Imine bond covalent organic framework material based on hummingbird sound resonance technology and preparation method

Abstract

The application discloses an imine bond covalent organic framework material based on a hummingbird sound resonance technology and a preparation method, and relates to the technical field of covalent organic framework material preparation. The method solves the problems of the prior art, such as the need for high-temperature and high-pressure equipment, the need for complex vacuum and inert environment control, a reaction period of several days, the need for the use of toxic organic solvents, and the problems of difficult control of product crystallinity, low efficiency of large-scale preparation and the like. The method comprises the following steps: using an amine-based compound, an aldehyde-based compound and an acid catalyst in an air atmosphere, mixing the mixture and reacting the mixture at room temperature and under normal pressure by adopting a hummingbird sound resonance mechanical ball milling method, and then performing solvent washing and neutralization to obtain the imine bond covalent organic framework material. The application meets the requirements of industrialized 'efficient mass production', realizes the environmental protection of the synthesis process and the stability of the product performance, and provides a powerful preparation method for realizing the industrialized production of COFs.

Description

Technical Field

[0001] This invention relates to the field of covalent organic framework material preparation technology, specifically to an imine bond covalent organic framework material based on hummingbird acoustic resonance technology and its preparation method. Background Technology

[0002] Since thermodynamically reversible reactions facilitate the formation of long-range ordered structures, the preparation of COFs typically relies on such reactions. Currently, the main preparation methods include solvothermal methods, ionothermal methods, microwave heating methods, ultrasonic methods, interfacial polymerization methods, and mechanical milling methods. Among these, the hydrothermal method is the mainstream approach for COF preparation, but it has significant limitations: firstly, it requires "freezing and evacuation" to replace air and provide a vacuum reaction environment, which places high demands on equipment and results in extremely small yields per batch; secondly, it usually requires heating and has a long reaction cycle (≥3 days); and thirdly, it commonly uses toxic organic solvents such as mesitylene and n-butanol. These problems limit the large-scale industrial preparation and application of COFs. In contrast, mechanical ball milling often uses solvent-free or low-solvent systems, effectively avoiding the interference of the solution environment on the COF structure. It also combines high efficiency with environmental friendliness, better aligning with modern green chemistry and sustainable development concepts, and providing a powerful preparation strategy for the industrial production of COFs. As a type of COF material, the preparation methods of imine COFs can be mainly summarized into the following five types: (1) vacuum sealing (ionothermal method, superacid catalysis, polyphosphoric acid catalysis, P2O5 catalysis); (2) reflux condensation (Schiff base condensation); (3) interfacial polymerization (superacid catalysis); (4) microwave synthesis (superacid catalysis); (5) mechanical ball milling (solid-phase Schiff base condensation). Among them, the vacuum sealing method: after mixing aldehyde and amine monomers, catalysts (such as superacid, polyphosphoric acid, P2O5) with solvent (or ionic liquid, used for ionothermal method), the mixture is placed in a glass tube, vacuumed and sealed, and placed in an oven or heating device for reaction (temperature usually 80-200 ℃, time from several hours to several days). Vacuum sealing isolates the reaction from air and moisture (preventing imine bond hydrolysis or oxidation), providing a closed, inert environment. In ionothermal reactions, ionic liquids act as both solvents and templates, while superacids and polyphosphoric acids enhance electrophilicity by protonating the aldehyde group, accelerating Schiff base condensation. The product exhibits high crystallinity and structural stability, making it suitable for monomers sensitive to water / oxygen or systems requiring high temperatures to promote the reaction. It is a common method for synthesizing highly crystalline imine-based COFs. Reflux condensation: The monomer is dissolved in an organic solvent (such as ethanol or dichloromethane), and a small amount of acid catalyst (such as formic acid or trifluoroacetic acid) is added. The mixture is heated in a reflux apparatus (at a temperature near the solvent's boiling point, typically 40-100 °C) for several hours to tens of hours. The evaporated solvent is recovered through a condenser to maintain the stability of the reaction system. Reflux avoids solvent loss and ensures stable reaction concentrations; acid catalysis promotes nucleophilic attack of the amino group by protonating the aldehyde group, accelerating C=N bond formation. It is simple to operate and requires little equipment, making it suitable for large-scale synthesis; however, due to the relatively low reaction temperature, the crystallinity of the product may be slightly lower than that of the vacuum sealing method, making it more suitable for scenarios where crystallinity requirements are not high.Interfacial polymerization: A two-phase interface (e.g., "organic phase-aqueous phase" or "gas phase-liquid phase") is constructed. Aldehyde monomers are dissolved in the organic phase (e.g., n-hexane), and amine monomers are dissolved in the aqueous phase (or amines diffuse from the gas phase to the liquid phase). A superacid catalyst (e.g., trifluoromethanesulfonic acid) is added at the interface. The concentration difference of the monomers at the interface drives Schiff base condensation, and the product grows in situ at the interface. The interface confinement effect directs the reaction, and the product easily forms a thin film or is loaded onto the substrate surface (e.g., electrodes, membrane materials), without the need for subsequent molding and processing. Imine-based COFs thin films or coatings can be directly prepared, exhibiting good mechanical properties and interfacial bonding, suitable for device applications (e.g., sensors, separation membranes), but batch synthesis is difficult and the product yield is small. Microwave synthesis: After mixing the monomers, superacid catalyst, and solvent, the mixture is placed in a microwave reactor and rapidly heated (80-150 °C) by microwave radiation (power typically 200-800 W). The reaction time is shortened from several days in traditional methods to several minutes to several hours. Microwave heating, with its "volume heating" characteristic, rapidly and uniformly raises the temperature of the reaction system, significantly accelerating the Schiff base condensation rate. Simultaneous catalysis with a strong acid further enhances reaction efficiency. It is highly efficient, time-saving, and energy-efficient, suitable for rapid screening of reaction conditions; however, strict control of microwave power and time is necessary to avoid localized overheating that could lead to product decomposition or decreased crystallinity. Mechanical ball milling: Solid aldehyde or amine monomers are added to a ball mill jar with a small amount of solid acid catalyst (such as p-toluenesulfonic acid). The mechanical impact force of the milling beads (typically at 300-600 rpm) ensures sufficient contact between the monomers, resulting in solid-phase Schiff base condensation. The reaction can last from several hours to tens of hours, requiring little or no solvent. Mechanical force breaks down intermolecular forces, promoting contact at active sites and achieving solvent-free or low-solvent reactions, making it environmentally friendly. It is simple to operate, requires no solvent recovery, and is suitable for large-scale green synthesis; however, due to limited mass transfer efficiency in solid-phase reactions, the crystallinity of the product may be low, necessitating optimization of milling parameters (such as rotation speed and time) to improve structural order.

