Schiff base-containing tetrahalogenated monomers, self-polymerized microporous polymers and methods of making the same

Abstract

The application discloses a Schiff base-containing tetrahalogen monomer, a self-polymerization microporous polymer and a preparation method thereof, and belongs to the technical field of polymer materials and preparation thereof. The Schiff base-containing tetrahalogen monomer is prepared first, and the introduction of the Schiff base unit greatly increases the solubility of the tetrahalogen monomer containing an anthracene structure. Then, a tetraphenol monomer, the Schiff base-containing tetrahalogen monomer, tetrafluoro-p-phenyldinitrile and DMAc, NMP and the like are added into a reaction container as solvents, a salt forming agent, anhydrous carbonate and toluene are added, then oil bath heating is performed until a co-boiling dehydration agent starts to reflux, toluene is added appropriately after the reaction system becomes viscous, the reaction system is viscous again, and then the reaction system is discharged into methanol, the obtained crude product is crushed and filtered, and the filtered product is washed and dried to obtain the self-polymerization microporous polymer. The self-polymerization microporous polymer prepared by the application has high specific surface area and porosity, and high heat resistance grade, and has excellent prospects in the fields of adsorption, separation, catalysis and the like.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials and their preparation technology, specifically relating to a tetrahalogenated monomer containing a Schiff base, a self-polymerizing microporous polymer, and its preparation method. Background Technology

[0002] Self-porous polymers (PIMs) have been extensively studied as a novel type of polymer since 2004. Due to their trapezoidal, highly rigid structure, these polymers typically possess excellent physical, mechanical, and thermal properties. Combined with their unique twisted structure, they also exhibit high specific surface area and porosity, showing great promise in adsorption, separation, and catalysis. Because there are few commercially available monomers for PIMs preparation, much research has focused on the preparation of novel monomers for PIMs synthesis. This invention designs a novel tetrahalogenated monomer containing a Schiff base based on its molecular structure and, through nucleophilic substitution reactions with a tetraphenol monomer, obtains a series of PIMs with high specific surface area and high heat resistance. This invention broadens the types of monomers available for PIMs preparation and provides insights for the molecular design and optimization of subsequent high-performance PIMs. Summary of the Invention

[0003] The purpose of this invention is to provide a tetrahalogenated monomer containing a Schiff base, a self-polymerizing microporous polymer, and a method for preparing the same.

[0004] The novel tetrahalogenated monomer containing a Schiff base prepared in this invention has four reaction sites and can be used as a reactive monomer for ladder-like self-polymerizing microporous polymers. The introduction of the Schiff base unit significantly increases the solubility of the anthracene-containing tetrahalogenated monomer. On the one hand, this broadens the types of monomers that can be used to prepare self-polymerizing microporous polymers; on the other hand, the increased monomer solubility allows for the production of polymers with higher molecular weights, thus ensuring sufficient mechanical properties and providing a structural basis for subsequent industrial applications. The self-polymerizing microporous polymers prepared from the novel tetrahalogenated monomer containing a Schiff base exhibit high specific surface area and porosity, as well as high heat resistance, showing excellent prospects in adsorption, separation, and catalysis.

[0005] (1) The novel tetrahalogenated monomer containing a Schiff base described in this invention has the following structural formula:

[0006]

[0007] Where R represents Ph, Ar, and Alkyl, corresponding to phenyl, aryl, and alkyl, respectively;

[0008] The preparation steps of the tetrahalogenated monomer containing a Schiff base described in this invention are as follows:

[0009] Method 1:

[0010]

[0011] Under the protection of inert gas, add tetrahaloanthraquinone into a reaction vessel, add AlCl3 and CHCl3 thereto, and dropwise add a mixed solution of organic amine (aniline, arylamine and alkylamine) and triethylamine into the reaction system, and react at 25-65 °C for 5-24 h; after the reaction is completed and cooled to room temperature, slowly pour the reaction mixture into 2-5 M NaOH solution, then extract with CHCl3 for 3-5 times, combine the organic phases, wash with distilled water for 2-6 times, concentrate by rotary evaporation, and separate by column chromatography to obtain the product, namely the tetrahalo monomer containing Schiff base; the molar ratio of the amounts of tetrahaloanthraquinone, organic amine, AlCl3 and triethylamine is 1:3.2-5:3.4-5:10.2-15; 1 mmol of tetrahaloanthraquinone is added with 10-25 mL of CHCl3;

