CN114539498B - Water-phase-dispersible composite material based on covalent organic framework and application thereof - Google Patents
Water-phase-dispersible composite material based on covalent organic framework and application thereof Download PDFInfo
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Abstract
The invention provides a water-phase dispersible composite material based on a covalent organic framework and application of a controllable release preservative thereof, wherein the material consists of the covalent organic framework and a hydrophilic polymer; the aqueous dispersibility is provided by its surface graft polymer. The covalent organic framework-based material provided by the invention has a nano pore canal and a hollow spherical structure, can adsorb chemical substance molecules with molecules smaller than the pore diameter, and realizes the controllable release of substances through the stimulated response of the polymer grafted on the outer layer to the temperature; the dispersibility and the stimulus response condition can be flexibly adjusted by selecting the polymer type and the molecular weight, so that the controllable slow-release effect of the composite material is adjusted. The material can be applied to the fields of foods, medicines and the like, and can be used for preserving vegetables, delivering medicines and the like.
Description
Technical Field
The invention relates to the field of controllable release materials, in particular to a water-phase dispersible composite material based on a covalent organic framework and application of a controllable release preservative thereof.
Background
Covalent organic framework materials are porous materials with high crystallinity, nanochannel structure and excellent thermal/chemical stability. The periodic topological structure which can be regulated in advance enables the micro-nano device to have great potential as a micro-nano device in the fields of catalysis, slow release, energy storage and the like. Most covalent organic framework materials are limited by their synthetic methods, and the products are water-insoluble, non-processable, solid powders that present significant challenges for their unique performance and subsequent use. The covalent organic framework material can be endowed with more performance through a post-modification strategy for modifying the surface of the covalent organic framework material, so that the hydrophobicity of the covalent organic framework material is improved. The covalent organic framework which can be dispersed in the water phase can lead the material to have wider application prospect and application range, and can realize the functions of slow release, processing, sensing and the like in the solution.
Disclosure of Invention
In view of the above, the invention provides a water-phase dispersible composite material based on a covalent organic framework and application of the composite material in controllable release of a preservative, so as to solve the problems of poor water solubility and too fast release of the preservative of the covalent organic framework.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a first aspect of embodiments of the present invention provides an aqueous dispersible composite based on a covalent organic framework, consisting of the covalent organic framework and a hydrophilic polymer; the composite material is of a hollow spherical structure, and the hollow spherical structure is provided by an organic framework material.
Further, the specific surface area of the composite material is 100-2000m 2 And/g, the surface is provided with a lamellar layer with the length of about 5-50nm and the thickness of 1-20nm; the outer diameter of the hollow spherical structure is 10-5000nm, and the inner diameter is 5-4000nm.
Further, the loading rate of the composite material on chemical substances is 0.5-10g/g.
Further, the covalent organic framework is formed by polycondensing a first monomer and a second monomer, and a hydrophilic polymer is grafted on the surface.
Further, the first monomer is formed by mixing one or more of tri (4-aminophenyl) amine, 1,3, 5-tri (4-aminophenyl) benzene, 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, melamine, 1,3, 5-triaminobenzene, 1,3, 5-tri (4-amino-3, 5-diethylphenyl) benzene and p-phenylenediamine in any proportion; the second monomer is formed by mixing one or more of trimellitic aldehyde, 2,4, 6-trihydroxy trimellitic aldehyde, 1,3, 5-tri (4-aldehyde phenyl) benzene, 2,4, 6-tri (4-aldehyde phenyl) -1,3, 5-triazine, terephthalaldehyde and glyoxal according to any proportion; the polymer is a product with molecular weight of 500-1000000 prepared by mixing and reacting one or more of glycol, N-isopropyl acrylamide and aminoacetaldehyde dimethyl acetal according to any proportion.
Further, the composite material can be dispersed in pure water and keep the solution stable for 1 to 180 days.
Further, the composite surface graft polymer provides stimulus response properties to temperatures of 15-80 ℃.
In a second aspect, embodiments of the present invention provide the use of a water-dispersible composite based on a covalent organic framework for the preparation of controlled release nanomaterials. The composite material is used as a container loaded with chemical substances and is used for preparing the controllable release nano material. The composite material is used for loading chemical substance molecules with molecules smaller than the hollow pore diameter.
The third aspect of the embodiment of the invention provides an application of the water-phase dispersible composite material based on the covalent organic framework in fruit and vegetable fresh-keeping.
