Anion exchange membranes based on poly(fluorene-p-terphenyl-piperidine) / vinyl polymer semi-interpenetrating network structure and preparation method

Abstract

The application belongs to the field of anion exchange membrane fuel cells, and particularly relates to an anion exchange membrane based on a semi-interpenetrating network structure of poly(fluorene-p-triphenyl-piperidine) / vinyl polymer and a preparation method. A poly(fluorene-p-triphenyl-piperidine) copolymer is first synthesized; after quaternization, QPDTP is obtained; vinyl benzyl chloride and N-methyl piperidine are reacted to obtain Vpip; Vpip, St and AN are dissolved in dimethyl sulfoxide, and then DVB and a QPDTP solution are added for polymerization to obtain a polymer film. Finally, SIPN-AEMs are obtained through ion replacement. The application CQP(Vpip x -AN y -St z ) and QPDTP both contain conductive cation groups, and the cation groups are all piperidine cations, so that the ion exchange capacity, conductivity and long-term alkali resistance are improved, and the semi-interpenetrating network structure ensures the conductivity while being conducive to improving the dimensional stability.

Description

Technical Field

[0001] The present invention belongs to the field of anion exchange membrane fuel cells, and in particular relates to an anion exchange membrane with a semi-interpenetrating network structure based on poly(fluorene-p-terphenyl-piperidine) / vinyl polymer and a preparation method thereof. Background Art

[0002] To address energy shortages, the development of clean energy technologies is being prioritized to address current environmental and energy challenges. Hydrogen, due to its high efficiency and cleanliness, is considered one of the most promising energy sources, and fuel cells are currently the best device for hydrogen energy applications. As a core component of fuel cells, polymer electrolyte membranes can be divided into two categories: proton exchange membranes (PEMs) and anion exchange membranes (AEMs).

[0003] Among them, anion exchange membrane fuel cells (AEMFCs) can operate under high pH conditions and have the advantages of using non-precious metal catalysts and low cost. Ideal AEMs should have good OH transfer performance. - However, in fact, most AEMs are currently facing the problem of OH - Key issues such as low conductivity and poor alkali stability need to be overcome urgently.

[0004] The most commonly used quaternary ammonium salt anion exchange membranes are prone to nucleophilic degradation, Hofmann degradation, and ylide degradation reactions under alkaline conditions, resulting in a serious decline in their performance. Summary of the Invention

[0005] In order to solve the technical problems existing in the prior art, the present invention provides a piperidine-containing SIPN-AEMs and a preparation method thereof. 9,9-dimethylfluorene, p-terphenyl and N-methyl-4-piperidone are subjected to a superacid-catalyzed Friedel-Crafts polymerization reaction to synthesize poly(fluorene-p-terphenyl-piperidine) (PDTP), which is then quaternized to obtain quaternized poly(fluorene-p-terphenyl-piperidine) (QPDTP). QPDTP is then blended with styrene (St), acrylonitrile (AN) and 4-vinyl-1-methyl-piperidinium chloride ionic liquid (Vpip), and divinylbenzene (DVB) is added to obtain SIPN-AEMs based on poly(fluorene-p-terphenyl-piperidine) / vinyl polymer by in-situ polymerization, which is denoted as CQP (Vpip). x -AN y -St z )-QPDTP-H.

[0006] The specific steps for preparing the SIPN-AEMs are as follows:

[0007] (1) Preparation of poly(fluorene-p-terphenyl-piperidine)

[0008] A copolymer, poly(fluorene-p-terphenyl-piperidine) (PDTP), was synthesized via a superacid-catalyzed Friedel-Crafts alkylation reaction. 9,9-Dimethylfluorene, p-terphenyl, and N-methyl-4-piperidone were dissolved in dichloromethane (the molar amount of N-methyl-4-piperidone was 1.1 times the total molar amount of 9,9-Dimethylfluorene and p-terphenyl; the material concentration was controlled at 30-50 wt%). Trifluoroacetic acid (TFA) and trifluoromethanesulfonic acid (TFSA) (volume ratio of 1:7-1:13) were added dropwise in an ice-water bath under nitrogen. The reaction mixture was then stirred in an ice-water bath for 24 hours. After the reaction, the mixture was poured into deionized water and washed with excess NaHCO₃. Finally, the mixture was washed with deionized water until neutral. The polymer was then dried in a vacuum oven at 60°C to obtain the fluorene-containing copolymer, PDTP.

