CN112940333A - Antibacterial food packaging film and preparation method thereof - Google Patents
Antibacterial food packaging film and preparation method thereof Download PDFInfo
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- CN112940333A CN112940333A CN202110472589.5A CN202110472589A CN112940333A CN 112940333 A CN112940333 A CN 112940333A CN 202110472589 A CN202110472589 A CN 202110472589A CN 112940333 A CN112940333 A CN 112940333A
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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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—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 aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—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 aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
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- C08J2325/00—Characterised 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 aromatic carbocyclic ring; Derivatives of such polymers
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- C08J2325/00—Characterised 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 aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
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Abstract
The invention discloses an antibacterial food packaging film and a preparation method thereof. The preparation route is 'cross-linking polymerization-sulfonation (optional) -ion exchange-in-situ reduction': styrene and/or p-styrene sulfonate is used as a monomer, p-phenylethene is used as a cross-linking agent, a base membrane is prepared by cross-linking polymerization reaction in a porous polymer matrix, ion base membranes are prepared by exchange with silver ions, copper ions and the like, and the simple substance nano-based antibacterial food packaging membrane is further prepared by in-situ reduction reaction. The antibacterial film prepared by the invention has stable antibacterial components, excellent antibacterial performance and the characteristic of replaceable antibacterial components.
Description
Technical Field
The invention relates to the technical field of food packaging, in particular to an antibacterial food packaging film and a preparation method thereof.
Background
Food safety is closely related to human health, and food packaging is an important factor affecting food safety. The food packaging film with excellent antibacterial property is developed, so that the food spoilage speed can be effectively slowed down, the quality guarantee period of food is prolonged, and the food safety is guaranteed.
At present, the antibacterial food packaging film is mostly prepared by adopting a physical blending method, namely, film-forming materials such as polyethylene, polypropylene, polylactic acid and the like are used as matrixes, antibacterial agents are added into the matrixes, and the antibacterial agents are physically mixed and then prepared into a film by the methods of co-extrusion, tape casting, solvent evaporation, pressing, electrostatic spinning and the like. For example, chinese patent 201710532864.1 discloses a method of preparing an antibacterial film by an extrusion casting method by blending an antibacterial agent and a film-forming material. However, a significant problem in the preparation of antibacterial films by this method is the stability of the antibacterial agent. This is because there is no chemical bond between the antibacterial agent and the film matrix, and therefore, the antibacterial agent may be detached or peeled off from the film, resulting in a decrease in antibacterial effect. In addition, the antibacterial agent used in the method is organic acid anisic acid, betulinic acid, and ursolic acid. The organic acid belongs to a natural antibacterial material, has the advantages of safety and no toxicity, but has low antibacterial efficiency and a narrow antibacterial range. Chinese patent 201710013317.2 discloses a method for preparing a novel edible antibacterial food packaging film by blending an antibacterial agent and a film-forming material and evaporating a solvent. The plant essential oil used in the method is a natural antibacterial agent, and has the problems of easy volatilization, easy decomposition and weak antibacterial property, so that the prepared antibacterial film has the defects of poor stability and low antibacterial performance.
Disclosure of Invention
In order to solve the problems of unstable antibacterial components and low antibacterial efficiency of the food packaging film in the prior art, the invention provides an antibacterial food packaging film and a preparation method thereof. The antibacterial food packaging film has strong binding force between the antibacterial agent and the film matrix and stable antibacterial performance.
The technical scheme adopted by the invention is as follows.
The invention provides a preparation method of an antibacterial food packaging film, which comprises the following specific steps:
(1) taking p-styrene sulfonate and styrene as monomers and p-phenylethene as a cross-linking agent, and performing cross-linking polymerization reaction in a porous polymer matrix to prepare a polystyrene sulfonate membrane;
(2) immersing the polystyrene sulfonate membrane prepared in the step (1) into a metal ion antibacterial agent solution, and enabling metal ions in the metal ion antibacterial agent to be combined with sulfonate in the polystyrene sulfonate membrane through ion exchange; after the reaction is finished, washing and drying to obtain an ion-based membrane;
(3) and reducing ions in the ion-based film into simple substance nano particles in situ to prepare the simple substance nano-based antibacterial film, namely the antibacterial food packaging film.
In the step (1), the p-styrene sulfonate is lithium p-styrene sulfonate or sodium p-styrene sulfonate; the crosslinking polymerization reaction comprises the following raw materials in parts by weight: 3-10 parts of p-styrene sulfonate, 5-10 parts of water, 0.5-2 parts of p-phenylenediethylene, 2-5 parts of styrene, 1-5 parts of porous polymer matrix, 0.2-1.0 part of emulsifier and 0.2-0.6 part of initiator.
The invention also provides another preparation method of the antibacterial food packaging film, which is characterized in that in the step (1), the monomer p-styrene sulfonate is omitted, the polystyrene film is prepared through cross-linking polymerization reaction, and then the polystyrene film is reacted with a sulfonating agent to prepare the polystyrene sulfonic acid film; in the step (2), the polystyrene sulfonate membrane is replaced by a polystyrene sulfonate membrane correspondingly.
