High-alkali-resistance benzimidazole salt-based anion exchange membrane and preparation method thereof
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a high-alkali-resistance imidazolium-based anion exchange membrane and a preparation method thereof.
Background
With the increasing shortage of non-renewable resources such as oil gas and the like and the continuous deep understanding of human beings on the problems of environmental pollution, energy crisis and the like, people pay more and more attention to the development of renewable clean energy. The anion exchange membrane fuel cell is a clean energy device which can convert chemical energy into electric energy directly with high efficiency and zero pollution, has the advantages of high specific power and specific energy, quick load response and no electrolyte loss, and is widely applied to industries of new energy automobiles and the like.
The anion exchange membrane is a core part of the anion exchange membrane fuel cell, and the ideal anion exchange membrane should have excellent mechanical property, chemical stability and alkali resistance and should have higher ion conductivity. However, the traditional quaternary ammonium salt anion exchange membrane in the prior art has poor high temperature resistance and alkali resistance, and cannot be used in an alkaline anion exchange membrane fuel cell for a long time, the benzimidazole salt has improved cation stability due to pi-conjugation effect of imidazole ring, but can still be degraded due to ring-opening reaction of imidazole ring under strong alkaline condition, in order to improve the stability of imidazole cation, various substituents introduced on benzimidazole ring to improve the imidazole ring stability is reported in the prior art, although some progress is made, the problem is not solved fundamentally, and the alkali resistance has great promotion space.
Therefore, there is a need to find a more efficient method for synthesizing anion exchange membranes based on benzimidazolates with better alkali and high temperature resistance.
Disclosure of Invention
The invention mainly aims to provide a high alkali-resistant benzimidazole salt-based anion exchange membrane and a preparation method thereof, wherein the preparation method is simple and easy to implement, has low requirements on equipment, easily available raw materials and low price; the prepared anion exchange membrane based on the benzimidazole salt has more excellent alkali resistance and high temperature resistance, and meets the use requirement of an alkali anion exchange membrane fuel cell.
In order to achieve the above purposes, the technical scheme adopted by the invention is as follows: a preparation method of a high alkali-resistant benzimidazole salt-based anion exchange membrane comprises the following steps:
1) synthesis of polymeric benzimidazole salt: dissolving 1-isopropyl-2-benzimidazolone in an organic solvent, adding 2, 6-dibromo-4, 8-bis [ (2-ethylhexyl) oxy ] benzo [1,2-b:4,5-b' ] dithiophene, a catalyst and a polymerization inhibitor, and stirring for reaction at room temperature for 14-16 hours. Washing with diethyl ether for 3-5 times, and removing solvent by rotary evaporation at 30-40 deg.C;
2) preparation of polymer film: mixing the polymeric benzimidazole salt obtained in the step 1), the polymeric monomer, the emulsifier and the initiator, and dripping the mixture on a glass plate;
3) ion exchange: soaking the polymer membrane prepared in the step 2) in 15-25% of KOH solution by mass percent for 60-74 hours at 50-60 ℃ for ion exchange. Finally, the film bubble is placed in deionized water for 22 to 30 hours, and then taken out to be dried in a vacuum drying oven at the temperature of 80 to 90 ℃ for 12 to 18 hours;
wherein the mass ratio of the 1-isopropyl-2-benzimidazolone, the organic solvent, the 2, 6-dibromo-4, 8-bis [ (2-ethylhexyl) oxy ] benzo [1,2-b:4,5-b' ] dithiophene, the catalyst and the polymerization inhibitor in the step 1) is 1: (5-8): (2-3) 0.5: 0.3;
the organic solvent is selected from one or more of diethyl ether, ethyl acetate and acetone;
the catalyst is selected from one or more of triethylamine, triphenylphosphine and pyridine;
the polymerization inhibitor is selected from one or more of hydroquinone, chloranil and limonene;
the mass ratio of the polymeric benzimidazole salt, the polymeric monomer, the emulsifier and the initiator in the step 2) is (1-2): (3-5): (0.05-0.08): (0.05-0.08);
the polymeric monomer is selected from one or more of styrene, sulfonated styrene, acrylonitrile, vinyl alcohol, methacrylonitrile and methyl methacrylate;
the emulsifier is one or more selected from octoxynol, dodecyl dimethylamine, alkylphenol polyoxyethylene phosphate and polyacrylamide;
the initiator is selected from one or more of benzoin ethyl ether, alpha-dimethoxy-alpha-phenylacetophenone, bis-benzoylphenyl phosphine oxide, 2, 4-dihydroxy benzophenone and thiopropoxy thioxanthone;
the high alkali-resistant benzimidazole salt-based anion exchange membrane is prepared by adopting the preparation method of the high alkali-resistant benzimidazole salt-based anion exchange membrane;
an anion exchange membrane fuel cell employing the highly alkali-resistant benzimidazole salt-based anion exchange membrane as a polymer electrolyte membrane;
due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
(1) the preparation method of the high alkali resistance benzimidazole salt anion-based exchange membrane designed by the invention has the advantages of easily available raw materials, low price, simple and feasible preparation method, low requirement on equipment, no use of substances harmful to the environment and environmental friendliness.
