A method for preparing a polyimide covalent organic framework

Abstract

The application belongs to the technical field of polymer synthesis, and provides a preparation method of a polyimide covalent organic framework.The application mixes anhydride compounds (one or more of the following: pyromellitic dianhydride, 1,4,5,8-naphthalene tetracarboxylic anhydride and 3,4,9,10-perylenetetracarboxylic dianhydride) and an alcohol solvent to perform pre-reaction to obtain a carboxylic esterate solution; disperses amino blocks (tris(4-aminophenyl)amine, 1,3,6,8-tetrakis(4-aminophenyl)pyrene, etc.) to obtain an amino block dispersion solution; mixes the amino block dispersion solution and the carboxylic esterate solution to perform reaction to obtain the polyimide covalent organic framework.The preparation method of the application can be performed under normal pressure, and the operation is safer; meanwhile, the preparation method of the application is not performed in a sealed tube, and can be used for mass production of the polyimide covalent organic framework.

Description

Technical Field

[0001] This invention relates to the field of polymer synthesis technology, and more particularly to a method for preparing a polyimide covalent organic framework. Background Technology

[0002] Two-dimensional covalent organic frameworks (2D COFs) have become a highly sought-after material due to their flexible structural design, long-range order, unique layered structure, customizable periodic framework, and ordered nanoporous structure. With researchers' increasing understanding of covalent organic frameworks, they have demonstrated enormous application potential in the field of mechanical friction and lubrication. Current techniques for preparing polyimide covalent organic frameworks generally require sealed tube conditions, which necessitate high pressure and pose significant operational risks. Summary of the Invention

[0003] In view of this, the purpose of this invention is to provide a method for preparing a polyimide covalent organic framework. The preparation method provided by this invention can be carried out under normal pressure, making the operation safer.

[0004] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0005] This invention provides a method for preparing a polyimide covalent organic framework, comprising the following steps:

[0006] An acid anhydride compound and an alcohol solvent are mixed and pre-reacted to obtain a carboxylic acid ester solution;

[0007] The amino building blocks were dispersed to obtain an amino building block dispersion.

[0008] The amino building block dispersion and the carboxylic acid ester solution are mixed and reacted to obtain the polyimide covalent organic framework;

[0009] The anhydride compounds include one or more of pyromellitic dianhydride, 1,4,5,8-naphthalenetetracarboxylic anhydride, and 3,4,9,10-perylenetetracarboxylic anhydride.

[0010] The amino building blocks include one or more of tris(4-aminophenyl)amine, 2,4,6-tris(4-aminophenyl)-1,3,5-triazine, 4,4',4”-(pyrimidin-2,4,6-triyl)triphenylamine, 4-(4-aminophenyl)-2,6-bis(4-aminophenyl)pyridine, 1,3,5-tris(4-aminophenyl)benzene, 1,3,6,8-tetra(4-aminophenyl)pyrene, and tetra-(4-aminophenyl)ethylene.

[0011] Preferably, the alcohol solvent is a small molecule alcohol, and the small molecule alcohol has 1 to 6 carbon atoms.

[0012] Preferably, the alcohol solvent includes one or more of methanol, ethanol, and propanol.

[0013] Preferably, the ratio of the acid anhydride compound to the alcohol solvent is 10-1000 mg: 1-10 mL.

[0014] Preferably, the pre-reaction temperature is 60–100°C, the pressure is atmospheric pressure, and the time is 2–12 hours.

[0015] Preferably, the dispersing agent is a mixed solvent of N-methylpyrrolidone and mesitylene, wherein the volume ratio of N-methylpyrrolidone to mesitylene in the mixed solvent is 5:1 to 1:5.

[0016] Preferably, the concentration of the amino block dispersion is 5–55 mg / mL.

[0017] Preferably, the volume ratio of the amino block dispersion to the carboxylic acid ester solution is 1-10:0.327-5.

