CN117143375A - Preparation method and application of composite antibacterial preservative film based on phase change material - Google Patents
Preparation method and application of composite antibacterial preservative film based on phase change material Download PDFInfo
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- CN117143375A CN117143375A CN202311130597.7A CN202311130597A CN117143375A CN 117143375 A CN117143375 A CN 117143375A CN 202311130597 A CN202311130597 A CN 202311130597A CN 117143375 A CN117143375 A CN 117143375A
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- attapulgite
- phase change
- change material
- essential oil
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 48
- 239000012782 phase change material Substances 0.000 title claims abstract description 48
- 239000003755 preservative agent Substances 0.000 title claims abstract description 34
- 230000002335 preservative effect Effects 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229960000892 attapulgite Drugs 0.000 claims abstract description 73
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 73
- 239000000341 volatile oil Substances 0.000 claims abstract description 52
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 23
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 claims abstract description 13
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- 241000196324 Embryophyta Species 0.000 claims description 12
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- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 9
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- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
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- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 claims description 2
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- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 claims description 2
- 229940113147 shellac Drugs 0.000 claims description 2
- 241000213006 Angelica dahurica Species 0.000 claims 1
- 239000003242 anti bacterial agent Substances 0.000 abstract description 7
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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Classifications
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
-
- 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
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/26—Cellulose ethers
- C08J2301/28—Alkyl ethers
-
- 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
- C08J2329/00—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 alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
- C08J2389/00—Characterised by the use of proteins; Derivatives thereof
-
- 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
- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/01—Hydrocarbons
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
Abstract
The invention provides a preparation method of a composite antibacterial preservative film based on a phase change material, which comprises the steps of carrying out acidification treatment on attapulgite to obtain acidified attapulgite, preparing the composite attapulgite by compounding the phase change material, plant essence and the oleic attapulgite, adding the composite attapulgite into a film forming solution, stirring, casting the film into a film forming flat plate to form a film-shaped material, and stripping the film-shaped material after natural drying to obtain the composite antibacterial preservative film based on the phase change material. By adopting a load adsorption mode, the modified attapulgite is used for loading the phase change material n-tetradecane and the plant essential oil, the heat absorption and release properties of the phase change material and the advantages of easy degradation and green environmental protection of the natural antibacterial agent are fully utilized, the purposes of keeping stable environment temperature and releasing the antibacterial agent in temperature responsiveness are achieved, and the purpose of intelligently releasing antibacterial substances for food preservation is achieved.
Description
Technical Field
The invention relates to the technical field of fresh-keeping packaging materials, in particular to a preparation method and application of a composite antibacterial fresh-keeping film based on a phase-change material.
Background
Food preservation technology is important for long-term preservation of food, and new ways and materials are always sought to prolong the shelf life of food. How to develop a green pollution-free antibacterial fresh-keeping material system while maintaining food quality is one of the important challenges facing human beings. The film package is one of the common technologies for maintaining the quality of the picked fruits and vegetables and prolonging the shelf life, has the advantages of low cost, simple operation and wide applicability, and is a commonly used fruit and vegetable fresh-keeping storage material. However, the traditional film material often has the defect of poor fresh-keeping effect, can not actively kill microorganisms such as bacteria and the like, and can not reduce the problems of decay and deterioration, which is reflected in a great deal of loss caused by the proliferation of the microorganisms such as bacteria and the like in the fresh keeping process. Therefore, the antibacterial activity and the fresh-keeping effect of the fruit and vegetable fresh-keeping film material need to be improved in a green and efficient way.
In recent years, food packaging films based on phase change materials are an emerging fresh-keeping technology. When the food storage temperature exceeds the phase transition temperature of the phase transition material, the phase transition material can be converted from solid state to liquid state, and absorbs heat released by the food, so that the temperature of the food is reduced, meanwhile, the loaded antibacterial substances can be released in an accelerated manner, the deterioration speed of the antibacterial substances is delayed, and the quality guarantee period of the food is further prolonged. The plant essential oil has broad-spectrum antibacterial effect, and the addition of the plant essential oil can provide additional antibacterial effect, further inhibit the growth of bacteria, and maintain the sanitation and safety of food. Therefore, the composite antibacterial preservative film based on the phase change material can effectively prolong the shelf life of food and reduce the risks of deterioration and pollution of the food.
