Preparation method of crystalline porous polymer forming body and crystalline porous polymer forming body

Abstract

The invention discloses a preparation method of a crystalline porous polymer molded body and the crystalline porous polymer molded body prepared by the method. The preparation method comprises the following steps: (1) mixing a crystalline porous polymer material and a composite material in water to prepare a precursor solution; (2) dissolving a curing material to prepare a curing liquid; (3) dispersing the precursor solution, and freeze-drying the precursor solution in liquid nitrogen to obtain a pre-curing molded body; and (4) soaking the pre-curing molded body in the curing liquid, and reacting the composite material with the curing material to obtain a cured molded body. The crystalline porous polymer molded body obtained by the method has a porous structure, is beneficial to dispersion and exposure of the crystalline porous polymer material, has ultrahigh crystalline porous polymer material loading capacity, is uniform in size and is easy to store and transport.

Description

Technical Field

[0001] The invention relates to a preparation method of a crystalline porous polymer molded body and the crystalline porous polymer molded body. Background Art

[0002] In recent years, crystalline porous polymer materials represented by metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) have developed rapidly. MOF materials are constructed by metal ions / clusters and organic ligands through coordination bonds, while COF materials are constructed by organic monomers through reversible covalent bonds. Compared with traditional materials, crystalline porous polymer materials have the following characteristics: 1) Structural diversity. By selecting building units with different geometric shapes or changing the connection method of building units, frameworks with different topological structures can be obtained; 2) Open and controllable pores. The size, shape and chemical environment of the pores can be controlled through structural design and functionalization. These characteristics make crystalline porous polymer materials show great application potential in the fields of separation, sensing, catalysis, energy storage, biomedicine, etc.

[0003] However, the progress of industrialization of crystalline porous polymer materials is limited by their rigidity and brittleness. Most of the synthesized crystalline porous polymer materials exist in the form of powders with poor processability. If you want to commercialize crystalline porous polymer materials and integrate them into other technologies, you need to process the powders into shapes to make them easy to store, transport and pack. In addition, molding crystalline porous polymers can effectively solve the problems of aggregation and inactivation, difficulty in recycling, and easy clogging of powders during the adsorption process. However, the difference in structural regulation at the macroscale and micro-nanoscale makes the design and preparation of molded bodies with no loss of performance relative to powder materials a research difficulty.

[0004] At present, traditional powder material molding methods mainly include pressure molding, bonding molding and embedding molding. Pressure molding is to achieve molding by adhering material powder particles into aggregates under high pressure. Under pressures ranging from tens of MPa to thousands of MPa, the bulk density of crystalline porous polymer materials can be greatly improved, thereby reducing the volume space occupied during storage and use. However, due to the limited stability of the framework of crystalline porous polymer materials, high-pressure molding will cause the crystalline porous polymer materials to transform into an amorphous state, reduce porosity, and affect their practical application performance. Bonding molding refers to the addition of certain liquid solvents, organic polymers or clays as additives to adjust the rheological properties of the molded body on the basis of pressure molding, molding under lower pressure, and obtaining molded crystalline porous polymer materials through subsequent activation treatment and other processes. Lower molding pressure can effectively avoid the collapse of the framework structure, but the binder will block and cover the pore structure and active metal sites of the crystalline porous polymer material, seriously affecting its practical application performance. The embedding molding method is represented by spray drying and electrospinning, but it is also unable to avoid the clogging of the pore structure by organic polymer chains. In addition, the loading amount of crystalline porous polymer materials in the composite materials prepared by the above traditional molding methods is limited, which makes the actual application performance of the molded body significantly attenuated compared with the powdered material. Therefore, it is very important to develop a new crystalline porous polymer material molding technology that can achieve ultra-high crystalline porous polymer loading and avoid the reduction of crystallinity and porosity of crystalline porous polymers.

[0005] In addition, crystalline porous polymers in powder form are often processed into membrane materials or spherical particles depending on their application scenarios. The granulation process is to convert powder materials into dust-free particles that are easy to compress and flow freely. In this process, it is necessary not only to consider the physical and chemical properties of the resulting particles (such as particle size, density, porosity, mechanical strength, etc.), but also the uniformity and stability of the material content in the particles. In the prior art, there are technical difficulties that it is not easy to process crystalline porous polymers into spherical particles, and the spherical particles have irregular shapes. Summary of the invention

[0006] In view of the problem that crystalline porous polymers are difficult to process and shape in the prior art, the present invention provides a new method for preparing a crystalline porous polymer molded body to solve the problems of low loading, reduced crystallinity and porosity of the crystalline porous polymer molded body in the prior art.

[0007] One aspect of the present invention provides a method for preparing a crystalline porous polymer molded body, characterized by comprising: (1) Mixing the crystalline porous polymer material and the composite material in water to prepare a precursor solution; (2) dissolving the curing material to prepare a curing liquid; (3) dispersing the precursor solution and placing it in liquid nitrogen for freeze drying to obtain a pre-cured molded body; (4) Immersing the pre-cured molded body in the curing liquid to allow the composite material to react with the curing material to obtain a post-cured molded body.

[0008] Preferably, the concentration of the crystalline porous polymer material in the precursor solution is 12.5-50 mg / mL, and the concentration of the composite material is 10-30 mg / mL.

[0009] More preferably, the concentration of the crystalline porous polymer material in the precursor solution is 40 mg / mL, and the concentration of the composite material is 15 mg / mL.

[0010] Preferably, the concentration of the solidifying liquid is 5% w / w-25% w / w.

[0011] Preferably, the method of dispersing the precursor liquid and placing it into liquid nitrogen includes spraying the precursor liquid into the liquid nitrogen with a spray gun.

[0012] Preferably, the nozzle diameter of the spray gun is 1.5 mm, and the air pressure of the precursor liquid sprayed into liquid nitrogen using the spray gun is 0.7 Mpa.

[0013] Preferably, the crystalline porous polymer material is a metal organic framework material or a covalent organic framework material.

[0014] More preferably, the metal organic framework material is formed by the action of a metal source and an organic ligand, the metal source is selected from at least one of In, Cu, Ni, Zn, and Cr, and the organic ligand is selected from at least one of 1,2,4,5-tetrakis(3-carboxyphenyl)benzene, 2-methylimidazole, terephthalic acid, benzene-1,3,5-tricarboxylic acid, and 4,4'-(1H,1'H-[2,2'-biimidazole]-1,1'-diyl)dibenzoic acid.

[0015] More preferably, the metal organic framework material is one or more of the following: The metal organic framework material is formed by the reaction of zinc nitrate hexahydrate and 2-methylimidazole. The X-ray powder diffraction spectrum of the formed metal organic framework material is as follows: Figure 1 As shown; The metal organic framework material is formed by the reaction of chromium nitrate nonahydrate and terephthalic acid. The X-ray powder diffraction spectrum of the formed metal organic framework material is as follows: Figure 6 As shown; The metal organic framework material is formed by the reaction of copper nitrate and benzene-1,3,5-tricarboxylic acid. The X-ray powder diffraction spectrum of the formed metal organic framework material is as follows: Fig.11 As shown; The metal organic framework material is formed by the reaction of nickel nitrate hexahydrate and 4,4'-(1H,1'H-[2,2'-biimidazole]-1,1'-diyl)dibenzoic acid. The X-ray powder diffraction spectrum of the formed metal organic framework material is as follows: Fig.16 As shown; The metal organic framework material is formed by the reaction of indium nitrate tetrahydrate and 1,2,4,5-tetrakis(3-carboxyphenyl)benzene. The X-ray powder diffraction spectrum of the formed metal organic framework material is as follows: Fig.21 As shown; The metal organic framework material is formed by the reaction of copper nitrate trihydrate and 4,4'-(1H,1'H-[2,2'-biimidazole]-1,1'-diyl)dibenzoic acid. The X-ray powder diffraction spectrum of the formed metal organic framework material is as follows: Fig.26 shown.

[0016] More preferably, the covalent organic framework material is formed by reacting a first monomer comprising an amino group and a second monomer comprising an aldehyde group.

[0017] More preferably, the first monomer is 1,3,5-tris-4-aminophenylbenzene, 2,4,6-tris(4-aminophenyl)-1,3,5-triazine, 1,3,6,8-tetrakis-(p-aminophenyl)-pyrene or tetrakis(4-aminophenyl)methane; and the second monomer is 4,4'-biphenyldicarboxaldehyde, 2,5-di-methoxyterephthalaldehyde or terephthalaldehyde.

[0018] More preferably, the covalent organic framework material is one or more of the following: The covalent organic framework material is formed by the reaction of 1,3,6,8-tetrakis-(p-aminophenyl)-pyrene and 4,4'-biphenyldicarboxaldehyde. The X-ray powder diffraction spectrum of the formed covalent organic framework material is as follows: Fig.31 As shown; The covalent organic framework material is formed by the reaction of 1,3,5-tri-4-aminophenylbenzene and 4,4'-biphenyldicarboxaldehyde. The X-ray powder diffraction spectrum of the formed covalent organic framework material is as follows: Fig.36 As shown; The covalent organic framework material is formed by the reaction of 2,4,6-tris(4-aminophenyl)-1,3,5-triazine and 4,4'-biphenyldicarboxaldehyde. The X-ray powder diffraction spectrum of the formed covalent organic framework material is as follows: Fig.41 As shown; The covalent organic framework material is formed by the reaction of 1,3,5-tri-4-aminophenylbenzene and 2,5-dimethoxyterephthalaldehyde. The X-ray powder diffraction spectrum of the formed covalent organic framework material is as follows: Fig.46 As shown; The covalent organic framework material is formed by the reaction of terephthalaldehyde and tetrakis(4-aminophenyl)methane. The X-ray powder diffraction spectrum of the formed covalent organic framework material is as follows: Fig.51 shown.

[0019] Preferably, the composite material is chitosan.

