CN113594520B - Preparation method of polybenzimidazole containing troger base and phosphoric acid doped high-temperature proton exchange membrane thereof - Google Patents
Preparation method of polybenzimidazole containing troger base and phosphoric acid doped high-temperature proton exchange membrane thereof Download PDFInfo
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- 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]
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Abstract
The invention provides a preparation method of a polybenzimidazole containing troger base and a phosphoric acid-doped high-temperature proton exchange membrane thereof. The polybenzimidazole containing the troger base has a structure shown in a formula 1, can be used as a high-temperature proton exchange membrane material, and is synthesized by a homogeneous solution method, phosphorus pentoxide is used as a catalyst, and tetramine A, dicarboxylic acid B and carboxylic acid C containing the troger base are polymerized under the dehydration action in a polyphosphoric acid or methanesulfonic acid solvent. The polybenzimidazole provided by the invention has a structure of the troger base, and the polybenzimidazole containing the troger base prepared by the polybenzimidazole has good solubility in a conventional organic solvent, and maintains excellent mechanical properties and high phosphoric acid doping amount. The polybenzimidazole containing the troger base for the high-temperature proton exchange membrane has outstanding fuel cell performance, high proton conductivity under the conditions of high temperature and no humidity, and wide application prospect in the high-temperature fuel cell.
Description
Technical Field
The invention belongs to the field of polybenzimidazole materials for fuel cells, and particularly relates to a preparation method of polybenzimidazole containing a troger base and a phosphoric acid-doped high-temperature proton exchange membrane thereof.
Background
The fuel cell is an energy conversion device which directly converts chemical energy into electric energy, and has the characteristics of simple product, greenness and safety. Among them, the pem fuel cell has many advantages and is considered to be the most commercially valuable fuel cell. The most mature proton exchange membrane material with excellent comprehensive performance is the Nafion membrane developed by DuPont in the United states, and has high conductivity and excellent chemical stability. Such as Nafion117 membrane, has a conductivity of up to 139mS/cm at 80 ℃ and 100% humidity (reference: J. Power Sources,2014,260, 307-316.). However, the Nafion membrane has some disadvantages, such as high fuel permeability, high dependence on humidity for proton transfer, expensive synthesis cost, etc. For example, when the operation temperature is above 80 ℃, the moisture-retaining ability of the membrane is poor, the performance of the battery is reduced sharply due to the reduction of proton carriers, and the conductivity data of the Nafion117 membrane is close to zero in a dry state (reference: J.Power Sources,2013,222, 202-209). These disadvantages limit the large-scale commercial application of Nafion. At present, the development of high-temperature fuel cells provides a thought for preparing high-performance proton exchange membranes. High temperature proton exchange membranes have many advantages at operating temperatures above 120 ℃, such as simplified water and thermal management systems; and the catalyst poisoning phenomenon caused by CO is reduced. Currently, phosphoric acid doped polybenzimidazole is the most successful high temperature proton exchange membrane material.
Polybenzimidazole is a high performance amorphous polymer containing N-heterocycles and has excellent thermal and chemical stability up to 300 ℃. Imidazole rings (-NH, C = N) within a polybenzimidazole molecule can bind to a phosphoric acid molecule by intermolecular interaction force. The combined phosphoric acid molecules or free phosphoric acid in the membrane can be used as proton carriers, so that the polybenzimidazole membrane can rapidly transfer protons under the conditions of high temperature and no humidity. The proton conduction mechanism is as shown in the following formula 5
The mechanism is that protons continuously jump between the phosphate molecules and imidazole rings to form a stable proton transfer channel.
