A nitrogen and phosphorus double active center polyaryl cyclic amine polymer, an anion exchange membrane, and a preparation method and application thereof

Abstract

The application discloses a nitrogen and phosphorus double active center polyaryl cyclic amine polymer, an anion exchange membrane and a preparation method and application thereof. First, aromatic compounds containing phosphorus elements are reacted with carbonyl compounds and aromatic hydrocarbon compounds in an organic solvent under acidic conditions to prepare nitrogen and phosphorus double cationic group-containing polyaryl piperidine, polyaryl quinine, polyaryl tropine and other phosphorus-containing polyaryl cyclic amine polymers. Through quaternization and quaternary phosphonation, the polymers have anion exchange capacity, are soaked in corresponding ion solutions and obtain specific functional anion exchange membranes. The anion exchange membranes have nitrogen and phosphorus two active centers for ion exchange, have excellent stability, mechanical properties and ion transmission performance and are mainly applied to technical fields of fuel cells, hydrogen production by water electrolysis, flow batteries, metal-air batteries, carbon dioxide electrolytic cells, electrodialysis, water treatment, salt lake lithium extraction and the like.

Description

Technical Field

[0001] This invention relates to a nitrogen- and phosphorus dual-active-center polyaryl cyclic amine polymer, anion exchange membrane, its preparation method, and its application in the field of ion transport or separation. Specifically, it relates to the structural design of materials such as polyarylpiperidine, polyarylquinine, and polyaryltropine, and belongs to the field of anion exchange membrane material technology. Background Technology

[0002] Hydrogen energy is a clean energy source with advantages such as high calorific value and pollution-free combustion products. Electrolysis of water is currently the most efficient hydrogen production technology. Anion exchange membrane (EEM) water electrolysis combines the advantages of traditional alkaline liquid electrolyte water electrolysis and proton exchange membrane (PEM) water electrolysis. In an alkaline medium, non-precious metal catalysts such as Ni, Co, and Fe can be used. Furthermore, anion exchange membranes, like proton exchange membranes, avoid the need for de-alkali treatment of the product gas. The alkaline system also avoids corrosion problems, significantly reducing equipment costs. Hydrogen fuel cell technology has long been considered the ultimate solution to the future energy crisis using hydrogen energy. A hydrogen fuel cell mainly consists of anode and cathode plates, a catalyst, a gas diffusion layer, and an ion exchange membrane, directly converting the chemical energy of hydrogen and oxygen into electrical energy. Among the many types of fuel cells, anion exchange membrane fuel cells have received widespread attention in recent decades due to their low cost, environmental friendliness, and corrosion resistance. Additionally, flow batteries are a novel electrochemical energy storage technology. Their positive and negative electrolytes are separate and circulated independently, featuring high capacity, wide application range, and long cycle life. In addition, anion exchange membranes are also required in fields such as electrocatalytic carbon dioxide reduction, metal-air batteries, capacitors, and the chlor-alkali industry, and the improvement of efficiency also depends heavily on high-performance anion exchange membranes.

[0003] Anion exchange membranes (AEMs) are a core component of the aforementioned technologies, and their anion conductivity, durability, and mechanical properties are crucial. Based on different functional groups, AEMs can be classified into quaternary ammonium salt anion exchange membranes, imidazole anion exchange membranes, and guanidine salt anion exchange membranes. Quaternary ammonium salt anion exchange membranes are favored due to their low cost and good stability, but their ionic conductivity, mechanical properties, and durability still need improvement. The key to improving the mechanical properties and durability of the membrane lies in the design of the polymer backbone. Another key factor limiting the performance of anion exchange membranes is their low ionic conductivity. Previous patents have reported phosphorus-containing anion exchange membranes, but their conductivity is too low (only 58 mS / cm at room temperature). -1 This limits its further application.

[0004] Currently, most commercially available anion exchange membranes are based on frameworks such as polyetheretherketone, polysulfone, and polybenzimidazole. Their ionic conductivity, chemical stability, and mechanical properties under alkaline conditions still require further improvement. In recent years, polyaryl cyclic amine anion exchange membranes have effectively improved membrane stability. In particular, anion exchange membranes with structures such as polyarylpiperidine, polyarylquinine, and polyaryltropine have recently attracted widespread attention and have great development potential due to their simple synthesis processes, low cost, and excellent performance. However, the structural types of these anion exchange membrane materials are still very limited, and their mechanical properties and ionic conductivity also need further improvement. Summary of the Invention

[0005] This invention is based on the inventor's discovery and understanding of the following facts and problems: the conductivity, mechanical properties and chemical stability of current anion exchange membrane materials need to be improved.

[0006] This invention aims to address one of the technical problems in related technologies to a certain extent. To this end, this invention proposes a nitrogen- and phosphorus-containing dual-active-center polyaryl cyclic amine polymer, anion exchange membrane, its preparation method, and its applications. Based on the strong stability of polyaryl cyclic amine membranes under alkaline conditions and their flexible structural designability, quaternary phosphonium salts are introduced into the membrane through direct copolymerization. By adjusting the type and ratio of comonomers, different applications of the anion exchange membrane can be achieved, improving the ionic conductivity, mechanical properties, and stability of the anion exchange membrane.

[0007] To achieve the above objectives, the present invention employs the following technical solution:

[0008] The first aspect of the present invention is to provide a phosphorus-containing polyaryl cyclic amine polymer containing both nitrogen and phosphorus active centers, having at least one of the structural formulas (1) to (4):

[0009]

[0010] in It is a benzene ring, naphthalene, or binaphthalene;

[0011] Where R is selected from polyarylpiperidine of the following formula Or the following formula: polyarylequinine Or the following formula of polyarylate Any one of them; X - It is an anion;

[0012] The molar ratio of phosphorus-containing groups is 1% to 50%.

[0013] This invention proposes polymers containing the above-mentioned triphenylphosphine, 1,2-bis(diphenylphosphine)ethane, racemic BINAP, R-type BINAP, or S-type BINAP configurations, wherein the chemical formulas of the BINAP-configured polymers are shown in formulas (5) to (7):

[0014]

[0015]

[0016] In the chemical formula, y represents the molar ratio of phosphorus-containing groups in the polymer, ranging from 1% to 50%.

[0017] The nitrogen- and phosphorus dual-active-center polyaryl cyclic amine polymer designed and synthesized in this invention has high ion conductivity. This polymer can be prepared into a high-strength membrane with large area, controllable size and thickness through film formation methods such as phase inversion or industrial coating, thereby enabling precise design and preparation of anion exchange membranes that can meet different needs in industrial production.

[0018] A second aspect of the present invention provides a method for preparing the above-mentioned nitrogen- and phosphorus-containing polyaryl cyclic amine polymers, comprising the following steps:

[0019] Step 1: Add phosphorus-containing monomers, aromatic compounds and carbonyl compounds to an organic solvent and react under strong acid catalysis. After the reaction is completed, neutralize, wash and dry to obtain the first polymer.