[0020] Preferably, the curing material is glutaraldehyde, and the pre-cured molded body is immersed in the curing liquid for 12-24 hours.

[0021] Preferably, a metal organic framework material or a covalent organic framework material is ultrasonically dispersed in water to form a suspension, chitosan and acetic acid are added to the suspension to obtain a precursor solution, wherein the concentration of the metal organic framework material or the covalent organic framework material is 12.5-50 mg / mL, and the concentration of the chitosan is 10-30 mg / mL; glutaraldehyde is dissolved in water to obtain a solidifying liquid, wherein the concentration of glutaraldehyde in the solidifying liquid is 5%w / w-25%w / w; the precursor solution is sprayed into liquid nitrogen using a spray gun, and freeze-dried for 24 hours to obtain a pre-solidified molded body; the pre-solidified molded body is immersed in the solidifying liquid for 12-24 hours to obtain a post-solidified molded body; and the post-solidified molded body is washed and dried.

[0022] Another aspect of the present invention provides a crystalline porous polymer molded body, wherein the crystalline porous polymer molded body is prepared by the above-mentioned method for preparing a crystalline porous polymer molded body.

[0023] Preferably, the crystalline porous polymer body is a metal organic framework material / chitosan body or a covalent organic framework material / chitosan body.

[0024] More preferably, the crystalline porous polymer shaped body is a spherical particle.

[0025] More preferably, the particle size of the crystalline porous polymer body is 150-1000 μm.

[0026] The crystalline porous polymer molded body obtained by the preparation method of the present invention has a porous structure, which is conducive to the dispersion and exposure of the crystalline porous polymer material, and the crystallinity and porosity of the crystalline porous polymer material in the molded body are not significantly reduced. In addition, the molded body prepared by the method of the present invention has an ultra-high crystalline porous polymer material loading amount and a uniform size, and is easy to store and transport. And when the method of the present invention is used to prepare a molded body of spherical particles, the spherical particles of the molded body have a regular shape. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] The accompanying drawings are used to provide further understanding of the present invention and constitute a part of the specification. Together with the following specific embodiments, they are used to explain the present invention, but do not constitute a limitation of the present invention.

[0028] Figure 1 X-ray powder sample diffraction patterns of MOF-A and MOF-A / CS; Figure 2 N of MOF-A and MOF-A / CS 2 Adsorption and desorption curves; Figure 3 Pore ​​size distribution diagrams of MOF-A and MOF-A / CS; Figure 4 Thermogravimetric analysis of MOF-A, CS, and MOF-A / CS; Figure 5 SEM image of MOF-A / CS; Figure 6 X-ray powder sample diffraction patterns of MOF-B and MOF-B / CS; Figure 7 N of MOF-B and MOF-B / CS 2 Adsorption and desorption curves; Figure 8 Pore ​​size distribution diagrams of MOF-B and MOF-B / CS; Fig. 9 Thermogravimetric analysis of MOF-B, CS, and MOF-B / CS; Fig.10 SEM image of MOF-B / CS; Fig.11 X-ray powder sample diffraction patterns of MOF-C and MOF-C / CS; Fig.12 N of MOF-C and MOF-C / CS 2 Adsorption and desorption curves; Fig.13 Pore ​​size distribution diagrams of MOF-C and MOF-C / CS; Fig.14 Thermogravimetric analysis of MOF-C, CS, and MOF-C / CS; Fig.15 SEM image of MOF-C / CS; Fig.16 X-ray powder sample diffraction patterns of MOF-D and MOF-D / CS; Fig.17 N of MOF-D and MOF-D / CS 2 Adsorption and desorption curves; Fig.18Pore ​​size distribution diagrams of MOF-D and MOF-D / CS; Fig.19 Thermogravimetric analysis of MOF-D, CS, and MOF-D / CS; Fig. 20 SEM image of MOF-D / CS; Fig.21 X-ray powder sample diffraction patterns of MOF-E and MOF-E / CS; Fig. 22 N of MOF-E and MOF-E / CS 2 Adsorption and desorption curves; Fig.23 Pore ​​size distribution diagrams of MOF-E and MOF-E / CS; Fig.24 Thermogravimetric analysis of MOF-E, CS, and MOF-E / CS; Fig.25 SEM image of MOF-E / CS; Fig.26 X-ray powder sample diffraction patterns of MOF-F and MOF-F / CS; Fig. 27 N of MOF-F and MOF-F / CS 2 Adsorption and desorption curves; Fig.28 Pore ​​size distribution diagrams of MOF-F and MOF-F / CS; Fig.29 Thermogravimetric analysis of MOF-F, CS, and MOF-F / CS; Fig.30 SEM image of MOF-F / CS; Fig.31 X-ray powder sample diffraction patterns of COF-A and COF-A / CS; Fig.32 N of COF-A and COF-A / CS 2 Adsorption and desorption curves; Fig.33 Pore ​​size distribution diagrams of COF-A and COF-A / CS; Fig.34 Thermogravimetric analysis of COF-A, CS, and COF-A / CS; Fig.35 SEM image of COF-A / CS; Fig.36 X-ray powder sample diffraction patterns of COF-B and COF-B / CS; Fig.37 N of COF-B and COF-B / CS 2Adsorption and desorption curves; Fig.38 Pore ​​size distribution diagrams of COF-B and COF-B / CS; Fig.39 Thermogravimetric analysis of COF-B, CS, and COF-B / CS; Fig.40 SEM image of COF-B / CS; Fig.41 X-ray powder sample diffraction patterns of COF-C and COF-C / CS; Fig.42 N of COF-C and COF-C / CS 2 Adsorption and desorption curves; Fig.43 Pore ​​size distribution diagrams of COF-C and COF-C / CS; Fig.44 Thermogravimetric analysis of COF-C, CS, and COF-C / CS; Fig.45 SEM image of COF-C / CS; Fig.46 X-ray powder sample diffraction patterns of COF-D and COF-D / CS; Fig.47 N of COF-D and COF-D / CS 2 Adsorption and desorption curves; Fig.48 Pore ​​size distribution diagrams of COF-D and COF-D / CS; Fig.49 Thermogravimetric analysis of COF-D, CS, and COF-D / CS; Fig.50 SEM image of COF-D / CS; Fig.51 X-ray powder sample diffraction patterns of COF-E and COF-E / CS; Fig.52 N of COF-E and COF-E / CS 2 Adsorption and desorption curves; Fig.53 Pore ​​size distribution diagrams of COF-E and COF-E / CS; Fig.54 Thermogravimetric analysis of COF-E, CS, and COF-E / CS; Fig.55 SEM image of COF-E / CS. DETAILED DESCRIPTION

[0029] The specific implementation of the present invention is described in detail below in conjunction with the accompanying drawings. It should be understood that the specific implementation described here is only used to illustrate and explain the present invention, and is not used to limit the present invention.

[0030] The terms used in the present invention have the meanings generally used in the art. Some technical terms used in the present invention are explained and defined below.

[0031] Crystalline porous polymer materials The "crystalline porous polymer material" in the present invention is a type of polymer porous material with ordered pores and crystallinity formed by organic monomers or the reaction of organic monomers and metal sources, mainly including metal organic frameworks (MOFs), covalent organic frameworks (COFs), etc., with a designable and ordered structure and a controllable pore environment (pore size, functional groups, guest molecules, etc.), and has broad application prospects in many fields such as guest molecule adsorption and separation, catalysis, energy storage, etc.

[0032] Covalent organic framework materials The "covalent organic framework material" in the present invention, also known as COFs, is a type of crystalline polymer material formed by long-range orderly connection of organic monomers through covalent bonds. The pore size of the covalent organic framework material is uniform, so it is also called "organic zeolite". The covalent organic framework material has the characteristics of regular and adjustable pores, large specific surface area, high porosity, good stability, and easy functionalization. The covalent organic framework material used in the present invention can be synthesized by methods known in the art, such as Xiong Chen et al. Towards covalent organic frameworks with predesignable and aligned open docking sites. Chem. Commun., 2014, 50, 6161-6163, DOI: 10.1039 / c4cc01825g; Laura Ascherl et al. Molecular docking sites designed for the generation of highly crystalline covalent organic frameworks. Nature Chemistry, 2016, DOI: 10.1038 / NCHEM.2444. The above patents or documents are fully introduced into the present invention.

[0033] Metal-organic framework materials The "metal organic framework material" in the present invention, also known as MOFs, is a type of functional porous material, which is constructed by the coordination of metal sources (such as metal clusters, metal oxides or metal salts, etc.) and organic ligands, and has the advantages of both inorganic and organic porous materials, and has the characteristics of high specific surface area, orderly and repeatable pores, rich functional groups, good stability, and diverse structures. The metal organic framework material used in the present invention can be synthesized using methods known in the art, such as hydrothermal method, stirring static method, electrolysis method, spinning method, microwave method, hot pressing method, etc. The above-mentioned synthesis method is recorded in, for example, Katz, MJ et al. Afacile synthesis of UiO-66, UiO-67 and their derivatives. Chem. Commun. 49,9449-9451, (2013); Park, KS et al. Exceptional chemical and thermalstability of zeolitic imidazolate frameworks. P. Natl. Acad. Sci. USA.103,10186-10191, (2006); Li S. et al. Creating Lithium-Ion Electrolytes withBiomimetic Ionic Channels in Metal-Organic Frameworks. DOI: 10.1002 / adma.201707476; ZL201510630401.X and other documents, and the above-mentioned patents or documents are fully introduced into the present invention.

[0034] Crystalline porous polymer molding The "crystalline porous polymer molded body" or "molded body" in the present invention refers to a substance with a certain shape and size formed by a crystalline porous polymer material in powder form through a certain processing and molding method. The crystalline porous polymer molded body can be changed according to different application scenarios, such as membranes, particles, etc., wherein the shape of the particles can also be changed according to actual applications, such as spherical, cylindrical, conical, triangular, cubic, rectangular, etc. After processing and molding, the crystalline porous polymer material is easy to store, transport and fill, and can effectively solve the problems of aggregation and inactivation of powders during adsorption, difficulty in recovery, and easy clogging.

