CN114634657A - Ag MOF composite chitosan-based film and preparation method and application thereof - Google Patents

Ag MOF composite chitosan-based film and preparation method and application thereof Download PDF

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CN114634657A
CN114634657A CN202210321143.7A CN202210321143A CN114634657A CN 114634657 A CN114634657 A CN 114634657A CN 202210321143 A CN202210321143 A CN 202210321143A CN 114634657 A CN114634657 A CN 114634657A
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mof
chitosan
film
solution
based film
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全鑫瑶
王毓宁
马佳佳
黄桂丽
孙灵湘
隋思瑶
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Suzhou Academy of Agricultural Sciences
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/02Wrappers or flexible covers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D81/00Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/24Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
    • B65D81/28Applications of food preservatives, fungicides, pesticides or animal repellants
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008Supramolecular polymers
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2305/00Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • C08J2305/08Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2429/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/02Homopolymers or copolymers of unsaturated alcohols
    • C08J2429/04Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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    • C08J2487/00Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/05Alcohols; Metal alcoholates
    • C08K5/053Polyhydroxylic alcohols
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K5/04Oxygen-containing compounds
    • C08K5/09Carboxylic acids; Metal salts thereof; Anhydrides thereof
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/13Phenols; Phenolates

Abstract

The invention provides an Ag MOF composite chitosan-based film and a preparation method and application thereof, wherein the preparation method comprises the following steps: 1) preparing a product Ag MOF by taking silver acetate and 2-amino terephthalic acid as raw materials through a solvothermal method; 2) different amounts of Ag MOF are added into the chitosan-based film forming solution for casting film. The Ag MOF composite chitosan-based film prepared by the method consists of Ag MOF nano particles and a film matrix, and the uniform Ag MOF particles are distributed on the surface of the film. The preparation method has the characteristics of simple preparation process, good air permeability and sterilization performance of the obtained film material, and the like, and can be used as a slow-release antibacterial food packaging material for prolonging the fresh-keeping period of food.

Description

Ag MOF composite chitosan-based film and preparation method and application thereof
Technical Field
The invention relates to the technical field of preparation of nano materials and high-molecular composite materials, in particular to an Ag MOF composite chitosan-based film and a preparation method and application thereof.
Background
Polymeric materials have good barrier properties to light, oxygen and water vapor, and play an important role in modern food packaging. Although polymer materials perform well, the non-degradability of their raw materials and the lack of functionality have hindered the widespread use of plastic films. The degradable nano composite material is prepared by adding the antibacterial agent and the deoxidant into the degradable film, so that the functional characteristics of the food packaging material can be enhanced, and the degradable nano composite material is expected to replace the non-degradable traditional plastic film and is more environment-friendly. The nano material composite high molecular material achieves remarkable results in the aspects of modified atmosphere preservation, material enhancement, steam sensing, antibacterial performance and the like.
Chitosan is also called chitosan and soluble chitin, is the only natural alkaline amino polysaccharide found in nature at present, and has the advantages of antibiosis, fresh keeping, easy film forming, biodegradability and the like. Compared with other degradable fruit and vegetable preservative films, the chitosan has the advantages that functional substances such as mineral substances or vitamins can be effectively doped, and the chitosan has antibacterial activity.
Metal Organic Frameworks (MOFs) are a class of porous nanomaterials, and are open crystal frameworks with stable porosity built by organic ligands and metal elements. Due to their flexibility in geometry, size and function, over 20000 different MOFs have been reported in the last decade, with more than 50% porosity in the crystal structure. MOFs have a larger porosity and are more versatile in porous materials and arrays than any other class of materials. These aspects allow MOFs to be ideal candidates for food packaging film materials through moisture capture and storage, gas and catalytic applications.
To date, MOFs have demonstrated their high efficiency and have become an indispensable active factor for food packaging due to their good biocompatibility and freshness-retaining activity during research. Zhao Jiayi et al added Fe-MOF as a nanocarrier to a gelatin/chitosan film matrix to make an antibacterial packaging film, greatly improved the water vapor permeability, uv blocking property and tensile strength of the film, and also showed good antibacterial activity against e.coli (Zhao, j., et al, Enhanced antibacterial performance of gelatin/chitosan film bonding loaded MOFs for food packaging, applied Surface Science, 2020.510: p.145418.). Chang et al synthesized a series of CS-PEO nanofibers with different ZIF-8 loadings by an electrospinning method. CS-PEO nanofibers have good hydrophobicity and suitable mechanical properties, have 100% antibacterial performance against Escherichia coli and Staphylococcus aureus, and are Potential food coatings and functional packaging Materials (Chang, Z., et al., Flexible Metal-Organic Frameworks: Recent Advances and Potential applications, advanced Materials, 2015.27 (36): p.5432-5441). The high-efficiency compounding of the MOFs and the high molecular materials aims to improve the quality safety of food in the storage and transportation processes.
