Preparation method of polyimide covalent organic framework

Abstract

The invention belongs to the technical field of polymer synthesis, and provides a preparation method of a polyimide covalent organic framework. The preparation method comprises the following steps: mixing an anhydride compound (one or more of pyromellitic dianhydride, 1, 4, 5, 8-naphthalene tetracarboxylic anhydride and 3, 4, 9, 10-perylenetetracarboxylic dianhydride) with an alcohol solvent, and carrying out pre-reaction to obtain a carboxylic acid ester solution; the preparation method comprises the following steps: dispersing amino building blocks (tris (4-aminophenyl) amine, 1, 3, 6, 8-tetra (4-aminophenyl) pyrene and the like) to obtain amino building block dispersion liquid; and mixing the amino block dispersion liquid and the carboxylic acid ester solution for reaction to obtain the polyimide covalent organic framework. The preparation method disclosed by the invention can be carried out under normal pressure and is safer to operate; meanwhile, the preparation method disclosed by the invention is not carried out in tube sealing, and can be used for preparing the polyimide covalent organic framework on a large scale.

Description

Technical Field

[0001] The invention relates to the technical field of polymer synthesis, and in particular to a method for preparing a polyimide covalent organic framework. Background Art

[0002] Two-dimensional covalent organic frameworks (2D COFs) have become a material of great interest due to their flexible structural design, long-range order, unique layered structure, customizable periodic skeleton, and ordered nanopore structure. With the understanding of covalent organic frameworks by researchers, they have shown great application potential in the field of mechanical friction and lubrication. The existing technology for preparing polyimide covalent organic frameworks generally requires sealing the tube, which requires high pressure and is very dangerous to operate. Summary of the invention

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

[0004] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

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

[0006] The acid anhydride compound and the alcohol solvent are mixed and pre-reacted to obtain a carboxylate solution;

[0007] dispersing the amino building blocks to obtain an amino building block dispersion;

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

[0009] The acid anhydride compound includes one or more of pyromellitic dianhydride, 1,4,5,8-naphthalenetetracarboxylic anhydride and 3,4,9,10-perylenetetracarboxylic dianhydride;

[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"-(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-tetrakis(4-aminophenyl)pyrene and tetrakis-(4-aminophenyl)ethylene.

[0011] Preferably, the alcohol solvent is a small molecule alcohol, and the number of carbon atoms in the small molecule alcohol is 1-6.

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

[0013] Preferably, the usage 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 normal pressure, and the time is 2-12 hours.

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

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

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

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

[0019] Preferably, after the reaction is completed, the method further comprises: filtering the obtained reaction liquid, collecting filter residues, and washing the filter residues to obtain the polyimide covalent organic framework.

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

[0021] The preparation method provided by the present invention can be carried out under normal pressure, and the operation is safer; at the same time, the preparation method of the present invention is not carried out in a sealed tube, and can be used for mass preparation of polyimide covalent organic frameworks. BRIEF DESCRIPTION OF THE DRAWINGS

[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-triyl)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 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;

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

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

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

[0031] The acid anhydride compound and the alcohol solvent are mixed and pre-reacted to obtain a carboxylate solution;

[0032] dispersing the amino building blocks to obtain an amino building block dispersion;

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

[0034] The acid anhydride compound includes one or more of pyromellitic dianhydride, 1,4,5,8-naphthalenetetracarboxylic anhydride and 3,4,9,10-perylenetetracarboxylic dianhydride;

[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"-(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-tetrakis(4-aminophenyl)pyrene and tetrakis-(4-aminophenyl)ethylene.

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

[0037] The present invention mixes an acid anhydride compound and an alcohol solvent, performs a preliminary reaction, and obtains a carboxylate ester solution.

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

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

[0040] In the present invention, the dosage ratio of the acid anhydride compound and the alcohol solvent is preferably 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, 50 g:500 mL.

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

[0042] After the pre-reaction, the present invention preferably directly obtains the carboxylate solution without any post-treatment.

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

[0044]

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

[0046] In the present invention, the amino building block includes 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-tetrakis(4-aminophenyl)pyrene and tetrakis-(4-aminophenyl)ethylene.

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

[0048] In the present invention, the concentration of the amino building block dispersion is preferably 5 to 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 carboxylate solution and the amino building block dispersion, the present invention mixes the amino building block dispersion and the carboxylate solution to react and obtain the polyimide covalent organic framework.