(2) The high alkali resistance anion exchange membrane based on the benzimidazole salt designed by the invention utilizes 2, 6-dibromo-4, 8-bis [ (2-ethylhexyl) oxy ] benzo [1,2-b:4,5-b' ] dithiophene to replace a benzimidazole ring, and the alkali resistance of the benzimidazole ring is stronger due to stronger electronic effect and steric effect.
(3) The high alkali resistance anion exchange membrane based on the benzimidazole salt, which is designed by the invention, is 2, 6-dibromo-4, 8-bis [ (2-ethylhexyl) oxy ] benzo [1,2-b:4,5-b' ] dithiophene which not only serves as a substituent to form benzimidazole salt, but also serves as a cross-linking agent to form a three-dimensional network structure by a polymer membrane, so that the mechanical property, the chemical stability and the heat resistance of the membrane are improved.
(4) The high alkali resistance anion exchange membrane based on the benzimidazole salt, which is designed by the invention, contains ether bonds in the molecular structure, is beneficial to the stability of cationic groups on one hand, and is beneficial to the emulsification compatibility with other polymerized monomers during polymerization on the other hand, and plays a role in emulsification assistance, thereby reducing the amount of an emulsifier and saving the cost.
(5) The high alkali resistance benzimidazole salt-based anion exchange membrane designed by the invention forms a hydrophilic chain segment and a lipophilic chain segment through the copolymerization of different monomers, and forms a special ion channel through the crosslinking of 2, 6-dibromo-4, 8-bis [ (2-ethylhexyl) oxy ] benzo [1,2-b:4,5-b' ] dithiophene, thereby being beneficial to improving the ionic conductivity.
Detailed Description
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art.
The raw materials described in this example were purchased from the national pharmaceutical group chemical agents limited.
Example 1
A preparation method of a high alkali-resistant benzimidazole salt-based anion exchange membrane comprises the following steps:
1) synthesis of polymeric benzimidazole salt: 10g of 1-isopropyl-2-benzimidazolone was dissolved in 50g of diethyl ether, 20g of 2, 6-dibromo-4, 8-bis [ (2-ethylhexyl) oxy ] benzo [1,2-b:4,5-b' ] dithiophene, 5g of triethylamine and 3g of hydroquinone were added thereto, and the mixture was stirred at room temperature for reaction for 14 hours. Washing with diethyl ether for 3 times, and removing solvent by rotary evaporation at 30 deg.C;
2) preparation of polymer film: mixing 1g of polymeric benzimidazole salt obtained in the step 1), 3g of styrene, 0.05g of octoxynol and 0.05g of benzoin ethyl ether, and dripping the mixture on a glass plate;
3) ion exchange: soaking the polymer membrane prepared in the step 2) in a KOH solution with the mass fraction of 15% for 60 hours at 50 ℃ to perform ion exchange. Finally, the film bubble is placed in deionized water for 22 hours, and then taken out to be dried in a vacuum drying oven at the temperature of 80 ℃ for 12 hours;
the high alkali-resistant benzimidazole salt-based anion exchange membrane is prepared by adopting the preparation method of the high alkali-resistant benzimidazole salt-based anion exchange membrane;
an anion exchange membrane fuel cell employing the highly alkali-resistant benzimidazole salt-based anion exchange membrane as a polymer electrolyte membrane.