[0020] Step 2: The first polymer obtained in Step 1 is reacted with a haloalkane through quaternization and quaternization reactions to obtain a second polymer, namely the nitrogen- and phosphorus-containing polyaryl cyclic amine polymer.

[0021] Preferably, the phosphorus-containing monomer in step 1 is triphenylphosphine, 1,2-bis(diphenylphosphine)ethane, 2,2'-bis(diphenylphosphine)-1,1'-binaphthyl, (R)-(+)-2,2'-bis(diphenylphosphine)-1,1'-binaphthyl or (S)-(-)-2,2'-bis(diphenylphosphine)-1,1'-binaphthyl; the amount of phosphorus-containing monomer can be adjusted so that the molar ratio of phosphorus-containing groups in the final polymer is 1% to 50%; the quaternary phosphonium salt, as a cationic group, can attract and fix negatively charged ions in the ion exchange membrane, and can effectively interact with hydroxide ions to form stable ion pairs. At the same time, it forms hydrophilic regions in the membrane through self-assembly or other interactions. These hydrophilic regions are interconnected to form continuous ion transport channels, reducing collisions and obstacles of ions during transport. Thanks to the high stability of quaternary phosphonium salts in alkaline environments, their good ion conductivity, and their optimization effect on membrane phase separation structure and ion transport channels, quaternary phosphonium salt cationic groups exhibit higher stability in alkaline environments compared to traditional quaternary ammonium salt cationic groups.

[0022] Preferably, the aromatic compound in step 1 is selected from at least one of biphenyl, p-terphenyl, 9,9-dimethylfluorene, dibenzofuran, dibenzothiophene, or other similar compounds;

[0023] Preferably, the carbonyl compound in step 1 is selected from at least one of 1-methyl-4-piperidinone, 3-quininecycloketone, tropinone, or other similar compounds. Piperidinone, quininecycloketone, and tropinone exhibit high alkaline stability due to their low ring strain and ability to form stable conformations. Furthermore, polyaryl polymers also exhibit high stability under alkaline conditions. In particular, the selection of polyarylquinine structures, with its quinine unit as the cationic group, requires a high activation energy for alkaline degradation, thus solving the problem of insufficient stability of the cationic group. Simultaneously, the conductivity of quinine-based phosphorus-containing polyaryl cyclic amine anion exchange membranes can reach up to 200 mS / cm. -1 above;

[0024] More preferably, the reaction temperature in step 1 is 0–25°C, with better reaction results at 5°C, and the reaction time is 2–48 hours. As the copolymerization ratio of phosphorus-containing monomers in the system increases, the reaction time needs to be adjusted or extended accordingly.

[0025] Polyaryl polymers have a large number of rigid aromatic rings in their molecular chains. Due to π-π stacking and other effects, the binding force between polymer molecular chains is enhanced. They are very stable under alkaline conditions and are difficult to degrade. The phosphorus-containing ligands used in the synthesis process all have electron-rich groups such as benzene rings and naphthalene units, which are also very stable under alkaline conditions. The polymer skeleton prepared in this way has good stability under alkaline conditions, which can solve the problem of easy degradation of ion exchange membranes in the existing technology.

[0026] In some embodiments, the strong acid used in step 1 is trifluoroacetic acid and trifluoromethanesulfonic acid, and the strong acid catalytic reaction process is carried out by stirring at low temperature until viscous.

[0027] Preferably, the molar ratio of the aromatic compound to the carbonyl compound reactant is 1:(1-2).

[0028] Preferably, the halogenated hydrocarbon in step 2 is iodomethane, bromoethane, or bromopropane.

[0029] Preferably, the reaction temperature in step 2 is room temperature, and the reaction time is 24 to 72 hours.

[0030] Preferably, the mass ratio of the halogenated hydrocarbon added in step 2 to the first polymer is (2-3):1.

[0031] A third aspect of the present invention is an anion exchange membrane prepared based on the above-mentioned nitrogen- and phosphorus-containing dual-active-center polyaryl cyclic amine polymer or the above-mentioned preparation method.

[0032] The fourth aspect of the present invention is a method for preparing the above-mentioned anion exchange membrane, wherein the aforementioned nitrogen- and phosphorus-containing polyaryl cyclic amine polymer is dissolved in a solvent and cast into a film, evaporated and dried, and then immersed in an anion solution for ion exchange, thereby obtaining the nitrogen- and phosphorus-containing polyaryl cyclic amine anion exchange membrane.

[0033] Wherein, the anion solution is I - ,Br - Cl - OH - HCO3 - Or other chemically acceptable anionic solutions; the ion exchange temperature is 25–80°C, and the exchange time is 24–96 hours.

[0034] The present invention also discloses the application of the above-mentioned anion exchange membrane in ion transport.

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] The present invention proposes a nitrogen- and phosphorus dual-active-center cyclic amine polymer, which introduces quaternary phosphonium salt into a polyaryl cyclic amine anion exchange membrane. The content of quaternary phosphonium salt (1%–50%) is controlled by adjusting the amount of phosphorus-containing monomer, forming nitrogen- and phosphorus dual cationic groups as ion transport exchange sites. This improves the stability of the cationic groups in the anion exchange membrane, thereby increasing the ion exchange capacity, ion conductivity, and electrical conductivity of the anion exchange membrane. Furthermore, the use of polyaryl groups as the framework of the anion exchange membrane further enhances its mechanical properties. Piperidinone, quinine cyclic ketone, tropine, and other polyaryl polymers also exhibit high stability under alkaline conditions, making the anion exchange membrane prepared by this invention less prone to decomposition under alkaline conditions and thus more durable.

[0037] The present invention provides a method for preparing phosphorus-containing polyaryl cyclic amines. First, phosphorus-containing aromatic monomers are reacted in an organic solvent with aromatic compounds (such as biphenyl, p-terphenyl, 9,9-dimethylfluorene, dibenzofuran, dibenzothiophene, etc.), 1-methyl-4-piperidinone, 3-quinine cyclic ketone, or tropine under acidic conditions to prepare several types of phosphorus-containing polyarylpiperidine, polyarylquinine, and polyaryltropine materials. These materials are then quaternized and quaternized to obtain the final product, which exhibits excellent ion transport properties. The synthesis process of this invention is simple and low-cost, and the resulting membranes have high conductivity, thus possessing broad industrial application prospects.

[0038] The anion exchange membrane prepared based on this nitrogen- and phosphorus-containing dual-active-center cyclic amine polymer has all the advantages and technical effects of the polymer. In some embodiments, different applications of the anion exchange membrane can be achieved by adjusting the type and ratio of comonomers.

[0039] The method for preparing anion exchange membranes proposed in this invention involves dissolving a cyclic amine polymer containing nitrogen and phosphorus dual active centers in a solvent to form a solution. Different anion solutions can be used to prepare anion exchange membranes suitable for different applications. For example, the prepared hydroxide-type anion exchange membrane can be used in hydrogen fuel cells, and the prepared bicarbonate-type anion exchange membrane can be used in flow batteries. Furthermore, thanks to the anion exchange membrane used in this invention being rich in aromatic monomers and possessing strong mechanical structural stability, no special processing methods are required during membrane formation to obtain membrane materials with excellent mechanical structural stability, making this preparation method promising for broad applications. Attached Figure Description

[0040] Figure 1 This is a schematic diagram of the synthesis of phosphorus-containing polyarylepiperidine prepared in Example 1 of the present invention.