[0009] (2) Quaternization treatment

[0010] The PDTP in step (1) is stirred and dissolved in dimethyl sulfoxide, and then a certain molar ratio of alkyl halide (alkyl halide is 2-bromoethane, 3-bromopropane, 4-bromobutane, 5-bromopentane, 6-bromohexane, 8-bromooctane or 12-bromododecane, etc.; the molar ratio of PDTP to alkyl halide is 1:2 to 1:5) is added. The reaction is carried out at 40-60°C for 48 hours. The product is poured into ethyl acetate for washing, and finally washed with deionized water three times until the product is washed to neutrality. The product is then dried in a vacuum oven at 60°C to obtain QPDTP.

[0011] (3) Preparation of 4-vinylbenzyl-1-methyl-piperidinium chloride (Vpip)

[0012] Dissolve vinylbenzyl chloride and N-methylpiperidine in ethyl acetate at a molar ratio of 1:1 to 1:1.3 in an ice-water bath. Stir the reaction mixture for 24 hours. Pour the white (light yellow) product into excess ethyl acetate and wash three times. Remove the ethyl acetate using a rotary evaporator, collect the product, and refrigerate.

[0013] (4) Cross-linking and film formation

[0014] Dissolve QPDTP in dimethyl sulfoxide to form a homogenous solution. Dissolve Vpip, St, and AN in dimethyl sulfoxide at a specific ratio and stir thoroughly. Then, add a small amount of DVB and QPDTP solution and sonicate to form a homogenous solution. Pour this homogenous film solution into a polytetrafluoroethylene mold and polymerize under a 250nm UV lamp for 45 minutes. The viscous film solution is dried in a 60°C vacuum oven to produce a polymer film.

[0015] Among them, the mass ratio of St to AN is 1:1 to 1:5; the mass ratio of the total mass of Vpip, AN, St and QPDTP is 1:0.4 to 1:2; and DVB is 3% of the total mass of Vpip, St and AN.

[0016] (5) The membrane obtained in step (4) was immersed in a 1M KOH aqueous solution at 60°C for 24 hours to replace the halogen ions in the membrane with OH - The SIPN-AEMs were taken out from the alkaline solution and washed with deionized water several times until neutral. The excess deionized water on the surface of the polymer membrane was wiped dry and stored in the air for future use. The SIPN-AEMs were recorded as CQP (Vpip x -AN y -St z )-QPDTP-H, x, y, z are the mass ratios of Vpip, AN, and St.

[0017] The structural formula of SIPN-AEMs is as follows:

[0018]

[0019] Wherein, n is an integer from 0 to 11, and the ratio of each monomer unit such as m, a, b, and c does not represent the actual number, wherein a+b+c=1, 0 <m<1。

[0020] The piperidine-containing SIPN-AEMs prepared by the present invention can be used in fuel cells.

[0021] Compared with the prior art, the present invention has the following advantages:

[0022] (1) CQP(Vpip x -AN y -St z ) and QPDTP both contain conductive cationic groups, which can increase the ion exchange capacity of SIPN-AEMs and help improve the conductivity of the membrane;

[0023] (2) Trapping QPDTP in CQP (Vpip x -AN y -St z ) in the cross-linked network to form SIPN-AEMs, which is more conducive to constructing a microphase separation structure.

[0024] (3) The design of the semi-interpenetrating network structure not only increases the ion exchange capacity and ensures the conductivity of SIPN-AEMs, but also helps to improve the dimensional stability of SIPN-AEMs;

[0025] (4) The SIPN-AEMs preparation process is simple, efficient, and suitable for large-scale preparation. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 PDTP 1 H NMR spectrum;

[0027] Figure 2 QPDTP 1 H NMR spectrum;

[0028] Figure 3 Vpip 1 H NMR spectrum. DETAILED DESCRIPTION

[0029] The present invention will be further described below with reference to specific embodiments.

[0030] Example 1

[0031] Under ice-water conditions, vinylbenzyl chloride (1.52 g, 10.00 mmol) was weighed into a round-bottom flask, followed by 10 mL of ethyl acetate and then N-methylpiperidine (1.09 g, 11.00 mmol). The mixture was allowed to react for 24 hours. The resulting yellow-white mixture was washed three times with ethyl acetate until the ethyl acetate in the upper layer of the flask was colorless, clear, and transparent. The ethyl acetate was evaporated using a rotary evaporator. Analysis by H-NMR spectroscopy confirmed the successful preparation of the ionic liquid Vpip. The product was stored in the refrigerator.

