CN108148212B - Preparation method of chitosan antibacterial film and product thereof - Google Patents
Preparation method of chitosan antibacterial film and product thereof Download PDFInfo
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- CN108148212B CN108148212B CN201810063719.8A CN201810063719A CN108148212B CN 108148212 B CN108148212 B CN 108148212B CN 201810063719 A CN201810063719 A CN 201810063719A CN 108148212 B CN108148212 B CN 108148212B
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- tartaric acid
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention relates to the field of food packaging, in particular to a preparation method of a chitosan antibacterial film and a product thereof. The preparation method of the chitosan antibacterial film provided by the invention comprises the following steps: soaking chitosan in tartaric acid, and washing with anhydrous ethanol; mixing tartaric acid and 1-ethyl-3-methylimidazolium acetate system, adding washed chitosan, adding chitinase, and cooling to obtain a coating solution; and scraping the obtained coating liquid, placing the coating liquid in a solvent for phase transfer film forming, and drying to obtain the chitosan antibacterial film. The chitosan bacteriostatic film obtained by the invention has good bacteriostatic effect and high film strength.
Description
Technical Field
The invention relates to the field of packaging, in particular to a preparation method of a chitosan antibacterial film and a product thereof.
Background
With the rapid development of economy, food safety issues have attracted global attention as topics that are closely related to our lives. The fresh food can be rotten and deteriorated when contacting with microorganisms in the environment, the food is difficult to preserve for a long time, and the preservation time of the food can be prolonged only by using materials with antibacterial property.
At present, petroleum-based high polymer materials are dominant in common food packaging materials, but the petroleum-based high polymer materials pollute the environment, namely, cause a white pollution problem. Especially, with the continuous consumption of petroleum-based polymer materials such as polyethylene, polyamide and the like, the human society faces unprecedented energy and environmental crises, and the polymer plastics are not easy to degrade, so that the problem of increasingly serious white pollution is caused by the large-scale use of the packaging materials. Therefore, under the current background, the discovery of renewable biomass resources for preparing antibacterial materials has important practical significance for relieving the increasingly serious crisis of fossil resources, and is a powerful way for solving the current predicaments. As a natural polymer, chitosan has the advantages of abundant raw materials, rapid regeneration, good environmental and biocompatibility, biodegradability, certain antibacterial effect, low toxicity, no harm to the ecological environment and the like, and is increasingly paid more attention by people. Therefore, the chitosan is used as a natural biomass resource with the dosage second to that of cellulose, has very wide development prospect in the field of food packaging, can reduce the dependence on petroleum-based packaging materials, and accords with the strategic significance of sustainable development.
Disclosure of Invention
The invention aims to provide a preparation method of a chitosan antibacterial film and a product thereof, so as to solve the problems in the prior art.
According to one aspect of the present invention, the present invention provides a method for preparing a chitosan antibacterial film, comprising the steps of: soaking chitosan in tartaric acid, and washing with anhydrous ethanol; mixing tartaric acid and 1-ethyl-3-methylimidazolium acetate system, adding washed chitosan, adding chitinase, and cooling to obtain a coating solution; and scraping the obtained coating liquid, placing the coating liquid in a solvent for phase transfer film forming, and drying to obtain the chitosan antibacterial film.
Further, the mass ratio of tartaric acid to 1-ethyl-3-methylimidazolium acetate is (0.4-1.4): 3.
Further, the concentration of the tartaric acid is 1.2-2.1%. The concentration is the ratio of tartaric acid to the total volume of (tartaric acid + water).
Further, the chitosan was impregnated with tartaric acid until the chitosan was swollen with tartaric acid.
Further, after adding chitinase, stirring at the speed of 300-500r/min at 50-70 ℃ until the chitosan is completely dissolved and the solution is transparent.
Further, the solvent used for phase transfer is ethanol or glycerol.
According to one aspect of the invention, the chitosan bacteriostatic film product is prepared by the method provided by the invention.
Further, the viscosity was 300-500 mPas and the strength was 5.3-6.7 kN/m.
Compared with the prior art, the invention has the following advantages:
1. the chitosan antibacterial membrane adopts 1-ethyl-3-methylimidazolium acetate and tartaric acid as solvents, and the solvents are environment-friendly, do not corrode equipment and do not pollute the environment;
2. the invention adopts tartaric acid and 1-ethyl-3-methylimidazolium acetate system to dissolve chitosan, and simultaneously adds chitinase, the method of the invention ensures that the chitosan dissolution speed is high, the dissolution temperature is low, and the dissolution concentration is high;
3. the chitosan bacteriostatic film obtained by the method has good bacteriostatic effect and high film strength.