Disclosure of Invention
The invention aims to provide a synthesis method for forming a porous antibacterial film by compounding Ag MOF and chitosan matrix added with different plasticizers.
The chemical general formula of the Ag MOF composite chitosan-based film is x% Ag MOF @ CS/M, wherein x is the percentage content of Ag MOF, CS is chitosan, and M is any one or a combination of polyvinyl alcohol, glycerol, palmitic acid and apple polyphenol.
The invention also provides a preparation method of the Ag MOF composite chitosan-based film, which comprises the following steps:
(1) preparing a silver acetate solution and a 2-amino terephthalic acid solution, mixing the two solutions, and standing;
(2) ultrasonically dispersing, centrifuging to obtain a product, washing, and drying in a vacuum drying oven to obtain Ag MOF;
(3) adding chitosan powder into an acetic acid solution, stirring to form a chitosan solution, adding a plasticizer, mixing to form a film-forming substrate liquid, adding Ag MOF into the film-forming substrate liquid, and continuously stirring to obtain a film-forming liquid;
(4) pouring the film forming solution into a grinding tool, and drying in an oven to strip the Ag MOF composite chitosan-based film.
Preferably, in the step (1), silver acetate is dissolved in deionized water and uniformly mixed to obtain a silver acetate solution, and 2-amino terephthalic acid is dissolved in absolute ethyl alcohol and uniformly stirred to obtain a 2-amino terephthalic acid solution.
In any of the above schemes, the mass ratio of the silver acetate solution and the 2-amino terephthalic acid solution in the step (1) is preferably 2-4: 1.
In any of the above schemes, the mass ratio of the silver acetate solution and the 2-amino terephthalic acid solution in the step (1) is preferably 2: 1.
In any of the above schemes, preferably, the mass ratio of the silver acetate solution and the 2-amino terephthalic acid solution mixed in the step (1) is 3: 1.
In any of the above schemes, preferably, the mass ratio of the silver acetate solution and the 2-amino terephthalic acid solution mixed in the step (1) is 4: 1.
In any of the above schemes, preferably, the time for mixing the silver acetate solution and the 2-amino terephthalic acid solution in the step (1) and then standing is 48h-72 h.
In any of the above schemes, preferably, the time for the silver acetate solution and the 2-amino terephthalic acid solution to stand after being mixed in the step (1) is 48 hours.
In any of the above schemes, preferably, the time for the silver acetate solution and the 2-amino terephthalic acid solution to stand after being mixed in the step (1) is 60 hours.
In any of the above schemes, the time for mixing the silver acetate solution and the 2-amino terephthalic acid solution in the step (1) and then standing is 72 hours.
In any of the above schemes, preferably, in the step (1), 60mg of silver acetate is dissolved in 20ml of deionized water and mixed uniformly to obtain a silver acetate solution, and 20mg of 2-amino terephthalic acid is dissolved in 20ml of anhydrous ethanol and stirred uniformly to obtain a 2-amino terephthalic acid solution.
In any of the above schemes, preferably, the mixed liquid after standing in the step (2) needs to be dispersed by ultrasonic for 4h to 6h, and the ultrasonic frequency is 25 kHz.
In any of the above schemes, preferably, the mixed liquid after standing in the step (2) needs to be dispersed by ultrasonic for 4 hours.
In any of the above schemes, preferably, the mixed liquid after standing in the step (2) needs to be dispersed by ultrasonic for 5 hours.
In any of the above schemes, it is preferable that the mixed liquid after standing in the step (2) needs to be dispersed by ultrasound for 6 hours.
In any of the above schemes, preferably, during the centrifugation operation in the step (2), the rotation speed is 8000r/min-10000r/min, the centrifugation time is 15min-20min, then the product in the centrifuge tube is washed by absolute ethyl alcohol, and the centrifugation washing operation is repeated for 3-5 times.
