Method for preparing single-crystalline vinylidene-bridged covalent organic framework

Abstract

The present invention belongs to the technical field of covalent organic frameworks, and particularly relates to a method for preparing a single-crystalline vinylidene-bridged covalent organic framework. The method for preparing a single-crystalline vinylidene-bridged covalent organic framework comprises: mixing a single-crystalline imine-linked covalent organic framework, an active monomer, a catalyst and an organic solvent until uniform, and then performing a substitution reaction, wherein the substitution reaction is one or more of an aldol condensation reaction, a Knoevenagel condensation reaction, and a Claisen-Schmidt reaction. The single-crystalline vinylidene-bridged covalent organic framework having good stability, rich active sites, high photoelectric activity and a high conjugation degree is obtained by means of a substitution reaction of the single-crystalline imine-linked covalent organic framework and the active monomer under the action of a catalyst.

Description

A method for preparing single-crystal vinyl-bridged covalent organic framework material

[0001] The invention belongs to the technical field of covalent organic framework materials, and particularly relates to a method for preparing a single-crystal vinyl-bridged covalent organic framework material. Background Art

[0002] Covalent organic frameworks (COFs) are porous crystalline frameworks with a two-dimensional topology formed by covalently linked π-conjugated building blocks. Their uniform pore size makes them suitable for applications in organic electronics, gas storage and separation, biomedicine, catalytic chemical engineering, desalination, fluorescence sensing, optoelectronic materials, and energy storage. COFs offer advantageous properties such as high crystallinity, large surface area, high electrical conductivity, high porosity, low skeleton density, and high thermochemical stability.

[0003] Among them, vinyl-bridged covalent organic framework materials (sp 2 C-COFs), is a type of 2 Carbon-connected organic porous materials have the characteristics of high conjugation, excellent carrier transport properties, high chemical and thermal stability, regular structure, strong designability and easy functionalization. They are widely used in the new generation of organic semiconductor devices, energy conversion and storage, sensing, gas adsorption and separation.

[0004] However, the vinyl bridged covalent organic framework materials synthesized by existing technologies are all polycrystalline or amorphous structures. 2 The main difficulty in preparing c-COFs is the excellent chemical stability of the vinyl bond, which causes the covalent organic framework materials based on reversible dynamic chemistry to lose the self-healing ability of the crystals. During the polymerization reaction, the stable vinyl connection mode makes the kinetically driven polymerization process dominant. The thermodynamically driven crystal self-healing process is constrained by the strong covalent bond connection mode, making it difficult to perform dynamic chemical self-repair of the crystals. As a result, the prepared covalent organic framework materials are partially ordered or completely disordered, causing structural defects and reduced performance. Technical issues

[0005] The purpose of the present invention is to solve the above technical problems and provide a method for preparing single-crystalline vinyl bridged covalent organic framework materials, which solves the problem of insufficient reversibility in traditional polymerization methods, resulting in polycrystalline or amorphous vinyl COFs, and can obtain single-crystalline vinyl bridged covalent organic framework materials (sc-sp) with excellent electrical conductivity and room temperature ferromagnetism. 2 c-COF). Technical Solutions

[0006] The preparation method of the single crystal vinyl bridged covalent organic framework material in the technical solution of the present invention comprises uniformly mixing the single crystal imine-based covalent organic framework material, an active monomer, a catalyst and an organic solvent and then performing a substitution reaction.

[0007] Single-crystal imine-based covalent organic framework materials have a highly ordered crystal structure and very regular molecular arrangement. Active monomers can be arranged and assembled in three-dimensional space, thereby avoiding the kinetic traps in the direct formation of stable carbon-carbon double bonds in traditional polymerization methods; at the same time, the imine bond is relatively unstable. During the single crystal transformation process, the imine monomers can be gradually replaced by active monomers to achieve the synthesis of single-crystal vinyl covalent organic frameworks. The resulting single-crystal vinyl-bridged covalent organic framework material has a long-range ordered crystal structure, good stability, rich active sites, high photoelectric activity, and high conjugation degree. It has excellent photoelectric activity and stability, thus exhibiting good conductivity and room-temperature ferromagnetism.

