Preparation method of carbazole modified triphenylamine type molecular skeleton alkaline membrane

Abstract

The invention provides a preparation method of a carbazole-modified triphenylamine type molecular skeleton alkaline membrane, and belongs to the technical field of anion exchange membrane fuel cell membranes. Aromatic amine and aryl which can reduce the stacking density and a carbazole derivative with a hydrophobic effect are copolymerized to obtain a carbazole-modified triphenylamine type molecular skeleton alkaline membrane; a poly (carbazole derivative-aromatic amine-aryl-piperidine) polymer skeleton is obtained; the ionic conductivity is improved by reducing the bulk density of the polymer and the series swelling ratio of the membrane; the cationic polymer of the poly (carbazole derivative-aromatic amine-aryl-piperidine) has a structure as shown in a formula (1), introducing carbazole into a polymer skeleton; long-chain alkane is introduced through modification, so that a hydrophilic and hydrophobic microphase separation structure is formed while the swelling ratio is reduced; triethylamine is used for modifying external cations so as to improve the ionic conductivity of the membrane. Iodobutane is adopted in the quaternization step, and the degradation resistance of the membrane is enhanced by increasing steric hindrance. Formula (1): # imgabs0 #

Description

Technical Field

[0001] The present invention belongs to the technical field of anion exchange membrane fuel cell membranes, and particularly relates to a method for preparing a carbazole-modified triphenylamine-type molecular skeleton alkaline membrane. Background Art

[0002] Carbazole is an aromatic heterocyclic compound with excellent chemical stability. Its structure is easily modified, allowing the introduction of various functional groups through reactions such as halogenation and nitration. It is widely used in dyes, pharmaceuticals, pesticides, and photoconductive materials. Carbazole incorporation into AEMs effectively constructs hydrophobic units, reduces the membrane swelling ratio, improves chemical stability, and, through side chain modification, forms a hydrophilic-hydrophobic microphase separation structure, promoting ion transport. For example, AEMs prepared with side chain-modified carbazole exhibit an OH- ion conductivity of 152.9 mS / cm at 80°C, a 26.7% increase compared to membranes without carbazole. Our AEMs, obtained by polymerizing triphenyl groups with carbazole, exhibit an ionic conductivity of 136 mS / cm at 80°C. Our developed flexible side-chain polycarbazole-based AEMs also exhibit excellent chemical properties. This demonstrates that excellent ion conductivity is essential for an efficient hydrophilic-hydrophobic microphase separation structure, and the incorporation of carbazole effectively constructs a well-defined hydrophobic structure. While effectively reducing the membrane swelling ratio and improving chemical stability, the modification also allows for increased cation loading, thereby enhancing ion transport. Furthermore, when an alkyl spacer unit is placed between the quaternary ammonium cation and the polymer backbone, the quaternary ammonium cation exhibits enhanced alkaline stability. Therefore, we modified carbazole with 1,5-dibromopentane and quaternized it with triethylamine, allowing some of the quaternary ammonium cations to be removed from the backbone, thereby improving the alkaline stability of the membrane series.

[0003] Comparing quaternization with iodine butane and iodine methyl ion, AEMs quaternized with iodine butane exhibited the highest IEC (3.37 mmol / g) and the greatest ionic conductivity (128.6 mS / cm at 80°C), and also demonstrated excellent alkaline stability. Extending the alkyl chain from butyl to decyl significantly decreased water absorption and ionic conductivity. Therefore, the alkyl moiety of iodine butane provides a suitable, stable, and substantial steric hindrance, effectively reducing OH- attack on the quaternary ammonium group.