Example 2
A preparation method of a high alkali-resistant benzimidazole salt-based anion exchange membrane comprises the following steps:
1) synthesis of polymeric benzimidazole salt: 10g of 1-isopropyl-2-benzimidazolone was dissolved in 60g of ethyl acetate, and 23g of 2, 6-dibromo-4, 8-bis [ (2-ethylhexyl) oxy ] benzo [1,2-b:4,5-b' ] dithiophene, 5g of triphenylphosphine and 3g of tetrachlorobenzoquinone were added thereto, and the mixture was stirred at room temperature for reaction for 15 hours. Washing with diethyl ether for 4 times, and removing solvent by rotary evaporation at 33 deg.C;
2) preparation of polymer film: mixing 1.4g of polymeric benzimidazole salt obtained in the step 1), 3.5g of sulfonated styrene, 0.06g of dodecyl dimethylamine and 0.07g of alpha, alpha-dimethoxy-alpha-phenylacetophenone, and dripping the mixture on a glass plate;
3) ion exchange: soaking the polymer membrane prepared in the step 2) in 17% KOH solution by mass for 68 hours at 54 ℃ to perform ion exchange. Finally, the film bubble is placed in deionized water for 27 hours, and then taken out to be dried for 15 hours in a vacuum drying oven at 85 ℃;
the high alkali-resistant benzimidazole salt-based anion exchange membrane is prepared by adopting the preparation method of the high alkali-resistant benzimidazole salt-based anion exchange membrane;
an anion exchange membrane fuel cell employing the highly alkali-resistant benzimidazole salt-based anion exchange membrane as a polymer electrolyte membrane.
Example 3
A preparation method of a high alkali-resistant benzimidazole salt-based anion exchange membrane comprises the following steps:
1) synthesis of polymeric benzimidazole salt: 10g of 1-isopropyl-2-benzimidazolone was dissolved in 70g of acetone, 26g of 2, 6-dibromo-4, 8-bis [ (2-ethylhexyl) oxy ] benzo [1,2-b:4,5-b' ] dithiophene, 5g of pyridine, and 3g of limonene were added thereto, and the reaction was stirred at room temperature for 15.2 hours. Washing with diethyl ether for 5 times, and removing solvent by rotary evaporation at 37 deg.C;
2) preparation of polymer film: mixing 1.5g of polymeric benzimidazole salt obtained in the step 1), 4g of acrylonitrile, 0.07g of alkylphenol polyoxyethylene phosphate and 0.06g of bis-benzoyl phenyl phosphine oxide, and dripping the mixture on a glass plate;
3) ion exchange: soaking the polymer membrane prepared in the step 2) in a KOH solution with the mass fraction of 20% for 69 hours at 56 ℃ for ion exchange. Finally, the film bubble is placed in deionized water for 27 hours, and then taken out to be dried for 16 hours in a vacuum drying oven at 86 ℃;
the high alkali-resistant benzimidazole salt-based anion exchange membrane is prepared by adopting the preparation method of the high alkali-resistant benzimidazole salt-based anion exchange membrane;
an anion exchange membrane fuel cell employing the highly alkali-resistant benzimidazole salt-based anion exchange membrane as a polymer electrolyte membrane.
Example 4
A preparation method of a high alkali-resistant benzimidazole salt-based anion exchange membrane comprises the following steps:
1) synthesis of polymeric benzimidazole salt: 10g of 1-isopropyl-2-benzimidazolone was dissolved in 75g of diethyl ether, 27g of 2, 6-dibromo-4, 8-bis [ (2-ethylhexyl) oxy ] benzo [1,2-b:4,5-b' ] dithiophene, 5g of triethylamine and 3g of chloranil were added thereto, and the mixture was stirred at room temperature for reaction for 15.5 hours. Washing with diethyl ether for 5 times, and removing solvent by rotary evaporation at 40 deg.C;
2) preparation of polymer film: mixing 1.8g of polymeric benzimidazole salt obtained in the step 1), 5g of vinyl alcohol, 0.08g of polyacrylamide and 0.07g of 2, 4-dihydroxy benzophenone, dripping the mixture on a glass plate, putting the glass plate into a radiation field in a nitrogen atmosphere, and irradiating the glass plate for 42 minutes by adopting an ultraviolet lamp with the wavelength of 240 nm;
3) ion exchange: soaking the polymer membrane prepared in the step 2) in KOH solution with the mass fraction of 22% for 70 hours at the temperature of 58 ℃ for ion exchange. Finally, the film bubble is put in deionized water for 28 hours, and then taken out to be dried for 16 hours in a vacuum drying oven at 88 ℃;
the high alkali-resistant benzimidazole salt-based anion exchange membrane is prepared by adopting the preparation method of the high alkali-resistant benzimidazole salt-based anion exchange membrane;
an anion exchange membrane fuel cell employing the highly alkali-resistant benzimidazole salt-based anion exchange membrane as a polymer electrolyte membrane.