[0008] Furthermore, the single crystal imine-based covalent organic framework material is obtained by adding a nucleation inhibitor and a catalyst to a polyaldehyde phenyl compound solution, then adding a polyaminophenyl compound solution, and allowing the mixture to react at room temperature.

[0009] Preferably, the nucleation inhibitor is aniline or 2,2,2-trifluoroethylamine.

[0010] Preferably, the catalyst is an aqueous solution of acetic acid with a concentration of 5 to 10 mol / L.

[0011] Preferably, the solvents of the polyaldehyde phenyl compound solution and the polyamino phenyl compound solution are both 1,4-dioxane, and the concentrations thereof are 0.05-0.20 mmol / mL.

[0012] Furthermore, the molar ratio of the polyaldehyde phenyl compound to the polyamino phenyl compound is 0.8-1.2:0.8-1.2.

[0013] Preferably, the polyaldehyde phenyl compound includes but is not limited to one or more of tetrakis(4-aldehyde phenyl)silane, tetraaldehyde tetraphenylene, and 1,3-bis(3,5-dialdehyde phenyl)benzene; the polyaminophenyl compound includes but is not limited to one or more of tetrakis(4-aminophenyl)methane, bis(2-methylaminophenyl)amine, and 4-(2-(4-aminophenyl)-1,2-diphenylvinyl)aniline.

[0014] Preferably, the volume of the nucleation inhibitor and the catalyst is 0.1 to 1.0 times the volume of the polyaldehyde phenyl compound solution.

[0015] Further, the reaction is allowed to stand at room temperature for 10 to 40 days.

[0016] Preferably, the crystals obtained after standing for reaction at room temperature are washed with 1,4-dioxane by Soxhlet extraction for 20-30 h, dried at room temperature for 10-20 h, then dried at 80-120° C. with forced air for 10-20 h, and then vacuum dried at 80-120° C. for 10-20 h.

[0017] Furthermore, the molar ratio of the active monomer to the smallest fragment of the single-crystalline imine-based covalent organic framework material is 3.0:0.1~1.0; the smallest fragment of the single-crystalline imine-based covalent organic framework material is the most basic geometric unit (Unit Cell) constituting the imine-based covalent organic framework material crystal.

[0018] Furthermore, the substitution reaction is one or more of an aldol condensation reaction, a Knoevenagel condensation reaction, and a Claisen-Schmidt reaction.

[0019] Further, when the substitution reaction is an aldol condensation reaction, the active monomer is one or two of an azine methyl monomer and an azole methyl monomer, including but not limited to 3,6-dimethylpyridazine, 2,3,5,6-tetramethylpyrazine, 2,2',6,6'-tetramethyl-4,4'-bipyridine, 4,7-dimethyl-[1,2,5]oxadiazolo[3,4-c]pyridine, 2,6-dimethylbenzo[1,2-d:4,5-d']bis(thiazole), 2,6-dimethylbenzo[1,2-d:5,4-d']bis(thiazole), One or more of 2,6-dimethylbenzo[1,2-d:4,5-d']bisoxazole, 5,10,15,20-tetrakis(2-methylpyrimidin-5-yl)porphyrin, 5,5',5'',5'''-(1,10-dihydroperene-2,5,8,11-tetrakis(2-methylpyrimidine), and 2,3,6,7,10,11-hexa(2-methylpyrimidin-5-yl)dipyrazino[2,3-f:2',3'-h]quinoxaline.

[0020] Furthermore, when the substitution reaction is a Knoevenagel condensation reaction, the active monomer is a cyano-substituted methylene monomer, including but not limited to terephthalonitrile, 2,2'-(perfluoro-1,4-phenylene)diacetonitrile, 2,2'-([1,1'-biphenyl]-4,4'-diyl)diacetonitrile, 2,2',2''-((1,3,5-triazine-2,4,6-triyl)tris(phenyl-4,1-diyl))triacetonitrile, 2,2' , one or more of 2'',2'''-(porphyrin-5,10,15,20-tetrayltetra(benzene-4,1-diyl))tetraacetonitrile, 2,2',2'',2'''-(pyrene-1,3,6,8-tetrayltetra(benzene-4,1-diyl))tetraacetonitrile, and 2,2',2'',2'''-((1,10-dihydroperene-2,5,8,11-tetrayl)tetra(benzene-4,1-diyl))tetraacetonitrile.

