CN107936581B - Preparation method of antibacterial film composite material - Google Patents
Preparation method of antibacterial film composite material Download PDFInfo
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- CN107936581B CN107936581B CN201711307526.4A CN201711307526A CN107936581B CN 107936581 B CN107936581 B CN 107936581B CN 201711307526 A CN201711307526 A CN 201711307526A CN 107936581 B CN107936581 B CN 107936581B
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Abstract
The invention discloses a preparation method of a bacteriostatic film composite material, which comprises the following steps: (1) dissolving chitosan with deacetylation degree of more than 90% in chitosan solvent at room temperature, and stirring for 25-40min to obtain chitosan solution with mass concentration of 1-5%; (2) adding zinc propoxide into the chitosan solution obtained in the step (1) at room temperature, and stirring for 55-75min to obtain a gel solution; (3) and (3) coating the gel solution obtained in the step (2) on a clean glass plate, then soaking in a triethanolamine solution for 15-25min, taking out the glass plate, drying in an oven, naturally cooling to room temperature, and removing the membrane to obtain the antibacterial membrane composite material. The antibacterial film prepared by the method provided by the invention has good mechanical strength and antibacterial performance.
Description
Technical Field
The invention belongs to the field of preparation of antibacterial materials, and particularly relates to a preparation method of an antibacterial film composite material.
Background
The bacteriostatic material is a novel functional material which has the function of inhibiting or killing microorganisms. Bacteriostatic agents are chemical substances which are highly sensitive to microorganisms and which, when added to a material in small amounts, impart antimicrobial properties to the material, i.e. bacteriostatic agents are substances which inhibit the development or growth of microorganisms, such as bacteria and fungi. In practical application, the material has the function of inhibiting and killing microorganisms, and is generally called as bacteriostatic property.
Chitosan (CTS) is the most main product of deacetylation of Chitin (Chitin), which is a natural biological polysaccharide with the chemical name of (1,4) -2-amino-2-deoxy- β -D-glucan and the molecular formula of [ C6H11NO4]n, the degree of deacetylation (D.D) of which determines the amount of amino groups present on the macromolecular chain of the chitosan.The chitosan is an excellent natural polymer functional membrane material with good permeability, film forming property and adsorbability. The molecular chain contains a large amount of hydroxyl and amino, which is beneficial to modifying the chitosan by various technologies, such as blending, crosslinking, copolymerization and ionization, or the amino on the chitosan molecular chain and transition metal ions form a coordination complex and the like, thereby preparing chitosan films with different purposes.
The chitosan has simple film preparation process and no toxic matter involved in the film preparation process, so that it may be used widely in food and medicine industry. In addition, chitosan and its degradation products have been applied to many fields in the aspect of antibiosis and bacteriostasis, and the chitosan not only has natural antibacterial performance, but also has the advantages of high bacteriostatic activity, broad spectrum, high bacteria killing rate and the like. In addition, because of its good reproducibility and biocompatibility, chitosan can be used as an adsorbent, a flocculant, an ion exchanger, and the like, and is widely used in the aspects of purification of drinking water, softening of hard water, treatment of industrial wastewater, decolorization of dye wastewater, separation and recovery of amino acid and protein, and the like, and covers a plurality of fields such as medicine, industry, food, biology, and the like.
Chitosan is the only cationic animal fiber and alkaline polysaccharide found so far, and the molecular chain thereof contains a large amount of hydroxyl and amino groups to make it easy to chemically modify and have multiple functions, but the chitosan film is limited in strength due to poor strength, and the antibacterial activity of chitosan is affected by many intrinsic factors and external environment.
The zinc propionate is used as a medical astringent, has good antibacterial effect, and has good inhibition effect on Candida albicans and Aspergillus niger.
In the prior art, chitosan is mixed with zinc inorganic compounds such as zinc oxide, zinc carbonate and the like to prepare the antibacterial film, and the mechanical strength of the film is poor due to poor compatibility of the chelated zinc inorganic compounds and chitosan; the antibacterial film is prepared from chitosan and titanium dioxide, but the titanium dioxide is easy to agglomerate, so that the functionality of the film is reduced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of an antibacterial film composite material, which can be used for preparing a chitosan composite material with good mechanical strength and antibacterial activity.
