Vinyl porous organic polymer and preparation method thereof

Abstract

The invention relates to the technical field of porous organic polymers, and discloses a vinyl porous organic polymer and a preparation method thereof. The preparation method comprises the following steps: carrying out melt polymerization on an organic molecule A, an organic molecule B and a fluxing agent in a closed reactor, and purifying a reaction product to obtain the vinyl porous organic polymer, wherein the organic molecule A is pyridine or pyrazine containing at least two methyl functional groups; the organic molecule B is an aromatic compound containing two aldehyde functional groups; the fluxing agent is a compound containing an anhydride functional group, a compound containing an acyl chloride functional group or a compound containing a carboxylic acid functional group. The vinyl porous organic polymer POPs is synthesized through the specific reaction monomer and the fluxing agent by a melt polymerization method, so that the synthesis process of the vinyl porous organic polymer is simplified, the phenomena of high temperature and high pressure caused by the use of a large amount of organic solvent are avoided, and large-scale industrial production can be realized.

Description

Technical Field

[0001] The present application relates to the technical field of porous organic polymers, and in particular to a vinyl porous organic polymer and a preparation method thereof. Background Art

[0002] Porous organic polymers (POPs) are a type of organic porous materials with microporous or mesoporous structures, usually composed of elements such as C, H, O, N, and B. POPs materials have the characteristics of large pore size, high specific surface area, good stability, and high designability, and are widely used in gas storage and separation, catalysis, energy conversion and storage, sensors, and biomedicine.

[0003] At present, the synthesis methods of POPs mainly include solution polycondensation, interfacial polymerization, microwave-assisted synthesis, solid-phase synthesis, etc. Traditional methods such as solution polymerization, microwave-assisted synthesis, and solvent thermal synthesis of POPs require the addition of different amounts of organic solvents, which volatilize at higher reaction temperatures to produce higher pressures, which is not conducive to large-scale industrial production; on the other hand, when synthesizing vinyl polymers using traditional methods, it is necessary to precisely control the reaction conditions, such as temperature, pressure, type and concentration of initiators, etc., and the preparation process is complicated.

[0004] The melt polymerization method has shown great advantages in the preparation of polymer materials such as polyester and polyamide, and has achieved remarkable results in the large-scale industrial production of crystalline framework materials. However, the melt polymerization method is suitable for reversible bonding, and the irreversible bond characteristics of vinyl covalent porous polymers are difficult to synthesize through existing melt polymerization processes.

[0005] Based on this, it is of great significance to develop a melt polymerization synthesis method for vinyl POPs. Summary of the invention

[0006] The present application provides a vinyl porous organic polymer and a preparation method thereof, aiming to solve the problem that the existing vinyl porous organic polymer preparation process is complicated and difficult to mass produce.

[0007] In order to achieve the above objectives, the present application adopts the following technical solutions.

[0008] In a first aspect of the present application, a method for preparing a vinyl porous organic polymer is provided, comprising:

[0009] The organic molecule A, the organic molecule B and the flux are melt-polymerized in a closed reactor, and the reaction product is purified to obtain a vinyl porous organic polymer;

[0010] Wherein, the organic molecule A is pyridine or pyrazine containing at least two methyl functional groups;

[0011] The organic molecule B is an aromatic compound containing two aldehyde functional groups;

[0012] The flux is a compound containing anhydride functional groups, a compound containing acyl chloride functional groups or a compound containing carboxylic acid functional groups.

[0013] Preferably, the organic molecule A is pyrazine containing 2 to 4 methyl functional groups, or pyridine containing 2 to 3 methyl functional groups;

[0014] The organic molecule B includes any one of benzene or its derivatives, biphenyl or its derivatives, naphthalene or its derivatives, pyridine or its derivatives, bipyridine or its derivatives, anthracene or its derivatives, pyrazine or its derivatives, or phenanthroline or its derivatives containing two aldehyde functional groups.