[0012] Method 2:

[0013]

[0014] Under the protection of inert gas, add tetrahaloanthraquinone into a reaction vessel, add CH2Cl2 thereto, and stir at -15 to -35 °C for 30-60 min; then slowly dropwise add a CH2Cl2 solution of 0.8-1.0 M TiCl4 into the system, stir for 30-60 min, and then dropwise add a CH2Cl2 solution of 0.8-1.0 M organic amine (aniline, arylamine and alkylamine); after stirring for another 30-60 min, dropwise add triethylamine; after the addition is completed, keep the whole reaction at -15 to -35 °C for 1-2 h, then slowly rise to room temperature, and continue to react at room temperature for 10-24 h; after the reaction is completed, pour the mixed solution into water, extract with CHCl3 for 3-5 times, combine the organic phases, wash with distilled water for 2-6 times, concentrate by rotary evaporation, and wash with ethanol for 3-5 times to obtain the tetrahalo monomer containing Schiff base; the molar ratio of the amounts of tetrahaloanthraquinone, organic amine, TiCl4 and triethylamine is 1:3-5:3-5:12-15; 1 mmol of tetrahaloanthraquinone is added with 10-25 mL of CH2Cl2.

[0015] (2) The novel tetrahalo monomer containing Schiff base prepared by applying the present invention can be further polymerized with a tetraphenol monomer to obtain a novel self-polymerized microporous polymer, and the obtained self-polymerized microporous polymer has the following structural formula: 6]

[0016]

[0017] where 0 < x ≤ 100; Y is any one of the structures shown in (I), (II), (III):

[0018] <o000051>

[0019] Where R1, R2, R3, and R4 are H; or R1 and R2 are methyl, and R3 and R4 are H; or R1, R2, R3, and R4 are methyl; or R1 is H, R2 is methyl, R3 is H, and R4 is methyl.

[0020]

[0021] Where R1, R2, R3, and R4 are H; or R1 and R2 are methyl groups and R3 and R4 are H; or R1, R2, R3, and R4 are methyl groups.

[0022] The novel tetrahalogenated monomers containing Schiff bases prepared using this invention can be further polymerized with tetraphenol monomers to obtain novel self-polymerizing microporous polymers. The preparation steps are as follows:

[0023] Under inert gas protection, tetraphenol monomer, tetrahalogenated monomer containing Schiff base, tetrafluoroterephthalonitrile (where the molar ratio of tetraphenol monomer, tetrahalogenated monomer containing Schiff base, and tetrafluoroterephthalonitrile is 100:x:(100-x)), and solvents such as DMAc and NMP are added to the reaction vessel, and the mixture is stirred and ventilated for 10-30 min. Then, anhydrous carbonate salt (the molar amount of the salting agent is 2.02-3.00 times that of the tetraphenol monomer) is added to the reaction system, and the mixture is stirred again for 10-30 min. Toluene is then added as an azeotropic dehydrating agent. Subsequently, the mixture is heated in an oil bath until the azeotropic dehydrating agent begins to reflux. After the reaction system becomes viscous, toluene is added appropriately. After the reaction system becomes viscous again, it is discharged into methanol. The crude product is pulverized and filtered. The filtered product is washed 4-6 times with distilled water at room temperature, then boiled and washed 4-6 times with ethanol, and then vacuum dried at 80-100℃ to obtain the self-polymerized microporous polymer. Attached Figure Description

[0024] Figure 1 This is the 1H NMR spectrum of 2,3,6,7-tetrafluoro-N,N-diphenylanthracene-9,10-diimide prepared in Example 1 (the NMR reagent is deuterated chloroform (CDCl3)).

[0025] Ha corresponds to the signal peak at 8.24 ppm. The hydrogens at all other positions are marked in the figure and correspond well with the compound, indicating that the desired monomer has been successfully synthesized.

[0026] Figure 2 This is the 1H NMR spectrum of N,N-bis(3,5-bis(trifluoromethyl)phenyl)-2,3,6,7-tetrafluoroanthracene-9,10-diimide prepared in Example 2 (the NMR reagent is deuterated chloroform (CDCl3)).

[0027] The hydrogen atoms at each position are labeled in the diagram and correspond well with the compounds, indicating that the desired monomer has been successfully synthesized.

[0028] Figure 3 This is the 1H NMR spectrum of N,N-bis(2,6-dimethylphenyl)-2,3,6,7-tetrafluoroanthracene-9,10-diimide prepared in Example 3 (the NMR reagent is deuterated chloroform (CDCl3)).