[0018] Preferably, the reaction temperature is 100–180°C, the pressure is atmospheric pressure, and the time is 4–24 hours.

[0019] Preferably, after the reaction is completed, the method further includes: filtering the obtained reaction solution, collecting the filter residue, washing the filter residue, and obtaining the polyimide covalent organic framework.

[0020] This invention provides a method for preparing a polyimide covalent organic framework.

[0021] The preparation method provided by this invention can be carried out under normal pressure, making the operation safer; at the same time, the preparation method of this invention does not take place in sealed tubes, and can be used for the mass production of polyimide covalent organic frameworks. Attached Figure Description

[0022] Figure 1 The powder X-ray diffraction pattern of the tris(4-aminophenyl)amine-polyimide covalent organic framework material (TAPA-PICOF) obtained in Example 1;

[0023] Figure 2 The powder X-ray diffraction pattern of the 2,4,6-tris(4-aminophenyl)-1,3,5-triazine-polyimide covalent organic framework material (TAPT-PI COF) obtained in Example 2;

[0024] Figure 3 The powder X-ray diffraction pattern of the 4,4',4”-(pyrimidine-2,4,6-trimethyl)triphenylamine-polyimide covalent organic framework material (TAPPm-PI COF) obtained in Example 3;

[0025] Figure 4 The powder X-ray diffraction pattern of the 4-(4-aminophenyl)-2,6-bis(4-aminophenyl)pyridine-polyimide covalent organic framework material (TAPP-PI COF) obtained in Example 4;

[0026] Figure 5 The powder X-ray diffraction pattern of the 1,3,5-tris(4-aminophenyl)benzene-polyimide covalent organic framework material (TAPB-PI COF) obtained in Example 5;

[0027] Figure 6 Powder X-ray diffraction pattern of 1,3,6,8-tetra(4-aminophenyl)pyrene-polyimide covalent organic framework material (Py-PI COF) obtained in Example 6;

[0028] Figure 7 The powder X-ray diffraction pattern of the tetra-(4-aminophenyl)ethylene-polyimide covalent organic framework material (AIE-PICOF) obtained in Example 7;

[0029] Figure 8 The powder X-ray diffraction pattern of the tris(4-aminophenyl)amine-polyimide covalent organic framework material (TAPA-PICOF) obtained in Example 8 is shown. Detailed Implementation

[0030] This invention provides a method for preparing a polyimide covalent organic framework, comprising the following steps:

[0031] An acid anhydride compound and an alcohol solvent are mixed and pre-reacted to obtain a carboxylic acid ester solution;

[0032] The amino building blocks were dispersed to obtain an amino building block dispersion.

[0033] The amino building block dispersion and the carboxylic acid ester solution are mixed and reacted to obtain the polyimide covalent organic framework;

[0034] The anhydride compounds include one or more of pyromellitic dianhydride, 1,4,5,8-naphthalenetetracarboxylic anhydride, and 3,4,9,10-perylenetetracarboxylic anhydride.

[0035] The amino building blocks include one or more of tris(4-aminophenyl)amine, 2,4,6-tris(4-aminophenyl)-1,3,5-triazine, 4,4',4”-(pyrimidin-2,4,6-triyl)triphenylamine, 4-(4-aminophenyl)-2,6-bis(4-aminophenyl)pyridine, 1,3,5-tris(4-aminophenyl)benzene, 1,3,6,8-tetra(4-aminophenyl)pyrene, and tetra-(4-aminophenyl)ethylene.

[0036] Unless otherwise specified, the raw materials used in this invention are preferably commercially available products.

[0037] This invention involves mixing an acid anhydride compound and an alcohol solvent to perform a pre-reaction, thereby obtaining a carboxylic acid ester solution.

[0038] In this invention, the acid anhydride compound includes one or more of pyromellitic dianhydride, 1,4,5,8-naphthalenetetracarboxylic anhydride and 3,4,9,10-perylenetetracarboxylic anhydride, preferably pyromellitic dianhydride.

