Method for synthesizing COFs (covalent organic frameworks) through emulsion polymerization of composite surfactant and application of COFs loaded with medicine
COFs were synthesized in an aqueous system via emulsion polymerization of composite surfactants, solving the problems of high temperature, high pressure and difficulty in morphology control, and realizing the controllable synthesis and efficient application of COF materials.
Patent Information
- Application Number
- CN202511858199.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-10
- Publication Date
- 2026-03-03
AI Technical Summary
Existing methods for synthesizing COFs materials are limited by high temperature and high pressure conditions, difficulty in morphology control, and issues with catalysts and solvents, resulting in environmentally unfriendly synthesis processes and difficulty in obtaining COFs materials with specific morphologies.
COFs were synthesized in an aqueous system using a mixed micelle system composed of cationic and anionic surfactants via emulsion polymerization. The morphology of the COF materials was controlled by ultrasonic treatment and polymerization reaction.
COFs materials with controllable morphology and good dispersibility were successfully prepared under mild conditions. They have high specific surface area and good chemical stability, and are suitable for catalysis, drug delivery and molecular sieving.
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Figure CN121591978A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of polymer organic porous materials technology, specifically relating to a method for preparing COFs-loaded drugs by emulsion polymerization of composite surfactants. Background Technology
[0002] Covalent organic frameworks (COFs) are crystalline porous materials assembled from light elements (such as C, H, O, N, B, etc.) through covalent bonds. Due to their high specific surface area, tunable pore size, and good chemical and thermal stability, they show great application potential in gas storage and separation, catalysis, sensing, and drug delivery. However, the synthesis of current COF materials typically relies on traditional methods such as solvothermal methods, electrospinning, or solution methods. These methods often suffer from the following problems: 1. Limitations of High Temperature and Pressure: Traditional solvothermal methods typically require high temperatures (above 150°C) and high pressures, which not only increases energy consumption and operational difficulty in the synthesis process but also limits the application of certain heat-sensitive or heat-intolerant functional molecules. 2. Difficulty in Morphology Control: In existing COF synthesis methods, especially solvothermal methods, although COF materials with good crystallinity can be prepared, controlling their morphology and size remains difficult. Particularly when synthesizing COF materials with specific morphologies (such as rings, nanotubes, monodisperse particles, etc.), even small changes in reaction conditions can lead to morphological inhomogeneity, making it difficult to achieve highly reproducible and stable production. 3. Complex Catalyst and Surfactant Systems: Many COF synthesis methods rely on complex catalyst and surfactant systems, which not only increases cost and operational difficulty but also, as some catalysts and surfactants may pollute the environment, reducing the green and environmentally friendly nature of the process. 4. Solvent Usage Issues: Traditional COF synthesis methods often rely on organic solvents, which may not only have adverse effects on the environment and human health but also increase costs and processing burdens in large-scale production. Therefore, developing a green and environmentally friendly synthesis method that operates under mild conditions, can precisely control the morphology of COFs materials, and is environmentally friendly has become an important topic in COFs material research and industrial application.
[0003] With the increasing demand for COF materials, several new synthesis methods have been proposed to overcome the limitations of traditional methods. For example, some researchers have proposed a low-temperature solution method, which synthesizes COF materials using mild reaction conditions (such as room temperature and pressure), thereby reducing energy consumption and cost. Other studies utilize ultrasound-assisted synthesis, using ultrasonic waves to accelerate the reaction, improve yield, and enhance material uniformity. Furthermore, novel synthesis techniques such as solid-state reaction methods and vapor deposition have also made some progress, enabling the synthesis of COF materials under relatively mild conditions. However, most of these methods struggle to precisely control the morphology of the materials, and some still require complex equipment and conditions.
[0004] It is evident that these emerging synthetic methods still have some shortcomings, particularly in morphology control and environmental friendliness, which urgently require further improvement. Therefore, developing a milder, greener, more controllable, and more efficient method for the synthesis of COFs has become an important research direction in the field of COFs. Summary of the Invention
[0005] The technical problem to be solved by this invention is that single surfactant systems have limited ability to control morphology in emulsion polymerization, making it difficult to obtain complex or specific morphological COFs materials; the poor dispersibility and uniformity of materials during synthesis affect the functionality and practical application of COFs; and the lack of flexible design strategies to simultaneously satisfy structural tunability and precise morphology control. This invention provides a novel method for preparing covalent organic frameworks.
