CN113004568A - Composite antibacterial food packaging film and preparation method thereof - Google Patents
Composite antibacterial food packaging film and preparation method thereof Download PDFInfo
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- CN113004568A CN113004568A CN202110472638.5A CN202110472638A CN113004568A CN 113004568 A CN113004568 A CN 113004568A CN 202110472638 A CN202110472638 A CN 202110472638A CN 113004568 A CN113004568 A CN 113004568A
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- C—CHEMISTRY; METALLURGY
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/14—Chemical modification with acids, their salts or anhydrides
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- C—CHEMISTRY; METALLURGY
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- 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
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K3/08—Metals
- C08K2003/0806—Silver
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Abstract
The invention discloses a composite antibacterial food packaging film and a preparation method thereof. The preparation route is 'casting film preparation-sulfonation-ion exchange-in-situ reduction': the preparation method comprises the steps of preparing casting slurry by taking polylactic acid as a film forming material, taking chitosan as a natural antibacterial agent and ethyl acetate as an organic solvent, preparing a chitosan polylactic acid blending base film by a casting method, reacting with a sulfonating agent to prepare a sulfonated film, further exchanging with metal ions with excellent antibacterial activity such as silver ions and copper ions to prepare an ion base film, and preparing the simple substance nano-based antibacterial food packaging film by an in-situ reduction reaction on the basis. The antibacterial film prepared by the invention combines the advantages of the natural antibacterial agent and the inorganic metal antibacterial agent, and overcomes the defect of weak antibacterial performance of the natural antibacterial agent, so that the antibacterial performance of the film is stronger.
Description
Technical Field
The invention relates to the technical field of food packaging, in particular to a composite antibacterial food packaging film and a preparation method thereof.
Background
Food safety is closely related to human health, and with the development of economy and society, people pay more and more attention to food safety. Food packaging is an important factor affecting food safety. The antibacterial food packaging is a new field which is gradually developed in recent years, plays a positive role in slowing down food spoilage caused by microorganisms, and has a wide development prospect. At present, most of the methods adopted for preparing the antibacterial food packaging film add natural antibacterial agents such as chitosan, plant essential oil, tea polyphenol and the like in the preparation process. For example, chinese patent 201711362453.9 discloses an antibacterial environment-friendly packaging film and a method for preparing the same, wherein the antibacterial effect is achieved by adding plant essential oil during the preparation process. The plant essential oil has the advantages of being natural and non-toxic, but the membrane prepared only by using the plant essential oil as an antibacterial component has the problem of low antibacterial efficiency and continuous antibacterial performance. Chinese patent 201710013317.2 discloses a novel antibacterial food packaging film prepared from chitosan, gelatin and cinnamon essential oil, wherein cinnamon essential oil is a common plant essential oil and is used as an antibacterial agent, and chitosan is used as both an antibacterial agent and a film-forming material. Chitosan is a common natural organic antibacterial material, can inhibit the growth and reproduction of various bacteria, has the advantages of being capable of forming films, non-toxic and biodegradable, but the film prepared from chitosan only has the defect of weak antibacterial performance.
Disclosure of Invention
The invention provides a novel composite antibacterial food packaging film and a preparation method thereof, aiming at solving the problem that a natural antibacterial agent used in the antibacterial food packaging film in the prior art is low in antibacterial performance. The antibacterial film prepared by the invention combines the advantages of the natural antibacterial agent and the inorganic metal antibacterial agent, and overcomes the defect of weak antibacterial performance of the natural antibacterial agent, so that the antibacterial performance of the film is stronger, and the synergistic effect is obtained.
The technical scheme adopted by the invention is as follows.
The invention provides a preparation method of a composite antibacterial food packaging film, which comprises the following steps:
(1) casting and film making: preparing casting slurry by taking polylactic acid as a film forming material, chitosan as a natural antibacterial agent and ethyl acetate as an organic solvent, and preparing a chitosan polylactic acid blended base film by casting;
(2) sulfonation: reacting the chitosan polylactic acid blended basement membrane prepared in the step (1) with a sulfonating agent to prepare a sulfonated membrane;
(3) ion exchange: immersing the sulfonated membrane prepared in the step (2) into a metal ion antibacterial agent solution, enabling metal ions to be combined with sulfonate radicals in the membrane by ionic bonds through ion exchange, and washing and drying to obtain an ion-based membrane;
(4) in-situ reduction: and (4) reducing ions in the ion-based antibacterial film prepared in the step (3) into simple substance nano particles in situ to prepare the simple substance nano-based antibacterial film, namely the composite antibacterial food packaging film.