In any of the above schemes, preferably, the rotation speed is 8000r/min and the centrifugation time is 20min during the centrifugation operation in the step (2).
In any of the above embodiments, preferably, the rotation speed in the centrifugation in the step (2) is 9000r/min, and the centrifugation time is 18 min.
In any of the above schemes, preferably, the rotation speed is 10000r/min and the centrifugation time is 15min during the centrifugation operation in the step (2).
In any of the above schemes, it is preferable that the product in step (2) needs to be dried in a vacuum drying oven for 24h-48h after centrifugation, and the drying temperature is 50 ℃ -60 ℃.
In any of the above schemes, it is preferable that the product in step (2) needs to be dried in a vacuum drying oven for 24h after centrifugation, and the drying temperature is 60 ℃.
In any of the above schemes, it is preferable that the product in step (2) needs to be dried in a vacuum drying oven for 36h after centrifugation, and the drying temperature is 50 ℃.
In any of the above schemes, it is preferable that the product in step (2) needs to be dried in a vacuum drying oven for 48h after centrifugation, and the drying temperature is 50 ℃.
In any of the above schemes, it is preferable that the chitosan powder deacetylation degree in the step (3) is greater than or equal to 95%, and the viscosity is 100-200 mpa.
In any of the above schemes, preferably, the concentration of the chitosan solution in the step (3) is 2% -3%.
In any of the above embodiments, preferably, the concentration of the chitosan solution in the step (3) is 2%.
In any of the above embodiments, preferably, the concentration of the chitosan solution in the step (3) is 2.5%.
In any of the above embodiments, preferably, the concentration of the chitosan solution in the step (3) is 3%.
In any of the above schemes, preferably, the plasticizer in step (3) includes any one or more of polyvinyl alcohol (PVA), Glycerol (GL), palmitic acid (PMD), and Apple Polyphenol (AP).
In any of the above embodiments, it is preferable that the Ag MOF is added to the film-forming matrix liquid in the step (3) for at least 48 hours of continuous stirring.
In any of the above schemes, preferably, in the step (3), 2g of chitosan powder is added into 100ml of 2% acetic acid solution and stirred to form chitosan solution, and at the same time, 10-20ml of plasticizer is added and mixed to form film-forming matrix liquid, and then Ag MOF is added into the film-forming matrix liquid and continuously stirred to obtain the film-forming liquid.
In any of the above schemes, preferably, the oven drying time in the step (4) is 5-6 days, and the drying temperature is 50-60 ℃.
The invention also provides application of the Ag MOF composite chitosan-based film prepared by the preparation method in the technical field of food packaging.
Advantageous effects
The invention provides an Ag MOF composite chitosan-based film and a preparation method and application thereof, wherein the preparation method comprises the following steps: 1) preparing a product Ag MOF by taking silver acetate and 2-amino terephthalic acid as raw materials through a solvothermal method; 2) different amounts of Ag MOF are added into the chitosan-based film forming solution for casting film. The chemical general formula of the material prepared by the method is x% Ag MOF @ CS/M, wherein x is the percentage content of Ag MOF; CS is chitosan; m can be any one or combination of several of polyvinyl alcohol (PVA), Glycerol (GL), palmitic acid (PMD) and Apple Polyphenol (AP) in any proportion. The Ag MOF composite chitosan-based film prepared by the method consists of Ag MOF nano particles and a film matrix, and the uniform Ag MOF particles are distributed on the surface of the film.
The Ag MOF composite chitosan-based film prepared by the method has the micro morphology that Ag MOF particles are uniformly distributed on a chitosan-based film matrix, and the Ag MOF is nano particles with the size of about 10-30 nm.
The Ag MOF composite chitosan-based film prepared by the invention has good slow-release antibacterial property, good mechanical property, a multi-stage pore structure and other good characteristics, and can be used as a food fresh-keeping packaging material, a fruit and vegetable fresh-keeping coating and the like. The preparation method has the advantages that the preparation process is simple, the obtained Ag MOF composite chitosan-based film material has the characteristics of good air permeability, sterilization performance and the like, and the Ag MOF composite chitosan-based film material can be used as a slow-release antibacterial food packaging material and is used for prolonging the fresh-keeping period of food.
