A polyarylate indigo / sulfonated microporous polymer composite and a preparation method and application thereof

Abstract

This invention discloses a polyaryl indigo / sulfonated microporous polymer composite, its preparation method, and its applications, belonging to the field of organic synthesis and energy conversion technology. This invention uses polyaryl indigo as a matrix, incorporating a sulfonated microporous polymer for modification. By optimizing the ratio of the two, the aim is to improve ionic conductivity while maintaining the chemical stability of the material. The designed and synthesized composite alkaline ion-solubilizing membrane consists of a polyaryl indigo main-chain polymer without aryl ether bonds and a sulfonated microporous polymer with a rigid and twisted structure. The skeleton of the sulfonated microporous polymer restricts conformational freedom and effective polymer chain stacking, thereby forming confined ion channels and achieving rapid and selective ion transport. Furthermore, the construction of polyaryl indigo forms continuous ion transport channels, exhibiting high hydroxide conductivity due to the presence of multiple transport sites. Simultaneously, the absence of aryl ether bonds in the main chain gives the membrane good alkali resistance.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis and energy conversion technology, specifically relating to a polyaryl indigo / sulfonated microporous polymer composite, its preparation method, and its application. Background Technology

[0002] Green hydrogen, as a clean and efficient renewable energy carrier, is crucial for driving energy structure transformation through large-scale production. Green hydrogen production pathways are mainly divided into three categories: hydrogen production via water electrolysis using renewable energy sources such as wind, hydro, and photovoltaics; hydrogen production via solar photocatalytic water splitting; and hydrogen production via biomass conversion. Among these, renewable energy-based water electrolysis has become the mainstream solution for green hydrogen production due to its highest technological maturity and widest application range, and it is also the core technological path for achieving large-scale green hydrogen production. Currently, the mainstream technologies for water electrolysis include alkaline water electrolysis (ALK), proton exchange membrane water electrolysis (PEM), anion exchange membrane water electrolysis (AEM), and solid oxide electrolysis (SOEC). PEM electrolyzers, due to their acidic operating environment, impose stringent requirements on the corrosion resistance of the electrolysis device and the stability of the catalytic materials, resulting in high overall system costs. SOEC technology requires operation under high-temperature conditions, with demanding operating conditions and high energy consumption; both are difficult to rapidly achieve large-scale commercialization. In contrast, AEM water electrolysis technology uses anion exchange membranes as the core electrolyte, cleverly integrating the low-cost advantages of ALK technology with the simple structure and high energy conversion efficiency of PEM electrolyzers. It is widely recognized as the most promising advanced water electrolysis technology currently available.

[0003] As a core component of AEM electrolyzers, the performance parameters of anion exchange membranes directly determine the operating efficiency, service life, and cost control of the electrolysis system. Although significant breakthroughs have been made in the ion conduction performance of AEM materials in recent years, their long-term stability under alkaline electrolysis environments remains a significant weakness. The main chain is prone to degradation, and functional groups are easily detached, becoming the core bottleneck restricting their large-scale application.

[0004] Alkaline ion-solvent membranes combine the advantages of traditional separators and anion exchange membranes. By incorporating alkali during polymerization, a ternary homogeneous system of electrolyte / water / polymer is formed. The polymer backbone does not contain easily degradable quaternary ammonium salt groups, significantly improving alkali resistance. Among them, ion-solvent membranes based on polyarylethemine (PIB) can construct continuous ion transport channels, and the backbone does not contain aryl ether bonds, exhibiting excellent alkali resistance. However, these membranes require the absorption of high-concentration alkali solutions (10–35 wt.%) to achieve high ion conductivity and ensure electrolyzer output efficiency. High-concentration alkali doping leads to a sharp decline in the membrane's mechanical properties, necessitating further technological improvements.

[0005] Single polymer ion-solvating membranes are difficult to simultaneously meet the requirements of hydroxide ion conduction, mechanical strength, and thermal stability. Polymer blending and compounding is an effective way to solve this problem. Porous organic polymers (PIMs) have a large number of microporous structures with a size less than 2 nm, which can provide ideal confinement channels for mass transport. Among them, sulfonated porous organic polymers can selectively and rapidly transport cations and improve conductivity due to the introduction of hydrophilic sulfonic acid groups. However, the water absorption of sulfonic acid groups will cause serious swelling of the membrane material and deterioration of mechanical properties. Summary of the Invention

[0006] The purpose of the present invention is to provide a polyaryl isatin / sulfonated microporous polymer composite, its preparation method and application. In the present invention, polyaryl isatin is used as the matrix, and sulfonated microporous polymer is incorporated for modification. By optimizing the ratio of the two, it aims to improve the ion conductivity while maintaining the chemical stability of the material. Among them, the sulfonated polymer backbone (including a rigid and twisted backbone) can limit the conformational freedom and polymer chain packing, forming an efficient confinement ion channel; PIB can construct a continuous ion transport channel, achieving high hydroxide conductivity with multiple transport sites, and the characteristics of its main chain ensure the alkali resistance stability of the membrane. The membrane material prepared from the composite of polyaryl isatin and sulfonated microporous polymer realizes ion conductivity by absorbing KOH. The membrane itself has no pore structure, and the risk of gas product crossover is small. The dense polymer membrane can be thinner than traditional diaphragms, thereby reducing the diaphragm voltage drop and improving the energy efficiency of the electrolyzer. The alkaline ion-solvating membrane prepared by compounding a sulfonated polymer with a rigid and twisted backbone and a main chain polymer polyaryl isatin without aryl ether bonds exhibits excellent performance in ion conductivity, chemical stability, mechanical properties, and thermal stability, which can improve the conductivity and durability of electrolytic water cells. By combining the advantages of the two, the present invention significantly improves the comprehensive performance of the membrane, is expected to solve the core bottleneck of traditional membrane materials, and provides support for the large-scale application of AEM electrolytic water technology.

[0007] To achieve the above object, the present invention provides the following technical solutions: <照 [[ID=照10]]One of the technical solutions of the present invention: Provide a polyaryl isatin / sulfonated microporous polymer composite, the structural general formula of which is shown in the following formula: [[ID=照11]] [[ID=照12]] [[ID=照13]]; [[ID=照14]] [[ID=照15]]In the above formula, n is the degree of polymerization, and the numerical range is 100 < n ≤ 1000; m is the degree of polymerization, and the numerical range is 100 < m ≤ 1000; [[ID=照16]] [[ID=照17]]Ar is selected from any of the following structures: [[ID=照18]] [[ID=照19]] [[ID=照20]]; [[ID=照21]] [[ID=照22]]R is selected from any of the following structures: [[ID=照23]] [[ID=照24]] [[ID=照25]]. [[ID=照26]] [[ID=照27]]

[0008] It should be noted that there seems to be an error in the "照" in the text you provided. I have translated it as it is, but it may need to be corrected according to the actual situation.The second technical solution of the present invention provides a method for preparing the above-mentioned polyaryl indigo / sulfonated microporous polymer composite, comprising the following steps: A monomer containing an aromatic ring structure, indigo, and a catalyst are co-dissolved in a solvent, and a polyaryl indigo polymer is obtained after the reaction. Dihydroxypolycyclic aromatic hydrocarbon, trifluoroacetophenone and catalyst are co-dissolved in a solvent, and a microporous polymer is obtained after reaction; the microporous polymer and chlorosulfonic acid are dissolved in a solvent, and sulfonated to obtain a sulfonated microporous polymer; The polyaryl indigo polymer and the sulfonated microporous polymer were co-dissolved in a solvent at a mass ratio of 1 to 9:1, and the polyaryl indigo / sulfonated microporous polymer composite was obtained after the reaction. The polymer unit provided by the monomer containing the aromatic ring structure has the structural formula shown in any of the following structures. ; The polymer unit provided by the dihydroxy polycyclic aromatic hydrocarbon has the structural formula shown in any of the following structures. .

[0009] Optionally, in the preparation step of the polyarylene indigo polymer, the solvent is dichloromethane.

[0010] Preferably, in the preparation step of the polyarylene indigo polymer, the molar ratio of the monomer containing the aromatic ring structure to the indigo is 1:1 to 1.3.

[0011] Preferably, in the preparation step of the polyarylene indigo polymer: the catalyst is trifluoromethanesulfonic acid, and the amount added is 20~25 eq; the reaction time is 4.5~6h.

[0012] Optionally, in the preparation step of the sulfonated microporous polymer, the solvent is dichloromethane.

[0013] Preferably, in the preparation step of the sulfonated microporous polymer: the molar ratio of the dihydroxy polycyclic aromatic hydrocarbon to the trifluoroacetophenone is 1:1 to 1.4; and the amount of chlorosulfonic acid added is 1.1 to 2.5 eq.