[0032] Under a nitrogen atmosphere, a 100 mL three-necked round-bottom flask equipped with a mechanical stirrer was charged with 9,9-dimethylfluorene (0.38 g, 2.00 mmol), p-terphenyl (4.14 g, 18.00 mmol), and N-methyl-4-piperidone (2.48 g, 22.00 mmol). Using dichloromethane (8 mL) as the solvent, trifluoroacetic acid (TFA, 1.58 mL) and trifluoromethanesulfonic acid (TFSA, 15.83 mL) were added dropwise at 0°C. The reaction mixture was stirred at 0°C for 24 hours, turning into a dark purple viscous solution. The resulting mixture was then poured into an aqueous solution and washed three times with 1 M aqueous NaHCO₃ and then three times with deionized water until neutral. The resulting pale yellow polymer was dried in a vacuum oven at 60°C. H-NMR spectroscopy confirmed the successful preparation of the PDTP polymer.

[0033] PDTP polymer (1.00 g, 3.10 mmol) was dissolved in 20 ml of dimethyl sulfoxide at 60°C to obtain a pale yellow solution, and the reaction temperature was then lowered to 40°C. Iodomethane (2.20 g, 15.50 mmol) was slowly added dropwise to the PDTP solution and allowed to react in the dark for 48 hours to obtain a brown solution. The brown solution was washed three times with ethyl acetate, dried, and then washed three times with deionized water. The resulting product was dried in a vacuum oven at 60°C. H-NMR spectroscopy analysis confirmed that PDTP had been successfully quaternized.

[0034] Take QPDTP (0.52g) and pour it into a round-bottom flask. Measure 10mL of dimethyl sulfoxide and add it to the flask. Stir in an oil bath at 60°C for 2 hours to fully dissolve. At the same time, take Vpip (0.24g) and dissolve it in 1ml of dimethyl sulfoxide. Add St (0.20g) and AN (0.60g) and stir for 90 minutes. Then add DVB (0.03g) and stir for 10 minutes to obtain a mixed solution. Add the dissolved QPDTP solution and benzoin ethyl ether (0.01g) to the mixed solution and stir for 10 minutes. Obtain a uniform solution by ultrasound. Pour the above-mentioned uniformly mixed membrane solution into a polytetrafluoroethylene mold, polymerize it under a 250nm ultraviolet lamp, and illuminate it for 45 minutes. Then, drop the membrane solution with a certain viscosity evenly on a glass plate and put it into a vacuum oven at 60°C to dry to obtain a fluorene membrane CQP (Vpip 1.2 -AN3-St1)-QPDTP-0.5.

[0035] CQP(Vpip after drying 1.2 -AN3-St1)-QPDTP-0.5 membrane was immersed in 1M KOH solution at 60℃ for 24 hours to make OH - The membrane was then removed from the alkaline solution and immersed in water to wash away excess alkali, and the deionized water was replaced several times until the pH of the solution after washing became about 7. The excess deionized water on the membrane surface was wiped dry and air-dried. SIPN-AEMs were obtained and recorded as CQP (Vpip 1.2 -AN3-St1)-QPDTP-0.5.

[0036] The membrane prepared in the above steps was tested, and the performance parameters were as follows: the ion exchange capacity of the membrane was 1.49 meq g -1 At 80℃, the ionic conductivity reaches 143.09mS cm -1 The membrane has excellent mechanical properties, with a tensile strength of 15.42 MPa at room temperature. After immersing the membrane in deionized water at 80°C for 24 hours, the water absorption rate and swelling degree of the membrane were measured to be 54.09% and 16.26%, respectively. The membrane has good electrical conductivity and good dimensional stability.

[0037] Example 2

[0038] This example is basically the same as Example 1, except that during the blending process, the mass of QPDTP is 0.42 g, and the SIPN-AEMs obtained are recorded as CQP (Vpip 1.2 -AN3-St1)-QPDTP-0.4.