[0015] Further preferably, the organic molecule A includes any one of 2,3,5,6-tetramethylpyrazine, 2,3,5,6-tetramethylpyrazine trihydrate, 2,3,5-trimethylpyrazine, 2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine, 2,3,5-trimethylpyridine, 2,4,5-trimethylpyridine or 2,3,6-trimethylpyridine.

[0016] Further preferably, the organic molecule B includes terephthalaldehyde, isophthalaldehyde, biphenyl dicarboxaldehyde, 2,5-dihydroxy-1,4-benzenedicarbaldehyde, 1,4-dialdehyde-2,5-divinylbenzene, 2,3-dihydroxyterephthalaldehyde, 2,5-dibromobenzene-1,4-dicarboxaldehyde, 2,5-diethoxy-1,4-terephthalaldehyde, 2,2'-bipyridine-5,5'-dicarboxaldehyde, 1,4-di(4-formylphenyl)benzene, 2,5-dialdehyde pyridine, 2,6-naphthalene dicarboxaldehyde, 5-hydroxyisophthalaldehyde, 1,10-phenanthroline Any one of 2,9-dicarboxaldehyde, 4-hydroxyisophthalaldehyde, anthracene-9,10-dicarboxaldehyde, 2,2'-bipyridine-4,4'-dicarboxaldehyde, 3,3'-bipyridine-6,6'-dicarboxaldehyde, 9,10-di(4-formylphenyl)anthracene, 3,6-dimethylterephthalaldehyde, pyridine-2,6-dicarboxaldehyde, 2-methoxy-4,6-diformylphenol, 2-nitroterephthalaldehyde, 2,5-diformylpyrazine, 2,3-hydroxy-1,4-diformylnaphthalene or 4,4'-dihydroxy-3,3'-glyoxalbiphenyl.

[0017] Further preferably, the flux includes at least one of benzoic anhydride, sodium benzoate, benzoyl chloride, 4-trifluoromethylbenzoic anhydride, 4-methoxybenzoic anhydride, acetic anhydride, trifluoroacetic anhydride, benzoic acid, 4-fluorobenzoic acid, acetic acid or propionic acid.

[0018] Preferably, the temperature of the melt polymerization is 120-200° C., and the reaction time is 24-120 h.

[0019] Preferably, the molar ratio of the organic molecule A, the organic molecule B and the flux is 1:(1τ2):(1-10).

[0020] Preferably, the pressure of the melt polymerization is normal pressure or negative pressure.

[0021] Preferably, the purification specifically comprises: soaking the reaction product in DMF, then performing Soxhlet extraction in methanol, and then drying at 80-200°C.

[0022] The second aspect of the present application provides a vinyl porous organic polymer prepared by the above preparation method.

[0023] Compared with the prior art, the beneficial effects of this application are:

[0024] The present application synthesizes vinyl porous organic polymer POPs by melt polymerization through specific reaction monomers and fluxes, which not only simplifies the synthesis process of vinyl porous organic polymers, but also avoids the high temperature and high pressure caused by the use of a large amount of organic solvents, so that it can be produced on a large scale in an industrialized manner. The melt polymerization method of the present application can prepare vinyl porous organic polymers with high surface area, high mechanical strength and high porosity, with a pore size of 0.5nm-3.0nm, high stability and high catalytic activity; it has important application value in the fields of gas storage and separation materials, catalysts, sensors, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following briefly introduces the drawings required for use in the description of the embodiments. Obviously, the drawings described below are only some embodiments recorded in the present application, and for ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0026] Figure 1 The infrared test spectra of the organic monomer A (2,3,5,6-tetramethylpyrazine), the organic monomer B (biphenyldicarboxaldehyde) and the vinyl porous organic polymer NKPOP-1 of Example 1;

[0027] Figure 2 The isothermal adsorption-desorption curve of nitrogen of the vinyl porous organic polymer NKPOP-1 at 77K;

[0028] Figure 3 is the pore size distribution curve of the vinyl porous organic polymer NKPOP-1;

[0029] Figure 4 This is a scanning electron microscope image of the vinyl porous organic polymer NKPOP-1;

