Preparation and application of a class of poly(carbazole)-based proton exchange membrane materials with high rigid twisted main chain
Patent Information
- Application Number
- CN202611060179.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-07-16
- Publication Date
- 2026-09-01
AI Technical Summary
但其固有的局限性日益凸显：首先，其质子传导高度依赖于水分子的参与，而柔性主链在大量吸水后容易膨胀导致膜的尺寸稳定性变差；其次，复杂的合成工艺导致造价高昂，严重制约了氢能技术的规模化应用
[0037]（1）本发明提供的具有高刚性扭曲主链的聚(咔唑)基质子交换膜材料，在主链结构引入3,6-二苯基咔唑这样高刚性的聚合单体，这类单体的引入可以提高主链刚性，保证膜材料在吸水的时候可以控制膜的溶胀，保证制备膜电极时不因溶胀而破损。
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Figure CN122668367A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of high-performance proton exchange membranes for H2 / O2 fuel cells and their preparation, and particularly relates to the preparation method and application of a class of poly(carbazole) proton exchange membrane materials with high rigidity twisted main chains. Background Technology
[0002] Against the backdrop of "dual carbon" goals and the globalization of energy transition, hydrogen energy, with its high energy density and zero carbon emissions, has become a key carrier for building a clean, low-carbon, safe, and efficient energy system for the future. Among them, water electrolysis hydrogen production technology (PEMWE) based on proton exchange membrane (PEM) and H2 / O2 fuel cells (PEMFC) are considered the most promising technological paths for achieving efficient green hydrogen production and end-use due to their advantages such as high energy conversion efficiency, fast response speed, and significant power density.
[0003] As the "heart" of these electrochemical devices, proton exchange membranes not only isolate reactant gases and prevent cross-contamination, but also bear the crucial responsibility of efficiently transferring protons. Their physicochemical properties directly determine the energy conversion efficiency and operational lifespan of the devices. Perfluorosulfonic acid polymer membranes (such as the Nafion series) still dominate commercial applications due to their high proton conductivity resulting from the unique microphase separation structure between the fluorinated backbone and the terminal sulfonic acid groups, as well as their good chemical stability in acidic environments. However, their inherent limitations are becoming increasingly apparent: firstly, their proton conduction is highly dependent on the participation of water molecules, and the flexible backbone is prone to swelling after absorbing a large amount of water, leading to poor dimensional stability of the membrane; secondly, the complex synthesis process results in high costs, severely restricting the large-scale application of hydrogen energy technology. This invention patent provides a type of poly(carbazole) matrix proton exchange membrane material with a high-rigidity twisted backbone. Introducing twisted monomers into the polymer backbone reduces chain entanglement in straight-chain polymer materials, while providing a certain cavity during ion transport. The high-rigidity polymer monomers can also control the water absorption and swelling of the membrane, improving its dimensional stability during application. Summary of the Invention
[0004] A type of poly(carbazole) matrix molecular exchange membrane material with a high-rigidity twisted backbone, characterized in that: the structural formula is: Formula 1, where n is the average degree of polymerization, and its value is such that the number average molecular weight (Mn) of the polymer is 80000 g / mol to 100000 g / mol.
[0005] .
[0006] Formula 1.
[0007] The structure of the Ketone part is as follows: .
[0008] The present invention also provides a method for preparing a poly(carbazole) matrix proton exchange membrane material with a high rigidity twisted main chain as described above, comprising: preparing a polymer carrying sodium sulfonate groups as shown in Formula 2 into a membrane, and performing proton exchange in a solvent to obtain a poly(carbazole) matrix proton exchange membrane material with a high rigidity twisted main chain as shown in Formula 1.
[0009] .
[0010] Formula 2.
[0011] Preferably, at room temperature, the prepared polymer carrying sodium sulfonate groups is prepared into a membrane (Formula 2) and immersed in a 1M H2SO4 solution to obtain the poly(carbazole) matrix exchange membrane with a high rigidity twisted main chain shown in Formula 1.
[0012] .
[0013] Formula 2.
[0014] This invention also provides a method for synthesizing a polymer carrying sodium sulfonate groups and preparing a membrane material, comprising: adding the Ketone portion of Formula 3 to a low-boiling-point solvent and stirring until homogeneous; then adding a catalyst and reacting at 0 °C; after the viscosity increases, pouring the mixture into a solvent to settle; then washing and drying to obtain a white polymer. The polymer is then dissolved in a high-boiling-point solvent, spread evenly on a glass plate, and dried in an oven.