[0035] The present invention is described in detail below.

[0036] Crystalline porous polymer materials usually exist in the form of nanometer or micrometer-sized powders, and their mechanical properties and processability are poor, which limits their application. The preparation method of the present invention is used to prepare the crystalline porous polymer material into a molded body, which can greatly improve the processability and mechanical properties of the crystalline porous polymer material on the one hand; on the other hand, it can also effectively overcome the shortcomings of traditional mixed matrix membranes (e.g., prepared by mixing crystalline porous polymer materials with polymers), such as surface defects, pore blockage, and particle aggregation.

[0037] The preparation method of the crystalline porous polymer molded body of the present invention comprises mixing a crystalline porous polymer material and a composite material in water to prepare a precursor solution; dissolving a solidifying material to prepare a solidifying liquid; dispersing the precursor solution and placing it in liquid nitrogen for freeze drying to obtain a pre-solidified molded body; soaking the pre-solidified molded body in the solidifying liquid to react the composite material with the solidifying material, thereby obtaining a solidified crystalline porous polymer molded body. The crystalline porous polymer molded body obtained by the preparation method of the present invention has a porous structure, which is conducive to the dispersion and exposure of the crystalline porous polymer material, and the crystallinity and porosity of the crystalline porous polymer material in the molded body are not significantly reduced. In addition, the molded body prepared by the method of the present invention has an ultra-high crystalline porous polymer material loading capacity and is uniform in size, and is easy to store and transport.

[0038] The preparation method of the present invention mainly includes two key steps of freeze drying and solidification, and both steps are indispensable. First, the preparation method of the present invention is to freeze dry the precursor liquid containing crystalline porous polymer material and composite material in liquid nitrogen to obtain the desired shape and size of the solidified pre-molded body. Wherein in the process of dispersing the precursor liquid into liquid nitrogen freeze drying, liquid nitrogen instantly freezes the liquid in the precursor liquid into a lot of ice crystals, and the ice crystals are present in the composite microspheres. After drying, a lot of macropores are formed, which can fully expose the crystalline porous material, and the porosity of the crystalline porous polymer material will not be reduced by the preparation method of the present application. And, since it does not involve the use of high pressure, it will not cause the collapse of the framework structure of the crystalline porous polymer material, and the crystallinity and porosity are not easy to reduce. Those skilled in the art can obtain the desired shape and size of the molded body using the method commonly used in the art, without particular limitation. From the perspective of making the size of the solidified pre-molded body more uniform, easy to obtain spherical particles and easier to operate, it is preferred to use a spray gun to spray the precursor liquid into liquid nitrogen. In addition, the desired molded body can be prepared by commonly used methods such as selecting a mold with an appropriate shape and size, adding a precursor liquid into the mold, and freezing the mold in liquid nitrogen.

[0039] As long as the precursor liquid is freeze-dried into a solid and does not disperse, there is no particular limit on the freeze-drying time. Those skilled in the art can determine the freeze-drying time based on the specific selection of the crystalline porous polymer material and the composite material by observing and testing the degree of drying. Preferably, the precursor liquid is dispersed and placed in liquid nitrogen for freeze drying for 24 hours.

[0040] After the freeze-drying step, the crystalline porous polymer material is fixed together only by the composite material in the pre-cured molded body, and its mechanical strength is low, and it is easy to collapse during storage and transportation. Therefore, the preparation method of the present invention immerses the pre-cured molded body in a curing liquid, and the composite material in the pre-cured molded body reacts with the curing material in the curing liquid to form a support structure on the surface and inside of the molded body, and the crystalline porous polymer material in the molded body is wrapped in the support structure, thereby enhancing the mechanical strength of the molded body without reducing the crystallinity and porosity of the crystalline porous polymer material.

[0041] In the preparation method of the present invention, a molded body with different crystalline porous polymer material loadings can be obtained by adjusting the content ratio of the crystalline porous polymer material and the composite material in the precursor solution. Using the preparation method of the present invention, a molded body with a high crystalline porous polymer material loading can be obtained, and the loading of the crystalline porous polymer material in the molded body is preferably greater than 60% w / w, and more preferably greater than 70% w / w. Preferably, the concentration of the crystalline porous polymer material in the precursor solution is 12.5-50 mg / mL, and the concentration of the composite material is 10-30 mg / mL. More preferably, the concentration of the crystalline porous polymer material in the precursor solution is 40 mg / mL, and the concentration of the composite material is 15 mg / mL.

[0042] There is no particular limitation on the amount of curing material in the curing liquid, as long as it can completely immerse the pre-cured molded body. Preferably, the curing material can make the composite material in the pre-cured molded body react basically completely. Those skilled in the art can adjust the amount appropriately based on the specific types of the composite material used, the curing material, and the stoichiometric ratio of the two. Preferably, the curing material is excessive. Preferably, the concentration of the curing liquid is 5% w / w-25% w / w.

[0043] Various crystalline porous polymer materials such as metal organic framework materials and covalent organic framework materials are suitable for preparing the molded body by the preparation method of the present invention. From the perspective of better mechanical strength, the crystalline porous polymer material is preferably a metal organic framework material and a covalent organic framework material.

[0044] The metal organic framework material in the preparation method of the present invention is formed by the action of a metal source and an organic ligand. Preferably, the metal source is selected from at least one of In, Cu, Ni, Zn, and Cr, and the organic ligand is selected from 1,2,4,5-tetrakis(3-carboxyphenyl)benzene, 2-methylimidazole, terephthalic acid, benzene-1,3,5-tricarboxylic acid, 4,4'-(1H,1'H-[2,2'-biimidazole]-1,1'-diyl)dibenzoic acid (H 2 BDA).

[0045] Furthermore, the metal organic framework material can be one or more of the following: formed by the reaction of zinc nitrate hexahydrate and 2-methylimidazole, the X-ray powder diffraction pattern of the metal organic framework material formed is as follows: Figure 1 As shown; the X-ray powder diffraction pattern of the metal organic framework material formed by the reaction of chromium nitrate nonahydrate and terephthalic acid is as shown Figure 6 As shown; the X-ray powder diffraction pattern of the metal organic framework material formed by the reaction of copper nitrate and benzene-1,3,5-tricarboxylic acid is as shown Fig.11 As shown; the X-ray powder diffraction pattern of the metal organic framework material formed by the reaction of nickel nitrate hexahydrate and 4,4'-(1H,1'H-[2,2'-biimidazole]-1,1'-diyl)dibenzoic acid is as shown Fig.16 As shown; the X-ray powder diffraction pattern of the metal organic framework material formed by the reaction of indium nitrate tetrahydrate and 1,2,4,5-tetrakis(3-carboxyphenyl)benzene is as shown Fig.21 As shown; it is formed by the reaction of copper nitrate trihydrate and 4,4'-(1H,1'H-[2,2'-biimidazole]-1,1'-diyl)dibenzoic acid, and the X-ray powder diffraction spectrum of the metal organic framework material formed is as shown Fig.26 shown.

[0046] Preferably, the covalent organic framework material in the preparation method of the present invention is formed by reacting a first monomer containing an amino group and a second monomer containing an aldehyde group. The first monomer may be 1,3,5-tri-4-aminophenylbenzene, 2,4,6-tris(4-aminophenyl)-1,3,5-triazine, 1,3,6,8-tetrakis-(p-aminophenyl)-pyrene or tetrakis(4-aminophenyl)methane; the second monomer may be 4,4'-biphenyldicarboxaldehyde, 2,5-di-methoxyterephthalaldehyde or terephthalaldehyde.

[0047] Furthermore, the covalent organic framework material in the preparation method of the present invention can be one or more of the following: formed by the reaction of 1,3,6,8-tetrakis-(p-aminophenyl)-pyrene and 4,4'-biphenyldicarboxaldehyde, and the X-ray powder diffraction pattern of the formed covalent organic framework is as follows: Fig.31As shown; formed by the reaction of 1,3,5-tri-4-aminophenylbenzene and 4,4'-biphenyldicarboxaldehyde, the X-ray powder diffraction spectrum of the covalent organic framework formed is as shown Fig.36 As shown; formed by the reaction of 2,4,6-tris(4-aminophenyl)-1,3,5-triazine and 4,4'-biphenyldicarboxaldehyde, the X-ray powder diffraction spectrum of the covalent organic framework formed is as shown Fig.41 As shown; formed by the reaction of 1,3,5-tri-4-aminophenylbenzene and 2,5-dimethoxyterephthalaldehyde, the X-ray powder diffraction spectrum of the covalent organic framework formed is as shown Fig.46 As shown; the X-ray powder diffraction pattern of the covalent organic framework formed by the reaction of terephthalaldehyde and tetrakis (4-aminophenyl) methane is as shown Fig.51 shown.

[0048] As long as the composite material and the curing material can react to form a support structure, for example, the composite material and the curing material can cross-link to form a network structure, can react to form a gel, etc., there is no particular limitation. Preferably, the composite material is chitosan. Chitosan has a certain viscosity after dissolving in water, which can be more conducive to maintaining the structure of the pre-curing molded body before curing. As long as the curing material can react with the composite material to form a support structure, those skilled in the art can select the curing material according to the type of the composite material. Preferably, the curing material is glutaraldehyde.

[0049] As long as the pre-cured molded body can be fully cured, the immersion time of the pre-cured molded body in the curing liquid is not particularly limited. Preferably, when the curing material is glutaraldehyde, the immersion time is 12-24 h.

[0050] The preparation method of the present invention further comprises washing and drying the solidified molded body.