[0030] Figure 5 Thermogravimetric curve of vinyl porous organic polymer NKPOP-1;

[0031] Figure 6 The infrared test spectra of the organic monomer A (2,6-dimethylpyrazine), the organic monomer B (isophthalaldehyde) and the vinyl porous organic polymer NKPOP-6 of Example 6;

[0032] Figure 7 The isothermal adsorption-desorption curve of nitrogen of the vinyl porous organic polymer NKPOP-6 at 77K;

[0033] Figure 8 is the pore size distribution curve of the vinyl porous organic polymer NKPOP-6;

[0034] Fig. 9 This is a scanning electron microscope image of the vinyl porous organic polymer NKPOP-6;

[0035] Fig.10 This is the thermogravimetric curve of the vinyl porous organic polymer NKPOP-6. DETAILED DESCRIPTION

[0036] The technical solutions in the embodiments of the present application will be described clearly and completely below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, rather than all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.

[0037] In the following description of this embodiment, the terms "include", "comprising", "having" and "containing" are all open terms, meaning including but not limited to.

[0038] In the following description of this embodiment, the term "and / or" is used to describe the association relationship of associated objects, indicating that there may be three relationships. For example, A and / or B can represent: A exists alone, B exists alone, and A and B exist at the same time. A and B can be singular or plural. The character " / " generally indicates that the associated objects before and after are in an "or" relationship.

[0039] In the following description of this embodiment, the term "at least one" refers to one or more, and "plurality" refers to two or more. "At least one of the following" or similar expressions refers to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b or c", or "at least one of a, b and c", can all represent: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, c can be single or multiple, respectively.

[0040] The terms used in the embodiments of the present application are only for the purpose of describing specific embodiments, and are not intended to limit the present application. The singular forms "a", "an" and "the" used in the embodiments of the present application and the appended claims are also intended to include plural forms, unless the context clearly indicates other meanings.

[0041] Those skilled in the art should understand that in the following description of the embodiments of the present application, the order of serial numbers does not mean the order of execution, some or all of the steps can be executed in parallel or sequentially, and the execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.

[0042] Those skilled in the art will appreciate that the numerical ranges in the embodiments of the present application are to be construed as specifically disclosing each intermediate value between the upper and lower limits of the scope. Each smaller range between the intermediate value in any stated value or stated range and any other stated value or intermediate value in the described range is also included in the present application. The upper and lower limits of these smaller ranges may be independently included or excluded in the scope.

[0043] Unless otherwise specified, the technical / scientific terms used herein have the same meanings as those generally understood by those skilled in the art to which this application belongs. Although this application only describes preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of this application. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials related to the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0044] In a first aspect, the present application provides a method for preparing a vinyl porous organic polymer, comprising:

[0045] The organic molecule A, the organic molecule B and the flux are melt-polymerized in a closed reactor, and the reaction product is purified to obtain a vinyl porous organic polymer;

[0046] Wherein, the organic molecule A is pyridine or pyrazine containing at least two methyl functional groups;

[0047] The organic molecule B is an aromatic compound containing two aldehyde functional groups;

[0048] The flux is a compound containing anhydride functional groups, a compound containing acyl chloride functional groups or a compound containing carboxylic acid functional groups.

[0049] Specifically, the present application adds organic molecule A, organic molecule B and flux into a closed reactor, such as a high temperature and high pressure resistant Pyrex tube, an ampoule that needs to be flame sealed, or a polytetrafluoroethylene lined autoclave, and heats to 120-200°C under normal pressure or negative pressure, reacts for 24-120 hours, and organic molecule A and organic molecule B undergo polymerization reaction, and the methyl group in organic molecule A and the aldehyde group in organic molecule B undergo polymerization reaction to form a carbon-carbon double bond, thereby obtaining a crude product containing a vinyl porous organic polymer. The crude product is soaked in DMF to remove unreacted monomers, and then Soxhlet extraction is performed in methanol to remove excess flux, and then dried in an oven at 80-200°C to obtain a powdery or blocky vinyl porous organic polymer.