The foregoing description is only an overview of the technical solutions of the present invention, and the embodiments of the present invention are described below in order to make the technical means of the present invention more clearly understood and to make the above and other objects, features, and advantages of the present invention more clearly understandable.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The preparation method of the chitosan antibacterial film comprises the following steps: soaking chitosan in tartaric acid, and washing with anhydrous ethanol; mixing tartaric acid and 1-ethyl-3-methylimidazolium acetate system, adding washed chitosan, adding chitinase, and cooling to obtain a coating solution; and scraping the obtained coating liquid, placing the coating liquid in a solvent for phase transfer film forming, and drying to obtain the chitosan antibacterial film.
The mechanism of action of each substance used in the present invention is described in detail below.
Tartaric acid and 1-ethyl-3-methylimidazolium acetate can dissolve chitosan respectively, but the 1-ethyl-3-methylimidazolium acetate is difficult to dissolve chitosan, needs high temperature and long time (about 6 hours), and has low dissolving concentration which is about 3% at most. Tartaric acid dissolves chitosan, so that the film-forming property is poor and the film is difficult to form. The tartaric acid is adopted for pretreatment, the dissolving speed can be improved, the chitosan and the tartaric acid are adopted for blending and dissolving, the dissolving time is further shortened, and finally the chitosan has good film-forming property and high film strength. The chitinase can play a catalytic role, shorten the dissolving time and reduce the dissolving temperature.
The present invention is illustrated below by specific examples, which should be understood by those skilled in the art as not limiting the scope of the claims of the present invention.
The embodiment of the invention adopts the following raw materials:
| obstetric apparatus | |
| Tartaric acid | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| Chitosan | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| Anhydrous ethanol | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| 1-ethyl-3-methylimidazolium acetate | Koksatch Industrial & trade Co Ltd, Lanzhou |
| Chitinase | Shanghai Kanglang Biotech Co Ltd |
| Glycerol | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
Example 1
Dissolving 0.49g of tartaric acid in 40ml of water, adding 0.5g of chitosan, heating to 60 ℃, pre-soaking for 10 minutes, then washing with absolute ethyl alcohol for three times, and carrying out suction filtration for later use;
dissolving 0.4g of tartaric acid in 40ml of water, mixing with 3g of 1-ethyl-3-methylimidazolium acetate, adding pretreated chitosan, adding chitinase, heating to 50 ℃, stirring for 5 minutes at the speed of 300r/min, completely dissolving the chitosan, and then cooling to room temperature to form a coating solution with the viscosity of 300mPa & s;
and (5) leveling the coating liquid on a flat plate, and controlling the thickness of the membrane to be 0.05 mm. Then putting the chitosan antibacterial membrane material into glycerol for solvent exchange, and drying for 8 hours after membrane formation to obtain the chitosan antibacterial membrane material.
Example 2
Dissolving 0.61g of tartaric acid in 40ml of water, adding 0.5g of chitosan, heating to 70 ℃, pre-soaking for 10 minutes, then washing with absolute ethyl alcohol for three times, and carrying out suction filtration for later use;
dissolving 1g of tartaric acid in 40ml of water, mixing with 3g of 1-ethyl-3-methylimidazolium acetate, adding pretreated chitosan, adding chitinase, heating to 60 ℃, stirring for 10 minutes at the speed of 400r/min, completely dissolving the chitosan, and then cooling to room temperature to form a coating liquid with the viscosity of 400mPa & s;
and (5) leveling the coating liquid on a flat plate, and controlling the thickness of the membrane to be 0.05 mm. Then the chitosan antibacterial membrane material is placed in ethanol for solvent exchange, and dried for 8 hours after membrane formation to obtain the chitosan antibacterial membrane material.
Example 3
Dissolving 0.86g of tartaric acid in 40ml of water, adding 0.5g of chitosan, heating to 80 ℃, pre-soaking for 10 minutes, then washing with absolute ethyl alcohol for three times, and carrying out suction filtration for later use;
dissolving 1.4g of tartaric acid in 40ml of water, mixing with 3g of 1-ethyl-3-methylimidazolium acetate, adding pretreated chitosan, adding chitinase, heating to 70 ℃, stirring for 20 minutes at the speed of 500r/min, completely dissolving the chitosan, and then cooling to room temperature to form a coating solution with the viscosity of 500mPa & s;
and (5) leveling the coating liquid on a flat plate, and controlling the thickness of the membrane to be 0.05 mm. Then putting the chitosan antibacterial membrane material into glycerol for solvent exchange, and drying for 8 hours after membrane formation to obtain the chitosan antibacterial membrane material.