[0041] Figure 2 The image shows an FT-IR image of the phosphorus-containing polyarylepiperidine prepared in Example 1 of this invention.

[0042] Figure 3 The image shows an FT-IR image of the phosphorus-containing polyarylene piperidine anion exchange membrane prepared in Example 1 of this invention.

[0043] Figure 4 The image shows the conductivity of the phosphorus-containing polyarylene piperidine anion exchange membrane prepared in Example 1 of this invention.

[0044] Figure 5 This is a schematic diagram of the synthesis of phosphorus-containing polyarylepiperidine prepared in Example 2 of the present invention.

[0045] Figure 6 The image shows an FT-IR image of the phosphorus-containing polyarylepiperidine prepared in Example 2 of this invention.

[0046] Figure 7 The image shown is an FT-IR image of the phosphorus-containing polyarylene piperidine anion exchange membrane prepared in Example 2 of this invention.

[0047] Figure 8 The image shows the conductivity of the phosphorus-containing polyarylene piperidine anion exchange membrane prepared in Example 2 of this invention.

[0048] Figure 9 This is a schematic diagram of the synthesis of phosphorus-containing polyarylepiperidine prepared in Example 3 of the present invention.

[0049] Figure 10The image shows an FT-IR image of the phosphorus-containing polyarylepiperidine prepared in Example 3 of this invention.

[0050] Figure 11 The image shown is an FT-IR image of the phosphorus-containing polyarylene piperidine anion exchange membrane prepared in Example 3 of this invention.

[0051] Figure 12 The image shows the conductivity of the phosphorus-containing polyarylene piperidine anion exchange membrane prepared in Example 3 of this invention.

[0052] Figure 13 The present invention provides the structural formulas for the phosphorus-containing polyaryl cyclic amine polymer and the anion exchange membrane prepared in this invention. Detailed Implementation

[0053] To enable those skilled in the art to better understand the present invention, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of the present invention.

[0054] It should be noted that the terms "first," "second," etc., in the specification, claims, and accompanying drawings of this invention are used to distinguish similar objects and are not necessarily used to describe a specific order or sequence. It should be understood that such data can be interchanged where appropriate so that the embodiments of the invention described herein can be implemented in orders other than those illustrated or described herein. Furthermore, the terms "comprising" and "having," and any variations thereof, are intended to cover a non-exclusive inclusion; for example, a process, method, system, product, or apparatus that comprises a series of steps or units is not necessarily limited to those steps or units explicitly listed, but may include other steps or units not explicitly listed or inherent to such processes, methods, products, or apparatus.

[0055] All reagents used in the examples were commercially available, 99.9% analytical grade, and no further processing was performed. The invention will now be described in further detail with reference to the accompanying drawings and specific embodiments:

[0056] Example 1

[0057] Step 1: Preparation of racemic phosphorus-containing polyarylepiperidine (M-BINAP-PAP-3%)

[0058] 2,2'-bis(diphenylphosphine)-1,1'-binaphthyl (93.4 mg, 0.15 mmol) and p-terphenyl (1117 mg, 4.85 mmol) were added to a 25 mL round-bottom flask. Dichloromethane (5 mL) was added as a solvent, followed by 1-methyl-4-piperidinone (0.7 mL). The flask was then immersed in an ice bath and stirred for ten minutes. Trifluoroacetic acid (0.4 mL) and trifluoromethanesulfonic acid (4.5 mL) were added sequentially. The mixture was then stirred at low temperature for 4–8 hours, stopping the reaction when the viscous liquid in the flask could no longer be stirred. After the reaction stopped, the liquid was poured into a mixed solution of methanol (100 mL) and 1 M KOH (100 mL), and the solid precipitated completely. The solid was then washed repeatedly with 1 M KOH and water until neutral, and dried under vacuum at 100 °C for 12 h to obtain the product.

[0059] Step 2: Preparation of I - Racemic polyarylpiperidine containing phosphorus (M-BINAP-PAP-3%-I) - )

[0060] Weigh 500 mg of the product from step 1 and 400 mg of potassium carbonate into a glass bottle, add 15 ml of DMSO and 0.5 ml of iodomethane, and react at room temperature in the dark for 48 h. After 48 h, pour the mixture into ethyl acetate to obtain a white solid, wash once with ethyl acetate, wash twice with water, and dry under vacuum at 100 °C.

[0061] Step 3: Preparation of OH - Racemic phosphorus-containing polyarylpiperidine anion exchange membrane (M-BINAP-PAP-3%-OH) - -AEM)

[0062] Disperse 500 mg of the product obtained in step 2 in 20 ml of DMSO, sonicate until completely dissolved, and cast the solution into a smooth glass petri dish. Dry at 80 °C for 6 h and then at 120 °C for 12 h to obtain a smooth anion exchange membrane. Immerse the membrane in 1 M KOH and perform ion exchange at 80 °C for 48 h to obtain OH-. - Type of anion exchange membrane.

[0063] The schematic diagram of the synthesis of phosphorus-containing polyarylepiperidine M-BINAP-PAP-3% obtained in step 1 is shown below. Figure 1 As shown. Figure 2 Based on its FT-IR (Fourier Transform Infrared Spectroscopy) test results, from Figure 2 The CP (1490 cm) belonging to the BINAP unit can be found in the middle. -1 ) and CN (1370cm -1The characteristic peaks demonstrate the successful synthesis of phosphorus-containing polyarylepiperidine.

[0064] Figure 3 For the FTIR of the membrane, through Figure 3 It can be found that CP (1490cm) -1 ) and CN (1370cm -1 The characteristic peaks weaken significantly, which proves the successful formation of quaternary phosphonium salt and quaternary ammonium salt groups.

[0065] pass Figure 4 The anion exchange membrane M-BINAP-PAP-3%-OH shown - The conductivity of the AEM as a function of temperature shows that the conductivity of the membrane at 80℃ is 180.1 mS / cm. -1 Anion exchange membrane M-BINAP-PAP-3%-OH - Mechanical property tests conducted by AEM showed that the membrane's tensile strength exceeded 60 MPa, demonstrating excellent mechanical properties. Anion exchange membrane M-BINAP-PAP-3%-OH - -AEM durability tests showed that the conductivity decreased by only 1.5% after immersion in 1M KOH for more than 1800 hours, demonstrating excellent alkali stability.