[0050] In the present application, the organic molecule A can be selected from pyrazine containing two, three or four methyl substituents, or pyridine containing two or three methyl substituents; for example, any one of 2,3,5,6-tetramethylpyrazine, 2,3,5,6-tetramethylpyrazine trihydrate, 2,3,5-trimethylpyrazine, 2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 2,3,5-trimethylpyridine, 2,4,5-trimethylpyridine or 2,3,6-trimethylpyridine.

[0051] In the present application, the organic molecule B is an aromatic compound containing two aldehyde functional groups, including but not limited to benzene, biphenyl, naphthalene, pyridine, bipyridine, anthracene, pyrazine or phenanthroline containing two aldehyde functional groups, or a benzene derivative, biphenyl derivative, naphthalene derivative, pyridine derivative, bipyridine derivative, anthracene derivative, pyrazine derivative or phenanthroline derivative containing two aldehyde functional groups. Among them, the above derivatives preferably include derivatives of hydroxyl substituents, nitro substituents, alkoxy or bromine substituents.

[0052] Specifically, the organic molecule B includes terephthalaldehyde, isophthalaldehyde, biphenyldicarboxaldehyde, 2,5-dihydroxy-1,4-benzenedicarboxylic acid aldehyde, 1,4-dialdehyde-2,5-divinylbenzene, 2,3-dihydroxyterephthalaldehyde, 2,5-dibromobenzene-1,4-dicarboxaldehyde, 2,5-diethoxy-1,4-terephthalaldehyde, 2,2'-bipyridine-5,5'-dicarboxaldehyde, 1,4-di(4-formylphenyl)benzene, 2,5-dialdehydepyridine, 2,6-naphthalene dicarboxylic acid aldehyde, 5-hydroxyisophthalaldehyde, 1,10-phenanthroline- Any one of 2,9-dicarboxaldehyde, 4-hydroxyisophthalaldehyde, anthracene-9,10-dicarboxaldehyde, 2,2'-bipyridine-4,4'-dicarboxaldehyde, 3,3'-bipyridine-6,6'-dicarboxaldehyde, 9,10-di(4-formylphenyl)anthracene, 3,6-dimethylterephthalaldehyde, pyridine-2,6-dicarboxaldehyde, 2-methoxy-4,6-diformylphenol, 2-nitroterephthalaldehyde, 2,5-diformylpyrazine, 2,3-hydroxy-1,4-diformylnaphthalene or 4,4'-dihydroxy-3,3'-glyoxalbiphenyl.

[0053] Preferably, the organic molecule B may be any one of the compounds having the following chemical structures:

[0054]

[0055] In the present application, the flux is used to promote the polymerization reaction between the methyl group in the organic molecule A and the aldehyde group in the organic molecule B to generate a carbon-carbon double bond, thereby obtaining a vinyl porous organic polymer. The flux includes at least one of benzoic anhydride, sodium benzoate, benzoyl chloride, 4-trifluoromethylbenzoic anhydride, 4-methoxybenzoic anhydride, acetic anhydride, trifluoroacetic anhydride, benzoic acid, 4-fluorobenzoic acid, acetic acid or propionic acid.

[0056] In the present application, the molar ratio of the organic molecule A, the organic molecule B and the flux is preferably 1:(1τ2):(1τ10); wherein the molar ratio of the organic molecule A to the flux is more preferably 1:(4-8). Within this ratio range, it is helpful to obtain a vinyl porous organic polymer.

[0057] The present application selects specific reaction monomers and fluxes to synthesize vinyl porous organic polymer POPs by melt polymerization, which not only has a simple preparation process, greatly simplifies the existing synthesis process of vinyl porous organic polymers, but also avoids the high temperature and high pressure caused by the use of a large amount of organic solvents, thereby improving the safety of the preparation process. Based on the advantages of melt polymerization, the present application can scale up the vinyl porous organic polymer to the kilogram level, which is much higher than the traditional synthesis method and can achieve large-scale industrial production.

