％溶液，抽真空0.5h，过滤，将滤液浇铸在洁净平板上铺膜，转入60℃烘箱干燥。将制得的膜，浸入1M NaOH溶液中24h，取出后用水浸泡24h，取出烘干，得到双铵离子PBI阴离子膜。The above product (1) was dissolved in NMP to prepare a 6 wt% solution, vacuumed for 0.5 h, filtered, and the filtrate was cast on a clean flat plate to spread a film, and then transferred to an oven at 60° C. for drying. The prepared membrane was immersed in a 1M NaOH solution for 24 hours, taken out and soaked in water for 24 hours, taken out and dried to obtain a diammonium ion PBI anion membrane.
经测试，80℃时该双铵离子PBI阴离子膜的OH -传导率为42mS/cm，该离子膜韧性好，在80℃1M的KOH溶液中浸泡1350h后，OH -离子传导率保持86％。 After testing, the OH - conductivity of the bisammonium PBI anion membrane at 80°C is 42mS/cm, and the ionic membrane has good toughness. After immersing in 1M KOH solution at 80°C for 1350h, the OH - ion conductivity remains 86%.
实施例7Example 7
主链聚苯并咪唑的合成同实施例1，其中，丁二酸和联苯二酸换成丙二酸和二苯醚二酸。The synthesis of the main chain polybenzimidazole is the same as in Example 1, wherein the succinic acid and the biphthalic acid are replaced with malonic acid and diphenyl ether diacid.
将10mol合成的聚苯并咪唑在氯仿中加热溶解得到10wt％溶液，加入8mol二溴戊烷，在60℃反应10h。反应结束，倒入大量乙醇中，过滤，滤饼用去离子水洗3次，产物干燥，得到产物(1)。10 mol of the synthesized polybenzimidazole is heated and dissolved in chloroform to obtain a 10 wt% solution, 8 mol of dibromopentane is added, and the reaction is carried out at 60° C. for 10 hours. After the reaction is completed, it is poured into a large amount of ethanol, filtered, the filter cake is washed with deionized water three times, and the product is dried to obtain the product (1).
将上述产物(1)溶解在N,N-二甲基乙酰胺(DMAc)中配制10wt％溶液，抽真空0.5h，过滤，将滤液浇铸在洁净平板上铺膜，转入60℃烘箱干燥。将制得的膜，浸入1M NaOH溶液中24h，取出后用水浸泡24h，取出烘干，得到双铵离子PBI阴离子膜。The above product (1) was dissolved in N,N-dimethylacetamide (DMAc) to prepare a 10wt% solution, vacuumed for 0.5h, filtered, and the filtrate was cast on a clean flat plate and then transferred to an oven at 60°C for drying. The prepared membrane was immersed in a 1M NaOH solution for 24 hours, taken out and soaked in water for 24 hours, taken out and dried to obtain a diammonium ion PBI anion membrane.
经测试，80℃时该双铵离子PBI阴离子膜的OH -传导率为40mS/cm，该离子膜韧性好，在80℃1M的KOH溶液中浸泡1400h后，OH -离子传导率保持84％。 After testing, the OH - conductivity of the diammonium ion PBI anion membrane at 80°C is 40mS/cm, and the ionic membrane has good toughness. After immersing in a 1M KOH solution at 80°C for 1400h, the OH - ion conductivity remains 84%.
实施例8Example 8
主链聚苯并咪唑的合成同实施例2，其中，乙二酸和对苯二酸换成辛二酸和对苯二酸。The synthesis of the main chain polybenzimidazole is the same as in Example 2, wherein the oxalic acid and terephthalic acid are replaced with suberic acid and terephthalic acid.
将10mol合成的聚苯并咪唑在DMAc中加热溶解得到5wt％溶液，加入15mol二溴戊烷，在70℃反应12h。反应结束，倒入大量甲醇中，过滤，滤饼用去离子水洗3次，产物干燥，得到产物(1)。10 mol of synthetic polybenzimidazole was heated and dissolved in DMAc to obtain a 5 wt% solution, 15 mol of dibromopentane was added, and the reaction was carried out at 70° C. for 12 hours. After the reaction is completed, it is poured into a large amount of methanol, filtered, the filter cake is washed with deionized water three times, and the product is dried to obtain the product (1).
