CN113150344A - Proton exchange membrane with main polymer chain of aromatic ring structure and preparation method thereof - Google Patents
Proton exchange membrane with main polymer chain of aromatic ring structure and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a polymer proton exchange membrane and a preparation method thereof, in particular to a proton exchange membrane with a polymer main chain of an aromatic ring structure and a preparation method thereof. Firstly, dissolving biphenyl, 2-dihydroxybiphenyl and trifluoroacetophenone in dichloromethane, adding a catalyst under an ice bath condition, and reacting to obtain a polymer containing a hydroxyl functional group; then adding a compound containing hydroxyl functional groups, 1, 3-propane sultone and strong base into a reactor containing a high-boiling point solvent, and reacting to obtain a polymer containing sulfonic groups; dissolving the prepared polymer and preparing the polymer by a solution casting methodThe proton exchange membrane is soaked in acid solution to obtain cation H+The proton exchange membrane of (1). The invention designs a high-performance proton exchange membrane with an aromatic ring as a main chain structure for a fuel cell, and improves the flexibility of the proton exchange membrane by introducing a flexible side chain. The obtained proton exchange membrane has high conductivity and good mechanical property and dimensional stability.
Description
Technical Field
The invention relates to a polymer proton exchange membrane and a preparation method thereof, in particular to a proton exchange membrane with a polymer main chain of an aromatic ring structure and a preparation method thereof.
Background
The Proton Exchange Membrane Fuel Cell (PEMFC) has the advantages of low working temperature, quick start, high specific power, simple structure, convenient operation and the like. The method is widely applied to the fields of electric automobiles, fixed power stations and the like. At present, PEMFCs mostly use perfluorosulfonic acid membranes such as Nation, and a commonly used Proton Exchange Membrane (PEM) is a Nation proton exchange membrane of dupont, usa, and has the advantages of high proton conductivity and good chemical stability, but the Nation proton exchange membrane also has the following disadvantages: firstly, the processing is difficult and the cost is high. The synthesis and sulfonation of perfluoro-materials are very difficult, and the hydrolysis and sulfonation in the film-forming process easily denature and degrade polymers, so that the film-forming is difficult and the cost is high; ② the requirement for temperature and water content is high. The optimum working temperature of the Nation series film is 70-90 ℃, and the water content of the Nation series film is sharply reduced and the conductivity is rapidly reduced when the temperature is exceeded, so that the electrode reaction speed is difficult to increase, and the catalyst is easy to be poisoned.
The excellent alkaline polymer proton exchange membrane has high ionic conductivity, good thermal stability and chemical stability, and also has good mechanical property and acid corrosion resistance. Therefore, the development of novel polymer proton exchange membrane materials for fuel cells has become a hot spot of research.
Disclosure of Invention
The invention aims to provide a high-performance proton exchange membrane taking an aromatic ring as a main chain structure and a preparation method thereof. The proton exchange membrane with the rigid main chain structure and the flexible functional group with the controllable length of the side chain, which is prepared by the method, has the advantages that the microphase separation structure can form a proton conduction channel, so that the conductivity is improved, and the prepared proton exchange membrane has lower swelling ratio due to the good dimensional stability of the rigid main chain structure.
The chemical structure of the proton exchange membrane with the main chain structure of the aromatic ring is as follows:
wherein n is 2 or 3, X and Y only represent two structural units, (X: Y ═ 9: 1-1: 2) does not represent the true chemical structural formula, and R is methyl or benzene ring.
The technical scheme adopted by the invention is as follows: a high-performance proton exchange membrane with an aromatic ring as a main chain structure and a preparation method thereof comprise the following steps:
(1) polycondensation reaction to prepare polymer: dissolving biphenyl, 2-dihydroxybiphenyl and trifluoroacetophenone in dichloromethane, respectively adding trifluoroacetic acid and trifluoromethanesulfonic acid as catalysts under an ice bath condition, removing the ice bath, stirring at room temperature for reaction for 48-72 hours until the solution is highly viscous, and obtaining the polymer containing hydroxyl functional groups after the reaction is finished and through precipitation, washing and drying.