[0014] Preferably, in the preparation step of the sulfonated microporous polymer: the catalyst is trifluoromethanesulfonic acid, and the amount added is 2.25-5.5 eq; the reaction time is 2-12 h; and the sulfonation time is 20-150 min.

[0015] Optionally, the solvent in which the polyaryl indigo polymer and the sulfonated microporous polymer are co-soluble includes one or more of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and N-methylpyrrolidone.

[0016] Preferably, after the polyarylene indigo polymer and the sulfonated microporous polymer are co-dissolved, the reaction temperature is 40~60℃ and the time is 24~72h.

[0017] The third technical solution of the present invention provides a polyaryl indigo / sulfonated microporous polymer composite alkaline ionic solvation membrane, the main component of which is the above-mentioned polyaryl indigo / sulfonated microporous polymer composite.

[0018] The fourth technical solution of the present invention provides a method for preparing the above-mentioned polyaryl indigo / sulfonated microporous polymer composite alkaline ionic solvation membrane, comprising the following steps: The casting solution containing the polyaryl indigo / sulfonated microporous polymer composite was cast and dried to obtain a polyaryl indigo / sulfonated microporous polymer composite membrane; the polyaryl indigo / sulfonated microporous polymer composite membrane was then immersed in KOH solution to obtain a polyaryl indigo / sulfonated microporous polymer composite alkaline ion solvation membrane.

[0019] Preferably, the solid content of the casting solution containing the polyaryl indigo / sulfonated microporous polymer composite is 2-5 wt.%.

[0020] Preferably, the drying temperature is 40~100℃ and the time is 24~72h.

[0021] The fifth technical solution of the present invention provides an application of the above-mentioned polyarylene indigo / sulfonated microporous polymer composite in the fields of alkaline water electrolysis, fuel cells, electroreduction of carbon dioxide, or zinc-air batteries.

[0022] The sixth technical solution of the present invention provides an application of the above-mentioned polyarylene indigo / sulfonated microporous polymer composite alkaline ion solvation membrane in the fields of alkaline water electrolysis, fuel cells, electroreduction of carbon dioxide, or zinc-air batteries.

[0023] The beneficial technical effects of the present invention are as follows: The polyaryl indigo / sulfonated microporous polymer composite provided by this invention is composed of polyaryl indigo without aryl ether bonds and a sulfonated microporous polymer with a rigid and tortuous skeleton. The skeleton of the sulfonated polymer restricts its conformational freedom and the effective stacking of polymer chains, thereby forming confined ion channels and promoting rapid and selective ion transport. The new material obtained by this invention through blending not only retains a wide range of properties of the raw materials but also possesses new superior properties, overcoming their inherent shortcomings.

[0024] The alkaline ionic solvation membrane of polyaryl indigo / sulfonated microporous polymer composite provided by the present invention has no aryl ether bonds in its polyaryl indigo copolymer backbone, thus exhibiting excellent alkali resistance and stability. The membrane is homogeneous and transparent, and has strong compatibility.

[0025] The preparation method provided by this invention is simple and efficient. Furthermore, the prepared composite alkaline ion solvation membrane material can be used not only in alkaline electrolyzers, but also extended to energy conversion technologies such as fuel cells, electroreduction of carbon dioxide, and zinc-air batteries, demonstrating promising application prospects. Attached Figure Description

[0026] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0027] Figure 1 The proton nuclear magnetic resonance spectra of polyaryl indigo (PIB) (a), microporous polymer (PX-BP) (b), and sulfonated microporous polymer (SPX-BP) (c) in Example 1 of this invention are shown. 1 (H NMR) image.

[0028] Figure 2 The Fourier transform infrared (FT-IR) spectra of polyarylene indigo (PIB) and sulfonated microporous polymer (SPX-BP) in Example 1 of the present invention, and the polyarylene indigo / sulfonated microporous polymer composite membranes in Examples 1 to 5.

[0029] Figure 3 The images show X-ray energy dispersive spectroscopy (EDS) images of the polyarylene indigo (PIB) and sulfonated microporous polymer (SPX-BP) composite membranes in Example 1 and the polyarylene indigo / sulfonated microporous polymer composite membranes in Example 2 of this invention.

[0030] Figure 4 The diagram shows the different elemental contents of polyarylene indigo (PIB) and sulfonated microporous polymer (SPX-BP) in Example 1 of the present invention, and polyarylene indigo / sulfonated microporous polymer composite membrane in Example 2.

[0031] Figure 5 The polarization curves of the PIB:SPX-BP composite ion solvation membranes with different degrees of compositeness prepared in Examples 1-5 of this invention are shown on an alkaline water electrolysis device. Detailed Implementation

[0032] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention. It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the present invention.

[0033] It should be noted that any aspects not described in detail in this invention are conventional practices in the field and are not the focus of this invention.

[0034] Furthermore, regarding the numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any stated value or intermediate value within a stated range, as well as each smaller range between any other stated value or intermediate value within said range, are also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0035] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar to or equivalent to those described herein may be used in the implementation or testing of this invention.

[0036] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0037] Unless otherwise specified, the room temperature in this invention is 25±2 ℃.

[0038] All raw materials used in the embodiments of the present invention were obtained through commercial purchase.

[0039] Example 1 A method for preparing a polyaryl indigo / sulfonated microporous polymer composite alkaline ionic solvation membrane: (1) Synthesis of polyaryl indigo polymer (PIB) Biphenyl (1.234 g, 8 mmol) and indigo (1.295 g, 8.8 mmol) (molar ratio 1:1.1) were dissolved in a three-necked flask containing 10 mL of dichloromethane. The mixture was stirred at room temperature for 20 min until completely dissolved. Trifluoromethanesulfonic acid (16.3 mL) was then slowly added dropwise to the mixture using a constant-pressure funnel in an ice-water bath at 0 °C (45 min). The ice-water bath was then removed, and the reaction was stirred at room temperature for 4.5 h. The reaction liquid changed from white to a dark reddish-brown viscous liquid. The reaction liquid was precipitated in methanol to obtain a white fibrous polymer PIB. This fibrous polymer was then cut into small pieces, washed with water until the washings were neutral, and then dried at room temperature to obtain polyaryl indigo polymer (PIB, degree of polymerization n = 645).

[0040] The reaction process in step (1) is as follows: .

[0041] (2) Synthesis of microporous polymer (PX-BP) 4,4'-Dihydroxybiphenyl (1.79 g, 9.6 mmol) and 2,2,2-trifluoroacetophenone (1.67 g, 9.6 mmol) were added to anhydrous dichloromethane (14 mL) and stirred at room temperature to dissolve. Then, trifluoromethanesulfonic acid (TFSA, 2 mL) was slowly added dropwise in an ice-water bath as a catalyst. The solution changed from milky white to blackish-green. After the addition was complete, the solution was transferred to an oil bath at 35 °C and stirred for 135 min until it became viscous. The reaction solution was precipitated in methanol and washed repeatedly with distilled water. After the washing solution became neutral, the product was removed and air-dried at room temperature to obtain a white fibrous microporous polymer (PX-BP, degree of polymerization m = 730).

[0042] Synthesis of sulfonated microporous polymer (SPX-BP) PX-BP (1.5 g) was dissolved in dichloromethane (25 mL) and stirred for 30 min. The solution was pale yellow. Chlorosulfonic acid (0.3 mL) was added to dichloromethane (10 mL) and slowly added dropwise to the pale yellow solution at 0 °C. The mixture was stirred vigorously (200 r / min) for 35 min, resulting in a black precipitate. The precipitate was filtered and washed several times with methanol. After drying at room temperature, a pale yellow product (SPX-BP, degree of polymerization m = 730) was obtained.

[0043] The reaction process in step (2) is as follows: .

[0044] (3) Preparation of polyaryl indigo / sulfonated microporous polymer composite membrane (PIB:SPX-BP mass ratio is 9:1): 0.1 g of sulfonated microporous polymer (SPX-BP) was dissolved in 5 mL of dimethyl sulfoxide and stirred until dissolved to obtain solution A. At the same time, 0.9 g of polyaryl indigo polymer (PIB) was dissolved in 45 mL of dimethyl sulfoxide and stirred until dissolved to obtain solution B. Then solution A was added to solution B and stirred at 50 °C for 24 h to obtain a casting solution containing polyaryl indigo / sulfonated microporous polymer composite. The casting solution was spread on a glass plate and the solvent was evaporated at 60 °C for 48 h. Then the glass plate was immersed in deionized water until the membrane separated from the glass plate to obtain a polyaryl indigo / sulfonated microporous polymer composite membrane with a PIB:SPX-BP composite ratio of 9:1 (the thickness of the membrane is 45 μm).

