CN115558150A - Preparation method and application of antibacterial fresh-keeping packaging film with porous structure - Google Patents
Preparation method and application of antibacterial fresh-keeping packaging film with porous structure Download PDFInfo
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- CN115558150A CN115558150A CN202211098297.0A CN202211098297A CN115558150A CN 115558150 A CN115558150 A CN 115558150A CN 202211098297 A CN202211098297 A CN 202211098297A CN 115558150 A CN115558150 A CN 115558150A
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- 239000012785 packaging film Substances 0.000 title claims abstract description 58
- 229920006280 packaging film Polymers 0.000 title claims abstract description 58
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 235000012055 fruits and vegetables Nutrition 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
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- 235000013311 vegetables Nutrition 0.000 claims abstract description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 60
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- 229920002678 cellulose Polymers 0.000 claims description 26
- 239000001913 cellulose Substances 0.000 claims description 26
- 239000000725 suspension Substances 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 17
- DYHSDKLCOJIUFX-UHFFFAOYSA-N tert-butoxycarbonyl anhydride Chemical compound CC(C)(C)OC(=O)OC(=O)OC(C)(C)C DYHSDKLCOJIUFX-UHFFFAOYSA-N 0.000 claims description 16
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 12
- 229920002201 Oxidized cellulose Polymers 0.000 claims description 11
- 229920002873 Polyethylenimine Polymers 0.000 claims description 11
- 229940107304 oxidized cellulose Drugs 0.000 claims description 11
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- 150000001767 cationic compounds Chemical class 0.000 claims description 10
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- 238000003756 stirring Methods 0.000 claims description 8
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 14
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- 235000015097 nutrients Nutrition 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS 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
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS 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
- B65D81/00—Containers, 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
- B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS 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
- B65D85/00—Containers, packaging elements or packages, specially adapted for particular articles or materials
- B65D85/30—Containers, packaging elements or packages, specially adapted for particular articles or materials for articles particularly sensitive to damage by shock or pressure
- B65D85/34—Containers, packaging elements or packages, specially adapted for particular articles or materials for articles particularly sensitive to damage by shock or pressure for fruit, e.g. apples, oranges or tomatoes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS 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
- B65D85/00—Containers, packaging elements or packages, specially adapted for particular articles or materials
- B65D85/50—Containers, packaging elements or packages, specially adapted for particular articles or materials for living organisms, articles or materials sensitive to changes of environment or atmospheric conditions, e.g. land animals, birds, fish, water plants, non-aquatic plants, flower bulbs, cut flowers or foliage
- B65D85/52—Containers, packaging elements or packages, specially adapted for particular articles or materials for living organisms, articles or materials sensitive to changes of environment or atmospheric conditions, e.g. land animals, birds, fish, water plants, non-aquatic plants, flower bulbs, cut flowers or foliage for living plants; for growing bulbs
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0028—Use of organic additives containing nitrogen
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- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
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- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
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- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
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Abstract
The invention discloses a preparation method and application of an antibacterial fresh-keeping packaging film with a porous structure. The antibacterial fresh-keeping packaging film obtained by the method has excellent permeation and antibacterial performance, when the packaging film is applied, the packaging film can directly wrap fresh fruits and vegetables, or the packaging film is attached to the open window of the box cover of the plastic fresh-keeping box, the box cover is used for sealing the plastic fresh-keeping box filled with the fresh fruits and vegetables, the porous structure of the packaging film enhances the exchange of internal gas and external gas, the concentration of carbon dioxide in the package is maintained at 1-10%, and the fresh-keeping shelf life of the fruits and vegetables can be effectively prolonged.
Description
Technical Field
The invention relates to the technical field of packaging films, in particular to a preparation method and application of an antibacterial fresh-keeping packaging film with a porous structure.
