A high-coordination block polymer, an anion exchange membrane, and preparation and electrochemical applications thereof

Abstract

The application discloses a high-conjugation block polymer, an anion exchange membrane and preparation and electrochemical application thereof, the high-conjugation block polymer comprises a structural unit shown in the following formula (I), and the application further discloses a preparation method of the high-conjugation block polymer and an anion exchange membrane prepared by the high-conjugation block polymer and application of the anion exchange membrane in electrolysis of water, preparation of fuel cells, preparation of supercapacitors and other electrochemistry.The application uses a high-conjugation, planar skeleton group to strengthen pi-pi interaction force on a polymer main chain in a non-polar phase, a high-conjugation block polymer is prepared, and the anion exchange membrane prepared by the high-conjugation block polymer has stronger mechanical strength, and a technical prejudice that mechanical strength and ion conductivity cannot be considered in the prior art is overcome.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of polymeric materials, in particular to a high-conjugated block polymer, an anion exchange membrane and its preparation and electrochemical applications. BACKGROUND

[0002] Ion exchange materials are a class of functional materials that can achieve specific functions through ion exchange. They are usually composed of a base with fixed charges (linked to the polymer structure through chemical bonds) and mobile counter ions. They are widely used in water treatment (such as deionization, softening and seawater desalination), fuel cells (as proton exchange membranes or anion exchange membranes), sensors and medical separation. In practical applications, the ion conductivity and mechanical properties of ion exchange materials are key indicators. High ion conductivity can ensure efficient ion conduction, while good mechanical properties can ensure the stability and durability of the material in complex environments. For example, in fuel cells, proton exchange membranes or anion exchange membranes need high ion conductivity to improve energy conversion efficiency, and must have excellent mechanical properties to withstand high temperature, high humidity and chemical corrosion in harsh working conditions, especially in automotive fuel cells and portable power sources, this performance balance is crucial. In addition, ion exchange membranes in reverse osmosis membranes and electrodeionization (EDI) devices require fast ion conduction to improve purification efficiency, and must have sufficient mechanical strength to withstand high pressure environments, especially in industrial wastewater treatment and seawater desalination applications. Ion exchange materials in high-precision electrochemical sensors require high conductivity to ensure sensitive signal transmission, and the mechanical properties of the material determine its service life and stability, especially in medical diagnosis and environmental monitoring, which requires long-term continuous operation.

[0003] However, the current materials are often difficult to meet the two requirements simultaneously: in order to improve the ion conductivity, it is possible to increase the number of ion exchange groups or improve their distribution, but this can cause the material to increase the water absorption, and the material will present a gel state after excessive water absorption, thereby affecting its mechanical stability. In addition, increasing the crosslinking agent can increase the strength of the polymer chain, but at the same time, it will also reduce the chain mobility and void volume, affecting the ion migration. Most of the anion exchange materials reported at present have a tensile strength of 60-80 Mpa, and their ion conductivity is usually only about 50 mS / cm; and if the ion conductivity is improved to 100 mS / cm, the tensile strength will drop to 20-40 Mpa. For example: Steven Holdcroft experimental group of Simon Fraser University in Canada published a kind of polybenzimidazole anion exchange material, which placed imidazole cations on the main chain of the polymer. Due to a large number of protecting groups around the active ions, the alkaline stability of the material is improved, and the tensile strength is about 70 Mpa. However, the Coulomb force between the ion pairs of the material is weak, resulting in weak ion transport and conductivity of about 70 mS / cm. Professor Chulsung Bae of Rensselaer Polytechnic Institute disclosed a polyaryl polymer electrolyte work which separates the charge group from the polymer backbone using a carbon chain, and also forms a nanoscale ion channel through block and main chain design. Such design ideas make the material have better ion conductivity (80-90 mS / cm @ 60 ℃), but to a certain extent, the mechanical strength of the film is sacrificed (30 Mpa tensile strength).

[0004] Therefore, achieving a balance between ion conductivity and mechanical properties is an important challenge in the research of ion exchange materials. SUMMARY

[0005] The first object of the present application is to overcome the shortcomings of the prior art and provide a high conjugation degree block polymer which has a highly conjugated π system, uses a larger volume of planar conjugated structure to enhance the interaction between the polymer backbone, and adjusts the ion concentration on the side chain to improve the ion conductivity and mechanical strength.

[0006] A high conjugation degree block polymer comprises the following structural unit shown in formula (I):

[0007]

[0008] (I)

[0009] wherein n and m are the number of repeating units; n is an integer from 1 to 2000; m is an integer from 1 to 2000;

[0010] Ar1is selected from one of the following structural fragments:

[0011] , , or ;

[0012] Ar2is selected from one of the following structural fragments:

[0013]

[0014] wherein x1, x2have a value from 0 to 10;

[0015] LK1and LK2are linking groups, independently selected from or ;

[0016] is an ionic group, wherein the cationic group ( ) is selected from one of the following structural fragments:

[0017]

[0018] the anionic group ( ) is selected from one of the following structural fragments:

[0019]

[0020] R1is an ionic group or a non-ionic group; when R1is an ionic group, it is defined as ; when R1is a non-ionic group, it is selected from one of the following structural fragments:

[0021]

[0022] As a preference, Ar1is selected from or .

[0023] As a preference, EWG is selected from one of the following structural fragments:

[0024]

[0025] As a preference, the high conjugation block polymer is selected from one of the following structural formulas:

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032] A second object of the present application is to provide a method for preparing the above high-conjugation block polymer, comprising the following steps (when LK1, LK2 are both , compound 1-17X):

[0033] (1) mixing Ar1, EWG(CO)Rii, Ar2, EWG(CO)R1 in a solvent, and reacting under the action of a catalyst to form a precursor;

[0034]

[0035] Rii is ;

[0036] As a preference, the solvent is an organic solvent, more preferably one of dichloromethane, chloroform, tetrachloromethane or chlorobenzene.

[0037] As a preference, the catalyst is a strong acid, more preferably one or a mixture of several of concentrated sulfuric acid, concentrated nitric acid, trifluoroacetic acid, triflic acid.

[0038] (2) dissolving the precursor in a solvent, adding a nucleophile to react, quenching, washing, and then adding a salt solution for ion exchange to obtain the high-conjugation block polymer;

[0039]

[0040] As a preference, the solvent is an organic solvent, more preferably tetrahydrofuran, dichloromethane, chloroform, methylpyrrolidone, ethylene carbonate, etc.

[0041] or comprising the following steps (when LK1, LK2 are independently selected from or , compound 18-23X):

[0042] (1) mixing Ar1, EWG(CO)Rii, Ar2, EWG(CO)R1 in a solvent, and reacting under the action of a catalyst to form a high-molecular precursor;

[0043]

[0044] Rii is ;

[0045] As a preference, the solvent is an organic solvent, more preferably one of dichloromethane, chloroform, tetrachloromethane or chlorobenzene.

[0046] As preferred, the catalyst is a strong acid, more preferably one or a mixture of several of concentrated sulfuric acid, concentrated nitric acid, trifluoroacetic acid, triflic acid.

[0047] (2) the precursor is dissolved in an organic solvent to obtain an intermediate, and then mixed with a linker , a nucleophile is added to react, quenched, and then ion exchanged by adding a salt solution to obtain the high conjugation block polymer.

[0048]

[0049] wherein Y6, Y7 are independently selected from F, Cl, Br or .

[0050] The third object of the present application is to provide an anion exchange membrane prepared from the high conjugation block polymer described above. The preparation process is as follows:

[0051] The high conjugation block polymer described above is dissolved in an organic solvent to prepare a slurry, which is then coated on a substrate by a roll-to-roll process, screen printing or doctor blade casting. The organic solvent in the slurry is volatilized by drying to solidify the high conjugation block polymer on the surface of the substrate into a film, and the anion exchange membrane is obtained by peeling off the film; wherein the organic solvent is one or a mixture of two or more of ethanol, methanol, isopropanol, trimethyl sulfoxide, methyl pyrrolidone, and ethylene carbonate.

[0052] The fourth object of the present application is to provide the application of the anion exchange membrane described above in electrochemistry.

[0053] The application includes: preparation of fuel cells, preparation of supercapacitors, preparation of organic flow batteries, electrolysis of water, electrolysis of CO2, electrolysis of CO, heavy metal separation equipment, CO2 purification equipment, electrically driven CO2 enrichment equipment, lithium salt recovery, and as a metal-air battery separator.

[0054] Compared with the prior art, the present application has the following advantages:

[0055] 1. The present application uses a high conjugation, planar backbone group to enhance the pi-pi interaction force on the main chain of the polymer in a non-polar phase, and a high conjugation block polymer is prepared, and the anion exchange membrane prepared therefrom has stronger mechanical strength;

[0056] 2. The present application regulates the ratio of the backbone block (Ar1+Ar2) to the ionic group on the side chain (1:1-10 molar equivalents), so that the mechanical strength is improved while the overall ionic conductivity of the material is improved;

[0057] 3. The present invention introduces cyclic ionic functional groups to enhance the chemical stability of the material in the use environment.