[0003] The aforementioned existing technologies rely on high-temperature and high-pressure equipment, require complex vacuum and inert environment control, have reaction cycles that can last for several days, and require the use of toxic organic solvents. They also suffer from problems such as difficulty in controlling the crystallinity of the product and low efficiency in large-scale preparation.

[0004] This shows that the existing technology needs further improvement. Summary of the Invention

[0005] One of the objectives of this invention is to provide a method for preparing imine-bonded covalent organic framework materials based on hummingbird acoustic resonance technology. This method meets the requirements of "high-efficiency mass production" in industrial applications while achieving environmental friendliness in the synthesis process and stability of product performance, thus solving the technical problems existing in the prior art.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: A method for preparing an imine-bonded covalent organic framework material based on hummingbird acoustic resonance technology includes the following steps: a. Add the amino compound, aldehyde compound and acid catalyst together into a ball mill jar, wherein the molar ratio of the amino compound to the aldehyde compound is 1:0.8 to 1.2; and the mass-volume ratio of the amino compound to the acid catalyst is 15 mg to 1 g: 20 to 1500 μL. b. In an air atmosphere, at room temperature and normal pressure, the mixture obtained in step a is thoroughly mixed by simultaneously performing hummingbird resonance and mechanical ball milling. The mixture is reacted at a frequency of 60 Hz for 45 seconds. After the reaction is completed, it is washed with an organic solvent to obtain the final product.

[0007] The above-mentioned method for preparing an imine-bonded covalent organic framework material based on hummingbird acoustic resonance technology, wherein the amine compound is 1,3,5-tris(4-aminophenyl)benzene or 2,4,6-tris(4-aminophenyl)-1,3,5-triazine.

[0008] The above-mentioned method for preparing an imine-bonded covalent organic framework material based on hummingbird acoustic resonance technology, wherein the aldehyde compound is 2,5-dimethoxybenzene-1,4-dicarboxaldehyde or 2,4,6-tris(4-aldehydephenyl)-1,3,5-triazine.