Some patents disclose Polybenzimidazoles (PBIs) for use in proton exchange membranes. The patent CN 108649255A discloses a polybenzimidazole proton exchange membrane, a preparation method and application thereof, wherein a 3,3' -diaminobenzidine monomer and a plurality of carboxylic acid monomers are polymerized to obtain the polybenzimidazole proton exchange membrane with excellent mechanical properties. Patent CN 112259769A relates to a polybenzimidazole proton exchange membrane with micropores, which is prepared by3,3' -diaminobenzidine is polymerized with dicarboxylic acids by nucleophilic reaction. The prepared polybenzimidazole has larger free volume, improves the doping amount of phosphoric acid and ensures that the doped phosphoric acid is not easy to run off. Meanwhile, the large-volume structure in the chain increases the distance between molecular chains, and improves the problem of poor solubility of the polymer in an organic solvent, so that the prepared proton exchange membrane has good thermal stability and mechanical property, the decomposition temperature of the polymer reaches 400-600 ℃, and the tensile strength can reach 70-120MPa. The maximum power density of the battery can reach 400-550mW/cm 2 . Patent CN 111574721A discloses a preparation method and application of a phosphonated polyolefin grafted benzimidazole polymer proton exchange membrane, and the prepared polybenzimidazole membrane can keep higher proton conductivity under low phosphoric acid doping level (less than 10) and low volume swelling (less than 200%). The conductivity can reach up to 90mS/cm at the test temperature of 180 ℃. The bipyridine polybenzimidazole (Bipy-PBI) proton exchange membrane has excellent performance, and a bipyridine structure in a molecule can adsorb phosphoric acid molecules, so that the proton conductivity is improved. The conductivity of the high molecular weight Bipy-PBI can reach 37mS/cm under the condition of 120 ℃ without humidity, which is 3 to 4 times that of the traditional PBI material. The Bipy-PBI power density is obviously improved by introducing additional N atoms, and the maximum power density can reach 779mW/cm 2 500mW/cm higher than that of the conventional PBI membrane 2 (reference: J.Membr. Sci.,2019, 591.). However, the rigid molecular chain of polybenzimidazole and the strong hydrogen bonding interaction of imidazole ring can lead to the polybenzimidazole material to have poor solubility, difficult processing and unfavorable commercial application of the material.
The problems of insufficient base sites, low conductivity and poor solubility of the conventional polybenzimidazole are solved. Therefore, the invention introduces a Touguer base structure into the prepared polybenzimidazole, improves the solubility problem of the traditional polybenzimidazole, and provides an additional base site for adsorbing more phosphoric acid. The polybenzimidazole proton exchange membrane containing the troger base has good thermal and chemical stability and mechanical properties. Meanwhile, a large amount of phosphoric acid is adsorbed, so that the proton conductivity of the imidazole membrane is improved, and the imidazole membrane has a wide application prospect in a high-temperature fuel cell.
Disclosure of Invention
Aiming at the defect that the traditional polybenzimidazole is used as a high-temperature proton exchange membrane, the invention mainly provides polybenzimidazole containing troger base and a preparation method of the proton exchange membrane. The polybenzimidazole containing the troger base has better solubility in an organic solvent, and simultaneously, the adsorption quantity of proton carrier phosphoric acid molecules is obviously improved. The prepared proton exchange membrane has high proton conductivity at high temperature without humidity, and maintains ultrahigh mechanical strength and chemical stability.
A preparation method of polybenzimidazole containing a troger base and a phosphoric acid-doped high-temperature proton exchange membrane thereof is characterized in that the synthesis of the polybenzimidazole containing the troger base, the product structure and the preparation method of the phosphoric acid-doped high-temperature proton exchange membrane are as follows:
(1) Synthesis of polybenzimidazole containing troger base
The process for synthesizing the polybenzimidazole containing the troger base is shown as a formula 1, the polybenzimidazole polymer M containing the troger base is prepared under the high-temperature dehydration of a tetramine monomer A, a dicarboxylic acid B and a carboxylic acid C containing the troger base, and the specific reaction steps are as follows:
adding the selected raw materials of the tetraamino monomer A, the dicarboxylic acid monomer B and the monomer C containing the troger base into a three-necked bottle, adopting a mechanical stirring device, and introducing nitrogen for protection. Sequentially adding one or a mixture of polyphosphoric acid or methanesulfonic acid serving as a solvent, heating to 110 ℃, reacting for 12-24h, cooling to room temperature, and adding a proper amount of phosphorus pentoxide serving as a catalyst. Continuously raising the temperature, reacting at 110 ℃ for 12-24h, at 160 ℃ for 12-24h, at 180 ℃ for 12-24h, and at 200 ℃ for 12-24h. After sufficient reaction, a brown polymer solution with higher viscosity is obtained. Fully precipitating the polybenzimidazole powder by using deionized water, absolute ethyl alcohol, methanol and other solvents respectively, washing, and drying for 6-12h at the temperature of 50-120 ℃ to obtain polybenzimidazole powder.