[0029] Ha corresponds to the signal peak at 8.24 ppm. The hydrogens at all other positions are marked in the figure and correspond well with the compound, indicating that the desired monomer has been successfully synthesized.

[0030] Figure 4 The images show the 1H NMR spectra of the self-polymerizing microporous polymers PIM-TFNAD-10, PIM-TFNAD-20, and PIM-TFNAD-30 prepared in Examples 4, 5, and 6 (the NMR reagent is deuterated chloroform (CDCl3)).

[0031] A new chemical shift peak appears at 7.26-7.80 ppm, corresponding to H6 and H9. The hydrogens at the other positions correspond well with the compound, indicating that the corresponding polymer has been successfully synthesized.

[0032] Figure 5 These are the infrared spectra of the self-polymerizing microporous polymers PIM-TFNAD-10, PIM-TFNAD-20, and PIM-TFNAD-30 prepared in Examples 4, 5, and 6.

[0033] The infrared spectrum shows a range of 1532-1708 cm⁻¹ -1 The peaks that appear correspond to the stretching vibration peaks of the six-membered ring in anthracene, proving the successful introduction of our novel monomer. Furthermore, the signal peaks at this location intensify with increasing monomer introduction ratio. The remaining -CN, C=C, and Ar-O-Ar peaks appear at 2239 cm⁻¹. -1 1445cm -1 and 1010cm -1 This demonstrates the successful preparation of the polymer.

[0034] Figure 6 These are thermogravimetric diagrams of the self-polymerizing microporous polymers PIM-TFNAD-10, PIM-TFNAD-20, and PIM-TFNAD-30 prepared in Examples 4, 5, and 6.

[0035] As can be seen from the figure, all polymers in this series have high thermal stability, with a 5% weight loss temperature all above 450℃.

[0036] Figure 7 This is a nitrogen adsorption-desorption curve of the self-polymerizing microporous polymer PIM-TFNAD-20 prepared in Example 5;

[0037] Based on the nitrogen adsorption-desorption curve, the BET specific surface area of ​​polymer PIM-TFNAD-20 is determined to be 609.89 m². 2 g -1 Furthermore, at p / p0 = 1, it exhibits a relatively high nitrogen adsorption capacity of 380.35 m. 2 g -1 This indicates that the polymer has a high specific surface area and porosity.

[0038] Figure 8 The figure shows the DSC curve of the polymer PIM-TFNAD-20 prepared in Example 5. It can be seen from the figure that the polymer does not reach the glass transition temperature Tg before 400℃, which proves its high rigidity and thermal stability. Detailed Implementation

[0039] Example 1: Synthesis of 2,3,6,7-tetrafluoro-N,N-diphenylanthracene-9,10-diimide (TFNAD)

[0040] Under nitrogen protection, 3.84 g (13.7 mmol) of tetrafluoroanthrone was added to a 500 mL three-necked flask, followed by 6.21 g (46.6 mmol) of AlCl3 and 200 mL of CHCl3. A mixed solution of 4.47 g (48.0 mmol) of aniline and 14.14 g (139.7 mmol) of triethylamine was added dropwise to the reaction system, and the reaction was allowed to proceed at room temperature for 12 h. After the reaction was completed and cooled to room temperature, the reaction mixture was slowly poured into 4 M NaOH solution. The mixture was then extracted three times with CH2Cl2. The combined organic phases were washed three times with distilled water, concentrated by rotary evaporation, and separated by column chromatography (developing solvent: CHCl3) to obtain a reddish-brown solid product, namely 5.90 g of 2,3,6,7-tetrafluoro-N,N-diphenylanthracene-9,10-diimide, with the structural formula shown below.

[0041]

[0042] Example 2: Synthesis of N,N-bis(3,5-bis(trifluoromethyl)phenyl)-2,3,6,7-tetrafluoroanthracene-9,10-diimide

[0043] Under nitrogen protection, 3.35 g (12.0 mmol) of tetrafluoroanthrone was added to a 500 mL three-necked flask, followed by 6.80 g (51.0 mmol) of AlCl3 and 300 mL of CHCl3. A mixed solution of 11.00 g (48.0 mmol) of 3,5-di(trifluoromethyl)aniline and 15.48 g (153.0 mmol) of triethylamine was added dropwise to the reaction system. After all the addition was complete, the reaction system was heated to 60 °C and refluxed, and the reaction progress was monitored by TLC. The reaction was completed after approximately 24 hours. After the reaction was complete and the mixture cooled to room temperature, the reaction mixture was slowly poured into a 4M NaOH solution. The mixture was then extracted three times with CH2Cl2. The combined organic phases were washed three times with distilled water, and the solid obtained after rotary evaporation and concentration was washed three times with ethanol to give a bright yellow solid product, namely 4.89 g of N,N-bis(3,5-bis(trifluoromethyl)phenyl)-2,3,6,7-tetrafluoroanthracene-9,10-diimide, with the structural formula shown below.

