CN112803053A - Preparation method of amino-functionalized polybenzimidazole proton exchange membrane - Google Patents
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Abstract
The invention relates to the technical field of electrochemistry and provides a preparation method of an amino-functional polybenzimidazole proton exchange membrane, wherein 3, 4-diaminobenzoic acid containing nitro is taken as a monomer to polymerize to obtain amino-functional polybenzimidazole, not only can-N = group on imidazole ring of each benzimidazole repeating unit interact with inorganic acid through hydrogen bond, but also-NH group on benzene ring of each benzimidazole repeating unit can interact with inorganic acid in a protonation way, so that compared with traditional PBI and AB type PBI, the amino-functional polybenzimidazole has more action sites with inorganic acid and stronger acid absorption capacity, thereby obviously improving the proton conductivity of the amino-functional polybenzimidazole proton exchange membrane. The prepared amino-functional polybenzimidazole proton exchange membrane has high proton conductivity, high ion selectivity and excellent chemical stability, and is not only suitable for proton exchange membrane fuel cells, but also suitable for the fields of flow batteries, electrochemical sensors and the like.
Description
Technical Field
The invention relates to the technical field of functional polymer materials and electrochemistry, in particular to a preparation method of an amino functional polybenzimidazole proton exchange membrane.
Background
Proton exchange membrane fuel cells can be divided into low-temperature and high-temperature proton exchange membrane fuel cells according to different use temperatures. The former is usually used at a temperature not exceeding 100 ℃ and the proton conducting medium is water, while the latter is used at a temperature ranging from 100 to 200 ℃ and the proton conducting medium is usually a non-aqueous protic solvent. The high-temperature proton exchange membrane fuel cell has the advantages of high electrochemical reaction activity, no water management system, simple heat management system, high CO tolerance and the like, and has wide application prospect in the industries of automobiles, energy generation, aerospace, household power supplies and the like.
Currently, most proton exchange membranes commonly used in high temperature proton exchange membrane fuel cells are Polybenzimidazole (PBI). PBI is an amorphous thermoplastic polymer containing imidazole rings in the backbone, first reported in the US patent in 1959, and the PBI membrane products were marketed by Hoechst Celanese in 1988. Because PBI has excellent thermal stability, chemical stability and good mechanical property, the PBI is widely applied to the fields of aerospace, heat-resistant textiles, adhesives, fuel cells, flow batteries and the like.
Since PBI is itself an insulator of electrons and ions, when used in a fuel cell, it is necessary to dope an inorganic acid (such as phosphoric acid) into a PBI membrane material, and the PBI membrane has proton transfer capability through hydrogen bonding using-N = group on imidazole ring on PBI skeleton and the doped inorganic acid. The doping amount of the acid directly determines the proton conductivity of the PBI membrane, i.e., the more the doping amount of the acid, the higher the proton conductivity the PBI membrane has. Therefore, the doping amount of the inorganic acid is directly determined by the content of the imidazole ring group in the PBI polymer. The synthesis of PBI polymers is currently divided into two categories: firstly, the catalyst is prepared by the condensation polymerization of double monomers, and mainly comprises tetramine and diacid, tetramine and diester, tetramine and dialdehyde, tetramine and diamide, and tetramine and dinitrile; another type is poly-2, 5-benzimidazole (AB-type PBI) prepared by polymerizing 3, 4-diaminobenzoic acid as a single monomer. Compared with PBI prepared by adopting the double-monomer polycondensation, the-NH group on each benzimidazole repeating unit of the AB type PBI can interact with inorganic acid, so that the acid absorption capacity of the AB type PBI is higher than that of PBI with other structures, and the performance of the proton exchange membrane fuel cell is better.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of an amino-functionalized polybenzimidazole proton exchange membrane, which mainly takes 3, 4-diaminobenzoic acid containing nitro as a monomer raw material, polymerizes to obtain polybenzimidazole containing nitro, and then converts the nitro into amino through chemical reaction to obtain the amino-functionalized polybenzimidazole. The introduction of amino can increase the hydrogen bond action site with inorganic acid, and increase the doped acid amount of the polybenzimidazole proton exchange membrane, thereby obviously improving the proton conductivity of the polybenzimidazole proton exchange membrane.
