Imino conjugated microporous polymer with high specific surface area and high conjugation degree as well as preparation method and application of imino conjugated microporous polymer

Abstract

The invention relates to an imino conjugated microporous polymer with high specific surface area and high conjugation degree as well as a preparation method and application of the imino conjugated microporous polymer. The imino conjugated microporous polymer with high specific surface area and high conjugation degree is synthesized based on a one-pot two-reaction of a Buchwald-Hartwh carbon-nitrogen coupling reaction and a Suzuki-Mipu carbon-carbon coupling reaction. Under the alkaline condition, the proportion of two monomers, namely aryl bromide and arylamine, is kept unchanged, and the specific surface area, the active sites and the conjugation degree can be effectively increased by introducing the boric acid monomers to carry out Suzuki-Miura C-C coupling reaction. The method is simple to operate, and the obtained conjugated microporous polymer with high specific surface area, high conjugation and high oxidation-reduction property has huge application potential in energy storage electrode materials, supercapacitors and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of microporous polymers, and particularly relates to an imine-based conjugated microporous polymer with high specific surface area and high conjugation degree, and a preparation method and application thereof. Background Art

[0002] Supercapacitors have been widely used in various fields due to their high power density and long life, such as electric vehicles, energy recovery systems, and devices with high instantaneous power requirements. Its working principle mainly utilizes the electrode and electrolyte interface to form an electric double layer to store charge, while the electrochemical reaction of the electrode material (such as redox reaction) can increase the total capacitance of the capacitor. The high specific surface area of ​​the electrode material can provide more active sites in a limited space, thereby achieving the purpose of increasing the total capacitance. Therefore, the preparation of electrode materials with high redox properties and high specific surface area is crucial to improving the performance of supercapacitors.

[0003] The imine-based conjugated microporous polymers (NCMPs) synthesized based on the Buchwald-Hartwig coupling reaction have excellent microporous structures and polyaniline-like high redox activity. These characteristics help to improve the double electric layer and pseudocapacitive reaction active sites of supercapacitor electrodes, thereby improving the capacitance and energy density of capacitors. It is a potential high-performance electrode material for capacitor energy storage. For example, CN201910753898 discloses a high redox spirobifluorene-based NCMPs prepared based on the Buchwald-Hartwig coupling reaction, which has good electrochemical properties. However, due to the easy distortion of the imine bond generated by the Buchwald-Hartwig coupling reaction and low planarity, it is often difficult to give NCMPs superior specific surface area and conjugation degree, which reduces the utilization rate of the active sites of the NCMPs electrode and the low cycle stability, limiting its further application in energy storage devices. Therefore, it is still challenging to prepare CMPs capacitor energy storage electrode materials with high specific surface area, high conjugation and high redox. Summary of the invention

[0004] The present invention provides an imine-based conjugated microporous polymer with high specific surface area and high conjugation degree, and a preparation method and application thereof, which further increases the specific surface area and conjugation degree of the conjugated microporous polymer while maintaining the high electrochemical redox property of the conjugated microporous polymer.

[0005] To achieve the above purpose, the present invention introduces a third monomer, a boric acid monomer, and further crosslinks the NCMPs based on the CC coupling of the Suzuki-Miyaura reaction. The present invention adopts one of the following technical solutions;

[0006] The invention discloses an imine-based conjugated microporous polymer with high specific surface area and high conjugation degree, wherein the structural formula of the polymer is as follows:

[0007]

[0008] The imine-based conjugated microporous polymer with high specific surface area and high conjugation degree of the present invention has the excellent characteristics of high specific surface area, high conjugation degree and multiple specific adsorption active sites compared to the imine-based conjugated microporous polymer. The imine-based conjugated microporous polymer prepared by one-pot two reactions has the excellent characteristics of high specific surface area, high conjugation degree and multiple specific adsorption active sites.

[0009] A method for preparing an imine-based conjugated microporous polymer with high specific surface area and high conjugation degree, wherein aromatic bromide, aromatic amine and boric acid monomers are synthesized in one pot through Buchwald-Hartwig coupling reaction and Suzuki-Miyaura reaction.

[0010] Preferably, the aromatic bromide monomer of the present invention is one of 2,2'-7,7'-tetrabromo-9,9'-spirobifluorene, 1,2,4,5-tetrabromobenzene, 1,3,6,8-tetrabromopyrene, etc.; the aromatic amine monomer is one of p-phenylenediamine, m-phenylenediamine, 2-nitro-1,4-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, etc.; the boric acid is one of 3-aminophenylboric acid, 3-bromophenylboric acid, 3-chlorophenylboric acid, 3-hydroxyphenylboric acid, etc.

