Polyaryletherketone resin, preparation method and application of polyaryletherketone resin in functional film

Abstract

The invention discloses polyaryletherketone resin, a preparation method and application of the polyaryletherketone resin in a functional film, and belongs to the technical field of functional polymer materials. The preparation method comprises the following steps: firstly, preparing an aromatic monomer 4, 4 '-((9-(6-(4-triphenylmethyl phenoxy) hexyl)-9H-carbazole-3, 6-diyl) bis (diphenylmethylene)) diphenol (monomer 1) of a dense benzene ring containing a flexible side group, then taking 1, 1-bis (4-fluorophenyl)-N-phenylmethane imine, 4, 4'-dihydroxydiphenylketone and the monomer 1 as raw materials, and carrying out a nucleophilic substitution reaction catalyzed by K2CO3, so as to obtain the high-molecular polymer. A polyaryletherketone precursor polymer containing Schiff base is prepared; a polyaryletherketone precursor polymer is sulfonated with concentrated sulfuric acid, polyaryletherketone resin containing sulfonic acid groups is prepared, the polyaryletherketone resin is dissolved in dichloroacetic acid, a film is laid through a casting method, the polyaryletherketone ion exchange functional membrane is prepared, and the membrane has the advantages of being excellent in anti-oxidation stability, good in size stability, good in solution processability and the like.

Description

Technical Field

[0001] This invention belongs to the field of functional polymer materials technology, specifically relating to a polyaryletherketone resin, its preparation method, and its application in functional membranes. Background Technology

[0002] For decades, perfluorosulfonic acid (PFSA) membranes have been the industry benchmark due to their superior proton conductivity, mechanical properties, and ideal oxidative stability. However, their high cost and complex fabrication process have hindered the diversified development of PFSA molecular design. The development of fluorine-free proton exchange functional membranes promises to solve these problems, offering advantages such as low cost, controllable structure, and simple fabrication process. Sulfonated polyarylether polymers, as inexpensive materials, possess excellent mechanical properties, high thermal stability, low fuel permeability, and processability, showing broad application prospects in fuel cell technology. The core challenge in fabricating high-performance proton exchange functional membranes lies in controlling the microstructure and ion exchange capacity (IEC) of the material. This requires optimizing the fabrication process and balancing inter- and intra-chain interactions within the material, a truly arduous task.

[0003] Therefore, recent research has focused on the microstructure regulation of polyaromatic proton exchange functional membranes (PEMs). Inducing phase separation by introducing additional driving forces can effectively improve the conductivity of PEMs, thereby enhancing their overall performance. Studies have shown that densely distributed sulfonic acid groups far from the main chain can promote the formation of phase-separated nanostructures and enhance the integrity of hydrophobic water areas. Therefore, the preparation of PEMs with excellent performance and good microphase separation morphology is of great significance for their applications. Summary of the Invention

[0004] The purpose of this invention is to design a polyaryletherketone resin, its preparation method, and its application in functional membranes, starting from the molecular structure.

[0005] This invention first prepares an aromatic monomer 4,4'-((9-(6-(4-triphenylmethylphenoxy)hexyl)-9H-carbazole-3,6-diyl)bis(diphenylmethylene))diphenol (monomer 1) containing a dense benzene ring with flexible side groups. Then, using 1,1-bis(4-fluorophenyl)-N-phenylmethaneimine, 4,4'-dihydroxydiphenyl ketone, and monomer 1 as raw materials, a Schiff base-containing polyaryletherketone precursor polymer is prepared through a K2CO3-catalyzed nucleophilic substitution reaction. After sulfonating the polyaryletherketone precursor polymer with concentrated sulfuric acid, a polyaryletherketone resin containing sulfonic acid groups is prepared. Then, the polyaryletherketone resin is dissolved in dichloroacetic acid and a membrane is laid using a flow casting method to prepare a polyaryletherketone ion exchange functional membrane. This polyaryletherketone ion exchange functional membrane has excellent antioxidant stability, good dimensional stability, and solution processability, and can be applied in the field of functional membranes.

[0006] The polyaryletherketone resin of this invention has the following structural formula. ; Where 0.01≤x≤0.2.