[0021] Furthermore, when the substitution reaction is a Claisen-Schmidt reaction, the active monomer is an acetylphenyl monomer, including but not limited to one or more of 1,1'-(1,4-phenylene)bis(ethane-1-one); 1,1'-(perfluoro-[1,1'-biphenyl]-4,4'-diyl)bis(ethane-1-one); 1,1'-(acetylene-1,2-diylbis(4,1-phenylene))bis(ethane-1-one); 1,1',1''-((1,3,5-triazine-2,4,6-triyl)tri(benzene-4,1-diyl))tri(ethane-1-one); and 1,1',1''-((benzene-1,3,5-tri(acetylene-2,1-diyl))tri(benzene-4,1-diyl))tri(ethane-1-one).

[0022] Furthermore, the catalyst is one or more of benzoic acid, benzoic anhydride, p-toluenesulfonic acid, trifluoroacetic acid, acetic acid, p-toluic anhydride, p-fluorobenzoic acid, phthalic acid, terephthalic acid, trimesic acid, pyromellitic acid, p-toluenesulfonic acid, m-toluic acid, cesium carbonate, sodium hydroxide, potassium hydroxide, and 1,8-diazabicycloundec-7-ene.

[0023] Preferably, the mass of the catalyst is 1.0-5.0% of the mass of the single crystal imine-based covalent organic framework material.

[0024] Furthermore, the organic solvent is one or more of o-dichlorobenzene, n-butanol, toluene, mesitylene, n-butanol, 1,4-dioxane, benzoic anhydride, and dimethylacetamide.

[0025] Preferably, 0.1-2.0 ml of organic solvent is added to 1 mg of the single-crystalline imine-based covalent organic framework material; more preferably, 0.1-0.5 ml of organic solvent is added to 1 mg of the single-crystalline imine-based covalent organic framework material.

[0026] Furthermore, in the above-mentioned method for preparing the single-crystalline vinyl-bridged covalent organic framework material, the components are mixed, vacuumed and filled with nitrogen, and the operation is repeated 3 to 10 times.

[0027] Furthermore, the substitution reaction temperature is 80-200° C., and the time is 3-15 days.

[0028] Preferably, the product obtained after the substitution reaction is washed with acetone and tetrahydrofuran solvents in sequence, and then vacuum dried.

[0029] The present invention also provides a single crystal vinyl bridged covalent organic framework material, which is prepared by the above-mentioned preparation method of the single crystal vinyl bridged covalent organic framework material.

[0030] Furthermore, the specific surface area of ​​single-crystal vinyl-bridged covalent organic framework materials is 100~2000m2 / g, pore size is 0.5~4.0nm.

[0031] Compared with the prior art, the technical solution of the present invention has the following beneficial effects:

[0032] (1) Through the substitution reaction of single-crystal imine-based covalent organic framework materials and active monomers under the action of catalysts, single-crystal vinyl-bridged covalent organic framework materials with good stability, rich active sites, high photoelectric activity, and high conjugation degree are obtained, which show excellent electrical conductivity and room-temperature ferromagnetism;

[0033] (2) Single-crystal imine-based covalent organic framework materials can arrange and assemble active monomers in three-dimensional space, thereby avoiding the kinetic traps in the process of directly forming stable carbon-carbon double bonds in traditional polymerization methods, and solving the problem that the traditional polymerization method is not reversible enough, resulting in vinyl COFs being polycrystalline or amorphous;

[0034] (3) The imine bond in the single-crystal imine-based covalent organic framework material is relatively unstable. During the single-crystal transformation process, the imine monomer can be gradually replaced by an active monomer, thus achieving the efficient synthesis of single-crystal vinyl-bridged covalent organic frameworks.