[0044]

[0045] Example 3: Synthesis of N,N-bis(2,6-dimethylphenyl)-2,3,6,7-tetrafluoroanthracene-9,10-diimine

[0046] Under nitrogen protection, 5.00 g (17.8 mmol) of tetrafluoroanthrone was added to a 500 mL three-necked flask, followed by 200 mL of CH₂Cl₂. The reaction was stirred at -35 °C for 30 min, and then a 1.0 M TiCl₄ solution (5.87 mL, 53.4 mmol) in CH₂Cl₂ was slowly added dropwise. After stirring for another 30 min, a 1.0 M 2,6-dimethylaniline solution (6.58 mL, 53.4 mmol) in CH₂Cl₂ was added dropwise. After stirring again for 30 min, triethylamine (29.69 mL, 213.6 mmol) was added dropwise. After the addition was complete, the reaction was maintained at -35 °C for 1 h, then slowly raised to room temperature and continued for 18 h at room temperature. After the reaction was complete, the mixed solution was poured into water, extracted three times with CHCl₃, and the combined organic phases were washed twice with distilled water. After rotary evaporation and concentration, the product was washed three times with ethanol to obtain an orange solid product, namely 5.20 g of N,N-bis(2,6-dimethylphenyl)-2,3,6,7-tetrafluoroanthracene-9,10-diimide, with the structural formula shown below.

[0047]

[0048] Example 4: Synthesis of PIMs (PIM-TFNAD-10) with a 10% molar content of 2,3,6,7-tetrafluoro-N,N-diphenylanthracene-9,10-diimine monomer.

[0049] Under nitrogen protection, 1.0212 g (3.0 mmol) of 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobinodinium monomer, 0.1291 g (0.3 mmol) of 2,3,6,7-tetrafluoro-N,N-diphenylanthracene-9,10-diimide monomer, 0.5402 g (2.7 mmol) of tetrafluoroterephthalonitrile, and 7.5 mL of DMAc were added to a 50 mL three-necked flask. After stirring and ventilating for 10 min, 1.2439 g (9.0 mmol) of anhydrous potassium carbonate, a salt-forming agent, was added to the reaction system. After stirring again for 10 min, 4 mL of toluene was added as an azeotropic dehydrating agent. The mixture was then heated in an oil bath until the azeotropic dehydrating agent began to reflux. After the reaction system became viscous, 2 mL of toluene was added. After the reaction system became viscous again, it was discharged into methanol. The crude product was pulverized and filtered. The filtered product was washed four times with distilled water at room temperature, then washed four times with boiling ethanol, and subsequently dried under vacuum at 80°C in an oven to obtain 1.32 g of PIM-TFNAD-10, with the structural formula shown below.

[0050]

[0051] Example 5: Synthesis of PIMs (PIM-TFNAD-20) with a molar content of 20% of 2,3,6,7-tetrafluoro-N,N-diphenylanthracene-9,10-diimine monomer.

[0052] Under nitrogen protection, 1.7021 g (5.0 mmol) of 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobinodinium monomer, 0.4304 g (1.0 mmol) of 2,3,6,7-tetrafluoro-N,N-diphenylanthracene-9,10-diimide monomer, 0.8004 g (4.0 mmol) of tetrafluoroterephthalonitrile, and 15 mL of DMAc were added to a 50 mL three-necked flask. After stirring and ventilating for 10 min, 2.0731 g (15.0 mmol) of anhydrous potassium carbonate, a salt-forming agent, was added to the reaction system. After stirring again for 10 min, 8 mL of toluene was added as an azeotropic dehydrating agent. The mixture was then heated in an oil bath until the azeotropic dehydrating agent began to reflux. After the reaction system became viscous, 4 mL of toluene was added. After the reaction system became viscous again, it was discharged into methanol. The crude product was pulverized and filtered. The filtered product was washed four times with distilled water at room temperature, then washed four times with boiling ethanol, and finally dried under vacuum at 80°C in an oven to obtain PIM-TFNAD-202.35g, with the structural formula shown below.