[0058] The vinyl porous organic polymer prepared by the melt polymerization method of the present application has high surface area, high mechanical strength and high porosity, and its pore size is 0.5nm-3.0nm, and has high stability and high catalytic activity. It can be used in gas storage and separation materials, catalysts, sensors and biomedicine fields, and has important application value.

[0059] The present application is further described below by way of examples.

[0060] Example 1

[0061] This embodiment provides a method for preparing a vinyl porous organic polymer, comprising:

[0062] Weigh 0.2mmol of 2,3,5,6-tetramethylpyrazine, 0.4mmol of biphenyl dicarboxaldehyde and 0.4mmol of benzoic anhydride, put them into a thick-walled glass tube resistant to high temperature and pressure, and seal the glass tube with the flame generated by the hydrogen generator to isolate the internal and external systems. The sealed glass tube was reacted in an oven at 180°C for 5 days to obtain a reddish-brown block solid. After soaking it in DMF, Soxhlet extraction was continued in methanol for 10 hours to obtain a red powder material with a yield of about 96%, recorded as NKPOP-1.

[0063] The reaction formula is as follows:

[0064]

[0065] Example 2

[0066] This embodiment provides a method for preparing a vinyl porous organic polymer, comprising:

[0067] Weigh 0.2mmol of 2,3,5,6-tetramethylpyrazine, 0.4mmol of isophthalaldehyde and 0.4mmol of benzoic anhydride, put them into a thick-walled glass tube resistant to high temperature and high pressure, evacuate until the pressure in the glass tube is 0.15mmHg, remove the glass tube from the vacuum line, and seal the glass tube with the flame generated by the hydrogen generator to isolate the internal and external systems. The sealed glass tube is reacted in an oven at 180℃ for 5 days to obtain an orange-yellow powder. After soaking it in DMF, Soxhlet extraction in methanol lasts for 10 hours to obtain an orange-yellow powder material with a yield of about 92%, recorded as NKPOP-2.

[0068] The reaction formula is as follows:

[0069]

[0070] Example 3

[0071] This embodiment provides a method for preparing a vinyl porous organic polymer, comprising:

[0072] Weigh 0.2mmol of 2,3,5-trimethylpyrazine, 0.2mmol of terephthalaldehyde and 0.4mmol of benzoic anhydride, put them into a thick-walled glass tube resistant to high temperature and high pressure, evacuate until the pressure in the glass tube is 0.15mmHg, remove the glass tube from the vacuum line, and seal the glass tube with the flame generated by the hydrogen generator to isolate the internal and external systems. The sealed glass tube is reacted in an oven at 180℃ for 5 days to obtain a yellow block solid. After soaking it in DMF, Soxhlet extraction in methanol lasts for 10h to obtain an orange block material with a yield of about 91%, recorded as NKPOP-3.

[0073] The reaction formula is as follows:

[0074]

[0075] Example 4

[0076] This embodiment provides a method for preparing a vinyl porous organic polymer, comprising:

[0077] Weigh 0.2mmol of 2,3,5-trimethylpyrazine, 0.2mmol of isophthalaldehyde and 0.4mmol of benzoic anhydride, put them into a thick-walled glass tube resistant to high temperature and pressure, and seal the glass tube with the flame generated by the hydrogen generator to isolate the internal and external systems. The sealed glass tube was reacted in an oven at 180°C for 5 days to obtain a yellow block solid. After soaking it in DMF, Soxhlet extraction was continued in methanol for 10 hours to obtain a yellow block material with a yield of about 85%, recorded as NKPOP-4.

[0078] The reaction formula is as follows:

[0079]

[0080] Example 5

[0081] This embodiment provides a method for preparing a vinyl porous organic polymer, comprising:

[0082] Weigh 0.6mmol of 2,6-dimethylpyrazine, 0.6mmol of terephthalaldehyde and 1.2mmol of benzoic anhydride, put them into a thick-walled glass tube resistant to high temperature and pressure, and seal the glass tube with the flame generated by the hydrogen generator to isolate the internal and external systems. The sealed glass tube was reacted in an oven at 180°C for 5 days to obtain a brown block solid. After soaking it in DMF, Soxhlet extraction in methanol lasted for 10 hours to obtain a brown block material with a yield of about 86%, recorded as NKPOP-5.