[0007] The preparation method of the polyaryletherketone resin of the present invention comprises the following steps: (1) Preparation of 4,4'-((9-(6-(4-triphenylmethylphenoxy)hexyl)-9H-carbazole-3,6-diyl)bis(diphenylmethylene))diol (monomer 1): Carbazole and 4-methoxytriphenylchloromethane were added to a reaction vessel at a molar ratio of 1:2 to 2.5. Then, 1,2-dichlorobenzene was slowly added dropwise. The reaction was carried out under nitrogen protection at 130–160 °C for 8–15 h. After the reaction was completed, 1,2-dichlorobenzene was removed by distillation at 180–200 °C. The product was then washed 3–5 times with ethanol and dried under vacuum at 70–80 °C to obtain a purple solid. Finally, the product was purified by column chromatography using CHCl3 as the eluent, and CHCl3 was removed by rotary evaporation. After vacuum drying, a white solid powder, 3,6-bis((4-methoxyphenyl)diphenylmethyl)-9H-carbazole, was obtained, denoted as compound 1. 4-Triphenylmethylphenol and potassium hydroxide were added to a reaction vessel and dissolved in DMF under nitrogen protection at an oil bath temperature of 70-100℃. Then, 1,6-dibromohexane was added. The molar ratio of 4-triphenylmethylphenol, potassium hydroxide and 1,6-dibromohexane was 1:1.1-1.3:5-6. Heating was stopped after 8-10 hours. The reaction product was cooled to room temperature and placed in water. After filtration, it was recrystallized with ethanol and then dried under vacuum at 70-90℃ to obtain a white powder ((4-((6-bromohexyl)oxy)phenyl)methanetrimethylene)triphenyl, denoted as compound 2. Compound 1 and Compound 2 were placed in a reaction vessel and dissolved in DMF under nitrogen protection at an oil bath temperature of 100-140℃. Then, sodium hydroxide (NaOH), sodium iodide (NaI), and tetrabutylammonium bromide (TBAB) were added sequentially. The molar ratio of Compound 1, Compound 2, NaOH, NaI, and TBAB was 1:1.1-1.3:7:0.2-0.25:0.2-0.25. Heating was stopped after reacting for 8-16 hours. After the reaction product cooled to room temperature, it was poured into ethanol and washed 3-5 times with ethanol. Then, it was dried under vacuum at 70-90℃ to obtain a white solid 3,6-bis((4-methoxyphenyl)diphenylmethyl)-9-(6-(4-triphenylmethylphenoxy)hexyl)-9H-carbazole, denoted as Compound 3. Compound 3 was dissolved in CHCl3, and insoluble impurities were removed by filtration. After being placed in an ice bath for 20–40 minutes, BBr3 was slowly added dropwise at a molar ratio of 1:6–10. The reaction was carried out in an ice bath for 12–36 hours. The reaction product was then placed in water, and the organic phase was washed 3–5 times with water and evaporated to dryness. The resulting product was washed 3–5 times with water and ethanol, respectively, and then vacuum dried at 50–70 °C to obtain a yellow powder, 4,4'-((9-(6-(4-triphenylmethylphenoxy)hexyl)-9H-carbazole-3,6-diyl)bis(diphenylmethylene))diol, denoted as monomer 1. Its reaction formula and product structure are shown below. ; (2) Preparation of polyaryletherketone precursor polymers: 1,1-bis(4-fluorophenyl)-N-phenylmethaneimine, monomer 1, 4,4′-dihydroxybenzophenone prepared in step (1), and an amount of anhydrous potassium carbonate (catalyst amount) were added to a dry reaction vessel. The molar ratio of 1,1-bis(4-fluorophenyl)-N-phenylmethaneimine, monomer 1, and 4,4′-dihydroxybenzophenone was 1:0.01~0.2:0.8~0.99, and the sum of the molar amounts of monomer 1 and 4,4′-dihydroxybenzophenone was equal to the molar amount of 1,1-bis(4-fluorophenyl)-N-phenylmethaneimine. Sulfolane was added as a solvent, toluene was added as a dehydrating agent, and N2O was continuously introduced. 5~2h; then the oil bath temperature is raised to 150~170℃ and toluene is used to remove water for 2~4h. After water removal, the toluene is removed; the oil bath temperature is raised to 220~230℃ and the polymerization reaction is carried out for 15~24h; after the reaction is completed, the mixture is cooled to room temperature, and the mixture is discharged into deionized water to obtain fibrous solid. After pulverization, it is washed with ethanol under reflux 3~5 times, 50~70 minutes each time; then washed with hot water at 70~100℃ 3~5 times, 50~70 minutes each time; finally, it is vacuum dried at 80~100℃ to obtain polyaryl ketone precursor polymer. Its reaction formula and product structure are shown below, where 0.01≤x≤0.2. ; (3) Preparation of polyaryletherketone resin: The polyaryletherketone precursor polymer prepared in step (2) was placed in concentrated sulfuric acid with a mass fraction of 95-98% and stirred at 20-35°C for 24-36 hours to dissolve it. 1 g of the polyaryletherketone precursor polymer was dissolved in 12-18 mL of 98% concentrated sulfuric acid. The solution was then poured into deionized water and washed until the pH reached 6.5-8.5. Finally, the reaction product was vacuum dried at 80-100°C to obtain the polyaryletherketone resin. Its reaction formula and product structural formula are shown below. .