[0051] The preferred embodiment of the present invention is to ultrasonically disperse the metal organic framework material or the covalent organic framework material in water to form a suspension, add chitosan and acetic acid to the suspension to obtain a precursor solution, in which the concentration of the metal organic framework material or the covalent organic framework material is 12.5-50 mg / mL, and the concentration of the chitosan is 10-30 mg / mL; dissolve glutaraldehyde in water to obtain a solidified liquid, in which the concentration of glutaraldehyde in the solidified liquid is 5-25% w / w; use a spray gun to spray the precursor solution into liquid nitrogen, freeze-dry for 24 hours, and obtain a pre-solidified molded body; soak the pre-solidified molded body in the solidified liquid for 12-24 hours to obtain a post-solidified molded body; wash and dry the post-solidified molded body. Through this embodiment, a covalent organic framework material / chitosan molded body can be prepared.

[0052] The structure and performance of the crystalline porous polymer molded body in the following examples of the present invention were characterized using an X-ray powder diffractometer, a gas adsorption instrument, a scanning electron microscope (SEM), and a thermogravimetric analyzer.

[0053] The structures of the crystalline porous polymer material and the crystalline porous polymer molded body were characterized using an X-ray powder diffractometer and a scanning electron microscope. The specific instruments and parameters are as follows: X-ray powder diffractometer: Model Bruker Foucus D8, Bruker, USA; the powder sample scanning temperature was 298 K, the pressure was 40 kV, the current was 50 mA, and the X-ray radiation source was Cu-Kα. Scanning electron microscope: Model SIGMA300, Zeiss, Germany; the sample was dipped on the conductive glue on the sample stage, the test voltage was 5 kV, and the test current was 10 μA.

[0054] The pores of the crystalline porous polymer material and the crystalline porous polymer molded body were characterized using a gas adsorption instrument. The instrument and parameters are as follows: Gas adsorption instrument: Model Quantachrome (ASiQMVH002-5), Quantachrome Company, USA; the adsorption of nitrogen by the prepared material was tested under standard atmospheric pressure (101 kPa), and the purity of the gas used in the test was 99.999%. The pore size of the crystalline porous polymer material and the crystalline porous polymer molded body was obtained by fitting the adsorption curve measured by the gas adsorption instrument.

[0055] The loading amount of the crystalline porous polymer material in the crystalline porous polymer molding was characterized using a thermogravimetric analyzer. The instrument and parameters are as follows: Thermogravimetric analyzer: Model Shimadzu (DTG-60), Shimadzu Co., Ltd., Japan; about 5 mg of sample was placed in the sample chamber, and the test temperature range was 35 o C-800 o C, the test atmosphere is N 2 , the heating rate is 10 o C min –1 .

[0056] Method for preparing crystalline porous polymer molded body The embodiments of the present invention are described by taking the molded body formed by the crystalline porous polymer material and chitosan as an example.

[0057] Preparation method of crystalline porous polymer material / chitosan molded body: The MOF or COF synthesized above is ultrasonically dispersed in deionized water to obtain a suspension. Chitosan and acetic acid are then added to the suspension, and stirring is continued to completely dissolve the chitosan to obtain a precursor solution. The precursor solution is sprayed into liquid nitrogen using a spray gun, the nozzle diameter of the spray gun is 1.5 mm, and the air pressure of the precursor solution sprayed into liquid nitrogen using the spray gun is 0.7 Mpa. After freeze drying for 24 h, the pre-cured microspheres are obtained, and the pre-cured microspheres are immersed in a glutaraldehyde solution for several hours, and then washed with deionized water 3 times, ethanol 3 times, 60 o C and dried overnight.

[0058] The added amount of MOF or COF is 25-100 mg, the concentration range of chitosan is 10-30 mg / mL, the volume fraction of acetic acid is 2-3%, the concentration range of glutaraldehyde is 5-25% w / w, and the immersion time of the microspheres in glutaraldehyde is 12-24 h. Example Example 1

[0059] (1) Synthesis of MOF-A: Dissolve 2.4 g of zinc nitrate hexahydrate in 30 mL of analytical grade methanol solution, stir with a magnetic stirrer for 1 h at room temperature, and record it as solution A; Dissolve 5.2 g of 2-methylimidazole in 30 mL of analytical grade methanol solution, stir with a magnetic stirrer for 1 h at room temperature, and record it as solution B. Mix solution A and solution B and stir at room temperature for 12 h. Centrifuge the obtained white emulsion to obtain a white solid, wash it three times with analytical grade methanol, and dry it at 65 °C overnight to obtain MOF-A material.

[0060] (2) Synthesis of MOF-A / CS microspheres: Ultrasonic dispersion of 80 mg of MOF-A prepared in step (1) in 2 mL of deionized water. Add 30 mg of chitosan and 0.04 mL of 2% v / v acetic acid to the above suspension, and continue stirring to completely dissolve the chitosan to obtain a precursor solution. Dissolve glutaraldehyde in water to obtain a solidifying solution with a glutaraldehyde concentration of 5% w / w. Use a spray gun to spray the precursor solution into liquid nitrogen, freeze-dry for 24 hours to obtain a pre-solidified molded body; soak the pre-solidified molded body in the solidifying liquid for 12 hours, then wash it with deionized water 3 times, and finally freeze-dry it for 24 hours to obtain a MOF-A / CS molded body.

[0061] Figure 1X-ray powder sample diffraction patterns of MOF-A and MOF-A / CS. Curve 1 in the figure represents the simulation curve of MOF-A. Those skilled in the art can obtain the simulation curve of X-ray powder diffraction of the metal organic framework materials involved in each embodiment of the present invention through a commonly used database, such as the database CSDS of the Cambridge Crystal Data Center CCDC. Curve 2 represents the measurement curve of the synthesized MOF-A, and curve 3 represents the measurement curve of the synthesized MOF-A / CS. The characteristic peak in curve 2 coincides with the characteristic peak in curve 1, indicating that the above-mentioned metal organic framework material has been successfully synthesized. The characteristic peak in curve 3 coincides with the characteristic peaks in curves 1 and 2, indicating that the crystal structure of MOF-A in the synthesized MOF-A / CS has not changed, and its crystallinity has not decreased.

[0062] Figure 2 N of MOF-A and MOF-A / CS 2 Adsorption and desorption curves. It can be seen from the figure that the porosity of the synthesized MOF-A / CS is not significantly reduced compared with that of MOF-A.

[0063] Figure 3 This is the pore size distribution diagram of MOF-A and MOF-A / CS. The pore size of the synthesized MOF-A / CS is consistent with that of MOF-A, and the pores of MOF-A / CS are uniform.

[0064] Figure 4 The thermogravimetric analysis diagram of MOF-A, CS, and MOF-A / CS shows that at 800°C, the residual weight of CS is 29.33% w / w of the initial weight, the residual weight of MOF-A is 54.02% w / w of the initial weight, and the residual weight of MOF-A / CS is 47.69% w / w of the initial weight. The presence of CS in MOF-A / CS makes the residual weight percentage of MOF-A / CS less than the residual weight percentage of MOF-A at the same temperature, and through the above values, through (MOF-A / CS residual mass percentage-CS residual mass percentage) / (MOF-A residual mass percentage-CS residual mass percentage)*100% (the following examples use similar calculation formulas), it can be calculated that the loading amount of MOF-A in MOF-A / CS is 74.36% w / w, and the loading amount of MOF-A in the molded body is high.

[0065] Figure 5 This is the SEM image of MOF-A / CS. It can be seen from the image that the synthesized MOF-A / CS is spherical particles with a particle size of about 180 μm. Example 2

[0066] (1) Synthesis of MOF-B: 2 g of chromium nitrate nonahydrate and 0.83 g of terephthalic acid were added to 20 mL of deionized water and ultrasonically treated for 30 min. The dark blue suspension was then transferred to a stainless steel reactor lined with polytetrafluoroethylene for reaction and heated at 220 °C for 18 h. After the reaction was completed, the hydrothermal reactor was taken out and cooled at room temperature. The sample was washed several times with water, N,N-dimethylformamide, and ethanol, respectively, and dried at 65 °C overnight to obtain MOF-B material.

[0067] (2) Synthesis of MOF-B / CS microspheres: Ultrasonic disperse 40 mg of MOF-B prepared in step (1) in 2 mL of deionized water. Add 25 mg of chitosan and 0.04 mL of 2% v / v acetic acid to the above suspension, and continue stirring to completely dissolve the chitosan to obtain a precursor solution. Dissolve glutaraldehyde in water to obtain a solidifying solution with a glutaraldehyde concentration of 10% w / w. Use a spray gun to spray the precursor solution into liquid nitrogen, freeze-dry for 24 hours to obtain a pre-solidified molded body; soak the pre-solidified molded body in the solidifying liquid for 12 hours, then wash it with deionized water 3 times, and finally freeze-dry it for 24 hours to obtain a MOF-B / CS molded body.

[0068] Figure 6 Figure 1 is the X-ray powder sample diffraction pattern of MOF-B and MOF-B / CS. Curve 1 in the figure represents the simulation curve of MOF-B, curve 2 represents the measurement curve of the synthesized MOF-B, and curve 3 represents the measurement curve of the synthesized MOF-B / CS. The characteristic peak in curve 2 is consistent with the characteristic peak in curve 1, indicating that the above metal organic framework material has been successfully synthesized. The characteristic peak in curve 3 is consistent with the characteristic peaks in curves 1 and 2, indicating that the crystal structure of MOF-B in the synthesized MOF-B / CS has not changed and its crystallinity has not decreased.

[0069] Figure 7 N of MOF-B and MOF-B / CS 2 Adsorption and desorption curves. It can be seen from the figure that the porosity of the synthesized MOF-B / CS is not significantly reduced compared with MOF-B.

[0070] Figure 8 The pore size distribution diagram of MOF-B and MOF-B / CS. The pore size of the synthesized MOF-B / CS is consistent with that of MOF-B, and the pores of MOF-B / CS are uniform.