[0045] (4) The structural formula of the polyaryl indigo / sulfonated microporous polymer composite in the polyaryl indigo / sulfonated microporous polymer composite membrane is as follows: .

[0046] (5) The prepared polyaryl indigo / sulfonated microporous polymer composite membrane with a PIB:SPX-BP=9:1 composite degree was immersed in a 6 mol / L potassium hydroxide (KOH) solution for 72 h at a temperature of 80 ℃ to obtain a polyaryl indigo / sulfonated microporous polymer composite alkaline ion solvation membrane with a PIB:SPX-BP=9:1 composite degree.

[0047] The PIB:SPX-BP=9:1 composite alkaline ionic solvation membrane prepared in Example 1 had a water absorption rate of 28.22% and a swelling rate of 11.16%; its tensile strength was 105.31 MPa and its tensile strength at break was 18.82% (method referred to GB 13022-1991 Thin Film Tensile Test Method 1.1, the same below), indicating that the membrane exhibited good mechanical strength and alkaline stability. The ionic conductivity of the PIB:SPX-BP=9:1 composite alkaline ionic solvation membrane was 184.5 mS / cm. The PIB:SPX-BP=9:1 composite alkaline ionic solvation membrane was loaded into an alkaline water electrolysis device (electrolyte was 6 mol / L KOH solution, the same below) for testing. The results showed that at 80 ℃ and 2.0 V, the current density could reach 1.252 A / cm. 2 .

[0048] Example 2 A method for preparing a polyaryl indigo / sulfonated microporous polymer composite alkaline ionic solvation membrane: (1) The synthesis and preparation of polyarylene indigo polymer (PIB) is the same as in Example 1.

[0049] (2) The synthesis of microporous polymer (PX-BP) and the synthesis and preparation of sulfonated microporous polymer (SPX-BP) are the same as in Example 1.

[0050] (3) Preparation of polyaryl indigo / sulfonated microporous polymer composite membrane (PIB:SPX-BP mass ratio is 8:2): 0.2 g of sulfonated microporous polymer (SPX-BP) was dissolved in 10 mL of dimethyl sulfoxide and stirred until dissolved to obtain solution A. At the same time, 0.8 g of polyaryl indigo polymer (PIB) was dissolved in 40 mL of dimethyl sulfoxide and stirred until dissolved to obtain solution B. Then solution A was added to solution B and stirred at 50 °C for 24 h to obtain a casting solution containing polyaryl indigo / sulfonated microporous polymer composite. The casting solution was spread on a glass plate and the solvent was evaporated at 60 °C for 48 h. Then the glass plate was immersed in deionized water until the membrane separated from the glass plate to obtain a polyaryl indigo / sulfonated microporous polymer composite membrane with a PIB:SPX-BP composite ratio of 8:2 (the membrane thickness is 48 μm).

[0051] (4) The structural formula of the polyaryl indigo / sulfonated microporous polymer composite in the polyaryl indigo / sulfonated microporous polymer composite membrane is the same as that in Example 1.

[0052] (5) The prepared polyaryl indigo / sulfonated microporous polymer composite membrane with a PIB:SPX-BP=8:2 composite degree was immersed in a 6 mol / L potassium hydroxide (KOH) solution for 72 h at a temperature of 80 ℃ to obtain a polyaryl indigo / sulfonated microporous polymer composite alkaline ion solvation membrane with a PIB:SPX-BP=8:2 composite degree.

[0053] The PIB:SPX-BP=8:2 composite alkaline ion solvation membrane prepared in Example 2 was found to have a water absorption rate of 32.88% and a swelling rate of 12.25%; its tensile strength was 118.08 MPa and its tensile strength at break was 20.37%, indicating that the membrane exhibited good mechanical strength and alkaline stability. The ionic conductivity of the PIB:SPX-BP=8:2 composite alkaline ion solvation membrane was 195.8 mS / cm. The PIB:SPX-BP=8:2 composite alkaline ion solvation membrane was tested in an alkaline water electrolysis device. The results showed that at 80 °C and 2.0 V, the current density could reach 1.75 A / cm. 2 .

[0054] Example 3 A method for preparing a polyaryl indigo / sulfonated microporous polymer composite alkaline ionic solvation membrane: (1) The synthesis and preparation of polyarylene indigo polymer (PIB) is the same as in Example 1.

[0055] (2) The synthesis of microporous polymer (PX-BP) and the synthesis and preparation of sulfonated microporous polymer (SPX-BP) are the same as in Example 1.

[0056] (3) Preparation of polyaryl indigo / sulfonated microporous polymer composite membrane (PIB:SPX-BP mass ratio is 7:3): 0.3 g of sulfonated microporous polymer (SPX-BP) was dissolved in 15 mL of dimethyl sulfoxide and stirred until dissolved to obtain solution A. At the same time, 0.7 g of polyaryl indigo polymer (PIB) was dissolved in 35 mL of dimethyl sulfoxide and stirred until dissolved to obtain solution B. Then solution A was added to solution B and stirred at 50 °C for 24 h to obtain a casting solution containing polyaryl indigo / sulfonated microporous polymer composite. The casting solution was spread on a glass plate and the solvent was evaporated at 60 °C for 48 h. Then the glass plate was immersed in deionized water until the membrane separated from the glass plate to obtain a polyaryl indigo / sulfonated microporous polymer composite membrane with a PIB:SPX-BP composite ratio of 7:3 (the thickness of the membrane is 50 μm).

[0057] (4) The structural formula of the polyaryl indigo / sulfonated microporous polymer composite in the polyaryl indigo / sulfonated microporous polymer composite membrane is the same as that in Example 1.

[0058] (5) The prepared polyaryl indigo / sulfonated microporous polymer composite membrane with a PIB:SPX-BP=7:3 composite degree was immersed in a 6 mol / L potassium hydroxide (KOH) solution for 72 h at a temperature of 80 ℃ to obtain a polyaryl indigo / sulfonated microporous polymer composite alkaline ion solvation membrane with a PIB:SPX-BP=7:3 composite degree.

[0059] The PIB:SPX-BP=7:3 composite alkaline ionic solvation membrane prepared in Example 3 was found to have a water absorption rate of 30.47% and a swelling rate of 11.90%; its tensile strength was 129.92 MPa and its tensile strength at break was 19.31%, indicating that the membrane exhibited good mechanical strength and alkaline stability. The ionic conductivity of the PIB:SPX-BP=7:3 composite alkaline ionic solvation membrane was 185.7 mS / cm. The PIB:SPX-BP=7:3 composite alkaline ionic solvation membrane was tested in an alkaline water electrolysis device. The results showed that at 80 °C and 2.0 V, the current density could reach 1.569 A / cm. 2 .

[0060] Example 4 A method for preparing a polyaryl indigo / sulfonated microporous polymer composite alkaline ionic solvation membrane: (1) The synthesis and preparation of polyarylene indigo polymer (PIB) is the same as in Example 1.

[0061] (2) The synthesis of microporous polymer (PX-BP) and the synthesis and preparation of sulfonated microporous polymer (SPX-BP) are the same as in Example 1.

[0062] (3) Preparation of polyaryl indigo / sulfonated microporous polymer composite membrane (PIB:SPX-BP mass ratio is 6:4): 0.4 g of sulfonated microporous polymer (SPX-BP) was dissolved in 20 mL of dimethyl sulfoxide and stirred until dissolved to obtain solution A. At the same time, 0.6 g of polyaryl indigo polymer (PIB) was dissolved in 30 mL of dimethyl sulfoxide and stirred until dissolved to obtain solution B. Then solution A was added to solution B and stirred at 50 °C for 24 h to obtain a casting solution containing polyaryl indigo / sulfonated microporous polymer composite. The casting solution was spread on a glass plate and the solvent was evaporated at 60 °C for 48 h. Then the glass plate was immersed in deionized water until the membrane separated from the glass plate to obtain a polyaryl indigo / sulfonated microporous polymer composite membrane with a PIB:SPX-BP composite ratio of 6:4 (the thickness of the membrane is 47 μm).

[0063] (4) The structural formula of the polyaryl indigo / sulfonated microporous polymer composite in the polyaryl indigo / sulfonated microporous polymer composite membrane is the same as that in Example 1.

[0064] (5) The prepared polyaryl indigo / sulfonated microporous polymer composite membrane with a PIB:SPX-BP=6:4 composite degree was immersed in a 6 mol / L potassium hydroxide (KOH) solution for 72 h at a temperature of 80 ℃ to obtain a polyaryl indigo / sulfonated microporous polymer composite alkaline ion solvation membrane with a PIB:SPX-BP=6:4 composite degree.