[0004] In summary, carbazole was introduced into the polymer backbone and modified with long-chain alkanes to form a hydrophilic-hydrophobic microphase separation structure while reducing the swelling ratio. Triethylamine was used to modify the external cations to improve the ionic conductivity of the membrane. Iodobutane was used in the quaternization step to enhance the membrane's resistance to degradation by increasing steric hindrance. Therefore, a series of poly(bromopentylcarbazole-triphenylamine-p-terphenyl-piperidine) (BBDPT-xy) alkaline membranes were prepared, and the effects of carbazole modification on membrane properties were studied. Summary of the Invention

[0005] The invention provides a method for preparing a carbazole-modified triphenylamine-type molecular skeleton alkaline film, which solves the problems in the prior art.

[0006] A method for preparing a carbazole-modified triphenylamine-type molecular skeleton alkaline membrane comprises copolymerizing an aromatic amine with reduced bulk density, an aromatic group, and a carbazole derivative with a hydrophobic effect to obtain a poly(carbazole derivative-aromatic amine-aryl-piperidine) polymer skeleton; by reducing the polymer bulk density and the series swelling ratio of the membrane, the ion conductivity is improved; the cationic polymer of the poly(carbazole derivative-aromatic amine-aryl-piperidine) has a structure as shown in formula (1):

[0007]

[0008] As a preferred embodiment, R1 in the structure of formula (1) independently selects one of the following structures:

[0009]

[0010] Wherein a=1, 2, 3, 4, b=1, 2, 3, 4, c=1, 2, 3, 4, and the corresponding bond connections are the connections on the benzene ring.

[0011] As a preferred embodiment, R2 in the formula (1) independently selects one of the following structures:

[0012]

[0013] As a preferred embodiment, R3 in the formula (1) is independently selected from one of the structures in formula (2):

[0014]

[0015] For the R5 structure in R3 in formula (2), one of the following structures is independently selected:

[0016]

[0017] Where: d is any integer value between 1 and 11; e is any integer value between 1 and 3; f is any integer value between 1 and 3; h is any integer value between 1 and 3;

[0018] For the structure of R4 in formula (1), one of the following structures is independently selected:

[0019]

[0020] Wherein: d is any integer value between 1 and 11, and e= is any integer value between 1 and 3.

[0021] As a preferred embodiment, in the formula (1), x is the proportion of aromatic amine fragments in the skeleton, y is the proportion of carbazole derivative fragments in the skeleton, 1-xy is the proportion of aromatic fragments in the skeleton, and the values ​​of x and y are: x>0, y≥0, x+y=1; in the formula (1), n ​​represents the degree of polymerization, and n is an integer between 10 and 1000000.

[0022] As a preferred embodiment, the method for preparing the polymer comprises the following steps:

[0023] Step (1) mixing a compound containing a carbazole fragment structure, a strong base, an organic solvent and a halogenated alkane, and performing a substitution reaction to obtain a polymer precursor having a structure shown in formula (3). The reaction equation is shown in formula (3):

[0024]

[0025] In step (2), an aromatic amine compound containing an R1 fragment structure, an aromatic compound containing an R2 fragment structure, a carbazole derivative containing an R3 fragment structure, a ketone monomer, an organic solvent, and an organic superacid are mixed to undergo a superacid condensation reaction to obtain a polymer precursor having a structure shown in formula (2). The reaction equation is shown in formula (3):

[0026]

[0027] Formula (3);

[0028]

[0029] As a preferred embodiment, the R1 fragment in the formula (2) independently selects one of the following structures:

[0030] Where: a = 1, 2, 3, 4, b = 1, 2, 3, 4, c = 1, 2, 3, 4, the corresponding bond connections are those on the benzene ring;

[0031] As a preferred embodiment, the independently selected R2 segments in the formula (2) have the same structure as the independently selected R2 segments in the formula (1).

[0032] As a preferred embodiment, in step (1) and formula (2), the molar ratio of the aromatic compound to the aromatic amine compound is 1:0-3:1; the ratio of the total moles of the aromatic amine and the aromatic compound to the mole number of N-methyl-4-piperidone is 1:1.1-1:1.2; the reaction time in step (1) is 6 hours, and the temperature is preferably 0°C.

