CN114539498A - Water-phase dispersible composite material based on covalent organic framework and application thereof - Google Patents
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Abstract
The invention provides a covalent organic framework-based water-phase dispersible composite material and application of a controlled release preservative thereof, wherein the material is composed of a covalent organic framework and a hydrophilic polymer; the water phase dispersibility is provided by the surface graft polymer thereof. The material based on the covalent organic framework has a nanometer 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 stimulation response of the polymer grafted on the outer layer to the temperature; by selecting the polymer type and molecular weight, the dispersibility and the stimulus response condition can be flexibly adjusted, thereby adjusting the controllable slow-release effect of the composite material. The material can be applied to the fields of food, medicine 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 controlled release materials, in particular to a water-phase dispersible composite material based on a covalent organic framework and application of a controlled release preservative thereof.
Background
Covalent organic framework materials are porous materials with high crystallinity, nanoporous structures and excellent thermal/chemical stability. The periodic topological structure which can be regulated and controlled in advance has 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 the synthesis method, and the product is solid powder which is insoluble in water and can not be processed, so that great challenges are brought to the exertion of unique properties and subsequent application of the covalent organic framework materials. The post-modification strategy of modifying the surface of the covalent organic framework material can endow the covalent organic framework material with more performances and improve the hydrophobicity of the covalent organic framework material. The covalent organic framework capable of being dispersed in the water phase can enable the material to have a wider application prospect and application range, and can realize the functions of slow release, processing, sensing and the like in a 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 a controllable release preservative thereof, so as to solve the problems of poor water solubility of the covalent organic framework and too fast release of the preservative.
In order to achieve the 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 a covalent organic framework and a hydrophilic polymer; the composite material is a hollow spherical structure, wherein the hollow structure is provided by an organic framework material.
Further, the specific surface area of the composite material is 100-2000m2Per g, the length of the flaky layer on the surface is about 5-50nm, and the thickness is 1-20 nm; the hollow spherical structure has an outer diameter of 10-5000nm and an inner diameter of 5-4000 nm.
Furthermore, the loading rate of the composite material to chemical substances is 0.5-10 g/g.
Further, the covalent organic framework is formed by condensation polymerization of 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 tris (4-aminophenyl) amine, 1,3, 5-tris (4-aminophenyl) benzene, 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, melamine, 1,3, 5-triaminobenzene, 1,3, 5-tris (4-amino-3, 5-diethylphenyl) benzene and p-phenylenediamine in any proportion; the second monomer is formed by mixing one or more of trimesic aldehyde, 2,4, 6-trihydroxy trimesic aldehyde, 1,3, 5-tri (4-aldehyde phenyl) benzene, 2,4, 6-tri (4-aldehyde phenyl) -1,3, 5-triazine, terephthalaldehyde and glyoxal in any proportion; the polymer is a product prepared by mixing and reacting one or more of ethylene glycol, N-isopropylacrylamide and aminoacetaldehyde dimethyl acetal in any proportion, and the molecular weight of the product is 500-1000000.
Further, the composite material is capable of being dispersed in pure water and keeping the solution stable for 1 to 180 days.
Further, the composite material surface graft polymer provides stimulus response performance to the temperature of 15-80 ℃.
A second aspect of embodiments of the invention provides the use of an aqueous dispersible composite based on a covalent organic framework for the preparation of controlled release nanomaterials. The composite material is used as a container for loading chemical substances and is used for preparing controllable-release nano materials. The composite material is used for loading chemical substance molecules with the 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 has a nanometer pore canal and a spherical hollow structure, a polymer grafting layer is arranged on the surface, the composite material has better hydrophilicity compared with the common covalent organic framework, the nanometer pore canal and the hollow structure can adsorb chemical substance molecules with the molecules smaller than the pore diameter, and the controllable release of substances is realized through the stimulation response of an outer layer graft polymer to the temperature. (2) The composite material adopts covalent organic framework material and hydrophilic polymer, the polycondensation synthesis process of the material is easy to control, and the dispersibility and the stimulus response condition are flexibly adjusted through selecting the type and the molecular weight of the polymer, so that the controllable slow release effect of the composite material is adjusted, and the composite material has controllable stable water phase dispersibility. (3) The composite material can be applied to the fields of food, medicine and the like, and can be used for preserving vegetables, delivering medicines and the like.