[0015] .
[0016] Formula 3.
[0017] Preferably, the amount of Formula 3 used in the reaction is 1 equivalent.
[0018] Preferably, the Ketone portion is 1 to 1.2 times that of Formula 3.
[0019] Preferably, the low-boiling-point solvent is dichloromethane, and the amount used is 3 mL to 6 mL.
[0020] Preferably, the catalyst is trifluoromethanesulfonic acid, and the amount used is 8 to 12 times that of the Ketone portion.
[0021] Preferably, the polymerization reaction time is 12 h to 24 h.
[0022] Preferably, the solvent used for sedimentation is water, and the amount used is 1000 mL.
[0023] Preferably, the solvent used for washing is ethanol, and the amount used is 500 mL.
[0024] Preferably, the drying temperature is 80 ℃ and the drying time is 24 h to 48 h.
[0025] Preferably, the high-boiling-point solvent used to prepare the membrane material is dimethyl sulfoxide or N-methylpyrrolidone.
[0026] The drying temperature is 60 ℃~80 ℃, and the time is 12 h~24 h.
[0027] The present invention also provides a method for preparing Formula 3, comprising: dissolving Formula 4a in a high-boiling-point solvent, adding a catalyst, stirring until the solution is clear, then adding Formula 4b, and after the reaction is completed, pouring the solution into a low-boiling-point solvent to settle, filtering and drying.
[0028] .
[0029] Formula 4.
[0030] Preferably, the amount of Formula 4a used for the reaction is 1 equivalent.
[0031] Preferably, the high-boiling-point solvent is dimethyl sulfoxide or N,N -Dimethylformamide, used at a concentration 100 to 200 times that of Formula 4a.
[0032] Preferably, the amount of Formula 4b is 1.2 to 1.5 times that of Formula 4a.
[0033] Preferably, the catalyst is NaH, and its amount is 1 to 1.5 times that of Formula 4a.
[0034] Preferably, the low-boiling-point solvent is ethyl acetate, and the amount used is 500 mL.
[0035] Preferably, the drying temperature is 80 ℃ and the drying time is 24 h to 48 h.
[0036] Compared with the prior art, the beneficial effects of the present invention are as follows:
[0037] (1) The poly(carbazole) matrix exchange membrane material with high rigidity twisted main chain provided by the present invention introduces a high rigidity polymer monomer such as 3,6-diphenylcarbazole into the main chain structure. The introduction of this monomer can improve the rigidity of the main chain, ensure that the membrane swelling can be controlled when the membrane material absorbs water, and ensure that the membrane electrode is not damaged due to swelling when it is prepared.
[0038] (2) The poly(carbazole) matrix proton exchange membrane material with high rigidity twisted main chain provided by the present invention introduces a twisted polymer monomer such as 3,6-diphenylcarbazole into the main chain structure. The introduction of the twisted monomer can build channels inside the polymer membrane, ensuring that there is space to accommodate water molecules and promoting the rapid transport of protons in the channels.
[0039] (3) The poly(carbazole) matrix proton exchange membrane material with high rigidity twisted main chain provided by the present invention is prepared by Friedel-Crafts reaction and can be directly prepared by casting film method. The prepared proton exchange membrane has good ion conductivity and dimensional stability.
[0040] Attached image description.
[0041] Figure 1 This is a synthetic route diagram of the poly(carbazole) matrix sub-exchange membrane material with a high-rigidity twisted main chain described in this invention; Figure 2 The nuclear magnetic resonance spectrum of Formula 3 as described in Embodiment 1 of the present invention; Figure 3 The NMR spectrum of the poly(carbazole) matrix quantum exchange membrane material with a high-rigidity twisted main chain described in Embodiment 1 of the present invention is shown. Detailed Implementation
[0042] The present invention will be further described in detail below with reference to the embodiments: Preferred embodiments of the present invention will now be described in more detail with reference to specific examples.