[0058] In summary, the present invention can simultaneously enhance the ionic conductivity and mechanical strength of the anion exchange membrane, regulate the self-assembly mode in the material, form a nanostructure to enhance ion transport, and adjust the size of the conjugated structure of the polymer backbone segment to increase the energy consumption and stability of the membrane material in the application scenarios of electrochemical devices, separation devices, etc. The membrane material obtained by the present invention can be used in fuel cells, organic flow batteries, water electrolysis, CO2 electrolysis, CO electrolysis, supercapacitors, lithium ion battery separators, lithium ion battery electrolytes, metal-air battery separators, heavy metal separation in water, CO2 purification, electrically driven CO2 enrichment, Li salt recovery, and other applications requiring high-quality electrolytes, providing more efficient and stable material solutions for downstream electrochemical applications. BRIEF DESCRIPTION OF DRAWINGS

[0059] Figure 1 Gel chromatography data for intermediates 1a-5a.

[0060] Figure 2 Hydrogen spectrum nuclear magnetic spectrum of polymer 22X.

[0061] Figure 3 Material performance test data comparison chart for preferred polymers 18X, 19X, 21X.

[0062] Figure 4 A is the water electrolysis test procedure and test bench design, B is the test battery structure, and C is the test battery.

[0063] Figure 5 Voltage data of polymer 22OH running for 1000 hours in water electrolysis test environment. DETAILED DESCRIPTION

[0064] The present invention is further described below in conjunction with the accompanying drawings and examples.

[0065] Examples 1-17:

[0066] As previously described, the synthesis of preferred structures 1X-17X is as follows:

[0067]

[0068] After preparing the intermediate, the synthesis of preferred structures 1X-5X is as follows:

[0069]

[0070]

[0071] The synthesis method of intermediate 1a-5a is as follows:

[0072] 1,1'-binaphthyl (9.9 g, 39 mmol), 4-bromo-1,1,1-trifluoro-2-butanone (8.7 g, 40 mmol) were placed in a two-necked round bottom flask, dichloromethane (40 mL) was added; dissolved at room temperature with mechanical stirring. The reaction system was cooled to 0 ℃, and a mixed solution of trifluoromethanesulfonic acid / trifluoroacetic acid (1:1, 20 g) was slowly added dropwise. After the dropwise addition was completed, the reaction system was stirred at 0 ℃ for 10 min, and then transferred to a 30 ℃ water bath. The average molecular weight reached 28 KDa every half hour after the system temperature reached 30 ℃, and the reaction liquid was poured into 800 mL of cold 1:1 methanol / water solution, and the solid was precipitated. The solid was collected and washed with deionized water. Dry, broken, the product is light green powder 1a (16.6 g), yield 90%. 1 H NMR (500 MHz CDCl3) δ 8.0-8.1 (m, 2H), 7.6-8.0 (m, 8Hs), 7.2-7.3 (m, 2Hs), 3.4 (m, 2Hs), 2.3(m, 2Hs), 1.6 (m, 2Hs).

[0073] The synthesis method of 2a is similar to that of 1a, and the reaction is stopped at 140 KDa. Dry, broken product is light green powder 2a (17.8 g) with a yield of 97%. 1 H NMR (500 MHz CDCl3) δ 8.0-8.1 (m, 2H), 7.6-8.0 (m, 8Hs), 7.2-7.3 (m, 2Hs), 3.4 (m, 2Hs), 2.3(m, 2Hs), 1.6 (m, 2Hs).

[0074] The synthesis method of 3a is similar to that of 1a, and the reaction is stopped at 253 KDa. Dry, broken product is light green powder 1a (18.0 g) with a yield of 98%. 1 H NMR (500 MHz CDCl3) δ 8.0-8.1 (m, 2H), 7.6-8.0 (m, 8Hs), 7.2-7.3 (m, 2Hs), 3.4 (m, 2Hs), 2.3(m, 2Hs), 1.7 (m, 2Hs).

[0075] 4a was synthesized in a similar way as 1a, with the addition of 80 mL of dichloromethane and the reaction system was refluxed at 45 degrees Celsius. The molecular weight of 4a was 460 KDa and the product was light green fiber 1a (18.3 g) with a yield of 99% when the reaction was terminated. 1 H NMR (500 MHz CDCl3) δ 8.0-8.1 (m, 2H), 7.6-8.0 (m, 8Hs), 7.2-7.3 (m, 2Hs), 3.4 (m, 2Hs), 2.3 (m, 2Hs), 1.7 (m, 2Hs).

[0076] 5a was synthesized in a similar way as 1a, with the addition of 80 mL of dichloromethane and the reaction system was refluxed at 45 degrees Celsius. The molecular weight of 5a was 863 KDa and the product was a tea green block (18.0 g) with a yield of 98% after drying. 1 H NMR (500 MHz CDCl3) δ 8.0-8.1 (m, 2H), 7.6-8.0 (m, 8Hs), 7.2-7.3 (m, 2Hs), 3.4 (m, 2Hs), 2.3 (m, 2Hs), 1.7 (m, 2Hs).

[0077] The preferred structure of intermediate 1b, and the preferred structure 1X were synthesized as follows:

[0078] In a three-necked round-bottom flask, 1a (10 g, 21.2 mmol) was dissolved in tetrahydrofuran 200 mL, and methyl imidazole (1.73 g, 21.2 mmol) was added, and the reaction system was protected by nitrogen. The reaction system was refluxed at 60 degrees Celsius for 72 hours, and 100 mL of ethanol was added when the reaction became turbid. TLC was used for detection and it was found that the consumption of methyl imidazole was complete, and the reaction system was poured into 2 L of anhydrous ether to obtain a flocculent precipitate. After drying the precipitate, it was washed with water 3 times, each time for 24 hours. After drying and powdering, a light yellow powder was obtained, 9.9 g, with a yield of 85.3%. 1 H NMR (500 MHz DMSO-d6) δ 9.2 (m, 1), 8.0-8.1 (m, 2H), 7.6-8.0 (m, 10Hs), 7.2-7.3 (m, 2Hs), 4.2 (m, 3Hs), 2.4 (m, 2Hs), 1.8 (m, 2Hs). 0.5 g of 1b was dissolved in 18 mL of 1:1 tetrahydrofuran methanol solution, and after filtration (0.2 μm filter), the solution was spread on a flat PTFE plate (25 cm 2), the surface was heated to 50 °C. After complete solvent evaporation (about 24 hours) the film was peeled off and immersed in water. The film material was rolled into a 20 cm high cylindrical container, 100 mL of 1 M NaCl solution was added and exchanged at room temperature using a shaker for 72 hours, replacing the NaCl solution every 24 hours. After the exchange was complete, the film material was washed with deionized water until the wash water had an ionic conductivity of less than 3 pS / cm. This resulted in a 1 Cl film material, a 1 OH film was obtained using the same procedure with 1 M NaOH as the exchange solution and a 1 KHCO3 film material (1X) was obtained using 1 M KHCO3 as the exchange solution. The 1X film material showed a Br content of less than 0.1 wt% in elemental analysis.

[0079] The synthesis of preferred structure intermediate 2b, preferred structure 2X, was similar to 1b, 1X. 2a (10 g, 21.2 mmol) and N-methyldicyclohexylamine (4.13 g, 21.2 mmol) were used as the reagents and propylene carbonate (PC) was used as the solvent at a reaction temperature of 90 °C. The product 2b was a tan powder 12.1 g in 86% yield. 1 H NMR (500 MHz DMSO-d6) δ 8.0-8.1 (m, 2H), 7.6-8.0 (m, 8Hs), 7.2-7.3 (m, 2Hs), 3.1 (m, 4Hs), 2.9 (m, 3Hs), 2.6 (m, 2Hs), 1.2-2.0 (m, 22Hs). The 2X film material was prepared in the same way as 1X and showed a Br content of less than 0.1 wt% in elemental analysis.

[0080] The synthesis of preferred structure intermediate 3b, preferred structure 3X, was similar to 1b, 1X. Pyridine (1.67 g, 21.2 mmol) and 3a (10 g, 21.2 mmol) were used as the reagents and the product 3b was a dark tan powder 11.0 g in 94.3% yield. 1 H NMR (500 MHz DMSO-d6) δ 9 (m, 2Hs), 8.5 (m, 2Hs), 8.1 (m, 2Hs), 7.9-8.0 (m, 2H), 7.6-8.0 (m, 8Hs), 7.2-7.3 (m, 2Hs), 4.5 (m, 2Hs), 2.4 (m, 2Hs), 1.7 (m, 2Hs). The 3X film material was prepared in the same way as 1X using sulfolane as the solvent and a drying temperature of 90 °C. The exchange procedure was the same as 1X and the 3X film showed a Br content of less than 0.1 wt% in elemental analysis.