[0011] Preferably, the solvent used in the Buchwald-Hartwig coupling reaction and the Suzuki-Miyaura reaction of the present invention is at least one of tetrahydrofuran, toluene, dioxane, acetonitrile, etc.; the palladium catalyst used is at least one of bis(dibenzylideneacetone)palladium, palladium acetate, bis(acetonitrile)palladium dichloride (II), bis(triphenylphosphine)palladium chloride, etc.; the ligand is at least one of 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, tri(o-methylphenyl)phosphine, 2-dicyclohexylphosphino-2'-(N,N-dimethylamino)biphenyl, etc.; the alkali used is at least one of sodium tert-butoxide, potassium tert-butoxide, etc.

[0012] Preferably, the molar ratio of the aromatic bromide monomer to the aromatic amine monomer of the present invention is 1:2, and the amount of the boric acid monomer added is 0%-50% of the molar ratio of the aromatic amine monomer.

[0013] Preferably, the coupling reaction system of the present invention is placed in a Schlenk tube and regulated according to the boiling point temperature of the solvent under a N2 atmosphere, and the reaction time is controlled to be 24-72 hours. The molar amounts of the palladium catalyst, ligand, and alkali in the coupling reaction are calculated according to 2%, 3%, and 133% of the theoretical molar amount of hydrogen bromide, respectively.

[0014] Preferably, the amount of the boric acid monomer added in the present invention is 20%, 30%, or 50% of the amine monomer.

[0015] Preferably, the ratio of the volume of the solvent to the amount of the aromatic bromide in the present invention is 200 mL:1 mmoL.

[0016] Preferably, the coupling reaction of the present invention is placed in a Schlenk tube and reacted at 65° C. for 24-48 h under a N 2 atmosphere.

[0017] Preferably, in the preparation method of the present invention, after the reaction is completed, the powder obtained by filtration is washed with N,N-dimethylformamide, water and chloroform, and finally dried in a vacuum drying oven for 24 hours to obtain an imine-based conjugated microporous polymer with a high specific surface area and a high degree of conjugation.

[0018] Disclosed is an imine-based conjugated microporous polymer with high specific surface area and high conjugation degree and its application in energy storage electrode materials and supercapacitors.

[0019] The technical solution of the present invention has the following advantages compared with the prior art:

[0020] (1) The present invention adopts a one-pot two-step method (Buchwald-Hartwig coupling reaction and Suzuki-Miyaura reaction) to prepare an imine-based conjugated microporous polymer with a high specific surface area and a high degree of conjugation; and explores the difference in the performance of the obtained polymer at a content of 0%-50% of the boric acid monomer. The results show that when the addition amount of the phenylboronic acid monomer is 20%, 30% and 50%, the specific capacitance and cycle stability of the obtained polymer material are improved compared with the performance of the unmodified polymer;

[0021] (2) The innovation of the present invention is that the two monomers are kept unchanged, and the introduction of a third monomer for Suzuki-Miyaura CC coupling can effectively increase the specific surface area, active sites and degree of conjugation.

[0022] (3) The present invention has a simple operation process. The one-pot method uses two reactions to achieve NCMPs while maintaining high redox properties, while also having improved conjugation degree, specific surface area and active sites, thereby improving the capacity and cycle stability of the electrode material, making it have good application prospects in supercapacitors. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 Fourier transform infrared spectra of the imino-conjugated microporous polymer (NCMP) synthesized in Example 1, the imino-conjugated microporous polymer (SNCMP2) with high specific surface area and high conjugation degree, and monomers 2,2'-7,7'-tetrabromo-9,9'-spirobifluorene (SF), p-phenylenediamine (TBA) and 3-aminophenylboronic acid (ABA);

[0024] Figure 2 The Fourier transform infrared spectrum of the imine-based conjugated microporous polymer (SNCMPs) synthesized by one-pot two-reaction in Example 1-4;

[0025] Figure 3The N2 adsorption-desorption curves of the polymer SNCMPs at 77.4K were obtained for Examples 1-4;

[0026] Figure 4 The pore size distribution curve of N2 of polymer SNCMPs at 77.4K was obtained for Examples 1-4;

[0027] Figure 5 The UV-visible diffuse reflectance spectra of polymer SNCMPs obtained for Examples 1-4;

[0028] Figure 6 The charge-discharge curves of polymer SNCMPs obtained for Examples 1-4;

[0029] Figure 7 The cyclic test curves of polymer SNCMPs were obtained for Examples 1-4. DETAILED DESCRIPTION

[0030] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall within the scope limited by the appended claims of the application equally.