[0043] The sources of the pharmaceuticals and reagents described in the examples are as follows: 3,6-Diphenyl-9H-carbazole: Shanghai Bide Pharmaceutical Technology Co., Ltd., ≥98.0%; 1,1,1-Trifluoroacetone: Shanghai Bide Pharmaceutical Technology Co., Ltd., ≥99.0%; 1-Methylindigo: Shanghai Bide Pharmaceutical Technology Co., Ltd., ≥99.0%; 2,2,2-Trifluoroacetophenone: Shanghai BIDE Pharmaceutical Technology Co., Ltd., ≥99.0%; 4'-Bromo-2,2,2-trifluoroacetophenone: Shanghai Bide Pharmaceutical Technology Co., Ltd., ≥98.0%; N -Methylpyrrolidone: Aladdin Biochemical Technology Co., Ltd., ≥99.5%; N,N - Dimethylformamide: Aladdin Biochemical Technology Co., Ltd., ≥99.5%; 1,4-Butyrolactone: Aladdin Biochemical Technology Co., Ltd., ≥98.7%; Dimethyl sulfoxide: Shanghai Lingfeng Chemical Reagent Co., Ltd., ≥99.0%; Ethyl acetate: Shanghai Lingfeng Chemical Reagent Co., Ltd., ≥99.0%; Sodium hydride: Shanghai Lingfeng Chemical Reagent Co., Ltd., ≥99.0%; Dichloromethane: Shanghai Lingfeng Chemical Reagent Co., Ltd., ≥99.0%; Trifluoromethanesulfonic acid: Shanghai Titan Technology Co., Ltd., ≥99.0%; Example
[0044] A method for preparing a class of poly(carbazole) matrix quantum exchange membrane materials with high rigidity twisted main chains includes the following steps.
[0045] (1) Synthesis of sodium 4-(3,6-diphenyl-9H-carbazole-9-yl)but-1-sulfonate.
[0046] 3,6-Diphenyl-9H-carbazole (10.0 mmol, 3.1940 g) was placed in a 500 mL Schlenk flask equipped with a magnetic stir bar, and then 100 mL of [unspecified ingredient] was added. N,N - Dimethylformamide. Stir the mixture until the solution is clear. Then, in three separate portions, 60% NaH (12.0 mmol, 0.4800 g) was added in an ice bath, each time only after the foaming of the previous addition had stopped and the solution had become clear. Then, 1,4-butyryl lactone (15.0 mmol, 2.0426 g) was introduced into the solution, and the reaction mixture was transferred to an oil bath preheated to 80 °C and reacted for 24 hours. After completion, the solution was cooled to room temperature, and the product was precipitated in ethyl acetate. The precipitate was washed repeatedly with ethyl acetate, filtered, and dried in a vacuum oven at 80 °C to give a white powdery final product in 87.5% yield.
[0047] (2) Synthesis of polymers carrying sodium sulfonate groups and preparation of membrane materials.
[0048] Sodium 4-(3,6-diphenyl-9H-carbazole-9-yl)but-1-sulfonate (10.0 mmol, 4.7755 g) and 1,1,1-trifluoroacetone (12.0 mmol, 1.3446 g) were placed in a pressure-resistant container, and then 3 mL of DCM was added. The mixture was stirred until homogeneous. Subsequently, 9 mL of TFSA was added dropwise, and the reaction mixture was kept at 0 °C for 24 hours. The resulting high-viscosity mixture was then poured into water to precipitate the polymer. The precipitate was washed repeatedly with deionized water and ethanol, filtered, and dried in a vacuum oven at 80 °C to give a fibrous polymer product. The yield was 91.3%.
[0049] 0.3 g of the fibrous proton exchange membrane precursor was dissolved in 12 mL of DMSO. The resulting yellow solution was filtered through a diatomaceous earth pad and then cast onto a clean, scratch-free glass plate. The mixture was evaporated at 80 °C for 24 hours. To achieve complete protonation via ion exchange, the membrane was immersed in a 1 M H₂SO₄ solution. Finally, the membrane was removed, thoroughly rinsed to remove any residual acid from the surface, and stored in deionized water before testing.
[0050] The synthetic route of the above preparation method is as follows: Figure 1 As shown, the NMR spectrum is as follows Figure 2 and Figure 3 As shown.
[0051] Tests showed that the poly(carbazole) matrix ion exchange membrane with a highly rigid twisted backbone prepared in this embodiment had an ion conductivity of 166.9 mS / cm at 80°C. -1 The membrane exhibited a water absorption rate of 54.2%, a swelling degree of 13.7%, and a membrane weight retention of 99.1% after immersion in Fenton's reagent at 80 °C for 2 h. The wet membrane tensile strength was 58.4 MPa, demonstrating good mechanical strength and oxidative stability. When the membrane was assembled into a fuel cell for testing, the maximum output power at 80 °C was 723 mW / cm². 2 . Example
[0052] A method for preparing a class of poly(carbazole) matrix quantum exchange membrane materials with high rigidity twisted main chains includes the following steps.