[0008] The polyaryletherketone resin described in this invention can be used in functional membranes, especially in the preparation of polyaryletherketone ion exchange functional membranes. Specifically, the polyaryletherketone resin prepared in step (3) is dissolved in dichloroacetic acid solution to prepare a membrane building solution. The ratio of polyaryletherketone resin to dichloroacetic acid solution is 1g:10~35mL. Then, the membrane is laid by the flow casting method and dried at 75~85℃, 95~105℃ and 110~130℃ for 10~15h respectively to obtain a polyaryletherketone ion exchange functional membrane with a thickness of 10~100μm. Attached Figure Description

[0009] Figure 1 This is the 1H NMR spectrum of 3,6-bis((4-methoxyphenyl)diphenylmethyl)-9H-carbazole prepared in Example 1 (the NMR reagent is deuterated chloroform). Figure 2 This is the 1H NMR spectrum of ((4-((6-bromohexyl)oxy)phenyl)methanetrimethylene)triphenyl prepared in Example 2 (the NMR reagent is deuterated chloroform); Figure 3 This is the 1H NMR spectrum of 3,6-bis((4-methoxyphenyl)diphenylmethyl)-9-(6-(4-triphenylmethylphenoxy)hexyl)-9H-carbazole prepared in Example 3 (the NMR reagent is deuterated chloroform). Figure 4 This is the 1H NMR spectrum of the 4,4'-((9-(6-(4-triphenylmethylphenoxy)hexyl)-9H-carbazole-3,6-diyl)bis(diphenylmethylene))diphenol monomer prepared in Example 4 (the NMR reagent is deuterated chloroform). Figure 5 These are the infrared spectra of the polyaryletherketone precursor polymers and polyaryletherketone resins prepared in Examples 5-8; Figure 6 These are photographs of the three polyaryletherketone ion-exchange functional membranes prepared in Example 9 with different proportions. Detailed Implementation

[0010] Example 1: Preparation of 3,6-bis((4-methoxyphenyl)diphenylmethyl)-9H-carbazole: Carbazole (5.0164 g, 30 mmol) and 4-methoxytriphenylchloromethane (19.4548 g, 63 mmol) were added to a 250 mL three-necked flask, and 1,2-dichlorobenzene (4 mL) was slowly added dropwise. The reaction was carried out at 135 °C for 10 hours under nitrogen protection. After the reaction was completed, 1,2-dichlorobenzene was removed by distillation at 190 °C. The solid was then placed in 600 mL of ethanol, washed four times with ethanol, and dried in a vacuum oven at 75 °C to obtain a purple solid. Finally, the solid was purified by column chromatography using CHCl3 as the eluent, and CHCl3 was removed by rotary evaporation. After vacuum drying, a white solid powder of 3,6-bis((4-methoxyphenyl)diphenylmethyl)-9H-carbazole (compound 1) (7.1 g) was obtained, with a yield of 33.4%. The structural formula of the product is shown below. ; like Figure 1 As shown, the signal peak located at 3.82~3.85 ppm corresponds to the hydrogen atom (-OCH3) in o-methoxyaniline, and the peak shift analysis indicates that compound 1 has been successfully prepared.