(2) Preparation of polybenzimidazole proton exchange membrane containing troger base
The prepared polybenzimidazole powder containing the troger base is dissolved in an organic solvent (such as N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc) and the like) to prepare a polymer solution with the solid content of 3-15 wt.%. Then the polymer solution is evenly casted on flat glass, and the thickness of the casting layer is adjusted to make the thickness after drying between 5 and 150 microns. And then putting the flat glass coated with the polymer solution into an inert atmosphere oven or a vacuum oven for drying, and performing heat treatment and drying on the solvent according to a temperature programming mode of 1-5h at 60 ℃, 1-5h at 90 ℃, 1-5h at 120 ℃, 1-5h at 150 ℃, 1-5h at 180 ℃, and 1-5 h at 210 ℃. And after cooling to room temperature, peeling the film from the flat glass to obtain the polybenzimidazole proton exchange membrane containing the troger base.
(3) Preparation of doped phosphoric acid polybenzimidazole proton exchange membrane containing troger base
Firstly, preparing a phosphoric acid solution with the mass fraction of 5-85%, and shaking up. And (3) soaking the proton exchange membrane prepared in the step (2) in a prepared phosphoric acid solution with a specific mass fraction, and keeping the solution at room temperature for 2-7 days to fully adsorb phosphoric acid. And then taking out the membrane, wiping the phosphoric acid on the surface of the membrane by using filter paper, and drying for 6-12h at the temperature of 80-150 ℃ to prepare the phosphoric acid doped polybenzimidazole proton exchange membrane capable of conducting protons at high temperature.
A preparation method of polybenzimidazole containing troger base and phosphoric acid doped high-temperature proton exchange membrane thereof. Characterized in that, in step (1) of the method, ar contained in the structure of a monomer containing a tetraamine group is used 1 The structure is described in the following formula 2. Preferably, ar in the tetraamino monomer A 1 Represents any one or more of D-I. X 1 -X 22 Represents a protonated, unprotonated sulfonate, methyl, hydroxyl, amino substituent, and X 1 -X 22 May or may not be identical to each other.
Preferably, ar in dicarboxylic acid B 2 Such as any one or more of J-U in the following formula 3. Preferably, R 1 -R 65 Represents a protonated, unprotonated sulfonate, methyl, hydroxyl, amino substituent, and R 1 -R 65 May or may not be identical to each other.
A preparation method of polybenzimidazole containing troger base and phosphoric acid doped high-temperature proton exchange membrane thereof. Characterized in that the novel dicarboxylic acid monomer used in step (1) of the process contains Ar in its structure 3 As described in the following formula 4. Preferably, ar is 3 Is any one or more of structures i-vi as follows. Preferably, Y in i-vi 1 -Y 37 Represents F, cl, br, I, CH 3 、OH、SO 3 H or H, and Y 1 -Y 37 May or may not be identical to each other.
A preparation method of polybenzimidazole containing troger base and phosphoric acid doped high-temperature proton exchange membrane thereof. The method is characterized in that polybenzimidazole prepared in the step (1) of the method is a copolymerization or homopolymerization product, wherein m and n are copolymerization ratios of chain segments, the ratio is selected from the range of 0-10, and the ratio is controlled by the feeding ratio of the reaction (1).
A method for preparing a polybenzimidazole containing a troger base group and a phosphoric acid-doped high-temperature proton exchange membrane thereof. The method is characterized in that the solvent used in the step (1) is one or a mixture of polyphosphoric acid and methanesulfonic acid.