Disclosure of Invention
The invention provides a preparation method and application of a composite antibacterial preservative film based on a phase change material, which adopts a load adsorption mode, and adopts modified attapulgite to load phase change material n-tetradecane and plant essential oil, so that the heat absorption and release properties of the phase change material and the advantages of easy degradation and environmental protection of a natural antibacterial agent are fully utilized, the purposes of keeping stable environment temperature and releasing the antibacterial agent in temperature responsiveness are achieved, and the purpose of intelligently releasing antibacterial substances for food preservation is achieved.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the first aspect of the invention provides a preparation method of a composite antibacterial preservative film based on a phase change material, which comprises the following steps:
s1: preparation of acidified attapulgite
Treating attapulgite with 0.1M hydrochloric acid and trace hydrogen peroxide solution under stirring for 24 h, and washing with distilled water for several times until AgNO is used 3 Detection of Cl-free - Ions; sodium hexametaphosphate is used as a dispersing agent, and after stirring, the mixture is centrifuged to obtain acidified attapulgite;
s2: preparation of composite attapulgite
Fully dissolving a phase change material and plant essential oil in absolute ethyl alcohol, carrying out ultrasonic treatment for 30 min, adding acidified attapulgite, carrying out ultrasonic treatment for 30 min, and carrying out vacuum drying at 40 ℃ to obtain composite attapulgite;
s3: preparation of composite antibacterial preservative film
Adding a film forming substrate into deionized water, gradually heating to 75 ℃ under magnetic stirring, cooling to room temperature when the film forming substrate is completely dissolved, adding composite attapulgite when the solution is clear and transparent, shearing for 10 min by a high-shear homogenizing emulsifying machine until the solution is uniformly dispersed, carrying out ultrasonic treatment on the prepared suspension for 1h, casting to a film making flat plate, and peeling the film-shaped material after natural drying to prepare the composite antibacterial preservative film based on the phase change material.
Preferably, the sodium hexametaphosphate dispersant in the S1 is 0.5 weight percent of attapulgite, and the concentration of the attapulgite is 15 percent.
Preferably, the particle size of the attapulgite in the step S1 is 1500-3000 meshes.
Preferably, the phase change material in S2 is n-tetradecane.
Preferably, the plant essential oil in S2 is one or more of angelica essential oil, white orchid essential oil, peppermint essential oil, cedar essential oil, wintergreen essential oil, lavender essential oil, tea tree essential oil, mugwort leaf essential oil, clove essential oil, bay essential oil, lemon essential oil, oregano essential oil, cinnamon essential oil, lemon essential oil and garlic essential oil.
Preferably, the mass ratio of the attapulgite, the phase change material and the plant essential oil in the step S2 is 1:1:0.5.
Preferably, the mass concentration of the film forming substrate in the step S3 is 2% -8%; the mass ratio of the film forming substrate to the composite attapulgite is 1:0.25-1:1.
Preferably, the film-forming substrate is one or more of polyvinyl alcohol, chitosan, carboxymethyl cellulose, gelatin and shellac.
Based on the same conception, the second aspect of the invention provides an application of a composite antibacterial preservative film based on a phase change material, wherein the biodegradable slow-release antibacterial preservative film is used for fruit and vegetable preservative packaging or food preservative packaging.