[0011] Example 2: Preparation of ((4-((6-bromohexyl)oxy)phenyl)methanetrimethylene)triphenyl: 10.0845 g (30 mmol) of 4-triphenylmethylphenol and 1.85 g (33 mmol) of potassium hydroxide were added to a 250 mL three-necked flask. The solid was dissolved under nitrogen protection using DMF (90 mL) as solvent and an oil bath at 80 °C. Then, 36.5955 g (150 mmol) of 1,6-dibromohexane was added, and heating was stopped after 10 hours. The reaction product was cooled to room temperature and placed in water. After filtration, it was recrystallized from ethanol and dried under vacuum at 80 °C to obtain a white powder ((4-((6-bromohexyl)oxy)phenyl)methanetrimethylene)triphenyl (compound 2) with a yield of 60.1%. The structural formula of the product is shown below. ; like Figure 2 As shown, the H on the alkyl chain of compound 2 1-6 The proton peak is located at 1.3~4.0 ppm, and the H on the phenyl group... 7-11 The proton peak was located at 6.6–7.5 ppm, and peak shift analysis indicated that compound 2 had been successfully prepared.

[0012] Example 3: Preparation of 3,6-bis((4-methoxyphenyl)diphenylmethyl)-9-(6-(4-triphenylmethylphenoxy)hexyl)-9H-carbazole: Compound 1 (1.7499 g, 2 mmol) prepared in Example 1 and Compound 2 (1.0989 g, 2.2 mmol) prepared in Example 2 were placed in a 50 mL three-necked flask. Using DMF as solvent (20 mL), the oil bath temperature was set to 120 °C, and Compound 1 and Compound 2 were dissolved under nitrogen protection. Then, NaOH (0.5599 g) was added sequentially. The reaction mixture was prepared with 14 mmol of NaI (0.0599 g, 0.4 mmol) and 0.1289 g of TBAB (0.4 mmol). Heating was stopped after 10 hours. The reaction product was cooled to room temperature and then poured into ethanol, washed four times with ethanol. It was then dried under vacuum in an oven at 80 °C to give a white solid, 3,6-bis((4-methoxyphenyl)diphenylmethyl)-9-(6-(4-triphenylmethylphenoxy)hexyl)-9H-carbazole (compound 3), with a yield of 79.6%. The structural formula of the product is shown below. ; like Figure 3 As shown, the signal peak of H1 at 3.82~3.85 ppm corresponds to the hydrogen atom (-OCH3) in o-methoxyaniline, and the H on the alkyl chain... 9-14 The proton peak was located at 1.3–4.5 ppm, and peak shift analysis indicated that compound 3 had been successfully prepared.

[0013] Example 4: Preparation of 4,4'-((9-(6-(4-triphenylmethylphenoxy)hexyl)-9H-carbazole-3,6-diyl)bis(diphenylmethylene))diphenol monomer (monomer 1): Compound 3 (0.4 g, 0.36 mmol) prepared in Example 3 was dissolved in CHCl3 (40 mL), and insoluble impurities were removed by filtration. After being placed in an ice bath for half an hour, BBr3 (2 mL) was slowly added dropwise, and the reaction was carried out in an ice bath for 24 hours. Subsequently, the reaction product was placed in water, and the organic phase was washed three times with water and then evaporated to dryness to obtain a yellow powder. The yellow powder was then washed four times with deionized water and ethanol, respectively, and dried under vacuum at 60 °C to obtain yellow powder 4,4'-((9-(6-(4-triphenylmethylphenoxy)hexyl)-9H-carbazole-3,6-diyl)bis(diphenylmethylene))diphenol (monomer 1) with a yield of 80.2%. The structural formula of the product is shown below. ; like Figure 4 As shown, the signal peak of H1 located at 9.30~9.50 ppm corresponds to the hydrogen atom (-OH) of the hydroxyl group. Peak shift analysis indicates that monomer 1 has been successfully prepared.