[0039] In this invention, the alcohol solvent is preferably a small molecule alcohol, and the number of carbon atoms in the small molecule alcohol is preferably 1 to 6, more preferably one or more of methanol, ethanol and propanol, and specifically preferably methanol.

[0040] In this invention, the preferred ratio of the acid anhydride compound to the alcohol solvent is 10-1000 mg: 1-10 mL, specifically preferably 50 mg: 1 mL, 1000 mg: 10 mL, 500 mg: 5 mL, 200 mg: 10 mL, 327 mg: 5 mL, 218.12 mg: 3 mL, 109.06 mg: 2 mL, or 50 g: 500 mL.

[0041] In this invention, the pre-reaction temperature is preferably 60–100°C, specifically 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, or 100°C; the pressure is preferably atmospheric pressure; and the time is preferably 2–12 hours, specifically 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, or 12 hours. In this invention, the pre-reaction is preferably carried out under nitrogen protection and stirring.

[0042] After the pre-reaction, the present invention preferably obtains the carboxylic acid ester solution directly without any post-processing.

[0043] In this invention, taking pyromellitic dianhydride as an example, the reaction formula for the pre-reaction is as follows:

[0044]

[0045] The present invention disperses amino building blocks to obtain an amino building block dispersion.

[0046] In this invention, the amino building block comprises one or more of tris(4-aminophenyl)amine, 2,4,6-tris(4-aminophenyl)-1,3,5-triazine, 4,4',4”-(pyrimidin-2,4,6-triyl)triphenylamine, 4-(4-aminophenyl)-2,6-bis(4-aminophenyl)pyridine, 1,3,5-tris(4-aminophenyl)benzene, 1,3,6,8-tetra(4-aminophenyl)pyrene, and tetra-(4-aminophenyl)ethylene.

[0047] In this invention, the dispersing agent is preferably a mixed solvent of N-methylpyrrolidone and mesitylene, and the volume ratio of N-methylpyrrolidone to mesitylene in the mixed solvent is preferably 5:1 to 1:5, specifically preferably 1:1, 1:2, 1:3, 1:5 or 5:1.

[0048] In this invention, the concentration of the amino block dispersion is preferably 5-55 mg / mL, specifically preferably 5 mg / mL, 10 mg / mL, 15 mg / mL, 17.55 mg / mL, 19.626 mg / mL, 20 mg / mL, 23.4 mg / mL, 25 mg / mL, 28.335 mg / mL, 29 mg / mL, 30 mg / mL, 35.1 mg / mL, 40 mg / mL, 45 mg / mL, 48.33 mg / mL, 50 mg / mL, 52.65 mg / mL, or 55 mg / mL.

[0049] After obtaining the carboxylic acid ester solution and the amino building block dispersion, the present invention mixes the amino building block dispersion and the carboxylic acid ester solution and reacts them to obtain the polyimide covalent organic framework.

[0050] In this invention, the volume ratio of the amino block dispersion to the carboxylic acid ester solution is preferably 1-10:0.327-5, more preferably 1:0.2-3, and specifically preferably 1:0.654, 1:0.327, 3:0.654, 2:4.905, 10:2.5, 10:3, 5:2 or 6:3.27.

[0051] In this invention, the mixing of the amino block dispersion and the carboxylic acid ester solution preferably includes the following steps: adding the carboxylic acid ester solution dropwise to the amino block dispersion; after the carboxylic acid ester solution is added, stirring and mixing are performed; the dropwise addition method is preferably dropwise addition; the stirring and mixing temperature is preferably 50-80°C, specifically preferably 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, or 80°C; the time is preferably 2-4 hours, specifically preferably 2 hours, 3 hours, or 4 hours; the mixing of the amino block dispersion and the carboxylic acid ester solution is preferably carried out under nitrogen protection.