Drawings
FIG. 1 is SEM and TEM pictures of h-COF-g-PNIPAM-1;
FIG. 2 is a DLS result graph showing the change of particle size of h-COF-g-PNIPAM-1 stably dispersed in an aqueous phase for 15 weeks;
FIG. 3 is a DLS result and a temperature response interval chart of the particle size change of h-COF-g-PNIPAM-1 after 15 temperature stimulus response cycles;
FIG. 4 is a picture of h-COF-g-PNIPAM-1 carrying hexanal for keeping cherry tomato fresh;
FIG. 5 is a result graph of slow release GC-MS of h-COF-g-PNIPAM-1 loaded with hexanal for keeping cherry tomatoes fresh;
FIG. 6 is a picture of h-COF-g-PNIPAM-1 loaded with hexenal on the preservation of cherry tomatoes;
FIG. 7 is a slow release GC-MS result chart of h-COF-g-PNIPAM-1 loaded with hexenal on the preservation of cherry tomatoes.
Detailed Description
Reference will now be made in detail to the exemplary embodiments, examples of which are illustrated in the accompanying drawings. When the following description refers to the accompanying drawings, like numbers in different drawings represent the same or similar elements unless otherwise indicated. The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present invention. Rather, they are merely examples of apparatus and methods consistent with certain aspects of the invention, as detailed in the appended 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 and all possible combinations of one or more of the associated listed items.
The water-dispersible composite material based on covalent organic frameworks and the application thereof are described in detail below with reference to the accompanying drawings. The features of the following examples and embodiments may be combined with each other without conflict.
Example 1
1,3, 5-tri (4-aminophenyl) benzene and mesitylene trimethyl aldehyde are taken as monomers, and a polymer with a copolymerization molecular weight of N-isopropylacrylamide and aminoacetaldehyde dimethyl acetal of 3000 is synthesized into the covalent organic framework water-phase dispersible composite material h-COF-g-PNIPAM, 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. After 22mg of scandium trifluoromethanesulfonate was dissolved in 3mL of acetonitrile, the solution 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 give intermediate AmoNS.
A solution was prepared by dissolving 60.0mg of AmoNS, 9.75mg of trimesic aldehyde, 182.1. mu.L of benzaldehyde, 182.1. mu.L of aniline, and 200mg of a polymer (N-isopropylacrylamide and aminoacetaldehyde dimethyl acetal copolymer, molecular weight 3000) in 30.0mL of a mixed solution of dioxane and mesitylene (dioxane/mesitylene, 1/2, v/v) under magnetic stirring. 1.5mg of scandium trifluoromethanesulfonate was dissolved in 0.2mL of a mixed solution of dioxane and mesitylene (dioxane/mesitylene, 2/1, v/v), and then added to the solution to prepare a reaction solution, followed by initiation of polycondensation reaction 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 yield 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 as shown in figure 1, the length of a flaky layer on the surface is about 10nm, and the thickness is 5 nm; the hollow spherical structure has an outer diameter of 239nm and an inner diameter of 150 nm. Of materialsBET specific surface area of 483m2(ii) in terms of/g. The h-COF-g-PNIPAM can be dispersed in an aqueous phase after being subjected to 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 is kept stable for a long time after 150 days and 15 temperature stimulation response cycles.
Example 2
1,3, 5-tri (4-aminophenyl) benzene and mesitylene triformol are taken as monomers, N-isopropyl acrylamide and polymer with aminoacetaldehyde dimethyl acetal copolymerization molecular weight of 3000 are synthesized into the water phase dispersible composite material h-COF-g-PNIPAM with the covalent organic framework, 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 of scandium trifluoromethanesulfonate was dissolved in 3mL of acetonitrile, and the solution 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 give intermediate AmoNS.
A solution was prepared by dissolving 60.0mg of AmoNS, 9.75mg of trimesic aldehyde, 182.1. mu.L of benzaldehyde, 182.1. mu.L of aniline, and 50mg of a polymer (N-isopropylacrylamide and aminoacetaldehyde dimethyl acetal copolymer, molecular weight 3000) in 30.0mL of a mixed solution of dioxane and mesitylene (dioxane/mesitylene, 1/2, v/v) under magnetic stirring. 1.5mg of scandium trifluoromethanesulfonate was dissolved in 0.2mL of a mixed solution of dioxane and mesitylene (dioxane/mesitylene, 2/1, v/v), and then added to the solution to prepare a reaction solution, followed by initiation of polycondensation reaction 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 yield 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, the length of a flaky layer on the surface of the composite material is about 10nm, and the thickness of the flaky layer is 5 nm; the hollow spherical structure has an outer diameter of 250nm and an inner diameter of 100 nm. The BET specific surface area of the material was 1127m2(iv) g. h-COF-g-PNIPAM superamAfter being sounded, the material can be dispersed in water phase for 1-90 days, and the temperature response range is 30-40 ℃.