[0083] The reaction formula is as follows:

[0084]

[0085] Example 6

[0086] This embodiment provides a method for preparing a vinyl porous organic polymer, comprising:

[0087] Weigh 0.6mmol of 2,6-dimethylpyrazine, 0.6mmol of isophthalaldehyde and 1.2mmol of benzoic anhydride, put them into a thick-walled glass tube resistant to high temperature and pressure, and seal the glass tube with the flame generated by the hydrogen generator to isolate the internal and external systems. The sealed glass tube was reacted in an oven at 180℃ for 5 days to obtain a brown block solid. After soaking it in DMF, Soxhlet extraction was continued in methanol for 10 hours to obtain a brown block material with a yield of about 85%, recorded as NKPOP-6.

[0088] The reaction formula is as follows:

[0089]

[0090] Example 7

[0091] This embodiment provides a method for preparing a vinyl porous organic polymer, comprising:

[0092] Weigh 0.6mmol of 2,5-dimethylpyrazine, 0.6mmol of isophthalaldehyde and 1.2mmol of benzoic anhydride, put them into a thick-walled glass tube resistant to high temperature and pressure, and seal the glass tube with the flame generated by the hydrogen generator to isolate the internal and external systems. The sealed glass tube was reacted in an oven at 180°C for 5 days to obtain a yellow block solid. After soaking it in DMF, Soxhlet extraction in methanol lasted for 10 hours to obtain a yellow block material with a yield of about 87%, recorded as NKPOP-7.

[0093] The reaction formula is as follows:

[0094]

[0095] Example 8

[0096] This embodiment provides a method for preparing a vinyl porous organic polymer, comprising:

[0097] Weigh 0.3mmol of 2,6-dimethylpyridine, 0.3mmol of terephthalaldehyde and 0.4mmol of benzoic anhydride, put them into a thick-walled glass tube resistant to high temperature and pressure, and seal the glass tube with the flame generated by the hydrogen generator to isolate the internal and external systems. The sealed glass tube was reacted in an oven at 180°C for 5 days to obtain a yellow block solid. After soaking it in DMF, Soxhlet extraction in methanol lasted for 10 hours to obtain an orange block material with a yield of about 84%, recorded as NKPOP-8.

[0098] The reaction formula is as follows:

[0099]

[0100] Example 9

[0101] This embodiment provides a method for preparing a vinyl porous organic polymer, comprising:

[0102] Weigh 0.3mmol of 2,6-dimethylpyridine, 0.3mmol of isophthalaldehyde and 0.4mmol of benzoic anhydride, put them into a thick-walled glass tube resistant to high temperature and pressure, and seal the glass tube with the flame generated by the hydrogen generator to isolate the internal and external systems. The sealed glass tube was reacted in an oven at 180°C for 5 days to obtain a yellow block solid. After soaking it in DMF, Soxhlet extraction in methanol lasted for 10 hours to obtain a yellow block material with a yield of about 89%, recorded as NKPOP-9.

[0103] The reaction formula is as follows:

[0104]

[0105] Example 10

[0106] This embodiment provides a method for preparing a vinyl porous organic polymer, comprising:

[0107] Weigh 0.2mmol of 2,3,5,6-tetramethylpyrazine trihydrate, 0.4mmol of terephthalaldehyde and 0.4mmol of benzoic anhydride, put them into a thick-walled glass tube resistant to high temperature and pressure, and seal the glass tube with the flame generated by the hydrogen generator to isolate the internal and external systems. The sealed glass tube was reacted in an oven at 200°C for 5 days to obtain a red block solid. After soaking it in DMF, Soxhlet extraction in methanol lasted for 10 hours to obtain a yellow block material with a yield of about 85%, recorded as NKPOP-10.