[0066] Example 2

[0067] Step 1: Preparation of R-type phosphorus-containing polyarylepiperidine (R-BINAP-PAP-3%)

[0068] (R)-(+)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (93.4 mg, 0.15 mmol) and p-terphenyl (1117 mg, 4.85 mmol) were added to a 25 mL round-bottom flask. Dichloromethane (5 mL) was added as a solvent, followed by 1-methyl-4-piperidinone (0.7 mL). The flask was then immersed in an ice bath and stirred for ten minutes. Trifluoroacetic acid (0.42 mL) and trifluoromethanesulfonic acid (4.5 mL) were added sequentially. The mixture was then stirred at low temperature for 4–8 hours until the viscous liquid in the flask could no longer be stirred. After the reaction stopped, the liquid was poured into a mixed solution of methanol (100 mL) and 1 M KOH (100 mL), and the solid precipitated completely. The solid was then washed repeatedly with 1 M KOH and water until neutral, and dried under vacuum at 100 °C for 12 h to obtain the product.

[0069] Step 2: Preparation of I - Type R phosphorus-containing polyarylepiperidine (R-BINAP-PAP-3%-I) - )

[0070] Weigh 500 mg of the product from step 1 and 400 mg of potassium carbonate into a glass bottle, add 15 ml of DMSO and 0.5 ml of iodomethane, and react at room temperature in the dark for 48 h. After 48 h, pour the mixture into ethyl acetate to obtain a white solid, wash once with ethyl acetate, wash twice with water, and dry under vacuum at 100 °C.

[0071] Step 3: Preparation of OH - Type R phosphorus-containing polyarylpiperidine anion exchange membrane (R-BINAP-PAP-3%-OH) - -AEM)

[0072] Disperse 500 mg of the product obtained in step 2 in 20 ml of DMSO, sonicate until completely dissolved, and cast the solution into a smooth glass petri dish. Dry at 80 °C for 6 h and then at 120 °C for 12 h to obtain a smooth anion exchange membrane. Immerse the membrane in 1 M KOH and perform ion exchange at 80 °C for 48 h to obtain OH-. - Type of anion exchange membrane.

[0073] The schematic diagram of the synthesis of phosphorus-containing polyarylepiperidine R-BINAP-PAP-3% obtained in step 2 is shown below. Figure 5 As shown. Figure 6 Its FT-IR test results, from Figure 6 The CP (1490 cm) belonging to the BINAP unit can be found in the middle. -1 ) and CN (1370cm -1 The characteristic peaks demonstrate the successful synthesis of phosphorus-containing polyarylepiperidine.

[0074] Figure 3 R-BINAP-PAP-3%-OH anion exchange membrane - -AEM's FT-IR, via Figure 7 It can be found that CP (1490cm) -1 ) and CN (1370cm -1 The characteristic peaks weaken significantly, which proves the successful formation of quaternary phosphine salt and quaternary ammonium salt groups.

[0075] pass Figure 8 The anion exchange membrane R-BINAP-PAP-3%-OH shown - The conductivity of the AEM as a function of temperature shows that the conductivity of the membrane at 80℃ is 207.1 mS / cm. -1 .

[0076] Example 3

[0077] Step 1: Preparation of S-type phosphorus-containing polyarylepiperidine (S-BINAP-PAP-3%)

[0078] (S)-(-)-2,2'-bis(diphenylphosphine)-1,1'-binaphthyl (93.4 mg, 0.15 mmol) and p-terphenyl (1117 mg, 4.85 mmol) were added to a 25 mL round-bottom flask. Dichloromethane (5 mL) was added as a solvent, followed by 1-methyl-4-piperidinone (0.7 mL). The flask was then immersed in an ice bath and stirred for ten minutes. Trifluoroacetic acid (0.42 mL) and trifluoromethanesulfonic acid (4.5 mL) were added sequentially. The mixture was then stirred at low temperature for 4–8 hours until the viscous liquid in the flask could no longer be stirred. After the reaction stopped, the liquid was poured into a mixed solution of methanol (100 mL) and 1 M KOH (100 mL), and the solid precipitated completely. The solid was then washed repeatedly with 1 M KOH and water until neutral, and dried under vacuum at 100 °C for 12 h to obtain the product.

[0079] Step 2: Preparation of I - Type S-type phosphorus-containing polyarylepiperidine (S-BINAP-PAP-3%-I) - )

[0080] Weigh 500 mg of the product from step 1 and 400 mg of potassium carbonate into a glass bottle, add 15 ml of DMSO and 0.5 ml of iodomethane, and react at room temperature in the dark for 48 h. After 48 h, pour the mixture into ethyl acetate to obtain a white solid, wash once with ethyl acetate, wash twice with water, and dry under vacuum at 100 °C.

[0081] Step 3: Preparation of OH - Type S-type phosphorus-containing polyarylpiperidine anion exchange membrane (S-BINAP-PAP-3%-OH) - -AEM)

[0082] Disperse 500 mg of the product obtained in step 2 in 20 ml of DMSO, sonicate until completely dissolved, and cast the solution into a smooth glass petri dish. Dry at 80 °C for 6 h and then at 120 °C for 12 h to obtain a smooth anion exchange membrane. Immerse the membrane in 1 M KOH and perform ion exchange at 80 °C for 48 h to obtain OH-. - Type of anion exchange membrane.

[0083] The schematic diagram of the synthesis of phosphorus-containing polyarylepiperidine S-BINAP-PAP-3% obtained in step 1 is shown below. Figure 9 As shown. Figure 10 Its FT-IR test results, from Figure 10 The CP (1490 cm) belonging to the BINAP unit can be found in the middle. -1 ) and CN (1370cm -1 The characteristic peaks demonstrate the successful synthesis of phosphorus-containing polyarylepiperidine.

[0084] Figure 11 S-BINAP-3%-OH anion exchange membrane - -AEM's FT-IR, via Figure 11 It can be found that CP (1490cm) -1 ) and CN (1370cm -1 The characteristic peaks weaken significantly, which proves the successful formation of quaternary phosphine salt and quaternary ammonium salt groups.

[0085] pass Figure 12 The anion exchange membrane S-BINAP-3%-OH shown - The conductivity of the AEM as a function of temperature shows that the conductivity of the membrane at 80℃ is 202.3 mS / cm. -1 .

[0086] Example 4

[0087] Step 1: Preparation of racemic phosphorus-containing polyarylequinine (M-BINAP-PAQ-3%)

[0088] 2,2'-bis(diphenylphosphine)-1,1'-binaphthyl (93.4 mg, 0.15 mmol) and p-terphenyl (1117 mg, 4.85 mmol) were added to a 25 mL round-bottom flask. Dichloromethane (5 mL) was added as a solvent, followed by 3-quininecyclohexanone (751 mg). The flask was then immersed in an ice bath and stirred for ten minutes. Trifluoromethanesulfonic acid (5 mL) was added. The mixture was then stirred overnight at low temperature until the viscous liquid in the flask could no longer be stirred, at which point the reaction was stopped. After the reaction was stopped, the liquid was poured into a mixed solution of methanol (100 mL) and 1 M KOH (100 mL), and the solid precipitated completely. The solid was then washed several times with 1 M KOH and water until neutral, and dried under vacuum at 100 °C for 12 h to obtain the product.