[0065] The PIB:SPX-BP=6:4 composite alkaline ionic solvation membrane prepared in Example 4 had a water absorption rate of 27.78% and a swelling rate of 10.13%; its tensile strength was 111.97 MPa and its tensile strength at break was 17.94%, indicating that the membrane exhibited good mechanical strength and alkaline stability. The ionic conductivity of the PIB:SPX-BP=6:4 composite alkaline ionic solvation membrane was 165.2 mS / cm. The PIB:SPX-BP=6:4 composite alkaline ionic solvation membrane was tested in an alkaline water electrolysis device. The results showed that at 80 °C and 2.0 V, the current density could reach 0.958 A / cm. 2 .

[0066] Example 5 A method for preparing a polyaryl indigo / sulfonated microporous polymer composite alkaline ionic solvation membrane: (1) The synthesis and preparation of polyarylene indigo polymer (PIB) is the same as in Example 1.

[0067] (2) The synthesis of microporous polymer (PX-BP) and the synthesis and preparation of sulfonated microporous polymer (SPX-BP) are the same as in Example 1.

[0068] (3) Preparation of polyaryl indigo / sulfonated microporous polymer composite membrane (PIB:SPX-BP mass ratio is 5:5): 0.5 g of sulfonated microporous polymer (SPX-BP) was dissolved in 25 mL of dimethyl sulfoxide and stirred until dissolved to obtain solution A. At the same time, 0.5 g of polyaryl indigo polymer (PIB) was dissolved in 25 mL of dimethyl sulfoxide and stirred until dissolved to obtain solution B. Then solution A was added to solution B and stirred at 50 °C for 24 h to obtain a casting solution containing polyaryl indigo / sulfonated microporous polymer composite. The casting solution was spread on a glass plate and the solvent was evaporated at 60 °C for 48 h. Then the glass plate was immersed in deionized water until the membrane separated from the glass plate to obtain a polyaryl indigo / sulfonated microporous polymer composite membrane with a PIB:SPX-BP composite ratio of 5:5 (the thickness of the membrane is 47 μm).

[0069] (4) The structural formula of the polyaryl indigo / sulfonated microporous polymer composite in the polyaryl indigo / sulfonated microporous polymer composite membrane is the same as that in Example 1.

[0070] (5) The prepared polyarylene indigo / sulfonated microporous polymer composite membrane with a PIB:SPX-BP=5:5 composite degree was immersed in a 6 mol / L potassium hydroxide (KOH) solution for 72 h at a temperature of 80 ℃ to obtain a polyarylene indigo / sulfonated microporous polymer composite alkaline ion solvation membrane with a PIB:SPX-BP=5:5 composite degree.

[0071] The PIB:SPX-BP=5:5 composite alkaline ionic solvation membrane prepared in Example 5 was found to have a water absorption rate of 24.50% and a swelling rate of 9.08%; its tensile strength was 134.93 MPa and its tensile strength at break was 13.78%, indicating that the membrane exhibited good mechanical strength and alkaline stability. The ionic conductivity of the PIB:SPX-BP=5:5 composite alkaline ionic solvation membrane was 157.3 mS / cm. The PIB:SPX-BP=5:5 composite alkaline ionic solvation membrane was tested in an alkaline water electrolysis device. The results showed that at 80 °C and 2.0 V, the current density could reach 0.834 A / cm. 2 .

[0072] The proton nuclear magnetic resonance spectra of polyaryl indigo (PIB) (a), microporous polymer (PX-BP) (b), and sulfonated microporous polymer (SPX-BP) (c) in Example 1 of this invention ( 1 (H NMR) image see Figure 1 .

[0073] pass Figure 1 Analysis of the proton nuclear magnetic resonance (NMR) spectra showed that PIB, PX-BP, and SPX-BP were successfully prepared.

[0074] The Fourier transform infrared (FT-IR) spectra of the polyarylene indigo (PIB) and sulfonated microporous polymer (SPX-BP) in Example 1 of this invention, and the polyarylene indigo / sulfonated microporous polymer composite membranes in Examples 1-5 are shown below. Figure 2 .

[0075] from Figure 2 Analysis revealed that PIB and SPX-BP polymers were successfully blended in different proportions with no change in chemical structure, ultimately forming a polyaryl indigo / sulfonated microporous polymer composite membrane.

[0076] X-ray energy dispersive spectroscopy (EDS) images of the polyaryl indigo (PIB) and sulfonated microporous polymer (SPX-BP) composite membranes in Example 1 and the polyaryl indigo / sulfonated microporous polymer composite membranes in Example 2 are shown below. Figure 3 .

[0077] from Figure 3 Analysis revealed that the elemental composition, content, and microscopic distribution of the membrane surface, as well as the elemental surface scan spectrum, all demonstrated that the components in the composite membrane were uniformly dispersed and showed no obvious phase separation or aggregation.

[0078] The elemental content diagrams of polyaryl indigo (PIB) and sulfonated microporous polymer (SPX-BP) in Example 1 and the polyaryl indigo / sulfonated microporous polymer composite membrane in Example 2 are shown below. Figure 4 .

[0079] from Figure 4 As can be seen from the data, the elemental composition and content of the raw materials (PIB and SPX-BP) in the PIB:SPX-BP=8:2 composite membrane are consistent with those of the polyarylene indigo / sulfonated microporous polymer composite membrane, proving that the component ratio of the PIB and SPX-BP blend meets the design requirements.

[0080] The polarization curves (80 °C, 6 mol / L KOH solution) of the PIB:SPX-BP composite ion-solventized membranes with different degrees of compositeness prepared in Examples 1-5 of this invention are shown in the figure. Figure 5 .

[0081] The experiment employed a low-cost, non-precious metal integrated electrode assembly electrolytic cell, and tested the membrane electrolysis performance under actual engineering conditions. Figure 5 As can be seen, the composite membrane with a ratio of PIB:SPX-BP = 8:2 exhibits excellent electrolytic polarization performance, with a current density of 1.75 A / cm² at 2.0 V. -1 Its performance is far superior to other blended membranes, and its overall electrolytic performance is outstanding.

[0082] Example 6 A method for preparing a polyaryl indigo / sulfonated microporous polymer composite alkaline ionic solvation membrane: (1) Synthesis of polyaryl indigo polymer PIPT 1.851 g (8 mmol) of terphenyl and 1.295 g (8.8 mmol) of indigo (molar ratio 1:1.1) were dissolved in a three-necked flask containing 12 mL of dichloromethane. The mixture was stirred at room temperature for 30 min until completely dissolved. Then, 16.3 mL of trifluoromethanesulfonic acid was slowly added dropwise to the mixture using a constant-pressure funnel in an ice-water bath at 0 °C (45 min). The ice-water bath was then removed, and the mixture was stirred at room temperature for 5 h. The reaction liquid changed from white to a dark reddish-brown viscous liquid. The reaction liquid was precipitated in methanol to obtain a white fibrous polymer PIPT. This fibrous polymer was then cut into small pieces, washed with water until the washings were neutral, and then dried at room temperature to obtain polyaryl indigo polymer (PIPT, degree of polymerization n = 672).

[0083] The reaction process in step (1) is as follows: .

[0084] (2) The synthesis of microporous polymer (PX-BP) and the synthesis and preparation of sulfonated microporous polymer (SPX-BP) are the same as in Example 1.

[0085] (3) Preparation of polyaryl indigo / sulfonated microporous polymer composite membrane (PIPT:SPX-BP mass ratio is 8:2): 0.2 g of sulfonated microporous polymer (SPX-BP) was dissolved in 10 mL of dimethyl sulfoxide and stirred until dissolved to obtain solution A. At the same time, 0.8 g of polyaryl indigo polymer (PIPT) was dissolved in 40 mL of dimethyl sulfoxide and stirred until dissolved to obtain solution B. Then solution A was added to solution B and stirred at 50 °C for 24 h to obtain a casting solution containing polyaryl indigo / sulfonated microporous polymer composite. The casting solution was spread on a glass plate and the solvent was evaporated at 60 °C for 48 h. Then the glass plate was immersed in deionized water until the membrane separated from the glass plate to obtain a polyaryl indigo / sulfonated microporous polymer composite membrane with a PIPT:SPX-BP composite ratio of 8:2 (the membrane thickness is 47 μm).

[0086] (4) The structural formula of the polyaryl indigo / sulfonated microporous polymer composite in the polyaryl indigo / sulfonated microporous polymer composite membrane is as follows: .

[0087] (5) The prepared polyaryl indigo / sulfonated microporous polymer composite membrane with a PIPT:SPX-BP=8:2 composite degree was immersed in a 6 mol / L potassium hydroxide (KOH) solution for 72 h at a temperature of 80 ℃ to obtain the polyaryl indigo / sulfonated microporous polymer composite alkaline ion solvation membrane with a PIPT:SPX-BP=8:2 composite degree.