将上述产物(1)溶解在DMAc中配制12wt％溶液，抽真空0.5h，过滤，将滤液浇铸在洁净平板上铺膜，转入60℃烘箱干燥。将制得的膜，浸入1M NaOH溶液中24h，取出后用水浸泡24h，取出烘干，得到双铵离子PBI阴离子膜。The above product (1) was dissolved in DMAc to prepare a 12 wt% solution, vacuumed for 0.5 h, filtered, and the filtrate was cast on a clean flat plate to spread a film, and then transferred to an oven at 60°C for drying. The prepared membrane was immersed in a 1M NaOH solution for 24 hours, taken out and soaked in water for 24 hours, taken out and dried to obtain a diammonium ion PBI anion membrane.
经测试，80℃时该双铵离子PBI阴离子膜的OH -传导率为50mS/cm，该离子膜韧性好，在80℃1M的KOH溶液中浸泡1300h后，OH -离子传导率保持87％。 After testing, the OH - conductivity of the diammonium ion PBI anion membrane at 80°C is 50mS/cm, and the ionic membrane has good toughness. After being soaked in a 1M KOH solution at 80°C for 1300h, the OH - ion conductivity remains 87%.
实施例9Example 9
主链聚苯并咪唑的合成同实施例2，其中，乙二酸和对苯二酸换成二苯醚二酸。The synthesis of the main chain polybenzimidazole is the same as in Example 2, wherein the oxalic acid and terephthalic acid are replaced with diphenyl ether diacid.
将10mol合成的聚苯并咪唑在DMSO中加热溶解得到10wt％溶液，加入20mol二溴戊烷，在45℃反应20h。反应结束，倒入大量乙醇中，过滤，滤饼用去离子水洗3次，产物干燥，得到产物(1)。10 mol of synthesized polybenzimidazole was heated and dissolved in DMSO to obtain a 10 wt% solution, 20 mol of dibromopentane was added, and the reaction was carried out at 45° C. for 20 hours. After the reaction is completed, it is poured into a large amount of ethanol, filtered, the filter cake is washed with deionized water three times, and the product is dried to obtain the product (1).
将上述产物(1)溶解在DMSO中配制10wt％溶液，抽真空0.5h，过滤，将滤液浇铸在洁净平板上铺膜，转入60℃烘箱干燥。将制得的膜，浸入1M NaOH溶液中24h，取出后用水浸泡24h，取出烘干，得到双铵离子PBI阴离子膜。The above-mentioned product (1) was dissolved in DMSO to prepare a 10 wt% solution, vacuumed for 0.5 h, filtered, and the filtrate was cast on a clean flat plate to spread a film, and then transferred to an oven at 60°C for drying. The prepared membrane was immersed in a 1M NaOH solution for 24 hours, taken out and soaked in water for 24 hours, taken out and dried to obtain a diammonium ion PBI anion membrane.
经测试，80℃时该双铵离子PBI阴离子膜的OH -传导率为45mS/cm，该离子膜韧性好，在80℃1M的KOH溶液中浸泡1200h后，OH -离子传导率保持86％。 After testing, the OH - conductivity of the bisammonium PBI anion membrane at 80°C is 45mS/cm, and the ionic membrane has good toughness. After immersing in a 1M KOH solution at 80°C for 1200h, the OH - ion conductivity remains 86%.