[0033] As a preferred embodiment, in step (2), the polymer precursor having the structure of formula (2) obtained in step (1), an organic solvent, and an alkyl halide having the structure R3 in formula (1) are mixed and reacted to obtain a cationic polymer containing poly(aromatic amine-piperidine-aryl) as shown in formula (1). In step (2), the reaction organic solvent is a mixed solvent of N-methylpyrrolidone and dimethyl sulfoxide in a ratio preferably of 1:1 to 3:1; the reaction time in step (2) is 72 hours and the temperature is 50°C.

[0034] After adopting the above technical solution, the beneficial effects of the present invention are: introducing carbazole into the polymer backbone, introducing long-chain alkanes through modification, forming a hydrophilic-hydrophobic microphase separation structure while reducing the swelling ratio; using triethylamine to modify the external cations to improve the ion conductivity of the membrane; using iodine butane in the quaternization step to enhance the membrane's anti-degradation ability by increasing steric hindrance. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0036] Figure 1 This is the H NMR spectrum of the small molecule 9-(5-bromopentyl)-9H-carbazole (BPHC);

[0037] Figure 2 This is the H-NMR spectrum of the precursor poly(bromopentylcarbazole-triphenylamine-p-terphenyl-piperidine) (BDTMP-xy);

[0038] Figure 3 This is the H NMR spectrum of quaternary ammonium functionalized poly(bromopentylcarbazole-triphenylamine-p-terphenyl-piperidine) (BBDPT-xy);

[0039] Figure 4 This is the infrared spectrum of quaternary ammonium functionalized poly (bromopentylcarbazole-triphenylamine-p-terphenyl-piperidine) (BBDPT-xy);

[0040] Figure 5 This is the UV spectrum of quaternary ammonium functionalized poly (bromopentylcarbazole-triphenylamine-p-terphenyl-piperidine) (BBDPT-xy);

[0041] Figure 6 The water absorption rate of quaternary ammonium functionalized poly (bromopentylcarbazole-triphenylamine-p-terphenyl-piperidine) (BBDPT-xy) varies with temperature;

[0042] Figure 7 The swelling rate of quaternary ammonium functionalized poly (bromopentylcarbazole-triphenylamine-p-terphenyl-piperidine) (BBDPT-xy) changes with temperature;

[0043] Figure 8 The ionic conductivity of quaternary ammonium functionalized poly (bromopentylcarbazole-triphenylamine-p-terphenyl-piperidine) (BBDPT-xy) varies with temperature.

[0044] Figure 9 Schematic diagram of the Arrhenius activation energy of quaternary ammonium functionalized poly(bromopentylcarbazole-triphenylamine-p-terphenyl-piperidine) (BBDPT-xy);

[0045] Figure 10 Schematic diagram of the conductivity change curve over time in the stability test of quaternary ammonium functionalized poly (bromopentylcarbazole-triphenylamine-p-terphenyl-piperidine) (BBDPT-xy);

[0046] Figure 11 This is the H NMR spectrum and degradation mechanism of quaternary ammonium functionalized poly(bromopentylcarbazole-triphenylamine-p-terphenyl-piperidine) (BBDPT-xy) after immersion in 3 mol / L NaOH solution for 2200 hours.

[0047] BPHC is the abbreviation for the small molecule 9-(5-bromopentyl)-9H-carbazole, BDTMP-xy is the abbreviation for the precursor poly(bromopentylcarbazole-triphenylamine-p-terphenyl-piperidine), x represents the proportion of triphenylamine copolymer in the polymer, and y represents the proportion of carbazole derivative copolymer. BBDPT-xy is the abbreviation for quaternary ammonium-functionalized poly(bromopentylcarbazole-triphenylamine-p-terphenyl-piperidine). DETAILED DESCRIPTION

[0048] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts shall fall within the scope of protection of the present invention.