Background
Fruits and vegetables are extremely perishable and perishable products, and the fruits and vegetables still can keep fresh after undergoing a packaging, transporting and storing link. Generally, the problems of enhanced respiration, enzymatic browning, surface softening, microorganism growth and reproduction and the like can occur after fruits and vegetables are picked, so that the shelf life and the quality of the fruits and vegetables are greatly shortened. The petroleum-based polymer packaging material used for packaging fruits and vegetables at present is very easy to cause high CO which is not beneficial to the fresh-keeping of the fruits and vegetables due to good gas and water vapor barrier property 2 The fresh-keeping effect is poor due to the environment in the package with high concentration and high humidity. In the transportation and storage process of fruits and vegetables, the respiration of the fruits and vegetables and the gas permeability of the packaging film jointly regulate the gas atmosphere in the package, and the respiration can cause CO in the package 2 The concentration rises. CO in the package 2 The concentration is higher than 1%, the aerobic respiration rate of the fruits and vegetables is reduced, and the consumption of nutrient substances is slowed down; but CO in the package 2 The concentration is higher than 10%, and partial fruits and vegetables have the problems of fruit softening, brown spots, dehydration and wilting, massive anaerobic bacteria breeding and the like. Therefore, the development of an antibacterial fresh-keeping packaging film with a porous structure, which can inhibit the growth and reproduction of microorganisms on the surfaces of fruits and vegetables and adjust the gas atmosphere in the packaging, is urgently needed to prolong the shelf life of the fruits and vegetables.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method and application of an antibacterial fresh-keeping packaging film with a porous structure.
The invention solves the technical problems by the following technical scheme:
the preparation method of the antibacterial fresh-keeping packaging film with the porous structure comprises the following operation steps:
(1) Respectively dissolving an amino-containing cationic compound and di-tert-butyl dicarbonate (BOC) in Dichloromethane (DCM) with the purity of 99.9 percent to prepare solutions with the mass concentration of 20 percent;
(2) Slowly dripping the prepared BOC solution into the prepared cationic compound solution at the speed of 1-3 mL/min, wherein the dosage of the BOC solution and the prepared cationic compound solution is 2:1 according to the volume ratio, and then magnetically stirring the solution for 8-12 hours at the speed of 500-800 rpm at the temperature of 20-30 ℃ to obtain white suspension;
(3) Centrifuging and washing the white suspension for 3-5 times by using N, N-dimethylacetamide (DMAc) at the rotating speed of 8000-10000 rpm, and removing Dichloromethane (DCM) to obtain a precipitate with a pore-forming function;
(4) Mixing the precipitate obtained in the step (3) with a cellulose film base material with the mass concentration of 2-5%, wherein the dosage of the two is 1-75 according to the mass ratio, then adding deionized water to prepare a suspension with the mass concentration of 0.6-0.8%, and magnetically stirring at the speed of 600-800 rpm for 8-12 h at the temperature of 20-30 ℃ to obtain a uniformly dispersed film forming solution;
(5) Casting the film forming liquid in a polytetrafluoroethylene mold, drying for 48-72 h under the environmental conditions of the temperature of 23-30 ℃ and the humidity of 50-60%, and atomizing and spraying hydrochloric acid on the surface of the film for 4-6 times in the drying process to obtain the antibacterial fresh-keeping packaging film with the porous structure.
In the step (1) of the present invention, the cationic compound having an amine group includes branched Polyethyleneimine (PEI) having a molecular weight of 800 to 25000, glycine (Gly), and polyhexamethylene biguanide hydrochloride (PHMG).
In the step (4), the cellulose film substrate comprises a cellulose nanofibril suspension which is prepared by a mechanical grinding method and has a diameter of 5-50 nm and an aspect ratio of more than 100, or a cellulose suspension which is prepared by mixing cellulose nanofibrils and TEMPO oxidized cellulose nanofibrils according to a mass ratio of 9-18.
In the step (4), the preparation method of the TEMPO oxidized cellulose nanofibrils comprises the following steps: the method comprises the steps of oxidizing cellulose nano-fibrils prepared by a mechanical grinding method by a TEMPO oxidation method, and then carrying out rotary evaporation and concentration for 30-50 min at 50-60 ℃ to obtain the TEMPO oxidized cellulose nano-fibrils with the diameter of 2-30 nm, the length-diameter ratio of more than 50 and the surface carboxyl content of 0.8-1.6 mmol/g.
In the step (5), the concentration of the used hydrochloric acid is 0.5-1 mol/L, a compression type atomizer is used for atomization, the atomization rate is 0.2-0.5 mL/min, the size of the atomized hydrochloric acid is 2-10 mu m, the spraying height is 10-15 cm, and the dosage of the hydrochloric acid in single atomization spraying is 3-8 times of the mass of the precipitate with the pore-forming function in the film-forming liquid.
The application method of the antibacterial fresh-keeping packaging film with the porous structure comprises the following steps: the fresh fruits and vegetables are directly wrapped by the antibacterial fresh-keeping packaging film with the porous structure, or the antibacterial fresh-keeping packaging film with the porous structure is attached to a box cover opening window of a plastic fresh-keeping box by using vacuum silicone grease, then the plastic fresh-keeping box filled with the fresh fruits and vegetables is sealed by using the box cover, and the packaged fruits and vegetables are stored under the environmental conditions of the temperature of 20-25 ℃ and the humidity of 50-70%.