[0014] Example 5: Preparation of polyaryletherketone precursor polymer (x=0.05, referring to the ratio of the number of moles of monomer 1 / (number of moles of monomer 1 + number of moles of 4,4'-dihydroxydiphenyl ketone) at the time of feeding): Add 0.2756 g (0.25 mmol) of monomer 1, 1.4666 g (5.00 mmol) of 1,1-bis(4-fluorophenyl)-N-phenylmethaneimine, 1.0175 g (4.75 mmol) of 4,4'-dihydroxydiphenyl ketone, and 0.8293 g (6.00 mmol) of anhydrous potassium carbonate to a dry 50 mL three-necked flask. 9 mL of sulfolane was added as a solvent, and 8 mL of toluene was added as a dehydrating agent. N2 was continuously bubbled through the solution for 1 hour. The oil bath was heated to 160°C, and toluene was used to remove water for 3 hours. After dehydration, the toluene was removed. The oil bath temperature was then increased to 220°C, and the polymerization reaction was carried out for 12 hours. After the reaction was completed, the solution was cooled to room temperature, and the resulting mixture was discharged into deionized water to obtain a fibrous solid. After pulverization, the solid was washed four times with ethanol under reflux for 60 minutes each time, followed by four times with hot water at 80°C for 60 minutes each time. Finally, the solid was dried under vacuum at 80°C to obtain the polyaryletherketone precursor polymer with a yield of 94%. Its structural formula is shown below. ; like Figure 5 As shown, at 1032cm -1 and 1068cm -1 The characteristic absorption peak of the sulfonic acid group appeared at 1661 cm⁻¹. -1 The presence of a carbonyl characteristic absorption peak at the point indicates the successful completion of the polymer nucleophilic condensation and subsequent sulfonation reaction, demonstrating the successful preparation of the polyaryletherketone precursor polymer and the polyaryletherketone resin.

[0015] Example 6: Preparation of polyaryletherketone precursor polymer (x=0.075, referring to the ratio of the number of moles of monomer 1 / (number of moles of monomer 1 + number of moles of 4,4'-dihydroxydiphenyl ketone) at the time of feeding): Add 0.4134 g (0.375 mmol) of monomer 1, 1.4666 g (5.0 mmol) of 1,1-bis(4-fluorophenyl)-N-phenylmethaneimine, 0.9908 g (4.625 mmol) of 4,4'-dihydroxydiphenyl ketone, and 0.8293 g (6.0 mmol) of anhydrous potassium carbonate to a dry 50 mL three-necked flask, and add... 12 mL of sulfolane was added to the bottle as a solvent, and 8 mL of toluene was added as a dehydrating agent. N2 was continuously bubbled through the solution for 1 hour. The oil bath was heated to 160 °C, and toluene was used to remove water for 3 hours. After dehydration, the toluene was removed. The oil bath temperature was then increased to 220 °C, and the polymerization reaction was carried out for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, and the resulting mixture was discharged into deionized water to obtain a fibrous solid. After pulverization, the solid was washed four times with ethanol under reflux for 60 minutes each time, followed by four times with hot water at 80 °C for 60 minutes each time. Finally, the solid was vacuum dried at 80 °C to obtain the polyaryletherketone precursor polymer with a yield of 92%. The structural formula of the product is as follows. ; like Figure 5 As shown, at 1032cm -1 and 1068cm -1 The characteristic absorption peak of the sulfonic acid group appeared at 1661 cm⁻¹. -1 The presence of a carbonyl characteristic absorption peak at the point indicates the successful completion of the polymer nucleophilic condensation and subsequent sulfonation reaction, demonstrating the successful preparation of the polyaryletherketone precursor polymer and the polyaryletherketone resin.

[0016] Example 7: Preparation of polyaryletherketone precursor polymer (x=0.1, referring to the ratio of the number of moles of monomer 1 / (number of moles of monomer 1 + number of moles of 4,4'-dihydroxydiphenyl ketone) at the time of feeding): Add 0.3825 g (0.35 mmol) of monomer 1, 1.0276 g (3.5 mmol) of 1,1-bis(4-fluorophenyl)-N-phenylmethaneimine, 0.6748 g (3.15 mmol) of 4,4'-dihydroxydiphenyl ketone, and 0.5805 g (4.2 mmol) of anhydrous potassium carbonate to a dry 50 mL three-necked flask. 7 mL of sulfolane was added as a solvent, and 7 mL of toluene was used as a dehydrating agent. N2 was continuously bubbled through the mixture for 1 hour. The oil bath was heated to 160°C, and toluene was used to remove water for 3 hours. After dehydration, the toluene was removed. The oil bath temperature was then increased to 220°C, and the polymerization reaction was carried out for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, and the resulting mixture was discharged into deionized water to obtain a fibrous solid. After pulverization, the solid was washed four times with ethanol under reflux for 60 minutes each time, followed by four times with hot water at 80°C for 60 minutes each time. Finally, the solid was vacuum dried at 80°C to obtain the polyaryletherketone precursor polymer with a yield of 93%. The structural formula of the product is as follows. ; like Figure 5 As shown, at 1032cm -1 and 1068cm -1 The characteristic absorption peak of the sulfonic acid group appeared at 1661 cm⁻¹. -1 The presence of a carbonyl characteristic absorption peak at the point indicates the successful completion of the polymer nucleophilic condensation and subsequent sulfonation reaction, demonstrating the successful preparation of the polyaryletherketone precursor polymer and the polyaryletherketone resin.