Wherein the molar ratio of biphenyl to 2, 2-dihydroxybiphenyl to trifluoroacetophenone is 9-1: 1-2: 11-3.3, and the flexibility and water absorption swelling of the polymer are controlled by controlling the amount of 2, 2-dihydroxybiphenyl.
The molar ratio of the total amount of biphenyl and dihydroxybiphenyl reactants, trifluoroacetic acid and trifluoromethanesulfonic acid is 1:4: 11.
(2) Polymer functionalization: and (2) adding the hydroxyl functional group-containing compound prepared in the step (1), 1, 3-propane sultone and strong base into a reactor containing a high-boiling point solvent, reacting for 6-8 hours at 60-80 ℃, and precipitating, washing and drying after the reaction is finished to obtain the polymer containing the sulfonic group.
The high boiling point solvent is one selected from N, N-dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone.
The molar ratio of the compound containing hydroxyl functional groups, 1, 3-propane sultone and strong base is 1:1.1: 2.
The strong base is sodium hydroxide, sodium hydride or potassium hydroxide.
(3) Film forming: dissolving the polymer prepared in the step (2) in N, N-dimethylformamide or dimethyl sulfoxide, preparing a proton exchange membrane by a solution casting method, and soaking the proton exchange membrane in an acidic solution (hydrogen chloride solution or dilute sulfuric acid) to obtain a cation H+The proton exchange membrane of (1).
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
(1) the invention designs a series of high-performance proton exchange membranes with aromatic rings as main chain structures, in particular designs a novel polymer proton exchange membrane for a fuel cell, the proton transmission channel and the electric conductivity of the novel polymer proton exchange membrane are controllable, and the water absorption swelling of the membrane can be inhibited.
(2) The polymer designed by the invention improves the flexibility of the proton exchange membrane by introducing the flexible side chain, and the proton exchange membrane has high conductivity, good mechanical property and dimensional stability.
Drawings
FIG. 1 example 1 Polymer Nuclear magnetic map.
Detailed Description
The present invention is further described below with reference to examples, but is not limited thereto.
Example 1
The embodiment provides a proton exchange membrane and a preparation method thereof, and the preparation method comprises the following specific steps:
1) to a three-necked flask, biphenyl (3.2mmol), 2, 2-dihydroxybiphenyl (3.2mmol), trifluoroacetophenone (7.0mmol) and 20ml of dichloromethane were added, and the acid catalyst was added under ice-water bath, 2ml of trifluoroacetic acid and 6ml of trifluoromethanesulfonic acid, and the reaction was mechanically stirred at room temperature for about 24 hours until the solution was highly viscous. And precipitating the obtained polymer containing phenolic hydroxyl by using deionized water, washing the polymer for multiple times by using deionized water and ethanol, and drying the polymer for later use.
To a flask, 1g of a polymer having a phenolic hydroxyl group, 0.8g of 1, 3-propanesultone (excess) and 30ml of N, N-dimethylformamide were added, 0.5g of sodium hydroxide as a catalyst was added, and the temperature was raised to 80 ℃ to react for 6 hours. The obtained polymer is precipitated and separated by deionized water and then washed by deionized water and ethanolDrying for later use. Using the obtained polymer1The structure was characterized by H NMR and the results are shown in FIG. 1.
2) Film forming: the obtained polymer was sufficiently dissolved in N, N-dimethylformamide, and the polymer solution was dropped onto a polytetrafluoroethylene plate and dried at 70 ℃ for 2 hours to prepare Na+A proton exchange membrane. The resulting membrane was placed in 1M HCl solution and soaked at 60 ℃ for 24 hours for Na+Complete exchange to H+Thereafter, residual HCl was removed with deionized water to give H+A proton exchange membrane.