In the step (1), the cross-linking polymerization reaction comprises the following raw materials in parts by weight: 0.5-2 parts of p-phenylene divinyl, 2-5 parts of styrene, 1-5 parts of porous polymer matrix and 0.2-0.6 part of initiator.
In the step (1), the sulfonating agent is sulfamic acid or concentrated sulfuric acid, and the weight ratio of the porous polymer matrix to the sulfonating agent is 1: 30-5: 10.
In the invention, the porous polymer matrix is polyethylene or polypropylene; the metal ion antibacterial agent is one or more of silver nitrate, copper nitrate or zinc nitrate, and the concentration of the metal ion antibacterial agent is 0.1 mol/L. The weight ratio of the porous polymer matrix to the metal ion antibacterial agent solution is 1: 40-5: 20.
In the invention, in the cross-linking polymerization reaction, the emulsifier is polyoxyethylene castor oil, and the initiator is benzoyl peroxide.
In the invention, ultraviolet light or visible light conditions are adopted during in-situ reduction, or reducing agents such as citric acid or ethanol are adopted for reduction.
The invention further provides the antibacterial food packaging film prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
the antibacterial component in the antibacterial food packaging film is combined with the polymer film matrix in a chemical bond mode, the binding force is stronger, and the problems of stability, uneven dispersion and easy aggregation of the antibacterial material in the film prepared by a common physical blending method are 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 system of examples 2 and 4 of the present invention.
The names of the parts indicated by the numerical references in the drawings are as follows: 1-reaction container, 2-reactant mixed liquid, 3-stirring magneton, 4-impregnation container, 5-porous polymer substrate, 6-polyester film, 7-stainless steel plate, 8-pressure, 9-cross-linking polymerization reaction, 10-polystyrene film, 11-sulfonating agent, 12-sulfonation reaction, 13-polystyrene sulfonic acid film, 14-metal ion antibacterial agent, 15-ion exchange reaction, 16-ion base film, 17-in-situ reduction reaction and 18-simple substance nano-base antibacterial food packaging film.
Detailed Description
Preferred embodiments of the present invention will be described in further detail below with reference to the accompanying drawings.
The preparation flow systems of example 2 and example 4 of the present invention are shown in FIG. 1.
Example 1
A novel antibacterial food packaging film is prepared from the following raw materials in parts by weight: 10 parts of lithium p-styrene sulfonate, 5 parts of water, 0.6 part of p-phenylenediethylene, 4.4 parts of styrene and 4 parts of porous polypropylene; 0.1 part of polyoxyethylene castor oil, 0.05 part of benzoyl peroxide and 30 parts of 0.1 mol/L silver nitrate solution. The preparation method comprises the following steps:
(1) weighing 10 parts of lithium p-styrene sulfonate, putting the lithium p-styrene sulfonate into a beaker, adding 5 parts of water, 0.6 part of p-styrene, 4.4 parts of styrene and 0.1 part of polyoxyethylene castor oil, and magnetically stirring for 24 hours to form uniform milky reaction mixed liquid;
(2) adding 0.05 part of benzoyl peroxide into the mixed solution, stirring uniformly, then putting 4 parts of porous polypropylene matrix into the mixed solution, taking out the matrix after the matrix fully absorbs the mixed solution, placing the matrix between two transparent polyester films, and then placing the matrix between two stainless steel plates. The stainless steel plate was fixed and placed in an oven to react at 80 ℃ for 8 hours. After the reaction is finished, peeling the film from the polyester film;
(3) immersing the prepared membrane into 30 parts of 0.1 mol/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;
(4) and drying the prepared film, and then placing the film in ultraviolet light for irradiation treatment for 24 hours to obtain the antibacterial food packaging film.
Example 2
A novel antibacterial food packaging film is prepared from the following raw materials in parts by weight: 7 parts of styrene, 1 part of p-phenylene divinyl, 2 parts of porous polypropylene, 0.07 part of benzoyl peroxide, 20 parts of sulfamic acid and 30 parts of 0.1 mol/L silver nitrate solution. The preparation method comprises the following steps:
(1) weighing 7 parts of styrene, putting the styrene into a beaker, adding 1 part of p-phenylenediethylene, and magnetically stirring for 1 hour to form a uniform reaction mixed solution;
(2) adding 0.07 part of benzoyl peroxide into the mixed solution, stirring uniformly, then putting 2 parts of porous polypropylene matrix into the mixed solution, taking out the matrix after the matrix fully absorbs the mixed solution, placing the matrix between two transparent polyester films, and then placing the matrix between two stainless steel plates. The stainless steel plate was fixed and placed in an oven to react at 80 ℃ for 8 hours. After the reaction is finished, peeling the film from the polyester film;
(3) immersing the prepared membrane into 20 parts of sulfamic acid aqueous solution, taking out the membrane after sulfonation reaction for 2 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 polystyrene sulfonic acid membrane;
(4) immersing the prepared membrane into 30 parts of 0.1 mol/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) and drying the prepared film, and then placing the film in ultraviolet light for irradiation treatment for 24 hours to obtain the antibacterial food packaging film.
