CN108586745B - Anion exchange membrane based on fluorinated polybenzimidazole and preparation method thereof - Google Patents

Anion exchange membrane based on fluorinated polybenzimidazole and preparation method thereof Download PDF

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CN108586745B
CN108586745B CN201810337091.6A CN201810337091A CN108586745B CN 108586745 B CN108586745 B CN 108586745B CN 201810337091 A CN201810337091 A CN 201810337091A CN 108586745 B CN108586745 B CN 108586745B
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林本才
徐斐
袁文森
陈乾
储富强
丁建宁
袁宁一
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Abstract

The invention relates to an anion exchange membrane based on fluorinated polybenzimidazole and a preparation method thereof, the anion exchange membrane comprises a repeating unit shown as a formula (1) in a structural general formula,
Figure DDA0001629540060000011
wherein n is the degree of polymerization; x is an integer of 2 to 12, and y is an integer of 0 to 11; r is H, methyl, ethyl, isopropyl or phenyl. The film thus prepared has excellent mechanical properties, alkali resistance, heat resistance, low water absorption and high electrical conductivity; and the preparation process is relatively simple and safe, and the use of carcinogenic chloromethyl ether in the traditional preparation process of the quaternary ammonium salt type anion membrane is avoided.

Description

Anion exchange membrane based on fluorinated polybenzimidazole and preparation method thereof
Technical Field
The invention belongs to the field of high polymer materials, relates to an anion exchange membrane, and particularly relates to an anion exchange membrane based on fluorinated polybenzimidazole and a preparation method thereof.
Background
Polymer electrolyte membrane fuel cells have attracted considerable attention because of their high efficiency and cleanliness characteristics. Polymer electrolyte membranes can be classified into proton exchange membrane fuel cells and alkaline anion exchange membrane fuel cells according to the kind of the polymer membrane. The proton conductivity of the acid polymer film represented by Nafion at present strongly depends on water, and when the temperature is higher than 90 ℃, the proton conductivity of the acid polymer film is lost due to the evaporation of the water, so that the high-performance design and application environment of the PEMFCs are limited, and the advantages of the PEMFCs in working at high temperature (such as improvement of CO tolerance, simplification of hydrothermal management and the like) cannot be reflected; in addition, the serious dependence of PEMFCs on noble metal catalysts makes their production cost high and also one of the factors limiting their widespread use.
Compared with proton exchange membrane fuel cells, anion exchange membrane fuel cell technology has the following advantages: (1) the catalyst has lower requirements, and silver or nickel can be used as the catalyst to replace noble metal platinum; (2) cations in the alkaline anion exchange membrane are all fixed on a polymer chain, free salt does not exist in a liquid phase, and the phenomenon that the conventional alkaline liquid electrolyte of the alkaline fuel cell is easy to react with CO can be avoided2The effect of the reaction; (3) the transmission direction of the conductive ions in the membrane is opposite to the diffusion direction of the fuel, so that the permeation of the fuel in the membrane is favorably inhibited. Anion Exchange Membranes (AEMs) are one of the core components of an anion exchange membrane fuel cell, and the performance of the AEMs directly determines the performance and the service life of the cell. The AEM study began in 1994. Guinot et al used PEO as a matrix to mix potassium hydroxide and water to form a polymer for the first time with a room temperature conductivity in the range of 10-3～10-4S/cm. Subsequently, a series of novel polymer electrolyte membranes suitable for use in alkaline anion exchange membrane fuel cells were successfully prepared. Wherein, the main part is quaternary ammonium type anion exchange membrane.
However, the conventional quaternary ammonium-type membranes have two major disadvantages to be solved: 1) the polymer electrolyte membrane for the alkaline fuel cell is mainly based on quaternary ammonium salt alkaline polymers, and has the advantages of poor dimensional stability, high water absorption, high swelling degree and poor mechanical properties; 2) in the preparation process of the traditional quaternary ammonium salt polymer, the highly toxic substance chloromethyl ether is one of the indispensable raw materials, so that the preparation of the alkaline anion-exchange membrane has great harm to human bodies and the environment. Therefore, it is necessary to prepare a polymer electrolyte membrane material having high electrical conductivity, good thermal stability, and good dimensional stability.
Disclosure of Invention
The object of the present invention is to overcome the disadvantages of the prior art by providing an anion exchange membrane based on fluorinated polybenzimidazole.
In order to achieve the purpose, the invention adopts the technical scheme that: an anion exchange membrane based on fluorinated polybenzimidazole, which comprises a repeating unit shown as a formula (1) in the structural general formula,
Figure BDA0001629540040000021
wherein n is the degree of polymerization; x is an integer of 2 to 12, and y is an integer of 0 to 11; r is H, methyl, ethyl, isopropyl or phenyl.