In the invention, in the step (1), the casting slurry comprises the following raw materials in parts by weight: 10-30 parts of polylactic acid, 80-130 parts of ethyl acetate, 5-20 parts of chitosan and 0.2-1.0 part of emulsifier.
In the invention, the emulsifier is polyoxyethylene castor oil or sorbitan fatty acid ester.
In the invention, the casting slurry is directly poured onto a glass flat plate for casting to form a film; or pouring the casting slurry onto a glass flat plate fixed with the porous polyester film for casting to form a film, wherein the porous polyester film has the advantages of improving the strength of the final film and prolonging the service life of the film; the casting slurry used for casting film formation has a temperature of 75 to 80 ℃.
In the invention, the sulfonating agent is sulfamic acid; the metal ion antibacterial agent solution is 0.1mol/L silver nitrate or copper nitrate solution; the weight ratio of the polylactic acid to the sulfamic acid to the metal ion antibacterial agent solution is (10-30): (20-30): (20-40).
In the invention, the weight ratio of polylactic acid, chitosan and metal ion antibacterial agent solution is as follows: 20:10: 30-20: 5: 30.
In the invention, in the step (4), the in-situ reduction condition is ultraviolet light or visible light, or a reducing agent ethanol, cinnamon extract or citric acid is adopted.
The invention also provides a composite antibacterial food packaging film prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
the polylactic acid, chitosan and other raw materials adopted by the invention are natural and non-toxic, ethyl acetate is an organic solvent, and metal ions with excellent antibacterial activity, such as silver, can be introduced into the membrane through ion exchange, so that the defect that the membrane prepared only from chitosan is weak in antibacterial performance can be solved.
Drawings
The present invention will become more apparent and readily understood from the following description of exemplary embodiments thereof taken in conjunction with the accompanying drawings.
FIG. 1 is a schematic view of the preparation process of the present invention.
The names of the parts indicated by the numerical references in the drawings are as follows: 1-raw material mixing container, 2-raw material mixed liquid, 3-stirring magneton, 4-tape casting, 5-glass plate, 6-chitosan polylactic acid blended basement membrane (semi-solid), 7-impregnation container, 8-ultrapure water, 9-chitosan polylactic acid blended basement membrane (solid), 10-sulfonating agent, 11-sulfonation reaction, 12-sulfonation membrane, 13-metal ion antibacterial agent, 14-ion exchange reaction, 15-ion basement membrane, 16-in-situ reduction reaction and 17-simple substance nano-based antibacterial food packaging membrane.
Detailed Description
Preferred embodiments of the present invention will be described in further detail below with reference to the accompanying drawings.
Example 1
A composite antibacterial food packaging film is prepared from the following raw materials in parts by weight: 20 parts of polylactic acid, 100 parts of ethyl acetate, 10 parts of chitosan, 0.1 part of polyoxyethylene castor oil, 30 parts of sulfamic acid and 30 parts of 0.1mol/L silver nitrate solution. The preparation method comprises the following steps:
(1) weighing 20 parts of polylactic acid, putting the polylactic acid into a beaker, adding 100 parts of ethyl acetate, 10 parts of chitosan and 0.1 part of polyoxyethylene castor oil, setting the temperature to 80 ℃, and magnetically stirring for 24 hours to form uniform raw material mixed liquor;
(2) slowly pouring the mixed solution onto a glass plate, casting the mixed solution into a film with the thickness of 300 microns, standing the film for 30 minutes, immersing the glass plate into ultrapure water, standing the glass plate for 24 hours, and peeling the film from the glass plate to obtain a chitosan polylactic acid blended base film;
(3) immersing the prepared membrane into 30 parts of sulfamic acid aqueous solution, taking out the membrane after sulfonation reaction for 3 hours, washing the membrane for multiple times by using ultrapure water until all sulfamic acid remained on the surface of the membrane is washed away, and drying to obtain a sulfonated membrane;
(4) immersing the prepared sulfonated membrane into 30 parts of 0.1mol/L silver nitrate solution for ion exchange, taking out the membrane after 24 hours, and washing the membrane for multiple times by using ultrapure water until all the silver nitrate solution remained on the surface of the membrane is washed away;
(5) after drying the prepared film, placing the film in ultraviolet light for irradiation treatment for 24 hours, the composite antibacterial food packaging film of the embodiment 1 can be obtained.