Comparative example 1
Dissolving 0.61g of tartaric acid in 40ml of water, adding 0.5g of chitosan, heating to 70 ℃, pre-soaking for 10 minutes, then washing with absolute ethyl alcohol for three times, and carrying out suction filtration for later use;
dissolving 1g of tartaric acid in 40ml of water, adding pretreated chitosan, adding chitinase, heating to 60 ℃, stirring at the speed of 400r/min for 10 minutes until the chitosan can be completely dissolved, and then cooling to room temperature to form a coating liquid with the viscosity of 300mPa & s;
and (5) leveling the coating liquid on a flat plate, and controlling the thickness of the membrane to be 0.05 mm. Then putting the chitosan antibacterial membrane material into glycerol for solvent exchange, and drying for 8 hours after membrane formation to obtain the chitosan antibacterial membrane material.
Comparative example 2
Dissolving 0.61g of tartaric acid in 40ml of water, adding 0.5g of chitosan, heating to 70 ℃, pre-soaking for 10 minutes, then washing with absolute ethyl alcohol for three times, and carrying out suction filtration for later use;
adding the pretreated chitosan into 3g of 1-ethyl-3-methylimidazolium acetate system, adding chitinase, heating to 60 ℃, stirring for 10 minutes at the speed of 400r/min, completely dissolving the chitosan, and then cooling to room temperature to form a coating liquid with the viscosity of 400mPa & s;
and (5) leveling the coating liquid on a flat plate, and controlling the thickness of the membrane to be 0.05 mm. Then putting the chitosan antibacterial membrane material into glycerol for solvent exchange, and drying for 8 hours after membrane formation to obtain the chitosan antibacterial membrane material.
Comparative example 3 (without chitinase)
Dissolving 0.61g of tartaric acid in 40ml of water, adding 0.5g of chitosan, heating to 70 ℃, pre-soaking for 10 minutes, then washing with absolute ethyl alcohol for three times, and carrying out suction filtration for later use;
dissolving 1g of tartaric acid in 40ml of water, mixing with 3g of 1-ethyl-3-methylimidazolium acetate, adding pretreated chitosan, heating to 60 ℃, stirring at the speed of 400r/min for 10 minutes, completely dissolving the chitosan, and then cooling to room temperature to form a coating solution with the viscosity of 500mPa & s;
and (5) leveling the coating liquid on a flat plate, and controlling the thickness of the membrane to be 0.05 mm. Then putting the chitosan antibacterial membrane material into glycerol for solvent exchange, and drying for 8 hours after membrane formation to obtain the chitosan antibacterial membrane material.
The results of using the chitosan antibacterial films of examples 1-3 of the present invention and the PE wrap film sold on the market to pack fresh pork respectively are shown in Table 1.
TABLE 1 time of preservation of fresh pork with the antibacterial film of examples 1-3
| Fresh-keeping time at 4 DEG C | Fresh-keeping time at normal temperature | |
| Example 1 | 96h | 72h |
| Example 2 | 96h | 72h |
| Example 3 | 96h | 72h |
| PE plastic wrap on market | 72h | 48h |
Through the tests on indexes such as total bacterial count, pH and volatile basic nitrogen of the fresh pork and the effectiveness analysis, the chitosan antibacterial film and the commercially available PE preservative film have certain preservation effect on the fresh pork under two storage conditions of 4 ℃ and normal temperature, and compared with the chitosan antibacterial film, the chitosan antibacterial film has better effect at 4 ℃ and better preservation performance. Under the conditions of 4 ℃ and normal temperature, the fresh-keeping time of the fresh pork can be respectively prolonged by 96 hours and 24 hours by using chitosan antibacterial film packaging.
TABLE 2 dissolution of chitosan by the methods of example 2 and comparative examples 1-3
| Concentration of dissolved | Dissolution temperature | Dissolution time | |
| Example 2 | 5-6％ | 60℃ | 10min |
| Comparative example 1 | 3-4％ | 70℃ | 30-40min |
| Comparative example 2 | 3-4％ | 100℃ | 6h |
| Comparative example 3 | 5-6％ | 60℃ | 30min |
The chitosan is dissolved by adopting 1-ethyl-3-methylimidazolium acetate, the dissolving concentration of the chitosan is 3-4%, the dissolving temperature is 100 ℃, the dissolving time is 6 hours, 10 hours are needed for completely dissolving the chitosan, and the chitosan coating liquid and the chitosan antibacterial film are difficult to form under the concentration.