图1的氢核磁谱图分析：Analysis of the hydrogen nuclear magnetic spectrum of Figure 1:
图1是主链螺环苯并咪唑阴离子交换膜的氢核磁谱图，溶剂为DMSO-d6，核磁仪器频率为400MHz。如图1所示，在化学位移11-13ppm之间没有出现主链中咪唑环上N-H的特征峰，且在3.5ppm左右处没有出现Br-CH 2中亚甲基的特征峰，说明聚合物主链咪唑N-H成功环化成螺环结构。化学位移3.51ppm、2.41ppm处是微量水分子、以及溶剂DMSO分子的特征峰。化学位移8.30、7.36ppm处是聚合物结构单元中二苯醚的苯环上H2、H1的特征峰。化学位移7.91ppm、7.73ppm、7.64ppm处是聚合物结构单元四胺相连苯环的H3、H4、H5的特征峰。化学位移4.40ppm处是螺环内与N正离子直接相连-CH 2上H6的特征峰，化学位移1.79ppm处是螺环内处于N正离子间位-CH 2上H7的特征峰。由以上分析可知，在PBI主链咪唑结构上成功环化为螺环铵结构，制备了主链螺环铵PBI阴离子交换膜。 Figure 1 is the hydrogen nuclear magnetic spectrum of the main chain spirocyclic benzimidazole anion exchange membrane, the solvent is DMSO-d6, and the frequency of the nuclear magnetic instrument is 400MHz. As shown in Figure 1, there is no characteristic peak of NH on the imidazole ring in the main chain between the chemical shift of 11-13 ppm, and the characteristic peak of methylene in Br-CH 2 does not appear at about 3.5 ppm, indicating that the polymer The main chain imidazole NH was successfully cyclized into a spiro ring structure. The chemical shifts at 3.51 ppm and 2.41 ppm are characteristic peaks of trace water molecules and solvent DMSO molecules. The chemical shifts of 8.30 and 7.36 ppm are the characteristic peaks of H2 and H1 on the benzene ring of diphenyl ether in the polymer structural unit. The chemical shifts at 7.91 ppm, 7.73 ppm, and 7.64 ppm are the characteristic peaks of H3, H4, and H5 of the benzene ring connected to the tetraamine of the polymer structural unit. The chemical shift at 4.40 ppm is the characteristic peak of H6 on CH 2 which is directly connected to the N positive ion in the spiro ring, and the chemical shift of 1.79 ppm is the characteristic peak of H7 on the N positive ion meta-position-CH 2 in the spiro ring. It can be seen from the above analysis that the imidazole structure of the main chain of PBI was successfully cyclized into a spirocyclic ammonium structure, and the main chain spirocyclic ammonium PBI anion exchange membrane was prepared.
实施例10Example 10
主链聚苯并咪唑的合成同实施例2，其中，乙二酸和对苯二酸换成间苯二酸。The synthesis of the main chain polybenzimidazole is the same as in Example 2, wherein the oxalic acid and terephthalic acid are replaced with isophthalic acid.
将10mol合成的聚苯并咪唑在NMP中加热溶解得到15wt％溶液，加入15mol二溴戊烷，在45℃反应15h。反应结束，倒入大量乙醇中，过滤，滤饼用去离子水洗3次，产物干燥，得到产物(1)。10 mol of the synthesized polybenzimidazole was heated and dissolved in NMP to obtain a 15 wt% solution, 15 mol of dibromopentane was added, and the reaction was carried out at 45° C. for 15 hours. After the reaction is completed, it is poured into a large amount of ethanol, filtered, the filter cake is washed with deionized water three times, and the product is dried to obtain the product (1).
将上述产物(1)溶解在NMP中配制10wt％溶液，抽真空0.5h，过滤，将滤液浇铸在洁净平板上铺膜，转入60℃烘箱干燥。将制得的膜，浸入1M NaOH溶液中24h，取出后用水浸泡24h，取出烘干，得到双铵离子PBI阴离子膜。The above product (1) was dissolved in NMP to prepare a 10 wt% solution, vacuumed for 0.5 h, filtered, and the filtrate was cast on a clean flat plate to spread a film, and then transferred to an oven at 60°C for drying. The prepared membrane was immersed in a 1M NaOH solution for 24 hours, taken out and soaked in water for 24 hours, taken out and dried to obtain a diammonium ion PBI anion membrane.
经测试，80℃时该双铵离子PBI阴离子膜的OH -传导率为40mS/cm，该离子膜韧性好，在80℃1M的KOH溶液中浸泡1300h后，OH -离子传导率保持84％。 After testing, the OH - conductivity of the diammonium PBI anion membrane at 80°C is 40mS/cm, and the ionic membrane has good toughness. After immersing in a 1M KOH solution at 80°C for 1300h, the OH - ion conductivity remains 84%.