[0039] The performance parameters of the SIPN-AEMs test are as follows: the ion exchange capacity of the membrane is 1.46 meq g -1 At 80℃, the ionic conductivity reaches 108.24mS cm -1 The membrane has excellent mechanical properties, with a tensile strength of up to 17.28 MPa at room temperature. After immersing the membrane in deionized water at 80°C for 24 hours, the water absorption rate of the membrane was measured to be 49.68% and the swelling degree was 15.24%.

[0040] Example 3

[0041] This example is basically the same as Example 1, except that during the blending process, the mass of QPDTP was 0.94 g, and the SIPN-AEMs obtained was recorded as CQP (Vpip 1.2 -AN3-St1)-QPDTP-0.9.

[0042] The performance parameters of the SIPN-AEMs test are as follows: the ion exchange capacity of the membrane is 1.40 meq g -1 The ionic conductivity at 80℃ reached 102.19mS cm -1 The membrane has excellent mechanical properties, with a tensile strength of up to 18.67 MPa at room temperature. After the membrane was immersed in deionized water at 80°C for 24 hours, the water absorption rate of the membrane was measured to be 60.58% and the swelling degree was 19.24%.

[0043] Example 4

[0044] This example is basically the same as Example 1, except that during the blending process, the mass of QPDTP was 2.08 g, and the SIPN-AEMs obtained was recorded as CQP (Vpip 1.2 -AN3-St1)-QPDTP-2.

[0045] The performance parameters of the SIPN-AEMs test are as follows: the ion exchange capacity of the membrane is 1.35 meq g -1 The ionic conductivity at 80℃ reached 88.88mS cm -1, the tensile strength of the membrane at room temperature can reach 21.86 MPa, and after the membrane is immersed in deionized water at 80℃ for 24 hours, the water absorption rate of the membrane is 83.95% and the swelling degree is 25.12%.

[0046] Example 5

[0047] This example is basically the same as Example 1, except that in the blending process, the mass of Vpip is 0.08g (10% of the total mass of AN and St), and the mass of QPDTP is 0.44g, to obtain SIPN-AEMs denoted as CQP(Vpip 0.4 -AN3-St1)-QPDTP-0.5.

[0048] The performance parameters of the prepared SIPN-AEMs are as follows: the ion exchange capacity of the membrane is 1.28 meq g -1 , and the ionic conductivity at 80℃ reaches 62.13 mS cm -1 , the membrane has excellent mechanical properties, the tensile strength at room temperature can reach 14.38 MPa, and after the membrane is immersed in deionized water at 80℃ for 24 hours, the water absorption rate of the membrane is 47.33% and the swelling degree is 17.24%.

[0049] Example 6

[0050] This example is basically the same as Example 1, except that in the blending process, the mass of Vpip is 0.16g (20% of the total mass of AN and St), and the mass of QPDTP is 0.48g, to obtain SIPN-AEMs denoted as CQP(Vpip 0.8 -AN3-St1)-QPDTP-0.5.

[0051] The performance parameters of the prepared SIPN-AEMs are as follows: the ion exchange capacity of the membrane is 1.29 meq g -1 , and the ionic conductivity at 80℃ reaches 64.29 mS cm -1 , the membrane has excellent mechanical properties, the tensile strength at room temperature can reach 15.22 MPa, and after the membrane is immersed in deionized water at 80℃ for 24 hours, the water absorption rate of the membrane is 55.14% and the swelling degree is 18.17%.

[0052] Example 7

[0053] This example is basically the same as Example 1, except that in the PDTP quaternization process, 3-bromopropane is used instead of iodomethane, to obtain SIPN-AEMs.

[0054] The performance parameters of the prepared SIPN-AEMs are as follows: the ion exchange capacity of the membrane is 1.39 meq g-1 The ion conductivity of the membrane reached 96.32 mS cm at 80 °C -1 The membrane has excellent mechanical properties, and the tensile strength at room temperature can reach 14.38 MPa. After the membrane is immersed in deionized water at 80 °C for 24 hours, the water absorption rate of the membrane is 44.28% and the swelling degree is 16.33%.

[0055] Example 8

[0056] This example is basically the same as Example 1, except that 6-bromohexane is used instead of iodomethane in the quaternization process of PDTP, and SIPN-AEMs are obtained.