[0049] Example 1

[0050] A method for preparing a carbazole-modified triphenylamine-type molecular skeleton alkaline membrane:

[0051] (1) Synthesis of the small molecule 9-(5-bromopentyl)-9H-carbazole (BPHC);

[0052] Carbazole (5.00 g, 29.94 mmol) was weighed into a three-necked flask and thoroughly stirred to dissolve in 75 mL of tetrahydrofuran. 8.40 g of KOH was then added and the mixture was heated under reflux at 40°C for 20 min under a nitrogen atmosphere. 1,5-Dibromopentane (10.00 g, 44.05 mmol) was then added and stirred thoroughly. The mixture was then heated under reflux for another 12 h under nitrogen. After the reaction, the mixed solution was poured into a beaker and an appropriate amount of deionized water was added. Extraction was performed using dichloromethane three times. The organic phases were combined and washed again with deionized water. The mixture was then dried over anhydrous MgSO₄ and the solvent removed using a rotary evaporator. The column was loaded with a mixture of petroleum ether and 200-mesh silica gel powder, using an eluent ratio of petroleum ether to ethyl acetate = 20:1 to allow the product to elute. After rotary evaporation, 12.27 g of yellow flaky crystals were obtained in a 65.5% yield. 1H NMR (400MHz, DMSO-d6) δ8.14(dt,J=7.8,0.9Hz,2H),7.51(ddd,J=8.3,7.0,1.2Hz,2H),7.43(dt,J=8.2,0.9Hz,2H),7 .27(ddd,J=7.9,7.1,1.0Hz,2H), 4.35(t,J=7.1Hz,2H), 3.38(t,J=6.7Hz,2H), 2.00~1.86(m,4H), 1.61~1.52(m,2H).

[0053] (2) Synthesis of poly(bromopentylcarbazole-p-terphenyl-triphenylamine-piperidine) (BDTMP-xy);

[0054] Taking BDTMP-9-15 as an example, a mixture of TPA (0.124 g, 0.514 mmol), BPHC (0.270 g, 0.858 mmol), and p-terphenyl (1.000 g, 4.30 mmol) was placed in a flask, and 2.50 mL of dichloromethane (DCM) and N-methyl-4-piperidone (0.97 mL, 7.90 mmol) were added. Trifluoroacetic acid (TFA, 0.75 mL) and trifluoromethanesulfonic acid (TFSA, 4.00 mL) were added sequentially in an ice-water bath, and the mixture was stirred continuously for 10 h. (The catalyst dosage, reaction time, and reaction temperature were determined experimentally and are preferred.) Finally, a viscous reaction mixture was obtained, which was precipitated in ethanol. The precipitate was a dark reddish-brown, fibrous solid polymer. After multiple washes in ethanol, it was dried in a vacuum oven at 80°C for later use. Other polymers in the BDTMP-xy series were synthesized using a similar method by adjusting the BPHC content.

[0055] (3) Synthesis of quaternary ammonium functionalized poly(bromopentylcarbazole-p-terphenyl-triphenylamine-piperidine) (BBDPT-xy);

[0056] The preparation process for BBDPT-xy is as follows: (x is the molar ratio of triphenylamine in the backbone, x = 9 (unit %); y is the molar ratio of BPHC in the backbone, y = 0, 5, 10, 15 (unit %).) Taking BBDPT-9-15 as an example, the precursor BDTMP-9-15 (0.3 g) was dissolved in a 1:1 mixture of N-methylpyrrolidone and dimethyl sulfoxide (DMSO). 1.5 mL of iodobutane was slowly added dropwise. After the addition, the mixture was stirred at 50°C for 72 hours. 2 mL of triethylamine was then added and stirring continued at 50°C for another 72 hours. After the reaction was complete, the solution was poured into EA for precipitation. The precipitate was washed several times with EA and DI to remove excess reactants. After multiple washings and filtration, the final product was dried in a vacuum oven at 80°C overnight to obtain BBDPT-9-15 as a light red fibrous solid. By adjusting the content of BPHC, other polymers in the BBDPT-xy series were synthesized using a similar method as described above.