[0017] Example 8: Preparation of polyaryletherketone resin: 1 g of the polyaryletherketone precursor polymers prepared in Examples 5, 6, and 7 were placed in concentrated sulfuric acid (15 mL, 98% by mass) and stirred at 30°C for 30 hours to dissolve. The solutions were then washed in deionized water until the pH reached 7.5. Finally, the products were dried in a vacuum oven at 90°C to obtain the polyaryletherketone resins, where x = 0.05, 0.075, and 0.1, respectively. The structural formulas of the products are shown below. ; like Figure 5 As shown, at 1032cm -1 and 1068cm -1 The characteristic absorption peak of the sulfonic acid group appeared at 1661 cm⁻¹. -1 The presence of a carbonyl characteristic absorption peak at the point indicates the successful completion of the polymer nucleophilic condensation and subsequent sulfonation reaction, demonstrating the successful preparation of the polyaryletherketone precursor polymer and the polyaryletherketone resin.

[0018] Example 9: Preparation of polyaryletherketone (PAE) ion-exchange functional membranes: Three different proportions of PAE resin (0.5 g) prepared in Example 8 were dissolved in dichloroacetic acid solution (15 mL) to prepare a membrane-building solution. The membrane was laid using a cast-line method, i.e., the membrane-building solution was poured onto an 8×8 cm glass plate and dried in ovens at 80℃, 100℃, and 120℃ for 12 h respectively, to obtain PAE ion-exchange functional membranes with a thickness of 50 μm. Figure 6 As shown, this indicates good film-forming properties.

[0019] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle 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 polyaryletherketone resin, characterized in that: Its structural formula is shown below. ； Where 0.01≤x≤0.

2.

2. The method for preparing a polyaryletherketone resin according to claim 1, characterized in that: The steps are as follows: (1) Preparation of 4,4'-((9-(6-(4-triphenylmethylphenoxy)hexyl)-9H-carbazole-3,6-diyl)bis(diphenylmethylene))diol: Carbazole and 4-methoxytriphenylchloromethane were added to a reaction vessel at a molar ratio of 1:2 to 2.

5. Then, 1,2-dichlorobenzene was slowly added dropwise. The reaction was carried out under nitrogen protection at 130–160 °C for 8–15 h. After the reaction was completed, 1,2-dichlorobenzene was removed by distillation at 180–200 °C. The product was then washed 3–5 times with ethanol and dried under vacuum at 70–80 °C to obtain a purple solid. Finally, the product was purified by column chromatography using CHCl3 as the eluent, and CHCl3 was removed by rotary evaporation. After vacuum drying, a white solid powder, 3,6-bis((4-methoxyphenyl)diphenylmethyl)-9H-carbazole, was obtained, denoted as compound 1. 4-Triphenylmethylphenol and potassium hydroxide were added to a reaction vessel and dissolved in DMF under nitrogen protection at an oil bath temperature of 70-100℃. Then, 1,6-dibromohexane was added. The molar ratio of 4-triphenylmethylphenol, potassium hydroxide and 1,6-dibromohexane was 1:1.1-1.3:5-6. Heating was stopped after 8-10 hours. The reaction product was cooled to room temperature and placed in water. After filtration, it was recrystallized with ethanol and then dried under vacuum at 70-90℃ to obtain a white powder ((4-((6-bromohexyl)oxy)phenyl)methanetrimethylene)triphenyl, denoted as compound 2. Compound 1 and Compound 2 were placed in a reaction vessel and dissolved in DMF under nitrogen protection at an oil bath temperature of 100-140℃. Then, NaOH, NaI, and TBAB were added sequentially. The molar ratio of Compound 1, Compound 2, NaOH, NaI, and TBAB was 1:1.1-1.3:7:0.2-0.25:0.2-0.