[0053] (1) Synthesis of sodium 4-(3,6-diphenyl-9H-carbazole-9-yl)but-1-sulfonate.
[0054] 3,6-Diphenyl-9H-carbazole (10.0 mmol, 3.1940 g) was placed in a 500 mL Schlenk flask equipped with a magnetic stir bar, and then 100 mL of [unspecified ingredient] was added. N,N - Dimethylformamide. Stir the mixture until the solution is clear. Then, in three separate portions, add 60% NaH (12.0 mmol, 0.4800 g) in an ice bath, adding each time only after the foaming has stopped and the solution is clear. Then, 1,4-butyryl lactone (15.0 mmol, 2.0426 g) is introduced into the solution, and the reaction mixture is transferred to an oil bath preheated to 80 °C and reacted for 24 hours. After completion, the solution is cooled to room temperature, and the product is precipitated in ethyl acetate. The precipitate is washed repeatedly with ethyl acetate, filtered, and dried in a vacuum oven at 80 °C to give a white powdery final product.
[0055] (2) Synthesis of polymers carrying sodium sulfonate groups and preparation of membrane materials.
[0056] Sodium 4-(3,6-diphenyl-9H-carbazole-9-yl)but-1-sulfonate (10.0 mmol, 4.7755 g) and 1-methylindigo (10.0 mmol, 1.6116 g) were placed in a pressure-resistant container, and then 6 mL of DCM was added. The mixture was stirred until homogeneous. Subsequently, 9 mL of TFSA was added dropwise, and the reaction mixture was kept at 0 °C for 12 hours. The resulting high-viscosity mixture was then poured into water to precipitate the polymer. The precipitate was washed repeatedly with deionized water and ethanol, filtered, and dried in a vacuum oven at 80 °C to obtain a fibrous polymer product.
[0057] 0.3 g of the fibrous proton exchange membrane precursor was dissolved in 12 mL of DMSO. The resulting yellow solution was filtered through a diatomaceous earth pad and then cast onto a clean, scratch-free glass plate. The mixture was evaporated at 80 °C for 24 hours. To achieve complete protonation via ion exchange, the membrane was immersed in a 1 M H₂SO₄ solution. Finally, the membrane was removed, thoroughly rinsed to remove any residual acid from the surface, and stored in deionized water before testing.
[0058] Tests showed that the poly(carbazole) matrix ion exchange membrane with a highly rigid twisted backbone prepared in this embodiment had an ion conductivity of 163.1 mS / cm at 80 °C. -1 The membrane exhibited a water absorption rate of 44.8%, a swelling degree of 10.8%, and a membrane weight retention of 97.5% after immersion in Fenton's reagent at 80 °C for 2 h. The wet membrane tensile strength was 71.5 MPa, demonstrating good mechanical strength and proton conductivity. When assembled into a fuel cell for testing, the maximum output power at 80 °C was 697 mW / cm². 2 . Example
[0059] A method for preparing a class of poly(carbazole) matrix quantum exchange membrane materials with high rigidity twisted main chains includes the following steps.
[0060] (1) Synthesis of sodium 4-(3,6-diphenyl-9H-carbazole-9-yl)but-1-sulfonate.
[0061] 3,6-Diphenyl-9H-carbazole (10.0 mmol, 3.1940 g) was placed in a 500 mL Schlenk flask equipped with a magnetic stir bar, and then 100 mL of [unspecified ingredient] was added. N,N- Dimethylformamide. Stir the mixture until the solution is clear. Then, in three separate portions, add 60% NaH (12.0 mmol, 0.4800 g) in an ice bath, adding each time only after the foaming has stopped and the solution is clear. Then, 1,4-butyryl lactone (15.0 mmol, 2.0426 g) is introduced into the solution, and the reaction mixture is transferred to an oil bath preheated to 80 °C and reacted for 24 hours. After completion, the solution is cooled to room temperature, and the product is precipitated in ethyl acetate. The precipitate is washed repeatedly with ethyl acetate, filtered, and dried in a vacuum oven at 80 °C to give a white powdery final product.
[0062] (2) Synthesis of polymers carrying sodium sulfonate groups and preparation of membrane materials.