[0031] An imine-based conjugated microporous polymer with high specific surface area and high conjugation degree, the structural formula of the polymer is as follows:

[0032]

[0033] The imine-based conjugated microporous polymer with high specific surface area and high conjugation degree of the present invention has the excellent characteristics of high specific surface area, high conjugation degree and multiple specific adsorption active sites compared to the imine-based conjugated microporous polymer. The imine-based conjugated microporous polymer prepared by one-pot two reactions has the excellent characteristics of high specific surface area, high conjugation degree and multiple specific adsorption active sites.

[0034] A method for preparing an imine-based conjugated microporous polymer with high specific surface area and high conjugation degree, wherein aromatic bromide, aromatic amine and boric acid monomers are synthesized in one pot through Buchwald-Hartwig coupling reaction and Suzuki-Miyaura reaction.

[0035] The aromatic bromide monomer of the present invention is one of 2,2'-7,7'-tetrabromo-9,9'-spirobifluorene, 1,2,4,5-tetrabromobenzene, 1,3,6,8-tetrabromopyrene, etc.; the aromatic amine monomer is one of p-phenylenediamine, m-phenylenediamine, 2-nitro-1,4-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, etc.; the boric acid is one of 3-aminophenylboric acid, 3-bromophenylboric acid, 3-chlorophenylboric acid, 3-hydroxyphenylboric acid, etc.

[0036] The solvent used in the Buchwald-Hartwig coupling reaction and the Suzuki-Miyaura reaction of the present invention is at least one of tetrahydrofuran, toluene, dioxane, acetonitrile and the like; the palladium catalyst used is at least one of bis(dibenzylideneacetone)palladium, palladium acetate, bis(acetonitrile)palladium dichloride (II), bis(triphenylphosphine)palladium chloride and the like; the ligand is at least one of 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, tri(o-methylphenyl)phosphine, 2-dicyclohexylphosphino-2'-(N,N-dimethylamino)biphenyl and the like; and the alkali agent used is at least one of sodium tert-butoxide, potassium tert-butoxide and the like.

[0037] The molar ratio of the aromatic bromide monomer to the aromatic amine monomer of the present invention is 1:2, the amount of the boric acid monomer added is 0%-50% of the molar ratio of the aromatic amine monomer, the amount of the boric acid monomer added is 20%, 30%, and 50% of the amine monomer, and the ratio of the solvent volume to the amount of the aromatic bromide is 200mL:1mmoL.

[0038] The coupling reaction system of the present invention is placed in a Schlenk tube and regulated according to the boiling point temperature of the solvent under a N2 atmosphere, and the reaction time is controlled to be 24-72 hours. The molar amounts of the palladium catalyst, the ligand, and the alkali agent in the coupling reaction are calculated according to 2%, 3%, and 133% of the theoretical molar amount of hydrogen bromide, respectively.

[0039] The coupling reaction of the present invention is placed in a Schlenk tube and reacted at 65° C. for 24-48 hours under a N 2 atmosphere.

[0040] The preparation method of the present invention comprises the following steps: after the reaction is completed, the powder obtained by suction filtration is washed with N,N-dimethylformamide, water and chloroform, and finally dried in a vacuum drying oven for 24 hours to obtain an imine-based conjugated microporous polymer with a high specific surface area and a high degree of conjugation.

[0041] Disclosed is an imine-based conjugated microporous polymer with high specific surface area and high conjugation degree and its application in energy storage electrode materials and supercapacitors.

[0042] The 2,2'-7,7'-tetrabromo-9,9'-spirobifluorene, Pd(dba)2 and XPhos used in the present invention were purchased from Shanghai Bid Pharmaceutical Technology Co., Ltd.; p-phenylenediamine and sodium tert-butoxide were purchased from Sinopharm Chemical Reagent Co., Ltd.; and 3-aminophenylboronic acid was purchased from Shanghai MacLean Biochemical Technology Co., Ltd.