Example 3
1,3, 5-tri (4-aminophenyl) benzene and mesitylene trimethyl aldehyde are taken as monomers, and a polymer with the copolymerization molecular weight of N-isopropyl acrylamide and aminoacetaldehyde dimethyl acetal of 6000 is synthesized into the covalent organic framework water phase dispersible composite material h-COF-g-PNIPAM, 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. After 22mg of scandium trifluoromethanesulfonate was dissolved in 3mL of acetonitrile, the solution 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 give intermediate AmoNS.
A solution was prepared by dissolving 60.0mg of AmoNS, 9.75mg of trimesic aldehyde, 182.1. mu.L of benzaldehyde, 182.1. mu.L of aniline, and 50mg of a polymer (N-isopropylacrylamide and aminoacetaldehyde dimethyl acetal copolymer, molecular weight 6000) in 30.0mL of a mixed solution of dioxane and mesitylene (dioxane/mesitylene, 1/2, v/v) under magnetic stirring. 0.5mg of scandium trifluoromethanesulfonate was dissolved in 0.2mL of a mixed solution of dioxane and mesitylene (dioxane/mesitylene, 2/1, v/v), and then added to the solution to prepare a reaction solution, followed by initiation of polycondensation reaction 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 polymer composite h-COF-g-PNIPAM-3.
The composite material h-COF-g-PNIPAM-3 has a hollow structure, the length of a flaky layer on the surface is about 25nm, and the thickness is 10 nm; the hollow spherical structure has an outer diameter of 2000nm and an inner diameter of 1500 nm. BET specific surface area of the material is 892m2(ii) in terms of/g. The h-COF-g-PNIPAM can be dispersed in the water phase for 1 to 15 days after being subjected to ultrasonic treatment, and the temperature response range is 60 to 70 ℃.
Example 4
1,3, 5-tri (4-aminophenyl) benzene and trimesic aldehyde are taken as monomers, and a polymer with a copolymerization molecular weight of 3000 of N-isopropylacrylamide and aminoacetaldehyde dimethyl acetal is synthesized into a covalent organic framework water-phase dispersible composite material h-COF-g-PNIPAM-1 by adopting the method of example 1, wherein the metamaterial has a nanopore and a hollow structure, and the outer diameter of a sphere is 239nm and the inner diameter of the sphere is 150nm through statistics. The composite material h-COF-g-PNIPAM-1 is loaded with the preservative n-hexanal, and the loading rate is 1.1 g/g. The n-hexanal-loaded composite material h-COF-g-PNIPAM-1 can be used for fresh keeping of cherry tomatoes, the fresh keeping time is prolonged for 4 days at room temperature, the temperature rise recovery material is realized through temperature stimulation response, and the material can be repeatedly used for at least 3 times. As shown in fig. 4-5, the Control group is the growth process of the tomatoes after the preservative n-hexanal is directly released and picked, and the part of the tomatoes is yellow at the beginning of day 5 and fully ripe and red at day 9; cycle1-3 is the growth process of the picked tomato under the condition of the slow release of preservative n-hexanal, and the part of the tomato is yellow on the 9 th day. GC-MS analysis results of gas phase components show that the non-loaded hexanal is completely released on the 2 nd day, and the hexanal loaded in the composite material h-COF-g-PNIPAM-1 still maintains the content of about 50 percent on the 2 nd day and can be continuously and slowly released to the 9 th day.
Example 5
1,3, 5-tri (4-aminophenyl) benzene and trimesic aldehyde are taken as monomers, and a polymer with a copolymerization molecular weight of 3000 of N-isopropylacrylamide and aminoacetaldehyde dimethyl acetal is synthesized into a covalent organic framework water-phase dispersible composite material h-COF-g-PNIPAM-1 by adopting the method of example 1, wherein the metamaterial has a nanopore and a hollow structure, and the outer diameter of a sphere is 239nm and the inner diameter of the sphere is 150nm through statistics. The composite material h-COF-g-PNIPAM-1 is loaded with the preservative hexenal, and the loading rate is 0.9 g/g. The hexenal-loaded composite material h-COF-g-PNIPAM-1 can be used for keeping cherry tomatoes fresh, the preservation time is prolonged for 4 days at room temperature, the temperature rise recovery material is realized through temperature stimulation response, and the material can be repeatedly used for at least 3 times. As shown in fig. 6-7, the Control group is the growth process of the tomatoes after the preservative hexenal is directly released and picked, and the part of the tomatoes is yellow from the beginning of day 5 to fully ripe and red from day 9; cycle1-3 is the growth process of the post-harvest tomatoes under the condition of slow release of the preservative hexenal, and the part of the tomato grows yellow on the 9 th day. GC-MS analysis results of gas phase components show that the non-loaded hexenal is completely released at the 2 nd day, and the hexenal loaded in the composite material h-COF-g-PNIPAM-1 still keeps about 50 percent of the content at the 2 nd day and can be continuously and slowly released to the 9 th day.