[0053]

[0054] Example 6: Synthesis of PIMs (PIM-TFNAD-30) with a 30% molar content of 2,3,6,7-tetrafluoro-N,N-diphenylanthracene-9,10-diimine monomer.

[0055] Under nitrogen protection, 1.7021 g (5.0 mmol) of 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobadienylmonomer, 0.6456 g (1.5 mmol) of 2,3,6,7-tetrafluoro-N,N-diphenylanthracene-9,10-diimide monomer, 0.7003 g (3.5 mmol) of tetrafluoroterephthalonitrile, and 15 mL of DMAc were added to a 50 mL three-necked flask. After stirring and ventilating for 10 min, 2.0731 g (15.0 mmol) of anhydrous potassium carbonate, a salt-forming agent, was added to the reaction system. After stirring again for 10 min, 8 mL of toluene was added as an azeotropic dehydrating agent. The mixture was then heated in an oil bath until the azeotropic dehydrating agent began to reflux. After the reaction system became viscous, 4 mL of toluene was added. After the reaction system became viscous again, it was discharged into methanol. The crude product was pulverized and filtered. The filtered product was washed four times with distilled water at room temperature, then washed four times with boiling ethanol, and finally dried under vacuum at 80°C in an oven to obtain 2.45 g of PIM-TFAD-30, with the structural formula shown below.

[0056]

[0057] Example 7: Synthesis of PIMs (PIM-CF3-50) with a 50% molar content of N,N-bis(3,5-bis(trifluoromethyl)phenyl)-2,3,6,7-tetrafluoroanthracene-9,10-diimide monomer.

[0058] Under nitrogen protection, 1.7021 g (5.0 mmol) of 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobanediene monomer, 1.7560 g (2.5 mmol) of N,N-bis(3,5-bis(trifluoromethyl)phenyl)-2,3,6,7-tetrafluoroanthracene-9,10-diimide monomer, 0.5003 g (2.5 mmol) of tetrafluoroterephthalonitrile and 16 mL of DMAc were added to a 50 mL three-necked flask. After stirring and ventilating for 10 min, 2.0731 g (15.0 mmol) of anhydrous potassium carbonate, a salt-forming agent, was added to the reaction system. After stirring again for 10 min, 8 mL of toluene was added as an azeotropic dehydrating agent. The mixture was then heated in an oil bath until the azeotropic dehydrating agent began to reflux. After the reaction system became viscous, 4 mL of toluene was added. After the reaction system became viscous again, it was discharged into methanol. The crude product was pulverized and filtered. The filtered product was washed four times with distilled water at room temperature, then washed four times with boiling ethanol, and finally dried under vacuum at 80°C in an oven to obtain 3.49 g of polymer PIM-CF3-50, with the structural formula shown below.

[0059]

[0060] Example 8: Synthesis of PIMs (PIM-CH3-30) with a molar content of 30% of N,N-bis(2,6-dimethylphenyl)-2,3,6,7-tetrafluoroanthracene-9,10-diimide monomer.

[0061] Under nitrogen protection, 1.7021 g (5.0 mmol) of 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobanediene monomer, 0.7298 g (1.5 mmol) of N,N-bis(2,6-dimethylphenyl)-2,3,6,7-tetrafluoroanthracene-9,10-diimide monomer, 0.7004 g (3.5 mmol) of tetrafluoroterephthalonitrile and 16 mL of DMAc were added to a 50 mL three-necked flask. After stirring and ventilating for 10 min, 2.0731 g (15.0 mmol) of anhydrous potassium carbonate, a salt-forming agent, was added to the reaction system. After stirring again for 10 min, 8 mL of toluene was added as an azeotropic dehydrating agent. The mixture was then heated in an oil bath until the azeotropic dehydrating agent began to reflux. After the reaction system became viscous, 4 mL of toluene was added. After the reaction system became viscous again, it was discharged into methanol. The crude product was pulverized and filtered. The filtered product was washed four times with distilled water at room temperature, then washed four times with boiling ethanol, and finally dried in an oven at 80°C to obtain 2.65 g of polymer PIM-CH3-30, with the structural formula shown below.