[0006] This invention presents the first method for synthesizing COF materials using emulsion polymerization with two surfactants. This innovative method employs a mixed micelle system composed of cationic and anionic surfactants, successfully achieving the controllable synthesis of cyclic COF materials and solving the problems of morphology control and dispersibility. This significantly improves the morphology controllability and dispersibility of COF materials. Cyclic COF materials possess high specific surface area, good chemical stability, and unique pore structure, and can be widely used in catalysis, drug delivery, molecular sieving, and other fields.
[0007] To achieve the above objectives, the present invention employs the following technical solution: This invention discloses a method for synthesizing COFs by emulsion polymerization of composite surfactants, comprising: adding a first covalently condensable organic compound to an aqueous system containing a composite surfactant, forming a stable emulsion by ultrasonic treatment, then adding a second covalently condensable organic compound, carrying out a polymerization reaction, and after the reaction is completed, performing post-treatment to obtain a COF precursor, and then obtaining COFs by crystallization treatment; The first covalently condensable organic compound and the second covalently condensable organic compound are a combination of monomers capable of undergoing a covalent condensation reaction, one of which is a monomer that provides an aldehyde group, and the other is a monomer that provides a polymerization reaction with the aldehyde group. Preferably, the composite surfactant is a type of surfactant including but not limited to those with a side chain alkyl chain length of twelve to sixteen, which can play a catalytic role or simultaneously play an emulsifying role. Preferably, the entire reaction system uses water as the main medium, and the surfactant micelles are dispersed in the water to form a continuous phase with an overall continuous distribution in the multiphase system.
[0008] Preferably, the compounds required for synthesizing the imine covalent organic framework are aldehydes and amines (or monomers capable of polymerizing with aldehydes). When the aldehyde is an organic compound containing at least two aldehyde groups, the amine is an organic compound containing at least three primary amine groups. When the aldehyde is an organic compound containing at least three aldehyde groups, the amine is an organic compound containing at least two primary amine groups. Preferably, the molar ratio of the amine compound (or other monomers capable of polymerizing with aldehydes) to the aldehyde compound is 1:1~2; Preferably, the reaction temperature is 18~60 ℃, the stirring speed is 300~800 rpm, and the polymerization reaction time is 1~24 h; Preferably, the reaction system is a pure aqueous phase system free of organic solvents; Preferably, the composite surfactant comprises a cationic surfactant and anionic surfactant in a volume ratio of 1:5~1; Preferably, the molar ratio of the organic compound containing a primary amine group to the organic compound containing an aldehyde group is 1:1~2, and the feed ratio of the organic compound containing an aldehyde group in the aqueous system is 0.01 mmol: (1~3.5) mL; Preferably, the second type of organic compound is a water-soluble component, which is directly added to the above emulsion system for reaction, and the reaction is carried out at room temperature for 4-24 hours; Preferably, the reaction system uses a micelle system formed by mixing composite surfactants, with a total concentration of 0.5-5 mg / mL; Preferably, the reacted material undergoes post-processing such as filtration, washing, and drying; Preferably, the washing method is as follows: first, washing with a good solvent of phase transfer catalyst (or surfactant) at least three times, and then washing with a good solvent of organic compound at least three times; Preferably, the drying conditions are: a temperature of 60~100 ℃ and a time of 12~24 h; Preferably, the crystallization conditions are: a temperature of 60~120 ℃ and a time of 24~48 h; This invention also discloses the application of covalent organic framework materials (COFs) synthesized by the above method in loading drugs, wherein the drugs are antitumor drugs.
[0009] Preferably, the antitumor drug is paclitaxel.
[0010] Preferably, the application conditions of the covalent organic framework material are as follows: paclitaxel is dissolved in an organic solvent, and an equal mass of covalent organic framework material is added at a mass ratio of 1:1. The mixture is stirred at room temperature for 3 hours. The solid is collected by centrifugation, washed with an organic solvent, and dried to obtain the paclitaxel-loaded covalent organic framework material.