Example 2
A composite antibacterial food packaging film is prepared from the following raw materials in parts by weight: 20 parts of polylactic acid, 100 parts of ethyl acetate, 10 parts of chitosan, 0.1 part of polyoxyethylene castor oil, 15 parts of porous polyester film, 30 parts of sulfamic acid and 30 parts of 0.1mol/L silver nitrate solution. The preparation method comprises the following steps:
(1) weighing 20 parts of polylactic acid, putting the polylactic acid into a beaker, adding 100 parts of ethyl acetate, 10 parts of chitosan and 0.1 part of polyoxyethylene castor oil, setting the temperature to 80 ℃, and magnetically stirring for 24 hours to form uniform raw material mixed liquor;
(2) fixing 15 parts of porous polyester film on a glass flat plate, slowly pouring the reaction mixed solution on the porous polyester film, casting the porous polyester film into a film with the thickness of 200 microns, standing for 30 minutes, immersing the glass flat plate into ultrapure water, standing for 24 hours, and peeling the film from the glass flat plate to obtain a chitosan polylactic acid blended basement membrane;
(3) immersing the prepared membrane into 30 parts of sulfamic acid, taking out the membrane after sulfonation reaction for 3 hours, washing the membrane for multiple times by using ultrapure water until all sulfamic acid remained on the surface of the membrane is washed away, and drying to obtain a sulfonated membrane;
(4) immersing the prepared sulfonated membrane into 30 parts of 0.1mol/L silver nitrate solution for ion exchange, taking out the membrane after 24 hours, and washing the membrane for multiple times by using ultrapure water until all the silver nitrate solution remained on the surface of the membrane is washed away;
(5) after drying the film prepared above, placing the film in ultraviolet light for irradiation treatment for 24 hours, the composite antibacterial food packaging film of example 2 can be obtained.
Example 3
Essentially the same as in example 1, except that: the antibacterial food packaging film of example 3 was obtained by changing the thickness of chitosan from 10 parts to 5 parts and from 200 micrometers to 100 micrometers, with the remaining conditions unchanged.
Example 4
Essentially the same as in example 1, except that: the silver nitrate solution was changed to a copper nitrate solution, and the ultraviolet irradiation treatment was changed to 30 parts per liter of a cinnamon extract solution of 0.1mol, to obtain the antibacterial food packaging film of example 4.
Example 5
Essentially the same as example 2, except that: the silver nitrate solution was changed to a copper nitrate solution, and the ultraviolet irradiation treatment was changed to 30 parts per liter of a cinnamon extract solution of 0.1mol, to obtain the antibacterial food packaging film of example 5.
The 5 kinds of antibacterial food packaging films obtained in examples 1 to 5 and a control group 1 (i.e., a common film containing no antibacterial component) were subjected to a zone of inhibition test using bacteria of standard strains of Escherichia coli ATCC25922 and Staphylococcus aureus ATCC6538, and the test method was: 1 ml of bacterial liquid with the concentration of 0.120 (OD 600 value) is poured into LB plate culture medium, and is gently shaken to enable the bacterial liquid to be evenly distributed on the surface of the plate, and then the plate is placed into a biochemical incubator to be cultured for 8 hours at the temperature of 37 ℃, and the experimental results are shown in Table 1. In addition, 2 kinds of antibacterial food packaging films obtained in examples 1-2 and a control group 2 (i.e., an antibacterial film prepared from only chitosan as a natural antibacterial agent) were subjected to a bacteriostasis rate test by: the 3 kinds of antibacterial films are respectively put into 2 ml of bacterial liquid with the concentration of 0.120 (OD 600 value), and put into a biochemical incubator together with the control group 3 (namely 2 ml of bacterial liquid with the same concentration without the antibacterial film), and cultured for 24 hours under the condition of 37 ℃, and the experimental result is that: the concentration of the bacterial liquid containing the 2 antibacterial food packaging films obtained in the example 1-2 is not increased, and the inhibition rate of the bacterial liquid on bacteria reaches 100 percent; the concentration of the bacterial liquid of the control group 2 is obviously increased; the increase of the concentration of the bacterial liquid in the control group 3 was the largest. It can be seen that the antibacterial film prepared only from chitosan has a certain antibacterial effect, but cannot completely inhibit the growth and propagation of bacteria.