The one or more technical schemes of the invention have the following technical effects:
according to the phase-change material-based composite antibacterial preservative film, the phase-change material-n-tetradecane and the antibacterial agent plant essential oil are dissolved in an ethanol solution, the solution is fully stirred, the solution is added into the pretreated attapulgite after ultrasonic oscillation, and the composite attapulgite is formed by drying in a vacuum drying oven. Then adding the mixture into a film forming solution for stirring, then casting the mixture onto a film forming flat plate to form a film-shaped material, and peeling the film-shaped material after natural drying to obtain the composite antibacterial preservative film based on the phase change material. The invention fully utilizes the heat absorption and release properties of the phase-change material and the advantages of easy degradation and green environmental protection of the natural antibacterial agent, achieves the purposes of keeping stable environment temperature and releasing the antibacterial agent in temperature response, and achieves the purpose of intelligently releasing antibacterial substances for food preservation. The prepared preservative film has good mechanical property, temperature control slow release property and antibacterial property, and can effectively maintain the original state of food and prolong the temperature rise time of the food.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the description of the embodiments will be briefly described below.
FIG. 1 is a preparation flow of a composite antibacterial preservative film based on a phase change material;
FIG. 2 is an infrared thermogram of chilled meat coated with the films of comparative example 1 and example 4 when thawed.
Wherein, in fig. 2: and (3) the following steps: comparative example 1 film, the following: example 4 film.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Throughout the specification, unless specifically indicated otherwise, the terms used herein should be understood as meaning as commonly used in the art. Accordingly, 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. In case of conflict, the present specification will control.
Comparative example 1
S1: adding 6% of polyvinyl alcohol by mass into deionized water, gradually heating to 75 ℃ under magnetic stirring, and stirring and cooling to room temperature when the polyvinyl alcohol solid particles are completely dissolved and the solution is clear and transparent.
S2: after the completion of the dissolution, the film-forming solution was poured into a polytetrafluoroethylene mold and dried at 55℃for 10h to obtain a film of comparative example 1, and the composite film was stored in a constant temperature and humidity oven (25℃and 75%).
Comparative example 2
S1: treating untreated attapulgite (1800 meshes) with 0.1M hydrochloric acid and a trace of hydrogen peroxide for 24 hours under stirring, and then washing with distilled water for several times until no Cl < - > is detected by AgNO 3; and then sodium hexametaphosphate is selected as a dispersing agent, the dosage is 0.5wt% of the attapulgite, the concentration of the attapulgite is 15%, and the acidized attapulgite is obtained after stirring and centrifugation.
S2: adding 6% of polyvinyl alcohol by mass into deionized water, gradually heating to 75 ℃ under magnetic stirring, and stirring and cooling to room temperature when the polyvinyl alcohol solid particles are completely dissolved and the solution is clear and transparent.
S3: adding 3% of acidified attapulgite according to the mass ratio (according to deionized water), shearing for 10 min by a high-shear homogenizing emulsifying machine until the attapulgite is uniformly dispersed, and carrying out ultrasonic treatment on the prepared suspension for 1h to obtain the film forming liquid.
S4: the film-forming solution was poured into a polytetrafluoroethylene mold and dried at 55℃for 10 hours to obtain a film of comparative example 2, and the composite film was stored in a constant temperature and humidity oven (25 ℃ C., 75%).
Comparative example 3
S1: adding 6% of polyvinyl alcohol by mass into deionized water, gradually heating to 75 ℃ under magnetic stirring, and stirring and cooling to room temperature when the polyvinyl alcohol solid particles are completely dissolved and the solution is clear and transparent.
S2: adding 3% of cinnamon essential oil (according to deionized water), shearing for 10 min by a high-shearing homogenizing emulsifying machine until the cinnamon essential oil is uniformly dispersed, and performing ultrasonic treatment on the prepared suspension for 1h to obtain a film forming liquid.
S3: the film-forming solution was poured into a polytetrafluoroethylene mold and dried at 55℃for 10 hours to obtain a film of comparative example 3, and the composite film was stored in a constant temperature and humidity oven (25 ℃ C., 75%).
As shown in fig. 1, the composite antibacterial preservative films based on the phase change material in examples 1 to 4 were all prepared by this process.