[0011] Compared with the prior art, the present invention has the following beneficial effects: This invention provides a green synthesis method for covalent organic framework materials (COFs) based on a pure water system. Using composite surfactants (including cationic and anionic surfactants) with both emulsifying and catalytic functions as functional components, this method successfully prepares COFs with high specific surface area, excellent crystallinity, and controllable morphology without the need for organic solvents or high temperatures. In this method, the composite surfactants not only effectively promote monomer interfacial transfer and condensation reactions but also achieve precise control over the product morphology through micellar template action, realizing the synergistic utilization of both catalytic and template functions. The reaction can be completed at room temperature, offering significant advantages such as ease of operation, mild conditions, and environmental friendliness. Compared with traditional solvothermal synthesis, microwave synthesis, and ionothermal synthesis methods, this invention has significant advantages in simplifying the process, reducing energy consumption, and increasing yield. Furthermore, compared with mechanical grinding synthesis, the COFs obtained by this method have higher specific surface area and structural integrity. This method is stable, reproducible, and possesses good scalability and industrial application prospects. Attached Figure Description
[0012] The accompanying drawings, which constitute a part of this invention, are used to provide a further understanding of the invention. The illustrative examples and descriptions of the invention are used to explain the invention and do not constitute an improper limitation of the invention.
[0013] Figure 1 SEM images of the covalent organic framework prepared in Example 1 of this invention; Figure 2 PXRD images of the covalent organic framework prepared in Example 1 of this invention; Figure 3 FT-IR image of the covalent organic framework prepared in Example 1 of this invention; Figure 4The nitrogen adsorption-desorption curve of the covalent organic framework prepared in Example 1 of this invention; Figure 5 SEM images of the covalent organic framework prepared in Example 2 of this invention; Figure 6 PXRD images of the covalent organic framework prepared in Example 2 of this invention; Figure 7 FT-IR image of the covalent organic framework prepared in Example 2 of this invention; Figure 8 The nitrogen adsorption-desorption curve of the covalent organic framework prepared in Example 2 of this invention; Figure 9 SEM images of the covalent organic framework prepared in Example 3 of this invention; Figure 10 PXRD images of the covalent organic framework prepared in Example 3 of this invention; Figure 11 FT-IR image of the covalent organic framework prepared in Example 3 of this invention; Figure 12 The nitrogen adsorption-desorption curve of the covalent organic framework prepared in Example 3 of this invention; Figure 13 SEM image of the covalent organic framework prepared in Example 4 of this invention; Figure 14 TEM image of the covalent organic framework prepared in Example 4 of this invention; Figure 15 PXRD images of the covalent organic framework prepared in Example 4 of this invention; Figure 16 FT-IR image of the covalent organic framework prepared in Example 4 of this invention; Figure 17 The nitrogen adsorption-desorption curve of the covalent organic framework prepared in Example 4 of this invention; Figure 18 The paclitaxel loading rates of different morphologies of covalent organic frameworks prepared in this invention; Figure 19 SEM image of the covalent organic framework prepared in Example 5 of this invention; Figure 20 PXRD image of the covalent organic framework prepared in Example 5 of this invention; Figure 21 SEM image of the covalent organic framework prepared in Example 6 of this invention; Figure 22 The image shows a PXRD pattern of the covalent organic framework prepared in Example 6 of this invention. Detailed Implementation
[0014] To enable those skilled in the art to better understand the present invention, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of the present invention.
[0015] It should be noted that the terms "first," "second," etc., in the specification, claims, and accompanying drawings of this invention are used to distinguish similar objects and are not necessarily used to describe a specific order or sequence. It should be understood that such data can be interchanged where appropriate so that the embodiments of the invention described herein can be implemented in orders other than those illustrated or described herein. Furthermore, the terms "comprising" and "having," and any variations thereof, are intended to cover a non-exclusive inclusion; for example, a process, method, system, product, or apparatus that comprises a series of steps or units is not necessarily limited to those steps or units explicitly listed, but may include other steps or units not explicitly listed or inherent to such processes, methods, products, or apparatus.