[0108] The reaction formula is as follows:

[0109]

[0110] Embodiment 11

[0111] This embodiment provides a method for preparing a vinyl porous organic polymer, comprising:

[0112] Weigh 0.2mmol of 2,3,5,6-tetramethylpyrazine or 2,3,5,6-tetramethylpyrazine trihydrate, 0.4mmol of 1,4-dialdehyde-2,5-divinylbenzene and 0.4mmol of benzoic anhydride, put them into a thick-walled glass tube resistant to high temperature and pressure, and seal the glass tube with the flame generated by the hydrogen generator to isolate the internal and external systems. The sealed glass tube was reacted in an oven at 180°C for 5 days to obtain a reddish-brown block solid. After soaking it in DMF, Soxhlet extraction in methanol lasted for 10 hours to obtain a reddish-brown block material with a yield of about 83%, recorded as NKPOP-11.

[0113] The reaction formula is as follows:

[0114]

[0115] The cyclic vinyl porous organic polymer NKPOP-1 prepared in Example 1 and the chain vinyl porous organic polymer NKPOP-6 prepared in Example 6 were characterized and their performance was evaluated.

[0116] in, Figure 1 The infrared spectrum test results of the organic monomer A (2,3,5,6-tetramethylpyrazine), the organic monomer B (biphenyl dicarboxaldehyde) and the vinyl porous organic polymer NKPOP-1 of Example 1 are shown in FIG. Figure 1 It can be seen that NKPOP-1 is at 1631cm -1 The peak corresponding to the stretching vibration of the carbon-carbon double bond proves that it is a vinyl-linked POPs material.

[0117] Figure 2 The isothermal adsorption-desorption curve of nitrogen for the vinyl porous organic polymer NKPOP-1 at 77K. Figure 2 It can be concluded that its BET surface area is 940m 2 / g, with high surface area.

[0118] Figure 3 is the pore size distribution curve of the vinyl porous organic polymer NKPOP-1, from Figure 3 It can be seen that its pore size distribution is 1.2nm, which is a microporous material with high porosity.

[0119] Figure 4 This is a scanning electron microscope image of the vinyl porous organic polymer NKPOP-1. Figure 4 It can be seen that the stacking of NKPOP-1 on the microscopic scale is irregular.

[0120] Figure 5 The thermogravimetric curve of the vinyl porous organic polymer NKPOP-1 is shown in Figure 2. Figure 5It can be seen that NKPOP-1 has good thermal stability and no obvious structural collapse occurs before 400°C.

[0121] Figure 6 The infrared test spectra of the organic monomer A (2,6-dimethylpyrazine), the organic monomer B (isophthalaldehyde) and the vinyl porous organic polymer NKPOP-6 of Example 6 are shown in FIG. Figure 6 It can be seen that

[0122] Vinyl porous organic polymer NKPOP-6 at 1628cm -1 The peak corresponding to the stretching vibration of the carbon-carbon double bond proves that it is a vinyl-linked POPs material.

[0123] Figure 7 The isothermal adsorption-desorption curve of nitrogen for the vinyl porous organic polymer NKPOP-6 at 77K. Figure 7 It can be concluded that its BET surface area is 102m 2 / g, the hysteresis loop of the curve proves the existence of mesopores and macropores in the material.

[0124] Figure 8 is the pore size distribution curve of vinyl porous organic polymer NKPOP-6, from Figure 8 It can be seen that the material has a multi-level pore structure, and its pore diameter is roughly distributed between 1.4-5nm.

[0125] Fig. 9 This is a scanning electron microscope image of the vinyl porous organic polymer NKPOP-6. Fig. 9 It can be seen that the stacking of NKPOP-6 on a microscopic scale is irregular.

[0126] Fig.10 The thermogravimetric curve of vinyl porous organic polymer NKPOP-6 is shown in Figure 2. Fig.10 It can be seen that NKPOP-6 has good thermal stability and no obvious structural collapse occurs before 500°C.

[0127] Although the present application has been described in detail in general terms and in specific embodiments in this specification, it is obvious to those skilled in the art that some modifications or improvements may be made to the present application. Therefore, these modifications or improvements made without departing from the spirit of the present application are within the scope of protection claimed in the present application.