[0062]

Claims

1. A tetrahalogenated monomer containing a Schiff base, the structural formula of which is shown below: ， in, X is F, Br, or Cl, and R is phenyl; Alternatively, the tetrahalogenated monomer containing a Schiff base may be a compound represented by one of the following structural formulas. 、 。 2. The method for preparing the tetrahalogenated monomer containing a Schiff base according to claim 1, characterized in that: Under inert gas protection, tetrahaloanthrone was added to a reaction vessel, along with AlCl3 and CHCl3. A mixed solution of organic amine and triethylamine was then added dropwise to the reaction system. The reaction was carried out at 25–65 °C for 5–24 h. After the reaction was completed and cooled to room temperature, the reaction mixture was slowly poured into a 2–5 M NaOH solution, then extracted 3–5 times with CHCl3. The combined organic phases were washed 2–6 times with distilled water, concentrated by rotary evaporation, and separated by column chromatography to obtain the product, i.e., the tetrahalomonomer containing a Schiff base. The molar ratio of tetrahaloanthrone, organic amine, AlCl3, and triethylamine was 1:3.2–5:3.4–5:10.2–15. 1 mmol of tetrahaloanthrone was added to 10–25 mL of CHCl3, and the organic amine was aniline.

3. The method for preparing the tetrahalogenated monomer containing a Schiff base as described in claim 1, characterized in that: Under an inert gas atmosphere, a tetrahaloanthrone was added to a reaction vessel, followed by CH2Cl2. The mixture was stirred at -15 to -35 °C for 30 to 60 min. Then, a 0.8 to 1.0 M solution of TiCl4 in CH2Cl2 was slowly added dropwise, and the mixture was stirred for 30 to 60 min. Next, a 0.8 to 1.0 M solution of an organic amine in CH2Cl2 was added dropwise. After stirring again for 30 to 60 min, triethylamine was added dropwise. After the addition was complete, the reaction was maintained at -15 to -35 °C for 1 to 2 h, then slowly raised to room temperature and continued for 10 to 24 h. After the reaction was complete, the mixed solution was poured into water and extracted 3 to 5 times with CHCl3. The combined organic phases were washed 2 to 6 times with distilled water, concentrated by rotary evaporation, and washed 3 to 5 times with ethanol to obtain a tetrahalomonomer containing a Schiff base. The molar ratio of tetrahaloanthrone, organic amine, TiCl4, and triethylamine was 1:

1. 3~5: 3~5: 12~15; 1 mmol of tetrahalothrone is added to 10~25 mL of CH2Cl2, and the organic amine is aniline.

4. A self-polymerizing microporous polymer, characterized in that: The self-polymerizing microporous polymer with the following structural formula was prepared using the tetrahalogenated monomer containing a Schiff base as described in claim 1. Where 0 < x ≤ 100; Y is any of the structures shown in (I), (II), and (III). (AND), (II) R1, R2, R3, and R4 are H; or R1 and R2 are methyl, and R3 and R4 are H; or R1, R2, R3, and R4 are methyl; or R1 is H, R2 is methyl, R3 is H, and R4 is methyl. (III) R1, R2, R3, and R4 are H; or R1 and R2 are methyl groups and R3 and R4 are H; or R1, R2, R3, and R4 are methyl groups.

5. The method for preparing the self-polymerizing microporous polymer according to claim 4, characterized in that: Under inert gas protection, tetraphenol monomer, tetrahalogenated monomer containing Schiff base, tetrafluoroterephthalonitrile, DMAc or NMP solvent are added to a reaction vessel and stirred and ventilated for 10-30 min. Then, anhydrous carbonate salt, a salt-forming agent, is added to the reaction system and stirred again for 10-30 min. Toluene is then added as an azeotropic dehydrating agent. Subsequently, the mixture is heated in an oil bath until the azeotropic dehydrating agent begins to reflux. After the reaction system becomes viscous, toluene is added appropriately. After the reaction system becomes viscous again, it is discharged into methanol. The crude product is pulverized and filtered. The filtered product is washed 4-6 times with distilled water at room temperature, then boiled and washed 4-6 times with ethanol. Finally, it is vacuum dried at 80-100 °C to obtain the self-polymerized microporous polymer. The molar ratio of tetraphenol monomer, tetrahalogenated monomer containing Schiff base, and tetrafluoroterephthalonitrile is 100:x:(100-x), and the molar amount of the salt-forming agent is 2.02-3.00 times that of the tetraphenol monomer.

Images