Preferably, R is isopropyl or phenyl.
Further, R is phenyl.
Further, x is an integer of 2 to 6.
Further, y is an integer of 0 to 3.
Still another object of the present invention is to provide a method for preparing the above anion exchange membrane based on fluorinated polybenzimidazole, which comprises the following steps:
(a) imidazole derivatives
Figure BDA0001629540040000022
Reacting with dihalo-hydrocarbon to produce organic salt monomer
Figure BDA0001629540040000023
(b) Dissolving the organic salt monomer and the fluorine-containing polybenzimidazole in an organic solvent, stirring for reaction, pouring into a mold, and drying to obtain a halogen-containing polymer electrolyte membrane;
(c) immersing the halogen-containing polymer electrolyte membrane in an OH-containing solution-Ion exchange is carried out in the alkaline aqueous solution.
Preferably, the organic solvent is DMF or DMSO.
Optimally, the molar ratio of the organic salt monomer to the fluorine-containing polybenzimidazole is 2: 1.
optimally, the synthesis of the fluorine-containing polybenzimidazole is as follows: adding polyphosphoric acid, 3' -diaminobiphenyldiamine and 2, 2-bis (4-carboxyphenyl) hexafluoropropane into a reaction container to form a mixed solution, then placing the mixed solution at 90-140 ℃ under the protection of nitrogen for gradient heating reaction, pouring the mixed solution into deionized water while the mixed solution is hot, and washing to obtain a precipitated polymer.
Preferably, in step (a), the imidazole derivative
Figure BDA0001629540040000024
And carrying out stirring reaction with excessive dihalogenated hydrocarbon for 6-24 hours under the condition of ice water bath.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: according to the anion exchange membrane based on the fluorinated polybenzimidazole, the fluorine-containing polybenzimidazole is used as a main polymer chain, and the imidazole derivative is used as a side chain, so that the prepared membrane has excellent mechanical property, alkali resistance, heat resistance, low water absorption and high conductivity; and the preparation process is relatively simple and safe, and the use of carcinogenic chloromethyl ether in the traditional preparation process of the quaternary ammonium salt type anion membrane is avoided.
Drawings
FIG. 1 is a nuclear magnetic spectrum of a halogen-containing polymer electrolyte membrane according to example 1.
Detailed Description
The invention relates to an anion exchange membrane based on fluorinated polybenzimidazole, which comprises a repeating unit shown as a formula (1) in a structural general formula,
Figure BDA0001629540040000031
wherein n is the degree of polymerization (n is sufficient if the anion exchange membrane can form a film); x is an integer of 2 to 12, and y is an integer of 0 to 11; r is H, methyl, ethyl, isopropyl or phenyl. By adopting fluorine-containing polybenzimidazole as a polymer main chain and imidazole derivatives as side chains, the prepared film has excellent mechanical properties, alkali resistance, heat resistance, low water absorption and high conductivity; and the preparation process is relatively simple and safe, and the use of carcinogenic chloromethyl ether in the traditional preparation process of the quaternary ammonium salt type anion membrane is avoided. x is usually an integer of 2 to 6, and y is usually an integer of 0 to 3.
The preparation method of the anion exchange membrane based on the fluorinated polybenzimidazole comprises the following steps: (a) imidazole derivatives
Figure BDA0001629540040000032
Reacting with dihalo-hydrocarbon to produce organic salt monomer
Figure BDA0001629540040000033
(b) Dissolving the organic salt monomer and the fluorine-containing polybenzimidazole in an organic solvent, stirring for reaction, pouring into a mold, and drying to obtain a halogen-containing polymer electrolyte membrane; (c) immersing the halogen-containing polymer electrolyte membrane in an OH-containing solution-Ion exchange is carried out in the alkaline aqueous solution. The organic solvent is DMF or DMSO, and the molar ratio of the organic salt monomer to the fluorine-containing polybenzimidazole is 2: 1. the synthesis of the fluorine-containing polybenzimidazole is as follows: adding polyphosphoric acid, 3' -diaminobiphenyldiamine and 2, 2-bis (4-carboxyphenyl) hexafluoropropane into a reaction container to form a mixed solution, then placing the mixed solution at 90-140 ℃ under the protection of nitrogen for gradient heating reaction, pouring the mixed solution into deionized water while the mixed solution is hot, and washing to obtain a precipitated polymer. In the step (a), the imidazole derivative
Figure BDA0001629540040000041
And (3) stirring and reacting with equimolar or excessive dihalogenated hydrocarbon for 6-24 hours under the condition of an ice water bath.