[0088] The PIPT:SPX-BP=8:2 composite alkaline ionic solvation membrane prepared in Example 6 was found to have a water absorption rate of 33.61% and a swelling rate of 11.80%; its tensile strength was 115 MPa and its tensile strength at break was 12%, indicating that the membrane exhibited good mechanical strength and alkaline stability. The ionic conductivity of the PIPT:SPX-BP=8:2 composite alkaline ionic solvation membrane was 195.8 mS / cm. The PIPT:SPX-BP=8:2 composite alkaline ionic solvation membrane was tested in an alkaline water electrolysis device. The results showed that at 80℃ and 2V, the current density could reach 1.75 A / cm². 2 .

[0089] Example 7 A method for preparing a polyaryl indigo / sulfonated microporous polymer composite alkaline ionic solvation membrane: (1) Synthesis of polyaryl indigo polymer PIMT 1.851 g (8 mmol) of m-terphenyl and 1.295 g (8.8 mmol) of indigo (molar ratio 1:1.1) were dissolved in a three-necked flask containing 12 mL of dichloromethane. The mixture was stirred at room temperature for 20 min until completely dissolved. Then, 16.3 mL of trifluoromethanesulfonic acid was slowly added dropwise to the mixture using a constant-pressure funnel in an ice-water bath at 0 °C (45 min). The ice-water bath was then removed, and the mixture was stirred at room temperature for 4.5 h. The reaction liquid changed from white to a dark reddish-brown viscous liquid. The reaction liquid was precipitated in methanol to obtain a white fibrous polymer PIPT. This fibrous polymer was then cut into small pieces, washed with water until the washings were neutral, and then dried at room temperature to obtain polyaryl indigo polymer (PIMT, degree of polymerization n = 620).

[0090] The reaction process in step (1) is as follows: .

[0091] (2) The synthesis of microporous polymer (PX-BP) and the synthesis and preparation of sulfonated microporous polymer (SPX-BP) are the same as in Example 1.

[0092] (3) Preparation of polyaryl indigo / sulfonated microporous polymer composite membrane (PIMT:SPX-BP mass ratio is 8:2): 0.2 g of sulfonated microporous polymer (SPX-BP) was dissolved in 10 mL of dimethyl sulfoxide and stirred until dissolved to obtain solution A. At the same time, 0.8 g of polyaryl indigo polymer (PIMT) was dissolved in 40 mL of dimethyl sulfoxide and stirred until dissolved to obtain solution B. Then solution A was added to solution B and stirred at 50 °C for 24 h to obtain a casting solution containing polyaryl indigo / sulfonated microporous polymer composite. The casting solution was spread on a glass plate and the solvent was evaporated at 60 °C for 48 h. Then the glass plate was immersed in deionized water until the membrane separated from the glass plate to obtain a polyaryl indigo / sulfonated microporous polymer composite membrane with a PIMT:SPX-BP composite ratio of 8:2 (the membrane thickness is 43 μm).

[0093] (4) The structural formula of the polyaryl indigo / sulfonated microporous polymer composite in the polyaryl indigo / sulfonated microporous polymer composite membrane is as follows: .

[0094] (5) The prepared polyaryl indigo / sulfonated microporous polymer composite membrane with a PIMT:SPX-BP=8:2 composite degree was immersed in a 6 mol / L potassium hydroxide (KOH) solution for 72 h at a temperature of 80 ℃ to obtain a polyaryl indigo / sulfonated microporous polymer composite alkaline ion solvation membrane with a PIMT:SPX-BP=8:2 composite degree.

[0095] The PIMT:SPX-BP=8:2 composite alkaline ionic solvation membrane prepared in Example 7 was found to have a water absorption rate of 30.84% ​​and a swelling rate of 11.06%; its tensile strength was 119.55 MPa and its tensile strength at break was 18.46%, indicating that the membrane exhibited good mechanical strength and alkaline stability. The ionic conductivity of the PIMT:SPX-BP=8:2 composite alkaline ionic solvation membrane was 185.8 mS / cm. The PIMT:SPX-BP=8:2 composite alkaline ionic solvation membrane was tested in an alkaline water electrolysis device. The results showed that at 80 °C and 2 V, the current density could reach 1.62 A / cm. 2 .

[0096] Example 8 A method for preparing a polyaryl indigo / sulfonated microporous polymer composite alkaline ionic solvation membrane: (1) Synthesis of polyaryl indigo polymer PIOT 1.851 g (8 mmol) of o-terphenyl and 1.295 g (8.8 mmol) of indigo (molar ratio 1:1.1) were dissolved in a three-necked flask containing 12 mL of dichloromethane. The mixture was stirred at room temperature for 20 min until completely dissolved. Then, 16.3 mL of trifluoromethanesulfonic acid was slowly added dropwise to the mixture using a constant-pressure funnel in an ice-water bath at 0 °C (45 min). The ice-water bath was then removed, and the mixture was stirred at room temperature for 4.5 h. The reaction liquid changed from white to a dark reddish-brown viscous liquid. The reaction liquid was precipitated in methanol to obtain a white fibrous polymer PIPT. This fibrous polymer was then cut into small pieces, washed with water until the washings were neutral, and then dried at room temperature to obtain polyaryl indigo polymer (PIOT, degree of polymerization n = 647).

[0097] The reaction process in step (1) is as follows: .

[0098] (2) The synthesis of microporous polymer (PX-BP) and the synthesis and preparation of sulfonated microporous polymer (SPX-BP) are the same as in Example 1.

[0099] (3) Preparation of polyaryl indigo / sulfonated microporous polymer composite membrane (PIOT:SPX-BP mass ratio is 8:2): 0.2 g of sulfonated microporous polymer (SPX-BP) was dissolved in 10 mL of dimethyl sulfoxide and stirred until dissolved to obtain solution A. At the same time, 0.8 g of polyaryl indigo polymer (PIOT) was dissolved in 40 mL of dimethyl sulfoxide and stirred until dissolved to obtain solution B. Then solution A was added to solution B and stirred at 50 °C for 24 h to obtain a casting solution containing polyaryl indigo / sulfonated microporous polymer composite. The casting solution was spread on a glass plate and the solvent was evaporated at 60 °C for 48 h. Then the glass plate was immersed in deionized water until the membrane separated from the glass plate to obtain a polyaryl indigo / sulfonated microporous polymer composite membrane with a PIOT:SPX-BP composite ratio of 8:2 (the membrane thickness is 44 μm).

[0100] (4) The structural formula of the polyaryl indigo / sulfonated microporous polymer composite in the polyaryl indigo / sulfonated microporous polymer composite membrane is as follows: .

[0101] (5) The prepared polyaryl indigo / sulfonated microporous polymer composite membrane with a PIOT:SPX-BP=8:2 composite degree was immersed in a 6 mol / L potassium hydroxide (KOH) solution for 72 h at a temperature of 80 ℃ to obtain the polyaryl indigo / sulfonated microporous polymer composite alkaline ion solvation membrane with a PIOT:SPX-BP=8:2 composite degree.

[0102] The PIOT:SPX-BP=8:2 composite alkaline ion solvation membrane prepared in Example 8 was found to have a water absorption rate of 27.03% and a swelling rate of 10.29%; its tensile strength was 101.76 MPa and its tensile strength at break was 14.33%, indicating that the membrane exhibits good mechanical strength and alkaline stability. The ionic conductivity of the PIOT:SPX-BP=8:2 composite alkaline ion solvation membrane was 147.9 mS / cm. The PIOT:SPX-BP=8:2 composite alkaline ion solvation membrane was tested in an alkaline water electrolysis device. The results showed that at 80 °C and 2 V, the current density could reach 1.05 A / cm. 2 .

[0103] Example 9 A method for preparing a polyaryl indigo / sulfonated microporous polymer composite alkaline ionic solvation membrane: (1) Synthesis of polyaryl indigo polymer PIPQ p-Tetraphenyl (2.468 g, 8 mmol) and indigo (1.295 g, 8.8 mmol) (molar ratio 1:1.1) were dissolved in a three-necked flask containing 12 mL of dichloromethane. The mixture was stirred at room temperature for 20 min until completely dissolved. Trifluoromethanesulfonic acid (16.3 mL) was then slowly added dropwise to the mixture using a constant-pressure funnel in an ice-water bath at 0 °C (45 min). The ice-water bath was then removed, and the reaction was stirred at room temperature for 4.5 h. The reaction liquid changed from white to a dark reddish-brown viscous liquid. The reaction liquid was precipitated in methanol to obtain a white fibrous polymer PIPT. This fibrous polymer was then cut into small pieces, washed with water until the washings were neutral, and then dried at room temperature to obtain polyaryl indigo polymer (PIPQ, degree of polymerization n = 653).