25. The reaction was carried out for 8-16 hours, after which heating was stopped. After the reaction product cooled to room temperature, it was poured into ethanol and washed 3-5 times with ethanol. Then, it was dried under vacuum at 70-90℃ to obtain a white solid 3,6-bis((4-methoxyphenyl)diphenylmethyl)-9-(6-(4-triphenylmethylphenoxy)hexyl)-9H-carbazole, denoted as Compound 3. Compound 3 was dissolved in CHCl3, and insoluble impurities were removed by filtration. After being placed in an ice bath for 20–40 minutes, BBr3 was slowly added dropwise at a molar ratio of 1:6–10. The reaction was carried out in an ice bath for 12–36 hours. The reaction product was then placed in water, and the organic phase was washed 3–5 times with water and evaporated to dryness. The resulting product was washed 3–5 times with water and ethanol, respectively, and then vacuum dried at 50–70 °C to obtain a yellow powder, 4,4'-((9-(6-(4-triphenylmethylphenoxy)hexyl)-9H-carbazole-3,6-diyl)bis(diphenylmethylene))diol, denoted as monomer 1. Its reaction formula and product structure are shown below. ； (2) Preparation of polyaryletherketone precursor polymers: 1,1-bis(4-fluorophenyl)-N-phenylmethaneimine, monomer 1, 4,4′-dihydroxybenzophenone prepared in step (1), and an amount of anhydrous potassium carbonate (catalyst amount) were added to a dry reaction vessel. The molar ratio of 1,1-bis(4-fluorophenyl)-N-phenylmethaneimine, monomer 1, and 4,4′-dihydroxybenzophenone was 1:0.01~0.2:0.8~0.99, and the sum of the molar amounts of monomer 1 and 4,4′-dihydroxybenzophenone was equal to the molar amount of 1,1-bis(4-fluorophenyl)-N-phenylmethaneimine. Sulfolane was added as a solvent, toluene was added as a dehydrating agent, and N2O was continuously introduced. 5~2h; then the oil bath temperature is raised to 150~170℃ and toluene is used to remove water for 2~4h. After water removal, the toluene is removed; the oil bath temperature is raised to 220~230℃ and the polymerization reaction is carried out for 15~24h; after the reaction is completed, the mixture is cooled to room temperature, and the mixture is discharged into deionized water to obtain fibrous solid. After pulverization, it is washed with ethanol under reflux 3~5 times, 50~70 minutes each time; then washed with hot water at 70~100℃ 3~5 times, 50~70 minutes each time; finally, it is vacuum dried at 80~100℃ to obtain polyaryl ketone precursor polymer. Its reaction formula and product structure are shown below, where 0.01≤x≤0.

2. ； (3) Preparation of polyaryletherketone resin: The polyaryletherketone precursor polymer prepared in step (2) was placed in concentrated sulfuric acid with a mass fraction of 95-98% and stirred at 20-35°C for 24-36 hours to dissolve it. 1 g of the polyaryletherketone precursor polymer was dissolved in 12-18 mL of 98% concentrated sulfuric acid. The solution was then poured into deionized water and washed until the pH reached 6.5-8.

5. Finally, the reaction product was vacuum dried at 80-100°C to obtain the polyaryletherketone resin. Its reaction formula and product structural formula are shown below. 。 3. The application of the polyaryletherketone resin according to claim 1 in the preparation of polyaryletherketone ion exchange functional membranes.

4. The application of the polyaryletherketone resin as described in claim 3 in the preparation of polyaryletherketone ion-exchange functional membranes, characterized in that: Polyaryletherketone resin was dissolved in dichloroacetic acid solution to prepare a membrane-building solution, with the ratio of polyaryletherketone resin to dichloroacetic acid solution being 1g: 10~35mL; then, the membrane was laid by the casting method and dried at 75~85℃, 95~105℃ and 110~130℃ for 10~15h respectively to obtain a polyaryletherketone ion exchange functional membrane with a thickness of 10~100μm.

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