Compared with the prior art, the invention has the following advantages:
(1) The antibacterial fresh-keeping packaging film with the porous structure adopts a green, environment-friendly and sustainable base material, is low in cost and is simple in preparation process.
(2) The packaging film prepared by the preparation method disclosed by the invention has a porous structure, the gas permeability of the film is obviously improved, the amino-containing cationic compound can bring excellent antibacterial performance, and the packaging film has the excellent mechanical performance and water vapor permeability of the cellulose nano-fiber film, and the excellent gas permeability and antibacterial performance have obvious fresh-keeping effect on fruits and vegetables.
(3) When the packaging film is applied, the packaging film can be directly wrapped on the surface of fresh fruits and vegetables or sealed window packaging can be carried out, the concentration of carbon dioxide in the packaging film is maintained at 1-10%, and the fresh-keeping shelf life of the fruits and vegetables is effectively prolonged.
Drawings
Fig. 1 is a scanning electron microscope image of the antibacterial fresh-keeping packaging film with a porous structure obtained in example 1 of the present invention.
Fig. 2 is a comparative image of the antibacterial experiment results of the antibacterial preservative packaging film with a porous structure obtained in example 1 of the present invention and a blank group (without the antibacterial packaging film) on listeria.
Detailed Description
The technical solution of the present invention is further explained below.
Cellulose is the most abundant renewable biomass material in nature, and has excellent mechanical properties, excellent film forming property, lower cost and renewability.
According to the invention, di-tert-butyl dicarbonate is combined with an amino-containing cationic compound to form a material with a pore-forming function, cellulose is used as a film substrate, the two are mixed and poured, a small amount of hydrochloric acid is used for spraying a film-forming solution for many times, the hydrochloric acid and di-tert-butyl dicarbonate generate carbon dioxide, a gas passage is left, and a porous structure of the film substrate is formed; meanwhile, the amino group is exposed and crosslinked with cellulose, so that the influence of the pore-forming functional material on the performance of the film is reduced, and the antibacterial fresh-keeping packaging film with a porous structure is obtained after drying, can be directly applied to fruit and vegetable fresh keeping, and is favorable for expanding the application of the cellulose film in the field of fresh keeping.
The following are examples of the present invention, but the scope of the present invention is not limited to the following examples.
In the following examples, the cellulose nanofibrils are prepared by mechanical milling, the diameter of the cellulose nanofibrils is 5-50 nm, and the aspect ratio is more than 100.
The preparation method of the TEMPO oxidized cellulose nanofibrils comprises the following steps: the method comprises the steps of oxidizing cellulose nano-fibrils prepared by a mechanical grinding method by using a TEMPO oxidation method, and then carrying out rotary evaporation and concentration for 30-50 min at 50-60 ℃ to obtain the TEMPO oxidized cellulose nano-fibrils, wherein the diameter of the TEMPO oxidized cellulose nano-fibrils is 2-30 nm, the length-diameter ratio is more than 50, and the surface carboxyl content is 0.8-1.6 mmol/g.
Example 1
Branched Polyethyleneimine (PEI) with a molecular weight of 800 and di-tert-butyl dicarbonate (BOC) are respectively dissolved in Dichloromethane (DCM) with a purity of 99.9 percent to prepare solutions with a mass concentration of 20 percent. Then 20mL of BOC solution was slowly added dropwise at a rate of 1mL/min to 10mL of branched Polyethyleneimine (PEI) solution, and magnetically stirred at 500rpm at 20 ℃ for 12h to give a white suspension. The white suspension was then washed with N, N-dimethylacetamide (DMAc) at 8000rpm by high speed centrifugation 5 times to remove DCM and obtain a precipitate with pore-forming function.
And (3) uniformly mixing 0.3g of the precipitate with 22.5g of cellulose nanofibril suspension with the solid content of 2%, adding deionized water to prepare 0.8% suspension, and magnetically stirring at 23 ℃ at 800rpm for 10 hours to obtain the membrane forming solution. And pouring the film forming solution into a polytetrafluoroethylene mold with the length and width =15cm and 15cm, drying for 72 hours under the environmental conditions of 25 ℃ and 60% humidity, wherein in the drying process, 0.5mol/L hydrochloric acid is used, a compression atomizer is adopted to atomize and spray the surface of the film at a fixed height of 10cm for 4 times, the atomizing rate is 0.4mL/min, the atomizing size is 10 mu m, 2mL is sprayed at a time, and the antibacterial fresh-keeping packaging film with the porous structure is obtained after drying. The oxygen transmission rate of the antibacterial fresh-keeping packaging film is 90.16cc/m 2 Day bar, carbon dioxide transmission 128.43cc/m 2 Day bar, water vapor transmission rate 746.52g/m 2 Day, listeria inhibition 97.31%.