[0104] The reaction process in step (1) is as follows: .

[0105] (2) The synthesis of microporous polymer (PX-BP) and the synthesis and preparation of sulfonated microporous polymer (SPX-BP) are the same as in Example 1.

[0106] (3) Preparation of polyaryl indigo / sulfonated microporous polymer composite membrane (PIPQ:SPX-BP mass ratio is 8:2): 0.2 g of sulfonated microporous polymer (SPX-BP) was dissolved in 10 mL of dimethyl sulfoxide and stirred until dissolved to obtain solution A. At the same time, 0.8 g of polyaryl indigo polymer (PIPQ) was dissolved in 40 mL of dimethyl sulfoxide and stirred until dissolved to obtain solution B. Then solution A was added to solution B and stirred at 50 °C for 24 h to obtain a casting solution containing polyaryl indigo / sulfonated microporous polymer composite. The casting solution was spread on a glass plate and the solvent was evaporated at 60 °C for 48 h. Then the glass plate was immersed in deionized water until the membrane separated from the glass plate to obtain a polyaryl indigo / sulfonated microporous polymer composite membrane with a PIPQ:SPX-BP composite ratio of 8:2 (the membrane thickness is 43 μm).

[0107] (4) The structural formula of the polyaryl indigo / sulfonated microporous polymer composite in the polyaryl indigo / sulfonated microporous polymer composite membrane is as follows: .

[0108] (5) The prepared polyaryl indigo / sulfonated microporous polymer composite membrane with a PIPQ:SPX-BP=8:2 composite degree was immersed in a 6 mol / L potassium hydroxide (KOH) solution for 72 h at a temperature of 80 ℃ to obtain the polyaryl indigo / sulfonated microporous polymer composite alkaline ion solvation membrane with a PIPQ:SPX-BP=8:2 composite degree.

[0109] The PIPQ:SPX-BP=8:2 composite alkaline ion solvation membrane prepared in Example 9 had a water absorption rate of 33.46% and a swelling rate of 11.30%; its tensile strength was 123.66 MPa and its tensile strength at break was 16.82%, indicating that the membrane exhibited good mechanical strength and alkaline stability. The ionic conductivity of the PIPQ:SPX-BP=8:2 composite alkaline ion solvation membrane was 175.9 mS / cm. The PIPQ:SPX-BP=8:2 composite alkaline ion solvation membrane was tested in an alkaline water electrolysis device. The results showed that at 80 °C and 2 V, the current density could reach 1.64 A / cm. 2 .

[0110] Example 10 A method for preparing a polyaryl indigo / sulfonated microporous polymer composite alkaline ionic solvation membrane: (1) The synthesis and preparation of polyarylene indigo polymer (PIB) is the same as in Example 1.

[0111] (2) Synthesis of microporous polymer PX-PT 4,4'-Dihydroxyterphenyl (2.60 g, 9.6 mmol) and 2,2,2-trifluoroacetophenone (1.71 g, 9.8 mmol) were added to dichloromethane (DCM, 14 mL) and stirred at room temperature to dissolve. Then, trifluoromethanesulfonic acid (TFSA, 2 mL) was slowly added dropwise in an ice-water bath as a catalyst. The solution changed from milky white to blackish-green. After the addition was complete, the solution was transferred to an oil bath at 38 °C and stirred for 135 min until it became viscous. The reaction solution was precipitated in methanol and washed several times with distilled water. After the washing solution became neutral, the product was removed and air-dried at room temperature to obtain the microporous polymer (PX-PT, degree of polymerization m = 734).

[0112] Synthesis of sulfonated microporous polymer SPX-PT PX-PT (1.5 g) was dissolved in dichloromethane (30 mL) and stirred for 30 min. Chlorosulfonic acid (0.3 mL) was added to dichloromethane (10 mL) and slowly added dropwise to the PX-PT solution at 0 °C. The mixture was stirred vigorously (220 r / min) for 50 min, resulting in a black precipitate. The precipitate was filtered and washed several times with methanol. After drying at room temperature, the product (SPX-PT, degree of polymerization m of 734) was obtained.

[0113] The reaction process in step (2) is as follows: .

[0114] (3) Preparation of polyaryl indigo / sulfonated microporous polymer composite membrane (PIB:SPX-PT mass ratio is 8:2): 0.2 g of sulfonated microporous polymer (SPX-PT) was dissolved in 10 mL of dimethyl sulfoxide and stirred until dissolved to obtain solution A. At the same time, 0.8 g of polyaryl indigo polymer (PIB) was dissolved in 40 mL of dimethyl sulfoxide and stirred until dissolved to obtain solution B. Then solution A was added to solution B and stirred at 50 °C for 24 h to obtain a casting solution containing polyaryl indigo / sulfonated microporous polymer composite. The casting solution was spread on a glass plate and the solvent was evaporated at 60 °C for 48 h. Then the glass plate was immersed in deionized water until the membrane separated from the glass plate to obtain a polyaryl indigo / sulfonated microporous polymer composite membrane with a PIB:SPX-PT composite ratio of 8:2 (the membrane thickness is 43 μm).

[0115] (4) The structural formula of the polyaryl indigo / sulfonated microporous polymer composite in the polyaryl indigo / sulfonated microporous polymer composite membrane is as follows: .

[0116] (5) The prepared polyaryl indigo / sulfonated microporous polymer composite membrane with a PIB:SPX-PT=8:2 composite degree was immersed in a 6 mol / L potassium hydroxide (KOH) solution for 72 h at a temperature of 80 ℃ to obtain a polyaryl indigo / sulfonated microporous polymer composite alkaline ion solvation membrane with a PIB:SPX-PT=8:2 composite degree.

[0117] The PIB:SPX-PT=8:2 composite alkaline ion solvation membrane prepared in Example 10 had a water absorption rate of 32.90% and a swelling rate of 10.82%; its tensile strength was 134.81 MPa and its tensile strength at break was 18.47%, indicating that the membrane exhibited good mechanical strength and alkaline stability. The ionic conductivity of the PIB:SPX-PT=8:2 composite alkaline ion solvation membrane was 175.6 mS / cm. The PIB:SPX-PT=8:2 composite alkaline ion solvation membrane was tested in an alkaline water electrolysis device. The results showed that at 80 °C and 2 V, the current density could reach 1.54 A / cm. 2 .

[0118] Example 11 A method for preparing a polyaryl indigo / sulfonated microporous polymer composite alkaline ionic solvation membrane: (1) The synthesis and preparation of polyarylene indigo polymer (PIB) is the same as in Example 1.

[0119] (2) Synthesis of microporous polymer PX-BPF 4,4'-Dihydroxydiphenylmethane (1.92 g, 9.6 mmol) and 2,2,2-trifluoroacetophenone (1.67 g, 9.6 mmol) were added to dichloromethane (DCM, 14 mL) and stirred at room temperature to dissolve. Then, trifluoromethanesulfonic acid (TFSA, 2 mL) was slowly added dropwise in an ice-water bath as a catalyst. The solution changed from milky white to blackish-green. After the addition was complete, the solution was transferred to an oil bath at 38 °C and stirred for 135 min until it became viscous. The reaction solution was precipitated in methanol and washed repeatedly with distilled water. After the washing solution became neutral, the product was removed and air-dried at room temperature to obtain the microporous polymer (PX-BPF, degree of polymerization m = 750).

[0120] Synthesis of sulfonated microporous polymer SPX-BPF PX-BPF (1.5 g) was dissolved in dichloromethane (30 mL) and stirred for 30 min. Chlorosulfonic acid (0.3 mL) was added to dichloromethane (10 mL) and slowly added dropwise to the PX-BPF solution at 0 °C. The mixture was stirred vigorously (220 r / min) for 40 min, resulting in a black precipitate. The precipitate was filtered and washed several times with methanol. After drying at room temperature, the product (SPX-BPF, degree of polymerization m = 750) was obtained.

[0121] The reaction process in step (2) is as follows: .

[0122] (3) Preparation of polyaryl indigo / sulfonated microporous polymer composite membrane (PIB:SPX-BPF mass ratio is 8:2): 0.2 g of sulfonated microporous polymer (SPX-BPF) was dissolved in 10 mL of dimethyl sulfoxide and stirred until dissolved to obtain solution A. At the same time, 0.8 g of polyaryl indigo polymer (PIB) was dissolved in 40 mL of dimethyl sulfoxide and stirred until dissolved to obtain solution B. Then solution A was added to solution B and stirred at 50 °C for 24 h to obtain a casting solution containing polyaryl indigo / sulfonated microporous polymer composite. The casting solution was spread on a glass plate and the solvent was evaporated at 60 °C for 48 h. Then the glass plate was immersed in deionized water until the membrane separated from the glass plate to obtain a polyaryl indigo / sulfonated microporous polymer composite membrane with a PIB:SPX-BPF composite ratio of 8:2 (the membrane thickness is 47 μm).