Example 1
S1: treating attapulgite with particle diameter of 1500 meshes with 0.1M hydrochloric acid and trace hydrogen peroxide for 24 hr under stirring, and washing with distilled water for several times until AgNO is used 3 Detection of Cl-free - The method comprises the steps of carrying out a first treatment on the surface of the Sodium hexametaphosphate is selected as a dispersing agent, the dosage is 0.5wt% of the attapulgite, the concentration of the attapulgite is 15%, and the acidized attapulgite is obtained after stirring and centrifugation;
s2: fully dissolving n-tetradecane and oregano essential oil in absolute ethanol according to a mass ratio of 1:0.5, performing ultrasonic treatment for 30 min, adding acidified attapulgite with the same mass as that of n-tetradecane, performing ultrasonic treatment for 30 min, and performing vacuum drying at 40 ℃ to obtain composite attapulgite;
s3: adding 2% by mass of carboxymethyl cellulose into deionized water, gradually heating to 75 ℃ under magnetic stirring, stirring and cooling to room temperature when the carboxymethyl cellulose solid particles are completely dissolved, adding 0.5% by mass (according to deionized water) of composite attapulgite, shearing for 10 min by a high-shearing homogenizing emulsifying machine until the composite attapulgite is uniformly dispersed, carrying out ultrasonic treatment on the prepared suspension for 1h to obtain film forming liquid, pouring the film forming liquid into a polytetrafluoroethylene mold, drying at 55 ℃ for 10h to obtain a composite film, and storing the composite film in a constant temperature and constant humidity box (25 ℃ and 75%).
Example 2
S1: treating 1800 mesh attapulgite with 0.1M hydrochloric acid and micro hydrogen peroxide solution for 24 hr under stirring, and washing with distilled water for several times until AgNO is used 3 Detection of Cl-free - The method comprises the steps of carrying out a first treatment on the surface of the Sodium hexametaphosphate is selected as a dispersing agent, the dosage is 0.5wt% of the attapulgite, the concentration of the attapulgite is 15%, and the acidized attapulgite is obtained after stirring and centrifugation;
s2: fully dissolving n-tetradecane and butyl essential oil in absolute ethyl alcohol according to a mass ratio of 1:0.5, carrying out ultrasonic treatment for 30 min, adding acidified attapulgite with the same mass as that of the n-tetradecane, carrying out ultrasonic treatment for 30 min, and carrying out vacuum drying at 40 ℃ to obtain composite attapulgite;
s3: adding 6% by mass of polyvinyl alcohol into deionized water, gradually heating to 75 ℃ under magnetic stirring, stirring and cooling to room temperature when polyvinyl alcohol particles are completely dissolved, adding 6% by mass (according to deionized water) of composite attapulgite, shearing for 10 min by a high-shearing homogenizing emulsifying machine until the composite attapulgite is uniformly dispersed, carrying out ultrasonic treatment on the prepared suspension for 1h to obtain a film forming liquid, pouring the film forming liquid into a polytetrafluoroethylene mold, drying at 55 ℃ for 10h to obtain a composite film, and placing the composite film into a constant temperature and humidity box (25 ℃ and 75%) for storage.
Example 3
S1: treating attapulgite with particle size of 3000 meshes with 0.1M hydrochloric acid and trace hydrogen peroxide for 24 hr under stirring, and washing with distilled water for several times until AgNO is used 3 Detection of Cl-free - The method comprises the steps of carrying out a first treatment on the surface of the Then sodium hexametaphosphate is selected as dispersant, and the dosage is0.5wt% of attapulgite, wherein the concentration of the attapulgite is 15%, and the acidized attapulgite is obtained by centrifuging after stirring;
s2: fully dissolving n-tetradecane and cinnamon essential oil in absolute ethyl alcohol according to a mass ratio of 1:0.5, carrying out ultrasonic treatment for 30 min, adding acidified attapulgite with the same mass as that of the n-tetradecane, carrying out ultrasonic treatment for 30 min, and carrying out vacuum drying at 40 ℃ to obtain composite attapulgite;
s3: adding gelatin with the mass ratio of 8% into deionized water, gradually heating to 75 ℃ under magnetic stirring, stirring and cooling to room temperature when gelatin particles are completely dissolved, adding compound attapulgite with the mass ratio of 4% (according to deionized water), shearing for 10 min by a high-shearing homogenizing emulsifying machine until the mixture is uniformly dispersed, and carrying out ultrasonic treatment on the prepared suspension for 1h to obtain the film forming liquid. Pouring the film forming liquid into a polytetrafluoroethylene mold, drying at 55 ℃ for 10h to obtain a composite film, and placing the composite film into a constant temperature and humidity box (25 ℃ and 75%) for storage.