A preparation method of polybenzimidazole containing troger base and phosphoric acid doped high-temperature proton exchange membrane thereof. The method is characterized in that the temperature programming process is adopted for preparing the product, the reaction is carried out for 12-24h at 110 ℃, for 12-24h at 160 ℃, for 12-24h at 180 ℃ and for 12-24h at 200 ℃.
A preparation method of polybenzimidazole containing troger base and phosphoric acid doped high-temperature proton exchange membrane thereof. The method is characterized in that the treatment temperature and the treatment time of the solid powder in the step (1) are respectively 50-120 ℃ and 6-12 h.
A method for preparing a polybenzimidazole containing a troger base group and a phosphoric acid-doped high-temperature proton exchange membrane thereof. The method is characterized in that the organic solvent adopted in the step (2) is one or a mixture of N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF) and N, N-dimethylacetamide (DMAc). The solid content ratio of the prepared polymer solution is 3-15 wt.%.
A method for preparing a polybenzimidazole containing a troger base group and a phosphoric acid-doped high-temperature proton exchange membrane thereof. The method is characterized in that in the step (2), a glass plate is selected for film forming, and the thickness of the film which is cast on the glass plate and dried is controlled to be 5-150 micrometers.
A method for preparing a polybenzimidazole containing a troger base group and a phosphoric acid-doped high-temperature proton exchange membrane thereof. The method is characterized in that the drying conditions of the film in the step (2) of the method are 1-5h at 60 ℃, 1-5h at 90 ℃, 1-5h at 120 ℃, 1-5h at 150 ℃, 1-5h at 180 ℃, and 1-5 h at 210 ℃.
A preparation method of polybenzimidazole containing troger base and phosphoric acid doped high-temperature proton exchange membrane thereof. The method is characterized in that in the step (3), 5-85% of phosphoric acid solution in percentage by mass is adopted to soak the polybenzimidazole membrane containing the troger base obtained in the step (2) for 2-7 days, so that the polybenzimidazole membrane can fully adsorb phosphoric acid.
A preparation method of polybenzimidazole containing troger base and phosphoric acid doped high-temperature proton exchange membrane thereof. The method is characterized in that in the step (3), phosphoric acid is used as a proton carrier for acid doping.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
In the following examples, the structure of the synthesized polymer was characterized by Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance hydrogen spectroscopy (1H-NMR). The mechanical properties were characterized using a tensile tester, the phosphoric acid adsorption level of the fagadine base imidazole-containing membrane was characterized using a phosphoric acid doping experiment, and the proton conductivity level of the membrane was characterized using an electrochemical workstation (PGSTAT 302N AUT 88079).
Example 1: the preparation method of the proton exchange membrane homopolymerizing the polybenzimidazole containing the Chaogel base group is shown as a formula 5, firstly, 3' -diaminobenzidine monomer D-1 (0.8570g 4mmol) is put into a 100ml three-mouth bottle protected by nitrogen, then 30g of solvent polyphosphoric acid and Chaogel base carboxylic acid ii-1 (1.8648g 4mmol) monomer are sequentially added, the mixture is uniformly stirred at room temperature, then the temperature is raised to 110 ℃ for reaction for 6h, then the mixture is cooled to a greenhouse, and 3g of dehydrating agent phosphorus pentoxide is added. Then, the temperature is continuously increased to 110 ℃ and kept for 12h,160 ℃ and 12h,180 ℃ and 12h, and 200 ℃ and 12h. And after the reaction is finished, obtaining a tan polymer with higher viscosity, separating out the tan polymer by using deionized water, washing and drying by using methanol and ethanol, and drying for 12 hours