The ion exchange capacity of the proton exchange membrane obtained in this example was 2.23mmol/g, the water absorption was 50%, the swelling ratio was 10.5%, and the ionic conductivity at room temperature was 5.16X 10-2S cm-1Ion conductivity at 80 ℃ of 8.42X 10-2S cm-1。
Example 2
This example provides a proton exchange membrane and a method for preparing the same, which is substantially the same as in example 1: except that in step (2), 1M HCl solution was replaced with 1M dilute sulfuric acid.
The ion exchange capacity of the proton exchange membrane obtained in this example was 2.57mmol/g, the water absorption was 50%, the swelling ratio was 11.1%, and the ionic conductivity at room temperature was 5.86X 10-2S cm-1Ion conductivity at 80 ℃ of 8.79X 10-2S cm-1。
Example 3
This example provides a proton exchange membrane and a method for preparing the same, which is substantially the same as in example 1: except that in step (1) trifluoroacetophenone (7.0mmol) was replaced with trifluoroacetone (7.0 mmol).
The ion exchange capacity of the proton exchange membrane obtained in this example was 2.59mmol/g, the water absorption was 51%, the swelling ratio was 10.8%, and the ionic conductivity at room temperature was 5.76X 10-2S cm-1Ion conductivity at 80 ℃ of 8.62X 10-2S cm-1。
Example 4
This example provides a proton exchange membrane and a method for preparing the same, which is substantially the same as in example 1: except that 1, 3-propane sultone was replaced with 1, 4-butane sultone in the step (2).
The ion exchange capacity of the proton exchange membrane obtained in this example was 2.16mmol/g, the water absorption was 46%, the swelling ratio was 9.1%, and the ionic conductivity at room temperature was 4.76X 10-2S cm-1And an ionic conductivity at 80 ℃ of 7.82X 10-2S cm-1。
Example 5
This example provides a proton exchange membrane and a method for preparing the same, which is substantially the same as in example 1: except that biphenyl (4.8mmol), 2, 2-dihydroxybiphenyl (1.6mmol) was used in step (1).
The ion exchange capacity of the proton exchange membrane obtained in this example was 1.32mmol/g, the water absorption was 34%, the swelling ratio was 5.4%, and the ionic conductivity at room temperature was 3.16X 10-2S cm-1Ion conductivity at 80 ℃ of 5.42X 10-2S cm-1。
Example 6
This example provides a proton exchange membrane and a method for preparing the same, which is substantially the same as in example 1: except that biphenyl (2.13mmol), 2, 2-dihydroxybiphenyl (4.26mmol) was used in step (1).
The ion exchange capacity of the proton exchange membrane obtained in this example was 2.70mmol/g, the water absorption rate was 80%, the swelling rate was 13.6%, and the ionic conductivity at room temperature was 6.16X 10-2S cm-1Ion conductivity at 80 ℃ of 1.02X 10-1S cm-1。
Comparative example 1
This comparative example, which is essentially identical to that of example 1: except that 2, 2-dihydroxybiphenyl is not added in the step (1).
The polymer electrolyte membrane obtained in this comparative example had a water absorption of 5.5%, a swelling ratio of 0.8%, and an ionic conductivity of 2.56X 10 at room temperature-6S cm-1And an ionic conductivity at 80 ℃ of 3.62X 10-6S cm-1。
Comparative example 2
This comparative example, which is essentially identical to that of example 1: except that 1, 3-propane sultone was not used for the sulfonation in step (1).
The polymer electrolyte membrane obtained in this comparative example had a water absorption of 4.9%, a swelling ratio of 1.1%, and an ionic conductivity of 5.56X 10 at room temperature-6S cm-1And an ionic conductivity at 80 ℃ of 7.62X 10-6S cm-1。
Claims (9)
1. A proton exchange membrane with a main polymer chain of an aromatic ring structure is characterized in that the chemical structure of the proton exchange membrane is shown as the following formula:
wherein n is 2 or 3, X, Y represents only two structural unit numbers, X: y is 9: 1-1: 2, R is methyl or benzene ring.