A preparation method of a bacteriostatic film composite material comprises the following steps:
(1) dissolving chitosan with deacetylation degree of more than 90% in chitosan solvent at room temperature, and stirring for 25-40min to obtain chitosan solution with mass concentration of 1-5%;
(2) adding zinc propoxide into the chitosan solution obtained in the step (1) at room temperature, and stirring for 55-75min to obtain a gel solution;
(3) and (3) coating the gel solution obtained in the step (2) on a clean glass plate, then soaking in a triethanolamine solution for 15-25min, taking out the glass plate, drying in an oven, naturally cooling to room temperature, and removing the membrane to obtain the antibacterial membrane composite material.
Preferably, the chitosan solvent is an acetic acid solution.
Preferably, the mass concentration of the acetic acid solution is 1-5%.
Preferably, the mass concentration of the acetic acid solution is 2%.
Preferably, the mass ratio of the chitosan to the zinc propionate is (3-4): 1.
preferably, the triethanolamine solution has a mass concentration of 7 to 14%.
Preferably, the triethanolamine solution has a mass concentration of 10%.
Preferably, the drying conditions are as follows: the drying temperature is 90-110 ℃, and the drying time is 3-5 h.
The preparation method of the zinc propionate is disclosed in patent CN 102060665B, and specifically comprises the following steps: the reaction vessel was charged with the reactants: anhydrous glycerol and zinc oxide, and adding an initiator to initiate a synthesis reaction, wherein the molar ratio of the added reactants is as follows: anhydrous glycerin/zinc oxide (4-10): 1, the molar ratio of the added initiator is as follows: zinc oxide initiator 1: (0.05-0.1), the reaction temperature is 150-160 ℃, the heat preservation time is 1-2h, and the initiator is C3-C8Of (3) an alkylene oxide.
Preferably, the initiator is propylene oxide or butylene oxide.
The invention has the advantages that:
the antibacterial film prepared by the method provided by the invention has good mechanical strength and antibacterial performance, the tensile strength of the dry film can reach 3.5MPa, the radius of an antibacterial ring for staphylococcus aureus can reach 27mm, and the radius of an antibacterial ring for escherichia coli can reach 29 mm.
Detailed Description
The preparation method of the zinc propanol is described in patent CN 102060665B.
In the embodiment of the invention, the preparation method of the adopted zinc propionate comprises the following steps: adding 200 g of anhydrous glycerol and 1.5 g of propylene oxide into a 500ml three-neck flask, starting stirring, adding 25 g of zinc oxide, heating to 150 ℃, keeping the temperature for reaction for 1.5 hours, stopping heating, cooling to below 30 ℃, pouring a reaction mixture into water, performing suction filtration, sequentially washing a filter cake with water, ethanol and acetone, drying for more than 4 hours at the temperature of more than 60 ℃ to obtain white crystalline powder, and analyzing by infrared spectroscopy, wherein a spectrogram is 1940cm-1The product is determined to be zinc propanol by a characteristic absorption peak with medium intensity.
Example 1
A preparation method of a bacteriostatic film composite material comprises the following steps:
(1) dissolving chitosan with deacetylation degree of more than 90% by using a chitosan solvent at room temperature, and stirring for 25min to obtain a chitosan solution with mass concentration of 1%; the chitosan solvent is an acetic acid solution with the mass concentration of 1%;
(2) adding zinc propionate into the chitosan solution obtained in the step (1) at room temperature, wherein the mass ratio of chitosan to zinc propionate is 3: 1, stirring for 55min to obtain a gel solution;
(3) and (3) coating the gel solution obtained in the step (2) on a clean glass plate, then soaking in a triethanolamine solution with the mass concentration of 7% for 15min, taking out the glass plate, drying at 90 ℃ in an oven for 5h, naturally cooling to room temperature, and removing the membrane to obtain the antibacterial membrane composite material.