[0071] Fig. 9The thermogravimetric analysis diagram of MOF-B, CS, and MOF-B / CS shows that at 800°C, the residual weight of CS is 29.33% w / w of the initial weight, the residual weight of MOF-B is 42.24% w / w of the initial weight, and the residual weight of MOF-B / CS is 37.41% w / w of the initial weight. The presence of CS in MOF-B / CS makes the residual weight percentage of MOF-B / CS less than the residual weight percentage of MOF-B at the same temperature, and through the above values, it can be calculated that the loading amount of MOF-B in MOF-B / CS is 62.59% w / w, and the loading amount of MOF-B in the molded body is high.

[0072] Fig.10 This is the SEM image of MOF-B / CS. It can be seen from the image that the synthesized MOF-B / CS is spherical particles with a particle size of about 500 μm. Example 3

[0073] (1) Synthesis of MOF-C: 1.82 g of copper nitrate and 0.875 g of benzene-1,3,5-tricarboxylic acid were dissolved in 50 mL of pure methanol respectively and vortexed until the solution was evenly dispersed. The copper nitrate solution was then transferred to the benzene-1,3,5-tricarboxylic acid solution for reaction and stirred at room temperature for 2 hours. After the reaction, the sample was washed several times by centrifugation with methanol and dried at 65 °C overnight to obtain MOF-C material.

[0074] (2) Synthesis of MOF-C / CS microspheres: Ultrasonic disperse 100 mg of MOF-C prepared in step (1) in 2 mL of deionized water. Add 50 mg of chitosan and 0.04 mL of 2% v / v acetic acid to the above suspension, and continue stirring to completely dissolve the chitosan to obtain a precursor solution. Dissolve glutaraldehyde in water to obtain a solidifying solution with a glutaraldehyde concentration of 20% w / w. Use a spray gun to spray the precursor solution into liquid nitrogen, freeze-dry for 24 hours to obtain a pre-solidified molded body; soak the pre-solidified molded body in the solidifying liquid for 12 hours, then wash it with deionized water 3 times, and finally freeze-dry it for 24 hours to obtain a MOF-C / CS molded body.

[0075] Fig.11 The X-ray powder sample diffraction patterns of MOF-C and MOF-C / CS. Curve 1 in the figure represents the simulation curve of MOF-C, curve 2 represents the measurement curve of the synthesized MOF-C, and curve 3 represents the measurement curve of the synthesized MOF-C / CS. The characteristic peaks in curve 2 coincide with the characteristic peaks in curve 1, indicating that the above metal organic framework material has been successfully synthesized. The characteristic peaks in curve 3 coincide with the characteristic peaks in curves 1 and 2, indicating that the crystal structure of MOF-C in the synthesized MOF-C / CS has not changed and its crystallinity has not decreased.

[0076] Fig.12 N of MOF-C and MOF-C / CS 2 Adsorption and desorption curves. It can be seen from the figure that the porosity of the synthesized MOF-C / CS is not significantly reduced compared with MOF-C.

[0077] Fig.13 This is the pore size distribution diagram of MOF-C and MOF-C / CS. The pore size of the synthesized MOF-C / CS is consistent with that of MOF-C, and the pores of MOF-C / CS are uniform.

[0078] Fig.14 The thermogravimetric analysis diagram of MOF-C, CS, and MOF-C / CS shows that at 800°C, the residual weight of CS is 29.33% w / w of the initial weight, the residual weight of MOF-C is 59.81% w / w of the initial weight, and the residual weight of MOF-C / CS is 49.46% w / w of the initial weight. The presence of CS in MOF-C / CS makes the residual weight percentage of MOF-C / CS less than the residual weight percentage of MOF-C at the same temperature, and through the above values, it can be calculated that the loading amount of MOF-C in MOF-C / CS is 66.15% w / w, and the loading amount of MOF-C in the molded body is high.

[0079] Fig.15 This is the SEM image of MOF-C / CS. It can be seen from the image that the synthesized MOF-C / CS is spherical particles with a particle size of about 880 μm. Example 4

[0080] (1) Synthesis of MOF-D: Ni(NO 3 ) 2 6H 2 O (0.0174 g, 0.06 mmol), H 2 BDA (0.0224 g, 0.06 mmol) was placed in a sealed 20 mL glass bottle, followed by the addition of N,N-dimethylformamide (DMF) (5.5 mL) and NH 3 ·H 2 O (0.3 mL), ultrasonically treated for 3 minutes to obtain a lavender mixed uniform turbid solution, and then heated in a Yamato oven preheated to 120 ° C for 48 hours. After the oven was cooled to room temperature, the green flaky crystals obtained from the mother liquor were separated and washed several times with DMF and ethanol to obtain MOF-D material.

[0081] (2) Synthesis of MOF-D / CS microspheres: Ultrasonic dispersion of 40 mg MOF-D prepared in step (1) in 2 mL deionized water. Add 25 mg chitosan and 0.05 mL 2% v / v acetic acid to the above suspension, and continue stirring to completely dissolve the chitosan to obtain a precursor solution. Dissolve glutaraldehyde in water to obtain a solidifying solution with a glutaraldehyde concentration of 25% w / w. Use a spray gun to spray the precursor solution into liquid nitrogen, freeze-dry for 24 hours to obtain a pre-solidified molded body; soak the pre-solidified molded body in the solidifying liquid for 18 hours, then wash it with deionized water 3 times, and finally freeze-dry it for 24 hours to obtain a MOF-D / CS molded body. Fig.16 The X-ray powder sample diffraction patterns of MOF-D and MOF-D / CS. Curve 1 in the figure represents the simulation curve of MOF-D, curve 2 represents the measurement curve of the synthesized MOF-D, and curve 3 represents the measurement curve of the synthesized MOF-D / CS. The characteristic peaks in curve 2 coincide with the characteristic peaks in curve 1, indicating that the above metal organic framework material has been successfully synthesized. The characteristic peaks in curve 3 coincide with the characteristic peaks in curves 1 and 2, indicating that the crystal structure of MOF-D in the synthesized MOF-D / CS has not changed and its crystallinity has not decreased.

[0082] Fig.17 The N of MOF-D and MOF-D / CS are 2 Adsorption and desorption curves. It can be seen from the figure that the porosity of the synthesized MOF-D / CS is not significantly reduced compared with that of MOF-D.

[0083] Fig.18 The pore size distribution diagram of MOF-D and MOF-D / CS. The pore size of the synthesized MOF-D / CS is consistent with that of MOF-D, and the pores of MOF-D / CS are uniform.

[0084] Fig.19 The thermogravimetric analysis diagram of MOF-D, CS, and MOF-D / CS shows that at 800°C, the residual weight of CS is 29.33% w / w of the initial weight, the residual weight of MOF-D is 42.61% w / w of the initial weight, and the residual weight of MOF-D / CS is 37.74% w / w of the initial weight. The presence of CS in MOF-D / CS makes the residual weight percentage of MOF-D / CS less than the residual weight percentage of MOF-D at the same temperature, and through the above values, it can be calculated that the loading amount of MOF-D in MOF-D / CS is 63.39% w / w, and the loading amount of MOF-D in the molded body is high.

[0085] Fig. 20 This is the SEM image of MOF-D / CS. It can be seen from the image that the synthesized MOF-D / CS is spherical particles with a particle size of about 950 μm. Example 5

[0086] (1) Synthesis of MOF-E: 0.0144 g of In(NO 3 ) 3 ·4H 2 O and 0.0135 g of 1,2,4,5-tetrakis(3-carboxyphenyl)benzene (H 4 TCPB) was added to a 20 mL glass reaction bottle, followed by 6 mL of N,N'-diethylformamide (DEF) and 90 μL of pure anhydrous acetic acid. The reaction vessel was placed in an oven and heated at 120 °C for 3 days, then cooled to room temperature for 10 hours. After the reaction was completed, it was washed with DEF and the reaction product MOF-E was collected.

[0087] (2) Synthesis of MOF-E / CS microspheres: Ultrasonic disperse 30 mg of MOF-E prepared in step (1) in 2 mL of deionized water. Add 20 mg of chitosan and 0.05 mL of 2% v / v acetic acid to the above suspension, and continue stirring to completely dissolve the chitosan to obtain a precursor solution. Dissolve glutaraldehyde in water to obtain a solidifying solution with a glutaraldehyde concentration of 10% w / w. Use a spray gun to spray the precursor solution into liquid nitrogen, freeze-dry for 24 hours, and obtain a pre-solidified molded body; soak the pre-solidified molded body in the solidifying liquid for 18 hours, then wash it with deionized water 3 times, and finally freeze-dry it for 24 hours to obtain a MOF-E / CS molded body.

[0088] Fig.21 The X-ray powder sample diffraction patterns of MOF-E and MOF-E / CS. Curve 1 in the figure represents the simulation curve of MOF-E, curve 2 represents the measurement curve of the synthesized MOF-E, and curve 3 represents the measurement curve of the synthesized MOF-E / CS. The characteristic peaks in curve 2 coincide with the characteristic peaks in curve 1, indicating that the above metal organic framework material has been successfully synthesized. The characteristic peaks in curve 3 coincide with the characteristic peaks in curves 1 and 2, indicating that the crystal structure of MOF-E in the synthesized MOF-E / CS has not changed and its crystallinity has not decreased.

[0089] Fig. 22 The N of MOF-E and MOF-E / CS 2 Adsorption and desorption curves. It can be seen from the figure that the porosity of the synthesized MOF-E / CS is not significantly reduced compared with MOF-E.

[0090] Fig.23 This is the pore size distribution diagram of MOF-E and MOF-E / CS. The pore size of the synthesized MOF-E / CS is consistent with that of MOF-E, and the pores of MOF-E / CS are uniform.