Example 6
1,3, 5-tri (4-aminophenyl) benzene and trimesic aldehyde are taken as monomers, and a polymer with a copolymerization molecular weight of 3000 of N-isopropylacrylamide and aminoacetaldehyde dimethyl acetal is synthesized into a covalent organic framework water-phase dispersible composite material h-COF-g-PNIPAM-1 by adopting the method of example 1, wherein the metamaterial has a nanopore and a hollow structure, and the outer diameter of a sphere is 239nm and the inner diameter of the sphere is 150nm through statistics. The composite material h-COF-g-PNIPAM-1 is loaded with a ripener 1-MCP, and the loading rate is 6.9 g/g. The composite material h-COF-g-PNIPAM-1 loaded with the 1-MCP can be used for ripening of green tomatoes.
Example 7
1,3, 5-tri (4-aminophenyl) benzene and trimesic aldehyde are taken as monomers, and a polymer with a copolymerization molecular weight of 3000 of N-isopropylacrylamide and aminoacetaldehyde dimethyl acetal is synthesized into a covalent organic framework water-phase dispersible composite material h-COF-g-PNIPAM-1 by adopting the method of example 1, wherein the metamaterial has a nanopore and a hollow structure, and the outer diameter of a sphere is 239nm and the inner diameter of the sphere is 150nm through statistics. The composite material h-COF-g-PNIPAM-1 is loaded with catalytic metal Pt, and the loading rate is 9.8 g/g. The Pt-loaded composite material h-COF-g-PNIPAM-1 can be used for aqueous phase catalytic reaction.
The above embodiments are only intended to illustrate the technical solution of the present invention and not to limit, and although the present invention has been described in detail by the above embodiments, it will 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 defined by the claims.
Claims (10)
1. An aqueous phase 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 a hollow spherical structure, and the hollow structure is provided by an organic framework material.
2. The water-phase dispersible composite based on a covalent organic framework according to claim 1, characterized in that the specific surface area of the composite is 100-2000m2Per g, the length of the flaky layer on the surface is about 5-50nm, and the thickness is 1-20 nm; the hollow spherical structure has an outer diameter of 10-5000nm and an inner diameter of 5-4000 nm.
3. The aqueous dispersible composite according to claim 1, characterized in that the loading rate of the composite with respect to chemical substances is between 0.5 and 10 g/g.
4. The aqueous-dispersible composite material according to claim 1, characterized in that the covalent organic framework is formed by polycondensation of a first monomer and a second monomer, and a hydrophilic polymer is grafted on the surface.
5. The water-dispersible composite material based on a covalent organic framework according to claim 4, characterized in that the first monomer is composed of one or more of tris (4-aminophenyl) amine, 1,3, 5-tris (4-aminophenyl) benzene, 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, melamine, 1,3, 5-triaminobenzene, 1,3, 5-tris (4-amino-3, 5-diethylphenyl) benzene, p-phenylenediamine mixed in any proportion; the second monomer is formed by mixing one or more of trimesic aldehyde, 2,4, 6-trihydroxy trimesic aldehyde, 1,3, 5-tri (4-aldehyde phenyl) benzene, 2,4, 6-tri (4-aldehyde phenyl) -1,3, 5-triazine, terephthalaldehyde and glyoxal in any proportion; the hydrophilic polymer is prepared by mixing and reacting one or more of ethylene glycol, N-isopropyl acrylamide and aminoacetaldehyde dimethyl acetal in any proportion to prepare a product with the molecular weight of 500-1000000.
6. The aqueous dispersible composite based on a covalent organic framework according to claim 1 characterized in that the composite is capable of dispersing in pure water and keeping the solution stable for 1-180 days.
7. The aqueous dispersible composite material based on a covalent organic framework according to claim 1, characterized in that the hydrophilic polymer grafted on the surface of the composite material has stimuli-responsive properties to temperatures of 15-80 ℃.
8. Use of an aqueous dispersible composite based on a covalent organic framework according to claims 1 to 7 for the preparation of controlled release nanomaterials.
9. Use according to claim 1, wherein the composite material is used to support molecules of chemical substances having molecules smaller than the hollow pore size.
10. Use of the aqueous dispersible composite material based on a covalent organic framework according to claims 1 to 7 for the preservation of fruits and vegetables.
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