[0050] In the present invention, the volume ratio of the amino building block dispersion to the carboxylate solution is preferably 1-10:0.327-5, more preferably 1:0.2-3, 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 the present invention, the mixing of the amino building block dispersion and the carboxylate solution preferably comprises the following steps: dropwise adding the carboxylate solution into the amino building block dispersion, and stirring and mixing after the dropwise addition of the carboxylate solution is completed; the dropping 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 2-4h, specifically preferably 2h, 3h or 4h; the mixing of the amino building block dispersion and the carboxylate solution is preferably carried out under nitrogen protection.

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

[0053] After the reaction is completed, the present invention preferably further comprises: filtering the obtained reaction liquid, collecting the filter residue, and washing the filter residue to obtain the polyimide covalent organic framework.

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

[0055] In the present invention, pyromellitic dianhydride is used as the anhydride compound, and the preparation formula of the preparation method provided by the present invention is as follows:

[0056]

[0057] In the present invention, pyromellitic dianhydride is used as an anhydride compound, 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 and 1,3,5-tris(4-aminophenyl)benzene are used as amino building blocks, and the structure of the prepared polyimide covalent organic framework is shown in the following formula:

[0058]

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

[0060]

[0061] The preparation method of the polyimide covalent organic framework provided by the present invention is described in detail below in conjunction with the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0062] Example 1

[0063] Take 50.00 mg of pyromellitic dianhydride and dissolve it in 1.0 mL of methanol. Heat it to 65° C. under nitrogen protection. Stir and react for 12 hours to obtain a clear and transparent carboxylate solution for standby 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 carboxylate solution was added dropwise to the above-prepared tri(4-aminophenyl)amine dispersion. After the addition was completed, the mixture was stirred at 65° C. for 3 h to obtain a clear and transparent solution. The mixture was stirred at 180° C. for 4 h under continuous nitrogen protection. The residue was filtered to obtain a filter residue. The filter residue was washed with methanol and tetrahydrofuran to obtain a 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 in FIG. Figure 1 It can be seen that TAPA-PI COF was successfully prepared.

[0067] Example 2

[0068] Take 1000.00 mg of pyromellitic dianhydride and dissolve it in 10.0 mL of ethanol. Heat it to 100° C. under nitrogen protection. Stir and react for 4 hours to obtain a clear and transparent carboxylate solution for standby 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 carboxylate solution was added dropwise to the above-prepared 2,4,6-tris(4-aminophenyl)-1,3,5-triazine dispersion. After the addition was completed, the mixture was stirred at 80° C. for 4 h to obtain a clear and transparent solution. The mixture was stirred at 120° C. for 24 h under continuous nitrogen protection. The residue was filtered to obtain a filter residue. The filter residue was washed with methanol and tetrahydrofuran to obtain a 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 2,4,6-tris(4-aminophenyl)-1,3,5-triazine-polyimide covalent organic framework material (TAPT-PI COF) obtained in Example 2 is shown in FIG. Figure 2 It can be seen that TAPT-PI COF was successfully prepared.

[0072] Example 3

[0073] Take 500.00 mg of pyromellitic dianhydride and dissolve it in 5.0 mL of propanol. Heat it to 80°C under nitrogen protection. Stir and react for 3 hours to obtain a clear and transparent carboxylate solution for standby 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 carboxylate solution was added dropwise to the above-prepared 4,4',4"-(pyrimidine-2,4,6-triyl)triphenylamine dispersion. After the addition was completed, the mixture was stirred at 60°C for 2 h to obtain a clear and transparent solution. The mixture was stirred at 100°C for 24 h under continuous nitrogen protection and filtered to obtain a filter residue. The filter residue was washed with methanol and tetrahydrofuran to obtain a 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 4,4',4"-(pyrimidine-2,4,6-triyl)triphenylamine-polyimide covalent organic framework material (TAPPm-PI COF) obtained in Example 3 is shown in FIG. Figure 3 It can be seen that TAPPm-PI COF was successfully prepared.

[0077] Example 4

[0078] Take 200.00 mg of pyromellitic dianhydride and dissolve it in 10.0 mL of ethanol. Heat it to 100° C. under nitrogen protection. Stir and react for 4 hours to obtain a clear and transparent carboxylate solution for standby 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 carboxylate solution was added dropwise to the above-prepared 4-(4-aminophenyl)-2,6-bis(4-aminophenyl)pyridine dispersion. After the addition was completed, the mixture was stirred at 65° C. for 4 h to obtain a clear and transparent solution. The mixture was stirred at 140° C. for 12 h under continuous nitrogen protection. The residue was filtered to obtain a filter residue. The filter residue was washed with methanol and tetrahydrofuran to obtain a 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 4-(4-aminophenyl)-2,6-di(4-aminophenyl)pyridine-polyimide covalent organic framework material (TAPP-PI COF) obtained in Example 4 is shown in FIG. Figure 4 It can be seen that TAPP-PI COF was successfully prepared.