[0123] (4) The structural formula of the polyaryl indigo / sulfonated microporous polymer composite in the polyaryl indigo / sulfonated microporous polymer composite membrane is as follows: .

[0124] (5) The prepared polyaryl indigo / sulfonated microporous polymer composite membrane with a PIB:SPX-BPF=8:2 composite degree was immersed in a 6 mol / L potassium hydroxide (KOH) solution for 72 h at a temperature of 80 ℃ to obtain a polyaryl indigo / sulfonated microporous polymer composite alkaline ion solvation membrane with a PIB:SPX-BPF=8:2 composite degree.

[0125] The PIB:SPX-BPF=8:2 composite alkaline ion solvation membrane prepared in Example 11 was found to have a water absorption rate of 29.70% and a swelling rate of 10.44%; its tensile strength was 104.81 MPa and its tensile strength at break was 15.61%, indicating that the membrane exhibited good mechanical strength and alkaline stability. The ionic conductivity of the PIB:SPX-BPF=8:2 composite alkaline ion solvation membrane was 165.9 mS / cm. The PIB:SPX-BPF=8:2 composite alkaline ion solvation membrane was tested in an alkaline water electrolysis device. The results showed that at 80 °C and 2 V, the current density could reach 1.25 A / cm. 2 .

[0126] Example 12 A method for preparing a polyaryl indigo / sulfonated microporous polymer composite alkaline ionic solvation membrane: (1) The synthesis and preparation of polyarylene indigo polymer (PIB) is the same as in Example 1.

[0127] (2) Synthesis of microporous polymer PX-BHPE 1,2-Di(4-hydroxyphenyl)ethane (2.06 g, 9.6 mmol) and 2,2,2-trifluoroacetophenone (1.67 g, 9.6 mmol) were added to dichloromethane (DCM, 14 mL) and stirred at room temperature to dissolve. Then, trifluoromethanesulfonic acid (TFSA, 2 mL) was slowly added dropwise in an ice-water bath as a catalyst. The solution changed from milky white to blackish-green. After the addition was complete, the solution was transferred to an oil bath at 38 °C and stirred for 135 min until it became viscous. The reaction solution was precipitated in methanol and washed repeatedly with distilled water. After the washing solution became neutral, the product was removed and air-dried at room temperature to obtain the microporous polymer (PX-BHPE, degree of polymerization m = 783).

[0128] Synthesis of sulfonated microporous polymer SPX-BHPE PX-BHPE (1.5 g) was dissolved in dichloromethane (30 mL) and stirred for 30 min. Chlorosulfonic acid (0.3 mL) was added to dichloromethane (10 mL) and slowly added dropwise to the PX-BHPE solution at 0 °C. The mixture was stirred vigorously (230 r / min) for 45 min, resulting in a black precipitate. The precipitate was filtered and washed several times with methanol. After drying at room temperature, the product (SPX-BHPE, degree of polymerization m = 783) was obtained.

[0129] The reaction process in step (2) is as follows: .

[0130] (3) Preparation of polyaryl indigo / sulfonated microporous polymer composite membrane (PIB:SPX-BHPE mass ratio is 8:2): 0.2 g of sulfonated microporous polymer (SPX-BHPE) was dissolved in 10 mL of dimethyl sulfoxide and stirred until dissolved to obtain solution A. At the same time, 0.8 g of polyaryl indigo polymer (PIB) was dissolved in 40 mL of dimethyl sulfoxide and stirred until dissolved to obtain solution B. Then solution A was added to solution B and stirred at 50 °C for 24 h to obtain a casting solution containing polyaryl indigo / sulfonated microporous polymer composite. The casting solution was spread on a glass plate and the solvent was evaporated at 60 °C for 48 h. Then the glass plate was immersed in deionized water until the membrane separated from the glass plate to obtain a polyaryl indigo / sulfonated microporous polymer composite membrane with a PIB:SPX-BHPE ratio of 8:2 (the membrane thickness is 43 μm).

[0131] (4) The structural formula of the polyaryl indigo / sulfonated microporous polymer composite in the polyaryl indigo / sulfonated microporous polymer composite membrane is as follows: .

[0132] (5) The prepared polyaryl indigo / sulfonated microporous polymer composite membrane with a PIB:SPX-BHPE=8:2 composite degree was immersed in a 6 mol / L potassium hydroxide (KOH) solution for 72 h at a temperature of 80 ℃ to obtain a polyaryl indigo / sulfonated microporous polymer composite alkaline ion solvation membrane with a PIB:SPX-BHPE=8:2 composite degree.

[0133] The PIB:SPX-BHPE=8:2 composite alkaline ion-solubilized membrane prepared in Example 12 was found to have a water absorption rate of 28.29% and a swelling rate of 10.36%; its tensile strength was 125.70 MPa and its elongation at break was 12.47%, indicating that the membrane exhibited good mechanical strength and alkaline stability. The ionic conductivity of the PIB:SPX-BHPE=8:2 composite alkaline ion-solubilized membrane was 155.9 mS / cm. The PIB:SPX-BHPE=8:2 composite alkaline ion-solubilized membrane was tested in an alkaline water electrolysis device. The results showed that at 80 °C and 2 V, the current density could reach 1.34 A / cm. 2 .

[0134] Example 13 A method for preparing a polyaryl indigo / sulfonated microporous polymer composite alkaline ionic solvation membrane: (1) The synthesis and preparation of polyarylene indigo polymer (PIPT) is the same as in Example 6.

[0135] (2) The synthesis and preparation of microporous polymer PX-BPF and sulfonated microporous polymer SPX-BPF are the same as in Example 11.

[0136] (3) Preparation of polyaryl indigo / sulfonated microporous polymer composite membrane (PIPT:SPX-BPF mass ratio is 8:2): 0.2 g of sulfonated microporous polymer (SPX-BPF) was dissolved in 10 mL of dimethyl sulfoxide and stirred until dissolved to obtain solution A. At the same time, 0.8 g of polyaryl indigo polymer (PIPT) was dissolved in 40 mL of dimethyl sulfoxide and stirred until dissolved to obtain solution B. Then solution A was added to solution B and stirred at 50 °C for 24 h to obtain a casting solution containing polyaryl indigo / sulfonated microporous polymer composite. The casting solution was spread on a glass plate and the solvent was evaporated at 60 °C for 48 h. Then the glass plate was immersed in deionized water until the membrane separated from the glass plate to obtain a polyaryl indigo / sulfonated microporous polymer composite membrane with a PIPT:SPX-BPF composite ratio of 8:2 (the membrane thickness is 47 μm).

[0137] (4) The structural formula of the polyaryl indigo / sulfonated microporous polymer composite in the polyaryl indigo / sulfonated microporous polymer composite membrane is as follows: .

[0138] (5) The prepared polyaryl indigo / sulfonated microporous polymer composite membrane with a PIPT:SPX-BPF=8:2 composite degree was immersed in a 6 mol / L potassium hydroxide (KOH) solution for 72 h at a temperature of 80 ℃ to obtain a polyaryl indigo / sulfonated microporous polymer composite alkaline ion solvation membrane with a PIPT:SPX-BPF=8:2 composite degree.

[0139] The PIPT:SPX-BPF=8:2 composite alkaline ionic solvation membrane prepared in Example 13 had a water absorption rate of 32.13% and a swelling rate of 11.04%; its tensile strength was 135.65 MPa and its tensile strength at break was 12.48%, indicating that the membrane exhibited good mechanical strength and alkaline stability. The ionic conductivity of the PIPT:SPX-BPF=8:2 composite alkaline ionic solvation membrane was 157.7 mS / cm. The PIPT:SPX-BPF=8:2 composite alkaline ionic solvation membrane was tested in an alkaline water electrolysis device. The results showed that at 80 °C and 2 V, the current density could reach 1.43 A / cm². 2 .

[0140] Example 14 A method for preparing a polyaryl indigo / sulfonated microporous polymer composite alkaline ionic solvation membrane: (1) The synthesis and preparation of polyarylene indigo polymer PIMT is the same as in Example 7.

[0141] (2) The synthesis and preparation of microporous polymer PX-BPF and sulfonated microporous polymer SPX-BPF are the same as in Example 11.