[0035] (4) The method for preparing the single-crystalline vinyl-bridged covalent organic framework material uses the single-crystalline imine-based covalent organic framework material as a template and does not require a large amount of solvent system for preparation. The target single-crystalline vinyl-bridged covalent organic framework material can be quickly prepared. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] FIG1 is a schematic diagram of a method for preparing a single-crystalline vinyl-bridged covalent organic framework material according to the present invention;

[0037] Figure 2 shows the single crystal vinyl bridged covalent organic framework material sc-sp obtained in Example 1 2 Infrared spectra of c-COF-1 and single-crystalline imine-based covalent organic framework material COF-303;

[0038] Figure 3 shows the single crystal vinyl bridged covalent organic framework material sc-sp obtained in Example 1 2 Raman spectra of c-COF-1 and single-crystalline imine-based covalent organic framework material COF-303;

[0039] Figure 4 shows the single crystal vinyl bridged covalent organic framework material sc-sp obtained in Example 1 2 X-ray diffraction pattern of c-COF-1;

[0040] Figure 5 shows the single crystal vinyl bridged covalent organic framework material sc-sp obtained in Example 1 2 Solid-state NMR carbon spectra of c-COF-1 and single-crystalline imine-based covalent organic framework material COF-303;

[0041] Figure 6 shows the single crystal vinyl bridged covalent organic framework material sc-sp obtained in Example 1 2 Optical images of c-COF-1 and single-crystalline imine-based covalent organic framework material COF-303;

[0042] Figure 7 Single crystal vinyl bridged covalent organic framework material sc-sp obtained in Example 1 2 Magnetic properties of c-COF-1 and single-crystalline imine-based covalent organic framework material COF-303;

[0043] Figure 8 shows the single crystal vinyl bridged covalent organic framework material sc-sp obtained in Example 2 and Example 3 2 c-COF-2 and sc-sp 2 X-ray diffraction spectrum of c-COF-3. Modes for Carrying Out the Invention

[0044] The technical solution of the present invention will be further described below by means of specific examples and accompanying drawings. It should be understood that the specific embodiments described herein are only used to help understand the present invention and are not intended to be limiting of the present invention. The accompanying drawings used herein are only for the purpose of better illustrating the present invention and do not limit the scope of protection. Unless otherwise specified, the raw materials used in the embodiments of the present invention are all commonly used raw materials in the art, and the methods used in the embodiments are all conventional methods in the art.

[0045] The preparation method of the single crystal imine-based covalent organic framework material used in the following examples refers to the preparation process of Example 1 in Chinese patent CN106083909A:

[0046] 22.4 mg of tetrakis(4-formylphenyl)silane (0.05 mmol) was dissolved in 0.5 mL of 1,4-dioxane, and aniline (0.3 mL, 70 eq) and aqueous acetic acid solution (6 M, 0.2 mL) were added. Then, 19.0 mg of tetrakis(4-aminophenyl)methane (0.05 mmol) was dissolved in 0.5 mL of 1,4-dioxane and added to the above mixed system. The reaction was allowed to stand at room temperature for 10 days. The obtained crystals were washed with 1,4-dioxane by Soxhlet extraction for 24 h, dried at room temperature for 12 h, dried at 100 ° C for 12 h, and dried in vacuum at 100 ° C for 12 h. Example 1

[0047] The preparation method of the single-crystalline vinyl-bridged covalent organic framework material in this embodiment includes adding a single-crystalline imine-based covalent organic framework material (COF-303, 8 mg), 2,5-dimethylpyrazine, trifluoroacetic acid (180 μL), mesitylene (0.5 ml), and 1,4-dioxane (0.5 ml) into a quartz glass tube and mixing them evenly. The molar ratio of 2,5-dimethylpyrazine to the smallest fragment of the single-crystalline imine-based covalent organic framework material is 3.0:0.5. The mixed reaction system is evacuated and filled with nitrogen for three cycles and then sealed. The system is heated at 120° C. for three days. After the reaction is completed, the product is washed with acetone and tetrahydrofuran solvents in sequence and dried under vacuum to obtain sc-sp. 2 c-COF-1.