[0082] Example 5

[0083] Take 327.00 mg of pyromellitic dianhydride and dissolve it in 5.0 mL of methanol. Heat it to 100° C. under nitrogen protection. Stir and react for 4 hours to obtain a clear and transparent carboxylate solution for standby 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 carboxylate solution was added dropwise to the 1,3,5-tri(4-aminophenyl)benzene dispersion prepared above. After the addition was completed, the mixture was stirred at 80° C. for 4 h to obtain a clear and transparent solution. The mixture was stirred at 140° C. for 10 h under continuous nitrogen protection. The residue was filtered to obtain a filter residue. The filter residue was washed with methanol and tetrahydrofuran to obtain a 1,3,5-tri(4-aminophenyl)benzene-polyimide covalent organic framework material (TAPB-PI COF).

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

[0087] Example 6

[0088] Take 218.12 mg of pyromellitic dianhydride and dissolve it in 3.0 mL of methanol. Heat it to 85°C under nitrogen protection. Stir and react for 8 hours to obtain a clear and transparent carboxylate solution for standby use.

[0089] 283.35 mg of 1,3,6,8-tetrakis(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-tetrakis(4-aminophenyl)pyrene dispersion.

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

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

[0092] Example 7

[0093] Take 109.06 mg of pyromellitic dianhydride and dissolve it in 2.0 mL of methanol. Heat it to 65°C under nitrogen protection. Stir and react for 4 hours to obtain a clear and transparent carboxylate solution for standby use.

[0094] 98.13 mg of tetrakis-(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 tetrakis-(4-aminophenyl)ethylene dispersion.

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

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

[0097] Example 8

[0098] Take 50.00 g of pyromellitic dianhydride and dissolve it in 500.0 mL of methanol. Heat it to 65° C. under nitrogen protection. Stir and react for 12 hours to obtain a clear and transparent carboxylate solution for standby 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 carboxylate solution was added dropwise to the above-prepared tri(4-aminophenyl)amine dispersion. After the addition was completed, the mixture was stirred at 65° C. for 3 h to obtain a clear and transparent solution. The mixture was stirred at 160° C. for 24 h under continuous nitrogen protection. The residue was filtered to obtain a filter residue, which was washed with methanol and tetrahydrofuran to obtain a 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 in FIG. Figure 8 It can be seen that large quantities of TAPA-PI COF were successfully prepared.

[0102] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for preparing a polyimide covalent organic framework, characterized in that: The following steps are involved: The acid anhydride compound and the alcohol solvent are mixed and pre-reacted to obtain a carboxylate solution; dispersing the amino building blocks to obtain an amino building block dispersion; The amino building block dispersion and the carboxylate solution are mixed and reacted to obtain the polyimide covalent organic framework; The acid anhydride compound includes one or more of pyromellitic dianhydride, 1,4,5,8-naphthalenetetracarboxylic anhydride and 3,4,9,10-perylenetetracarboxylic dianhydride; 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"-(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-tetrakis(4-aminophenyl)pyrene and tetrakis-(4-aminophenyl)ethylene.

2. The preparation method according to claim 1, characterized in that: The alcohol solvent is a small molecule alcohol, and the number of carbon atoms of the small molecule alcohol is 1-6.

3. The preparation method according to claim 2, characterized in that: The alcohol solvent includes one or more of methanol, ethanol and propanol.

4. The preparation method according to claim 1, characterized in that: The usage ratio of the acid anhydride compound to the alcohol solvent is 10-1000 mg:1-10 mL.

5. The preparation method according to claim 1, characterized in that: The temperature of the pre-reaction is 60-100° C., the pressure is normal pressure, and the time is 2-12 hours.

6. The preparation method according to claim 1, characterized in that: The dispersed reagent is a mixed solvent of N-methylpyrrolidone and mesitylene, and the volume ratio of N-methylpyrrolidone to mesitylene in the mixed solvent of N-methylpyrrolidone and mesitylene is 5:1 to 1:

5.

7. The preparation method according to claim 1 or 6, characterized in that: The concentration of the amino building block dispersion is 5-55 mg / mL.

8. The preparation method according to claim 1, characterized in that: The volume ratio of the amino building block dispersion to the carboxylate solution is 1-10:0.327-5.

9. The preparation method according to claim 1, characterized in that: The reaction temperature is 100-180° C., the pressure is normal pressure, and the reaction time is 4-24 hours.

10. The preparation method according to claim 1 or 9, characterized in that: After the reaction is completed, the method further comprises: filtering the obtained reaction liquid, collecting the filter residue, and washing the filter residue to obtain the polyimide covalent organic framework.

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