[0081] Intermediate 4b, Preferred Structure 4X, was synthesized in a similar manner as 1b, 1X. Intermediate 4a (10 g, 21.2 mmol) was dissolved in 400 mL of tetrahydrofuran and the reaction reagent was selected to be dodecyl dimethyl tertiary amine (4.5 g, 21.2 mmol). The product 4b was a light brown powder 12.8 g in 88.3% yield. 1 H NMR (500 MHz DMSO-d6) δ 8.0-8.1 (m, 2H), 7.6-8.0 (m, 8Hs), 7.2-7.3 (m, 2Hs), 3.1 (m, 4Hs), 2.9 (m, 3Hs), 2.6 (m, 2Hs), 1.7 (m, 2Hs), 1.0-1.5 (m, 23.2Hs). 4X membrane material was prepared in a similar manner as 1X with propylene carbonate (PC) as the solvent and a drying temperature of 90 °C. The ion exchange after demolding was the same as 1X and elemental analysis showed that the Br content in the 4X membrane was less than 0.1 wt%.

[0082] Intermediate 5b, Preferred Structure 5X, was synthesized in a similar manner as 1b, 1X. Intermediate 5a (10 g, 21.2 mmol) was dissolved in 400 mL of tetrahydrofuran and the reaction reagent was selected to be N,N-dimethylhexylamine (2.7 g, 21 mmol). The product 5b was a light yellow powder 11.9 g in 93.4% yield. 1 H NMR (500 MHz DMSO-d6) δ 8.0-8.1 (m, 2H), 7.6-8.0 (m, 8Hs), 7.2-7.3 (m, 2Hs), 3.2 (m, 4Hs), 3.0 (m, 6Hs), 2.6 (m, 2Hs), 1.7 (m, 2Hs), 1.0-1.5 (m, 10.9Hs). 5X membrane material was prepared in the same manner as 1X membrane material and elemental analysis showed that the Br content in the product 5X membrane was less than 0.1 wt%.

[0083] The synthesis of Preferred Structures 6X-8X is as follows:

[0084]

[0085] Polymerization to obtain 6a-8a:

[0086] 1,1'-binaphthalene (9.9 g, 39 mmol), 5-bromo-1,1,1-trifluoro-2-hexanone (4.7 g, 20 mmol), trifluoroacetone (2.2 g, 20 mmol) were placed in a two-necked round bottom flask, dichloromethane (40 mL) was added; dissolved by mechanical stirring at room temperature. The reaction system was cooled to 0 °C, and a mixed solution of trifluoromethanesulfonic acid / trifluoroacetic acid (1:1, 20 g) was slowly added dropwise. After the addition was completed, the reaction system was stirred at 0 °C for 10 min, and then transferred to a 30 °C water bath. After the temperature of the system reached 30 °C, the molecular weight increase was detected every half hour using gel chromatography. When the average molecular weight reached 215 KDa, the reaction solution was poured into 800 mL of cold 1:1 methanol / water solution, and the solid was precipitated. The solid was collected and washed with deionized water. After drying, the product was broken into a greenish powder 7a (15.8 g) with a yield of 95%. 1 H NMR (500 MHz CDCl3) δ 8.0-8.1 (m, 2H), 7.6-8.0 (m, 8Hs), 7.2-7.3 (m, 2Hs), 3.4 (m, 1Hs), 2.3-2.4(m, 2.5Hs), 1.2-1.4 (m, 2Hs). NMR, molecular weight calculation n:m=251:251.

[0087] 6a was synthesized using the same method as 7a, with the reactant ratio adjusted to 1,1'-binaphthalene (9.9 g, 39 mmol), 6-bromo-1,1,1-trifluoro-2-hexanone (8.4 g, 36 mmol), trifluoroacetone (0.4 g, 4 mmol). The product was a light greenish powder (18.1 g) with a yield of 98% and a molecular weight of 230 KDa. 1 H NMR (500 MHz CDCl3) δ 8.0-8.1 (m, 2H), 7.6-8.0 (m, 8Hs), 7.2-7.3 (m, 2Hs), 3.4 (m, 1.8Hs), 2.3-2.4(m, 2.1Hs), 1.2-1.4 (m, 3.7Hs). NMR, molecular weight calculation n:m=436:48.

[0088] 8a was synthesized using the same method as 7a, with the reactant ratio adjusted to 1,1'-binaphthalene (9.9 g, 39 mmol), 6-bromo-1,1,1-trifluoro-2-hexanone (0.9 g, 4 mmol), trifluoroacetone (4.04 g, 36 mmol). The product was a greenish powder (14.1 g) with a yield of 96% and a molecular weight of 213 KDa. 1¹H NMR (500 MHz CDCl₃) δ 8.0–8.1 (m, 2H), 7.6–8.0 (m, 8Hs), 7.2–7.3 (m, 2Hs), 3.4 (m, 0.2Hs), 2.3–2.4 (m, 2.9Hs), 1.2–1.4 (m, 0.4Hs). Molecular weight calculation yielded n:m = 56:507.

[0089] The preferred structural intermediate 6b and preferred structural intermediate 6X were synthesized using the same method as 3b and 3X. The reaction reagents used were N-methylpiperidine (1.88 g, 1 equiv.) and 6a (10 g, 1 equiv.), yielding 11.0 g of product 6b as a brown powder, with a yield of 92.6%. 1 ¹H NMR (500 MHz DMSO-d₆): 8.0–8.1 (m, 2H), 7.6–8.0 (m, 8Hs), 7.2–7.3 (m, 2Hs), 3.2 (m, 5.5Hs), 2.9 (m, 2.7Hs), 2.3–2.4 (m, 2.1Hs), 1.0–1.4 (m, 9Hs). The 6X membrane material was prepared similarly to 3X, using sulfolane as the solvent and drying at 90 °C. The exchange process was the same as 1X. Elemental analysis showed that the Br content of the 6X membrane was less than 0.1 wt%.

[0090] The preferred structural intermediate 7b and preferred structural intermediate 7X were synthesized using the same method as 3b and 3X. The reaction reagents used were N-methylpiperidine (1.16 g, 1 equiv.) and 7a (10 g, 1 equiv.), yielding 10.5 g of product 7b as a brown powder, with a yield of 94.1%. 1 ¹H NMR (500 MHz DMSO-d₆): 8.0–8.1 (m, 2H), 7.6–8.0 (m, 8Hs), 7.2–7.3 (m, 2Hs), 3.2 (m, 3Hs), 2.9 (m, 1.5Hs), 2.3–2.4 (m, 2.5Hs), 1.0–1.4 (m, 5Hs). The 7X membrane material was prepared similarly to 3X, using sulfolane as the solvent and drying at 90 °C. The exchange process was the same as 1X. Elemental analysis showed that the Br content of the 7X membrane was less than 0.1 wt%.

[0091] The preferred structural intermediates 8b and 8X were synthesized using the same methods as 3b and 3X. The reaction reagents used were N-methylpiperidine (0.3 g, 1 equiv.) and 8a (10 g, 1 equiv.), yielding 10.0 g of product 7b as a white-brown powder, with a yield of 97.0%. 11¹H NMR (500 MHz DMSO-d⁶): 8.0–8.1 (m, 2H), 7.6–8.0 (m, 8Hs), 7.2–7.3 (m, 2Hs), 3.2 (m, 0.6Hs), 2.9 (m, 0.3Hs), 2.3–2.4 (m, 2.9Hs), 1.0–1.4 (m, 1Hs). The 8X membrane material was prepared similarly to 3X, using ethylene carbonate as the solvent and drying at 90 °C. The exchange process was the same as 1X. Elemental analysis showed that the Br content of the 8X membrane was less than 0.1 wt%.

[0092] The preferred synthesis method for structures 9X-11X is as follows:

[0093] Polymer intermediate 9a was synthesized using the same method as 6a, with 1,1'-binaphthyl (9.9 g, 39 mmol), 6-bromo-1,1,1-trifluoro-2-heptanone (8.8 g, 36 mmol), and trifluoroacetophenone (0.69 g, 4 mmol) as the reaction substrates. The reaction was terminated when gel permeation chromatography showed a molecular weight of 180 kDa. The product was a light brown powder, 19 g in volume, with a yield of 99%. 1 ¹H NMR (500 MHz CDCl₃) δ 8.0–8.1 (m, 2H), 7.6–8.0 (m, 8Hs), 7.1–7.3 (m, 2.3Hs), 7.1 (m, 0.2Hs), 3.4 (m, 1.8Hs), 2.4 (m, 1.8Hs), 1.7 (m, 1.8Hs), 1.2–1.4 (m, 3.6Hs). Based on NMR and molecular weight data, n:m = 330:36.