Claims (10)

  1. 一种杂环铵离子聚苯并咪唑，其特征在于，具有以下结构：A heterocyclic ammonium ion polybenzimidazole, which is characterized in that it has the following structure:
    Figure PCTCN2020091453-appb-100001
    Figure PCTCN2020091453-appb-100001
    其中，n＝0～0.8；Among them, n=0～0.8;
    Z是Cl -,Br -,或OH -离子； Z is Cl -, Br -, or OH - ions;
    A为单键、亚甲基-CH 2-，醚键-O-或羰基-CO-； A is a single bond, methylene -CH 2 -, ether bond -O- or carbonyl -CO-;
    X取以下结构：
    Figure PCTCN2020091453-appb-100002
    其中2≤n’≤18；     X takes the following structure:
    Figure PCTCN2020091453-appb-100002
    Where 2≤n'≤18;
    Y具有以下结构：Y has the following structure:
    Figure PCTCN2020091453-appb-100003
    Figure PCTCN2020091453-appb-100003
  2. 如权利要求1所述一种杂环铵离子聚苯并咪唑的制备方法，特征在于，包含以下步骤：步骤1，聚苯并咪唑的合成The method for preparing heterocyclic ammonium ion polybenzimidazole according to claim 1, characterized in that it comprises the following steps: Step 1, synthesis of polybenzimidazole
    所述聚苯并咪唑是由四胺单体(Ⅱ)和二酸单体(Ⅲ)通过溶液缩聚反应合成；The polybenzimidazole is synthesized from tetraamine monomer (II) and diacid monomer (III) through solution polycondensation;
    所述四胺单体(Ⅱ)的结构如下：The structure of the tetraamine monomer (II) is as follows:
    Figure PCTCN2020091453-appb-100004
    Figure PCTCN2020091453-appb-100004
    其中，A为单键、亚甲基-CH 2-、醚键-O-或羰基-CO-； Wherein, A is a single bond, methylene -CH 2 -, ether bond -O- or carbonyl -CO-;
    所述二酸单体(Ⅲ)的结构如下：The structure of the diacid monomer (III) is as follows:
    HOOC-X-COOH和HOOC-Y-COOHHOOC-X-COOH and HOOC-Y-COOH
    其中，X取以下结构：
    Figure PCTCN2020091453-appb-100005
    其中2≤n’≤18；     Among them, X takes the following structure:
    Figure PCTCN2020091453-appb-100005
    Where 2≤n'≤18;
    Y具有以下结构：Y has the following structure:
    Figure PCTCN2020091453-appb-100006
    Figure PCTCN2020091453-appb-100006
    在带搅拌的反应器中加入多聚磷酸，在N 2保护下，加入四胺单体(Ⅱ)和等摩尔比的二酸单体(Ⅲ)HOOC-X-COOH和HOOC-Y-COOH，搅拌溶解，使单体Ⅱ和Ⅲ的总质量浓度为1～20wt％；升温到90～140℃搅拌反应0.5～10h，然后升温到140～160℃搅拌反应0.5～10h，升温到160～190℃反应8～30h；聚合反应结束，将产物倒入大量去离子水中，加入过量NaHCO 3，搅拌过夜；过滤，用去离子水洗聚合物直至中性；产物干燥，得到聚苯并咪唑； Add polyphosphoric acid into a stirred reactor. Under the protection of N 2 , add tetraamine monomer (Ⅱ) and diacid monomer (Ⅲ) HOOC-X-COOH and HOOC-Y-COOH in equal molar ratio. Stir and dissolve so that the total mass concentration of monomers II and III is 1-20wt%; increase the temperature to 90-140℃, stir and react for 0.5-10h, then increase the temperature to 140-160℃, stir and react for 0.5-10h, and increase the temperature to 160～190℃ The reaction is 8-30h; the polymerization reaction is over, the product is poured into a large amount of deionized water, excess NaHCO 3 is added, and the mixture is stirred overnight; filtered and washed with deionized water until the polymer is neutral; the product is dried to obtain polybenzimidazole;