The technical scheme for realizing the purpose of the invention is as follows: a preparation method of an amino-functionalized polybenzimidazole proton exchange membrane comprises the following synthetic route:
or
Or
Comprises the following preparation steps:
s1 Synthesis of Nitropolybenzimidazoles
Under the conditions of nitrogen atmosphere and stirring, adding 3, 4-diaminobenzoic acid monomer containing nitro and phosphorus pentoxide into a solvent A, heating the reactant to 220 ℃ for 1-24 hours, cooling, pouring the reactant into a solvent B for precipitation, neutralizing with NaOH aqueous solution, washing the obtained product with a solvent C until the product is neutral, and finally vacuum-drying the product at 200 ℃ for 12-36 hours to obtain the polybenzimidazole containing nitro;
the nitro-containing 3, 4-diaminobenzoic acid monomer has the structure as follows:
S2 Synthesis of amino-functionalized polybenzimidazole
The obtained polybenzimidazole containing the nitro is subjected to hydrogen catalytic hydrogenation reaction under the condition of heating and pressurizing catalysts or reduction reaction in chemical reducing agents to reduce the nitro into amino, so that amino functionalized polybenzimidazole is obtained;
s3 preparation of amino-functionalized polybenzimidazole proton exchange membrane
Dissolving amino-functional polybenzimidazole into p-toluenesulfonic acid, wherein the concentration is 1-5wt%, stirring at room temperature for 12-24 hours, pouring on a glass plate to form a film, and evaporating the p-toluenesulfonic acid at 180-200 ℃ to obtain an amino-functional polybenzimidazole proton exchange membrane;
the structural formula of the amino-functionalized polybenzimidazole proton exchange membrane is as follows:
In the technical scheme S1, the solvent a is one of polyphosphoric acid and p-toluenesulfonic acid; the solvent B is one of deionized water, ice water, ethanol and acetone; and the solvent C is deionized water.
In the above technical scheme S1, the reactant is heated to 180-200 ℃; the reaction time is 2-10 hours.
In the above technical solution S1, the concentration of the NaOH aqueous solution is 5-20 wt%.
In the above technical solution S1, the concentration of the NaOH aqueous solution is 8-15 wt%.
In the technical scheme S2, the heating temperature is 20-300 ℃; the pressure of the pressurization is 1 x 105-2×107And (6) handkerchief.
In the above technical solution S2, the heating temperature is 20 to 200 ℃.
In the technical scheme S2, the catalyst is one or more of Pd, Pt, Ni and Co, and the dosage of the catalyst is 0.1-5wt% of the mass of the nitro-containing polybenzimidazole.
In the above technical solution S2, the chemical reducing agent is one of a metal and an acid, stannous chloride and hydrochloric acid.
According to the technical scheme, the metal is one of iron or zinc, the acid is dilute hydrochloric acid, the molar weight of iron is 2-4 times that of the polymer containing the nitro-polybenzimidazole, the concentration of the dilute hydrochloric acid is 0.5-1mol/L, a solvent used by the dilute hydrochloric acid is a mixed solution with the volume ratio of ethanol to water being 50%, the molar weight of stannous chloride is 1-4 times that of the polymer containing the nitro-polybenzimidazole, the concentration of the hydrochloric acid is 10-12mol/L, and the reaction temperature of the polymer containing the nitro-polybenzimidazole during the reduction reaction of the chemical reducing agent is 60-90 ℃.