Example 3
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 of a 0.1 mol/l citric acid solution, to obtain the antibacterial food packaging film of example 3.
Example 4
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 of a 0.1 mol/l citric acid solution, to obtain the antibacterial food packaging film of example 4.
The four antibacterial food packaging films obtained in examples 1 to 4 and a control group (i.e., a common film containing no metal 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 methods were: 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. Meanwhile, the antibacterial food packaging films obtained in example 1 and example 2 were placed in a 0.1 mol/l sodium chloride solution for 15 hours for exchange, and the turbidity change of the solution before and after the measurement was observed, and the results showed: the turbidity of the solution before and after the exchange is not obviously changed, which indicates that the antibacterial component silver stably exists in the membrane and is not exchanged into the solution to neutralize chloride ions to generate insoluble silver chloride. Therefore, in combination with table 1, it can be seen that the antibacterial food packaging film prepared by the present patent has stable antibacterial properties.
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 (10)
1. The preparation method of the antibacterial food packaging film is characterized by comprising the following specific steps:
(1) taking p-styrene sulfonate and styrene as monomers and p-phenylethene as a cross-linking agent, and performing cross-linking polymerization reaction in a porous polymer matrix to prepare a polystyrene sulfonate membrane;
(2) immersing the polystyrene sulfonate membrane prepared in the step (1) into a metal ion antibacterial agent solution, and enabling metal ions in the metal ion antibacterial agent to be combined with sulfonate in the polystyrene sulfonate membrane through ion exchange; after the reaction is finished, washing and drying to obtain an ion-based membrane;
(3) and reducing ions in the ion-based film into simple substance nano particles in situ to prepare the simple substance nano-based antibacterial film, namely the antibacterial food packaging film.
2. The preparation method according to claim 1, wherein in the step (1), the cross-linking polymerization reaction comprises the following raw materials in parts by weight: 3-10 parts of p-styrene sulfonate, 5-10 parts of water, 0.5-2 parts of p-phenylenediethylene, 2-5 parts of styrene, 1-5 parts of porous polymer matrix, 0.2-1.0 part of emulsifier and 0.2-0.6 part of initiator.
3. The method according to claim 1, wherein in the step (1), the p-styrene sulfonate is lithium p-styrene sulfonate or sodium p-styrene sulfonate.
4. The preparation method according to claim 1, wherein in the step (1), the polystyrene sulfonate monomer is omitted, a polystyrene film is prepared through a cross-linking polymerization reaction, and then the polystyrene film is reacted with a sulfonating agent to prepare a polystyrene sulfonic acid film; in the step (2), the polystyrene sulfonate membrane is replaced by a polystyrene sulfonate membrane correspondingly.
5. The preparation method according to claim 4, wherein the cross-linking polymerization reaction comprises the following raw materials in parts by weight: 0.5-2 parts of p-phenylene divinyl, 2-5 parts of styrene, 1-5 parts of porous polymer matrix and 0.2-0.6 part of initiator.
6. The preparation method according to claim 4, wherein the sulfonating agent is sulfamic acid or concentrated sulfuric acid, and the weight ratio of the porous polymer matrix to the sulfonating agent is 1: 30-5: 10.
7. The method of claim 1 or 4, wherein the porous polymer matrix is polyethylene or polypropylene; the metal ion antibacterial agent is one or more of silver nitrate, copper nitrate or zinc nitrate, and the concentration of the metal ion antibacterial agent is 0.1 mol/L.
8. The preparation method according to claim 7, wherein the weight ratio of the porous polymer matrix to the metal ion antibacterial agent is 1:40 to 5: 20.
9. The method of claim 1 or 4, wherein the in-situ reduction is carried out by using ultraviolet light or visible light, or using citric acid or ethanol as a reducing agent.
10. An antibacterial food packaging film produced by the production method according to claim 1 or 4.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1114237A (en) * | 1994-06-20 | 1996-01-03 | 中国科学院化学研究所 | Ionic exchange membrane using polypropylene micro-porous membrane as basal membrane and making method thereof |
| JPH09302137A (en) * | 1996-05-15 | 1997-11-25 | Nippon Shokubai Co Ltd | Antibacterial resin |
| 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 |
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- 2021-04-29 CN CN202110472589.5A patent/CN112940333A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1114237A (en) * | 1994-06-20 | 1996-01-03 | 中国科学院化学研究所 | Ionic exchange membrane using polypropylene micro-porous membrane as basal membrane and making method thereof |
| JPH09302137A (en) * | 1996-05-15 | 1997-11-25 | Nippon Shokubai Co Ltd | Antibacterial resin |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 张丹慧等: "《贵金属/石墨烯纳米复合材料的合成及性能》", 31 December 2015, 国防工业出版社 * |
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