Compared with the prior art, the invention has the beneficial effects that: (1) The invention provides a water-phase dispersible composite material based on a covalent organic framework, which is provided with a nano pore canal and a spherical hollow structure, wherein the surface of the composite material is provided with a polymer grafting layer, compared with a common covalent organic framework, the composite material is better in hydrophilicity, the nano pore canal and the hollow structure can adsorb chemical substance molecules with molecules smaller than the pore diameter, and the controllable release of substances is realized through the stimulation response of an outer layer grafted polymer to temperature. (2) The composite material adopts covalent organic framework materials and hydrophilic polymers, the polycondensation synthesis process of the material is easy to control, and the dispersibility and the stimulus response conditions are flexibly adjusted by selecting the types and the molecular weights of the polymers, so that the controllable slow-release effect of the composite material is adjusted, and the composite material has controllable stable dispersion performance of water phase. (3) The composite material can be applied to the fields of foods, medicines and the like, and can be used for preserving vegetables, delivering medicines and the like.
Drawings
FIG. 1 is SEM and TEM images of h-COF-g-PNIPAM-1;
FIG. 2 is a graph showing the results of DLS in particle size change of h-COF-g-PNIPAM-1 stably dispersed in an aqueous phase for 15 weeks;
FIG. 3 is a graph of DLS results and temperature response intervals of particle size change over 15 temperature stimulus response cycles for h-COF-g-PNIPAM-1;
FIG. 4 is a photograph of n-hexanal-loaded h-COF-g-PNIPAM-1 for preserving cherry tomatoes;
FIG. 5 is a graph showing the results of slow-release GC-MS of n-hexanal-loaded h-COF-g-PNIPAM-1 for preserving cherry tomatoes;
FIG. 6 is a photograph of hexenal-loaded h-COF-g-PNIPAM-1 for preserving cherry tomatoes;
FIG. 7 is a graph showing the results of hexenal-loaded h-COF-g-PNIPAM-1 on slow-release GC-MS for cherry tomato preservation.
Detailed Description
Reference will now be made in detail to exemplary embodiments, examples of which are illustrated in the accompanying drawings. When the following description refers to the accompanying drawings, the same numbers in different drawings refer to the same or similar elements, unless otherwise indicated. The implementations described in the following exemplary examples do not represent all implementations consistent with the invention. Rather, they are merely examples of apparatus and methods consistent with aspects of the invention as detailed in the accompanying claims.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in this specification and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It should also be understood that the term "and/or" as used herein refers to and encompasses any or all possible combinations of one or more of the associated listed items.
The aqueous dispersible composites based on covalent organic frameworks and their use according to the invention are described in detail below with reference to the accompanying drawings. The features of the examples and embodiments described below may be combined with each other without conflict.
Example 1
The water-phase dispersible composite material h-COF-g-PNIPAM of a covalent organic framework is synthesized by taking 1,3, 5-tris (4-aminophenyl) benzene and trimesoyl trimethyl aldehyde as monomers and N-isopropyl acrylamide and aminoacetaldehyde dimethyl acetal polymer with a molecular weight of 3000, and the specific process is as follows: 350.0mg of 1,3, 5-tris (4-aminophenyl) benzene and 200.0mg of terephthalaldehyde were dissolved in 200mL of acetonitrile under magnetic stirring to obtain a precursor solution. 22mg scandium triflate was dissolved in 3mL of acetonitrile, and the mixture was added to the precursor solution to prepare a reaction solution, and the reaction was started at 25 ℃. After 1 day, the precipitate was collected by filtration and washed with acetonitrile. The product was dried overnight in a fume hood and dried in a vacuum oven at 40 ℃ for 1 day to afford intermediate AmoNS.
60.0mg of AmoNS, 9.75mg of trimellitic aldehyde, 182.1. Mu.L of benzaldehyde, 182.1. Mu.L of aniline and 200mg of a polymer (N-isopropylacrylamide and aminoacetaldehyde dimethanol copolymer, molecular weight 3000) were dissolved in 30.0mL of a mixed solution of dioxane and mesitylene (dioxane/mesitylene, 1/2, v/v) under magnetic stirring to prepare a solution. 1.5mg of scandium triflate was dissolved in 0.2mL of a mixed solution of dioxane and mesitylene (dioxane/mesitylene, 2/1, v/v), and the mixture was added to the solution to prepare a reaction solution, and polycondensation was started at 25 ℃. After 1 day, the precipitate was collected by filtration and washed with a mixed solution of dioxane and mesitylene (dioxane/mesitylene, 1/2, v/v). The product was dried overnight in a fume hood and dried in a vacuum oven at 40℃for 1 day to give the covalent organic framework material and the polymer composite h-COF-g-PNIPAM-1.