[0048] The obtained sc-sp 2 The infrared spectrum characterization results of c-COF-1 are shown in Figure 2. -1 The infrared vibration peak at indicates the formation of carbon-carbon double bonds; the Raman spectrum characterization results are shown in Figure 3, and the formation of carbon-carbon double bonds can also be seen; the X-ray diffraction pattern is shown in Figure 4, and it can be seen that the material has good crystallinity; the optical image (Figure 6) shows that after the single crystal conversion, the sc-sp 2 c-COF-1 still maintains a single crystal morphology; sc-sp 2 The solid-state NMR carbon spectra of c-COF-1 and imine-based COF-303 are shown in Figure 5. After the single crystal conversion, the carbon signal on the imine at 158 ​​ppm disappears, and a new carbon-carbon double bond signal is generated at 128, indicating that the single crystal imine-based covalent organic framework material is completely transformed from the chemical structure to the single crystal vinyl-bridged covalent organic framework material; Figure 7 shows the obtained sc-sp 2 The magnetic intensity of c-COF-1 is 8.04×10 -2 emug -1 , showing good room-temperature ferromagnetism. Example 2

[0049] The preparation method of the single-crystalline vinyl-bridged covalent organic framework material in this embodiment includes adding a single-crystalline imine-based covalent organic framework material (COF-303, 8 mg), 3,6-dimethylpyridazine, trifluoroacetic acid (180 μL), mesitylene (0.5 ml), and 1,4-dioxane (0.5 ml) into a quartz glass tube and mixing them evenly. The molar ratio of 3,6-dimethylpyridazine to the smallest fragment of the single-crystalline imine-based covalent organic framework material is 3.0:0.8. The mixed reaction system is evacuated and filled with nitrogen for three cycles and then sealed. The system is heated at 150° C. for three days. After the reaction is completed, the product is washed with acetone and tetrahydrofuran solvents in sequence and dried in vacuo to obtain sc-sp. 2 c-COF-2, as shown in Figure 8, it can be seen that the material has good crystallinity. Example 3

[0050] The preparation method of the single-crystalline vinyl-bridged covalent organic framework material in this embodiment includes adding a single-crystalline imine-based covalent organic framework material (COF-303, 8 mg), 3,6-dimethyl-1,2,4,5-tetrazine, trifluoroacetic acid (180 μL), mesitylene (0.5 ml), and 1,4-dioxane (0.5 ml) into a quartz glass tube and mixing them evenly. The molar ratio of 3,6-dimethyl-1,2,4,5-tetrazine to the smallest fragment of the single-crystalline imine-based covalent organic framework material is 3.0:0.5. The mixed reaction system is evacuated and filled with nitrogen for three cycles and then sealed. The mixture is heated at 100° C. for 5 days. After the reaction is completed, the product is washed with acetone and tetrahydrofuran solvents in sequence and dried in vacuo to obtain sc-sp. 2 c-COF-3, as shown in Figure 8, it can be seen that the material has good crystallinity. Example 4

[0051] The preparation method of the single-crystalline vinyl-bridged covalent organic framework material in this embodiment includes adding a single-crystalline imine-based covalent organic framework material (COF-303, 8 mg), 1,1'-(1,4-phenylene)bis(ethan-1-one), cesium carbonate (0.1 mL, 1M aqueous solution), and dimethylacetamide (1 mL) into a quartz glass tube and mixing them evenly. The molar ratio of 1,1'-(1,4-phenylene)bis(ethan-1-one) to the smallest fragment of the single-crystalline imine-based covalent organic framework material is 3.0:0.5. The mixed reaction system is evacuated and filled with nitrogen for 4 cycles and then sealed. The system is heated at 120°C for 3 days. After the reaction, the product is washed with acetone and tetrahydrofuran solvents in sequence and dried in vacuo to obtain sc-sp. 2 c-COF-4. Example 5

[0052] The preparation method of the single-crystalline vinyl-bridged covalent organic framework material in this embodiment includes adding a single-crystalline imine-based covalent organic framework material (COF-303, 8 mg), 1,1'-(2,3,5,6-tetramethyl-1,4-phenylene)bisethane-1-one, cesium carbonate (0.1 mL, 1M aqueous solution) and dimethylacetamide (1 mL) into a quartz glass tube and mixing them evenly. The molar ratio of 1,1'-(2,3,5,6-tetramethyl-1,4-phenylene)bisethane-1-one to the smallest fragment of the single-crystalline imine-based covalent organic framework material is 3.0:0.5. The mixed reaction system is evacuated and filled with nitrogen for 3 cycles and then sealed. The system is heated at 120°C for 3 days. After the reaction, the product is washed with acetone and tetrahydrofuran solvents in sequence and dried in vacuo to obtain sc-sp. 2 c-COF-5. Example 6