After the technical scheme is adopted, the invention has the following positive effects:
according to the invention, the amino-functionalized polybenzimidazole is obtained by polymerizing 3, 4-diaminobenzoic acid containing nitro group as a monomer, not only can the-N = group on the imidazole ring of each benzimidazole repeating unit interact with inorganic acid through hydrogen bonds, but also the-NH group on the benzene ring of each benzimidazole repeating unit can also interact with inorganic acid in a protonation manner, so that compared with the traditional PBI and AB type PBI, the amino-functionalized polybenzimidazole has more action sites with inorganic acid and stronger acid absorption capacity, and the proton conductivity of the amino-functionalized polybenzimidazole proton exchange membrane can be obviously improved. The prepared amino-functional polybenzimidazole proton exchange membrane has high proton conductivity, high ion selectivity and excellent chemical stability, and is not only suitable for proton exchange membrane fuel cells, but also suitable for the fields of flow batteries, electrochemical sensors and the like.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments.
Example 1: the method comprises the following steps:
(1) synthesis of nitro-containing polybenzimidazole
Adding 2-nitro-3, 4-diaminobenzoic acid monomer and phosphorus pentoxide into polyphosphoric acid under the conditions of nitrogen atmosphere and stirring, heating reactants to 200 ℃, reacting for 24 hours, cooling, pouring the reactants into deionized water for precipitation, neutralizing with 8wt% of NaOH aqueous solution, washing the obtained product with deionized water until the product is neutral, and finally, drying the product at 200 ℃ in vacuum for 36 hours to obtain the nitrobenzene imidazole containing the nitro group.
(2) Synthesis of amino-functionalized polybenzimidazole
The obtained nitro-containing polybenzimidazole is reacted at 20 ℃ and 1X 105And (3) under a Pa and Ni catalyst, carrying out catalytic hydrogenation reaction on the hydrogen to reduce the nitro group into amino group, thus obtaining the amino-functionalized polybenzimidazole. Wherein the amount of the Ni catalyst is 5wt% of the mass of the nitro-containing polybenzimidazole.
(3) Preparation of amino-functional polybenzimidazole proton exchange membrane
Dissolving the obtained amino-functionalized polybenzimidazole into p-toluenesulfonic acid, stirring at room temperature for 12 hours, casting the mixture on a glass plate to form a membrane, and evaporating the p-toluenesulfonic acid at 180 ℃ to obtain the amino-functionalized polybenzimidazole proton exchange membrane, wherein the thickness of the membrane is 50 +/-2 mu m.
Example 2: the method comprises the following steps:
(1) synthesis of nitro-containing polybenzimidazole
Adding 5-nitro-3, 4-diaminobenzoic acid monomer and phosphorus pentoxide into polyphosphoric acid under the conditions of nitrogen atmosphere and stirring, heating the reactants to 150 ℃, reacting for 1 hour, cooling, pouring the reactants into ethanol for precipitation, neutralizing with 15wt% of NaOH aqueous solution, washing the obtained product with deionized water until the product is neutral, and finally drying the product in vacuum at 180 ℃ for 12 hours to obtain the nitrobenzene imidazole containing the nitro group.
(2) Synthesis of amino-functionalized polybenzimidazole
The obtained nitro-containing polybenzimidazole is reacted at 300 ℃ and 2 multiplied by 107And (3) under the catalyst of Pa and Co, the nitro is reduced into amino through hydrogen generation catalytic hydrogenation reaction, and the amino-functionalized polybenzimidazole is obtained. Wherein the dosage of the Co catalyst is 5wt% of the mass of the nitro-containing polybenzimidazole.
(3) Preparation of amino-functional polybenzimidazole proton exchange membrane
Dissolving the obtained amino-functionalized polybenzimidazole into p-toluenesulfonic acid, stirring at room temperature for 12 hours to form a membrane on a glass plate, and evaporating the p-toluenesulfonic acid at 200 ℃ to obtain the amino-functionalized polybenzimidazole proton exchange membrane, wherein the thickness of the membrane is 50 +/-2 mu m.
Example 3: the method comprises the following steps:
(1) synthesis of nitro-containing polybenzimidazole
Under the conditions of nitrogen atmosphere and stirring, 6-nitro-3, 4-diaminobenzoic acid monomer and phosphorus pentoxide are added into polyphosphoric acid, reactants are heated to 220 ℃ and react for 24 hours, the reactants are poured into ice water to be separated out after cooling, then 5wt% of NaOH aqueous solution is used for neutralization, the obtained product is washed by deionized water until the product is neutral, and finally the product is dried in vacuum at 180 ℃ for 36 hours to obtain the nitrobenzene imidazole containing nitro.