Example 4
S1: treating attapulgite with particle size of 3000 meshes with 0.1M hydrochloric acid and trace hydrogen peroxide for 24 hr under stirring, and washing with distilled water for several times until AgNO is used 3 Detection of Cl-free - The method comprises the steps of carrying out a first treatment on the surface of the Sodium hexametaphosphate is selected as a dispersing agent, the dosage is 0.5wt% of the attapulgite, the concentration of the attapulgite is 15%, and the acidized attapulgite is obtained after stirring and centrifugation;
s2: fully dissolving n-tetradecane, oregano essential oil and clove essential oil in absolute ethyl alcohol according to a mass ratio of 1:0.5:0.5, carrying out ultrasonic treatment for 30 min, adding acidified attapulgite with the same mass as that of the n-tetradecane, carrying out ultrasonic treatment for 30 min, and carrying out vacuum drying at 40 ℃ to obtain composite attapulgite;
s3: adding 6% of gelatin in mass ratio into deionized water, gradually heating to 75 ℃ under magnetic stirring, stirring and cooling to room temperature when gelatin particles are completely dissolved, adding 6% of composite attapulgite in mass ratio (according to deionized water), shearing for 10 min by a high-shearing homogenizing emulsifying machine until the mixture is uniformly dispersed, and carrying out ultrasonic treatment on the prepared suspension for 1h to obtain the film forming liquid. Pouring the film forming liquid into a polytetrafluoroethylene mold, drying at 55 ℃ for 10h to obtain a composite film, and placing the composite film into a constant temperature and humidity box (25 ℃ and 75%) for storage.
The examples were subjected to related chemistry tests, under conditions that all adopted national related standards.
Test example 1 Water vapor Transmission test of composite film
The water vapor barrier performance of the composite film with different proportions is tested by adopting a W3-031 water vapor transmittance tester of Jinan blue opto-mechanical instrument company, the test area is 33.18 cm < 2 >, the test temperature is 38 ℃, the humidity is 90%, the thickness of the preservative film is 0.073-0.083 and mm, and the test method adopts a cup test method.
TABLE 1 Water vapor Transmission Rate of different composite films
As can be seen from Table 1, the film of comparative example 1 had a water vapor transmission rate of 451.351 g/(m) 2 24, h), the WVP value of the preservative film of comparative example 2 is reduced to 326.487 g/(m) after a small amount of attapulgite is added 2 24 h); with the increase of the content of the composite attapulgite, the water vapor permeation quantity of the composite film is gradually reduced, which is beneficial to enhancing the food fresh-keeping performance of the composite film.
Test example 2 essential oil sustained release Performance test of composite film
Taking example 2 as an example, it was placed in different food simulant solutions, the solvent being selected from the reference GB 31604.1-2005. Absorbance values were measured every 1h, 2 h, 4 h, 8 h, 12 h, 24 h, 48 h over two days and the concentration of essential oil in the solution was determined with an ultraviolet spectrophotometer. Each sample was tested in triplicate.
TABLE 2 Release amount (%)
As can be seen from table 2, as the temperature increases, the release rate of the composite film increases; the release rate of the composite film increases with time. The composite film is best released in the acidic food simulation liquid, the release rate is 34.10% at 1 and h, and the release rate reaches 54.14% after 48 and h. By integrating all data, the phase change material can respond to the change of the external temperature and regulate and control the release of active substances so as to achieve the aim that the release amount is matched with the decay trend of food at different temperatures.