[0016] The present invention will now be described in further detail with reference to the accompanying drawings: Example 1 30 mL of an aqueous solution of a cationic surfactant was added to a 50 mL round-bottom flask. Then, trialdehyde phloroglucinol (Tp) (31.5 mg, 0.15 mmol) was added, and the mixture was sonicated for 10 min. Bacitracin dihydrazide (BAH) (32.85 mg, 0.225 mmol) was added to the aqueous mixture. The solution was stirred at room temperature for 30 min. After the reaction was complete, the solid was precipitated with 15 mL of ethanol, and filtered to obtain a yellow powder. The yellow powder (33.7 mg, yield 87.9%) was Soxhlet extracted with methanol and THF for 12 h, and dried under vacuum at 100 °C. The mixture was reacted in a reactor with 0.8 mL of 6 M acetic acid in a mixed organic solvent of 2 mL O-DCB and 2 mL DMAc for 24 h. The mixture was thoroughly washed with anhydrous methanol and tetrahydrofuran to remove residual reagents, and then dried at 100 °C to obtain the final BAH-COF. Paclitaxel was dissolved in isopropanol, and an equal mass of covalent organic framework material (BAH-COF) was added at a mass ratio of 1:1. The mixture was stirred at room temperature for 3 hours, and the solid was collected by centrifugation. After washing three times with anhydrous ethanol, the solid was dried under vacuum at 40°C to obtain paclitaxel-loaded covalent organic framework material. See results Figures 1-4 ,from Figure 1 It is evident that this method synthesizes BAH-COF with a spherical morphology. Figure 2 It can be seen that BAH forms a highly crystalline two-dimensional covalent organic framework, and the diffraction peaks of BAH-COF are located at 2θ values of 7.1, 12.1, and 27. Figure 3 Infrared characterization of BAH-COF clearly shows that the characteristic stretching peaks of the C=C and C=N bonds are located at 1636 and 1283 cm⁻¹, respectively. -1 Simultaneously, a Tp monomer carbonyl stretching peak (1640 cm⁻¹) was observed. -1 The disappearance of the COF framework further confirms its successful construction. Figure 4 The nitrogen adsorption-desorption curves for BAH-COF are shown. The calculated specific surface area is 385.8 m². 2 / g.
[0017] Example 2 30 mL of anionic surfactant aqueous solution was added to a 50 mL round-bottom flask. Then, trialdehyde phloroglucinol (Tp) (31.5 mg, 0.15 mmol) was added, and the mixture was sonicated for 10 min. Succinic dihydrazide (BAH) (32.85 mg, 0.225 mmol) was added to the aqueous mixture. The solution was stirred at room temperature for 30 min. After the reaction was complete, the solid was precipitated with 15 mL of ethanol, and filtered to obtain a yellow powder. The yellow powder (33.7 mg, yield 87.9%) was Soxhlet extracted with methanol and THF for 12 h, and dried under vacuum at 100 °C. The mixture was reacted in a reactor with 0.8 mL of 6M acetic acid solution in a mixed organic solvent of 2 mL O-DCB and 2 mL DMAc for 24 h. The mixture was thoroughly washed with anhydrous methanol and tetrahydrofuran to remove residual reagents, and then dried at 100 °C to obtain the final BAH-COF. Paclitaxel was dissolved in isopropanol, and an equal mass of covalent organic framework material (BAH-COF) was added at a mass ratio of 1:1. The mixture was stirred at room temperature for 3 hours, and the solid was collected by centrifugation. After washing three times with anhydrous ethanol, the solid was dried under vacuum at 40°C to obtain paclitaxel-loaded covalent organic framework material.
[0018] See results Figures 5-8 ,from Figure 5 It is evident that this method synthesizes BAH-COF with a blocky morphology. Figure 6 It can be seen that BAH forms a highly crystalline two-dimensional covalent organic framework, and the diffraction peaks of BAH-COF are located at 2θ values of 7.1, 12.1, and 27. Figure 7 Infrared characterization of BAH-COF clearly shows that the characteristic stretching peaks of the C=C and C=N bonds are located at 1636 and 1283 cm⁻¹, respectively. -1 Simultaneously, a carbonyl stretching peak (1640 cm⁻¹) of the Tp monomer was observed. -1The disappearance of the COFs further verifies the successful construction of the COFs framework. Figure 8 The nitrogen adsorption-desorption curves for BAH-COF are shown. The calculated specific surface area is 134.9 m². 2 / g.