(2) Synthesis of amino-functionalized polybenzimidazole
Will getThe obtained nitro-containing polybenzimidazole is at 300 ℃ and 1 multiplied by 107And (3) under a Pa and Pd catalyst, carrying out catalytic hydrogenation reaction on hydrogen to reduce the nitro group into amino group, thus obtaining the amino-functionalized polybenzimidazole. Wherein the dosage of the Pd catalyst is 1wt percent of the mass of the nitro-containing polybenzimidazole.
(3) Preparation of amino-functional polybenzimidazole proton exchange membrane
Dissolving the obtained amino-functionalized polybenzimidazole into p-toluenesulfonic acid, stirring at room temperature for 24 hours to form a membrane by casting on a glass plate, and evaporating the p-toluenesulfonic acid at 180 ℃ to obtain the amino-functionalized polybenzimidazole proton exchange membrane, wherein the thickness of the membrane is 50 +/-2 mu m.
Example 4: the method comprises the following steps:
(1) synthesis of nitro-containing polybenzimidazole
Under the conditions of nitrogen atmosphere and stirring, adding 5-nitro-3, 4-diaminobenzoic acid monomer and phosphorus pentoxide into p-toluenesulfonic acid, heating the reactant to 180 ℃, reacting for 10 hours, cooling, pouring the reactant into acetone for precipitation, neutralizing with 20wt% of NaOH aqueous solution, washing the obtained product with deionized water until the product is neutral, and finally, drying the product at 200 ℃ in vacuum for 24 hours to obtain the nitrobenzene imidazole containing the nitro group.
(2) Synthesis of amino-functionalized polybenzimidazole
The obtained nitro-containing polybenzimidazole is reacted at 300 ℃ and 2 multiplied by 107And (3) under a Pa and Pt catalyst, carrying out catalytic hydrogenation reaction on hydrogen to reduce the nitro group into amino group, thus obtaining the amino-functionalized polybenzimidazole. Wherein the dosage of the Pt catalyst is 0.1wt% of the mass of the nitro-containing polybenzimidazole.
(3) Preparation of amino-functional polybenzimidazole proton exchange membrane
Dissolving the obtained amino-functionalized polybenzimidazole into p-toluenesulfonic acid, stirring at room temperature for 24 hours to form a membrane on a glass plate, and evaporating the p-toluenesulfonic acid at 200 ℃ to obtain the amino-functionalized polybenzimidazole proton exchange membrane, wherein the thickness of the membrane is 50 +/-2 mu m.
Example 5: the method comprises the following steps:
(1) synthesis of nitro-containing polybenzimidazole
Under the conditions of nitrogen atmosphere and stirring, 6-nitro-3, 4-diaminobenzoic acid monomer and phosphorus pentoxide are added into polyphosphoric acid, reactants are heated to 150 ℃ and react for 20 hours, the reactants are poured into deionized water to be separated out after cooling, then 10wt% of NaOH aqueous solution is used for neutralization, the obtained product is washed by the deionized water until the product is neutral, and finally the product is dried in vacuum at 180 ℃ for 24 hours to obtain the nitrobenzene imidazole containing nitro.
(2) Synthesis of amino-functionalized polybenzimidazole
And reducing the nitro group into amino group at 90 ℃ in a solution of which the volume ratio of ethanol to water is 50% by using iron powder and 0.5mol/L diluted hydrochloric acid as catalysts, wherein the molar weight of the iron powder is 4 times that of the nitro group-containing polybenzimidazole, so as to obtain the amino group-functionalized polybenzimidazole.