Test example 3 sustained release antibacterial Performance test of composite film
Taking example 3 as an example and comparative example 3 as a control, the prepared phase-change material composite antibacterial film is cut into a disc shape by using a puncher of 6 mm, and the disc shape, the prepared phase-change material composite antibacterial film, the prepared solid culture medium, a gun head and a centrifuge tube are placed in a biosafety cabinet for ultraviolet sterilization for 30 min, and ventilation is carried out for 15 min. Taking out the bacterial suspension after the expansion culture from the refrigerator, centrifuging at 4000 rpm for 5 min, removing the liquid culture medium, adding secondary water of 1 mL, repeatedly blowing and sucking for ten times by using a pipette to uniformly mix the bacterial suspension, and preparing the bacterial suspension with the bacterial concentration of 1 multiplied by 10 5 CFU mL -1 And 1X 10 6 CFU mL -1 Is a bacterial suspension of the above-mentioned plant.
Pouring the bacterial suspension of 1 mL into a solid culture medium uniformly, covering a culture medium cover, and when the bacterial suspension is fully solidified with the solid culture medium, namely when no obvious liquid flows on the surface, lightly placing the cut disc-shaped preservative film above the solid culture medium inoculated with the strain by using sterilized tweezers, and after the bacterial suspension is fully adhered to the solid culture medium, pouring the bacterial suspension into a constant-temperature incubator at 37 ℃ for culture. Coli culture 12 h, staphylococcus aureus culture 24 h.
After the cultivation is finished, the diameter of the inhibition zone is measured by using a crisscross method and an electronic vernier caliper, three groups of parallel experiments are carried out on each group of experiments, and finally, the measured values are averaged for calculation.
Table 3 diameter of zone of inhibition (mm) of composite membrane
As can be seen from table 3, the composite film has a larger diameter of the inhibition zone for staphylococcus aureus, which indicates that the antibacterial performance for staphylococcus aureus is stronger. There is also a zone of inhibition at 5 daysThe slow release effect of the phase change material composite antibacterial film is good. Meanwhile, it can be seen that the phase change material composite antibacterial film kills 1×10 in 1 day 6 CFU mL -1 When bacteria in (2) are in a bacteria zone of more than 1 multiplied by 10 6 CFU mL -1 The method comprises the steps of carrying out a first treatment on the surface of the At 5 days, the inhibition zone of the high-concentration bacteria is obviously smaller than that of the low-concentration bacteria, which indicates that the essential oil volatilizes to some extent and the antibacterial property is slightly reduced. In the comparative example, the initial inhibition zone of the film is large due to the absence of the phase change material and the attapulgite, but the inhibition zone is rapidly reduced along with the extension of time, so that the aim of long-acting antibiosis cannot be achieved.
Test example 4 phase Change Material composite antibacterial film Performance test for prolonging food thawing time
Chilled meat was cut into pieces of about 100 g, washed with cold water, and after the surface moisture was absorbed by absorbent paper, the front and back sides of the treated chilled meat were wrapped with the comparative example 1 film and the example 4 film, respectively. The wrapped meat was placed in 13 x 13cm square media, the media gap was sealed with a sealing film, and finally the media was placed in a-18 ℃ refrigerator to cool 24 h. Chilled meat was tested for time variation from thawing in frozen state to room temperature.
As can be seen from the infrared thermal imaging chart of fig. 2, the temperature rising rate of the chilled meat wrapped by the film of example 4 is obviously lower than that of the chilled meat wrapped by the film of comparative example 1 when the chilled meat is thawed, which indicates that the phase change material n-tetradecane absorbs heat in the phase change process from solid state to liquid state, so that part of heat of the chilled meat wrapped by the film of example 4 is absorbed by the phase change material when the temperature is raised, and the temperature is raised slowly.
As can be seen from Table 4, the films of comparative example 1 and example 4 coated chilled meat exhibited no significant behavior in the frozen state, as the time taken to reach the same temperature was different during the thawing process to room temperature. However, the time difference to reach the same temperature is significantly increased in the process of cooling to room temperature, and when the temperature reaches 18 ℃, the chilled meat wrapped by the film of example 4 is 12.2min later than the chilled meat wrapped by the film of comparative example 1. Experiments show that: example 4 the film can significantly extend the thawing time of the food product during transportation.