[0019] Example 3 A mixture of 20 mL of cationic surfactant aqueous solution and 10 mL of anionic surfactant aqueous solution was added to a 50 mL round-bottom flask. Then, trialdehyde phloroglucinol (Tp) (31.5 mg, 0.15 mmol) was added, and the mixture was sonicated for 10 min. Finally, succinic dihydrazide (BAH) (32.85 mg, 0.225 mmol) was added to the aqueous mixture. The solution was stirred at room temperature for 30 min. After the reaction was complete, the solid was precipitated with 15 mL of ethanol, and filtered to obtain a yellow powder. The yellow powder (33.7 mg, yield 87.9%) was Soxhlet extracted with methanol and THF for 12 h, and dried under vacuum at 100 °C. The mixture was reacted in a reactor with 0.8 mL of 6M acetic acid solution in a mixed organic solvent of 2 mL O-DCB and 2 mL DMAc for 24 h. The mixture was thoroughly washed with anhydrous methanol and tetrahydrofuran to remove residual reagents, and then dried at 100 °C to obtain the final BAH-COF. Paclitaxel was dissolved in isopropanol, and an equal mass of covalent organic framework material (BAH-COF) was added at a mass ratio of 1:1. The mixture was stirred at room temperature for 3 hours, and the solid was collected by centrifugation. After washing three times with anhydrous ethanol, the solid was dried under vacuum at 40°C to obtain paclitaxel-loaded covalent organic framework material.
[0020] See results Figures 9-12 ,from Figure 9 It is evident that this method synthesizes BAH-COF with a bowl-shaped morphology. Figure 10 It can be seen that BAH forms a highly crystalline two-dimensional covalent organic framework, and the diffraction peaks of BAH-COF are located at 2θ values of 7.1, 12.1, and 27. Figure 11 Infrared characterization of BAH-COF clearly shows that the characteristic stretching peaks of the C=C and C=N bonds are located at 1636 and 1283 cm⁻¹, respectively. -1 Simultaneously, a carbonyl stretching peak (1640 cm⁻¹) of the Tp monomer was observed. -1 The disappearance of the COFs further verifies the successful construction of the COFs framework. Figure 12 The nitrogen adsorption-desorption curves for BAH-COF are shown. The calculated specific surface area is 172.3 m². 2 / g.
[0021] Example 4 A mixture of 10 mL of cationic surfactant aqueous solution and 20 mL of anionic surfactant aqueous solution was added to a 50 mL round-bottom flask. Then, trialdehyde phloroglucinol (Tp) (31.5 mg, 0.15 mmol) was added, and the mixture was sonicated for 10 min. Finally, succinic dihydrazide (BAH) (32.85 mg, 0.225 mmol) was added to the aqueous mixture. The solution was stirred at room temperature for 30 min. After the reaction was complete, the solid was precipitated with 15 mL of ethanol, and the precipitate was filtered to obtain a yellow powder. The yellow powder (28.8 mg, yield 75.0%) was Soxhlet extracted with methanol and THF for 12 h, and then dried under vacuum at 100 °C. The mixture was reacted in a reactor with 0.8 mL of 6 M acetic acid solution in a mixed organic solvent of 2 mL O-DCB and 2 mL DMAc for 24 h. The mixture was thoroughly washed with anhydrous methanol and tetrahydrofuran to remove residual reagents, and then dried at 100 °C to obtain the final BAH-COF. Paclitaxel was dissolved in isopropanol, and an equal mass of covalent organic framework material (BAH-COF) was added at a mass ratio of 1:1. The mixture was stirred at room temperature for 3 hours, and the solid was collected by centrifugation. After washing three times with anhydrous ethanol, the solid was dried under vacuum at 40°C to obtain paclitaxel-loaded covalent organic framework material.