[0052] In this invention, the reaction temperature is preferably 100–180°C, specifically 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, or 180°C; the pressure is preferably atmospheric pressure; and the time is preferably 4–24 hours, specifically 4 hours, 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 15 hours, 16 hours, 18 hours, 20 hours, 22 hours, or 24 hours. In this invention, the reaction is preferably carried out under stirring and nitrogen protection.

[0053] After the reaction is completed, the present invention preferably further includes: filtering the obtained reaction solution, collecting the filter residue, washing the filter residue, and obtaining the polyimide covalent organic framework.

[0054] In this invention, the cleaning method is preferably solvent extraction cleaning, and the reagents for solvent extraction cleaning are preferably methanol and tetrahydrofuran. In a specific embodiment of this invention, the cleaning is preferably performed sequentially by methanol solvent extraction cleaning and tetrahydrofuran solvent extraction cleaning.

[0055] In this invention, pyromellitic dianhydride is used as the anhydride compound, and the preparation method provided by this invention is shown in the following formula:

[0056]

[0057] In this invention, using pyromellitic dianhydride as the anhydride compound and tris(4-aminophenyl)amine, 2,4,6-tris(4-aminophenyl)-1,3,5-triazine, 4,4',4”-(pyrimidin-2,4,6-triyl)triphenylamine, 4-(4-aminophenyl)-2,6-bis(4-aminophenyl)pyridine, and 1,3,5-tris(4-aminophenyl)benzene as amino building blocks, the structure of the polyimide covalent organic framework prepared is shown in the following formula:

[0058]

[0059] In this invention, using pyromellitic dianhydride as the anhydride compound and tetra-(4-aminophenyl)ethylene and 1,3,6,8-tetra(4-aminophenyl)pyrene as amino building blocks, the structure of the polyimide covalent organic framework prepared is shown in the following formula:

[0060]

[0061] The following detailed description of the preparation method of the polyimide covalent organic framework provided by the present invention, with reference to the embodiments, should not be construed as limiting the scope of protection of the present invention.

[0062] Example 1

[0063] Dissolve 50.00 mg of pyromellitic dianhydride in 1.0 mL of methanol, heat to 65 °C under nitrogen protection, and stir for 12 h to obtain a clear and transparent carboxylic acid ester solution for later use.

[0064] 29.00 mg of tris(4-aminophenyl)amine (TAPA) was weighed and dispersed in 1.0 mL of a mixed solvent of N-methylpyrrolidone and mesitylene (1:1, v:v) to obtain a tris(4-aminophenyl)amine dispersion.

[0065] Under nitrogen protection, 0.654 mL of the carboxylic acid ester solution was added dropwise to the prepared tri(4-aminophenyl)amine dispersion. After the addition was complete, the mixture was stirred at 65°C for 3 h to obtain a clear and transparent solution. Under continuous nitrogen protection, the mixture was stirred at 180°C for 4 h. The residue was filtered and washed with methanol and tetrahydrofuran to obtain the tri(4-aminophenyl)amine-polyimide covalent organic framework material (TAPA-PI COF).

[0066] Figure 1 The powder X-ray diffraction pattern of the tris(4-aminophenyl)amine-polyimide covalent organic framework material (TAPA-PICOF) obtained in Example 1 is shown below. Figure 1 It can be seen that TAPA-PI COF was successfully prepared.

[0067] Example 2

[0068] Dissolve 1000.00 mg of pyromellitic dianhydride in 10.0 mL of ethanol, heat to 100 °C under nitrogen protection, and stir for 4 h to obtain a clear and transparent carboxylic acid ester solution for later use.

[0069] 35.1 mg of 2,4,6-tris(4-aminophenyl)-1,3,5-triazine (TAPT) was weighed and dispersed in 1.0 mL of a mixed solvent of N-methylpyrrolidone and mesitylene (1:1, v:v) to obtain a 2,4,6-tris(4-aminophenyl)-1,3,5-triazine dispersion.