(3) Preparation of amino-functional polybenzimidazole proton exchange membrane
Dissolving the obtained amino-functionalized polybenzimidazole into p-toluenesulfonic acid, stirring at room temperature for 24 hours to form a membrane on a glass plate, and evaporating the p-toluenesulfonic acid at 200 ℃ to obtain the amino-functionalized polybenzimidazole proton exchange membrane, wherein the thickness of the membrane is 50 +/-2 mu m.
Example 6: the method comprises the following steps:
(1) synthesis of nitro-containing polybenzimidazole
Under the conditions of nitrogen atmosphere and stirring, 2-nitro-3, 4-diaminobenzoic acid monomer and phosphorus pentoxide are added into p-toluenesulfonic acid, reactants are heated to 200 ℃ for 10 hours, the reactants are poured into deionized water to be separated out after cooling, then 15wt% of NaOH aqueous solution is used for neutralization, the obtained product is washed by the deionized water until the product is neutral, and finally the product is dried in vacuum at 200 ℃ for 24 hours to obtain the nitrobenzene imidazole containing nitro.
(2) Synthesis of amino-functionalized polybenzimidazole
And (2) reducing the nitro group into amino group to obtain the amino-functionalized polybenzimidazole in a solution with the volume ratio of ethanol to water of 50 percent by using zinc powder and 1.0mol/L diluted hydrochloric acid as catalysts, wherein the molar weight of the zinc powder is 2 times that of the nitro-functionalized polybenzimidazole, the reaction temperature is 60 ℃, and the nitro group is reduced into the amino group.
(3) Preparation of amino-functional polybenzimidazole proton exchange membrane
Dissolving the obtained amino-functionalized polybenzimidazole into p-toluenesulfonic acid, stirring at room temperature for 24 hours to form a membrane on a glass plate, and evaporating the p-toluenesulfonic acid at 200 ℃ to obtain the amino-functionalized polybenzimidazole proton exchange membrane, wherein the thickness of the membrane is 50 +/-2 mu m.
Example 7: the method comprises the following steps:
(1) synthesis of nitro-containing polybenzimidazole
Adding 5-nitro-3, 4-diaminobenzoic acid monomer and phosphorus pentoxide into polyphosphoric acid under the conditions of nitrogen atmosphere and stirring, heating the reactants to 200 ℃, reacting for 15 hours, cooling, pouring the reactants into ice water for precipitation, neutralizing with 5wt% of NaOH aqueous solution, washing the obtained product with deionized water until the product is neutral, and finally drying the product in vacuum at 180 ℃ for 24 hours to obtain the nitrobenzene imidazole containing the nitro group.
(2) Synthesis of amino-functionalized polybenzimidazole
And (2) reducing the nitro into amino to obtain the amino-functionalized polybenzimidazole in a 12mol/L solution of hydrochloric acid and stannous chloride, wherein the molar weight of the stannous chloride is 4 times that of the nitrobenzimidazole-containing polybenzimidazole, the reaction temperature is 90 ℃.
(3) Preparation of amino-functional polybenzimidazole proton exchange membrane
Dissolving the obtained amino-functionalized polybenzimidazole into p-toluenesulfonic acid, stirring at room temperature for 24 hours to form a membrane on a glass plate, and evaporating the p-toluenesulfonic acid at 200 ℃ to obtain the amino-functionalized polybenzimidazole proton exchange membrane, wherein the thickness of the membrane is 50 +/-2 mu m.
Example 8: the method comprises the following steps:
(1) synthesis of nitro-containing polybenzimidazole
Adding 6-nitro-3, 4-diaminobenzoic acid monomer and phosphorus pentoxide into polyphosphoric acid under the conditions of nitrogen atmosphere and stirring, heating the reactants to 200 ℃, reacting for 20 hours, cooling, pouring the reactants into ethanol for precipitation, neutralizing with 5wt% of NaOH aqueous solution, washing the obtained product with deionized water until the product is neutral, and finally drying the product in vacuum at 200 ℃ for 24 hours to obtain the nitrobenzene imidazole containing the nitro group.