Drawings
FIG. 1 is an XRD ray diffraction pattern of the Ag MOF composite chitosan/polyvinyl alcohol film prepared in example 1;
FIG. 2 is a picture of a digital camera of the Ag MOF composite chitosan/polyvinyl alcohol film prepared in example 1;
FIG. 3 is a photograph of a digital camera with small tomatoes coated with Ag MOF composite chitosan/polyvinyl alcohol film prepared in example 1;
FIG. 4 is a scanning electron microscope photograph of the Ag MOF composite chitosan/polyvinyl alcohol film prepared in example 1;
FIG. 5 is a scanning electron microscope photograph of the Ag MOF composite chitosan/glycerol film prepared in example 2;
FIG. 6 is a graph of the sustained release profile of the Ag MOF composite chitosan/glycerol film prepared in example 2;
FIG. 7 is a comparison of the mechanical property curves of different films of Ag MOF composite chitosan base prepared in examples 1-4.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below. It should be understood, however, that the detailed description herein of specific embodiments is intended to illustrate the invention and not to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and the terms used herein in the specification of the present invention are for the purpose of describing particular embodiments only and are not intended to limit the present invention.
Example 1
A preparation method of an Ag MOF composite chitosan-based film specifically comprises the following steps:
(1) 60mg of silver acetate AgC2H3O2Dissolving in 20ml deionized water, mixing to obtain silver acetate solution, and mixing with 20mg of 2-amino terephthalic acid C8H7NO4Dissolving the two solutions in 20ml of absolute ethyl alcohol, uniformly mixing to form a 2-amino terephthalic acid solution, quickly mixing the two solutions, standing for 48 hours, performing ultrasonic dispersion for 4 hours at the ultrasonic frequency of 25kHz, then washing a product in a centrifugal tube by adopting the absolute ethyl alcohol after performing centrifugal operation for 15 minutes at the rotating speed of 10000r/min, and repeating the centrifugal washing operation for 3 times. Drying the mixture in a vacuum drying oven at a drying temperature of 60 ℃ for 24h, and taking out the product to obtain Ag MOF。
(2) 2g of chitosan powder is added into 100ml of 2% acetic acid solution, the mixture is stirred evenly to form chitosan solution, the stirring speed is 500rpm, the mixture is stirred for 12 hours, and then 20ml of polyvinyl alcohol (PVA) solution is added, and the membrane-forming matrix liquid is formed after even mixing. Adding 12mg of Ag MOF prepared in the step (1) into the film forming substrate liquid, and continuously stirring for 48h to ensure that the film forming liquid is uniformly mixed.
(3) And (3) pouring the film forming solution obtained in the step (2) into a grinding tool, and drying for 5 days at the temperature of 50 ℃ in an oven to obtain a 10% Ag MOF composite chitosan/polyvinyl alcohol film sample.
The phase of the 10% Ag MOF composite chitosan-based film prepared in this example is Ag MOF @ CS/PVA, and as shown in FIG. 1, the phase is an XRD picture of the composite film. Fig. 2 is a picture of a digital camera of the composite film, and it can be seen that the film prepared by the method has better film-forming property. Fig. 3 is a picture of a digital camera with a small tomato wrapped by the composite film, which illustrates that the composite film prepared by the method has certain applicability in fruit and vegetable fresh-keeping packaging. FIG. 4 is a scanning electron microscope photograph of the composite film showing that Ag MOF particles having a size of about 15nm are uniformly distributed on the substrate of the chitosan/polyvinyl alcohol composite film.
Example 2
A preparation method of the Ag MOF composite chitosan-based film is similar to that of the example 1, and the difference is that the method specifically comprises the following steps:
(1) mixing 60mgAgC2H3O2Dissolving in 20ml deionized water, mixing to obtain silver acetate solution, and mixing with 20mgC8H7NO4Dissolving the two solutions in 20ml of absolute ethyl alcohol, uniformly mixing to form a 2-amino terephthalic acid solution, quickly mixing the two solutions, standing for 56 hours, performing ultrasonic dispersion for 5 hours at the ultrasonic frequency of 25kHz, then performing centrifugal operation for 20 minutes at the rotating speed of 8000r/min, washing a product in a centrifugal tube by using the absolute ethyl alcohol, and repeating the centrifugal washing operation for 3 times. And drying for 36h at the temperature of 60 ℃ in a vacuum drying oven, and taking out the product to be Ag MOF.