The composite material h-COF-g-PNIPAM-1 has a hollow structure shown in figure 1, and the surface of the composite material h-COF-g-PNIPAM-1 has a lamellar layer with the length of about 10nm and the thickness of 5nm; the outer diameter of the hollow spherical structure is 239nm, and the inner diameter is 150nm. BET specific surface area of the material is 483m 2 And/g. The h-COF-g-PNIPAM can be dispersed in water phase after ultrasonic treatment, the temperature response range is 30-35 ℃, as shown in figures 2 and 3, the DLS result shows that the particle size is single in distribution and remains stable for a long time after 150 days and 15 temperature stimulus response cycles.
Example 2
The water-phase dispersible composite material h-COF-g-PNIPAM of a covalent organic framework is synthesized by taking 1,3, 5-tris (4-aminophenyl) benzene and trimesoyl trimethyl aldehyde as monomers and N-isopropyl acrylamide and aminoacetaldehyde dimethyl acetal polymer with a molecular weight of 3000, and the specific process is as follows: 350.0mg of 1,3, 5-tris (4-aminophenyl) benzene and 200.0mg of terephthalaldehyde were dissolved in 200mL of acetonitrile under magnetic stirring to obtain a precursor solution. 22mg scandium triflate was dissolved in 3mL of acetonitrile, and the mixture was added to the precursor solution to prepare a reaction solution, and the reaction was started at 25 ℃. After 1 day, the precipitate was collected by filtration and washed with acetonitrile. The product was dried overnight in a fume hood and dried in a vacuum oven at 40 ℃ for 1 day to afford intermediate AmoNS.
60.0mg of AmoNS, 9.75mg of trimellitic aldehyde, 182.1. Mu.L of benzaldehyde, 182.1. Mu.L of aniline and 50mg of a polymer (N-isopropylacrylamide and aminoacetaldehyde dimethanol copolymer, molecular weight 3000) were dissolved in 30.0mL of a mixed solution of dioxane and mesitylene (dioxane/mesitylene, 1/2, v/v) under magnetic stirring to prepare a solution. 1.5mg of scandium triflate was dissolved in 0.2mL of a mixed solution of dioxane and mesitylene (dioxane/mesitylene, 2/1, v/v), and the mixture was added to the solution to prepare a reaction solution, and polycondensation was started at 25 ℃. After 1 day, the precipitate was collected by filtration and washed with a mixed solution of dioxane and mesitylene (dioxane/mesitylene, 1/2, v/v). The product was dried overnight in a fume hood and dried in a vacuum oven at 40℃for 1 day to give the covalent organic framework material and the polymer composite h-COF-g-PNIPAM-2.
The composite material h-COF-g-PNIPAM-2 has a hollow structure, and the surface of the composite material h-COF-g-PNIPAM-2 has a lamellar layer with the length of about 10nm and the thickness of 5nm; the outer diameter of the hollow spherical structure is 250nm, and the inner diameter is 100nm. BET specific surface area of 1127m 2 And/g. The H-COF-g-PNIPAM can be dispersed in water phase for 1-90 days after ultrasonic treatment, and the temperature response range is 30-40 ℃.
Example 3
The water-phase dispersible composite material h-COF-g-PNIPAM of a covalent organic framework is synthesized by taking 1,3, 5-tris (4-aminophenyl) benzene and trimesoyl trimethyl aldehyde as monomers and N-isopropyl acrylamide and aminoacetaldehyde dimethyl acetal polymer with a molecular weight of 6000, and the specific process is as follows: 350.0mg of 1,3, 5-tris (4-aminophenyl) benzene and 200.0mg of terephthalaldehyde were dissolved in 200mL of acetonitrile under magnetic stirring to obtain a precursor solution. 22mg scandium triflate was dissolved in 3mL of acetonitrile, and the mixture was added to the precursor solution to prepare a reaction solution, and the reaction was started at 25 ℃. After 1 day, the precipitate was collected by filtration and washed with acetonitrile. The product was dried overnight in a fume hood and dried in a vacuum oven at 40 ℃ for 1 day to afford intermediate AmoNS.