[0053] The preparation method of the single-crystalline vinyl-bridged covalent organic framework material in this embodiment includes adding a single-crystalline imine-based covalent organic framework material (COF-303, 8 mg), terephthalonitrile, cesium carbonate (0.1 mL, 1 M aqueous solution), and dimethylacetamide (1 mL) into a quartz glass tube and mixing them uniformly. The molar ratio of terephthalonitrile to the smallest fragment of the single-crystalline imine-based covalent organic framework material is 3.0:0.6. The mixed reaction system is evacuated and filled with nitrogen for three cycles and then sealed. The system is heated at 180°C for three days. After the reaction is completed, the product is washed with acetone and tetrahydrofuran solvents in sequence and dried under vacuum to obtain sc-sp. 2 c-COF-6. Example 7

[0054] The preparation method of the single-crystalline vinyl-bridged covalent organic framework material in this embodiment includes adding a single-crystalline imine-based covalent organic framework material (COF-303, 8 mg), [1,1'-biphenyl]-4,4'-dicarbonitrile, cesium carbonate (0.1 mL, 1 M aqueous solution) and dimethylacetamide (1 mL) into a quartz glass tube and mixing them evenly. The molar ratio of [1,1'-biphenyl]-4,4'-dicarbonitrile to the smallest fragment of the single-crystalline imine-based covalent organic framework material is 3.0:1.0. The mixed reaction system is evacuated and filled with nitrogen for 3 cycles and then sealed. The system is heated at 120°C for 3 days. After the reaction is completed, the product is washed with acetone and tetrahydrofuran solvents in sequence and dried in vacuo to obtain sc-sp 2 c-COF-7. Example 8

[0055] The preparation method of the single-crystalline vinyl-bridged covalent organic framework material in this embodiment includes adding a single-crystalline imine-based covalent organic framework material (COF-303, 8 mg), 2,3,5,6-tetramethylterephthalonitrile, cesium carbonate (0.1 mL, 1 M aqueous solution) and dimethylacetamide (1 mL) into a quartz glass tube and mixing them evenly. The molar ratio of 2,3,5,6-tetramethylterephthalonitrile to the smallest fragment of the single-crystalline imine-based covalent organic framework material is 3.0:0.5. The mixed reaction system is evacuated and filled with nitrogen for 3 cycles and then sealed. The system is heated at 150°C for 5 days. After the reaction is completed, the product is washed with acetone and tetrahydrofuran solvents in sequence and dried in vacuo to obtain sc-sp. 2 c-COF-8. Comparative Example 1

[0056] The preparation method of the vinyl-bridged covalent organic framework material in this comparative example includes adding 10.8 mg of tetrakis(4-formylphenyl)methane, 12.5 mg of 1,2,5-trimethylpyrazine-1-iodide, 0.5 mL of mesitylene, 0.5 mL of 1,4-dioxane, and 0.2 mL of trifluoroacetic acid into a quartz glass tube and mixing them evenly, vacuuming and filling the mixed reaction system with nitrogen, performing three cycles, and then sealing the system. The system is heated at 150° C. for 3 days. After the reaction is completed, the product is washed with acetone and tetrahydrofuran solvents in sequence, and vacuum dried to obtain the vinyl-bridged covalent organic framework material.

[0057] As shown in Figure 1, the present invention involves a substitution reaction between a single crystal imine-based covalent organic framework material and an active monomer under the action of a catalyst, and the conversion of an imine single crystal to a vinyl single crystal is achieved through monomer replacement, ultimately obtaining a single crystal vinyl-bridged covalent organic framework material with good stability, abundant active sites, high photoelectric activity, and high conjugation. Examples 1-8 involve a substitution reaction between a single crystal imine-based covalent organic framework material and an active monomer under the action of a catalyst, and the resulting single crystal vinyl-bridged covalent organic framework material has good stability, abundant active sites, high photoelectric activity, high conjugation, excellent electrical conductivity, and room temperature ferromagnetism. The vinyl-bridged covalent organic framework material obtained in Comparative Example 1 is a polycrystalline structure with poor electrical conductivity and room temperature ferromagnetism.