[0063] Sodium 4-(3,6-diphenyl-9H-carbazole-9-yl)but-1-sulfonate (10.0 mmol, 4.7755 g) and 2,2,2-trifluoroacetophenone (11.0 mmol, 1.9143 g) were placed in a pressure-resistant container, and then 3 mL of DCM was added. The mixture was stirred until homogeneous. Subsequently, 9 mL of TFSA was added dropwise, and the reaction mixture was kept at 0 °C for 18 hours. The resulting high-viscosity mixture was then poured into water to precipitate the polymer. The precipitate was washed repeatedly with deionized water and ethanol, filtered, and dried in a vacuum oven at 80 °C to obtain a fibrous polymer product.
[0064] 0.3 g of the fibrous proton exchange membrane precursor was dissolved in 12 mL of DMSO. The resulting yellow solution was filtered through a diatomaceous earth pad and then cast onto a clean, scratch-free glass plate. The mixture was evaporated at 80 °C for 24 hours. To achieve complete protonation via ion exchange, the membrane was immersed in a 1 M H₂SO₄ solution. Finally, the membrane was removed, thoroughly rinsed to remove any residual acid from the surface, and stored in deionized water before testing.
[0065] Tests showed that the poly(carbazole) matrix ion exchange membrane with a highly rigid twisted backbone prepared in this embodiment had an ion conductivity of 142.7 mS / cm at 80 °C. -1 The membrane exhibited a water absorption rate of 72.8%, a swelling degree of 20.1%, and a membrane weight retention of 98.8% after immersion in Fenton's reagent at 80 °C for 2 h. The wet membrane tensile strength was 51.6 MPa, demonstrating good mechanical strength and proton conductivity. When the membrane was assembled into a fuel cell for testing, the maximum output power at 80 °C was 638 mW / cm². 2 . Example
[0066] A method for preparing a class of poly(carbazole) matrix quantum exchange membrane materials with high rigidity twisted main chains includes the following steps.
[0067] (1) Synthesis of sodium 4-(3,6-diphenyl-9H-carbazole-9-yl)but-1-sulfonate.
[0068] 3,6-Diphenyl-9H-carbazole (10.0 mmol, 3.1940 g) was placed in a 500 mL Schlenk flask equipped with a magnetic stir bar, and then 100 mL of [unspecified ingredient] was added. N,N - Dimethylformamide. Stir the mixture until the solution is clear. Then, in three portions, add 60% NaH (12.0 mmol, 0.4800 g) in an ice bath, adding each time only after the foaming has stopped and the solution is clear. Then, 1,4-butyryl lactone (15.0 mmol, 2.0426 g) is introduced into the solution, and the reaction mixture is transferred to an oil bath preheated to 80 °C and reacted for 24 hours. After completion, the solution is cooled to room temperature and the product is precipitated in ethyl acetate. The precipitate is washed repeatedly with ethyl acetate, filtered, and dried in a vacuum oven at 80 °C to give a white powdery final product.
[0069] (2) Synthesis of polymers carrying sodium sulfonate groups and preparation of membrane materials.
[0070] Sodium 4-(3,6-diphenyl-9H-carbazole-9-yl)but-1-sulfonate (10.0 mmol, 4.7755 g) and 4'-bromo-2,2,2-trifluoroacetophenone (10.0 mmol, 2.5302 g) were placed in a pressure-resistant container, and then 3 mL of DCM was added. The mixture was stirred until homogeneous. Subsequently, 9 mL of TFSA was added dropwise, and the reaction mixture was kept at 0 °C for 12 hours. The resulting high-viscosity mixture was then poured into water to precipitate the polymer. The precipitate was washed repeatedly with deionized water and ethanol, filtered, and dried in a vacuum oven at 80 °C to obtain a fibrous polymer product.
[0071] 0.3 g of the fibrous proton exchange membrane precursor was dissolved in 12 mL of DMSO. The resulting yellow solution was filtered through a diatomaceous earth pad and then cast onto a clean, scratch-free glass plate. The mixture was evaporated at 80 °C for 24 hours. To achieve complete protonation via ion exchange, the membrane was immersed in a 1 M H₂SO₄ solution. Finally, the membrane was removed, thoroughly rinsed to remove any residual acid from the surface, and stored in deionized water before testing.