[0009] The above-mentioned method for preparing an imine-bonded covalent organic framework material based on hummingbird acoustic resonance technology uses trifluoromethanesulfonic acid, methanesulfonic acid, trifluoroacetic acid, benzoic acid, acetic acid, or polyphosphoric acid as the acid catalyst.

[0010] In the above-mentioned method for preparing an imine-bonded covalent organic framework material based on hummingbird acoustic resonance technology, the reaction product obtained in step b is washed or refluxed using a solvent method. The solvent used is ultrapure water, DMF, DMAc, dichloromethane, ethanol, methanol, tetrahydrofuran, or toluene.

[0011] The above-mentioned method for preparing an imine-bonded covalent organic framework material based on hummingbird acoustic resonance technology uses a grinding jar made of stainless steel, zirconium oxide, tungsten oxide, plastic, or glass in the mechanical ball milling method of hummingbird acoustic resonance. The grinding jar has a volume of 1.5-50 mL and the grinding ball diameter is 0.1-1 cm.

[0012] Another object of the present invention is to provide an imine-bonded covalent organic framework material based on hummingbird acoustic resonance technology.

[0013] The aforementioned imine-bonded covalent organic framework material based on hummingbird acoustic resonance technology has a specific surface area of ​​100-2730 m² / g and a pore size of 0.3-5 nm.

[0014] Compared with the prior art, the present invention brings the following beneficial technical effects: (1) This invention proposes a method for preparing imine bond covalent organic framework materials based on hummingbird acoustic resonance technology. The material can be prepared at room temperature and pressure by mechanical ball milling using hummingbird acoustic resonance, without the use of toxic organic solvents. That is, through the innovative combination of hummingbird acoustic resonance technology and solvent-free acid catalytic system, the synthesis of crystalline COFs is achieved in a "highly efficient, green, mass-produced and controllable" manner.

[0015] (2) This invention does not require high temperature and high pressure equipment and vacuum / inert gas control system. Under normal temperature and pressure conditions, the equipment investment and maintenance costs are reduced by more than 60%. The reaction cycle is only 2-20 min (compared to more than 3 days in traditional methods), and it can directly achieve single preparation at the level of 15 mg-1 g. This invention provides strong support for the technology to go to market.

[0016] (3) Green and environmentally friendly, in line with industrial guidance. The reaction system contains only monomers and acid catalysts, completely avoiding the use of toxic organic solvents. This reduces environmental pollution during the production process and saves subsequent costs such as solvent recovery and wastewater treatment, which is in line with the national green chemical industry and sustainable development industrial policy.

[0017] (4) The product performance is stable and controllable, expanding the application scenarios. Hummingbird resonance technology can not only accelerate the reaction process by precisely controlling the mechanical force and acoustic energy input, but also optimize the crystal structure of the product in a targeted manner. This solves the problem of "low mass transfer efficiency and poor crystallinity" in the traditional mechanical ball milling method, ensuring the consistency of product structure in mass production. The crystalline COFs obtained can have a specific surface area of ​​100~2730 m² / g and a uniform pore size distribution (0.3~5 nm). They have stable application performance in industrial scenarios such as catalytic reactions (such as organic synthesis catalysis), separation and purification (such as gas adsorption), and energy storage devices (such as battery electrode carriers), laying the core preparation foundation for the industrialization of COFs. Attached Figure Description

[0018] The present invention will be further described below with reference to the accompanying drawings: Figure 1 X-ray powder diffraction characterization pattern of TPB-DMTP-COF prepared in Example 1; Figure 2 (a) is the nitrogen isothermal adsorption-desorption curve of TPB-DMTP-COF prepared in Example 1 at 77 K, with a BET surface area of ​​2730 m². 2 / g; Figure 2 (b) is the nitrogen isothermal adsorption-desorption curve of TPB-DMTP-COF prepared in Example 1 at 77K, with a pore size distribution of 3.2 nm; Figure 3 The solid-state carbon NMR spectrum of TPB-DMTP-COF prepared in Example 1 is shown, and the peaks in the solid-state NMR spectrum are assigned. Figure 4 The image shows the X-ray powder diffraction characterization pattern of the TPB-DMTP-COF prepared in Example 2. Figure 5 (a) is the nitrogen isotherm adsorption-desorption curve of TPB-DMTP-COF prepared in Example 2 at 77 K, with a BET surface area of ​​1592 m². 2 / g, Figure 5 (b) is a nitrogen isothermal adsorption-desorption curve of TPB-DMTP-COF prepared in Example 2 at 77 K, with a pore size distribution of 2.2 nm; Figure 6 The solid-state carbon NMR spectrum of the TPB-DMTP-COF prepared in Example 2 is shown. Figure 7 , Figure 8 The present invention describes the reaction process by which amine and aldehyde compounds are polymerized in the presence of an acid catalyst to obtain crystalline covalent organic framework materials. Detailed Implementation