[0058] Finally, it should be noted that the specific embodiments described herein are merely illustrative of the spirit of the present invention and are not intended to limit the manner in which the present invention is intended to be implemented. Persons skilled in the art may make various modifications, additions, or substitutions to the described embodiments, and it is not necessary or possible to provide a comprehensive list of all possible embodiments. However, any obvious changes or modifications arising from the essential spirit of the present invention remain within the scope of protection of the present invention, and interpreting them as any additional limitations would be contrary to the spirit of the present invention.

Claims

1. A method for preparing a single-crystalline vinyl-bridged covalent organic framework material, characterized in that: The method comprises uniformly mixing a single crystal imine-based covalent organic framework material, an active monomer and a catalyst and then performing a substitution reaction.

2. The preparation method according to claim 1, characterized in that The preparation method comprises the steps of uniformly mixing a single crystal imine-based covalent organic framework material, an active monomer, a catalyst and an organic solvent and then performing a substitution reaction.

3. The preparation method according to claim 1 or 2, characterized in that The single crystal imine-based covalent organic framework material is obtained by adding a nucleation inhibitor and a catalyst into a polyaldehyde phenyl compound solution, then adding a polyaminophenyl compound solution, and allowing the mixture to react at room temperature.

4. The preparation method according to claim 1 or 2, characterized in that The molar ratio of active monomer to the smallest fragment of single-crystal imine-based covalent organic framework material is 3.0:0.1~1.

0.

5. The preparation method according to claim 1, characterized in that The substitution reaction is one or more of an aldol condensation reaction, a Knoevenagel condensation reaction, and a Claisen-Schmidt reaction.

6. The preparation method according to claim 1, 2 or 5, characterized in that: When the substitution reaction is an aldol condensation reaction, the active monomer is one or both of an oxazine methyl monomer and an azole methyl monomer.

7. The preparation method according to claim 1, 2 or 5, characterized in that: When the substitution reaction is a Knoevenagel condensation reaction, the active monomer is a cyano-substituted methylene monomer.

8. The preparation method according to claim 1, 2 or 5, characterized in that: When the substitution reaction is a Claisen-Schmidt reaction, the active monomer is an acetylphenyl monomer.

9. The preparation method according to claim 1 or 2, characterized in that: The catalyst is one or more of benzoic acid, benzoic anhydride, p-toluenesulfonic acid, trifluoroacetic acid, acetic acid, p-toluic anhydride, p-fluorobenzoic acid, phthalic acid, terephthalic acid, trimesic acid, pyromellitic acid, p-toluenesulfonic acid, m-toluic acid, cesium carbonate, sodium hydroxide, potassium hydroxide, and 1,8-diazabicycloundec-7-ene.

10. The preparation method according to claim 1 or 2, characterized in that: The mass of the catalyst is 1.0-5.0% of the mass of the single crystal imine-based covalent organic framework material.

11. The preparation method according to claim 2, characterized in that The organic solvent is one or more of o-dichlorobenzene, n-butanol, toluene, mesitylene, n-butanol, 1,4-dioxane, benzoic anhydride, and dimethylacetamide.

12. The preparation method according to claim 1 or 2, characterized in that: In the preparation method, the components are mixed, vacuumed and filled with nitrogen, and the operation is repeated 3 to 10 times.

13. The preparation method according to claim 1 or 2, characterized in that The temperature of the substitution reaction is 80~200°C and the time is 3~15 days.

14. A single crystal vinyl bridged covalent organic framework material, characterized in that: The single crystal vinyl bridged covalent organic framework material is prepared by the preparation method of the single crystal vinyl bridged covalent organic framework material according to claim 1 or 2.

15. The single crystal vinyl bridged covalent organic framework material according to claim 14, characterized in that: The specific surface area of ​​the single crystal vinyl bridged covalent organic framework material is 100-2000 m 2 / g, pore size is 0.5~4.0nm.

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