The present invention will be further illustrated with reference to the following examples.
Example 1
This example provides a method for preparing an anion exchange membrane based on fluorinated polybenzimidazole, comprising the steps of:
(a) preparation of organic salt monomer: dissolving 0.96g (0.01mol) of 1, 2-dimethylimidazole in 20ml of ethyl acetate, stirring until the solution is dissolved, adding 2.44g (0.01mol) of 1, 6-dibromohexane in an ice-water bath, and reacting for 12 hours to generate white precipitate; washing the crude product with ethyl acetate, standing, separating and purifying; repeating the steps for three times to obtain the organic salt monomer, wherein the molecular structure of the organic salt monomer is as follows:
Figure BDA0001629540040000042
(see the step for the preparation method of other imidazole structure-containing organic salt monomers described below);
(b) 0.30g (0.559mmol) of a fluorine-containing polymer was addedBenzimidazoles and
Figure BDA0001629540040000043
(0.37g, 1.118mmol) in dimethyl sulfoxide, stirring at 60 deg.C for 24 hr, pouring the reaction solution into a clean polytetrafluoroethylene mold, and drying at 75 deg.C for 48 hr to obtain halogen-containing polymer electrolyte membrane (the structure and nuclear magnetic spectrum of halogen-containing polymer electrolyte membrane are shown in FIG. 1); the preparation of the fluorine-containing polybenzimidazole comprises the following steps: adding 126g of polyphosphoric acid (PPA) into a clean three-neck flask, stirring at 90 ℃ under the condition of introducing nitrogen, and extruding internal air until the solution is clear and transparent; adding 2.68g of 3,3 '-diaminobenzidine into a flask, and stirring until the 3, 3' -diaminobenzidine is completely dissolved; then 2, 2-bis (4-carboxyphenyl) hexafluoropropane is added into the mixed solution (the molar ratio of 3, 3' -diaminobiphenyldiamine to 2, 2-bis (4-carboxyphenyl) hexafluoropropane is 1:1), and the mixture is reacted for 3 hours at 90 ℃, and then the mixture is reacted for 12 hours, 12 hours and 6 hours at 100 ℃, 120 ℃ and 140 ℃ respectively (nitrogen protection is introduced in the whole reaction process); pouring the reaction product into deionized water while the reaction product is hot, and washing until the pH value of the washing liquid is 7, wherein the separated filamentous polymer is fluorine-containing polybenzimidazole (specifically, the reference can be made to J.Polym.Sci., Part A: Polym.Chem.,2006,44, 4508-one-phase 4513);
(c) the prepared halogen-containing polymer electrolyte membrane was immersed in a 1M KOH solution at 60 ℃ for 24 hours to allow halogen anions to be exchanged with OH-Removing residual KOH on the surface of the halogen-containing polymer electrolyte membrane by using deionized water, and measuring the performance parameters of the anion exchange membrane as follows: the water absorption rate at room temperature is 32.82 percent, the swelling degree is 7.71 percent, the ion exchange capacity is 2.09mmol/g, the tensile strength is 41.29MPa, the ionic conductivity at room temperature can reach 20.12mS/cm, and the ionic conductivity at 80 ℃ is 52.69 mS/cm; the membrane is soaked in 2M KOH at 60 ℃ for 300h, and the ionic conductivity of the membrane is measured again at room temperature and is 18.98mS/cm, so that the membrane is proved to have good alkali resistance.
Example 2
This example provides a process for the preparation of an anion exchange membrane based on fluorinated polybenzimidazole, which is essentially identical to that of example 1, except that: 1-methylimidazole is used in step (a); the performance parameters of the anion exchange membrane were measured as: the water absorption rate at room temperature is 28.33 percent, the swelling degree is 6.54 percent, the ion exchange capacity is 2.32mmol/g, the tensile strength is 43.02MPa, the ionic conductivity at room temperature can reach 21.22mS/cm, and the ionic conductivity at 80 ℃ is 53.09 mS/cm; the membrane was soaked in 2M KOH at 60 ℃ for 300h, and its ionic conductivity was measured again at room temperature and was 20.98mS/cm, demonstrating good alkali resistance.