[0070] Under nitrogen protection, 0.327 mL of the carboxylic acid ester solution was added dropwise to the 2,4,6-tris(4-aminophenyl)-1,3,5-triazine dispersion prepared above. After the addition was complete, the mixture was stirred at 80 °C for 4 h to obtain a clear and transparent solution. Under continuous nitrogen protection, the mixture was stirred at 120 °C for 24 h. The residue was filtered and washed with methanol and tetrahydrofuran to obtain 2,4,6-tris(4-aminophenyl)-1,3,5-triazine-polyimide covalent organic framework material (TAPT-PI COF).

[0071] Figure 2The powder X-ray diffraction pattern of the 2,4,6-tris(4-aminophenyl)-1,3,5-triazine-polyimide covalent organic framework material (TAPT-PI COF) obtained in Example 2 is shown below. Figure 2 It can be seen that TAPT-PI COF was successfully prepared.

[0072] Example 3

[0073] Dissolve 500.00 mg of pyromellitic dianhydride in 5.0 mL of propanol, heat to 80 °C under nitrogen protection, and stir for 3 h to obtain a clear and transparent carboxylic acid ester solution for later use.

[0074] 70.2 mg of 4,4',4”-(pyrimidine-2,4,6-triyl)triphenylamine (TAPPm) was weighed and dispersed in 3.0 mL of a mixed solvent of N-methylpyrrolidone and mesitylene (5:1, v:v) to obtain a 4,4',4”-(pyrimidine-2,4,6-triyl)triphenylamine dispersion.

[0075] Under nitrogen protection, 0.654 mL of the carboxylic acid ester solution was added dropwise to the 4,4',4”-(pyrimidine-2,4,6-triyl)triphenylamine dispersion prepared above. After the addition was complete, the mixture was stirred at 60 °C for 2 h to obtain a clear and transparent solution. Under continuous nitrogen protection, the mixture was stirred at 100 °C for 24 h. The residue was filtered and washed with methanol and tetrahydrofuran to obtain 4,4',4”-(pyrimidine-2,4,6-triyl)triphenylamine-polyimide covalent organic framework material (TAPPm-PI COF).

[0076] Figure 3 The powder X-ray diffraction pattern of the 4,4',4”-(pyrimidin-2,4,6-trimethyl)triphenylamine-polyimide covalent organic framework material (TAPPm-PI COF) obtained in Example 3 is shown below. Figure 3 It can be seen that TAPPm-PI COF was successfully prepared.

[0077] Example 4

[0078] Dissolve 200.00 mg of pyromellitic dianhydride in 10.0 mL of ethanol, heat to 100 °C under nitrogen protection, and stir for 4 h to obtain a clear and transparent carboxylic acid ester solution for later use.

[0079] 105.3 mg of 4-(4-aminophenyl)-2,6-bis(4-aminophenyl)pyridine (TAPP) was weighed and dispersed in 2.0 mL of a mixed solvent of N-methylpyrrolidone and mesitylene (1:5, v:v) to obtain a 4-(4-aminophenyl)-2,6-bis(4-aminophenyl)pyridine dispersion.

[0080] Under nitrogen protection, 4.905 mL of the carboxylic acid ester solution was added dropwise to the 4-(4-aminophenyl)-2,6-bis(4-aminophenyl)pyridine dispersion prepared above. After the addition was complete, the mixture was stirred at 65 °C for 4 h to obtain a clear and transparent solution. Under continuous nitrogen protection, the mixture was stirred at 140 °C for 12 h. The residue was filtered and washed with methanol and tetrahydrofuran to obtain 4-(4-aminophenyl)-2,6-bis(4-aminophenyl)pyridine-polyimide covalent organic framework material (TAPP-PI COF).