[0089] Step 2: Preparation of I - Racemic polyarylquinine containing phosphorus (M-BINAP-PAQ-3%-I) - )

[0090] Weigh 500 mg of the product from step 1 and 400 mg of potassium carbonate into a glass bottle, add 15 ml of DMSO and 0.5 ml of iodomethane, and react at room temperature in the dark for 48 h. After 48 h, pour the mixture into ethyl acetate to obtain a white solid, wash once with ethyl acetate, wash twice with water, and dry under vacuum at 100 °C.

[0091] Step 3: Preparation of OH - Racemic phosphorus-containing polyarylquinine anion exchange membrane (M-BINAP-PAQ-3%-OH) - -AEM)

[0092] Disperse 500 mg of the product obtained in step 2 in 20 ml of DMSO, sonicate until completely dissolved, and cast the solution into a smooth glass petri dish. Dry at 80 °C for 6 h and then at 120 °C for 12 h to obtain a smooth anion exchange membrane. Immerse the membrane in 1 M KOH and perform ion exchange at 80 °C for 48 h to obtain OH-. - Type of anion exchange membrane.

[0093] Example 5

[0094] Step 1: Preparation of R-type phosphorus-containing polyarylequinine (R-BINAP-PAQ-3%)

[0095] (R)-(+)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (93.4 mg, 0.15 mmol) and p-terphenyl (1117 mg, 4.85 mmol) were added to a 25 mL round-bottom flask. Dichloromethane (5 mL) was added as a solvent, followed by 3-quininecyclohexanone (751 mg). The flask was then immersed in an ice bath and stirred for ten minutes, followed by the addition of trifluoromethanesulfonic acid (5 mL). The mixture was then stirred overnight at low temperature until the viscous liquid in the flask could no longer be stirred, at which point the reaction was stopped. After the reaction was stopped, the liquid was poured into a mixed solution of methanol (100 mL) and 1 M KOH (100 mL), and the solid precipitated completely. The solid was then washed repeatedly with 1 M KOH and water until neutral, and dried under vacuum at 100 °C for 12 h to obtain the product.

[0096] Step 2: Preparation of I - Type R phosphorus-containing polyarylequinine (R-BINAP-PAQ-3%-I) - )

[0097] Weigh 500 mg of the product from step 1 and 400 mg of potassium carbonate into a glass bottle, add 15 ml of DMSO and 0.5 ml of iodomethane, and react at room temperature in the dark for 48 h. After 48 h, pour the mixture into ethyl acetate to obtain a white solid, wash once with ethyl acetate, wash twice with water, and dry under vacuum at 100 °C.

[0098] Step 3: Preparation of OH - Type R phosphorus-containing polyarylequinine anion exchange membrane (R-BINAP-PAQ-3%-OH) - -AEM)

[0099] Disperse 500 mg of the product obtained in step 2 in 20 ml of DMSO, sonicate until completely dissolved, and cast the solution into a smooth glass petri dish. Dry at 80 °C for 6 h and then at 120 °C for 12 h to obtain a smooth anion exchange membrane. Immerse the membrane in 1 M KOH and perform ion exchange at 80 °C for 48 h to obtain OH-. - Type of anion exchange membrane.

[0100] Example 6

[0101] Step 1: Preparation of S-type phosphorus-containing polyarylequinine (S-BINAP-PAQ-3%)

[0102] (S)-(-)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (93.4 mg, 0.15 mmol) and p-terphenyl (1117 mg, 4.85 mmol) were added to a 25 mL round-bottom flask. Dichloromethane (5 mL) was added as a solvent, followed by 3-quininecyclohexanone (751 mg). The flask was then immersed in an ice bath and stirred for ten minutes, followed by the addition of trifluoromethanesulfonic acid (5 mL). The mixture was then stirred overnight at low temperature until the viscous liquid in the flask could no longer be stirred, at which point the reaction was stopped. After the reaction was stopped, the liquid was poured into a mixed solution of methanol (100 mL) and 1 M KOH (100 mL), and the solid precipitated completely. The solid was then washed repeatedly with 1 M KOH and water until neutral, and dried under vacuum at 100 °C for 12 h to obtain the product.

[0103] Step 2: Preparation of I - Type S-type phosphorus-containing polyarylequinine (S-BINAP-PAQ-3%-I) - )

[0104] Weigh 500 mg of the product from step 1 and 400 mg of potassium carbonate into a glass bottle, add 15 ml of DMSO and 0.5 ml of iodomethane, and react at room temperature in the dark for 48 h. After 48 h, pour the mixture into ethyl acetate to obtain a white solid, wash once with ethyl acetate, wash twice with water, and dry under vacuum at 100 °C.

[0105] Step 3: Preparation of OH - Type S-type phosphorus-containing polyarylequinine anion exchange membrane (S-BINAP-PAQ-3%-OH) - -AEM)

[0106] Disperse 500 mg of the product obtained in step 2 in 20 ml of DMSO, sonicate until completely dissolved, and cast the solution into a smooth glass petri dish. Dry at 80 °C for 6 h and then at 120 °C for 12 h to obtain a smooth anion exchange membrane. Immerse the membrane in 1 M KOH and perform ion exchange at 80 °C for 48 h to obtain OH-. - Type of anion exchange membrane.

[0107] Example 7

[0108] Step 1: Preparation of racemic phosphorus-containing polyaryltropine (M-BINAP-PAT-3%)

[0109] 2,2'-bis(diphenylphosphine)-1,1'-binaphthyl (93.4 mg, 0.15 mmol) and p-terphenyl (1117 mg, 4.85 mmol) were added to a 25 mL round-bottom flask. Dichloromethane (5 mL) was added as a solvent, followed by tropidine (835.2 mg). The flask was then immersed in an ice bath and stirred for ten minutes. Trifluoromethanesulfonic acid (5 mL) was added. The mixture was then stirred overnight at low temperature until the viscous liquid in the flask could no longer be stirred, at which point the reaction was stopped. After the reaction was stopped, the liquid was poured into a mixed solution of methanol (100 mL) and 1 M KOH (100 mL), and the solid precipitated completely. The solid was then washed repeatedly with 1 M KOH and water until neutral, and dried under vacuum at 100 °C for 12 h to obtain the product.

[0110] Step 2: Preparation of I - Racemic polyaryl tropane (M-BINAP-PAT-3%-I) - )

[0111] Weigh 500 mg of the product from step 1 and 400 mg of potassium carbonate into a glass bottle, add 15 ml of DMSO and 0.5 ml of iodomethane, and react at room temperature in the dark for 48 h. After 48 h, pour the mixture into ethyl acetate to obtain a white solid, wash once with ethyl acetate, wash twice with water, and dry under vacuum at 100 °C.

[0112] Step 3: Preparation of OH - Racemic phosphorus-containing polyaryltropine anion exchange membrane (M-BINAP-PAT-3%-OH) - -AEM)

[0113] Disperse 500 mg of the product obtained in step 2 in 20 ml of DMSO, sonicate until completely dissolved, and cast the solution into a smooth glass petri dish. Dry at 80 °C for 6 h and then at 120 °C for 12 h to obtain a smooth anion exchange membrane. Immerse the membrane in 1 M KOH and perform ion exchange at 80 °C for 48 h to obtain OH-. - Type of anion exchange membrane.