[0043] Example 1

[0044] First, 2,2'-7,7'-tetrabromo-9,9'-spirobifluorene (SF, 252.8 mg, 0.15 mmoL), p-phenylenediamine (TBA, 88.6 mg, 0.3 mmoL), Pd(dba)2 (18.4 mg, 0.032 mmoL), XPhos (23.3 mg, 0.048 mmoL), sodium tert-butoxide (204.3 mg, 2.128 mmoL) were placed in a 1 00mL Schlenk tube was evacuated and backfilled with nitrogen three times. Next, 40ml of tetrahydrofuran was added into the Schlenk tube and stirred to disperse evenly. Then, the reaction device was reacted at 65°C for 48h. After the reaction, it was filtered in a sand core funnel and then washed with DMF, water and chloroform for 12h each. Finally, it was dried in a vacuum drying oven at 60°C for 24h to obtain an imine-based conjugated microporous polymer, which was recorded as NCMP.

[0045] like Figure 1 As shown, at 1509cm -1 and 1460cm -1 The stretching vibration of the benzene ring caused by the aniline structure and the vibration of the benzene ring skeleton caused by the spirobifluorene structure were observed, indicating that NCMP has the structure of both TBA and SF. -1 The intensity of the characteristic peak of C-Br bond at 1277cm -1 The CN bond was observed at , proving the successful Buchwald-Hartwig coupling reaction. Figure 3 As shown, the specific surface area of ​​NCMP is 587m 2 g -1 The charge-discharge curve (GCD) and cycle test of NCMP obtained in this example are as follows: Figure 6 and Figure 7 As shown, at a current density of 1Ag -1 The specific capacitance is 725Fg -1 , the capacitance retention rate is 44.6% after 6000 cycles.

[0046] Example 2

[0047] First, 2,2'-7,7'-tetrabromo-9,9'-spirobifluorene (SF, 252.8 mg, 0.15 mmoL), p-phenylenediamine (TBA, 88.6 mg, 0.3 mmoL), 3-aminophenylboronic acid (ABA, 8.2 mg, 0.06 mmol), Pd(dba)2 (18.4 mg, 0.032 mmoL), XPhos (23.3 mg, 0.048 mmoL), tert-butyl Sodium alcoholate (204.3 mg, 2.128 mmol) was placed in a 100 mL Schlenk tube, and vacuumed and backfilled with nitrogen three times. Next, 40 ml of tetrahydrofuran was added to the Schlenk tube and stirred to disperse evenly. Then, the reaction device was reacted at 65 ° C for 48 hours. After the reaction, it was filtered in a sand core funnel, and then washed with DMF, water, and chloroform for 12 hours each, and finally dried in a vacuum drying oven at 60 ° C for 24 hours. The imine-based conjugated microporous polymer synthesized by one-pot two-step reaction was obtained, which was recorded as SNCMP1.

[0048] The infrared test graph of SNCMP1 obtained in this example is shown in Figure 2, and the characteristic peaks are basically the same as the infrared spectrum of NCMP obtained in Example 2. Figure 1 To. Figure 3 As shown, the specific surface area of ​​SNCMP1 is 627m 2 g -1 , which is higher than the specific surface area of ​​Example 1. Figure 5 The UV-visible diffuse reflectance spectra of NCMP and SNCMP1 show that SNCMP1 has a wider visible light absorption wavelength than NCMP, which means that the conjugation degree of SNCMP1 is higher than that of NCMP. The GCD and cycle tests of SNCMP1 obtained in this example are shown in Figure 2. Figure 6 and Figure 7 As shown, at a current density of 1Ag -1 The specific capacitance is 972Fg -1 After 6000 cycles, the capacitance retention rate is 75.7%. It is obvious that the specific capacitance of SNCMP1 is increased by 247Fg relative to NCMP. -1 , the cycle stability performance is improved by 31.1%.

[0049] Example 3

[0050] First, 2,2'-7,7'-tetrabromo-9,9'-spirobifluorene (SF, 252.8 mg, 0.15 mmoL), p-phenylenediamine (TBA, 88.6 mg, 0.3 mmoL), 3-aminophenylboronic acid (ABA, 12.3 mg, 0.09 mmol), Pd(dba)2 (18.4 mg, 0.032 mmoL), XPhos (23.3 mg, 0.048 mmoL), tert-butyl Sodium alcoholate (204.3 mg, 2.128 mmol) was placed in a 100 mL Schlenk tube, and vacuumed and backfilled with nitrogen three times. Next, 40 ml of tetrahydrofuran was added to the Schlenk tube and stirred to disperse evenly. Then, the reaction device was reacted at 65 ° C for 48 hours. After completion, it was filtered in a sand core funnel, and then washed with DMF, water, and chloroform, respectively, for 12 hours each, and finally dried in a vacuum drying oven at 60 ° C for 24 hours. The imine-based conjugated microporous polymer synthesized by one-pot two-step reaction was obtained, which was recorded as SNCMP2.