(2) Synthesis of amino-functionalized polybenzimidazole
And (2) reducing the nitro into amino to obtain the amino-functionalized polybenzimidazole in a solution of 10mol/L hydrochloric acid and stannous chloride, wherein the molar weight of the stannous chloride is 1 time of that of the nitrobenzimidazole-containing polybenzimidazole, the reaction temperature is 90 ℃.
(3) Preparation of amino-functional polybenzimidazole proton exchange membrane
Dissolving the obtained amino-functionalized polybenzimidazole into p-toluenesulfonic acid, stirring at room temperature for 24 hours to form a membrane on a glass plate, and evaporating the p-toluenesulfonic acid at 200 ℃ to obtain the amino-functionalized polybenzimidazole proton exchange membrane, wherein the thickness of the membrane is 50 +/-2 mu m.
Example 9: the method comprises the following steps:
(1) synthesis of nitro-containing polybenzimidazole
Adding 2-nitro-3, 4-diaminobenzoic acid monomer and phosphorus pentoxide into polyphosphoric acid under the conditions of nitrogen atmosphere and stirring, heating the reactants to 200 ℃, reacting for 24 hours, cooling, pouring the reactants into ice water for precipitation, neutralizing with 5wt% of NaOH aqueous solution, washing the obtained product with deionized water until the product is neutral, and finally drying the product in vacuum at 200 ℃ for 24 hours to obtain the nitrobenzene imidazole containing the nitro group.
(2) Synthesis of amino-functionalized polybenzimidazole
And (2) reducing the nitro into amino to obtain the amino-functionalized polybenzimidazole in a 12mol/L solution of hydrochloric acid and stannous chloride, wherein the molar weight of the stannous chloride is 4 times that of the nitrobenzimidazole-containing polybenzimidazole, the reaction temperature is 60 ℃.
(3) Preparation of amino-functional polybenzimidazole proton exchange membrane
Dissolving the obtained amino-functionalized polybenzimidazole into p-toluenesulfonic acid, stirring at room temperature for 24 hours to form a membrane on a glass plate, and evaporating the p-toluenesulfonic acid at 200 ℃ to obtain the amino-functionalized polybenzimidazole proton exchange membrane, wherein the thickness of the membrane is 50 +/-2 mu m.
Comparative example: preparation of AB type polybenzimidazole proton exchange membrane
Adding 3, 4-diaminobenzoic acid monomer and phosphorus pentoxide into polyphosphoric acid under the conditions of nitrogen atmosphere and stirring, heating reactants to 200 ℃ for 24 hours, cooling, pouring the reactants into ice water for precipitation, then neutralizing with 5wt% of NaOH aqueous solution, washing the obtained product with deionized water until the product is neutral, and finally drying the product in vacuum at 200 ℃ for 24 hours to obtain AB type polybenzimidazole. Dissolving the obtained AB type polybenzimidazole into p-toluenesulfonic acid, stirring at room temperature for 24 hours to form a film on a glass plate, and evaporating the p-toluenesulfonic acid at 200 ℃ to obtain the AB type polybenzimidazole proton exchange membrane, wherein the thickness of the film is 50 +/-2 mu m.
Finally, the proton exchange membranes prepared in the examples and the comparative examples are cut into membranes with the diameter of 2 cm, the membranes are soaked in 85wt% phosphoric acid aqueous solution at room temperature for doping for 7 days and then taken out, the phosphoric acid aqueous solution on the surfaces of the membranes is sucked off by paper and then weighed, then the membranes are dried at 120 ℃ for 8 hours to remove water and then weighed, and the doping amount of the phosphoric acid is calculated according to the weight difference of the membranes before and after doping the acid. The proton conductivity of the phosphoric acid-doped membrane was measured by an alternating current impedance method using two electrodes. By comparing the data in table 1, it can be found that the phosphoric acid doping amount and proton conductivity of the amino functionalized polybenzimidazole proton exchange membrane are superior to those of the samples in the comparative example.