When the antibacterial preservative packaging film with the porous structure is used, fresh plums are directly wrapped by the antibacterial preservative packaging film with the porous structure, and after the fresh plums are stored for 20 days in an environment with the temperature of 23 ℃ and the humidity of 60%, the plums are slightly wrinkled, the pulp part is softened, the color of the peel is changed into dark red, but no rotten odor and no mould are generated, and the plums have longer shelf life when wrapped by the antibacterial preservative packaging film with the porous structure.
The scanning electron microscope image of the antibacterial fresh-keeping packaging film obtained in the embodiment is shown in fig. 1, and it can be seen that the porous structure of the antibacterial fresh-keeping packaging film of the product is formed, which is beneficial to the exchange of gas inside and outside the film. The results of the antibacterial experiment on listeria by applying the antibacterial preservative packaging film and the blank group (namely, the antibacterial packaging film is not adopted) are shown in fig. 2, and it can be seen that the antibacterial preservative film of the invention has excellent antibacterial performance and can effectively inhibit the breeding of bacteria in the package.
Example 2
Branched Polyethyleneimine (PEI) with a molecular weight of 25000 and di-tert-butyl dicarbonate (BOC) are respectively dissolved in Dichloromethane (DCM) with a purity of 99.9% to prepare solutions with a mass concentration of 20%. 20mL of BOC solution was slowly added dropwise at a rate of 1mL/min to 10mL of PEI solution and magnetically stirred at 600rpm for 12h at 25 ℃ to give a white suspension. And then the white suspension is subjected to high-speed centrifugal washing 3 times at 10000rpm by N, N-dimethylacetamide (DMAc), DCM is removed, and precipitate with a pore-forming function is obtained.
And (2) uniformly mixing 0.3g of the precipitate with 11.25g of mixed cellulose suspension (prepared by mixing cellulose nano-fibrils and TEMPO oxidized cellulose nano-fibrils according to the mass ratio of 9:1) with the solid content of 4%, adding deionized water to prepare the suspension with the mass concentration of 0.8%, and magnetically stirring at the rotating speed of 600rpm at 25 ℃ for 10 hours to obtain the film-forming solution. And pouring the film forming solution into a polytetrafluoroethylene mold with the length and width =15cm and 15cm, drying for 48 hours under the environmental conditions of the temperature of 23 ℃ and the humidity of 60%, wherein in the drying process, 0.5mol/L hydrochloric acid is used, a compression atomizer is used for atomizing and spraying the surface of the film for 4 times at the fixed height of 15cm, the atomizing rate is 0.5mL/min, the atomizing size is 5 mu m, 2mL is sprayed for one time, and the antibacterial preservative packaging film with the porous structure is obtained after drying. The antibacterial fresh-keeping packaging film has oxygen transmission rate of 139.18cc/m 2 Day bar, carbon dioxide transmission 146.34cc/m 2 Day bar, water vapor transmission rate 776.56g/m 2 Day, the rate of listeria inhibition was 99.99%.
When in use, the product of the invention has porous structureVacuum silicone grease is attached to the plastic box cover window for the fungus preservation packaging film, then the plastic preservation box with fresh loquat is sealed by the plastic box cover, the plastic preservation box is stored for 14 days in an environment with the temperature of 20 ℃ and the humidity of 70 percent, and CO in the packaging box 2 The gas concentration is 6.8%, the loquat has slight surface wrinkles, the pulp loses water and becomes soft, the color of the peel becomes dark, but no rotten smell exists, and the loquat has longer shelf life under the window body package attached by the antibacterial fresh-keeping packaging film with the porous structure.
Example 3
Glycine (Gly) and di-tert-butyl dicarbonate (BOC) are respectively dissolved in Dichloromethane (DCM) with a purity of 99.9% and are prepared into solutions with a mass concentration of 20%. 20mL of BOC solution was slowly added dropwise to 10mL of Gly solution at a rate of 3mL/min, and magnetically stirred at 500rpm at 25 ℃ for 12h to obtain a white suspension. And then centrifuging and washing the white suspension at a high speed of 10000rpm for 3 times by using N, N-dimethylacetamide (DMAc), and removing DCM to obtain a precipitate with a pore-forming function.