[0057] (4) membrane preparation;

[0058] Taking BBDPT-9-15 as an example, the membrane was prepared using a solution casting method. The dried solid polymer (0.30 g) was placed in a 40 mL beaker, and 10 mL of NMP was added for ultrasonically accelerated dissolution. The completely dissolved solution was then aspirated with a syringe and squeezed through a filter membrane to obtain a clear, translucent solution. The filtered solution was then placed in a Petri dish and the solvent was evaporated at 80°C. After 24 hours, a membrane containing I- and Br- species was obtained. Finally, the membrane was immersed in a NaOH solution for 48 hours to completely exchange the halogen ions in the membrane for OH-. The residual alkaline solution on the membrane surface was then washed with deionized water and the membrane surface was dried. The resulting BBDPT-9-15 alkaline membrane was prepared.

[0059] Example 2

[0060] (1) Synthesis of the small molecule 9-(5-bromopentyl)-9H-carbazole (BPHC);

[0061] Carbazole (5.00 g, 29.94 mmol) was weighed into a three-necked flask and thoroughly stirred to dissolve in 75 mL of tetrahydrofuran. 8.40 g of KOH was then added and the mixture was heated under reflux at 40°C for 20 min under a nitrogen atmosphere. 1,5-Dibromopentane (10.00 g, 44.05 mmol) was then added and stirred thoroughly. The mixture was then heated under reflux for another 12 h under nitrogen. After the reaction, the mixed solution was poured into a beaker and an appropriate amount of deionized water was added. Extraction was performed using dichloromethane three times. The organic phases were combined and washed again with deionized water. The mixture was then dried over anhydrous MgSO₄ and the solvent removed using a rotary evaporator. The column was loaded with a mixture of petroleum ether and 200-mesh silica gel powder, using an eluent ratio of petroleum ether to ethyl acetate = 20:1 to allow the product to elute. After rotary evaporation, 12.27 g of yellow flaky crystals were obtained in a 65.5% yield. 1H NMR (400MHz, DMSO-d6) δ8.14(dt,J=7.8,0.9Hz,2H),7.51(ddd,J=8.3,7.0,1.2Hz,2H),7.43(dt,J=8.2,0.9Hz,2H),7 .27(ddd,J=7.9,7.1,1.0Hz,2H), 4.35(t,J=7.1Hz,2H), 3.38(t,J=6.7Hz,2H), 2.00~1.86(m,4H), 1.61~1.52(m,2H).

[0062] (2) Synthesis of poly(bromopentylcarbazole-p-terphenyl-triphenylamine-piperidine) (BDTMP-xy);

[0063] Taking BDTMP-9-15 as an example, a mixture of TPA (0.124 g, 0.514 mmol), BPHC (0.270 g, 0.858 mmol), and p-terphenyl (1.000 g, 4.30 mmol) was placed in a flask, and 2.50 mL of dichloromethane (DCM) and N-methyl-4-piperidone (0.97 mL, 7.90 mmol) were added. Trifluoroacetic acid (TFA, 0.75 mL) and trifluoromethanesulfonic acid (TFSA, 4.00 mL) were added sequentially in an ice-water bath, and the mixture was stirred continuously for 10 h. (The catalyst dosage, reaction time, and reaction temperature were determined experimentally and are preferred.) Finally, a viscous reaction mixture was obtained, which was precipitated in ethanol. The precipitate was a dark reddish-brown, fibrous solid polymer. After multiple washes in ethanol, it was dried in a vacuum oven at 80°C for later use. Other polymers in the BDTMP-xy series were synthesized using a similar method by adjusting the BPHC content.