(2) 2g of chitosan powder (the deacetylation degree is more than or equal to 95 percent, the viscosity is 100-200mpa) is added into 100ml of 2 percent acetic acid solution, the mixture is stirred uniformly to form chitosan solution (the stirring speed is 500rpm, the stirring time is 12 hours), and then 10ml of Glycerol (GL) is added, and the mixture is mixed uniformly to form membrane-forming matrix fluid. 5.5mgAg MOF is added into the film forming substrate liquid, and the film forming liquid is continuously stirred (the stirring speed is 500rpm) for 52h to ensure the uniform mixing of the film forming liquid.
(3) And then pouring the film forming solution into a grinding tool, and drying in an oven (at the temperature of 50 ℃) for 6 days to strip out a 5% Ag MOF composite chitosan/glycerol film sample.
The phase of the 5% Ag MOF composite chitosan-based film prepared in this example is Ag MOF @ CS/GL, and FIG. 5 is a scanning electron microscope picture of the composite film, and it can be seen that Ag MOF particles with a size of about 20nm are uniformly distributed on the matrix of the chitosan/glycerol composite film. Fig. 6 is a graph showing the release of Ag MOF from the composite film in a buffer solution with pH 6, and it can be seen that Ag MOF is continuously released on the surface of the film with the passage of time.
Example 3
A preparation method of the Ag MOF composite chitosan-based film is similar to that of the embodiment 1, and the difference is that the preparation method specifically comprises the following steps:
(1) mixing 60mgAgC2H3O2Dissolving in 20ml deionized water, mixing to obtain silver acetate solution, and mixing with 20mgC8H7NO4Dissolving the two solutions in 20ml of absolute ethyl alcohol, uniformly mixing to form a 2-amino terephthalic acid solution, quickly mixing the two solutions, standing for 72 hours, performing ultrasonic dispersion for 6 hours at the ultrasonic frequency of 25kHz, then performing centrifugal operation for 20 minutes at the rotating speed of 10000r/min, washing a product in a centrifugal tube by adopting the absolute ethyl alcohol, and repeating the centrifugal washing operation for 5 times. And drying the mixture for 48 hours at 60 ℃ in a vacuum drying oven, and taking out the product to obtain the Ag MOF.
(2) 2g of chitosan powder is added into 100ml of 2% acetic acid solution, and is stirred uniformly to form chitosan solution (the stirring speed is 500rpm, and is stirred for 12 hours), and then 20ml of palmitic acid (PMD) solution is added and is mixed uniformly to form membrane-forming matrix liquid. Adding 9.6mgAg MOF into the film forming substrate liquid, and continuously stirring for 60h to ensure the uniform mixing of the film forming liquid.
(3) And then pouring the film forming solution into a grinding tool, and drying in an oven (at the temperature of 50 ℃) for 6 days to strip out an 8% Ag MOF composite chitosan/palmitic acid film sample.
The phase of the 8% Ag MOF composite chitosan-based film prepared in the embodiment is Ag MOF @ CS/PMD, and Ag MOF particles with the micro-morphology of about 20nm are uniformly distributed on the matrix of the chitosan/palmitic acid composite film.
Example 4
A preparation method of the Ag MOF composite chitosan-based film is similar to that of the example 1, and the difference is that the method specifically comprises the following steps:
(1) mixing 60mgAgC2H3O2Dissolving in 20ml deionized water, mixing to obtain silver acetate solution, and mixing with 20mgC8H7NO4Dissolving the two solutions in 20ml of absolute ethyl alcohol, uniformly mixing to form a 2-amino terephthalic acid solution, quickly mixing the two solutions, standing for 48 hours, performing ultrasonic dispersion for 5 hours at the ultrasonic frequency of 25kHz, then, at the rotating speed of 9000r/min, washing a product in a centrifugal tube by using absolute ethyl alcohol after centrifugal operation for 18 minutes, and repeating the centrifugal washing operation for 4 times. And drying the product in a vacuum drying oven at 60 ℃ for 36h, and taking out the product as Ag MOF.
(2) Adding 2g of chitosan powder into 100ml of 2% acetic acid solution, stirring uniformly to form chitosan solution (stirring speed 500rpm, stirring for 12h), then adding 15ml of Apple Polyphenol (AP) solution, and mixing uniformly to form film-forming matrix fluid. 11.5mgAg MOF is added into the film forming substrate liquid, and the film forming liquid is continuously stirred (the stirring speed is 500rpm) for 50h to ensure the uniform mixing of the film forming liquid.