[0094] Polymer intermediate 10a was synthesized using the same method as 6a, with 1,1'-binaphthyl (9.9 g, 39 mmol), 6-bromo-1,1,1-trifluoro-2-heptanone (4.9 g, 20 mmol), and trifluoroacetophenone (3.5 g, 20 mmol) as the reaction substrates. The reaction was terminated when gel permeation chromatography showed a molecular weight of 173 kDa. The product was a light brown powder, 17.1 g in weight, with a yield of 94.4%. 1 ¹H NMR (500 MHz CDCl₃) δ 8.0–8.1 (m, 2H), 7.6–8.0 (m, 8Hs), 7.1–7.3 (m, 3.5Hs), 7.1 (m, 1Hs), 3.4 (m, 1Hs), 2.4 (m, 1Hs), 1.7 (m, 1Hs), 1.2–1.4 (m, 2Hs). Based on NMR and molecular weight data, n:m = 187:187.

[0095] Polymer intermediate 11a was synthesized using the same method as 6a, with 1,1'-binaphthyl (9.9 g, 39 mmol), 6-bromo-1,1,1-trifluoro-2-heptanone (6.3 g, 36 mmol), and trifluoroacetophenone (0.99 g, 4 mmol) as the reaction substrates. The reaction was terminated when gel permeation chromatography showed a molecular weight of 142 kDa. The product was a light brown powder, 15.7 g in weight, with a yield of 92.6%. 1 ¹H NMR (500 MHz CDCl₃) δ 8.0–8.1 (m, 2H), 7.6–8.0 (m, 8Hs), 7.1–7.3 (m, 4.8Hs), 7.1 (m, 1.8Hs), 3.4 (m, 0.2Hs), 2.4 (m, 0.2Hs), 1.7 (m, 0.2Hs), 1.2–1.4 (m, 0.4Hs). Based on NMR and molecular weight data, n:m = 36:330.

[0096] The preferred structural intermediates 9b and 9X were synthesized using the same methods as 8b and 8X. Quinine ring (2.0 g, 1 equiv.) and 9a (10 g, 1 equiv.) were used as reaction reagents, yielding 11.3 g of product 9b as a brown powder, with a yield of 93.9%. 1 ¹H NMR (500 MHz DMSO-d⁶): 8.0–8.1 (m, 2H), 7.6–8.0 (m, 8Hs), 7.2–7.3 (m, 2.3Hs), 7.1 (m, 0.2Hs), 3.3 (m, 5.4Hs), 3.0 (m, 1.8Hs), 2.4 (m, 1.8Hs), 1.8 (m, 5.4Hs), 1.6 (m, 1.8Hs), 1.0–1.4 (m, 4.5Hs). The preparation method of the 9X membrane material is similar to that of 6X, and the exchange process is the same as that of 1X. Elemental analysis shows that the Br content of the 9X membrane is less than 0.1 wt%.

[0097] The preferred structural intermediate 10b and preferred structural intermediate 10X were synthesized using the same method as 8b and 8X. Quinine ring (1.2 g, 1 equiv.) and 9a (10 g, 1 equiv.) were used as reaction reagents. 10.1 g of product 9b was obtained as a light brown powder, with a yield of 93.9%. 1¹H NMR (500 MHz DMSO-d₆): 8.0–8.1 (m, 2H), 7.6–8.0 (m, 8Hs), 7.2–7.3 (m, 3.5Hs), 7.1 (m, 1Hs), 3.3 (m, 3Hs), 3.0 (m, 1Hs), 2.4 (m, 1Hs), 1.8 (m, 3Hs), 1.6 (m, 1Hs), 1.0–1.4 (m, 2.5Hs). The 10X membrane material was prepared similarly to the 6X membrane, with the same exchange process as the 1X membrane. Elemental analysis showed that the Br content of the 10X membrane was less than 0.1 wt%.

[0098] The preferred structural intermediates 11b and 11X were synthesized using the same method as 8b and 8X. Quinine ring (0.3 g, 1 equiv.) and 9a (10 g, 1 equiv.) were used as the reaction reagents. 10.0 g of product 9b was obtained as a light brown powder, with a yield of 99%. 1 ¹H NMR (500 MHz DMSO-d⁶): 8.0–8.1 (m, 2H), 7.6–8.0 (m, 8Hs), 7.2–7.3 (m, 4.8Hs), 7.1 (m, 1.8Hs), 3.3 (m, 0.6Hs), 3.0 (m, 0.2Hs), 2.4 (m, 0.2Hs), 1.8 (m, 0.6Hs), 1.6 (m, 0.2Hs), 1.0–1.4 (m, 0.5Hs). The 9X membrane material was prepared using ethylene carbonate as the solvent, similar to the 6X type, and the exchange process was the same as 1X. Elemental analysis showed that the Br content of the 11X membrane was less than 0.1 wt%.

[0099] The preferred synthesis method for structure 12-14X is as follows:

[0100] The preferred method for synthesizing intermediate 12a is as follows:

[0101] In a two-necked reaction flask A, 9,10-diphenylanthracene (9.7 g, 29 mmol) and 7-bromo-1,1,1-trifluoro-2-octanone (8.2 g, 30 mmol) were added and mechanically stirred in 75 mL of dichloromethane at room temperature. The reaction system was cooled to 0 °C, and a trifluoromethanesulfonic acid / trifluoroacetic acid mixture (1:1, 35 g) was slowly added dropwise. After the addition was complete, the mixture was stirred at 0 °C for 10 min, and then transferred to a 30 °C water bath. In a two-necked reaction flask B, m-terphenyl (2.2 g, 9.9 mmol) and 3-bromo-1,1,1-trifluoro-2-propanone (1.9 g, 10 mmol) were dissolved in 25 mL of dichloromethane. After the temperature of the system in reaction flask A reached 30 °C, the molecular weight increase was monitored by gel permeation chromatography every half hour. When the average molecular weight reached 10 kDa, the solution from reaction flask B was added to the system in reaction A, and the reaction continued until the molecular weight of the product reached 113 kDa. The reaction solution was poured into 1000 mL of cold 1:1 methanol / water solution, and a solid precipitated out. The solid was collected and washed with deionized water. After drying and crushing, the product was a brown powder 12a (20 g), with a yield of 94.7%. 1 ¹H NMR (500 MHz CDCl₃) δ 6.5–8.1 (m, 19H), 4.2 (m, 0.7Hs), 3.2 (m, 2Hs), 2.4 (m, 2Hs), 1.8 (m, 2Hs), 0.8–1.4 (m, 8Hs). Molecular weight calculation yielded n:m = 162:54.

[0102] The preferred method for synthesizing intermediate 13a is similar to that for 12a:

[0103] In two-necked flask A, a solution of 9,10-diphenylanthracene (6.4 g, 19 mmol) and 7-bromo-1,1,1-trifluoro-2-octanone (5.5 g, 20 mmol) was dissolved in 50 mL of dichloromethane with mechanical stirring at room temperature. In two-necked flask B, a solution of m-terphenyl (4.5 g, 19 mmol) and 3-bromo-1,1,1-trifluoro-2-propanone (3.8 g, 20 mmol) was dissolved in 50 mL of dichloromethane. The reaction was stopped when the molecular weight of the product reached 100 kDa. The product was 18.2 g of a brown solid, with a yield of 94.3%. 1 ¹H NMR (500MHz CDCl₃) δ 6.5–8.1 (m, 28H), 4.2 (m, 2Hs), 3.2 (m, 2Hs), 2.4 (m, 2Hs), 1.8 (m, 2Hs), 0.8–1.4 (m, 8Hs). Based on NMR and molecular weight calculations, n:m = 10¹:10¹.

[0104] The preferred method for synthesizing intermediate 14a is similar to that for 12a:

[0105] In two-necked flask A, a solution of 9,10-diphenylanthracene (3.2 g, 9.8 mmol) and 7-bromo-1,1,1-trifluoro-2-octanone (2.75 g, 10 mmol) was dissolved in 27 mL of dichloromethane with mechanical stirring at room temperature. In two-necked flask B, a solution of m-terphenyl (6.7 g, 29.3 mmol) and 3-bromo-1,1,1-trifluoro-2-propanone (5.7 g, 30 mmol) was dissolved in 75 mL of dichloromethane. The reaction was stopped when the molecular weight of the product reached 97 kDa. The product was a pale brown solid, 16.1 g in weight, with a yield of 92%. 1 ¹H NMR (500 MHz CDCl₃) δ 6.5–8.1 (m, 52H), 4.2 (m, 6Hs), 3.2 (m, 2Hs), 2.4 (m, 2Hs), 1.8 (m, 2Hs), 0.8–1.4 (m, 8Hs). Molecular weight calculation yielded n:m = 54:162.

[0106] The preferred intermediate 12b and the preferred product structure 12X were synthesized using a method similar to that of 1b and 1X. The reaction substrates used were trimethylamine (0.8 g, 1 equiv.) and 12a (10 g, 1 equiv.), and the reaction temperature was 30 °C. 10.0 g of product 12b was obtained as a brown powder, with a yield of 92.3%. 1 ¹H NMR (500 MHz DMSO-d⁶) δ 6.5–8.1 (m, 19H), 4.2 (m, 0.7Hs), 3.2 (m, 2Hs), 3 (m, 9H), 2.3 (m, 2Hs), 1.8 (m, 2Hs), 0.8–1.4 (m, 8Hs). The preparation method of the 12X membrane material is similar to that of 6X, and the exchange process is the same as that of 1X. Elemental analysis showed that the Br content of the 12X membrane was less than 0.1 wt%.