[0022] See results Figures 13-17 ,from Figure 13 , Figure 14 It is evident that this method synthesizes BAH-COF with a bowl-shaped morphology. Figure 15 It can be seen that BAH forms a highly crystalline two-dimensional covalent organic framework, and the diffraction peaks of BAH-COF are located at 2θ values of 7.1, 12.1, and 27. Figure 16 Infrared characterization of BAH-COF clearly shows that the characteristic stretching peaks of the C=C and C=N bonds are located at 1636 and 1283 cm⁻¹, respectively. -1 Simultaneously, a carbonyl stretching peak (1640 cm⁻¹) of the Tp monomer was observed. -1 The disappearance of the COFs further verifies the successful construction of the COFs framework. Figure 17 The nitrogen adsorption-desorption curves for BAH-COF are shown. The calculated specific surface area is 577.2 m². 2 / g.
[0023] Example 5 A mixture of 15 mL of cationic surfactant aqueous solution and 15 mL of anionic surfactant aqueous solution was added to a 50 mL round-bottom flask. Then, trialdehyde phloroglucinol (Tp) (31.5 mg, 0.15 mmol) was added, and the mixture was sonicated for 10 min. Next, p-phenylenediamine (Pa) (31.4 mg, 0.225 mmol) was added to the aqueous mixture. The solution was stirred at room temperature for 30 min. After the reaction was complete, the solid was precipitated with 15 mL of ethanol, and filtered to obtain a yellow powder. The red powder (50 mg, yield 84.9%) was extracted with methanol and THF for 12 h each, and then dried under vacuum at 100 °C. The mixture was reacted in a reactor with 0.8 mL of 9 M acetic acid solution in a mixed organic solvent of 2 mL of 1,4-dioxane and 2 mL of mesitylene for 24 h. The mixture was thoroughly washed with anhydrous methanol and tetrahydrofuran to remove residual reagents, and then dried at 100 °C to obtain the final TpPa-COF. Paclitaxel was dissolved in isopropanol, and an equal mass of covalent organic framework material (TpPa-COF) was added at a mass ratio of 1:1. The mixture was stirred at room temperature for 3 hours, and the solid was collected by centrifugation. After washing three times with anhydrous ethanol, the solid was dried under vacuum at 40°C to obtain paclitaxel-loaded covalent organic framework material.
[0024] See results Figures 19-20 ,from Figure 19 It is evident that this method synthesizes TpPa-COF with a needle-like morphology. Figure 20 It can be seen that TpPa-COF forms a highly crystalline two-dimensional covalent organic framework.
[0025] Example 6 A mixture of 15 mL of cationic surfactant aqueous solution and 15 mL of anionic surfactant aqueous solution was added to a 50 mL round-bottom flask. Then, trialdehyde phloroglucinol (Tp) (31.5 mg, 0.15 mmol) was added, and the mixture was sonicated for 10 min. Dihydrazine terephthalate (TD) (43.7 mg, 0.225 mmol) was added to the aqueous mixture. The solution was stirred at room temperature for 30 min. After the reaction was complete, the solid was precipitated with 15 mL of ethanol, and the precipitate was filtered to obtain a yellow powder. The yellow powder (56.8 mg, yield 79.8%) was Soxhlet extracted with methanol and THF for 12 h, respectively, and dried under vacuum at 100 °C. The mixture was reacted in a reaction vessel with 4 mL of acetonitrile organic solvent and 0.8 mL of 6M acetic acid solution for 24 h. The mixture was thoroughly washed with anhydrous methanol and tetrahydrofuran to remove residual reagents, and then dried at 100 °C to obtain the final TD-COF. Paclitaxel was dissolved in isopropanol, and an equal mass of covalent organic framework material (TD-COF) was added at a mass ratio of 1:1. The mixture was stirred at room temperature for 3 hours, and the solid was collected by centrifugation. After washing three times with anhydrous ethanol, the solid was dried under vacuum at 40°C to obtain paclitaxel-loaded covalent organic framework material.
[0026] See results Figures 21-22 ,from Figure 21 It is evident that this method synthesizes TD-COF with a sheet-like block morphology. Figure 22 It can be seen that TD-COF forms a highly crystalline two-dimensional covalent organic framework.
[0027] also, Figure 18 The figures show the paclitaxel loading rates of different morphologies of covalent organic frameworks prepared in this invention. It can be seen that the cyclic covalent organic frameworks have the highest loading rates.