[0114] Example 8

[0115] Step 1: Preparation of R-type phosphorus-containing polyaryltropine (R-BINAP-PAT-3%)

[0116] (R)-(+)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (93.4 mg, 0.15 mmol) and p-terphenyl (1117 mg, 4.85 mmol) were added to a 25 mL round-bottom flask. Dichloromethane (5 mL) was added as a solvent, followed by tropidine (835.2 mg). The flask was then immersed in an ice bath and stirred for ten minutes, followed by the addition of trifluoromethanesulfonic acid (5 mL). The mixture was then stirred overnight at low temperature until the viscous liquid in the flask could no longer be stirred, at which point the reaction was stopped. After the reaction was stopped, the liquid was poured into a mixed solution of methanol (100 mL) and 1 M KOH (100 mL), and the solid precipitated completely. The solid was then washed repeatedly with 1 M KOH and water until neutral, and dried under vacuum at 100 °C for 12 h to obtain the product.

[0117] Step 2: Preparation of I - Type R-type phosphorus-containing polyaryltropine (R-BINAP-PAT-3%-I) - )

[0118] Weigh 500 mg of the product from step 1 and 400 mg of potassium carbonate into a glass bottle, add 15 ml of DMSO and 0.5 ml of iodomethane, and react at room temperature in the dark for 48 h. After 48 h, pour the mixture into ethyl acetate to obtain a white solid, wash once with ethyl acetate, wash twice with water, and dry under vacuum at 100 °C.

[0119] Step 3: Preparation of OH - Type R phosphorus-containing polyaryltropine anion exchange membrane (R-BINAP-PAT-3%-OH) - -AEM)

[0120] Disperse 500 mg of the product obtained in step 2 in 20 ml of DMSO, sonicate until completely dissolved, and cast the solution into a smooth glass petri dish. Dry at 80 °C for 6 h and then at 120 °C for 12 h to obtain a smooth anion exchange membrane. Immerse the membrane in 1 M KOH and perform ion exchange at 80 °C for 48 h to obtain OH-. - Type of anion exchange membrane.

[0121] Example 9

[0122] Step 1: Preparation of S-type phosphorus-containing polyaryltropine (S-BINAP-PAT-3%)

[0123] (S)-(-)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (93.4 mg, 0.15 mmol) and p-terphenyl (1117 mg, 4.85 mmol) were added to a 25 mL round-bottom flask. Dichloromethane (5 mL) was added as a solvent, followed by tropidine (835.2 mg). The flask was then immersed in an ice bath and stirred for ten minutes, followed by the addition of trifluoromethanesulfonic acid (5 mL). The mixture was then stirred overnight at low temperature until the viscous liquid in the flask could no longer be stirred, at which point the reaction was stopped. After the reaction was stopped, the liquid was poured into a mixed solution of methanol (100 mL) and 1 M KOH (100 mL), and the solid precipitated completely. The solid was then washed repeatedly with 1 M KOH and water until neutral, and dried under vacuum at 100 °C for 12 h to obtain the product.

[0124] Step 2: Preparation of I - Type S-type phosphorus-containing polyaryleutone (S-BINAP-PAT-3%-I) - )

[0125] Weigh 500 mg of the product from step 1 and 400 mg of potassium carbonate into a glass bottle, add 15 ml of DMSO and 0.5 ml of iodomethane, and react at room temperature in the dark for 48 h. After 48 h, pour the mixture into ethyl acetate to obtain a white solid, wash once with ethyl acetate, wash twice with water, and dry under vacuum at 100 °C.

[0126] Step 3: Preparation of OH - Type S-type phosphorus-containing polyaryltropine anion exchange membrane (S-BINAP-PAT-3%-OH) - -AEM)

[0127] Disperse 500 mg of the product obtained in step 2 in 20 ml of DMSO, sonicate until completely dissolved, and cast the solution into a smooth glass petri dish. Dry at 80 °C for 6 h and then at 120 °C for 12 h to obtain a smooth anion exchange membrane. Immerse the membrane in 1 M KOH and perform ion exchange at 80 °C for 48 h to obtain OH-. - Type of anion exchange membrane.

[0128] Example 10

[0129] Step 1: Preparation of triphenylphosphine-type polyarylpiperidine (TPP-PAP-3%)

[0130] Triphenylphosphine (39.4 mg, 0.15 mmol) and p-terphenyl (1117 mg, 4.85 mmol) were added to a 25 mL round-bottom flask. Dichloromethane (5 mL) was added as a solvent, followed by 1-methyl-4-piperidinone (0.7 mL). The flask was then immersed in an ice bath and stirred for ten minutes. Trifluoroacetic acid (0.4 mL) and trifluoromethanesulfonic acid (4.5 mL) were added sequentially. The mixture was then stirred at low temperature for 4–8 hours until the viscous liquid in the flask could no longer be stirred. After the reaction stopped, the liquid was poured into a mixed solution of methanol (100 mL) and 1 M KOH (100 mL), and the solid precipitated completely. The solid was then washed repeatedly with 1 M KOH and water until neutral, and dried under vacuum at 100 °C for 12 h to obtain the product.

[0131] Step 2: Preparation of I - Type Triphenylphosphine Polyarylepiperidine (TPP-PAP-3%-I) - )

[0132] Weigh 500 mg of the product from step 1 and 400 mg of potassium carbonate into a glass bottle, add 15 ml of DMSO and 0.5 ml of iodomethane, and react at room temperature in the dark for 48 h. After 48 h, pour the mixture into ethyl acetate to obtain a white solid, wash once with ethyl acetate, wash twice with water, and dry under vacuum at 100 °C.

[0133] Step 3: Preparation of OH - Type Triphenylphosphine Polyarylepiperidine Anion Exchange Membrane (TPP-PAP-3%-OH) - -AEM)

[0134] Disperse 500 mg of the product obtained in step 2 in 20 ml of DMSO, sonicate until completely dissolved, and cast the solution into a smooth glass petri dish. Dry at 80 °C for 6 h and then at 120 °C for 12 h to obtain a smooth anion exchange membrane. Immerse the membrane in 1 M KOH and perform ion exchange at 80 °C for 48 h to obtain OH-. - Type of anion exchange membrane.

[0135] Example 11

[0136] Step 1: Preparation of triphenylphosphine polyarylquinine (TPP-PAQ-3%)

[0137] Triphenylphosphine (39.4 mg, 0.15 mmol) and p-terphenyl (1117 mg, 4.85 mmol) were added to a 25 mL round-bottom flask. Dichloromethane (5 mL) was added as a solvent, followed by 3-quininecyclohexanone (751 mg). The flask was then immersed in an ice bath and stirred for ten minutes. Trifluoromethanesulfonic acid (5 mL) was added. The mixture was then stirred overnight at low temperature until the viscous liquid in the flask could no longer be stirred, at which point the reaction was stopped. After the reaction was stopped, the liquid was poured into a mixed solution of methanol (100 mL) and 1 M KOH (100 mL), and the solid precipitated completely. The solid was then washed repeatedly with 1 M KOH and water until neutral, and dried under vacuum at 100 °C for 12 h to obtain the product.