[0107] The preferred intermediate 13b and the preferred product structure 13X were synthesized using a method similar to that of 1b and 1X. The reaction substrates used were trimethylamine (0.6 g, 1 equiv.) and 13a (10 g, 1 equiv.), and the reaction temperature was 30 °C. 10.1 g of product 13b was obtained as a brown powder, with a yield of 96.3%. 1¹H NMR (500 MHz DMSO-d⁶) δ 6.5–8.1 (m, 28H), 4.2 (m, 2Hs), 3.2 (m, 2Hs), 3 (m, 9H), 2.3 (m, 2Hs), 1.8 (m, 2Hs), 0.8–1.4 (m, 8Hs). The preparation method of the 13X membrane material is similar to that of 6X, and the exchange process is the same as that of 1X. Elemental analysis showed that the Br content of the 13X membrane was less than 0.1 wt%.

[0108] The preferred intermediate 14b and the preferred product structure 14X were synthesized using a method similar to that of 1b and 1X. The reaction substrates used were trimethylamine (0.6 g, 1 equiv.) and 14a (10 g, 1 equiv.), and the reaction temperature was 30 °C. 10.2 g of product 14b was obtained as a light brown powder, with a yield of 98.7%. 1 ¹H NMR (500 MHz DMSO-d⁶) δ 6.5–8.1 (m, 52H), 4.2 (m, 6Hs), 3.2 (m, 2Hs), 3 (m, 9H), 2.3 (m, 2Hs), 1.8 (m, 2Hs), 0.8–1.4 (m, 8Hs). The 14X membrane material was prepared in a similar manner to 6X, with the same exchange process as 1X. Elemental analysis showed that the Br content of the 14X membrane was less than 0.1 wt%.

[0109] The preferred synthesis method for structures 15X-17X is as follows:

[0110]

[0111] The preferred structural intermediate 15a is synthesized using a method similar to that of 12a.

[0112] In a two-necked reaction flask A, 9,10-diphenylanthracene (9.7 g, 29 mmol) and 7-bromo-1,1,1-trifluoro-2-octanone (8.2 g, 30 mmol) were added and dissolved in 75 mL of dichloromethane with mechanical stirring at room temperature. The reaction system was cooled to 0 °C, and a trifluoromethanesulfonic acid / trifluoroacetic acid mixture (1:1, 35 g) was slowly added dropwise. After the addition was complete, the mixture was stirred at 0 °C for 10 min, and then transferred to a 30 °C water bath. In a two-necked reaction flask B, fluorene (2.6 g, 9.8 mmol) and 6-bromo-1,1,1-trifluoro-2-heptanone (2.6 g, 10 mmol) were dissolved in 25 mL of dichloromethane. After the temperature of the system in reaction flask A reached 30 °C, the molecular weight increase was monitored by gel permeation chromatography every half hour. When the average molecular weight reached 10 kDa, the solution from reaction flask B was added to the system in reaction A, and the reaction continued until the molecular weight of the product reached 65 kDa. The reaction solution was poured into 1000 mL of cold 1:1 methanol / water solution, and a solid precipitated out. The solid was collected and washed with deionized water. After drying, the product was crushed to obtain a brownish-yellow powder 15a (18.7 g), with a yield of 88.3%. 1 ¹H NMR (500 MHz CDCl₃) δ 6.5–8.1 (m, 54Hs), 3.8 (m, 2Hs), 3.2 (m, 8Hs), 2.4 (m, 8Hs), 1.8 (m, 8Hs), 0.6–1.4 (m, 30Hs). Molecular weight calculation yielded n:m = 30:90.

[0113] The preferred structural intermediate 16a is synthesized using a method similar to that of 15a.

[0114] The two-necked flask A contained a solution of 9,10-diphenylanthracene (6.4 g, 19.5 mmol), 7-bromo-1,1,1-trifluoro-2-octanone (5.5 g, 20 mmol), and 50 mL of dichloromethane. The two-necked flask B contained a solution of fluorene (3.2 g, 19.5 mmol), 6-bromo-1,1,1-trifluoro-2-heptanone (5.2 g, 20 mmol), and 50 mL of dichloromethane. The reaction was terminated when the molecular weight of the product reached 45 kDa. The product was a brownish-yellow powder, 16a (17.3 g), with a yield of 89%. 1 ¹H NMR (500 MHz CDCl₃) δ 6.5–8.1 (m, 22Hs), 3.8 (m, 2Hs), 3.2 (m, 4Hs), 2.4 (m, 4Hs), 1.8 (m, 4Hs), 0.6–1.4 (m, 14Hs). Based on NMR and molecular weight calculations, n:m = 45:45.

[0115] The preferred structural intermediate 17a is synthesized using a method similar to that of 15a.

[0116] The two-necked flask A contained a solution of 9,10-diphenylanthracene (3.2 g, 9.8 mmol), 7-bromo-1,1,1-trifluoro-2-octanone (2.7 g, 10 mmol), and 25 mL of dichloromethane. The two-necked flask B contained a solution of fluorene (4.9 g, 29 mmol), 6-bromo-1,1,1-trifluoro-2-heptanone (7.8 g, 30 mmol), and 75 mL of dichloromethane. The reaction was terminated when the molecular weight of the product reached 97 kDa. The product was a brownish-yellow powder, 17a (15.9 g), with a yield of 89.8%. 1 ¹H NMR (500 MHz CDCl₃) δ 6.5–8.1 (m, 34Hs), 3.8 (m, 6Hs), 3.2 (m, 6Hs), 2.4 (m, 8Hs), 1.8 (m, 8Hs), 0.6–1.4 (m, 26Hs). Molecular weight calculation yielded n:m = 54:162.

[0117] The preferred intermediate 15b and the preferred product structure 15X were synthesized using a method similar to that of 1b and 1X. The reaction substrates were methylpiperidine (1.8 g, 1 equiv.) and 15a (10 g, 1 equiv.), and the reaction temperature was 60 °C. 10.0 g of product 15b was obtained as a brown powder, with a yield of 84.7%. 1 ¹H NMR (500 MHz DMSO-d⁶) δ 6.5–8.1 (m, 54Hs), 3.8 (m, 2Hs), 3.2 (m, 24Hs), 2.8 (m, 12Hs), 2.4 (m, 8Hs), 1.8 (m, 8Hs), 0.6–1.4 (m, 54Hs). The 15X membrane material was prepared similarly to the 6X membrane, with the same exchange process as the 1X membrane. Elemental analysis showed that the Br content of the 15X membrane was less than 0.1 wt%.

[0118] The preferred intermediate 16b and the preferred product structure 16X were synthesized using a method similar to that of 1b and 1X. The reaction substrates used were methylpiperidine (2.0 g, 1 equiv.) and 16a (10 g, 1 equiv.), and the reaction temperature was 60 °C. 10.8 g of product 16b was obtained as a brown powder, with a yield of 90.1%. 1¹H NMR (500 MHz DMSO-d⁶) δ 6.5–8.1 (m, 22Hs), 3.8 (m, 2Hs), 3.2 (m, 12Hs), 2.8 (m, 6Hs), 2.4 (m, 4Hs), 1.8 (m, 4Hs), 0.6–1.4 (m, 26Hs). The 16X membrane material was prepared in a similar manner to 6X, with the same exchange process as 1X. Elemental analysis showed that the Br content of the 16X membrane was less than 0.1 wt%.

[0119] The preferred intermediate 17b and the preferred product structure 17X were synthesized using a method similar to that of 1b and 1X. The reaction substrates used were methylpiperidine (2.2 g, 1 equiv.) and 17a (10 g, 1 equiv.), and the reaction temperature was 60 °C. 11.8 g of product 17b was obtained as a brown powder, with a yield of 96.9%. 1 ¹H NMR (500 MHz DMSO-d⁶) δ 6.5–8.1 (m, 34Hs), 3.8 (m, 6Hs), 3.2 (m, 24Hs), 2.8 (m, 12Hs), 2.4 (m, 8Hs), 1.8 (m, 8Hs), 0.6–1.4 (m, 50Hs). The 17X membrane material was prepared similarly to 6X, with the same exchange process as 1X. Elemental analysis showed that the Br content of the 17X membrane was less than 0.1 wt%.