at 120 ℃ under reduced pressure to obtain a high-molecular-weight polybenzimidazole product containing the troger base, wherein the yield is 94.08%. Nuclear magnetic resonance hydrogen spectrum ( 1 H-NMR) showed that the synthesized polymer corresponded to the spectrum. The polymer showed a peak at 13ppm for hydrogen shift of imidazole ring N-H and 4-5ppm for hydrogen shift towards the Gurlel base. Infra-red (FT-IR) at 3628cm -1 And 1617cm -1 The N-H and N = C characteristic absorption peaks of the imidazole ring appear respectively. The polymer successfully synthesized is dissolved by dimethyl sulfoxide (DMSO), the solid content is controlled to be 4%, the polymer is cast on a glass plate to form a film, the film is placed in a vacuum oven to be dried, and the solvent is dried in a temperature programming mode of 2h at 60 ℃, 2h at 90 ℃, 1h at 120 ℃, 1h at 150 ℃, 1h at 180 ℃ and 1h at 210 ℃. After drying completely, slowly cooling to room temperature, and peeling the film from the flat plate to prepare the homopolypolybenzimidazole film, wherein the thickness of the homopolypolybenzimidazole film is controlled to be 25-30 micrometers. It was soaked in 75% phosphoric acid solution at room temperature for 72h to sufficiently adsorb phosphoric acid. Then, the film was cut into a film sample having a length of 3cm by 1cm by drying and the thickness thereof was measuredAnd conducting conductivity test by using the electrochemical workstation.
Example 2: the preparation of the proton exchange membrane copolymerized with the polybenzimidazole containing the comber base is shown as a formula 6, and the prepared polybenzimidazole is a copolymerization product of 5. Firstly, putting a tetraamino monomer F-1 (0.9204g 4 mmol) into a 100ml nitrogen-protected three-neck flask, then sequentially adding 30g of solvent polyphosphoric acid, containing a p-Gerbyl carboxylic acid iv-1 (1.5803g 2mmol) monomer and terephthalic acid J-1 (0.3320g 2mmol) at room temperature, uniformly stirring, then heating to 110 ℃ for reaction for 6 hours, then cooling to a greenhouse, and adding 3g of a dehydrating agent phosphorus pentoxide. Then, the temperature is continuously increased to 110 ℃ and kept for 12h,160 ℃ and 12h,180 ℃ and 12h, and 200 ℃ and 12h. And after the reaction is finished, obtaining a tan polymer with higher viscosity, separating out the tan polymer by using deionized water, washing and drying by using methanol and ethanol, and drying for 12 hours at 120 ℃ under reduced pressure to obtain a high-molecular-weight polybenzimidazole product containing the troger base, wherein the yield is 95.39%. Nuclear magnetic resonance hydrogen spectrum ( 1 H-NMR) showed that the synthesized polymer corresponded to the spectrum. The polymer showed a peak at 12.5-13.5ppm for hydrogen shift of 2N-H copolymerized imidazole rings and a peak at 4-5ppm for hydrogen shift toward the Gule base. Infra-red (FT-IR) at 3630cm -1 And 1610cm -1 The N-H and N = C characteristic absorption peaks of the imidazole ring appear respectively. The polymer which is successfully synthesized is dissolved by dimethyl sulfoxide (DMSO), the solid content is controlled to be 4%, the polymer is cast on a glass plate to form a film, the film is placed in a vacuum oven to be dried, and the solvent is dried in a temperature programming mode of 2h at 60 ℃, 2h at 90 ℃, 1h at 120 ℃, 1h at 150 ℃, 1h at 180 ℃, 1h at 210 ℃ and 1h at 210 ℃. After drying completely, slowly cooling to room temperature, and peeling the film from the flat plate to prepare the polybenzimidazole copolymer membrane containing the troger base, wherein the thickness of the polybenzimidazole copolymer membrane is controlled to be 25-30 micrometers. It was soaked in 65% phosphoric acid solution at room temperature for 72h to sufficiently adsorb phosphoric acid. Then, the film was dried and cut into a film sample having a length by width of 3cm by 1cm, and the thickness thereof was measured to conduct a conductivity test using an electrochemical workstation.