(3) And then pouring the film forming solution into a grinding tool, and drying in an oven (at the temperature of 50 ℃) for 6 days to strip out a 10% Ag MOF composite chitosan/apple polyphenol film sample.
The phase of the 10% Ag MOF composite chitosan-based film prepared by the embodiment is Ag MOF @ CS/AP, and Ag MOF particles with the microscopic morphology of about 30nm are uniformly distributed on the matrix of the chitosan/apple polyphenol composite film. FIG. 7 is a comparison of the mechanical property curves of different films of Ag MOF composite chitosan base prepared in examples 1-4, which shows that the prepared composite film shows better tensile strength and plastic deformation.
Example 5
A preparation method of the Ag MOF composite chitosan-based film is similar to that of the embodiment 1, and the difference is that the preparation method specifically comprises the following steps:
(1) mixing 60mgAgC2H3O2Dissolving in 20ml deionized water, mixing to obtain silver acetate solution, and mixing with 20mgC8H7NO4Dissolving the two solutions in 20ml of absolute ethyl alcohol, uniformly mixing to form a 2-amino terephthalic acid solution, quickly mixing the two solutions, standing for 72 hours, performing ultrasonic dispersion for 5 hours at the ultrasonic frequency of 25kHz, then performing centrifugal operation for 15 minutes at the rotating speed of 8000r/min, washing a product in a centrifugal tube by using the absolute ethyl alcohol, and repeating the centrifugal washing operation for 5 times. And drying the mixture in a vacuum drying oven at 60 ℃ for 48 hours, and taking out the product to obtain the Ag MOF.
(2) 2g of chitosan powder is added into 100ml of 2% acetic acid solution and stirred uniformly to form chitosan solution (the stirring speed is 500rpm, the stirring is carried out for 12 hours), then 10ml of polyvinyl alcohol (PVA) solution and 10ml of Glycerol (GL) are added and mixed uniformly to form membrane-forming matrix fluid. 6mgAg MOF is added into the film forming substrate liquid, and the film forming liquid is continuously stirred (the stirring speed is 500rpm) for 72h to ensure the uniform mixing of the film forming liquid.
(3) And then pouring the film forming solution into a grinding tool, and drying in an oven (at the temperature of 50 ℃) for 6 days to strip out a 5% Ag MOF composite chitosan/polyvinyl alcohol/glycerol film sample.
The phase of the 5% Ag MOF composite chitosan-based film prepared by the embodiment is Ag MOF @ CS/PVA/GL, and Ag MOF particles with the micro morphology of about 25nm are uniformly distributed on a matrix of the chitosan/polyvinyl alcohol/glycerol composite film.
Example 6
A preparation method of the Ag MOF composite chitosan-based film is similar to that of the example 1, and the difference is that the method specifically comprises the following steps:
(1) mixing 60mgAgC2H3O2Dissolving in 20ml deionized water, mixing to obtain silver acetate solution, and mixing with 20mgC8H7NO4DissolutionThe preparation method comprises the steps of uniformly mixing the two solutions in 20ml of absolute ethyl alcohol to form a 2-amino terephthalic acid solution, rapidly mixing the two solutions, standing for 48 hours, carrying out ultrasonic dispersion for 6 hours at an ultrasonic frequency of 25kHz, then washing a product in a centrifugal tube by using absolute ethyl alcohol after carrying out centrifugal operation for 20 minutes at a rotating speed of 10000r/min, and repeating the centrifugal washing operation for 4 times. And drying the product in a vacuum drying oven at 60 ℃ for 36h, and taking out the product as Ag MOF.
(2) Adding 2g of chitosan powder into 100ml of 2% acetic acid solution, stirring uniformly to form chitosan solution (stirring speed 500rpm, stirring for 12h), then adding 10ml of polyvinyl alcohol (PVA) solution and 10ml of Apple Polyphenol (AP) solution, and mixing uniformly to form film-forming matrix fluid. 9.6mgAg MOF is added into the film forming substrate liquid, and the film forming liquid is continuously stirred (the stirring speed is 500rpm) for 60 hours to ensure the uniform mixing of the film forming liquid.
(3) And then pouring the film forming solution into a grinding tool, and drying in an oven (at the temperature of 50 ℃) for 5 days to obtain a 8% Ag MOF composite chitosan/polyvinyl alcohol/apple polyphenol film sample.