[0120] The synthesis methods for Examples 18-23 are shown below:

[0121]

[0122] The preferred synthesis method for polymer structures 18X-20X is shown in the following formula:

[0123]

[0124] The preferred intermediate 18a is synthesized using the following method:

[0125] In a two-necked reaction flask A, 1,1'-binaphthyl (6.6 g, 26.1 mmol) and 6-bromo-1,1,1-trifluoro-2-hexanone (6.6 g, 26.8 mmol) were added and dissolved in 67 mL of dichloromethane with mechanical stirring at room temperature. The reaction system was cooled to 0 °C, and a trifluoromethanesulfonic acid / trifluoroacetic acid mixture (1:1, 35 g) was slowly added dropwise. After the addition was complete, the mixture was stirred at 0 °C for 10 min, and then transferred to a 30 °C water bath. In a two-necked reaction flask B, 9,9-dimethylfluorene (2.5 g, 12.9 mmol) and 1,1,1-trifluoro-2-heptanone (2.4 g, 13.2 mmol) were dissolved in 33 mL of dichloromethane. After the temperature of reaction flask A reached 30 °C, the molecular weight increase was detected by gel permeation chromatography every half hour. When the average molecular weight reached 10 kDa, the solution from reaction flask B was added to reaction system A to continue the reaction until the molecular weight of the product reached 265 kDa. The reaction solution was poured into 1000 mL of cold 1:1 methanol / water solution, and a solid precipitated out. The solid was collected, washed three times with ethanol, and then redissolved in 100 mL of tetrahydrofuran. Dimethylamine (11.8 g, 261 mmol) was added, and the reaction was stirred for 48 hours. A solid precipitated out in anhydrous diethyl ether at 0 °C, dried, and crushed. The product was a light brown powder, 18a (15.1 g), with a yield of 87.7%. 1 ¹H NMR (500 MHz CDCl₃) δ 8.0–8.1 (m, 6Hs), 7.6–8.0 (m, 18Hs), 7.3–7.4 (m, 2Hs), 7.2–7.3 (m, 4Hs), 2.4 (m, 6Hs), 2.2 (m, 12Hs), 1.7 (m, 6Hs), 0.6–1.4 (m, 27Hs). Based on NMR, molecular weight calculation yielded n:m = 402:203.

[0126] The preferred intermediate 19a is synthesized using a method similar to that of 18a.

[0127] The two-necked flask A contained a solution of 1,1'-binaphthyl (5.0 g, 19.5 mmol), 6-bromo-1,1,1-trifluoro-2-hexanone (4.9 g, 20 mmol), and 67 mL of dichloromethane. The two-necked flask B contained a solution of 9,9-dimethylfluorene (3.8 g, 19.5 mmol), 1,1,1-trifluoro-2-heptanone (3.6 g, 20 mmol), and 33 mL of dichloromethane. The reaction was quenched at a molecular weight of 253 kDa, and post-treatment was performed using dimethylamine (8.8 g, 195 mmol). The product was a pale brown powder, 19a (13.6 g), with a yield of 87.7%. 1¹H NMR (500 MHz CDCl₃) δ 8.0–8.1 (m, 4Hs), 7.6–8.0 (m, 10Hs), 7.3–7.4 (m, 2Hs), 7.2–7.3 (m, 2Hs), 2.4 (m, 4Hs), 2.2 (m, 6Hs), 1.7 (m, 4Hs), 0.6–1.4 (m, 21Hs). Based on NMR, molecular weight calculation yielded n:m = 302:302.

[0128] The preferred intermediate 20a is synthesized using a method similar to that of 18a.

[0129] The two-necked flask A contained a solution of 1,1'-binaphthyl (3.3 g, 13 mmol), 6-bromo-1,1,1-trifluoro-2-hexanone (3.3 g, 13.4 mmol), and 33 mL of dichloromethane. The two-necked flask B contained a solution of 9,9-dimethylfluorene (5.0 g, 26 mmol), 1,1,1-trifluoro-2-heptanone (4.8 g, 26.6 mmol), and 67 mL of dichloromethane. The reaction was quenched at a molecular weight of 211 kDa, and post-treatment was performed using dimethylamine (5.9 g, 131 mmol). The product was a pale brown powder, 20a (13.6 g), with a yield of 89.3%. 1 ¹H NMR (500 MHz CDCl₃) δ 8.0–8.1 (m, 6Hs), 7.6–8.0 (m, 12Hs), 7.3–7.4 (m, 4Hs), 7.2–7.3 (m, 2Hs), 2.4 (m, 6Hs), 2.2 (m, 6Hs), 1.7 (m, 6Hs), 0.6–1.4 (m, 36Hs). Based on NMR and molecular weight calculations, n:m = 181:362.

[0130] The synthesis of preferred intermediate 18b and preferred structure 18X is similar to that of 1a and 1X:

[0131] Substrate 18a (10 g, 1 equiv.) was dissolved in 100 mL of tetrahydrofuran-methanol (1:1) solution. N1,N4-bis(6-bromohexyl)-N1-methaneimino-N1,N4,N4-trimethylbutane-1,4-diammonium (47.6 g, 5 equiv.) was dissolved in 200 mL of tetrahydrofuran-methanol mixture (1:1). Solution 18a was added to this mixture at 60 °C, and the reaction was continued for 2 days. After cooling the reaction system to 30 °C, trimethylamine (18 g, 20 equiv.) was added, and the reaction was stirred for another 2 days. The reaction solution was concentrated and added to a dialysis bag (permeable to molecules up to 50 K) and washed with deionized water until the ionic conductivity of the washings was the same as that of deionized water. The product 18b was dried and pulverized to obtain 18.5 g of a light brown powder, with a yield of 90.7%. 1 ¹H NMR (500MHz DMSO-d⁶) δ 8.0–8.1 (m, 6Hs), 7.6–8.0 (m, 18Hs), 7.3–7.4 (m, 2Hs), 7.2–7.3 (m, 4Hs), 3.3 (m, 28Hs), 3.1 (m, 54Hs), 2.4 (m, 6Hs), 1.7 (m, 30Hs), 0.6–1.4 (m, 39Hs). The 18X membrane material was prepared similarly to the 6X membrane, using sulfolane as the solvent, and the exchange process was the same as for 1X. Elemental analysis showed that the Br content of the 18X membrane was less than 0.1 wt%.

[0132] The synthesis of preferred intermediate 19b and preferred structure 19X is similar to that of 18a and 18X:

[0133] Substrate 19a (10 g, 1 equiv.) was dissolved in 100 mL of tetrahydrofuran-methanol (1:1) solution. N1,N4-bis(6-bromohexyl)-N1-methaneimino-N1,N4,N4-trimethylbutane-1,4-diammonium (37.3 g, 5 equiv.) was dissolved in 200 mL of a tetrahydrofuran-methanol mixture (1:1). Solution 19a was added to this mixture at 60 °C, and the reaction was continued for 2 days. After cooling the reaction system to 30 °C, trimethylamine (14 g, 20 equiv.) was added, and the reaction was stirred for another 2 days. The reaction solution was concentrated and added to a dialysis bag (permeable to molecules up to 50 K) and washed with deionized water until the ionic conductivity of the washings was the same as that of deionized water. The solution was dried and ground to obtain product 18b as a light brown powder, 16.5 g, 90.9% yield. 1¹H NMR (500MHz DMSO-d⁶) δ 8.0–8.1 (m, 4Hs), 7.6–8.0 (m, 10Hs), 7.3–7.4 (m, 2Hs), 7.2–7.3 (m, 2Hs), 3.3 (m, 14Hs), 3.1 (m, 27Hs), 2.4 (m, 4Hs), 1.7 (m, 16Hs), 0.6–1.4 (m, 27Hs). The 19X membrane material was prepared using the same method as 18X, and the exchange process was the same as 1X. Elemental analysis showed that the Br content of the 19X membrane was less than 0.1 wt%.

[0134] The synthesis of preferred intermediate 20b and preferred structure 20X is similar to that of 19a and 19X:

[0135] Substrate 20a (10 g, 1 equiv.) was dissolved in 100 mL of tetrahydrofuran-methanol (1:1) solution. N1,N4-bis(6-bromohexyl)-N1-methaneimino-N1,N4,N4-trimethylbutane-1,4-diammonium (26.6 g, 5 equiv.) was dissolved in 200 mL of a tetrahydrofuran-methanol mixture (1:1). Solution 20a was added to this mixture at 60 °C, and the reaction was continued for 2 days. After cooling the reaction system to 30 °C, trimethylamine (10 g, 20 equiv.) was added, and the reaction was stirred for another 2 days. The reaction solution was concentrated and added to a dialysis bag (permeable to molecules up to 50 K) and washed with deionized water until the ionic conductivity of the washings was the same as that of deionized water. The product 20b was dried and pulverized to obtain 13.5 g of a light brown powder, with a yield of 85.4%. ¹H NMR (500MHz DMSO-d⁶) δ 8.0–8.1 (m, 6Hs), 7.6–8.0 (m, 12Hs), 7.3–7.4 (m, 4Hs), 7.2–7.3 (m, 2Hs), 3.3 (m, 14Hs), 3.1 (m, 27Hs), 2.4 (m, 6Hs), 1.7 (m, 18Hs), 0.6–1.4 (m, 42Hs). The 20X membrane material was prepared using the same method as the 19X membrane, and the exchange process was the same as the 1X membrane. Elemental analysis showed that the Br content of the 20X membrane was less than 0.1 wt%.