[0051] The infrared test results of SNCMP2 obtained in this embodiment are as follows: Figure 1 As shown, at 1509cm -1 and 1460cm -1 The stretching vibration of the benzene ring caused by the aniline structure and the vibration of the benzene ring skeleton caused by the spirobifluorene structure were observed, indicating that SNCMP2 has both TBA and SF structures. -1 The weakening of the C-Br bond at 1277 cm -1 The presence of a CN bond at 3355 cm -1 The stretching vibration of the -OH bond of boric acid was observed at 1382 cm -1 (CB stretching vibration) and 1044cm -1 The new peak at 827 cm-1 (BO stretching vibration) indicates the presence of a third monomer in SNCMP3. -1 The red shift of the characteristic peak at indicates that the conjugation degree of SNCMPs is enhanced, which may be due to the CC coupling reaction leading to more extensive π electron delocalization, thereby increasing the conjugation degree. Figure 3 As shown, the specific surface area of ​​SNCMP2 is 867 m 2 g -1 , which is higher than the specific surface area of ​​Example 1. Figure 5 The UV-visible diffuse reflectance spectra of NCMP and SNCMP2 show that SNCMP2 has a wider visible light absorption wavelength than NCMP, which means that the conjugation degree of SNCMP2 is higher than that of NCMP, which will affect the electrochemical performance of the electrode material. The GCD and cycle tests of SNCMP2 obtained in this example are as follows: Figure 6 and Figure 7 As shown, at a current density of 1Ag -1 The specific capacitance is 1035Fg -1 After 6000 cycles, the capacitance retention rate is 86.3%. It is obvious that the specific capacitance of SNCMP2 is increased by 310Fg relative to NCMP. -1 , the cycle stability performance is improved by 41.7%.

[0052] Example 4

[0053] First, 2,2'-7,7'-tetrabromo-9,9'-spirobifluorene (SF, 252.8 mg, 0.15 mmoL), p-phenylenediamine (TBA, 88.6 mg, 0.3 mmoL), 3-aminophenylboronic acid (ABA, 20.5 mg, 0.15 mmol), Pd(dba)2 (18.4 mg, 0.032 mmoL), XPhos (23.3 mg, 0048 mmoL), tert-butyl Sodium alcoholate (204.3 mg, 2.128 mmol) was placed in a 100 mL Schlenk tube, and vacuumed and backfilled with nitrogen three times. Next, 40 ml of tetrahydrofuran was added to the Schlenk tube and stirred to disperse evenly. Then, the reaction device was reacted at 65 ° C for 48 hours. After the reaction, it was filtered in a sand core funnel, and then washed with DMF, water, and chloroform for 12 hours each, and finally dried in a vacuum drying oven at 60 ° C for 24 hours. The imine-based conjugated microporous polymer synthesized by one-pot two-step reaction was obtained, which was recorded as SNCMP3.

[0054] The SNCMP3 infrared test obtained in this embodiment is as follows Figure 2 The characteristic peaks are basically the same as those of the SNCMP2 infrared spectrum obtained in Example 3. Figure 1 The specific surface area of ​​SNCMP3 obtained in this embodiment is tested as follows Figure 3 As shown, the specific surface area of ​​SNCMP3 is 568m 2 g -1 .like Figure 5 The UV-visible diffuse reflectance spectra of NCMP and SNCMP3 show that SNCMP3 has a wider visible light absorption wavelength than NCMP in Example 1, indicating that the conjugation degree of SNCMP3 is higher than that of NCMP, which will affect the electrochemical properties of the electrode material. The GCD and cycle tests of SNCMP3 obtained in this example are as follows: Figure 6 and Figure 7 As shown, at a current density of 1Ag -1 The specific capacitance is 897Fg -1, after 6000 cycles, the capacitance retention rate is 77.8%. From the infrared test of SNCMP3 obtained in Example 4, it can be seen that boric acid is successfully introduced into CMP, which will also affect the electrochemical properties of the material. It is obvious that the specific capacitance of SNCMP3 is increased by 172Fg relative to NCMP. -1 , the cycle stability performance is improved by 33.2%. CN111484614A discloses a conjugated microporous polymer with 3+3 structural units. -1 At this current density, the specific capacitance of the polymer reaches up to 312 F g -1 CN110483769B discloses a spirobifluorene conjugated microporous organic polymer, which can -1 The specific capacitance is 182F g -1 , after 8000 cycles, the capacitance retention rate is 33%. Compared with the present invention, the present invention increases its specific surface area and conjugation degree without changing the nitrogen content, which can effectively improve the redox property.