Phosphoric acid doping amount and conductivity of the film
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The preparation method of the amino-functionalized polybenzimidazole proton exchange membrane is characterized by comprising the following synthetic routes:
or
Or
Comprises the following preparation steps:
s1 Synthesis of Nitropolybenzimidazoles
Under the conditions of nitrogen atmosphere and stirring, adding 3, 4-diaminobenzoic acid monomer containing nitro and phosphorus pentoxide into a solvent A, heating the reactant to 220 ℃ for 1-24 hours, cooling, pouring the reactant into a solvent B for precipitation, neutralizing with NaOH aqueous solution, washing the obtained product with a solvent C until the product is neutral, and finally vacuum-drying the product at 200 ℃ for 12-36 hours to obtain the polybenzimidazole containing nitro;
the nitro-containing 3, 4-diaminobenzoic acid monomer has the structure as follows:
S2 Synthesis of amino-functionalized polybenzimidazole
The obtained polybenzimidazole containing the nitro is subjected to hydrogen catalytic hydrogenation reaction under the condition of heating and pressurizing catalysts or reduction reaction in chemical reducing agents to reduce the nitro into amino, so that amino functionalized polybenzimidazole is obtained;
s3 preparation of amino-functionalized polybenzimidazole proton exchange membrane
Dissolving amino-functional polybenzimidazole into p-toluenesulfonic acid, wherein the concentration is 1-5wt%, stirring at room temperature for 12-24 hours, pouring on a glass plate to form a film, and evaporating the p-toluenesulfonic acid at 180-200 ℃ to obtain an amino-functional polybenzimidazole proton exchange membrane;
the structural formula of the amino-functionalized polybenzimidazole proton exchange membrane is as follows:
In S1, the solvent A is one of polyphosphoric acid and p-toluenesulfonic acid; the solvent B is one of deionized water, ice water, ethanol and acetone; and the solvent C is deionized water.
2. The preparation method of the amino-functionalized polybenzimidazole proton exchange membrane according to claim 1, which is characterized in that: in S1, the reactant is heated to 180-200 ℃; the reaction time is 2-10 hours.
3. The preparation method of the amino-functionalized polybenzimidazole proton exchange membrane according to claim 1, which is characterized in that: in S1, the concentration of the NaOH aqueous solution is 5-20 wt%.
4. The preparation method of the amino functionalized polybenzimidazole proton exchange membrane according to claim 3, which is characterized in that: in S1, the concentration of the NaOH aqueous solution is 8-15 wt%.
5. The preparation method of the amino-functionalized polybenzimidazole proton exchange membrane according to claim 1, which is characterized in that: in S2, the heating temperature is 20-300 ℃; the pressure of the pressurization is 1 x 105-2×107And (6) handkerchief.
6. The preparation method of the amino functionalized polybenzimidazole proton exchange membrane according to claim 5, which is characterized in that: in S2, the heating temperature is 20-200 ℃.
7. The preparation method of the amino-functionalized polybenzimidazole proton exchange membrane according to claim 1, which is characterized in that: in S2, the catalyst is one or more of Pd, Pt, Ni and Co, and the amount of the catalyst is 0.1-5wt% of the mass of the nitro-containing polybenzimidazole.
8. The preparation method of the amino-functionalized polybenzimidazole proton exchange membrane according to claim 1, which is characterized in that: in S2, the chemical reducing agent is one of a metal and an acid, stannous chloride and hydrochloric acid.
9. The method for preparing an amino-functionalized polybenzimidazole proton exchange membrane according to claim 8, which is characterized in that: the metal is one of iron or zinc, the acid is dilute hydrochloric acid, the molar weight of the iron is 2-4 times of that of the polymer containing the nitro-polybenzimidazole, the concentration of the dilute hydrochloric acid is 0.5-1mol/L, the solvent used by the dilute hydrochloric acid is a mixed solution with the volume ratio of ethanol to water being 50%, the molar weight of stannous chloride is 1-4 times of that of the polymer containing the nitro-polybenzimidazole, the concentration of the hydrochloric acid is 10-12mol/L, and the reaction temperature of the polymer containing the nitro-polybenzimidazole during the reduction reaction of the chemical reducing agent is 60-90 ℃.
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