[0138] Step 2: Preparation of I - Type Triphenylphosphine Polyarylequinine (TPP-PAQ-3%-I) - )

[0139] Weigh 500 mg of the product from step 1 and 400 mg of potassium carbonate into a glass bottle, add 15 ml of DMSO and 0.5 ml of iodomethane, and react at room temperature in the dark for 48 h. After 48 h, pour the mixture into ethyl acetate to obtain a white solid, wash once with ethyl acetate, wash twice with water, and dry under vacuum at 100 °C.

[0140] Step 3: Preparation of OH - Type Triphenylphosphine Polyarylequinine Anion Exchange Membrane (TPP-PAQ-3%-OH) - -AEM)

[0141] Disperse 500 mg of the product obtained in step 2 in 20 ml of DMSO, sonicate until completely dissolved, and cast the solution into a smooth glass petri dish. Dry at 80 °C for 6 h and then at 120 °C for 12 h to obtain a smooth anion exchange membrane. Immerse the membrane in 1 M KOH and perform ion exchange at 80 °C for 48 h to obtain OH-. - Type of anion exchange membrane.

[0142] Example 12

[0143] Step 1: Preparation of triphenylphosphine polyaryltropine (TPP-PAT-3%)

[0144] Triphenylphosphine (39.4 mg, 0.15 mmol) and p-terphenyl (1117 mg, 4.85 mmol) were added to a 25 mL round-bottom flask. Dichloromethane (5 mL) was added as a solvent, followed by tropidine (835.2 mg). The flask was then immersed in an ice bath and stirred for ten minutes. Trifluoromethanesulfonic acid (5 mL) was added. The mixture was then stirred overnight at low temperature until the viscous liquid in the flask could no longer be stirred, at which point the reaction was stopped. After the reaction was stopped, the liquid was poured into a mixed solution of methanol (100 mL) and 1 M KOH (100 mL), and the solid precipitated completely. The solid was then washed repeatedly with 1 M KOH and water until neutral, and dried under vacuum at 100 °C for 12 h to obtain the product.

[0145] Step 2: Preparation of I - Triphenylphosphine polyaryltropine (TPP-PAT-3%-I) - )

[0146] Weigh 500 mg of the product from step 1 and 400 mg of potassium carbonate into a glass bottle, add 15 ml of DMSO and 0.5 ml of iodomethane, and react at room temperature in the dark for 48 h. After 48 h, pour the mixture into ethyl acetate to obtain a white solid, wash once with ethyl acetate, wash twice with water, and dry under vacuum at 100 °C.

[0147] Step 3: Preparation of OH - Triphenylphosphine polyaryltropine anion exchange membrane (TPP-PAT-3%-OH) - -AEM)

[0148] Disperse 500 mg of the product obtained in step 2 in 20 ml of DMSO, sonicate until completely dissolved, and cast the solution into a smooth glass petri dish. Dry at 80 °C for 6 h and then at 120 °C for 12 h to obtain a smooth anion exchange membrane. Immerse the membrane in 1 M KOH and perform ion exchange at 80 °C for 48 h to obtain OH-. - Type of anion exchange membrane.

[0149] Example 13

[0150] Step 1: Preparation of 1,2-bis(diphenylphosphine)ethane polyarylpiperidine (BDPE-PAP-3%)

[0151] 1,2-Bis(diphenylphosphine)ethane (59.8 mg, 0.15 mmol) and p-terphenyl (1117 mg, 4.85 mmol) were added to a 25 mL round-bottom flask. Dichloromethane (5 mL) was added as a solvent, followed by 1-methyl-4-piperidinone (0.7 mL). The flask was then immersed in an ice bath and stirred for ten minutes. Trifluoroacetic acid (0.4 mL) and trifluoromethanesulfonic acid (4.5 mL) were added sequentially. The mixture was then stirred at low temperature for 4–8 hours, stopping the reaction when the viscous liquid in the flask could no longer be stirred. After the reaction stopped, the liquid was poured into a mixed solution of methanol (100 mL) and 1 M KOH (100 mL), and the solid precipitated completely. The solid was then washed repeatedly with 1 M KOH and water until neutral, and dried under vacuum at 100 °C for 12 h to obtain the product.

[0152] Step 2: Preparation of I - Type 1,2-bis(diphenylphosphine) ethane polyarylpiperidine (BDPE-PAP-3%-I) - )

[0153] Weigh 500 mg of the product from step 1 and 400 mg of potassium carbonate into a glass bottle, add 15 ml of DMSO and 0.5 ml of iodomethane, and react at room temperature in the dark for 48 h. After 48 h, pour the mixture into ethyl acetate to obtain a white solid, wash once with ethyl acetate, wash twice with water, and dry under vacuum at 100 °C.

[0154] Step 3: Preparation of OH - Type 1,2-bis(diphenylphosphine)ethane polyarylpiperidine anion exchange membrane (BDPE-PAP-3%-OH) - -AEM)

[0155] Disperse 500 mg of the product obtained in step 2 in 20 ml of DMSO, sonicate until completely dissolved, and cast the solution into a smooth glass petri dish. Dry at 80 °C for 6 h and then at 120 °C for 12 h to obtain a smooth anion exchange membrane. Immerse the membrane in 1 M KOH and perform ion exchange at 80 °C for 48 h to obtain OH-. - Type of anion exchange membrane.

[0156] Example 14

[0157] Step 1: Preparation of 1,2-bis(diphenylphosphine)ethane polyarylquinine (BDPE-PAQ-3%)

[0158] 1,2-bis(diphenylphosphine)ethane (59.8 mg, 0.15 mmol) and p-terphenyl (1117 mg, 4.85 mmol) were added to a 25 mL round-bottom flask. Dichloromethane (5 mL) was added as a solvent, followed by 3-quininecyclohexanone (751 mg). The flask was then immersed in an ice bath and stirred for ten minutes, followed by the addition of trifluoromethanesulfonic acid (5 mL). The mixture was then stirred overnight at low temperature until the viscous liquid in the flask could no longer be stirred, at which point the reaction was stopped. After the reaction was stopped, the liquid was poured into a mixed solution of methanol (100 mL) and 1 M KOH (100 mL), and the solid precipitated completely. The solid was then washed repeatedly with 1 M KOH and water until neutral, and dried under vacuum at 100 °C for 12 h to obtain the product.

[0159] Step 2: Preparation of I - Type 1,2-bis(diphenylphosphine) ethane polyarylquinine (BDPE-PAQ-3%-I) - )

[0160] Weigh 500 mg of the product from step 1 and 400 mg of potassium carbonate into a glass bottle, add 15 ml of DMSO and 0.5 ml of iodomethane, and react at room temperature in the dark for 48 h. After 48 h, pour the mixture into ethyl acetate to obtain a white solid, wash once with ethyl acetate, wash twice with water, and dry under vacuum at 100 °C.