[0055] An imine-based conjugated microporous polymer with high specific surface area and high conjugation degree, and a preparation method and application thereof, using three monomers of aromatic bromide, aromatic amine and boric acid, based on the Buchwald-Hartwig carbon-nitrogen coupling reaction and the Suzuki-Miyaura carbon-carbon coupling reaction, a one-pot two-reaction synthesis of an imine-based conjugated microporous polymer with both high specific surface area and high conjugation degree. Under alkaline conditions, the present invention keeps the ratio of aromatic bromide and aromatic amine monomers unchanged, introduces boric acid monomers for Suzuki-Miyaura CC coupling reaction, and can effectively increase the specific surface area, active sites and degree of conjugation. The method is simple to operate, and the obtained conjugated microporous polymer with high specific surface area, high conjugation and high redox property has great application potential in energy storage electrode materials, supercapacitors, etc.

Claims

1. An imine-based conjugated microporous polymer having a high specific surface area and a high degree of conjugation, characterized in that: The structural formula of the polymer is as follows:

2. An imine-based conjugated microporous polymer having a high specific surface area and a high degree of conjugation as claimed in claim 1, characterized in that The invention discloses an imine-based conjugated microporous polymer with relatively low electroactivity, wherein the imine-based conjugated microporous polymer has high specific surface area, high conjugation degree and multiple specific adsorption active sites.

3. A method for preparing the imine-based conjugated microporous polymer having a high specific surface area and a high degree of conjugation according to claim 1, characterized in that: Aromatic bromides, aromatic amines, and phenylboronic acid monomers were prepared via a one-pot two-reaction Buchwald-Hartwig coupling reaction and Suzuki-Miyaura reaction.

4. The preparation method according to claim 3, characterized in that: The aromatic bromide monomer is at least one of 2,2'-7,7'-tetrabromo-9,9'-spirobifluorene, 1,2,4,5-tetrabromobenzene, and 1,3,6,8-tetrabromopyrene; the aromatic amine monomer is at least one of p-phenylenediamine, m-phenylenediamine, -2-nitro-1,4-phenylenediamine, and 2,5-dimethyl-1,4-phenylenediamine; and the boric acid monomer is at least one of 3-aminophenylboric acid, 3-bromophenylboric acid, 3-chlorophenylboric acid, and 3-hydroxyphenylboric acid.

5. The preparation method according to claim 3, characterized in that: The molar ratio of the aromatic bromide monomer to the aromatic amine monomer is 1:2, and the added amount of the boric acid monomer is 0%-50% of the molar ratio of the aromatic amine monomer.

6. The preparation method according to claim 3, characterized in that: The solvent used in the Buchwald-Hartwig coupling reaction and the Suzuki-Miyaura reaction is at least one of tetrahydrofuran, toluene, dioxane and acetonitrile; the palladium catalyst used is at least one of bis(dibenzylideneacetone)palladium, palladium acetate, bis(acetonitrile)palladium dichloride (II) and bis(triphenylphosphine)palladium chloride; the ligand is at least one of 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, tri(o-methylphenyl)phosphine, 2-dicyclohexylphosphino-2'-(N,N-dimethylamino)biphenyl and the like; and the alkali used is at least one of sodium tert-butoxide and potassium tert-butoxide.

7. The preparation method according to claim 3, characterized in that: The coupling reaction system is placed in a Schlenk tube and regulated according to the boiling point temperature of the solvent under a N2 atmosphere, and the reaction time is controlled at 24-72 hours; the molar amounts of the palladium catalyst, the ligand, and the alkali in the coupling reaction are calculated according to 2%, 3%, and 133% of the theoretical molar amount of hydrogen bromide, respectively.

8. The preparation method according to claim 3, characterized in that: The ratio of solvent volume to aromatic bromide is 200mL:1mmoL.

9. The preparation method according to claim 3, characterized in that: After the reaction is completed, the powder obtained by filtration is washed with N,N-dimethylformamide, water and chloroform, and finally dried in a vacuum drying oven for 24 hours to obtain an imine-based conjugated microporous polymer with a high specific surface area and a high degree of conjugation.

10. Use of the imine-based conjugated microporous polymer with high specific surface area and high conjugation degree as claimed in claim 1 in energy storage electrode materials and supercapacitors.

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