[0064] (3) Synthesis of quaternary ammonium functionalized poly(bromopentylcarbazole-p-terphenyl-triphenylamine-piperidine) (DBBDPT-xy) with iodomethane;

[0065] The preparation process for DBBDPT-xy is as follows: (x is the molar ratio of triphenylamine in the backbone, x = 9 (unit %); y is the molar ratio of BPHC in the backbone, y = 0, 5, 10, 15 (unit %).) Taking BBDPT-9-15 as an example, the precursor BDTMP-9-15 (0.3 g) was dissolved in a 1:1 mixture of N-methylpyrrolidone and dimethyl sulfoxide. 1.5 mL of iodomethane was slowly added dropwise. After the addition, the mixture was stirred at 50°C for 72 hours. 2 mL of triethylamine was then added and stirring continued at 50°C for another 72 hours. After the reaction was complete, the solution was poured into EA for precipitation. The precipitate was washed several times with EA and DI to remove excess reactants. After multiple washings and filtration, the final product was dried in a vacuum oven at 80°C overnight to obtain DBBDPT-9-15 as a light red fibrous solid. By adjusting the content of BPHC, other polymers in the DBBDPT-xy series were synthesized using a similar method as described above.

[0066] (4) membrane preparation;

[0067] Taking DBBDPT-9-15 as an example, the membrane was prepared using a solution casting method. The dried solid polymer (0.30 g) was placed in a 40 mL beaker, and 10 mL of NMP was added for ultrasonically accelerated dissolution. The completely dissolved solution was then aspirated with a syringe and squeezed through a filter membrane to obtain a clear, translucent solution. The filtered solution was then placed in a Petri dish and the solvent evaporated at 80°C. After 24 hours, a membrane containing I- and Br- species was obtained. Finally, the membrane was immersed in a NaOH solution for 48 hours to completely exchange the halogen ions in the membrane for OH-. The residual alkaline solution on the membrane surface was then washed with deionized water and the membrane surface was dried. Finally, a DBBDPT-9-15 alkaline membrane was prepared.

[0068] The alkaline membrane of the invention was immersed in 3M NaOH for 2200 hours and then subjected to NMR characterization. Taking BBDPT-9-15 as an example, its NMR results are as follows: Figure 11 As shown, almost no distinct signals are visible. Comparing the 1H NMR spectra before and after immersion reveals only slightly increased signals at 4.83ppm-5.26ppm and 6.55ppm. These weak signals are products of Hofmann degradation of the backbone cations. No other proton peaks are observed, indicating that Hofmann degradation is the primary degradation mechanism for this series of AEMs. This demonstrates that the unique steric hindrance of the triphenylamine unit prevents OH- from entering the cationic groups, and the addition of hydrophobic groups slows the degradation process.

[0069] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing a carbazole-modified triphenylamine-type molecular skeleton alkaline membrane, characterized in that: Aromatic amines with reduced bulk density, aromatic groups, and hydrophobic carbazole derivatives are copolymerized to obtain a poly(carbazole derivative-aromatic amine-aryl-piperidine) polymer skeleton; by reducing the polymer bulk density and the series swelling ratio of the membrane, the ion conductivity is improved; the cationic polymer of poly(carbazole derivative-aromatic amine-aryl-piperidine) has the structure shown in formula (1):

2. The method for preparing a novel triangular pyramidal poly (aromatic amine-piperidine-aryl) skeleton alkaline anion exchange membrane according to claim 1, characterized in that: In the structure of formula (1), R1 independently selects one of the following structures: Wherein a=1, 2, 3, 4, b=1, 2, 3, 4, c=1, 2, 3, 4, and the corresponding bond connections are the connections on the benzene ring.