[0072] Tests showed that the poly(carbazole) matrix ion exchange membrane with a highly rigid twisted backbone prepared in this embodiment had an ion conductivity of 147.2 mS / cm at 80 °C.-1 The membrane exhibited a water absorption rate of 66.7%, a swelling degree of 17.3%, and a membrane weight retention of 98.4% after immersion in Fenton's reagent at 80 °C for 2 h. The wet membrane tensile strength was 55.2 MPa, demonstrating good mechanical strength and proton conductivity. When assembled into a fuel cell, the membrane achieved a maximum output power of 651 mW / cm² at 80 °C. 2 .
Claims
1. A type of poly(carbazole) matrix interphase exchange membrane material with a highly rigid twisted backbone, characterized in that: The structural formula is: ； Formula 1 In Formula 1, n is the average degree of polymerization, and its value is such that the number average molecular weight (Mn) of the polymer is 80,000 g / mol to 100,000 g / mol. The structure of the Ketone part is as follows: 。 2. The method for preparing the poly(carbazole) matrix interphase exchange membrane material with a high-rigidity twisted backbone according to claim 1, characterized in that, The process includes the following steps: replacing the sodium sulfonate groups in the polymer carrying sodium sulfonate groups shown in Formula 2 with sulfonic acid groups to obtain the poly(carbazole) matrix quantum exchange membrane material with a high-rigidity twisted main chain shown in Formula 1. ； Equation 2.
3. The method for preparing a poly(carbazole) matrix interphase exchange membrane with a highly rigid twisted backbone according to claim 1, characterized in that, The process also includes the following steps: at room temperature, the prepared polymer carrying sodium sulfonate groups is prepared into a membrane (Formula 2) and immersed in a 1 M H2SO4 solution to obtain the poly(carbazole) matrix exchange membrane with a high rigidity twisted main chain shown in Formula 1.
4. The method for preparing a polymer film carrying sodium sulfonate groups according to claim 3, characterized in that, The process includes the following steps: dissolving the polymer in a high-boiling-point solvent and drying it in an oven.
5. The method for preparing a polymer film carrying sodium sulfonate groups according to claim 4, characterized in that, The high-boiling-point solvent used to dissolve the polymer is dimethyl sulfoxide or N-methylpyrrolidone, and the drying temperature is 60 ℃~80 ℃, and the time is 12 h~24 h.
6. The method for preparing the polymer film carrying sodium sulfonate groups according to claim 3, characterized in that, The process includes the following steps: adding the Ketone portion of Formula 3 to a low-boiling-point solvent and stirring until homogeneous; then adding a catalyst and reacting at 0 °C; after the viscosity increases, pouring the mixture into a solvent to settle; then washing and drying. ； Formula 3.
7. The method for preparing a polymer film carrying sodium sulfonate groups according to claim 3, characterized in that, The amount of Formula 3 used in the reaction is 1 equivalent, the Ketone portion is 1 to 1.2 times that of Formula 3, the low-boiling solvent is dichloromethane, the amount is 3 mL to 6 mL, the catalyst is trifluoromethanesulfonic acid, the amount is 8 to 12 times that of the Ketone portion, the solvent used for precipitation is water, the amount is 1000 mL, the solvent used for washing is ethanol, the amount is 500 mL, the drying temperature is 80 ℃, and the drying time is 24 h to 48 h.
8. The preparation method of Formula 3 according to claim 6, characterized in that, The process includes the following steps: dissolving Formula 4a in a high-boiling-point solvent, adding a catalyst, stirring until the solution is clear, then adding Formula 4b, and after the reaction is complete, pouring the solution into a low-boiling-point solvent to settle, filtering, and drying.
9. The preparation method of Formula 3 according to claim 8, characterized in that, The amount of Formula 4a used in the reaction is 1 equivalent; the high-boiling solvent is dimethyl sulfoxide or N-methylpyrrolidone, and the amount is 100 to 200 times that of Formula 4a; the amount of Formula 4b is 1.2 to 1.5 times that of Formula 4a; the catalyst is NaH, and the amount is 1 to 1.5 times that of Formula 4a; the low-boiling solvent is ethyl acetate, and the amount is 500 mL; the drying temperature is 80 °C; and the drying time is 24 h to 48 h. ； Formula 4.
10. The application of the poly(carbazole) matrix interphase exchange membrane material with a high-rigidity twisted backbone according to claim 1, characterized in that: It is used in H2 / O2 fuel cells.