2. The preparation method of the proton exchange membrane with the polymer main chain of the aromatic ring structure according to claim 1 is characterized by comprising the following specific steps:
(1) polycondensation reaction to prepare polymer: dissolving biphenyl, 2-dihydroxybiphenyl and trifluoroacetophenone in dichloromethane, respectively adding trifluoroacetic acid and trifluoromethanesulfonic acid as catalysts under an ice bath condition, removing the ice bath, stirring at room temperature for reaction until the solution is highly viscous, and precipitating, washing and drying after the reaction is finished to obtain a polymer containing a hydroxyl functional group;
(2) polymer functionalization: adding the hydroxyl functional group-containing compound prepared in the step (1), 1, 3-propane sultone and strong base into a reactor containing a high-boiling point solvent for reaction, and after the reaction is finished, precipitating, washing and drying to obtain a polymer containing sulfonic groups;
(3) film forming: dissolving the polymer prepared in the step (2) in N, N-dimethylformamide or dimethyl sulfoxide, preparing a proton exchange membrane by a solution casting method, and preparing the proton exchange membraneSoaking in acidic solution to obtain cation H+The proton exchange membrane of (1).
3. The preparation method of the proton exchange membrane with the main polymer chain of the aromatic ring structure according to claim 2, wherein the molar ratio of the biphenyl, the 2, 2-dihydroxybiphenyl and the trifluoroacetophenone in the step (1) is 9-1: 1-2: 11-3.3.
4. The method for preparing a proton exchange membrane with an aromatic ring structure on the polymer main chain according to claim 2, wherein the molar ratio of the total amount of the biphenyl and dihydroxybiphenyl reactants in the step (1) to the trifluoroacetic acid to the trifluoromethanesulfonic acid is 1:4: 11.
5. The method for preparing a proton exchange membrane with a polymer main chain of an aromatic ring structure according to claim 2, wherein the reaction in the step (1) is a stirring reaction at room temperature for 48-72 hours.
6. The method for preparing a proton exchange membrane with an aromatic ring structure in the polymer main chain according to claim 2, wherein the high boiling point solvent in the step (2) is one selected from N, N-dimethylformamide, dimethylsulfoxide and N-methylpyrrolidone, and the strong base is sodium hydroxide, sodium hydride or potassium hydroxide.
7. The method for preparing a proton exchange membrane with an aromatic ring structure in the polymer main chain according to claim 2, wherein the molar ratio of the hydroxyl functional group-containing compound in the step (2), 1, 3-propane sultone and strong base is 1:1.1: 2.
8. The preparation method of the proton exchange membrane with the main polymer chain of the aromatic ring structure according to claim 2, wherein the reaction temperature in the step (2) is 60-80 ℃, and the reaction time is 6-8 hours.
9. The method for preparing a proton exchange membrane with a polymer main chain of an aromatic ring structure according to claim 2, wherein the acidic solution in the step (3) is a hydrogen chloride solution or a dilute sulfuric acid solution, and the soaking time is 24 hours.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114276572A (en) * | 2021-12-07 | 2022-04-05 | 常州大学 | Polyether ether ketone group bifunctional ion exchange membrane for all-vanadium redox flow battery and preparation method thereof |
| CN115057980A (en) * | 2022-06-30 | 2022-09-16 | 中国科学院长春应用化学研究所 | Fluorine-containing sulfonated aromatic polymer, preparation method and application thereof |
| CN115181307A (en) * | 2022-08-25 | 2022-10-14 | 池州学院 | Preparation method of amphoteric ion exchange membrane based on polymer |
| CN116253912A (en) * | 2022-12-30 | 2023-06-13 | 厦门大学 | Aromatic polymer proton exchange membrane and preparation method and application thereof |
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