[0136] The synthesis method of the preferred structures 21X-23X is as follows:

[0137]

[0138] The synthesis method of preferred intermediate 21a is similar to that of preferred structural intermediate 18a:

[0139] Two-necked flask A contained 1,1'-binaphthyl (6.6 g, 26.1 mmol), 7-bromo-1,1,1-trifluoro-2-heptanone (7.0 g, 26.8 mmol), dissolved in 67 mL of dichloromethane with mechanical stirring at room temperature. Two-necked flask B contained biphenyl (1.98 g, 12.9 mmol), 7-bromo-1,1,1-trifluoro-2-heptanone (3.4 g, 13.2 mmol), and 33 mL of dichloromethane. The reaction was stopped when the molecular weight of the product reached 696 K. After washing three times with ethanol, the product was redissolved in 100 mL of tetrahydrofuran, and dimethylamine (11.8 g, 261 mmol) was added. The reaction was stirred for 48 hours, and a solid precipitated in anhydrous diethyl ether at 0 °C. After drying and crushing, the product was a light brown powder, 21a (16.6 g), with a yield of 92.7%. 1 ¹H NMR (500 MHz CDCl₃) δ 8.0–8.1 (m, 4Hs), 7.6–8.0 (m, 20Hs), 7.3–7.4 (m, 4Hs), 7.2–7.3 (m, 4Hs), 2.4 (m, 6Hs), 2.2 (m, 18Hs), 1.7 (m, 6Hs), 0.6–1.4 (m, 27Hs). Based on NMR, molecular weight calculation yielded n:m = 1002:501.

[0140] The synthesis method of preferred intermediate 22a is similar to that of preferred structural intermediate 18a:

[0141] Two-necked flask A contained 1,1'-binaphthyl (4.96 g, 19.5 mmol) and 7-bromo-1,1,1-trifluoro-2-heptanone (5.2 g, 20 mmol), dissolved in 50 mL of dichloromethane with mechanical stirring at room temperature. Two-necked flask B contained biphenyl (3.0 g, 19.5 mmol), 7-bromo-1,1,1-trifluoro-2-heptanone (5.2 g, 20 mmol), and 50 mL of dichloromethane. The reaction was stopped when the molecular weight of the product reached 745 K. After washing three times with ethanol, the product was redissolved in 100 mL of tetrahydrofuran, and dimethylamine (8.8 g, 195 mmol) was added. The reaction was stirred for 48 hours, and a solid precipitated in anhydrous diethyl ether at 0 °C. After drying and crushing, the product was a light brown powder, 22a (16.1 g), with a yield of 92.5%. 1¹H NMR (500 MHz CDCl₃) δ 8.0–8.1 (m, 2Hs), 7.6–8.0 (m, 12Hs), 7.3–7.4 (m, 4Hs), 7.2–7.3 (m, 2Hs), 2.4 (m, 4Hs), 2.2 (m, 12Hs), 1.7 (m, 4Hs), 0.6–1.4 (m, 16Hs). Based on NMR and molecular weight calculations, n:m = 835:835.

[0142] The synthesis method of preferred intermediate 23a is similar to that of preferred structural intermediate 18a:

[0143] Two-necked flask A contained 1,1'-binaphthyl (3.3 g, 13.1 mmol) and 7-bromo-1,1,1-trifluoro-2-heptanone (3.5 g, 13.4 mmol), dissolved in 33 mL of dichloromethane with mechanical stirring at room temperature. Two-necked flask B contained biphenyl (4.0 g, 26 mmol), 7-bromo-1,1,1-trifluoro-2-heptanone (6.9 g, 26.6 mmol), and 67 mL of dichloromethane. The reaction was stopped when the molecular weight of the product reached 654 K. After washing three times with ethanol, the product was redissolved in 100 mL of tetrahydrofuran, and dimethylamine (5.9 g, 130 mmol) was added. The reaction was stirred for 48 hours, and a solid precipitated in anhydrous diethyl ether at 0 °C. After drying and crushing, the product was a light brown powder, 23a (16.1 g), with a yield of 93.9%. 1 ¹H NMR (500 MHz CDCl₃) δ 8.0–8.1 (m, 2Hs), 7.6–8.0 (m, 16Hs), 7.3–7.4 (m, 8Hs), 7.2–7.3 (m, 2Hs), 2.4 (m, 6Hs), 2.2 (m, 18Hs), 1.7 (m, 6Hs), 0.6–1.4 (m, 24Hs). Based on NMR, molecular weight calculation yielded n:m = 518:10³⁶.

[0144] The synthesis of preferred intermediate 21b and preferred structure 21X is similar to that of 19a and 19X:

[0145] The reaction substrate 21a (10 g, 1 equiv.) was dissolved in 100 mL of tetrahydrofuran-methanol (1:1) solution. 4,4'-(dimethyl-1,4-azadiyl)bis(N-(4-bromobutyl)-N,N-dimethylbutane-1-ammonium) (81 g, 5 equiv.) was dissolved in 600 mL of a tetrahydrofuran-methanol mixture (1:1). Solution 21a was added to this solution at 60 °C, and the reaction was continued for 2 days. After cooling the reaction system to 30 °C, trimethylamine (25.5 g, 20 equiv.) was added, and the reaction was stirred for another 2 days. The reaction solution was concentrated and added to a dialysis bag (permeable to molecules up to 50 K) and washed with deionized water until the ionic conductivity of the washings was the same as that of deionized water. After drying, the product 21b was obtained as a light brown powder, 26.5 g, with a yield of 96.4%. ¹H NMR (500 MHz DMSO-d6) δ 8.5 (m, 4Hs), 7.6–8.2 (m, 20Hs). 7.3-7.4 (m, 8Hs), 7.2-7.3 (m, 2Hs), 3.2-3.4 (m, 54Hs), 3.0 (m, 99Hs), 2.4 (m, 6Hs), 1.2-1.8 (m, 72Hs). The preparation method of the 21X membrane material is the same as that of 19X, and the exchange process is the same as that of 1X. Elemental analysis shows that the Br content of the 21X membrane is less than 0.1 wt%.

[0146] The synthesis of preferred intermediate 22b and preferred structure 22X is similar to that of 19a and 19X:

[0147] The reaction substrate 22a (10 g, 1 equiv.) was dissolved in 100 mL of tetrahydrofuran-methanol (1:1) solution. 4,4'-(dimethyl-1,4-azadiyl)bis(N-(4-bromobutyl)-N,N-dimethylbutane-1-ammonium) (84 g, 5 equiv.) was dissolved in 600 mL of a tetrahydrofuran-methanol mixture (1:1). Solution 22a was added to this solution at 60 °C, and the reaction was continued for 2 days. After cooling the reaction system to 30 °C, trimethylamine (26.5 g, 20 equiv.) was added, and the reaction was stirred for another 2 days. The reaction solution was concentrated and added to a dialysis bag (permeable to molecules up to 50 K) and washed with deionized water until the ionic conductivity of the washings was the same as that of deionized water. After drying, the product 22b was obtained as a light brown powder, 27.5 g, with a yield of 97.7%. ¹H NMR (500 MHz DMSO-d6) δ 8.5 (m, 2Hs), 7.6–8.2 (m, 12Hs). 7.2-7.4 (m, 6Hs), 3.2-3.4 (m, 36Hs), 3.0 (m, 66Hs), 2.4 (m, 4Hs), 1.2-1.8 (m, 48Hs). The preparation method of the 22X membrane material is the same as that of 19X, and the exchange process is the same as that of 1X. Elemental analysis shows that the Br content of the 22X membrane is less than 0.1 wt%.

[0148] The synthesis of preferred intermediate 23b and preferred structure 23X is similar to that of 19a and 19X:

[0149] The reaction substrate 23a (10 g 1 equiv.) was dissolved in 100 mL of tetrahydrofuran-methanol (1:1) solution. 4,4'-(dimethyl-1,4-azadiyl)bis(N-(4-bromobutyl)-N,N-dimethylbutane-1-ammonium) (89 g, 5 equiv.) was dissolved in 600 mL of a tetrahydrofuran-methanol mixture (1:1). Solution 23a was added to this solution at 60 °C, and the reaction was continued for 2 days. After cooling the reaction system to 30 °C, trimethylamine (26.5 g, 20 equiv.) was added, and the reaction was stirred for another 2 days. The reaction solution was concentrated and added to a dialysis bag (permeable to molecules up to 50 K) and washed with deionized water until the ionic conductivity of the washings was the same as that of deionized water. After drying, the product 23b was obtained as a light brown powder, 28.5 g, with a yield of 97.5%. ¹H NMR (500 MHz DMSO-d6) δ 8.5 (m, 2Hs), 7.6–8.2 (m, 16Hs). 7.2-7.4 (m, 10Hs), 3.2-3.4 (m, 54Hs), 3.0 (m, 99Hs), 2.4 (m, 6Hs), 1.2-1.8 (m, 72Hs). The preparation method of the 22X membrane material is the same as that of 19X, and the exchange process is the same as that of 1X. Elemental analysis shows that the Br content of the 22X membrane is less than 0.1 wt%.