Example 5
A preparation method of a high alkali-resistant benzimidazole salt-based anion exchange membrane comprises the following steps:
1) synthesis of polymeric benzimidazole salt: 10g of 1-isopropyl-2-benzimidazolone was dissolved in 80g of ethyl acetate, 30g of 2, 6-dibromo-4, 8-bis [ (2-ethylhexyl) oxy ] benzo [1,2-b:4,5-b' ] dithiophene, 5g of pyridine and 3g of hydroquinone were added thereto, and the mixture was stirred at room temperature for reaction for 16 hours. Washing with diethyl ether for 5 times, and removing solvent by rotary evaporation at 40 deg.C;
2) preparation of polymer film: mixing 2g of polymeric benzimidazole salt obtained in the step 1), 5g of methacrylonitrile, 0.08g of alkylphenol polyoxyethylene ether phosphate and 0.08g of thiopropoxy thioxanthone, dripping the mixture on a glass plate, putting the glass plate into a radiation field in a nitrogen atmosphere, and irradiating for 45 minutes by adopting an ultraviolet lamp with the wavelength of 250 nm;
3) ion exchange: soaking the polymer membrane prepared in the step 2) in a KOH solution with the mass fraction of 25% for 74 hours at the temperature of 60 ℃ to perform ion exchange. Finally, the film bubble is placed in deionized water for 30 hours, and then taken out to be dried in a vacuum drying oven at the temperature of 90 ℃ for 18 hours;
the high alkali-resistant benzimidazole salt-based anion exchange membrane is prepared by adopting the preparation method of the high alkali-resistant benzimidazole salt-based anion exchange membrane;
an anion exchange membrane fuel cell employing the highly alkali-resistant benzimidazole salt-based anion exchange membrane as a polymer electrolyte membrane.
Comparative example
The preparation method of the traditional imidazolium anion-exchange membrane comprises the following steps:
1) preparation of vinylimidazole salts: dissolving 10g of vinyl imidazole in 80g of ethyl acetate, adding 30g of methyl iodide, continuously stirring at room temperature for 16 hours, washing with diethyl ether for 5 times, and then removing the solvent by rotary evaporation at 40 ℃;
2) preparation of polymer film: mixing 2g of vinyl imidazole salt obtained in the step 1), 5g of methacrylonitrile, 0.08g of alkylphenol polyoxyethylene phosphate and 0.08g of thiopropoxy thioxanthone, dripping the mixture on a glass plate, placing the glass plate in a radiation field in a nitrogen atmosphere, and irradiating for 45 minutes by adopting an ultraviolet lamp with the wavelength of 250 nm;
3) ion exchange: soaking the polymer membrane prepared in the step 2) in a KOH solution with the mass fraction of 25% for 74 hours at the temperature of 60 ℃ to perform ion exchange. Finally, the film bubble is placed in deionized water for 30 hours, and then taken out to be dried in a vacuum drying oven at the temperature of 90 ℃ for 18 hours;
the samples obtained in the above examples 1 to 5 and comparative example were subjected to the relevant performance tests, the test results are shown in table 1, the test methods are as follows,
(1) and (3) testing tensile strength: the test is carried out according to GB/T1040-2006 method for testing the tensile property of plastics.
(2) Conductivity: the impedance of the prepared anion-exchange membrane is measured on an electrochemical workstation (Zahner IM6EX) by adopting a two-electrode alternating-current impedance method, and the test frequency is 1 Hz-1 MHz. The conductivity test was performed in a vessel filled with deionized water in order to ensure that the relative humidity of the membrane was 100% and the temperature was controlled at 30 ℃. Before the test at this temperature point, the sample was kept at this temperature for 30min, and the conductivity was calculated according to the following formula:
wherein σIs the electrical conductivity (S cm)-1) L is the distance (cm) between the two electrodes, R is the AC impedance of the sample being measured, and S is the cross-sectional area of the membrane.
(3) Alkali resistance: the alkali resistance of the membrane was measured by immersing the membrane in a 1mol/L KOH aqueous solution at 60 ℃ for 30 days and calculating the rate of change in conductivity before and after immersion. The calculation formula is as follows: change rate (conductivity before soaking-conductivity after soaking)/conductivity before soaking × 100%.
TABLE 1 Properties of samples of examples and comparative examples
As can be seen from the above table, the high alkali resistance based on benzimidazole anion-exchange membrane disclosed in the embodiment of the invention has the tensile strength of 62-73MPa, the elongation at break of 171-193% and the electrical conductivity of 0.0780-0.0940S cm-1Alkali resistance of 0.01-0.1%, tensile strength of 26MPa, elongation at break of 97% and conductivity of 0.026S cm-1Alkali resistance is 2.2%; therefore, the high alkali-resistant benzimidazole-based anion-exchange membrane disclosed by the invention has better mechanical property, ion conductivity and alkali resistance, and meets the use requirement of an alkaline anion-exchange membrane fuel cell.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.