Example 3
This example provides a process for the preparation of an anion exchange membrane based on fluorinated polybenzimidazole, which is essentially identical to that of example 1, except that: 1-methyl-2-ethylimidazole is used in step (a); the performance parameters of the anion exchange membrane were measured as: the water absorption rate at room temperature is 24.32 percent, the swelling degree is 6.02 percent, the ion exchange capacity is 2.18mmol/g, the tensile strength is 44.21MPa, the ionic conductivity at room temperature can reach 19.67mS/cm, and the ionic conductivity at 80 ℃ is 47.02 mS/cm; the membrane is soaked in 2M KOH at 60 ℃ for 300h, and the ionic conductivity of the membrane is measured again at room temperature and is 19.54mS/cm, so that the membrane is proved to have good alkali resistance.
Example 4
This example provides a process for the preparation of an anion exchange membrane based on fluorinated polybenzimidazole, which is essentially identical to that of example 1, except that: 1-methyl-2-isopropylimidazole is used in step (a); the performance parameters of the anion exchange membrane were measured as: the water absorption rate at room temperature is 23.83%, the swelling degree is 5.88%, the ion exchange capacity is 2.13mmol/g, the tensile strength is 45.87MPa, the ionic conductivity at room temperature can reach 18.22mS/cm, and the ionic conductivity at 80 ℃ is 40.72 mS/cm; the membrane is soaked in 2M KOH at 60 ℃ for 300h, and the ionic conductivity of the membrane is measured again at room temperature and is 17.79mS/cm, so that the membrane is proved to have good alkali resistance.
Example 5
This example provides a process for the preparation of an anion exchange membrane based on fluorinated polybenzimidazole, which is essentially identical to that of example 1, except that: 1-methyl-2-phenylimidazole is used in step (a); the performance parameters of the anion exchange membrane were measured as: the water absorption rate at room temperature is 22.01 percent, the swelling degree is 5.09 percent, the ion exchange capacity is 2.06mmol/g, the tensile strength is 49.32MPa, the ionic conductivity at room temperature can reach 17.62mS/cm, and the ionic conductivity at 80 ℃ is 38.75 mS/cm; the membrane is soaked in 2M KOH at 60 ℃ for 300h, and the ionic conductivity of the membrane is measured again at room temperature and is 16.93mS/cm, so that the membrane is proved to have good alkali resistance. Comparing examples 1 to 5, it can be concluded that such anion exchange membranes have higher electrical conductivity and better mechanical strength while maintaining lower water absorption and swelling capacity, and excellent alkali resistance.
Example 6
This example provides a process for the preparation of an anion exchange membrane based on fluorinated polybenzimidazole, which is essentially identical to that of example 1, except that: in the step (a), the molecular structure of the prepared organic salt monomer is
Figure BDA0001629540040000061
The performance parameters of the anion exchange membrane were measured as: the water absorption rate at room temperature is 48.98%, the swelling degree is 15.01%, the ion exchange capacity is 1.72mmol/g, the tensile strength is 32.06MPa, the ionic conductivity is 15.38mS/cm, and the water absorption rate at 80 ℃ can reach 42.10 mS/cm; the membrane is soaked in 2M KOH at 60 ℃ for 300h, and the ionic conductivity of the membrane is measured to be 12.23mS/cm again at room temperature, so that the membrane is proved to have good alkali resistance.
Example 7
This example provides a process for the preparation of an anion exchange membrane based on fluorinated polybenzimidazole, which is essentially identical to that of example 1, except that: in the step (a), the molecular structure of the prepared organic salt monomer is
Figure BDA0001629540040000062
The performance parameters of the anion exchange membrane were measured as: the water absorption rate at room temperature is 23.70 percent, the swelling degree is 6.38 percent, the ion exchange capacity is 2.18mmol/g, the tensile strength is 38.86MPa, the ionic conductivity is 24.99mS/cm, and the water absorption rate can reach 50.37mS/cm at 80 ℃. The membrane is soaked in 2M KOH at 60 ℃ for 300h, and the ionic conductivity of the membrane is measured to be 23.56mS/cm again at room temperature, so that the membrane is proved to have good alkali resistance.
Example 8
This example provides a process for the preparation of an anion exchange membrane based on fluorinated polybenzimidazole, which is essentially identical to that of example 1, except that: in the step (a), the molecular structure of the prepared organic salt monomer is
Figure BDA0001629540040000063
The performance parameters of the anion exchange membrane were measured as: the water absorption rate at room temperature is 32.98 percent, the swelling degree is 7.93 percent, the ion exchange capacity is 2.02mmol/g, the tensile strength is 29.14MPa, the ionic conductivity is 19.96mS/cm, and the water absorption rate can reach 39.87mS/cm at 80 ℃. The membrane is soaked in 2M KOH at 60 ℃ for 300h, and the ionic conductivity of the membrane is measured to be 18.65mS/cm again at room temperature, so that the membrane is proved to have good alkali resistance.