[0091] Fig.24 The thermogravimetric analysis diagram of MOF-E, CS, and MOF-E / CS shows that at 800°C, the residual weight of CS is 29.33% w / w of the initial weight, the residual weight of MOF-E is 41.34% w / w of the initial weight, and the residual weight of MOF-E / CS is 36.58% w / w of the initial weight. The presence of CS in MOF-E / CS makes the residual weight percentage of MOF-E / CS less than the residual weight percentage of MOF-E at the same temperature, and through the above values, it can be calculated that the loading amount of MOF-E in MOF-E / CS is 60.36% w / w, and the loading amount of MOF-E in the molded body is high.

[0092] Fig.25 This is the SEM image of MOF-E / CS. It can be seen from the image that the synthesized MOF-E / CS is spherical particles with a particle size of about 800 μm. Example 6

[0093] (1) Synthesis of MOF-F: Cu(NO 3 ) 2 ·3H 2 O (0.0535 g, 0.06 mmol), H 2 BDA (0.0224 g, 0.06 mmol) was placed in a sealed 20 mL glass bottle, followed by the addition of DMF (7 mL) and NH 3 ·H 2 O (0.3 mL) was added and ultrasonicated for 3 minutes to obtain a blue turbid solution, which was then heated in a Yamato oven preheated to 120°C for 48 hours. After the oven was cooled to room temperature, the blue block crystals obtained by separating the mother liquor were washed several times with DMF and ethanol to obtain MOF-F.

[0094] (2) Synthesis of MOF-F / CS microspheres: Ultrasonic dispersion of 90 mg of MOF-F prepared in step (1) in 2 mL of deionized water. Add 60 mg of chitosan and 0.05 mL of 2% v / v acetic acid to the above suspension, and continue stirring to completely dissolve the chitosan to obtain a precursor solution. Dissolve glutaraldehyde in water to obtain a solidifying solution with a glutaraldehyde concentration of 20% w / w. Use a spray gun to spray the precursor solution into liquid nitrogen, freeze-dry for 24 hours to obtain a pre-solidified molded body; soak the pre-solidified molded body in the solidifying liquid for 18 hours, then wash it with deionized water 3 times, and finally freeze-dry it for 24 hours to obtain a MOF-F / CS molded body.

[0095] Fig.26Figure 1 is the X-ray powder sample diffraction pattern of MOF-F and MOF-F / CS. Curve 1 in the figure represents the simulation curve of MOF-F, curve 2 represents the measurement curve of the synthesized MOF-F, and curve 3 represents the measurement curve of the synthesized MOF-F / CS. The characteristic peak in curve 2 is consistent with the characteristic peak in curve 1, indicating that the above metal organic framework material has been successfully synthesized. The characteristic peak in curve 3 is consistent with the characteristic peaks in curves 1 and 2, indicating that the crystal structure of MOF-F in the synthesized MOF-F / CS has not changed and its crystallinity has not decreased.

[0096] Fig. 27 The N of MOF-F and MOF-F / CS 2 Adsorption and desorption curves. It can be seen from the figure that the porosity of the synthesized MOF-F / CS is not significantly reduced compared with MOF-F.

[0097] Fig.28 This is the pore size distribution diagram of MOF-F and MOF-F / CS. The pore size of the synthesized MOF-F / CS is consistent with that of MOF-F, and the pores of MOF-F / CS are uniform.

[0098] Fig.29 The thermogravimetric analysis diagrams of MOF-F, CS, and MOF-F / CS show that at 800°C, the residual weight of CS is 29.33% w / w of the initial weight, the residual weight of MOF-F is 46.58% w / w of the initial weight, and the residual weight of MOF-F / CS is 39.64% w / w of the initial weight. The presence of CS in MOF-F / CS makes the residual weight percentage of MOF-F / CS less than the residual weight percentage of MOF-F at the same temperature, and through the above values, it can be calculated that the loading amount of MOF-F in MOF-F / CS is 59.84% w / w, and the loading amount of MOF-F in the molded body is high.

[0099] Fig.30 This is the SEM image of MOF-F / CS. It can be seen from the image that the synthesized MOF-F / CS is spherical particles with a particle size of about 850μm. Example 7

[0100] (1) Synthesis of COF-A: 1,3,6,8-Tetrakis-(p-aminophenyl)-pyrene (PyTTA: 0.04 mmol, 22.7 mg) and 4,4'-biphenyldicarboxaldehyde (BPDA: 0.08 mmol, 16.8 mg) were added to a 10 mL Pyrex tube, and 1 mL of o-dichlorobenzene and 1 mL of n-butanol were accurately measured and added dropwise using a pipette. After 15 min of ultrasonic treatment, a uniform dispersion system was obtained. Then, an aqueous acetic acid solution (6 M, 0.2 mL) was added as a catalyst and ultrasonic treatment was continued for 5 min. After three operations of liquid nitrogen freezing-vacuuming-thawing, the Pyrex tube was melt-sealed and reacted at a constant temperature of 120 °C for three days. After the reaction was completed, it was cooled to room temperature. The solid product was collected by centrifugation and extracted with THF for one day. Finally, it was replaced with n-hexane several times and dried in a vacuum at 80 °C for 12 h to prepare COF-A.

[0101] (2) Synthesis of COF-A / CS microspheres: Ultrasonic dispersion of 50 mg COF-A prepared in step (1) in 2 mL deionized water. Add 20 mg chitosan and 0.06 mL 2% v / v acetic acid to the above suspension, and continue stirring to completely dissolve the chitosan to obtain a precursor solution. Dissolve glutaraldehyde in water to obtain a solidifying solution with a glutaraldehyde concentration of 15% w / w. Use a spray gun to spray the precursor solution into liquid nitrogen, freeze-dry for 24 hours to obtain a pre-solidified molded body; soak the pre-solidified molded body in the solidifying liquid for 24 hours, then wash it with deionized water 3 times, and finally freeze-dry it for 24 hours to obtain a COF-A / CS molded body.

[0102] Fig.31 The X-ray powder sample diffraction patterns of COF-A and COF-A / CS. Curve 1 in the figure represents the simulation curve of COF-A, curve 2 represents the measurement curve of the synthesized COF-A, and curve 3 represents the measurement curve of the synthesized COF-A / CS. The characteristic peaks in curve 2 coincide with the characteristic peaks in curve 1, indicating that the above covalent organic framework material has been successfully synthesized. The characteristic peaks in curve 3 coincide with the characteristic peaks in curves 1 and 2, indicating that the crystal structure of COF-A in the synthesized COF-A / CS has not changed and its crystallinity has not decreased.

[0103] Fig.32 N of COF-A and COF-A / CS 2 Adsorption and desorption curves. It can be seen from the figure that the porosity of the synthesized COF-A / CS is not significantly reduced compared with that of COF-A.

[0104] Fig.33The pore size distribution diagram of COF-A and COF-A / CS. The pore size of the synthesized COF-A / CS is consistent with that of COF-A, and the pores of COF-A / CS are uniform.

[0105] Fig.34 The thermogravimetric analysis diagrams of COF-A, CS, and COF-A / CS show that at 800°C, the residual weight of CS is 29.33% w / w of the initial weight, the residual weight of COF-A is 36.07% w / w of the initial weight, and the residual weight of COF-A / CS is 34.11% w / w of the initial weight. The presence of CS in COF-A / CS makes the residual weight percentage of COF-A / CS less than the residual weight percentage of COF-A at the same temperature, and through the above values, it can be calculated that the loading amount of COF-A in COF-A / CS is 70.89% w / w, and the loading amount of COF-A in the molded body is high.

[0106] Fig.35 This is the SEM image of COF-A / CS. It can be seen from the image that the synthesized COF-A / CS is spherical particles with a particle size of about 450 μm. Example 8

[0107] (1) Synthesis of COF-B: 1,3,5-tri-4-aminophenylbenzene (TAPB: 0.08 mmol, 28.1 mg) and 4,4'-biphenyldicarboxaldehyde (BPDA: 0.12 mmol, 25.2 mg) were added to a 10 mL Pyrex tube, and 0.5 mL of dioxane and 1.5 mL of mesitylene were accurately measured with a pipette and added dropwise. After 15 min of ultrasonic treatment, a uniform dispersion system was obtained. Then, an aqueous acetic acid solution (6 M, 0.2 mL) was added as a catalyst and ultrasonic treatment was continued for 5 min. After three operations of liquid nitrogen freezing-vacuuming-thawing, the Pyrex tube was melt-sealed and reacted at a constant temperature of 120 °C for three days. After the reaction was completed, it was cooled to room temperature. The solid product was collected by centrifugation and extracted with THF for one day. Finally, it was replaced with methanol several times and supercritically dried to prepare COF-B.

[0108] (2) Synthesis of COF-B / CS microspheres: Ultrasonic dispersion of 60 mg COF-B prepared in step (1) in 2 mL deionized water. Add 30 mg chitosan and 0.06 mL 2% v / v acetic acid to the above suspension, and continue stirring to completely dissolve the chitosan to obtain a precursor solution. Dissolve glutaraldehyde in water to obtain a solidifying solution with a glutaraldehyde concentration of 10% w / w. Use a spray gun to spray the precursor solution into liquid nitrogen, freeze-dry for 24 hours to obtain a pre-solidified molded body; soak the pre-solidified molded body in the solidifying liquid for 24 hours, then wash it with deionized water 3 times, and finally freeze-dry it for 24 hours to obtain a COF-B / CS molded body.

[0109] Fig.36 The X-ray powder sample diffraction patterns of COF-B and COF-B / CS. Curve 1 in the figure represents the simulation curve of COF-B, curve 2 represents the measurement curve of the synthesized COF-B, and curve 3 represents the measurement curve of the synthesized COF-B / CS. The characteristic peaks in curve 2 are consistent with the characteristic peaks in curve 1, indicating that the above covalent organic framework material has been successfully synthesized. The characteristic peaks in curve 3 are consistent with the characteristic peaks in curves 1 and 2, indicating that the crystal structure of COF-B in the synthesized APB-BPDA-COF / CS has not changed and its crystallinity has not decreased.