[0142] (3) Preparation of polyaryl indigo / sulfonated microporous polymer composite membrane (PIMT:SPX-BPF mass ratio is 8:2): 0.2 g of sulfonated microporous polymer (SPX-BPF) was dissolved in 10 mL of dimethyl sulfoxide and stirred until dissolved to obtain solution A. At the same time, 0.8 g of polyaryl indigo polymer (PIMT) was dissolved in 40 mL of dimethyl sulfoxide and stirred until dissolved to obtain solution B. Then solution A was added to solution B and stirred at 50 °C for 24 h to obtain a casting solution containing polyaryl indigo / sulfonated microporous polymer composite. The casting solution was spread on a glass plate and the solvent was evaporated at 60 °C for 48 h. Then the glass plate was immersed in deionized water until the membrane separated from the glass plate to obtain a polyaryl indigo / sulfonated microporous polymer composite membrane with a PIMT:SPX-BPF composite ratio of 8:2 (the membrane thickness is 49 μm).

[0143] (4) The structural formula of the polyaryl indigo / sulfonated microporous polymer composite in the polyaryl indigo / sulfonated microporous polymer composite membrane is as follows: .

[0144] (5) The prepared polyaryl indigo / sulfonated microporous polymer composite membrane with a PIMT:SPX-BPF=8:2 composite degree was immersed in a 6 mol / L potassium hydroxide (KOH) solution for 72 h at a temperature of 80 ℃ to obtain a polyaryl indigo / sulfonated microporous polymer composite alkaline ion solvation membrane with a PIMT:SPX-BPF=8:2 composite degree.

[0145] The PIMT:SPX-BPF=8:2 composite alkaline ion solvation membrane prepared in Example 14 was found to have a water absorption rate of 31.92% and a swelling rate of 10.70%; its tensile strength was 95.28 MPa and its tensile strength at break was 13.37%, indicating that the membrane exhibited good mechanical strength and alkaline stability. The ionic conductivity of the PIMT:SPX-BPF=8:2 composite alkaline ion solvation membrane was 145.3 mS / cm. The PIMT:SPX-BPF=8:2 composite alkaline ion solvation membrane was tested in an alkaline water electrolysis device. The results showed that at 80 °C and 2 V, the current density could reach 1.12 A / cm. 2 .

[0146] Example 15 A method for preparing a polyaryl indigo / sulfonated microporous polymer composite alkaline ionic solvation membrane: (1) The synthesis and preparation of polyarylene indigo polymer PIOT is the same as in Example 8.

[0147] (2) The synthesis and preparation of microporous polymer PX-BPF and sulfonated microporous polymer SPX-BPF are the same as in Example 11.

[0148] (3) Preparation of polyaryl indigo / sulfonated microporous polymer composite membrane (PIOT:SPX-BPF mass ratio is 8:2): 0.2 g of sulfonated microporous polymer (SPX-BPF) was dissolved in 10 mL of dimethyl sulfoxide and stirred until dissolved to obtain solution A. At the same time, 0.8 g of polyaryl indigo polymer (PIOT) was dissolved in 40 mL of dimethyl sulfoxide and stirred until dissolved to obtain solution B. Then solution A was added to solution B and stirred at 50 °C for 24 h to obtain a casting solution containing polyaryl indigo / sulfonated microporous polymer composite. The casting solution was spread on a glass plate and the solvent was evaporated at 60 °C for 48 h. Then the glass plate was immersed in deionized water until the membrane separated from the glass plate to obtain a polyaryl indigo / sulfonated microporous polymer composite membrane with a PIOT:SPX-BPF composite ratio of 8:2 (the membrane thickness is 47 μm).

[0149] (4) The structural formula of the polyaryl indigo / sulfonated microporous polymer composite in the polyaryl indigo / sulfonated microporous polymer composite membrane is as follows: .

[0150] (5) The prepared polyaryl indigo / sulfonated microporous polymer composite membrane with a PIOT:SPX-BPF=8:2 composite degree was immersed in a 6 mol / L potassium hydroxide (KOH) solution for 72 h at a temperature of 80 ℃ to obtain a polyaryl indigo / sulfonated microporous polymer composite alkaline ion solvation membrane with a PIOT:SPX-BPF=8:2 composite degree.

[0151] The PIOT:SPX-BPF=8:2 composite alkaline ion solvation membrane prepared in Example 15 was found to have a water absorption rate of 32.84% and a swelling rate of 10.77%; its tensile strength was 121.03 MPa and its tensile strength at break was 12.66%, indicating that the membrane exhibited good mechanical strength and alkaline stability. The ionic conductivity of the PIOT:SPX-BPF=8:2 composite alkaline ion solvation membrane was 165.4 mS / cm. The PIOT:SPX-BPF=8:2 composite alkaline ion solvation membrane was tested in an alkaline water electrolysis device. The results showed that at 80 °C and 2 V, the current density could reach 1.16 A / cm. 2 .

[0152] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications and improvements made by those skilled in the art to the technical solutions of the present invention without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims

1. A polyaryl indigo / sulfonated microporous polymer composite, characterized in that, The structural general formula of the polyaryl isatin / sulfonated microporous polymer composite is shown as follows: ； In the above formula, n is the degree of polymerization, and the numerical range is 100 < n ≤ 1000; m is the degree of polymerization, and the numerical range is 100 < m ≤ 1000; Ar is selected from any of the following structures: ； R is selected from any of the following structures: 。 2. A method for preparing the polyaryl indigo / sulfonated microporous polymer composite of claim 1, characterized in that, It includes the following steps: Dissolve a monomer containing an aromatic ring structure, isatin, and a catalyst in a solvent, and obtain a polyaryl isatin polymer after the reaction; Dissolve a dihydroxy polycyclic aromatic hydrocarbon, trifluoroacetophenone, and a catalyst in a solvent, and obtain a microporous polymer after the reaction; dissolve the microporous polymer and chlorosulfonic acid in a solvent, and obtain a sulfonated microporous polymer after sulfonation; Co-dissolve the polyaryl isatin polymer and the sulfonated microporous polymer in a solvent at a mass ratio of 1-9:1, and obtain the polyaryl isatin / sulfonated microporous polymer composite after the reaction; The structural formula of the polymer unit provided by the monomer containing an aromatic ring structure is shown as any of the following structures: ； The structural formula of the polymer unit provided by the dihydroxy polycyclic aromatic hydrocarbon is shown as any of the following structures: 。 3. The method for preparing the polyaryl indigo / sulfonated microporous polymer composite according to claim 2, characterized in that, In the preparation step of the polyaryl isatin polymer: the molar ratio of the monomer containing an aromatic ring structure to the isatin is 1:1-1.3; the catalyst is trifluoromethanesulfonic acid, and the addition amount is 20-25eq; the reaction time is 4.5-6h.

4. The method for preparing the polyaryl indigo / sulfonated microporous polymer composite according to claim 2, characterized in that, In the preparation step of the sulfonated microporous polymer: the molar ratio of the dihydroxy polycyclic aromatic hydrocarbon to the trifluoroacetophenone is 1:1-1.4; the addition amount of the chlorosulfonic acid is 1.1-2.5eq; in the preparation step of the sulfonated microporous polymer: the catalyst is trifluoromethanesulfonic acid, and the addition amount is 2.25-5.5eq; the reaction time is 2-12h; the sulfonation time is 20-150min.

5. The method for preparing the polyaryl indigo / sulfonated microporous polymer composite according to claim 2, characterized in that, After the polyaryl isatin polymer and the sulfonated microporous polymer are co-dissolved: the reaction temperature is 40-60°C, and the time is 24-72h.

6. A polyaryl indigo / sulfonated microporous polymer composite alkaline ionic solvation membrane, characterized in that, The main component is the polyaryl isatin / sulfonated microporous polymer composite described in claim 1.

7. A method for preparing the polyaryl indigo / sulfonated microporous polymer composite alkaline ionic solvation membrane according to claim 6, characterized in that, It includes the following steps: Pour and dry a casting solution containing the polyaryl isatin / sulfonated microporous polymer composite to obtain a polyaryl isatin / sulfonated microporous polymer composite membrane; immerse the polyaryl isatin / sulfonated microporous polymer composite membrane in a KOH solution to obtain the polyaryl isatin / sulfonated microporous polymer composite alkaline ion solvent membrane.

8. The method for preparing the polyaryl indigo / sulfonated microporous polymer composite alkaline ionic solvation membrane according to claim 7, characterized in that, The solid content of the casting solution containing the polyaryl isatin / sulfonated microporous polymer composite is 2-5wt.%; the drying temperature is 40-100°C, and the time is 24-72h.

9. Application of the polyaryl isatin / sulfonated microporous polymer composite described in claim 1 in the fields of alkaline electrolyzed water, fuel cells, electroreduction of carbon dioxide, or zinc-air batteries.

10. Application of the polyaryl isatin / sulfonated microporous polymer composite alkaline ion solvent membrane described in claim 6 in the fields of alkaline electrolyzed water, fuel cells, electroreduction of carbon dioxide, or zinc-air batteries.

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