TABLE 4 time (min) taken for chilled meat to reach the same temperature during thawing
In conclusion, the composite antibacterial preservative film based on the phase change material provided by the invention has the advantages of low cost and excellent thermal stability, and after the phase change material and the plant essential oil are loaded on the attapulgite, the prepared preservative film has good mechanical property, slow release property and antibacterial property, and can effectively maintain the original state of food and prolong the shelf life of the food.
Claims (9)
1. The preparation method of the composite antibacterial preservative film based on the phase change material is characterized by comprising the following steps of:
s1: preparation of acidified attapulgite
Treating attapulgite with 0.1M hydrochloric acid and trace hydrogen peroxide solution under stirring for 24 h, and washing with distilled water for several times until AgNO is used 3 Detection of Cl-free - Ions; sodium hexametaphosphate is used as a dispersing agent, and after stirring, the mixture is centrifuged to obtain acidified attapulgite;
s2: preparation of composite attapulgite
Fully dissolving a phase change material and plant essential oil in absolute ethyl alcohol, carrying out ultrasonic treatment for 30 min, adding acidified attapulgite, carrying out ultrasonic treatment for 30 min, and carrying out vacuum drying at 40 ℃ to obtain composite attapulgite;
s3: preparation of composite antibacterial preservative film
Adding a film forming substrate into deionized water, gradually heating to 75 ℃ under magnetic stirring, cooling to room temperature when the film forming substrate is completely dissolved, adding composite attapulgite when the solution is clear and transparent, shearing for 10 min by a high-shear homogenizing emulsifying machine until the solution is uniformly dispersed, carrying out ultrasonic treatment on the prepared suspension for 1h, casting to a film making flat plate, and peeling the film-shaped material after natural drying to prepare the composite antibacterial preservative film based on the phase change material.
2. The method for preparing the composite antibacterial preservative film based on the phase change material according to claim 1, which is characterized in that: the dosage of the sodium hexametaphosphate dispersant in the S1 is 0.5wt% of that of the attapulgite, and the concentration of the attapulgite is 15%.
3. The method for preparing the composite antibacterial preservative film based on the phase change material according to claim 1, which is characterized in that: the particle size of the attapulgite in the step S1 is 1500-3000 meshes.
4. The method for preparing the composite antibacterial preservative film based on the phase change material according to claim 1, which is characterized in that: the phase change material in the S2 is n-tetradecane.
5. The method for preparing the composite antibacterial preservative film based on the phase change material according to claim 1, which is characterized in that: the plant essential oil in the step S2 is one or more of Chinese angelica essential oil, white orchid leaf essential oil, peppermint essential oil, cedar essential oil, wintergreen essential oil, lavender essential oil, tea tree essential oil, mugwort leaf essential oil, clove essential oil, bay essential oil, lemon essential oil, oregano essential oil, cinnamon essential oil, lemon essential oil and garlic essential oil.
6. The method for preparing the composite antibacterial preservative film based on the phase change material according to claim 1, which is characterized in that: the mass ratio of the attapulgite to the phase change material to the plant essential oil in the step S2 is 1:1:0.5.
7. The method for preparing the composite antibacterial preservative film based on the phase change material according to claim 1, which is characterized in that: the mass concentration of the film forming substrate in the step S3 is 2% -8%; the mass ratio of the film forming substrate to the composite attapulgite is 1:0.25-1:1.
8. The method for preparing the composite antibacterial preservative film based on the phase change material, which is characterized by comprising the following steps of: the film forming substrate is one or more of polyvinyl alcohol, chitosan, carboxymethyl cellulose, gelatin and shellac.
9. The application of the composite antibacterial preservative film based on the phase change material according to any one of claims 1 to 8, which is characterized in that: the biodegradable slow-release antibacterial preservative film is used for fruit and vegetable fresh-keeping packaging or food fresh-keeping packaging.
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