60.0mg of AmoNS, 9.75mg of trimellitic aldehyde, 182.1. Mu.L of benzaldehyde, 182.1. Mu.L of aniline and 50mg of a polymer (N-isopropylacrylamide and aminoacetaldehyde dimethanol copolymer, molecular weight 6000) were dissolved in 30.0mL of a mixed solution of dioxane and mesitylene (dioxane/mesitylene, 1/2, v/v) under magnetic stirring to prepare a solution. After 0.5mg scandium triflate was dissolved in 0.2mL of a mixed solution of dioxane and mesitylene (dioxane/mesitylene, 2/1, v/v), the mixture was added to prepare a reaction solution, and polycondensation reaction was started at 25 ℃. After 1 day, the precipitate was collected by filtration and washed with a mixed solution of dioxane and mesitylene (dioxane/mesitylene, 1/2, v/v). The product was dried overnight in a fume hood and dried in a vacuum oven at 40℃for 1 day to give the covalent organic framework material and the polymer composite h-COF-g-PNIPAM-3.
The composite material h-COF-g-PNIPAM-3 has a hollow structure, and the surface of the composite material h-COF-g-PNIPAM-3 has a lamellar layer with the length of about 25nm and the thickness of 10nm; the outer diameter of the hollow spherical structure is 2000nm, and the inner diameter is 1500nm. BET specific surface area of the material is 892m 2 And/g. The h-COF-g-PNIPAM can be dispersed in the water phase for 1-15 days after ultrasonic treatment, and the temperature response range is 60-70 ℃.
Example 4
The aqueous-phase-dispersible composite material h-COF-g-PNIPAM-1 of a covalent organic framework is synthesized by adopting the method of the example 1 and taking 1,3, 5-tri (4-aminophenyl) benzene and trimesoyl aldehyde as monomers and N-isopropyl acrylamide and aminoacetaldehyde dimethyl acetal as polymers with the molecular weight of 3000, and the metamaterial has a nano pore canal and a hollow structure, and the outer diameter of a sphere is 239nm and the inner diameter of the sphere is 150nm after statistics. The loading rate of the composite material h-COF-g-PNIPAM-1 loaded preservative hexanal is 1.1g/g. The n-hexanal-loaded composite h-COF-g-PNIPAM-1 can be used for preserving cherry tomatoes, the preserving time is prolonged for 4 days at room temperature, and the temperature rising recovery material is realized through temperature stimulation response and can be reused at least 3 times. As shown in fig. 4-5, the Control group is the growth process of the tomatoes after the fresh-keeping agent hexanal is directly released and picked, and the beginning part of the tomato is yellow to the full ripeness of 9 days; cycle1-3 is the growth process of tomato after picking under the slow release condition of the preservative n-hexanal, and the beginning part of 9 th day is yellow. The GC-MS analysis results on the gas phase components show that the non-supported n-hexanal is completely released at the 2 nd day, the n-hexanal supported in the composite h-COF-g-PNIPAM-1 still maintains the content of about 50% at the 2 nd day, and can be continuously and slowly released to the 9 th day.
Example 5
The aqueous-phase-dispersible composite material h-COF-g-PNIPAM-1 of a covalent organic framework is synthesized by adopting the method of the example 1 and taking 1,3, 5-tri (4-aminophenyl) benzene and trimesoyl aldehyde as monomers and N-isopropyl acrylamide and aminoacetaldehyde dimethyl acetal as polymers with the molecular weight of 3000, and the metamaterial has a nano pore canal and a hollow structure, and the outer diameter of a sphere is 239nm and the inner diameter of the sphere is 150nm after statistics. The loading rate of the composite material h-COF-g-PNIPAM-1 loaded with the preservative hexenal is 0.9g/g. The hexenal-loaded composite h-COF-g-PNIPAM-1 can be used for preserving cherry tomatoes, the preserving time is prolonged for 4 days at room temperature, and the temperature rising recovery material is realized through temperature stimulation response and can be reused at least 3 times. As shown in fig. 6-7, the Control group is the growth process of tomatoes after the antistaling agent hexenal is directly released and picked, and the beginning part of the 5 th day is yellow to the 9 th day is fully cooked and red; cycle1-3 is the growth process of tomato after picking under the slow release condition of hexenal as a preservative, and the beginning part of 9 th day is yellow. The GC-MS analysis results of the gas phase components show that the unsupported hexenal is completely released at the 2 nd day, the hexenal loaded in the composite h-COF-g-PNIPAM-1 still maintains about 50% content at the 2 nd day, and can be continuously and slowly released until the 9 th day.