[0028] In summary, this invention presents the first method for synthesizing COF materials using emulsion polymerization with two surfactants. This innovative method employs a mixed micelle system composed of cationic and anionic surfactants, successfully achieving the controllable synthesis of cyclic COF materials and solving the problems of morphology control and dispersibility. This significantly improves the morphology controllability and dispersibility of COF materials. Cyclic COF materials possess high specific surface area, good chemical stability, and unique pore structure, and can be widely used in catalysis, drug delivery, molecular sieving, and other fields.
[0029] The above content is only for illustrating the technical concept of the present invention and should not be construed as limiting the scope of protection of the present invention. Any modifications made to the technical solution based on the technical concept proposed in this invention shall fall within the scope of protection of the claims of this invention.
Claims
1. A method for synthesizing COFs via emulsion polymerization of composite surfactants, characterized in that, include: A first covalently condensable organic compound is added to an aqueous system containing a composite surfactant, and a stable emulsion is formed by ultrasonic treatment. Then, a second covalently condensable organic compound is added to carry out a polymerization reaction. After the reaction is completed, a covalent organic framework material (COF) precursor is obtained through post-treatment, and then the COF is obtained through crystallization treatment. The first covalently condensable organic compound and the second covalently condensable organic compound are a combination of monomers capable of undergoing a covalent condensation reaction, one of which is a monomer that provides an aldehyde group, and the other is a monomer that provides a polymerization reaction with an aldehyde group. The composite surfactant includes cationic surfactants and anionic surfactants, which form a mixed micelle system in an aqueous phase.
2. The method for synthesizing COFs via emulsion polymerization of composite surfactants according to claim 1, characterized in that, The volume ratio of cationic surfactants to anionic surfactants is 1:5~1, and the total concentration of both in the aqueous system is 0.5-5 mg / mL.
3. The method for synthesizing COFs via emulsion polymerization of composite surfactants according to claim 1, characterized in that, When the monomer providing the aldehyde group is an organic compound containing at least two aldehyde groups, the other monomer capable of polymerizing with the aldehyde group is an organic compound containing at least three primary amine groups. Alternatively, when the monomer providing the aldehyde group is an organic compound containing at least three aldehyde groups, the other monomer capable of polymerizing with the aldehyde group is an organic compound containing at least two primary amine groups.
4. The method for synthesizing COFs via emulsion polymerization of composite surfactants according to claim 3, characterized in that, The molar ratio of organic compounds containing primary amine groups to organic compounds containing aldehyde groups is 1:1~2, and the feed ratio of organic compounds containing aldehyde groups in the aqueous system is 0.01 mmol: (1~3.5) mL.
5. The method for synthesizing COFs via emulsion polymerization of composite surfactants according to claim 1, characterized in that, The polymerization reaction is carried out at a temperature of 18~60℃, a stirring speed of 300~800 rpm, and a reaction time of 1~24 h.
6. The method for synthesizing COFs via emulsion polymerization of composite surfactants according to claim 1, characterized in that, The post-treatment includes filtration, washing, and drying; the washing is performed by first washing with a good solvent containing a surfactant at least three times, and then washing with a good solvent containing a first / second covalently condensable organic compound at least three times; the drying temperature is 60~100℃ and the time is 12~24 h.
7. The method for synthesizing COFs via emulsion polymerization of composite surfactants according to claim 1, characterized in that, The crystallization process uses a mixed solvent of hydrophilic and hydrophobic solvents, and an acidic component is added during the crystallization process. After crystallization, the material is naturally cooled to room temperature, filtered, washed with alcohol, and dried to obtain covalent organic framework materials (COFs).
8. Covalent organic framework materials (COFs) synthesized using the method described in any one of claims 1-7, characterized in that, Synthesized covalent organic framework (COF) materials include imines, enoneamines, hydrazones, azazines, olefins, or polyimides.
9. The application of the covalent organic framework (COF) materials according to claim 8 in drug loading, characterized in that, The drug in question is an anti-tumor drug.
10. The application as described in claim 9, characterized in that, After dissolving the drug to be loaded in an organic solvent, the covalent organic framework material (COFs) of claim 8 is added at a mass ratio of 1:
1. The mixture is stirred thoroughly at room temperature, the solid is collected by centrifugation, washed with an organic solvent, and dried to obtain the drug-loaded organic framework material (COFs).