[0081] Figure 4 The powder X-ray diffraction pattern of the 4-(4-aminophenyl)-2,6-bis(4-aminophenyl)pyridine-polyimide covalent organic framework material (TAPP-PI COF) obtained in Example 4 is shown below. Figure 4 It can be seen that TAPP-PI COF was successfully prepared.

[0082] Example 5

[0083] Dissolve 327.00 mg of pyromellitic dianhydride in 5.0 mL of methanol, heat to 100 °C under nitrogen protection, and stir for 4 h to obtain a clear and transparent carboxylic acid ester solution for later use.

[0084] 175.5 mg of 1,3,5-tris(4-aminophenyl)benzene (TAPB) was weighed and dispersed in 10.0 mL of a mixed solvent of N-methylpyrrolidone and mesitylene (1:2, v:v) to obtain a 1,3,5-tris(4-aminophenyl)benzene dispersion.

[0085] Under nitrogen protection, 2.500 mL of the carboxylic acid ester solution was added dropwise to the 1,3,5-tris(4-aminophenyl)benzene dispersion prepared above. After the addition was complete, the mixture was stirred at 80 °C for 4 h to obtain a clear and transparent solution. Under continuous nitrogen protection, the mixture was stirred at 140 °C for 10 h. The residue was filtered and washed with methanol and tetrahydrofuran to obtain 1,3,5-tris(4-aminophenyl)benzene-polyimide covalent organic framework material (TAPB-PI COF).

[0086] Figure 5 The powder X-ray diffraction pattern of the 1,3,5-tris(4-aminophenyl)benzene-polyimide covalent organic framework material (TAPB-PI COF) obtained in Example 5 is shown below. Figure 5 It can be seen that TAPB-PI COF was successfully prepared.

[0087] Example 6

[0088] Dissolve 218.12 mg of pyromellitic dianhydride in 3.0 mL of methanol, heat to 85 °C under nitrogen protection, and stir for 8 h to obtain a clear and transparent carboxylic acid ester solution for later use.

[0089] 283.35 mg of 1,3,6,8-tetra(4-aminophenyl)pyrene was weighed and dispersed in 10.0 mL of a mixed solvent of N-methylpyrrolidone and mesitylene (1:3, v:v) to obtain a 1,3,6,8-tetra(4-aminophenyl)pyrene dispersion.

[0090] Under nitrogen protection, the carboxylate ester solution obtained above was added dropwise to the 1,3,6,8-tetra(4-aminophenyl)pyrene dispersion prepared above, and stirred and mixed at 50°C for 2 h to obtain a clear and transparent solution. Under continuous nitrogen protection, the mixture was stirred at 130°C for 20 h, and the residue was filtered. The residue was washed with methanol and tetrahydrofuran to obtain 1,3,6,8-tetra(4-aminophenyl)pyrene-polyimide covalent organic framework material (Py-PI COF).

[0091] Figure 6 The powder X-ray diffraction pattern of the 1,3,6,8-tetrakis(4-aminophenyl)pyrene-polyimide covalent organic framework material (Py-PI COF) obtained in Example 6 is shown below. Figure 6 It can be seen that Py-PI COF was successfully prepared.

[0092] Example 7

[0093] Dissolve 109.06 mg of pyromellitic dianhydride in 2.0 mL of methanol, heat to 65 °C under nitrogen protection, and stir for 4 h to obtain a clear and transparent carboxylic acid ester solution for later use.

[0094] 98.13 mg of tetra-(4-aminophenyl)ethylene was weighed and dispersed in 5.0 mL of a mixed solvent of N-methylpyrrolidone and mesitylene (1:5, v:v) to obtain a tetra-(4-aminophenyl)ethylene dispersion.

[0095] Under nitrogen protection, the carboxylic acid ester solution obtained above was added dropwise to the tetra-(4-aminophenyl)ethylene dispersion prepared above, and stirred and mixed at 50°C for 2 h to obtain a clear and transparent solution. Under continuous nitrogen protection, the mixture was stirred at 130°C for 15 h, filtered to obtain the filter residue, and washed with methanol and tetrahydrofuran to obtain tetra-(4-aminophenyl)ethylene-polyimide covalent organic framework material (AIE-PI COF).