[0019] This invention proposes an imine-bonded covalent organic framework material based on hummingbird acoustic resonance technology and its preparation method. To make the advantages and technical solutions of this invention clearer and more explicit, the invention will be further described below with reference to specific embodiments.

[0020] The technical concept of this invention lies in the efficient catalysis of Schiff base reactions between amine and aldehyde monomers using mechanical ball milling (hummingbird resonance technology) and a conventional acid catalyst (acetic acid) to obtain crystalline framework materials. Due to the convenience of ball milling, this method can be used to prepare gram-scale crystallinity COFs with high specific surface area. Furthermore, this method can be extended to the synthesis of COFs with different molecular structures.

[0021] The mechanical ball milling method (hummingbird acoustic resonance technology) described in this invention employs the following main components and structures: a core integrated ball mill main unit (including a variable frequency speed control unit and a grinding chamber), a hummingbird acoustic resonance unit (resonance generation + signal acquisition and modulation module), grinding media, material feeding and discharging components, and a temperature-controlled vibration damping base. The hummingbird resonance unit is linked with the core integrated ball mill main unit, capable of emitting adaptive acoustic resonance waves into the grinding chamber and acquiring the resonance feedback signal of the grinding system inside the grinding chamber in real time. The specific usage method and parameter control conditions when applied to this invention are as follows: First, the material to be ground and the grinding media are mixed in a specific ratio, placed into the sealed grinding chamber, and fixed. The hummingbird resonance unit pre-acquires the inherent resonance frequency of the material and generates adaptive acoustic resonance wave parameters. Then, the ball mill main unit is started and adjusted to the set grinding speed, and the hummingbird resonance unit is simultaneously activated to emit acoustic resonance waves of the appropriate frequency and power, achieving coordinated grinding by mechanical ball milling and acoustic resonance. During the grinding process, the temperature of the grinding chamber is controlled at room temperature by the temperature-controlled base. The resonance feedback signal is monitored in real time, and the resonance parameters are fine-tuned to control the grinding time. After grinding is completed, the machine is stopped for cooling and unloading. The ball milling frequency is 15-60Hz, and the ball milling reaction time is 5s-20mins.

[0022] Combination Figure 7 and Figure 8 As shown, this invention utilizes an amine compound, an aldehyde compound, and an acid catalyst to fully mix and react the mixture in an air atmosphere at room temperature and atmospheric pressure using a mechanical ball milling method based on hummingbird resonance. After solvent washing and neutralization, an imine-bonded covalent organic framework material is prepared.

[0023] The aforementioned amine compounds include, but are not limited to, 1,3,5-tris(4-aminophenyl)benzene and 2,4,6-tris(4-aminophenyl)-1,3,5-triazine; the aforementioned aldehyde compounds include, but are not limited to, 2,5-dimethoxybenzene-1,4-dicarboxaldehyde and 2,4,6-tris(4-aldehydephenyl)-1,3,5-triazine; the aforementioned acid catalysts include, but are not limited to, trifluoromethanesulfonic acid, methanesulfonic acid, trifluoroacetic acid, benzoic acid, acetic acid, or polyphosphoric acid. The aforementioned solvents include, but are not limited to, ultrapure water, DMF, DMAc, dichloromethane, ethanol, methanol, tetrahydrofuran, and toluene.

[0024] This invention discloses a method for preparing an imine-bonded covalent organic framework material based on hummingbird acoustic resonance technology, comprising the following steps: Step 1: Place the amine compound, aldehyde compound, and acid catalyst into a ball mill jar. The molar ratio of the amine compound to the aldehyde compound is 1:0.8-1.2. The mass-to-volume ratio of the amine compound to the acid catalyst is 15 mg-1 g: 20-1500 μL. The second step involves ball milling at a specific frequency for a period of time to allow the reaction to proceed. The preferred material for the ball mill jar is one or more of stainless steel, zirconium oxide, tungsten oxide, plastic, and glass. The volume of the ball mill jar is 1.5-50 mL, and the diameter of the grinding balls is 0.1-1 cm. The reacted product is then washed with a solvent to neutralize residual catalyst, unreacted monomers, and some small molecule products, yielding an imine-bonded covalent organic framework material.