    步骤2-1,杂环铵离子聚苯并咪唑(1)的合成Step 2-1, synthesis of heterocyclic ammonium ion polybenzimidazole (1)
    将一定量聚苯并咪唑在溶剂2中加热溶解得到质量体积比浓度0.5～10％溶液，加入二溴戊烷和碱性化合物2，在30～150℃反应8～100h；反应结束，倒入沉淀剂1，过滤，滤饼用去离子水洗3次，产物干燥，得到杂环铵离子聚苯并咪唑(1)；Heat and dissolve a certain amount of polybenzimidazole in solvent 2 to obtain a solution with a mass volume ratio of 0.5-10%, add dibromopentane and basic compound 2, and react at 30-150℃ for 8-100h; when the reaction is over, pour Precipitant 1, filtered, the filter cake was washed 3 times with deionized water, and the product was dried to obtain heterocyclic ammonium ion polybenzimidazole (1);
    步骤2-2,杂环铵离子聚苯并咪唑(2)的合成Step 2-2, Synthesis of heterocyclic ammonium ion polybenzimidazole (2)
    将一定量哌啶加入到含二卤代烷P-(CH 2) m-P的溶剂2中，升温到30～90℃搅拌反应6～72h；反应结束，过滤，干燥得到M’； A certain amount of piperidine is added to solvent 2 containing dihaloalkane P-(CH 2 ) m -P, and the temperature is raised to 30-90° C. and the reaction is stirred for 6-72 hours; the reaction is completed, filtered and dried to obtain M';
    将一定量聚苯并咪唑在溶剂2中加热溶解得到0.5～10wt％溶液，加入M’，在30～150℃反应8～100h；反应结束，倒入沉淀剂1，过滤，滤饼用去离子水洗3次，产物干燥，得到杂环铵离子聚苯并咪唑(2)；其中，P选自Cl或Br原子，0＜m≤6的整数。Heat and dissolve a certain amount of polybenzimidazole in solvent 2 to obtain a 0.5-10wt% solution, add M', and react at 30-150℃ for 8-100h; after the reaction is over, pour into precipitant 1, filter, and deionize the filter cake After washing with water three times, the product is dried to obtain heterocyclic ammonium ion polybenzimidazole (2); wherein, P is selected from Cl or Br atoms, and an integer of 0<m≤6.
  3. 根据权利要求2所述的杂环铵离子聚苯并咪唑的制备方法，其特征在于，所述溶剂1是甲苯、甲醇、乙醇、二氯甲烷、四氢呋喃、乙腈、丙酮、乙酸乙酯、N，N-二甲基乙酰胺、二甲基亚砜、N，N-二甲基甲酰胺、N-甲基吡咯烷酮中的一种或几种的混合物； 所述溶剂2是甲苯、二氯甲烷、氯仿、N，N-二甲基乙酰胺、二甲基亚砜、N，N-二甲基甲酰胺、N-甲基吡咯烷酮中的一种或几种的混合物。The method for preparing heterocyclic ammonium ion polybenzimidazole according to claim 2, wherein the solvent 1 is toluene, methanol, ethanol, dichloromethane, tetrahydrofuran, acetonitrile, acetone, ethyl acetate, N, One or a mixture of one or more of N-dimethylacetamide, dimethyl sulfoxide, N,N-dimethylformamide, and N-methylpyrrolidone; the solvent 2 is toluene, dichloromethane, One or a mixture of chloroform, N,N-dimethylacetamide, dimethylsulfoxide, N,N-dimethylformamide, and N-methylpyrrolidone.
  4. 根据权利要求2所述的杂环铵离子聚苯并咪唑及的制备方法，其特征在于，步骤2-1中聚苯并咪唑与二溴戊烷的摩尔比是0.1～1:1；The method for preparing heterocyclic ammonium ion polybenzimidazole according to claim 2, wherein the molar ratio of polybenzimidazole to dibromopentane in step 2-1 is 0.1-1:1;
    步骤2-2中，哌啶与二卤烷烃P-(CH 2) m-P的摩尔比是0.05～1:1；聚苯并咪唑与M’的摩尔比是0.1～1:1。 In step 2-2, the molar ratio of piperidine to dihaloalkane P-(CH 2 ) m -P is 0.05-1:1; the molar ratio of polybenzimidazole to M'is 0.1-1:1.