[0110] Fig.37 N of COF-B and COF-B / CS 2 Adsorption and desorption curves. It can be seen from the figure that the porosity of the synthesized COF-B / CS is not significantly reduced compared with that of COF-B.

[0111] Fig.38 The pore size distribution diagram of COF-B and COF-B / CS. The pore size of the synthesized COF-B / CS is consistent with that of COF-B, and the pores of COF-B / CS are uniform.

[0112] Fig.39 The thermogravimetric analysis diagrams of COF-B, CS, and COF-B / CS show that at 800°C, the residual weight of CS is 29.33% w / w of the initial weight, the residual weight of COF-B is 59.91% w / w of the initial weight, and the residual weight of COF-B / CS is 50.11% w / w of the initial weight. The presence of CS in COF-B / CS makes the residual weight percentage of COF-B / CS less than the residual weight percentage of COF-B at the same temperature, and through the above values, it can be calculated that the loading amount of COF-B in COF-B / CS is 67.96% w / w, and the loading amount of COF-B in the molded body is high.

[0113] Fig.40This is the SEM image of COF-B / CS. It can be seen from the image that the synthesized COF-B / CS is spherical particles with a particle size of about 300 μm. Example 9

[0114] (1) Synthesis of COF-C: 2,4,6-tris(4-aminophenyl)-1,3,5-triazine (TAPT: 0.1 mmol, 35.3 mg) and 4,4'-biphenyldicarboxaldehyde (BPDA: 0.15 mmol, 31.5 mg) were added to a 10 mL Pyrex tube, and 1 mL of o-dichlorobenzene and 1 mL of n-butanol were accurately measured and added dropwise with a pipette. After 15 min of ultrasonic treatment, a uniform dispersion system was obtained. Then, an aqueous acetic acid solution (6 M, 0.2 mL) was added as a catalyst and ultrasonic treatment was continued for 5 min. After three operations of liquid nitrogen freezing-vacuuming-thawing, the Pyrex tube was melt-sealed and reacted at a constant temperature of 120 °C for three days. After the reaction was completed, it was cooled to room temperature. The solid product was collected by centrifugation and extracted with THF for one day. Finally, it was replaced with methanol several times and supercritically dried to prepare COF-C.

[0115] (2) Synthesis of COF-C / CS microspheres: Ultrasonic dispersion of 80 mg COF-C prepared in step (1) in 2 mL deionized water. Add 30 mg chitosan and 0.06 mL 2% v / v acetic acid to the above suspension, and continue stirring to completely dissolve the chitosan to obtain a precursor solution. Dissolve glutaraldehyde in water to obtain a solidifying solution with a glutaraldehyde concentration of 20% w / w. Use a spray gun to spray the precursor solution into liquid nitrogen, freeze-dry for 24 hours to obtain a pre-solidified molded body; soak the pre-solidified molded body in the solidifying liquid for 24 hours, then wash it with deionized water 3 times, and finally freeze-dry it for 24 hours to obtain a COF-C / CS molded body.

[0116] Fig.41 The X-ray powder sample diffraction patterns of COF-C and COF-C / CS. Curve 1 in the figure represents the simulation curve of COF-C, curve 2 represents the measurement curve of the synthesized COF-C, and curve 3 represents the measurement curve of the synthesized COF-C / CS. The characteristic peaks in curve 2 coincide with the characteristic peaks in curve 1, indicating that the above covalent organic framework material has been successfully synthesized. The characteristic peaks in curve 3 coincide with the characteristic peaks in curves 1 and 2, indicating that the crystal structure of COF-C in the synthesized COF-C / CS has not changed and its crystallinity has not decreased.

[0117] Fig.42 N of COF-C and COF-C / CS 2 Adsorption and desorption curves. It can be seen from the figure that the porosity of the synthesized COF-C / CS is not significantly reduced compared with that of COF-C.

[0118] Fig.43 The pore size distribution diagram of COF-C and COF-C / CS. The pore size of the synthesized COF-C / CS is consistent with that of COF-C, and the pores of COF-C / CS are uniform.

[0119] Fig.44 The thermogravimetric analysis diagram of COF-C, CS, and COF-C / CS shows that at 800°C, the residual weight of CS is 29.33% w / w of the initial weight, the residual weight of COF-C is 58.29% w / w of the initial weight, and the residual weight of COF-C / CS is 50.21% w / w of the initial weight. The presence of CS in COF-C / CS makes the residual weight percentage of COF-C / CS less than the residual weight percentage of COF-C at the same temperature, and through the above values, it can be calculated that the loading amount of COF-C in COF-C / CS is 72.18% w / w, and the loading amount of COF-C in the molded body is high.

[0120] Fig.45 This is the SEM image of COF-C / CS. It can be seen from the image that the synthesized COF-C / CS is spherical particles with a particle size of about 800 μm. Example 10

[0121] (1) Synthesis of COF-D: 1,3,5-tri-4-aminophenylbenzene (TAPB: 0.08 mmol, 28.1 mg) and 2,5-dimethoxyterephthalaldehyde (DMTA: 0.12 mmol, 23.4 mg) were added to a 10 mL Pyrex tube, and 1 mL of o-dichlorobenzene and 1 mL of n-butanol were accurately measured and added dropwise using a pipette. After 15 min of ultrasonic treatment, a uniform dispersion system was obtained. Then, an aqueous acetic acid solution (6 M, 0.2 mL) was added as a catalyst and ultrasonic treatment was continued for 5 min. After three operations of liquid nitrogen freezing-vacuuming-thawing, the Pyrex tube was melt-sealed and reacted at a constant temperature of 120 °C for three days. After the reaction was completed, it was cooled to room temperature, and the obtained solid product was collected by centrifugation and thoroughly washed with THF. Finally, it was replaced with n-hexane several times and then dried in a vacuum at 80 °C for 12 h to prepare COF-D.

[0122] (2) Synthesis of COF-D / CS microspheres: Ultrasonic dispersion of 25 mg COF-D prepared in step (1) in 2 mL deionized water. Add 20 mg chitosan and 0.06 mL 2% v / v acetic acid to the above suspension, and continue stirring to completely dissolve the chitosan to obtain a precursor solution. Dissolve glutaraldehyde in water to obtain a solidifying solution with a glutaraldehyde concentration of 10% w / w. Use a spray gun to spray the precursor solution into liquid nitrogen, freeze-dry for 24 hours to obtain a pre-solidified molded body; soak the pre-solidified molded body in the solidifying liquid for 24 hours, then wash it with deionized water 3 times, and finally freeze-dry it for 24 hours to obtain a COF-D / CS molded body.

[0123] Fig.46 The X-ray powder sample diffraction patterns of COF-D and COF-D / CS. Curve 1 in the figure represents the simulation curve of COF-D, curve 2 represents the measurement curve of the synthesized COF-D, and curve 3 represents the measurement curve of the synthesized COF-D / CS. The characteristic peaks in curve 2 coincide with the characteristic peaks in curve 1, indicating that the above covalent organic framework material has been successfully synthesized. The characteristic peaks in curve 3 coincide with the characteristic peaks in curves 1 and 2, indicating that the crystal structure of COF-D in the synthesized COF-D / CS has not changed and its crystallinity has not decreased.

[0124] Fig.47 N of COF-D and COF-D / CS 2 Adsorption and desorption curves. It can be seen from the figure that the porosity of the synthesized COF-D / CS is not significantly reduced compared with that of COF-D.

[0125] Fig.48 The pore size distribution diagram of COF-D and COF-D / CS. The pore size of the synthesized COF-D / CS is consistent with that of COF-D, and the pores of COF-D / CS are uniform.

[0126] Fig.49 The thermogravimetric analysis diagram of COF-D, CS, and COF-D / CS shows that at 800°C, the residual weight of CS is 29.33% w / w of the initial weight, the residual weight of COF-D is 68.53% w / w of the initial weight, and the residual weight of COF-D / CS is 52.90% w / w of the initial weight. The presence of CS in COF-D / CS makes the residual weight percentage of COF-D / CS less than the residual weight percentage of COF-D at the same temperature, and through the above values, it can be calculated that the loading amount of COF-D in COF-D / CS is 60.13% w / w, and the loading amount of COF-D in the molded body is high.

[0127] Fig.50This is the SEM image of COF-D / CS. It can be seen from the image that the synthesized COF-D / CS is spherical particles with a particle size of about 450 μm. Embodiment 11

[0128] (1) Synthesis of COF-E: terephthalaldehyde (0.089 mmol, 12 mg) and tetrakis(4-aminophenyl)methane (0.052 mmol, 20 mg) were added to a 10 mL Pyrex tube, and 1 mL of anhydrous dioxane was accurately measured with a pipette and added dropwise. After 15 min of ultrasonic treatment, a uniform dispersion system was obtained. Then, an acetic acid aqueous solution (3 M, 0.2 mL) was added as a catalyst and ultrasonic treatment was continued for 5 min. After three operations of liquid nitrogen freezing-vacuuming-thaw, the Pyrex tube was melt-sealed and reacted at a constant temperature of 120 °C for three days. After the reaction was completed, it was cooled to room temperature, and the obtained solid product was collected by centrifugation and thoroughly washed with anhydrous dioxane and THF. The obtained powder was finally soaked in THF for 24 h and then dried in vacuum at 100 °C for 12 h to prepare COF-E.

[0129] (2) Synthesis of COF-E / CS microspheres: Ultrasonic dispersion of 50 mg COF-E prepared in step (1) in 2 mL deionized water. Add 20 mg chitosan and 0.06 mL 2% v / v acetic acid to the above suspension, and continue stirring to completely dissolve the chitosan to obtain a precursor solution. Dissolve glutaraldehyde in water to obtain a solidifying solution with a glutaraldehyde concentration of 15% w / w. Use a spray gun to spray the precursor solution into liquid nitrogen, freeze-dry for 24 hours to obtain a pre-solidified molded body; soak the pre-solidified molded body in the solidifying liquid for 24 hours, then wash it with deionized water 3 times, and finally freeze-dry it for 24 hours to obtain a COF-E / CS molded body.