[0025] The imine-bonded covalent organic framework material prepared by the method of this invention has a specific surface area of ​​100~2000 m². 2 / g, with a pore size of 0.3~5nm.

[0026] More preferably, the specific surface area of ​​the imine-bonded covalent organic framework material prepared by the method of the present invention is 200~1300 m². 2 / g, with a pore size of 0.5~2nm.

[0027] The technical solution of the present invention will be further described in detail below with reference to several preferred embodiments and accompanying drawings. This embodiment is implemented on the premise of the technical solution of the invention, and provides detailed implementation methods and specific operation processes. However, the protection scope of the present invention is not limited to the following embodiments.

[0028] Unless otherwise specified, the experimental materials used in the examples below can be purchased from conventional biochemical reagent companies.

[0029] Example 1: A method for preparing an imine-bonded covalent organic framework material based on hummingbird acoustic resonance technology, specifically including the following steps: Step 1: Place 1.2 g of 1,3,5-tris(4-aminophenyl)benzene (TAPB), 1 g of 2,5-dimethoxyterephthalaldehyde (DMTA), and 1.5 mL of acetic acid into a 50 mL ball mill jar along with the ball milling balls.

[0030] Step 2: Ball milling was performed at room temperature and a ball milling frequency of 60 Hz for 20 mins. After the reaction was completed, the ball mill jar was cooled to room temperature, the jar was opened, the solid powder was taken out, and then refluxed in a solution of tetrahydrofuran and N,N-dimethylformamide for 24 hours to remove oligomers. Finally, the product was obtained by suction filtration, and a yellow product was obtained. The product was dried overnight in a vacuum oven at 120 ℃ to obtain 1.7 g of solid product, denoted as TPB-DMTP-COF.

[0031] Figure 1X-ray powder diffraction characterization was performed on the TPB-DMTP-COF obtained in this embodiment. The results showed that the COF prepared by ball milling had diffraction peaks at 2.76°, 4.82°, 5.60°, 7.42°, 9.70°, 14.08° and 25.2°, corresponding to the (100), (110), (200), (210), (220), (500) and (001) crystal planes, respectively.

[0032] Figure 2 (a) and (b) are the nitrogen isotherm adsorption-desorption curves of the material at 77 K, and its BET surface area is 2730 m². 2 / g, with a pore size distribution of 3.2 nm.

[0033] In addition, TPB-DMTP-COF was characterized by solid-state carbon NMR spectroscopy. Figure 3 The peaks in the solid-state NMR spectrum were assigned, confirming the presence of all carbon atoms in the COF framework. The 50 ppm NMR signal was assigned to methoxy carbon.

[0034] Example 2: A method for preparing an imine-bonded covalent organic framework material based on hummingbird acoustic resonance technology, specifically including the following steps: Step 1: Place 1.0 g of 2,4,6-tris(4-aminophenyl)-1,3,5-triazine (TAPT), 1.11 g of 2,5-dimethoxytetraphenyldialdehyde (DMTA), and 1.5 mL of acetic acid into a 50 mL ball mill jar along with the ball milling balls.

[0035] The second step involves ball milling at room temperature and a ball milling frequency of 60 Hz for 20 mins. After the reaction is complete, the ball mill jar is cooled to room temperature, the jar is opened, the solid powder is removed, and then refluxed in a solution of tetrahydrofuran and N,N-dimethylformamide for 24 hours to remove oligomers. Finally, the product is obtained by suction filtration, resulting in a yellow product. The product is then dried overnight in a vacuum oven at 120°C to obtain 1.85 g of solid product, which is the imine-bonded covalent organic framework material of this invention.

[0036] The X-ray powder diffraction characterization pattern of the TPB-DMTP-COF prepared in this embodiment is as follows: Figure 4 As shown.

[0037] Figure 5 (a) and (b) are the nitrogen isotherm adsorption-desorption curves of TPB-DMTP-COF prepared in this embodiment at 77 K, with a BET surface area of ​​1592 m². 2 / g, with a pore size distribution of 2.2 nm.