[0161] Step 3: Preparation of OH - Type 1,2-bis(diphenylphosphine)ethane polyarylquinine anion exchange membrane (BDPE-PAQ-3%-OH) - -AEM)

[0162] Disperse 500 mg of the product obtained in step 2 in 20 ml of DMSO, sonicate until completely dissolved, and cast the solution into a smooth glass petri dish. Dry at 80 °C for 6 h and then at 120 °C for 12 h to obtain a smooth anion exchange membrane. Immerse the membrane in 1 M KOH and perform ion exchange at 80 °C for 48 h to obtain OH-. - Type of anion exchange membrane.

[0163] Example 15

[0164] Step 1: Preparation of 1,2-bis(diphenylphosphine)ethane polyaryltropine (BDPE-PAT-3%)

[0165] 1,2-bis(diphenylphosphine)ethane (59.8 mg, 0.15 mmol) and p-terphenyl (1117 mg, 4.85 mmol) were added to a 25 mL round-bottom flask. Dichloromethane (5 mL) was added as a solvent, followed by tropidine (835.2 mg). The flask was then immersed in an ice bath and stirred for ten minutes, followed by the addition of trifluoromethanesulfonic acid (5 mL). The mixture was then stirred overnight at low temperature until the viscous liquid in the flask could no longer be stirred, at which point the reaction was stopped. After the reaction was stopped, the liquid was poured into a mixed solution of methanol (100 mL) and 1 M KOH (100 mL), and the solid precipitated completely. The solid was then washed repeatedly with 1 M KOH and water until neutral, and dried under vacuum at 100 °C for 12 h to obtain the product.

[0166] Step 2: Preparation of I - Type 1,2-bis(diphenylphosphine) ethane polyaryltropine (BDPE-PAT-3%-I) - )

[0167] Weigh 500 mg of the product from step 1 and 400 mg of potassium carbonate into a glass bottle, add 15 ml of DMSO and 0.5 ml of iodomethane, and react at room temperature in the dark for 48 h. After 48 h, pour the mixture into ethyl acetate to obtain a white solid, wash once with ethyl acetate, wash twice with water, and dry under vacuum at 100 °C.

[0168] Step 3: Preparation of OH - Type 1,2-bis(diphenylphosphine) ethane polyaryltropine anion exchange membrane (BDPE-PAT-3%-OH) - -AEM)

[0169] Disperse 500 mg of the product obtained in step 2 in 20 ml of DMSO, sonicate until completely dissolved, and cast the solution into a smooth glass petri dish. Dry at 80 °C for 6 h and then at 120 °C for 12 h to obtain a smooth anion exchange membrane. Immerse the membrane in 1 M KOH and perform ion exchange at 80 °C for 48 h to obtain OH-. - Type of anion exchange membrane.

[0170] The structural formulas of the phosphorus-containing polyaryl cyclic amine polymer and the anion exchange membrane prepared in the above embodiments are as follows: Figure 13 As shown.

[0171] The above content is only for illustrating the technical concept of the present invention and should not be construed as limiting the scope of protection of the present invention. Any modifications made to the technical solution based on the technical concept proposed in this invention shall fall within the scope of protection of the claims of this invention.

Claims

1. A polyaryl cyclic amine polymer containing nitrogen and phosphorus dual active centers, characterized in that, Contains nitrogen and phosphorus dual active centers, and has structural formula (1) or (2): ， in It is a benzene ring, naphthalene, or binaphthalene; Where R is selected from polyarylpiperidine of the following formula , , Or the following formula: polyarylequinine , , Or the following formula of polyarylate , Any one of them; X - It is an anion; The molar ratio of phosphorus-containing groups is 1% to 50%.

2. A method for preparing the nitrogen- and phosphorus-containing dual-active-center polyaryl cyclic amine polymer according to claim 1, characterized in that, Includes the following steps: Step 1: Add phosphorus-containing monomers, aromatic compounds and carbonyl compounds to an organic solvent and react under strong acid catalysis. After the reaction is completed, neutralize, wash and dry to obtain the first polymer. Step 2: The first polymer is subjected to quaternization and quaternization reactions with a haloalkane to obtain the second polymer, namely the polyaryl cyclic amine polymer containing nitrogen and phosphorus dual active centers; The phosphorus-containing monomer mentioned in step 1 is 1,2-bis(diphenylphosphine)ethane, racemic-2,2'-bis(diphenylphosphine)-1,1'-binaphthyl, (R)-(+)-2,2'-bis(diphenylphosphine)-1,1'-binaphthyl or (S)-(-)-2,2'-bis(diphenylphosphine)-1,1'-binaphthyl; The aromatic compound is selected from at least one of biphenyl and p-terphenyl; The carbonyl compound is selected from 1-methyl-4-piperidinone, 3-quininecycloone, or tropinone; The halohydrocarbon mentioned in step 2 is iodomethane, and the mass ratio of the halohydrocarbon to the first polymer is (2~3):

1.

3. The method for preparing the nitrogen- and phosphorus-containing dual-active-center polyaryl cyclic amine polymer as described in claim 2, characterized in that, The reaction temperature in step 1 is 0~25℃, and the reaction time is 2~48 hours.

4. The method for preparing the nitrogen- and phosphorus-containing dual-active-center polyaryl cyclic amine polymer as described in claim 2, characterized in that, The reaction temperature in step 2 is room temperature, and the reaction time is 24 to 72 hours.

5. The nitrogen- and phosphorus-containing polyaryl cyclic amine polymer prepared by the method for preparing nitrogen- and phosphorus-containing polyaryl cyclic amine polymers as described in claim 2.

6. A polyaryl cyclic amine anion exchange membrane containing nitrogen and phosphorus dual active centers, characterized in that, The polymer is prepared by using the nitrogen- and phosphorus-containing dual-active-center polyaryl cyclic amine polymer as described in claim 1 or by the preparation method of any one of claims 2-4.

7. A method for preparing a nitrogen- and phosphorus-containing dual-active-center polyaryl cyclic amine anion exchange membrane as described in claim 6, characterized in that, The nitrogen- and phosphorus-containing dual-active-center polyaryl cyclic amine polymer is dissolved in a solvent and cast into a film. After evaporation and drying, it is immersed in an anion solution for ion exchange, thus obtaining the nitrogen- and phosphorus-containing dual-active-center polyaryl cyclic amine anion exchange membrane. The anion solution is I - ,Br - Cl - OH - or HCO3 - The anionic solution; the ion exchange temperature is 25~80℃, and the ion exchange time is 24~96 hours.

8. The application of the nitrogen- and phosphorus-containing dual-active-center polyaryl cyclic amine anion exchange membrane according to claim 6 or the nitrogen- and phosphorus-containing dual-active-center polyaryl cyclic amine anion exchange membrane prepared by the method described in claim 7 in ion transport.

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