[0150] The molecular weight determination method during the synthesis process is as follows:

[0151] Take a small sample (10 mg) and dissolve it in chromatographic grade tetrahydrofuran (1 mL). Filter the solution and take 50 μL of the filtrate. After removing any obvious air bubbles from the injection needle, inject 10 μL of the liquid into an EClassical 3100 liquid chromatograph. Use gel permeation chromatography with tetrahydrofuran as the mobile phase at a flow rate of 1 mL / min at 30 °C. n = 50-1800; typical chromatograms (intermediates 1a-5a) are shown below. Figure 1 As shown.

[0152] The NMR testing methods involved in the synthesis process are as follows:

[0153] 10 mg of sample was dissolved in 1 mL of the corresponding deuterated solvent. The test was performed using a Burker 500 MHz NMR spectrometer, with T1=2 s and at least 16 scans. The NMR spectra of the obtained preferred polymer structure 22X are shown below. Figure 2 As shown.

[0154] Test Example 1:

[0155] The performance of polymers 1X-23X prepared in Examples 1-23 was tested using the following methods:

[0156] AC impedance test:

[0157] Electrochemical impedance spectroscopy (EIS) was performed on the 1X-23X membrane using an electrochemical workstation (Chenhua CHI660E). The membrane sample (4 cm long, 1 cm wide) was securely fixed in a specially designed electrochemical test cell (4 electrodes, platinum as the electrode material), ensuring tight contact between the membrane and the electrode system. Before testing, the test solution (such as an electrolyte solution of a specific concentration) was injected into the test cell to fully wet the membrane sample. If the test temperature was not at room temperature, the sample was allowed to equilibrate in the electrolyte for at least 30 minutes to reach the test temperature. The test parameters of the electrochemical workstation were set, with the scan frequency range set to 1*10⁻⁶. 6 The AC excitation signal amplitude was 2 sec and the voltage was 100 mV, ranging from Hz to 0.1 Hz. The impedance value was obtained when the phase angle was closest to 0°, and the ionic conductivity was calculated based on the sample size and thickness.

[0158] Tensile strength test:

[0159] Tensile strength tests were performed on membrane samples using a universal tensile testing machine (Instron-3367, Instron, USA). The membrane samples were precisely cut into standard dumbbell shapes, with dimensions strictly conforming to the national standard GB / T 1040.3-2 (length 150 mm, width 20 mm, thickness 20-60 μm). The samples were mounted between the upper and lower clamps of the universal tensile testing machine, and the tensile rate was set to 50 mm / min. After starting the test, the tensile force acting on the sample and the corresponding elongation were monitored and recorded in real time until the sample broke. The tensile strength of the membrane was calculated based on the recorded data (the tensile force at break divided by the original cross-sectional area of ​​the sample).

[0160] The material performance test results are shown in Table 1 below:

[0161] Table 1. Test results of mechanical strength and ionic conductivity of the preferred structure.

[0162]

[0163] Note: References 1-3 are from the literature: Nat Commun 10, 2306 (2019), patent US11230626B2; Reference 4 is from Nat Energy 4, 392–398 (2019); References 5-7 are from ACS Macro Lett 4, 814−818 (2015), patent CN111647138 B, patent US11173456B2; References 8-9 are from patent US10435504B2; References 10-12 are from ACS Macro Lett, 6, 566−570 (2017).

[0164] Figure 3 The graph shows a comparison of the material performance test data for the preferred polymers 18X, 19X, and 21X, with the data for each control group shown in the lower left corner.

[0165] Test results show that ion exchange membrane materials with large pi systems exhibit excellent mechanical strength (e.g., 1-6, 18-23), and molecular weight is positively correlated with mechanical strength. However, when n+m exceeds 500, the increase in mechanical strength due to molecular weight increase is limited. The structure of the ionic functional groups An-, CA+, and LK is crucial for ionic conductivity. Compared with control groups in other literature / patents, the framework structure based on large pi groups and the preferred ionic groups, along with the contrast of side chain structures, can effectively enhance both the conductivity and mechanical strength of electrolyte materials simultaneously, thereby breaking the trade-off between mechanical stability and electrochemical performance in such materials.

[0166] Application Example 1

[0167] The thin film prepared from polymer 22X obtained in Example 22 was subjected to anion exchange membrane water electrolysis test (X=OH during electrolysis). The test procedure, battery structure and physical image are shown below. Figure 4 As shown:

[0168] Cut to the appropriate size (usually 5*5cm) 2The test cell consists of a PTFE gasket, electrodes, and an anion exchange membrane. The current collector is bolted to the cathode channel plate through the positioning holes and placed in the fixture. The PTFE is placed on the channel area, with the cathode electrode inserted into the central opening. The anode channel plate and current collector are passed through the positioning holes to cover the PTFE. The entire test cell is then tightened with nuts and bolts through the positioning holes, and the torque of the test cell is adjusted with a torque wrench. The installed cell is connected to the corresponding inlet and outlet water pipes according to the anode and cathode, and the circulation pump is turned on and the flow rate is set to circulate the heated electrolyte into the system. The positive and negative terminals of the power supply and the voltage, current, and temperature detection devices are connected to the test cell. The program and current are set, and the pump is turned on to circulate the system to the appropriate temperature. The power supply and the corresponding program are turned on to start the electrolysis experiment, collecting operating parameters such as temperature, current, and voltage.

[0169] Figure 5 The voltage data of 22OH after 1000 hours of operation in a water electrolysis test environment are presented.

[0170] The electrolysis test shown in the figure uses NiFeSOx oxide as a hydrogen evolution catalyst attached to a nickel grid, and NiMo oxygen evolution catalyst attached to the nickel grid. The operating environment is 1 M KOH at 60 °C. After 1000 hours of testing, the back pressure valve was opened to achieve a hydrogen production end pressure of 3 MPa. The system operated continuously for 200 hours without any gas or liquid leakage. The electrolysis cell test demonstrates the chemical and mechanical stability of the membrane of this invention and provides excellent electrolysis performance.

[0171] The above are merely preferred embodiments of the present invention. It should be noted that the above preferred embodiments should not be considered as limitations on the present invention, and the scope of protection of the present invention should be determined by the scope defined in the claims. For those skilled in the art, several improvements and modifications can be made without departing from the spirit and scope of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A highly conjugated block polymer, characterized in that, It includes the structural unit shown in equation (I): ； （I） Where n and m are the number of repeating units; n is an integer from 1 to 2000; m is an integer from 1 to 2000; Ar1 is a segment of the following structure: ; Ar2 is selected from one of the following structural segments: ； The values ​​of x1 and x2 range from 0 to 10; LK1 and LK2 are linking groups, each independently selected from... or ; It is an ionic group, in which Selected from one of the following structural fragments: ； Selected from one of the following structural fragments: ； R1 can be an ionic or nonionic group; when R1 is an ionic group, its definition is the same as... Same; when R1 is a nonionic group, it is selected from one of the following structural segments: ； EWG consists of the following structural segments: 。 2. The highly conjugated block polymer according to claim 1, characterized in that, The highly conjugated block polymer has the following structural formula: 。 3. A method for preparing a highly conjugated block polymer as described in claim 1 or 2, characterized in that, When LK1 and LK2 are both When the method is used, it includes the following steps: Step (1): Mix A1, EWG(CO)RII, A2, and EWG(CO)LK2-R1 in a solvent and react them under the action of a catalyst to generate a precursor; ； Where RII is A1 is A2 is selected from one of the following structural segments: ； Step (2): Dissolve the precursor in a solvent, add a nucleophile to react, quench and rinse, then add a salt solution for ion exchange to obtain the high conjugation block polymer. 。 4. The preparation method according to claim 3, characterized in that, The solvent mentioned in step (1) is one of dichloromethane, chloroform, tetrachloromethane or chlorobenzene.

5. The preparation method according to claim 3, characterized in that, The catalyst mentioned in step (1) is one or a mixture of concentrated sulfuric acid, concentrated nitric acid, trifluoroacetic acid, and trifluoromethanesulfonic acid.

6. An anion exchange membrane, characterized in that, It is prepared from the highly conjugated block polymer described in claim 1 or 2.

7. The anion exchange membrane according to claim 6, characterized in that, The anion exchange membrane is prepared by dissolving a highly conjugated block polymer in an organic solvent to obtain a slurry, which is then coated onto a substrate using a roll-to-roll process, screen printing, or doctor blade casting. The organic solvent in the slurry is dried and evaporated, allowing the highly conjugated block polymer to solidify into a film on the substrate surface. The membrane is then peeled off to obtain the anion exchange membrane.

8. The application of the anion exchange membrane as described in claim 6 in electrochemistry.

9. The application according to claim 8, characterized in that, The applications include: preparing fuel cells, preparing supercapacitors, preparing organic flow batteries, electrolyzing water, electrolyzing CO2, electrolyzing CO, CO2 purification, heavy metal separation, electrically driven CO2 enrichment, lithium salt recovery, and as a metal-air battery membrane.

Images