And (3) uniformly mixing 0.3g of the precipitate with 15g of cellulose nanofibril suspension with the solid content of 3%, adding deionized water to prepare the suspension with the mass concentration of 0.7%, and magnetically stirring at the rotating speed of 600rpm at 20 ℃ for 12 hours to obtain a film-forming solution. And pouring the film forming solution into a polytetrafluoroethylene mold with the length and width =15cm and 15cm, and drying for 72 hours under the environmental conditions of the temperature of 25 ℃ and the humidity of 60%, wherein in the drying process, 1mol/L hydrochloric acid is used, a compression atomizer is used for atomizing and spraying the surface of the film for 6 times at the fixed height of 15cm, the atomizing rate is 0.2mL/min, the atomizing size is 2 microns, and 1mL is sprayed for one time. And drying to obtain the antibacterial fresh-keeping packaging film with the porous structure. The antibacterial fresh-keeping packaging film has oxygen transmission rate of 142.24cc/m 2 Day bar, carbon dioxide transmission 150.65cc/m 2 Day bar, water vapor transmission rate 515.34g/m 2 Day, listeria inhibition 93.93%.
When the antibacterial preservative packaging film with the porous structure is used, fresh loquats are directly wrapped by the antibacterial preservative packaging film, after the loquats are stored for 12 days at the temperature of 23 ℃ and the humidity of 60%, the loquats have slight surface wrinkles, the pulp part loses water, the color part becomes dark, but no rotten odor exists, and the loquats have longer shelf life when wrapped by the antibacterial preservative packaging film with the porous structure.
Example 4
Polyhexamethylene biguanide hydrochloride (PHMG) and di-tert-butyl dicarbonate (BOC) are respectively dissolved in Dichloromethane (DCM) with the purity of 99.9 percent to prepare solutions with the mass concentration of 20 percent. 20mL of BOC solution was slowly added dropwise at a rate of 1mL/min to 10mL of PHMG solution, and magnetically stirred at 800rpm at 30 ℃ for 8h to give a white suspension. The white suspension was then washed with N, N-dimethylacetamide (DMAc) at 8000rpm for 5 times by high speed centrifugation to remove DCM and obtain a precipitate with pore-forming function.
Uniformly mixing 0.3g of the precipitate with 9g of mixed cellulose suspension (prepared by mixing cellulose nanofibrils and TEMPO oxidized cellulose nanofibrils according to a mass ratio of 18 to 1) with a solid content of 5%, adding deionized water to prepare a suspension with a mass concentration of 0.6%, and magnetically stirring at a rotating speed of 800rpm for 8 hours at 30 ℃ to obtain a film-forming solution. And pouring the film forming solution into a polytetrafluoroethylene mold with the length and width =15cm and 15cm, and drying for 72 hours under the environmental conditions of the temperature of 30 ℃ and the humidity of 50%, wherein in the drying process, 1mol/L hydrochloric acid is used, a compression atomizer is used for atomizing and spraying the surface of the film for 6 times at the fixed height of 10cm, the atomizing rate is 0.5mL/min, the atomizing size is 8 microns, and 1mL is sprayed for one time. And drying to obtain the antibacterial fresh-keeping packaging film with the porous structure. The oxygen transmission rate of the antibacterial fresh-keeping packaging film is 145.38cc/m 2 Day bar, carbon dioxide transmission 152.34cc/m 2 Day bar, water vapor transmission rate 506.81g/m 2 Day, the rate of listeria inhibition was 99.99%.
When in use, the antibacterial and fresh-keeping vacuum silicone grease with porous structure of the product is attached to a plastic box cover window, then the plastic fresh-keeping box with fresh plums is sealed by the plastic box cover, and after the plastic fresh-keeping box is stored for 21 days in an environment with the temperature of 25 ℃ and the humidity of 70 percent, CO in the packaging box 2 The gas concentration is 6.5%, the plum has slight skin wrinkle, soft pulp, and dark peel colorThe rotten smell, the plum has longer shelf life under the window body package that the antibiotic fresh-keeping packaging film with porous structure is laminated.