Example 3: the preparation of the proton exchange membrane containing the polybenzimidazole containing the troger base in the sulfonation copolymerization is shown as a formula 7, and the prepared polybenzimidazole is a copolymerization product of 5. Firstly, 1,2,4, 5-benzene tetramine tetrahydrochloride monomer E-1 (1.1360g 4 mmol) is put into a 100ml three-neck flask protected by nitrogen, and then 30g of solvent polyphosphoric acid is added in sequence. The reaction monomer is in a hydrochloride form, and is heated to remove hydrochloride and then reacts, and the specific process comprises the following steps: stirring at normal temperature for 24h, stirring at 60 ℃ for 48h to remove hydrochloride, wherein the hydrochloride residue can influence the molecular weight of the synthesized product. After the hydrochloride is completely removed, the temperature is reduced to the room temperature, monomer containing the p-Gelsel carboxylic acid i-1 (0.6766g 2mmol) and monosodium 2-sulfoterephthalate K-1 (0.5364g 2mmol) are added and stirred evenly at the room temperature, and then the temperature is raised to 110 ℃ for reaction for 6 hours. Then the temperature is lowered to the greenhouse, and 3g of dehydrating agent phosphorus pentoxide is added. Then, the temperature is continuously increased to 110 ℃ and kept for 12h,160 ℃ and 12h,180 ℃ and 12h, and 200 ℃ and 12h. And (3) after the reaction is finished, obtaining a tan polymer with larger viscosity, precipitating the tan polymer by using deionized water, washing and drying by using methanol and ethanol, and drying for 12 hours at 120 ℃ under reduced pressure to obtain a high-molecular-weight polybenzimidazole product containing the troger base, wherein the yield is 95.39%. Nuclear magnetic resonance hydrogen spectrum ( 1 H-NMR) showed that the synthesized polymer corresponded to the spectrum. The polymer has a hydrogen shift peak of 2 copolymerized imidazole ring N-H at 12.5-13.3ppm and-SO at 9ppm 3 The H hydrogen shift peak and the hydrogen shift peak toward the Gel base appeared at 4 to 5 ppm. Infra-red (FT-IR) showed at 3620cm -1 And 1623cm -1 Respectively shows N-H and N = C characteristic absorption peaks of imidazole ring at 1020cm -1 SO appears 3 - Characteristic peak. The polymer successfully synthesized is dissolved by dimethyl sulfoxide (DMSO), the solid content is controlled to be 4%, the polymer is cast on a glass plate to form a film, the film is placed in a vacuum oven to be dried, and the solvent is dried in a temperature programming mode of 2h at 60 ℃, 2h at 90 ℃, 1h at 120 ℃, 1h at 150 ℃, 1h at 180 ℃ and 1h at 210 ℃. After drying completely, slowly cooling to room temperature, peeling the film from the flat plate, and preparing the sulfonated copolymerization polymerThe thickness of the benzimidazole film is controlled to be 25-30 microns. It was soaked in 65% phosphoric acid solution at room temperature for 72h to sufficiently adsorb phosphoric acid. Then, the film was dried and cut into a film sample having a length by width of 3cm by 1cm, and the thickness thereof was measured to conduct a conductivity test using an electrochemical workstation.
Performance testing was performed on the polymers of examples 1-3 and their proton exchange membranes. The polymers were tested for mechanical properties using the tensile test at a tensile rate of 5mm/min. And soaking the film in a phosphoric acid solution to perform a phosphoric acid doping amount test. The PEM conductivity was tested using a four electrode system with an electrochemical workstation. The oxidation resistance of the membrane was tested using the mass change of Fenton's reagent before and after 1h immersion at 80 ℃.