[0096] Figure 7 The powder X-ray diffraction pattern of the tetra-(4-aminophenyl)ethylene-polyimide covalent organic framework material (AIE-PICOF) obtained in Example 7 is shown below. Figure 7It can be seen that AIE-PI COF was successfully prepared.

[0097] Example 8

[0098] Dissolve 50.00 g of pyromellitic dianhydride in 500.0 mL of methanol, heat to 65 °C under nitrogen protection, and stir for 12 h to obtain a clear and transparent carboxylic acid ester solution for later use.

[0099] 29.00 g of tris(4-aminophenyl)amine (TAPA) was weighed and dispersed in 600.0 mL of a mixed solvent of N-methylpyrrolidone and mesitylene (1:2, v:v) to obtain a tris(4-aminophenyl)amine dispersion.

[0100] Under nitrogen protection, 327 mL of the carboxylic acid ester solution was added dropwise to the prepared tri(4-aminophenyl)amine dispersion. After the addition was complete, the mixture was stirred at 65 °C for 3 h to obtain a clear and transparent solution. Under continuous nitrogen protection, the mixture was stirred at 160 °C for 24 h. The residue was filtered and washed with methanol and tetrahydrofuran to obtain the tri(4-aminophenyl)amine-polyimide covalent organic framework material (TAPA-PI COF).

[0101] Figure 8 The powder X-ray diffraction pattern of the tris(4-aminophenyl)amine-polyimide covalent organic framework material (TAPA-PICOF) obtained in Example 8 is shown below. Figure 8 It can be seen that a large batch of TAPA-PI COF was successfully prepared.

[0102] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method of preparing a polyimide covalent organic framework, characterized by, The method comprises the following steps: Step 1: mixing an anhydride compound and an alcohol solvent to perform pre-reaction to obtain a carboxylic ester solution; Step 2: dispersing an amino building block to obtain an amino building block dispersion solution; Step 3: mixing the amino building block dispersion solution and the carboxylic ester solution to perform reaction to obtain the polyimide covalent organic framework; In step 1, the anhydride compound comprises one or more of pyromellitic dianhydride, 1,4,5,8-naphthalenetetracarboxylic anhydride and 3,4,9,10-perylenetetracarboxylic dianhydride; the alcohol solvent is one or more of methanol, ethanol and propanol; the use amount ratio of the anhydride compound and the alcohol solvent is 10-1000 mg: 1-10 mL; the pre-reaction temperature is 60-100 DEG C, the pressure is normal pressure, and the time is 2-12 h; In step 2, the amino building block comprises one or more of tris(4-aminophenyl)amine, 2,4,6-tris(4-aminophenyl)-1,3,5-triazine, 4,4',4''-(pyrimidine-2,4,6-triyl)triphenylamine, 4-(4-aminophenyl)-2,6-di(4-aminophenyl)pyridine, 1,3,5-tris(4-aminophenyl)benzene, 1,3,6,8-tetra(4-aminophenyl)pyrene and tetra-(4-aminophenyl)ethylene; the dispersing reagent is a mixed solvent of N-methylpyrrolidone and mesitylene, the volume ratio of the N-methylpyrrolidone and the mesitylene is 5:1-1:5; and the concentration of the amino building block dispersion solution is 5-55 mg / mL; In step 3, the volume ratio of the amino building block dispersion solution and the carboxylic ester solution is 1-10:0.327-5; the reaction temperature is 100-180 DEG C, the pressure is normal pressure, and the time is 4-24 h.

2. The production method according to claim 1, characterized by, In step 3, after the reaction is completed, the method further comprises: filtering the obtained reaction liquid, collecting the filter residue, cleaning the filter residue, and obtaining the polyimide covalent organic framework.

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