Example 6
The aqueous-phase-dispersible composite material h-COF-g-PNIPAM-1 of a covalent organic framework is synthesized by adopting the method of the example 1 and taking 1,3, 5-tri (4-aminophenyl) benzene and trimesoyl aldehyde as monomers and N-isopropyl acrylamide and aminoacetaldehyde dimethyl acetal as polymers with the molecular weight of 3000, and the metamaterial has a nano pore canal and a hollow structure, and the outer diameter of a sphere is 239nm and the inner diameter of the sphere is 150nm after statistics. The loading rate of the composite material h-COF-g-PNIPAM-1 loaded with the ripening agent 1-MCP is 6.9g/g. The composite material h-COF-g-PNIPAM-1 loaded with 1-MCP can be used for ripening of green tomatoes.
Example 7
The aqueous-phase-dispersible composite material h-COF-g-PNIPAM-1 of a covalent organic framework is synthesized by adopting the method of the example 1 and taking 1,3, 5-tri (4-aminophenyl) benzene and trimesoyl aldehyde as monomers and N-isopropyl acrylamide and aminoacetaldehyde dimethyl acetal as polymers with the molecular weight of 3000, and the metamaterial has a nano pore canal and a hollow structure, and the outer diameter of a sphere is 239nm and the inner diameter of the sphere is 150nm after statistics. The composite material h-COF-g-PNIPAM-1 carries catalytic metal Pt, and the loading rate is 9.8g/g. The Pt-loaded composite h-COF-g-PNIPAM-1 can be used for aqueous phase catalytic reaction.
Although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (8)
1. An aqueous dispersible composite based on a covalent organic framework, characterized in that the composite is composed of a covalent organic framework and a hydrophilic polymer; the composite material is of a hollow spherical structure, and the hollow spherical structure is provided by an organic framework material;
the covalent organic framework is formed by polycondensing a first monomer and a second monomer, and hydrophilic polymer is grafted on the surface of the covalent organic framework;
the first monomer is formed by mixing one or more of tri (4-aminophenyl) amine, 1,3, 5-tri (4-aminophenyl) benzene, 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, melamine, 1,3, 5-triaminobenzene, 1,3, 5-tri (4-amino-3, 5-diethylphenyl) benzene and p-phenylenediamine according to any proportion; the second monomer is formed by mixing one or more of trimellitic aldehyde, 2,4, 6-trihydroxy trimellitic aldehyde, 1,3, 5-tri (4-aldehyde phenyl) benzene, 2,4, 6-tri (4-aldehyde phenyl) -1,3, 5-triazine, terephthalaldehyde and glyoxal according to any proportion; the hydrophilic polymer is a product with molecular weight of 500-1000000 prepared by mixing and reacting one or more of glycol, N-isopropyl acrylamide and aminoacetaldehyde dimethyl acetal according to any proportion.
2. The aqueous dispersible composite based on covalent organic frameworks according to claim 1, characterized in that the specific surface area of the composite is 100-2000m 2 And/g, the surface is provided with a lamellar layer with the length of about 5-50nm and the thickness of 1-20nm; the outer diameter of the hollow spherical structure is 10-5000nm, and the inner diameter is 5-4000nm.
3. The aqueous dispersible composite based on a covalent organic framework according to claim 1, characterized in that the composite has a chemical loading rate of 0.5-10g/g.
4. The aqueous dispersible composite based on a covalent organic framework according to claim 1, characterized in that it is capable of dispersing in pure water and keeping the solution stable for 1-180 days.
5. The aqueous dispersible composite based on a covalent organic framework according to claim 1, wherein the hydrophilic polymer grafted to the surface of the composite has stimulus response properties to temperatures ranging from 15 ℃ to 80 ℃.
6. Use of an aqueous dispersible composite based on a covalent organic framework according to any one of claims 1 to 5 for the preparation of controlled release nanomaterials.
7. The use according to claim 6, wherein the composite is for supporting chemical molecules having molecules smaller than the hollow pore size.
8. Use of the aqueous dispersible composite based on a covalent organic framework according to any one of claims 1 to 5 for preserving fruits and vegetables.
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CN111116906B (en) * | 2020-01-13 | 2022-03-29 | 曲阜师范大学 | Fluorescent covalent organic framework material and preparation method and application thereof |
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CN112521567B (en) * | 2020-12-02 | 2022-05-27 | 新乡学院 | Temperature-controlled ionic liquid functionalized temperature response covalent organic framework material and preparation method thereof |
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