The phase of the 8% Ag MOF composite chitosan-based film prepared in the embodiment is Ag MOF @ CS/PVA/AP, and Ag MOF particles with the micro-morphology of about 20nm are uniformly distributed on the matrix of the chitosan/polyvinyl alcohol/apple polyphenol composite film.
Example 7
A preparation method of the Ag MOF composite chitosan-based film is similar to that of the example 1, and the difference is that the method specifically comprises the following steps:
(1) mixing 60mgAgC2H3O2Dissolving in 20ml deionized water, mixing to obtain silver acetate solution, and mixing with 20mgC8H7NO4Dissolving the two solutions in 20ml of absolute ethyl alcohol, uniformly mixing to form a 2-amino terephthalic acid solution, quickly mixing the two solutions, standing for 52 hours, performing ultrasonic dispersion for 5 hours at the ultrasonic frequency of 25kHz, then, at the rotating speed of 9000r/min, washing a product in a centrifugal tube by using absolute ethyl alcohol after centrifugal operation for 18 minutes, and repeating the centrifugal washing operation for 5 times. And drying the product for 24 hours in a vacuum drying oven at 60 ℃ and taking out the product as Ag MOF.
(2) 2g of chitosan powder is added into 100ml of 2% acetic acid solution and stirred uniformly to form chitosan solution (the stirring speed is 500rpm, the stirring is 12 hours), then 10ml of Glycerol (GL) and 10ml of palmitic acid (PMD) solution are added and mixed uniformly to form membrane-forming matrix fluid. Adding 12mg of Ag MOF into the film forming substrate liquid, and continuously stirring (stirring speed 500rpm) for 48h to ensure the uniform mixing of the film forming liquid.
(3) And then pouring the film forming solution into a grinding tool, and drying in an oven (at the temperature of 50 ℃) for 6 days to strip out a 10% Ag MOF composite chitosan/glycerol/palmitic acid film sample.
The phase of the 10% Ag MOF composite chitosan-based film prepared in the embodiment is Ag MOF @ CS/GL/PMD, and Ag MOF particles with the micro-morphology of about 30nm are uniformly distributed on a matrix of the chitosan/glycerol/palmitic acid composite film.
Example 8
A method for preparing an Ag MOF composite chitosan-based film, which is similar to example 1, except that the mass ratio of the silver acetate solution and the 2-amino terephthalic acid solution mixed in the step (1) is 2: 1.
Example 9
A method for preparing an Ag MOF composite chitosan-based film, which is similar to example 1, except that the mass ratio of the silver acetate solution and the 2-amino terephthalic acid solution mixed in the step (1) is 4: 1.
Example 10
A preparation method of the Ag MOF composite chitosan-based film is similar to that of the example 1, except that the time of standing after mixing the silver acetate solution and the 2-amino terephthalic acid solution in the step (1) is 60 hours.
Example 11
A method for preparing an Ag MOF composite chitosan-based film, which is similar to example 1, except that the concentration of the chitosan solution in the step (2) is 2.5%.
Example 12
A method for preparing an Ag MOF composite chitosan-based film, similar to example 1, except that the concentration of the chitosan solution in the step (2) is 3%.
Example 13
A method for preparing an Ag MOF composite chitosan-based film, which is similar to example 1, except that the plasticizer in the step (2) is a mixture of polyvinyl alcohol (PVA), Glycerol (GL), palmitic acid (PMD) and Apple Polyphenol (AP) in equal proportion.
Example 14
A method for preparing Ag MOF composite chitosan-based film, similar to example 1, except that the plasticizer in step (2) is a mixture of polyvinyl alcohol (PVA) and Glycerol (GL) in equal proportion.
Example 15
A method for preparing an Ag MOF composite chitosan-based film, which is similar to example 1, except that the plasticizer in the step (2) is an equal proportion mixture of palmitic acid (PMD) and Apple Polyphenol (AP).
Example 16
A method for preparing an Ag MOF composite chitosan-based film, which is similar to example 1, except that the plasticizer in the step (2) is a mixture of polyvinyl alcohol (PVA), Glycerol (GL) and palmitic acid (PMD) in equal proportion.
Example 17
A method for preparing an Ag MOF composite chitosan-based film, which is similar to example 1, except that the plasticizer in step (2) is a mixture of Glycerol (GL), palmitic acid (PMD), and Apple Polyphenol (AP) in equal proportion.