[0130] Fig.51 The X-ray powder sample diffraction patterns of COF-E and COF-E / CS. Curve 1 in the figure represents the simulation curve of COF-E, curve 2 represents the measurement curve of the synthesized COF-E, and curve 3 represents the measurement curve of the synthesized COF-E / CS. The characteristic peaks in curve 2 coincide with the characteristic peaks in curve 1, indicating that the above covalent organic framework material has been successfully synthesized. The characteristic peaks in curve 3 coincide with the characteristic peaks in curves 1 and 2, indicating that the crystal structure of COF-E in the synthesized COF-E / CS has not changed and its crystallinity has not decreased.

[0131] Fig.52 N of COF-E and COF-E / CS 2 Adsorption and desorption curves. It can be seen from the figure that the porosity of the synthesized COF-E / CS is not significantly reduced compared with that of COF-E.

[0132] Fig.53 The pore size distribution diagram of COF-E and COF-E / CS. The pore size of the synthesized COF-E / CS is consistent with that of COF-E, and the pores of COF-E / CS are uniform.

[0133] Fig.54 The thermogravimetric analysis diagram of COF-E, CS, and COF-E / CS shows that at 800°C, the residual weight of CS is 29.33% w / w of the initial weight, the residual weight of COF-E is 46.82% w / w of the initial weight, and the residual weight of COF-E / CS is 41.57% w / w of the initial weight. The presence of CS in COF-E / CS makes the residual weight percentage of COF-E / CS less than the residual weight percentage of COF-E at the same temperature, and through the above values, it can be calculated that the loading amount of COF-E in COF-E / CS is 70% w / w, and the loading amount of COF-E in the molded body is high.

[0134] Fig.55 This is the SEM image of COF-E / CS. It can be seen from the image that the synthesized COF-E / CS is spherical particles with a particle size of about 380 μm.

[0135] It can be known from the above embodiments and experimental data that the loading amount of the crystalline porous polymer material in the crystalline porous polymer molded body obtained by the preparation method of the present invention is high, which can reach more than 60%w / w, or even more than 70%w / w, and the crystallinity and porosity of the crystalline porous polymer material in the molded body are not significantly reduced compared with the powder material. The maintenance of crystallinity and porosity makes the molded body of the present invention superior in performance when used for separation, sensing, catalysis and other applications. In addition, a molded body with adjustable shape and size and uniform size can be obtained by the preparation method of the present invention, which is easy to store and transport. The preparation method of the present invention can greatly improve the processability and mechanical properties of the crystalline porous polymer molded body.

[0136] The above are only preferred embodiments of the present invention and are not intended to limit the protection scope of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing a crystalline porous polymer molded body, It is characterized in that include: (1) Mixing the crystalline porous polymer material and the composite material in water to prepare a precursor solution; (2) dissolving the curing material to prepare a curing liquid; (3) dispersing the precursor solution and placing it in liquid nitrogen for freeze drying to obtain a pre-cured molded body; (4) Immersing the pre-cured molded body in the curing liquid to allow the composite material to react with the curing material to obtain a post-cured molded body.

2. The preparation method according to claim 1, It is characterized in that The concentration of the crystalline porous polymer material in the precursor solution is 12.5-50 mg / mL, and the concentration of the composite material is 10-30 mg / mL.

3. The preparation method according to claim 2, It is characterized in that The concentration of the crystalline porous polymer material in the precursor solution is 40 mg / mL, and the concentration of the composite material is 15 mg / mL.

4. The preparation method according to claim 1, It is characterized in that The concentration of the solidifying liquid is 5% w / w-25% w / w.

5. The preparation method according to claim 1, It is characterized in that The method of dispersing the precursor liquid and placing it into liquid nitrogen includes spraying the precursor liquid into the liquid nitrogen with a spray gun.

6. The preparation method according to claim 5, It is characterized in that The nozzle diameter of the spray gun is 1.5 mm, and the air pressure of the precursor liquid sprayed into liquid nitrogen using the spray gun is 0.7 Mpa.

7. The preparation method according to claim 1, It is characterized in that The crystalline porous polymer material is a metal organic framework material or a covalent organic framework material.

8. The preparation method according to claim 7, It is characterized in that The metal organic framework material is formed by the action of a metal source and an organic ligand, wherein the metal source is selected from at least one of In, Cu, Ni, Zn, and Cr, and the organic ligand is selected from at least one of 1,2,4,5-tetrakis(3-carboxyphenyl)benzene, 2-methylimidazole, terephthalic acid, benzene-1,3,5-tricarboxylic acid, and 4,4'-(1H,1'H-[2,2'-biimidazole]-1,1'-diyl)dibenzoic acid.

9. The preparation method according to claim 8, It is characterized in that The metal organic framework material is one or more of the following: The metal organic framework material is formed by the reaction of zinc nitrate hexahydrate and 2-methylimidazole, and the X-ray powder diffraction pattern of the formed metal organic framework material is shown in FIG1 ; The metal organic framework material is formed by the reaction of chromium nitrate nonahydrate and terephthalic acid, and the X-ray powder diffraction pattern of the formed metal organic framework material is shown in FIG6 ; The metal organic framework material is formed by the reaction of copper nitrate and benzene-1,3,5-tricarboxylic acid, and the X-ray powder diffraction pattern of the formed metal organic framework material is shown in FIG11 ; The metal organic framework material is formed by the reaction of nickel nitrate hexahydrate and 4,4'-(1H,1'H-[2,2'-biimidazole]-1,1'-diyl)dibenzoic acid, and the X-ray powder diffraction pattern of the formed metal organic framework material is shown in FIG16 ; The metal organic framework material is formed by the reaction of indium nitrate tetrahydrate and 1,2,4,5-tetrakis(3-carboxyphenyl)benzene, and the X-ray powder diffraction pattern of the formed metal organic framework material is shown in FIG21 ; The metal organic framework material is formed by the reaction of copper nitrate trihydrate and 4,4'-(1H,1'H-[2,2'-biimidazole]-1,1'-diyl)dibenzoic acid. The X-ray powder diffraction pattern of the formed metal organic framework material is shown in FIG26 . 10 . The preparation method according to claim 7 , wherein the covalent organic framework material is formed by reacting a first monomer comprising an amino group and a second monomer comprising an aldehyde group.

11. The preparation method according to claim 10, wherein the first monomer is 1,3,5-tris-4-aminophenylbenzene, 2,4,6-tris(4-aminophenyl)-1,3,5-triazine, 1,3,6,8-tetrakis-(p-aminophenyl)-pyrene or tetrakis(4-aminophenyl)methane; and the second monomer is 4,4'-biphenyldicarboxaldehyde, 2,5-dimethoxyterephthalaldehyde or terephthalaldehyde.

12. The preparation method according to claim 11, wherein the covalent organic framework material is one or more of the following: The covalent organic framework material is formed by the reaction of 1,3,6,8-tetrakis-(p-aminophenyl)-pyrene and 4,4'-biphenyldicarboxaldehyde, and the X-ray powder diffraction pattern of the formed covalent organic framework material is shown in FIG31 ; The covalent organic framework material is formed by the reaction of 1,3,5-tri-4-aminophenylbenzene and 4,4'-biphenyldicarboxaldehyde, and the X-ray powder diffraction pattern of the formed covalent organic framework material is shown in FIG36 ; The covalent organic framework material is formed by the reaction of 2,4,6-tris(4-aminophenyl)-1,3,5-triazine and 4,4'-biphenyldicarboxaldehyde, and the X-ray powder diffraction pattern of the formed covalent organic framework material is shown in FIG41 ; The covalent organic framework material is formed by the reaction of 1,3,5-tri-4-aminophenylbenzene and 2,5-dimethoxyterephthalaldehyde, and the X-ray powder diffraction pattern of the formed covalent organic framework material is shown in FIG46 ; The covalent organic framework material is formed by the reaction of terephthalaldehyde and tetrakis(4-aminophenyl)methane, and the X-ray powder diffraction pattern of the formed covalent organic framework material is shown in Figure 51.

13. The preparation method according to claim 1, It is characterized in that The composite material is chitosan.

14. The preparation method according to claim 1, It is characterized in that The curing material is glutaraldehyde, and the pre-cured molded body is immersed in the curing liquid for 12-24 hours.

15. The preparation method according to claim 1, It is characterized in that Ultrasonic dispersion of a metal organic framework material or a covalent organic framework material in water to form a suspension, and chitosan is added to the suspension to obtain a precursor solution, wherein the concentration of the metal organic framework material or the covalent organic framework material is 12.5-50 mg / mL, and the concentration of the chitosan is 10-30 mg / mL; glutaraldehyde is dissolved in water to obtain a solidifying solution, wherein the concentration of glutaraldehyde in the solidifying solution is 5% w / w-25% w / w; the precursor solution is sprayed into liquid nitrogen using a spray gun, and freeze-dried for 24 hours to obtain a pre-solidified molded body; Soaking the pre-cured molded body in the curing liquid for 12-24 hours to obtain a post-cured molded body; The solidified molded body is washed and dried.

16. A crystalline porous polymer molded body, It is characterized in that The crystalline porous polymer molded body is prepared by the preparation method according to any one of claims 1-15.

17. The crystalline porous polymer molded body according to claim 16, It is characterized in that The crystalline porous polymer body is a metal organic framework material / chitosan body or a covalent organic framework material / chitosan body.

18. The crystalline porous polymer molded body according to claim 16, It is characterized in that The crystalline porous polymer molded body is a spherical particle.

19. The crystalline porous polymer molded body according to claim 18, It is characterized in that The particle size of the crystalline porous polymer body is 150-1000 μm.

Images