Claims (6)
1. The preparation method of the antibacterial fresh-keeping packaging film with the porous structure is characterized by comprising the following operation steps:
(1) Respectively dissolving an amino-containing cationic compound and di-tert-butyl dicarbonate (BOC) in Dichloromethane (DCM) with the purity of 99.9 percent to prepare solutions with the mass concentration of 20 percent;
(2) Slowly dripping the prepared BOC solution into the prepared cationic compound solution at the speed of 1-3 mL/min, wherein the dosage of the BOC solution and the prepared cationic compound solution is 2:1 according to the volume ratio, and then magnetically stirring the solution for 8-12 hours at the speed of 500-800 rpm at the temperature of 20-30 ℃ to obtain white suspension;
(3) Centrifuging and washing the white suspension for 3-5 times by using N, N-dimethylacetamide (DMAc) at the rotating speed of 8000-10000 rpm, and removing Dichloromethane (DCM) to obtain a precipitate with a pore-forming function;
(4) Mixing the precipitate obtained in the step (3) with a cellulose film base material with the mass concentration of 2-5%, wherein the dosage of the two is 1-75 according to the mass ratio, then adding deionized water to prepare a suspension with the mass concentration of 0.6-0.8%, and magnetically stirring at the speed of 600-800 rpm for 8-12 h at the temperature of 20-30 ℃ to obtain a uniformly dispersed film forming solution;
(5) Casting the film forming liquid in a polytetrafluoroethylene mold, drying for 48-72 h under the environmental conditions of the temperature of 23-30 ℃ and the humidity of 50-60%, and atomizing and spraying hydrochloric acid on the surface of the film for 4-6 times in the drying process to obtain the antibacterial fresh-keeping packaging film with the porous structure.
2. The method for preparing an antibacterial freshness-retaining packaging film having a porous structure according to claim 1, wherein in the step (1), the cationic compound containing an amine group includes branched Polyethyleneimine (PEI) having a molecular weight of 800 to 25000, glycine (Gly), and polyhexamethylene biguanide hydrochloride (PHMG).
3. The method for preparing the antibacterial fresh-keeping packaging film with the porous structure according to claim 1, wherein in the step (4), the cellulose film substrate comprises a cellulose nano-fibril suspension which is prepared by a mechanical grinding method and has a diameter of 5-50 nm and an aspect ratio of more than 100, or a cellulose suspension which is prepared by mixing cellulose nano-fibrils and TEMPO oxidized cellulose nano-fibrils according to a mass ratio of 9-18.
4. The method for preparing the antibacterial fresh-keeping packaging film with the porous structure according to claim 3, wherein in the step (4), the TEMPO oxidized cellulose nanofibrils are prepared by: the method comprises the steps of oxidizing cellulose nano-fibrils prepared by a mechanical grinding method by a TEMPO oxidation method, and then carrying out rotary evaporation and concentration for 30-50 min at 50-60 ℃ to obtain the TEMPO oxidized cellulose nano-fibrils with the diameter of 2-30 nm, the length-diameter ratio of more than 50 and the surface carboxyl content of 0.8-1.6 mmol/g.
5. The preparation method of the antibacterial and refreshing packaging film with the porous structure according to claim 1, wherein in the step (5), the concentration of the hydrochloric acid is 0.5-1 mol/L, a compression type atomizer is used for atomization, the atomization rate is 0.2-0.5 mL/min, the size of the atomized hydrochloric acid is 2-10 μm, the spraying height is 10-15 cm, and the amount of the hydrochloric acid in single atomization spraying is 3-8 times of the amount of the precipitate with the pore-forming function in the film-forming liquid.
6. The use of the antibacterial freshness-retaining packaging film with a porous structure according to any one of claims 1 to 5, characterized in that the application method is: the fresh fruits and vegetables are directly wrapped by the antibacterial fresh-keeping packaging film with the porous structure, or the antibacterial fresh-keeping packaging film with the porous structure is attached to a box cover opening window of a plastic fresh-keeping box by using vacuum silicone grease, then the plastic fresh-keeping box filled with the fresh fruits and vegetables is sealed by using the box cover, and the packaged fruits and vegetables are stored under the environmental conditions of the temperature of 20-25 ℃ and the humidity of 50-70%.
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| CN114656665A (en) * | 2022-04-19 | 2022-06-24 | 江阴市德惠热收缩包装材料有限公司 | Fruit and vegetable fresh-keeping packaging film and preparation method thereof |
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| US4876146A (en) * | 1986-05-01 | 1989-10-24 | Toyo Boseki Kabushiki Kaisha | Anti-fogging multilayered film and bag produced therefrom for packaging vegetables and fruits |
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