[0057] The performance parameters of the prepared SIPN-AEMs are as follows: the ion exchange capacity of the membrane is 1.36 meq g -1 The ion conductivity of the membrane reached 88.64 mS cm at 80 °C -1 The membrane has excellent mechanical properties, and the tensile strength at room temperature can reach 17.34 MPa. After the membrane is immersed in deionized water at 80 °C for 24 hours, the water absorption rate of the membrane is 39.56% and the swelling degree is 14.89%.

[0058] Example 9

[0059] This example is basically the same as Example 1, except that 12-bromododecane is used instead of iodomethane in the quaternization process of PDTP, and SIPN-AEMs are obtained.

[0060] The performance parameters of the prepared SIPN-AEMs are as follows: the ion exchange capacity of the membrane is 1.31 meq g -1 The ion conductivity of the membrane reached 84.22 mS cm at 80 °C -1 The membrane has excellent mechanical properties, and the tensile strength at room temperature can reach 20.12 MPa. After the membrane is immersed in deionized water at 80 °C for 24 hours, the water absorption rate of the membrane is 35.22% and the swelling degree is 12.67%.

[0061] Example 10

[0062] This example is basically the same as Example 1, except that the mass of AN and St is 0.4 g in the preparation of CQP(Vpip 1.2 -AN1-St1), and the rest remains unchanged.

[0063] The membrane is difficult to dry and partially dissolves in water, and cannot be measured.

[0064] Comparative Example 1

[0065] This comparative example provides a method for preparing AEMs, which is prepared according to the method of Example 1, except that QPDTP is not incorporated into the crosslinked network.

[0066] Vpip was prepared according to Example 1. Vpip (0.24 g) was dissolved in 1 mL of dimethyl sulfoxide, St (0.20 g) and AN (0.60 g) were added and stirred for 90 min, DVB (0.03 g) and benzoin ethyl ether (0.01 g) were added and stirred for 10 min, and a uniform solution was obtained by ultrasonic. The above membrane solution was poured into a polytetrafluoroethylene mold, and polymerization was carried out under a 250 nm ultraviolet lamp for 30 min. After that, the membrane solution with certain viscosity was evenly dropped on a glass plate and placed in a 60°C vacuum oven for drying, obtaining a membrane. Then the dried membrane was soaked in 1M KOH at 60°C for 24 hours to complete the replacement of OH - , and then the membrane was taken out, soaked in water to wash off the excess alkali, and the surface of the membrane was wiped dry with deionized water and air dried, obtaining AEMs, which is denoted as CQP(Vpip 1.2 -AN3-St1).

[0067] The performance parameters of the prepared AEMs are as follows: the ion exchange capacity of the membrane is 1.21 meq g -1 , the ion conductivity at 80°C reaches 27.24 mS cm -1 , the tensile strength at room temperature can reach 10.82 MPa, and the water absorption is 252.42% and the swelling degree is 52.33%.

[0068] Comparative Example 2

[0069] This example provides a method for preparing AEMs, which is prepared according to the method of Example 1, except that QPDTP is used alone to form a membrane in this example.

[0070] QPDTP was prepared according to Example 1. QPDTP (0.50 g) was dissolved in 10 mL of dimethyl sulfoxide, and then the membrane solution was evenly dropped on a glass plate and placed in a 60°C vacuum oven for drying, obtaining a membrane. Then the dried membrane was soaked in 1M KOH at 60°C for 24 hours to complete the replacement of OH - , and then the membrane was taken out, soaked in water to wash off the excess alkali, and the surface of the membrane was wiped dry with deionized water and air dried, obtaining AEMs, which is denoted as QPDTP.

[0071] The performance parameters of the prepared AEMs are as follows: the ion exchange capacity of the membrane is 1.32 meq g -1 , the ion conductivity at 80°C reaches 78.49 mS cm -1The tensile strength at room temperature can reach 25.15MPa, and it has a water absorption rate of 30.11% and a swelling degree of 9.19%.

[0072] The above implementation cases are intended to illustrate the design concept of the present invention. In addition, it should be understood that after reading the description of the present invention, researchers in this field can implement and modify the present invention, but this should not constitute a limitation on the scope of protection of the present invention.