[0038] The TPB-DMTP-COF prepared in this embodiment was characterized by solid-state carbon NMR spectroscopy. Figure 6 The peaks in the solid-state NMR spectrum were assigned, confirming the presence of all carbon atoms in the COF framework.

[0039] Example 3: The difference from Example 1 is that: In the first step, the aldehyde compound selected is 2,4,6-tris(4-aldehydephenyl)-1,3,5-triazine.

[0040] Guided by the above-described Examples 1-3, those skilled in the art can also select and form multiple combinations of examples within the scope of the above-described raw materials.

[0041] In summary, the method of this invention has the following advantages over existing technologies: 1) It is simple to operate; the reaction raw materials are mixed with an acidic catalyst and then ball-milled at room temperature under air conditions to synthesize the material; 2) It greatly shortens the synthesis time, typically obtaining crystalline materials in just 2 minutes; 3) The synthesis process is more environmentally friendly, as the reaction does not require the participation of organic solvents; 4) It facilitates large-scale preparation, yielding gram-level materials in just 20 minutes. In conclusion, mechanochemical synthesis is a convenient, environmentally friendly, time-saving method for large-scale production of COFs, providing a powerful preparation strategy for the industrial production of COFs.

[0042] Any parts not mentioned in this invention can be achieved by referring to existing technologies.

[0043] Those skilled in the art should recognize that the above embodiments are only used to illustrate this application and are not intended to limit this application. Any appropriate changes and variations made to the above embodiments within the essential spirit and scope of this application fall within the scope of protection claimed in this application.

Claims

1. A method for preparing an imine-bonded covalent organic framework material based on hummingbird acoustic resonance technology, characterized in that, The steps are as follows: a. Add the amino compound, aldehyde compound and acid catalyst together into a ball mill jar, wherein the molar ratio of the amino compound to the aldehyde compound is 1:0.8 to 1.2; and the mass-volume ratio of the amino compound to the acid catalyst is 15 mg to 1 g: 20 to 1500 μL. b. In an air atmosphere, at room temperature and normal pressure, the mixture obtained in step a is thoroughly mixed by simultaneously performing hummingbird resonance and mechanical ball milling. The mixture is reacted at a frequency of 60 Hz for 45 seconds. After the reaction is completed, it is washed with an organic solvent to obtain the final product.

2. The method for preparing an imine-bonded covalent organic framework material based on hummingbird acoustic resonance technology according to claim 1, characterized in that: The amine compound is 1,3,5-tris(4-aminophenyl)benzene or 2,4,6-tris(4-aminophenyl)-1,3,5-triazine.

3. The method for preparing an imine-bonded covalent organic framework material based on hummingbird acoustic resonance technology according to claim 1, characterized in that: The aldehyde compound is 2,5-dimethoxybenzene-1,4-dicarboxaldehyde or 2,4,6-tris(4-aldehydephenyl)-1,3,5-triazine.

4. The method for preparing an imine-bonded covalent organic framework material based on hummingbird acoustic resonance technology according to claim 1, characterized in that: The acid catalyst is trifluoromethanesulfonic acid, methanesulfonic acid, trifluoroacetic acid, benzoic acid, acetic acid, or polyphosphoric acid.

5. The method for preparing an imine-bonded covalent organic framework material based on hummingbird acoustic resonance technology according to claim 1, characterized in that: The reaction product obtained in step b is washed or refluxed using a solvent, such as ultrapure water, DMF, DMAc, dichloromethane, ethanol, methanol, tetrahydrofuran, or toluene.

6. The method for preparing an imine-bonded covalent organic framework material based on hummingbird acoustic resonance technology according to claim 1, characterized in that: The mechanical ball milling method using hummingbird resonance employs grinding jars made of stainless steel, zirconium oxide, tungsten oxide, plastic, or glass, with a volume of 1.5-50 mL and grinding balls with a diameter of 0.1-1 cm.

7. An imine-bonded covalent organic framework material based on hummingbird acoustic resonance technology, characterized in that, It is prepared by the preparation method described in any one of claims 1 to 6.

8. The imine-bonded covalent organic framework material based on hummingbird acoustic resonance technology according to claim 7, characterized in that: Its specific surface area is 100-2730 m² / g, and its pore size is 0.3-5 nm.

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