Example 18
A method for preparing an Ag MOF composite chitosan-based film, which is similar to example 1, except that the plasticizer in the step (2) is a mixture of polyvinyl alcohol (PVA), palmitic acid (PMD), and Apple Polyphenol (AP) in equal proportion.
Example 19
A method for preparing an Ag MOF composite chitosan-based film, which is similar to that in example 1, except that the plasticizer in the step (2) is a mixture of polyvinyl alcohol (PVA), Glycerol (GL) and Apple Polyphenol (AP) in equal proportion.
Example 20
A method for preparing an Ag MOF composite chitosan-based film, which is similar to example 1, except that the plasticizer in the step (2) is a mixture of polyvinyl alcohol (PVA) and palmitic acid (PMD) in equal proportion.
Example 21
A method for preparing an Ag MOF composite chitosan-based film, which is similar to that in example 1, except that the plasticizer in the step (2) is a mixture of polyvinyl alcohol (PVA) and Apple Polyphenol (AP) in equal proportion.
Example 22
A method for preparing an Ag MOF composite chitosan-based film, which is similar to example 1, except that the plasticizer in step (2) is a mixture of Glycerol (GL) and palmitic acid (PMD) in equal proportion.
Example 23
A method for preparing an Ag MOF composite chitosan-based film, which is similar to example 1, except that the plasticizer in step (2) is a mixture of Glycerol (GL) and Apple Polyphenol (AP) in equal proportion.
The above embodiments are only for illustrative purpose and not for restrictive purpose, and any insubstantial modifications made by those skilled in the art based on the present invention shall fall within the scope of the present invention.

Claims (10)

1. The Ag MOF composite chitosan-based film is characterized in that the chemical general formula is x% Ag MOF @ CS/M, wherein x is the percentage content of Ag MOF, CS is chitosan, and M is any one or a combination of polyvinyl alcohol, glycerol, palmitic acid and apple polyphenol.
2. A method for preparing a Ag MOF composite chitosan-based film according to claim 1, comprising the following steps:
(1) preparing a silver acetate solution and a 2-amino terephthalic acid solution, mixing the two solutions, and standing;
(2) ultrasonically dispersing, centrifuging to obtain a product, washing, and drying in a vacuum drying oven to obtain Ag MOF;
(3) adding chitosan powder into an acetic acid solution, stirring to form a chitosan solution, adding a plasticizer, mixing to form a film-forming matrix fluid, adding Ag MOF into the film-forming matrix fluid, and continuously stirring to obtain a film-forming solution;
(4) pouring the film forming solution into a grinding tool, and drying in an oven to strip the Ag MOF composite chitosan-based film.
3. The method according to claim 2, wherein in the step (1), the silver acetate is dissolved in deionized water and uniformly mixed to obtain a silver acetate solution, and the 2-amino terephthalic acid is dissolved in anhydrous ethanol and uniformly stirred to obtain a 2-amino terephthalic acid solution.
4. The method according to claim 2, wherein the silver acetate solution and the 2-aminoterephthalic acid solution are mixed in the step (1) at a mass ratio of 2-4: 1.
5. The preparation method according to claim 2, wherein the mixed liquid after standing in the step (2) is dispersed by ultrasonic for 4 to 6 hours at an ultrasonic frequency of 25 kHz.
6. The preparation method of claim 2, wherein the centrifugation in step (2) is performed at 8000r/min to 10000r/min for 15min to 20min, and the product in the centrifuge tube is washed with absolute ethanol and the centrifugation washing is repeated 3 to 5 times.
7. The method of claim 2, wherein the concentration of the chitosan solution in step (3) is 2% -3%.
8. The method of claim 2, wherein the plasticizer in the step (3) comprises any one or more of polyvinyl alcohol (PVA), Glycerol (GL), palmitic acid (PMD) and Apple Polyphenol (AP).
9. The method of claim 2, wherein the oven drying time in step (4) is 5 to 6 days and the drying temperature is 50 ℃ to 60 ℃.
10. The Ag MOF composite chitosan-based film prepared by the preparation method according to any one of claims 2-9 is applied to the technical field of food packaging.
CN202210321143.7A 2022-03-30 2022-03-30 Ag MOF composite chitosan-based film and preparation method and application thereof Pending CN114634657A (en)

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