Example 9
This example provides a process for the preparation of an anion exchange membrane based on fluorinated polybenzimidazole, which is essentially identical to that of example 1, except that: in the step (a), the molecular structure of the prepared organic salt monomer is
Figure BDA0001629540040000071
The performance parameters of the anion exchange membrane were measured as: the water absorption rate at room temperature is 34.45%, the swelling degree is 9.12%, the ion exchange capacity is 1.98mmol/g, the tensile strength is 26.67MPa, the ionic conductivity is 18.47mS/cm, and the ionic conductivity can reach 38.76mS/cm at 80 ℃. The membrane was immersed in 2MKOH at 60 ℃ for 300h and its ionic conductivity was again measured at room temperature to be 17.10mS/cm, demonstrating good alkali resistance.
Comparative example 1
This example provides a method for preparing an anion-exchange membrane, which is disclosed in chinese patent application No. 201610357185.0, example 2, and under the same experimental conditions, the performance parameters of the anion-exchange membrane measured are: the ionic conductivity at room temperature is 11.00mS/cm, the ionic conductivity can reach 29.56mS/cm at 80 ℃, and the tensile strength is 15.04 Mpa; the water absorption at room temperature was 68.23% and the degree of swelling was 25.77%.
Comparative example 2
This example provides a method for preparing an anion-exchange membrane, which is disclosed in chinese patent application No. 201210212672.X, in example 10, and under the same experimental conditions, the measured performance parameters of the anion-exchange membrane are: the ionic conductivity at room temperature is 16.20mS/cm, the ionic conductivity can reach 37.00mS/cm at the temperature of 80 ℃, and the tensile strength is 16.32 Mpa; the water absorption at room temperature was 55.22%, and the degree of swelling was 21.82%.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.

Claims (10)

1. An anion exchange membrane based on fluorinated polybenzimidazole is characterized in that the anion exchange membrane comprises a repeating unit shown as a formula (1) in a structural general formula,
Figure FDA0001629540030000011
wherein n is the degree of polymerization; x is an integer of 2 to 12, and y is an integer of 0 to 11; r is H, methyl, ethyl, isopropyl or phenyl.
2. The fluorinated polybenzimidazole-based anion exchange membrane according to claim 1, characterized in that: r is isopropyl or phenyl.
3. The fluorinated polybenzimidazole-based anion exchange membrane according to claim 2, characterized in that: r is phenyl.
4. The fluorinated polybenzimidazole-based anion exchange membrane according to claim 3, characterized in that: x is an integer from 2 to 6.
5. The fluorinated polybenzimidazole-based anion exchange membrane according to claim 4, characterized in that: y is an integer of 0 to 3.
6. Process for the preparation of a fluorinated polybenzimidazole based anion exchange membrane according to any of claims 1 to 5, characterized in that it comprises the following steps:
(a) imidazole derivatives
Figure FDA0001629540030000012
Reacting with dihalo-hydrocarbon to produce organic salt monomer
Figure FDA0001629540030000013
(b) Dissolving the organic salt monomer and the fluorine-containing polybenzimidazole in an organic solvent, stirring for reaction, pouring into a mold, and drying to obtain a halogen-containing polymer electrolyte membrane;
(c) immersing the halogen-containing polymer electrolyte membrane in an OH-containing solution-Ion exchange is carried out in the alkaline aqueous solution.
7. The process for the preparation of anion exchange membranes based on fluorinated polybenzimidazole according to claim 6, characterized in that: the organic solvent is DMF or DMSO.
8. The process for the preparation of anion exchange membranes based on fluorinated polybenzimidazole according to claim 6, characterized in that: the molar ratio of the organic salt monomer to the fluorine-containing polybenzimidazole is 2: 1.
9. the method for preparing an anion exchange membrane based on fluorinated polybenzimidazole according to claim 6, characterized in that the synthesis of said fluorinated polybenzimidazole is: adding polyphosphoric acid, 3' -diaminobiphenyldiamine and 2, 2-bis (4-carboxyphenyl) hexafluoropropane into a reaction container to form a mixed solution, then placing the mixed solution at 90-140 ℃ under the protection of nitrogen for gradient heating reaction, pouring the mixed solution into deionized water while the mixed solution is hot, and washing to obtain a precipitated polymer.
10. The process for the preparation of anion exchange membranes based on fluorinated polybenzimidazole according to claim 6, characterized in that: in the step (a), the imidazole derivative
Figure FDA0001629540030000021
And carrying out stirring reaction with excessive dihalogenated hydrocarbon for 6-24 hours under the condition of ice water bath.
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