The tartaric acid can also be used for dissolving chitosan, but the strength of the formed coating liquid is poor, and the finally formed chitosan bacteriostatic film has no strength.
In summary, firstly, the mixed system of the invention has high chitosan dissolution concentration which can be increased to 5-6%; secondly, the dissolving temperature is greatly reduced, and the solvent can be dissolved at 60 ℃; the dissolution time is also reduced from 6h of 1-ethyl-3-methylimidazolium acetate system to 10 min; the strength of the finally formed film is high and can reach 5.3kN/m, while the strength of the film formed by dissolving chitosan with tartaric acid is not high (cannot be measured).
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. A preparation method of a chitosan antibacterial film is characterized by comprising the following steps:
soaking chitosan in tartaric acid, and washing with anhydrous ethanol;
mixing tartaric acid and 1-ethyl-3-methylimidazole acetate system, adding chitosan obtained after washing, adding chitinase, and cooling until a coating solution is obtained, wherein the mass ratio of tartaric acid to 1-ethyl-3-methylimidazole acetate system is (0.4-1.4): 3;
and scraping the obtained coating liquid, placing the coating liquid in a solvent for phase transfer film forming, and drying to obtain the chitosan antibacterial film.
2. The method of claim 1, wherein the tartaric acid is present at a concentration of 1.2-2.1%.
3. The method of claim 1, wherein the chitosan is impregnated with tartaric acid until the chitosan is swollen with tartaric acid.
4. The method for preparing chitosan antibacterial film as claimed in claim 1, wherein the chitosan is completely dissolved and the solution is transparent by stirring at a speed of 300-500r/min at 50-70 ℃ after the chitinase is added.
5. The method of claim 1, wherein the solvent used for phase transfer is ethanol or glycerol.
6. A chitosan bacteriostatic film product prepared by the method of any one of claims 1-5.
7. The chitosan bacteriostatic film product of claim 6, wherein the viscosity is 300-500mPa · s, and the strength is 5.3-6.7 kN/m.
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| CN110615920A (en) * | 2019-10-21 | 2019-12-27 | 青岛科技大学 | Degradable biomass-based antibacterial film and preparation method thereof |
| CN110818955B (en) * | 2019-11-15 | 2022-01-18 | 青岛科技大学 | MOF (Metal organic framework) proanthocyanidin-loaded antibacterial film and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102168323A (en) * | 2011-02-24 | 2011-08-31 | 天津工业大学 | Method for preparing chitosan and chitin functional materials by taking ionic liquid as solvent |
| WO2014018586A1 (en) * | 2012-07-24 | 2014-01-30 | The Board Of Trustees Of The University Of Alabama | Process for electrospinning chitin fibers from chitinous biomass solution and fibers and articles produced thereby |
| CN102936762B (en) * | 2012-10-22 | 2015-04-08 | 中国纺织科学研究院 | Preparation method of chitosan/cellulose homogeneous spinning solution |
| CN105085940A (en) * | 2015-09-23 | 2015-11-25 | 山东商业职业技术学院 | Chitosan rapid dissolving method |
| CN106380620A (en) * | 2016-09-21 | 2017-02-08 | 福州大学 | Preparation method of chitosan/ionic liquid composite membrane |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102168323A (en) * | 2011-02-24 | 2011-08-31 | 天津工业大学 | Method for preparing chitosan and chitin functional materials by taking ionic liquid as solvent |
| WO2014018586A1 (en) * | 2012-07-24 | 2014-01-30 | The Board Of Trustees Of The University Of Alabama | Process for electrospinning chitin fibers from chitinous biomass solution and fibers and articles produced thereby |
| CN102936762B (en) * | 2012-10-22 | 2015-04-08 | 中国纺织科学研究院 | Preparation method of chitosan/cellulose homogeneous spinning solution |
| CN105085940A (en) * | 2015-09-23 | 2015-11-25 | 山东商业职业技术学院 | Chitosan rapid dissolving method |
| CN106380620A (en) * | 2016-09-21 | 2017-02-08 | 福州大学 | Preparation method of chitosan/ionic liquid composite membrane |
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