Claims

1. A method for preparing a vinyl porous organic polymer, characterized in that: include: The organic molecule A, the organic molecule B and the flux are melt-polymerized in a closed reactor, and the reaction product is purified to obtain a vinyl porous organic polymer; Wherein, the organic molecule A is pyridine or pyrazine containing at least two methyl functional groups; The organic molecule B is an aromatic compound containing two aldehyde functional groups; The flux is a compound containing anhydride functional groups, a compound containing acyl chloride functional groups or a compound containing carboxylic acid functional groups.

2. The preparation method according to claim 1, characterized in that: The organic molecule A is pyrazine containing 2 to 4 methyl functional groups, or pyridine containing 2 to 3 methyl functional groups; The organic molecule B includes any one of benzene or its derivatives, biphenyl or its derivatives, naphthalene or its derivatives, pyridine or its derivatives, bipyridine or its derivatives, anthracene or its derivatives, pyrazine or its derivatives, or phenanthroline or its derivatives containing two aldehyde functional groups.

3. The preparation method according to claim 2, characterized in that: The organic molecule A includes any one of 2,3,5,6-tetramethylpyrazine, 2,3,5,6-tetramethylpyrazine trihydrate, 2,3,5-trimethylpyrazine, 2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine, 2,3,5-trimethylpyridine, 2,4,5-trimethylpyridine or 2,3,6-trimethylpyridine.

4. The preparation method according to claim 3, characterized in that: The organic molecules B include terephthalaldehyde, isophthalaldehyde, biphenyldicarboxaldehyde, 2,5-dihydroxy-1,4-benzenedicarbaldehyde, 1,4-dialdehyde-2,5-divinylbenzene, 2,3-dihydroxyterephthalaldehyde, 2,5-dibromobenzene-1,4-dicarboxaldehyde, 2,5-diethoxy-1,4-terephthalaldehyde, 2,2'-bipyridine-5,5'-dicarboxaldehyde, 1,4-di(4-aldehydephenyl)benzene, 2,5-dialdehydepyridine, 2,6-naphthalene dicarboxaldehyde, 5-hydroxyisophthalaldehyde, 1,10-phenanthroline-2 , 9-dicarboxaldehyde, 4-hydroxyisophthalaldehyde, anthracene-9,10-dicarboxaldehyde, 2,2'-bipyridine-4,4'-dicarboxaldehyde, 3,3'-bipyridine-6,6'-dicarboxaldehyde, 9,10-di(4-formylphenyl)anthracene, 3,6-dimethylterephthalaldehyde, pyridine-2,6-dicarboxaldehyde, 2-methoxy-4,6-diformylphenol, 2-nitroterephthalaldehyde, 2,5-diformylpyrazine, 2,3-hydroxy-1,4-diformylnaphthalene or 4,4'-dihydroxy-3,3'-glyoxalbiphenyl.

5. The preparation method according to claim 3, characterized in that: The flux includes at least one of benzoic anhydride, sodium benzoate, benzoyl chloride, 4-trifluoromethylbenzoic anhydride, 4-methoxybenzoic anhydride, acetic anhydride, trifluoroacetic anhydride, benzoic acid, 4-fluorobenzoic acid, acetic acid or propionic acid.

6. The preparation method according to claim 1, characterized in that: The temperature of the melt polymerization is 120-200° C., and the reaction time is 24-120 hours.

7. The preparation method according to claim 1, characterized in that: The molar ratio of the organic molecule A, the organic molecule B and the flux is 1:(1-2):(1-10).

8. The preparation method according to claim 1, characterized in that: The pressure of the melt polymerization is normal pressure or negative pressure.

9. The preparation method according to claim 1, characterized in that: The purification specifically comprises: The reaction product was soaked in DMF, then subjected to Soxhlet extraction in methanol, and then dried at 80-200°C.

10. The vinyl porous organic polymer prepared by the preparation method according to any one of claims 1 to 9.

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