3. The method for preparing a novel triangular pyramidal poly (aromatic amine-piperidine-aryl) skeleton alkaline anion exchange membrane according to claim 1, characterized in that: In the formula (1), R2 independently selects one of the following structures:

4. The method for preparing a novel triangular pyramidal poly (aromatic amine-piperidine-aryl) skeleton alkaline anion exchange membrane according to claim 1, characterized in that: In the formula (1), R3 is independently selected from one of the structures in formula (2): For the R5 structure in R3 in formula (2), one of the following structures is independently selected: Where: d is any integer value between 1 and 11; e is any integer value between 1 and 3; f is any integer value between 1 and 3; h is any integer value between 1 and 3; For the structure of R4 in formula (1), one of the following structures is independently selected: Wherein: d is any integer value between 1 and 11, and e= is any integer value between 1 and 3.

5. The method for preparing a novel triangular pyramidal poly (aromatic amine-piperidine-aryl) skeleton alkaline anion exchange membrane according to claim 1, characterized in that: In the formula (1), x is the proportion of aromatic amine segments in the skeleton, y is the proportion of carbazole derivative segments in the skeleton, 1-xy is the proportion of aromatic segments in the skeleton, and the values ​​of x and y are: x>0, y≥0, x+y=1; in the formula (1), n ​​represents the degree of polymerization, and n is an integer between 10 and 1,000,000.

6. The method for preparing a novel triangular pyramidal poly (aromatic amine-piperidine-aryl) skeleton alkaline anion exchange membrane according to claim 1, characterized in that: The preparation method of the polymer comprises the following steps: Step (1) mixing a compound containing a carbazole fragment structure, a strong base, an organic solvent and a halogenated alkane, and performing a substitution reaction to obtain a polymer precursor having a structure shown in formula (3). The reaction equation is shown in formula (3): In step (2), an aromatic amine compound containing an R1 fragment structure, an aromatic compound containing an R2 fragment structure, a carbazole derivative containing an R3 fragment structure, a ketone monomer, an organic solvent, and an organic superacid are mixed to undergo a superacid condensation reaction to obtain a polymer precursor having a structure shown in formula (2). The reaction equation is shown in formula (3): Formula (2); Formula (3).

7. The method for preparing a novel triangular pyramidal poly (aromatic amine-piperidine-aryl) skeleton alkaline anion exchange membrane according to claim 1, characterized in that: The R1 fragment in the formula (2) independently selects one of the following structures: Among them: a=1, 2, 3, 4, b=1, 2, 3, 4, c=1, 2, 3, 4, and the corresponding bond connections are the connections on the benzene ring.

8. The method for preparing a novel triangular pyramidal poly (aromatic amine-piperidine-aryl) skeleton alkaline anion exchange membrane according to claim 1, characterized in that: The independent selection of R2 segments in the formula (2) is the same as the independent selection of R2 segments in the formula (1).

9. The method for preparing a novel triangular pyramidal poly (aromatic amine-piperidine-aryl) skeleton alkaline anion exchange membrane according to claim 6, characterized in that: In step (1) and formula (2), the molar ratio of the aromatic compound to the aromatic amine compound is 1:0-3:1; the ratio of the total moles of the aromatic amine and the aromatic compound to the mole of N-methyl-4-piperidone is 1:1.1-1:1.2; the reaction time in step (1) is 6 hours, and the temperature is preferably 0°C.

10. The method for preparing a novel triangular pyramidal poly (aromatic amine-piperidine-aryl) skeleton alkaline anion exchange membrane according to claim 6, characterized in that: In step (2), the polymer precursor having the structure of formula (2) obtained in step (1), an organic solvent, and an alkyl halide having the structure R3 in formula (1) are mixed and reacted to obtain a cationic polymer containing poly(aromatic amine-piperidine-aryl) as shown in formula (1). In step (2), the reaction organic solvent is a mixed solvent of N-methylpyrrolidone and dimethyl sulfoxide in a ratio preferably of 1:1 to 3:1; the reaction time in step (2) is 72 hours and the temperature is 50°C.

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