TABLE 1 antibacterial food packaging film zone of inhibition experiment results
In light of the above teachings, those skilled in the art will be able to make various modifications and alterations to the above embodiments without departing from the scope of the invention. It will be appreciated by persons skilled in the art that the foregoing detailed description is provided for the purpose of illustrating the invention and is not to be construed as limiting the invention.
Claims (7)
1. The preparation method of the composite antibacterial food packaging film is characterized by comprising the following steps:
(1) casting and film making: preparing casting slurry by taking polylactic acid as a film forming material, chitosan as a natural antibacterial agent and ethyl acetate as an organic solvent, and preparing a chitosan polylactic acid blended base film by casting;
(2) sulfonation: reacting the chitosan polylactic acid blended basement membrane prepared in the step (1) with a sulfonating agent to prepare a sulfonated membrane;
(3) ion exchange: immersing the sulfonated membrane prepared in the step (2) into a metal ion antibacterial agent solution, enabling metal ions to be combined with sulfonate radicals in the membrane by ionic bonds through ion exchange, and washing and drying to obtain an ion-based membrane;
(4) in-situ reduction: and (4) reducing ions in the ion-based antibacterial film prepared in the step (3) into simple substance nano particles in situ to prepare the simple substance nano-based antibacterial film, namely the composite antibacterial food packaging film.
2. The production method according to claim 1, wherein in the step (1), the casting slurry comprises the following raw materials in parts by weight: 10-30 parts of polylactic acid, 80-130 parts of ethyl acetate, 5-20 parts of chitosan and 0.2-1.0 part of emulsifier.
3. The method according to claim 2, wherein the emulsifier is a polyoxyethylene castor oil or a sorbitan fatty acid ester.
4. A production method according to claim 1 or 2, wherein the casting slurry is directly poured onto a flat glass plate to be cast into a film; or pouring the casting slurry onto a glass flat plate fixed with the porous polyester film for casting to form a film; the casting slurry used for casting film formation has a temperature of 75 to 80 ℃.
5. The process according to claim 1, wherein the sulfonating agent is sulfamic acid; the metal ion antibacterial agent solution is 0.1mol/L silver nitrate or copper nitrate solution; the weight ratio of the polylactic acid to the sulfamic acid to the metal ion antibacterial agent solution is (10-30): (20-30): (20-40).
6. The method according to claim 1, wherein in step (4), the in-situ reduction conditions are ultraviolet light or visible light, or ethanol, cinnamon extract or citric acid, which are reducing agents, is used.
7. A composite antibacterial food packaging film prepared according to the preparation method of claim 1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114907678A (en) * | 2022-05-06 | 2022-08-16 | 青岛科技大学 | pH response polylactic acid-based composite membrane and preparation method thereof |
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| CN101798403A (en) * | 2010-03-30 | 2010-08-11 | 东华大学 | Method for preparing chitosan/polyving alcohol/polylactic acid blended dense membrane |
| CN106215724A (en) * | 2016-07-28 | 2016-12-14 | 华南理工大学 | A kind of antibacterial composite nanometer filtering film of loading nano silvery and preparation method thereof |
| CN110639372A (en) * | 2019-06-26 | 2020-01-03 | 浙江工业大学 | Method for preparing antibacterial anti-swelling cation exchange membrane |
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2021
- 2021-04-29 CN CN202110472638.5A patent/CN113004568A/en active Pending
Patent Citations (3)
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| CN101798403A (en) * | 2010-03-30 | 2010-08-11 | 东华大学 | Method for preparing chitosan/polyving alcohol/polylactic acid blended dense membrane |
| CN106215724A (en) * | 2016-07-28 | 2016-12-14 | 华南理工大学 | A kind of antibacterial composite nanometer filtering film of loading nano silvery and preparation method thereof |
| CN110639372A (en) * | 2019-06-26 | 2020-01-03 | 浙江工业大学 | Method for preparing antibacterial anti-swelling cation exchange membrane |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114907678A (en) * | 2022-05-06 | 2022-08-16 | 青岛科技大学 | pH response polylactic acid-based composite membrane and preparation method thereof |
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