  5. 根据权利要求2所述的杂环铵离子聚苯并咪唑的制备方法，其特征在于，所述沉淀剂1是甲醇、乙醇、乙醚、乙酸乙酯、二氯甲烷、四氢呋喃、丙酮和水中的一种或几种的混合物；The method for preparing heterocyclic ammonium ion polybenzimidazole according to claim 2, wherein the precipitating agent 1 is one of methanol, ethanol, ether, ethyl acetate, dichloromethane, tetrahydrofuran, acetone and water. Species or mixture of several;
    所述碱性化合物2选自碳酸氢钠、碳酸氢钾、碳酸钠、碳酸钾、碳酸铯，氢化钠、氢化锂中的一种或几种。The basic compound 2 is selected from one or more of sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydride, and lithium hydride.
  6. 根据权利要求2所述的杂环铵离子聚苯并咪唑的制备方法，其特征在于，聚苯并咪唑的粘均分子量为10,000～450,000g/mol，聚合度n为20～1200。The method for preparing heterocyclic ammonium ion polybenzimidazole according to claim 2, wherein the viscosity average molecular weight of polybenzimidazole is 10,000-450,000 g/mol, and the degree of polymerization n is 20-1200.
  7. 一种杂环铵离子聚苯并咪唑阴离子交换膜的制备方法，其特征在于：A preparation method of heterocyclic ammonium ion polybenzimidazole anion exchange membrane, characterized in that:
    将权利要求1中杂环铵离子聚苯并咪唑(1)或杂环铵离子聚苯并咪唑(2)在溶剂3中加热溶解配制1～15wt％溶液，过滤，将滤液浇铸在洁净平板上铺膜，转入烘箱干燥；将制得的膜，放入1M NaOH或1M KOH溶液中24～48h，取出后用水浸泡24h，取出烘干，得到杂环铵离子聚苯并咪唑阴离子交换膜(1)或杂环铵离子聚苯并咪唑阴离子交换膜(2)。The heterocyclic ammonium ion polybenzimidazole (1) or heterocyclic ammonium ion polybenzimidazole (2) of claim 1 is heated and dissolved in solvent 3 to prepare a 1-15 wt% solution, filtered, and the filtrate is cast on a clean plate Lay the membrane and transfer it to an oven to dry; put the prepared membrane in a 1M NaOH or 1M KOH solution for 24 to 48 hours, take it out and soak it in water for 24 hours, take it out and dry it to obtain a heterocyclic ammonium ion polybenzimidazole anion exchange membrane 1) Or heterocyclic ammonium ion polybenzimidazole anion exchange membrane (2).
  8. 根据权利要求7所述的制备方法，特征在于，所述溶剂3选自是甲苯、甲醇、乙醇、二氯甲烷、四氢呋喃、乙腈、丙酮、乙酸乙酯、N，N-二甲基乙酰胺、二甲基亚砜、N，N-二甲基甲酰胺、N-甲基吡咯烷酮中的一种或几种的混合物。The preparation method according to claim 7, characterized in that the solvent 3 is selected from toluene, methanol, ethanol, dichloromethane, tetrahydrofuran, acetonitrile, acetone, ethyl acetate, N,N-dimethylacetamide, One or a mixture of dimethyl sulfoxide, N,N-dimethylformamide, and N-methylpyrrolidone.
  9. 如权利要求1所述杂环铵离子聚苯并咪唑作为电解质在燃料电池、液流电池、水电解、电渗析及膜分离中的应用。The heterocyclic ammonium ion polybenzimidazole according to claim 1 is used as an electrolyte in fuel cells, flow batteries, water electrolysis, electrodialysis and membrane separation applications.
  10. 如权利要求7或8所述的杂环铵离子聚苯并咪唑阴离子交换膜在燃料电池、液流电池、水电解、电渗析及膜分离领域的应用。The application of the heterocyclic ammonium ion polybenzimidazole anion exchange membrane according to claim 7 or 8 in the fields of fuel cells, flow batteries, water electrolysis, electrodialysis and membrane separation.
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