The test results are shown in the following table.
| Example 1 | Example 2 | Example 3 | |
| Tensile Strength, MPa (25 ℃ C.) | 110-145 | 180-200 | 140-180 |
| Tensile modulus, GPa (25 ℃ C.) | 0.5-1.05 | 3.25-4.55 | 3.00-3.85 |
| Phosphoric acid adsorption amount (%) | ﹥200 | ﹥190 | ﹥170 |
| Phosphoric acid solution Length swelling ratio (%) | 14-15 | 10-13 | 7-9 |
| Conductivity, mS cm -1 (0％RH,160℃) | ﹥50 | ﹥80 | ﹥45 |
| Oxidation resistance (80 ℃ for 1h, residual mass%) | ﹥94 | ﹥96 | ﹥98 |
Claims (1)
1. A preparation method of a phosphoric acid-doped polybenzimidazole proton exchange membrane containing a troger base is characterized by comprising the following steps:
(1) Synthesis of polybenzimidazole containing troger base
The specific reaction steps for synthesizing polybenzimidazole containing troger base are shown as the following formula 1:
the method specifically comprises the following steps: adding a tetra-amino monomer A, a dicarboxylic acid monomer B and a monomer C containing a troger base into a three-necked bottle, adopting a mechanical stirring device, and introducing nitrogen for protection; then adding a solvent, wherein the solvent is one or more of polyphosphoric acid or methanesulfonic acid, heating to 110 ℃ for reaction for 12-24h, then cooling to room temperature, adding a proper amount of phosphorus pentoxide, continuously heating, and carrying out heat treatment according to a temperature programming mode of reacting at 110 ℃ for 12-24h, reacting at 160 ℃ for 12-24h, reacting at 180 ℃ for 12-24h, and reacting at 200 ℃ for 12-24 h; after full reaction, obtaining brown polymer solution with higher viscosity; fully separating the powder by using deionized water, washing the powder by using methanol and ethanol, and drying the washed powder for 6 to 12 hours at the temperature of between 50 and 120 ℃ to obtain polybenzimidazole powder containing the troger base;
(2) Preparation of polybenzimidazole proton exchange membrane containing troger base
Dissolving prepared polybenzimidazole powder containing the TOGEL base in an organic solvent, wherein the organic solvent is one or more of N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide to prepare a polymer solution with the solid content of 3-15 wt%, then uniformly casting the polymer solution on flat glass, adjusting the thickness of the casting layer to enable the thickness of the casting layer to be 5-150 micrometers after drying, then putting the flat glass coated with the polymer solution into an inert atmosphere oven or a vacuum oven for drying, carrying out heat treatment and drying on the solvent according to a programmed heating mode of 1-5h at 60 ℃, 1-5h at 90 ℃, 1-5h at 120 ℃, 1-5h at 150 ℃, 1-5h at 180 ℃, and 1-5h at 210 ℃, and peeling the film from the flat glass after cooling to room temperature to obtain a polybenzimidazole exchange membrane containing the TOGEL base;
(3) Preparation of phosphoric acid-doped polybenzimidazole proton exchange membrane containing troger base
Firstly, preparing a phosphoric acid solution with the mass fraction of 5-85%, and shaking up; soaking the proton exchange membrane prepared in the step (2) in a prepared phosphoric acid solution with a specific mass fraction, and keeping the solution at room temperature for 2-7 days to fully adsorb phosphoric acid; then taking out the membrane, wiping the phosphoric acid on the surface of the membrane by using filter paper, and drying for 6-12h at the temperature of 80-150 ℃ to prepare the phosphoric acid doped polybenzimidazole proton exchange membrane containing the troger base;
wherein Ar in the tetraamino monomer A 1 The structure of (a) is any one or more of the structures shown in the following formula 2; wherein X 1 -X 22 Each independently is an unprotonated sulfonate, methyl, hydroxyl or amino group;
ar in dicarboxylic acid monomer B 2 The structure of (a) is any one or more of the structures shown in the following formula 3; wherein R is 1 -R 65 Each independently is an unprotonated sulfonate, methyl, hydroxyl or amino group;
ar in monomer C containing troger base 3 The structure of (a) is any one or more of the structures shown in the following formula 4; wherein Y is 1 -Y 37 Each independently of the other is F, cl, br, I, CH 3 、OH、SO 3 H or H;
the ratio of m to n in the polybenzimidazole prepared in the step (1) is 0-10.
Priority Applications (1)
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