Claims

1. An anion exchange membrane based on a semi-interpenetrating network structure of poly(fluorene-p-terphenyl-piperidine) / vinyl polymer, characterized in that: The steps of the preparation method of the anion exchange membrane are as follows: (1) Preparation of poly(fluorene-p-terphenyl-piperidine) 9,9-Dimethylfluorene, p-terphenyl, and N-methyl-4-piperidone were dissolved in dichloromethane, and trifluoroacetic acid and trifluoromethanesulfonic acid were added dropwise in an ice-water bath under nitrogen protection. The reaction mixture was then stirred in an ice-water bath for 24 hours. After the reaction, the mixture was poured into deionized water and washed with NaHCO3. Finally, it was washed with deionized water until neutral. The polymer was then dried in a vacuum oven at 60°C to obtain a fluorene-containing copolymer PDTP. (2) Quaternization treatment The PDTP in step (1) was stirred and dissolved in dimethyl sulfoxide, and then an alkyl halide was added. After the reaction, the product was poured into ethyl acetate for washing, and finally washed with deionized water for 3 times until the product was washed to neutrality. The product was then dried in a vacuum oven at 60°C to obtain QPDTP; (3) Preparation of 4-vinylbenzyl-1-methylpiperidinium chloride (Vpip) Dissolve vinylbenzyl chloride and N-methylpiperidine in ethyl acetate in an ice-water bath according to the molar ratio. Stir the reaction mixture for 24 hours. Pour the white / light yellow product into ethyl acetate and wash three times. Remove the ethyl acetate using a rotary evaporator. Collect the product and store it in a refrigerator. (4) Cross-linking and film formation QPDTP was dissolved in dimethyl sulfoxide to form a homogeneous solution; Vpip, St, and AN were dissolved in dimethyl sulfoxide (DMSO) according to their mass ratios. After thorough stirring, DVB and QPDTP solutions were added and ultrasonicated to obtain a homogeneous solution. The ultrasonicated solution was poured into a polytetrafluoroethylene mold and polymerized under a 250 nm UV lamp for 45 minutes before drying in a 60°C vacuum oven to obtain a polymer film. (5) The membrane obtained in step (4) was immersed in a 1 M KOH aqueous solution at 60°C for 24 hours to replace the halogen ions in the membrane with OH - The SIPN-AEMs were removed from the alkaline solution and washed with deionized water until neutral. The excess deionized water on the surface of the polymer membrane was wiped dry and stored in the air for later use. The SIPN-AEMs were recorded as CQP (Vpip x -AN y -St z )-QPDTP-H, x, y, z are the mass ratios of Vpip, AN, and St.

2. The anion exchange membrane based on a semi-interpenetrating network structure of poly(fluorene-p-terphenyl-piperidine) / vinyl polymer according to claim 1, characterized in that: In step (1), the molar amount of N-methyl-4-piperidone is 1.1 times the total molar amount of 9,9-dimethylfluorene and p-terphenyl; and the material concentration is controlled at 30-50 wt%.

3. The anion exchange membrane based on a semi-interpenetrating network structure of poly(fluorene-p-terphenyl-piperidine) / vinyl polymer according to claim 1, characterized in that: In step (1), the volume ratio of trifluoroacetic acid to trifluoromethanesulfonic acid is 1:7 to 1:

13.

4. The anion exchange membrane based on a semi-interpenetrating network structure of poly(fluorene-p-terphenyl-piperidine) / vinyl polymer according to claim 1, characterized in that: In step (2), the alkyl halide is 2-bromoethane, 3-bromopropane, 4-bromobutane, 5-bromopentane, 6-bromohexane, 8-bromooctane or 12-bromododecane, and the molar ratio of PDTP to the alkyl halide is 1:2 to 1:

5.

5. The anion exchange membrane based on a semi-interpenetrating network structure of poly(fluorene-p-terphenyl-piperidine) / vinyl polymer according to claim 1, characterized in that: In step (2), the reaction temperature is 40-60°C and the reaction time is 48 hours.

6. The anion exchange membrane based on a semi-interpenetrating network structure of poly(fluorene-p-terphenyl-piperidine) / vinyl polymer according to claim 1, characterized in that: In step (3), the molar ratio of vinylbenzyl chloride to N-methylpiperidine is 1:1 to 1:1.

3.

7. The anion exchange membrane based on a semi-interpenetrating network structure of poly(fluorene-p-terphenyl-piperidine) / vinyl polymer according to claim 1, characterized in that: In step (4), the mass ratio of St to AN is 1:1 to 1:5; the mass ratio of the total mass of Vpip, AN, and St to QPDTP is 1:0.4 to 1:2; and DVB is 3% of the total mass of Vpip, St, and AN.

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