Example 2
A preparation method of a bacteriostatic film composite material comprises the following steps:
(1) dissolving chitosan with deacetylation degree of more than 90% by using a chitosan solvent at room temperature, and stirring for 40min to obtain a chitosan solution with mass concentration of 5%; the chitosan solvent is an acetic acid solution with the mass concentration of 5%;
(2) adding zinc propionate into the chitosan solution obtained in the step (1) at room temperature, wherein the mass ratio of the chitosan to the zinc propionate is 4: 1, stirring for 75min to obtain a gel solution;
(3) and (3) coating the gel solution obtained in the step (2) on a clean glass plate, then soaking in a triethanolamine solution with the mass concentration of 14% for 25min, taking out the glass plate, drying in an oven at 110 ℃ for 3h, naturally cooling to room temperature, and removing the membrane to obtain the antibacterial membrane composite material.
Example 3
A preparation method of a bacteriostatic film composite material comprises the following steps:
(1) dissolving chitosan with deacetylation degree of more than 90% by using a chitosan solvent at room temperature, and stirring for 30min to obtain a chitosan solution with mass concentration of 2%; the chitosan solvent is an acetic acid solution with the mass concentration of 2%;
(2) adding zinc propionate into the chitosan solution obtained in the step (1) at room temperature, wherein the mass ratio of chitosan to zinc propionate is 3: 1, stirring for 60min to obtain a gel solution;
(3) and (3) coating the gel solution obtained in the step (2) on a clean glass plate, then soaking in a triethanolamine solution with the mass concentration of 10% for 20min, taking out the glass plate, drying in an oven at 100 ℃ for 4h, naturally cooling to room temperature, and removing the membrane to obtain the antibacterial membrane composite material.
Comparative example 1
The zinc alkoxide in example 3 was replaced with zinc oxide, and the procedure was otherwise the same as in example 3.
Comparative example 2
Zinc carbonate was used instead of zinc propionate in example 3, and the procedure was otherwise the same as in example 3.
Antimicrobial testing was performed according to the disinfection specification 2002 edition; the mechanical strength properties were measured according to GB/T228-2010 with a film thickness of 0.5mm, the results are shown in Table 1.
TABLE 1 detection of mechanical and bacteriostatic properties
As can be seen from Table 1, the antibacterial film composite material prepared by the method provided by the invention has good mechanical strength and good antibacterial performance.
Claims (8)
1. A preparation method of a bacteriostatic film composite material is characterized by comprising the following steps: the method comprises the following steps:
(1) dissolving chitosan with deacetylation degree of more than 90% in chitosan solvent at room temperature, and stirring for 25-40min to obtain chitosan solution with mass concentration of 1-5%;
(2) adding zinc propoxide into the chitosan solution obtained in the step (1) at room temperature, and stirring for 55-75min to obtain a gel solution;
(3) and (3) coating the gel solution obtained in the step (2) on a clean glass plate, then soaking in a triethanolamine solution for 15-25min, taking out the glass plate, drying in an oven, naturally cooling to room temperature, and removing the membrane to obtain the antibacterial membrane composite material.
2. The preparation method of the bacteriostatic film composite material according to claim 1, characterized in that: the chitosan solvent is acetic acid solution.
3. The preparation method of the bacteriostatic film composite material according to claim 2, characterized in that: the mass concentration of the acetic acid solution is 1-5%.
4. The preparation method of the bacteriostatic film composite material according to claim 3, characterized in that: the mass concentration of the acetic acid solution is 2%.
5. The preparation method of the bacteriostatic film composite material according to claim 1, characterized in that: the mass ratio of the chitosan to the zinc propionate is (3-4): 1.
6. the preparation method of the bacteriostatic film composite material according to claim 1, characterized in that: the mass concentration of the triethanolamine solution is 7-14%.
7. The preparation method of the bacteriostatic film composite material according to claim 1, characterized in that: the mass concentration of the triethanolamine solution is 10%.
8. The preparation method of the bacteriostatic film composite material according to claim 1, characterized in that: the drying conditions are as follows: the drying temperature is 90-110 ℃, and the drying time is 3-5 h.
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| CN107936581B true CN107936581B (en) | 2020-07-28 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008076339A3 (en) * | 2006-12-15 | 2008-12-18 | Univ Drexel | Multilayer films |
| CN102060665A (en) * | 2011-01-07 | 2011-05-18 | 陕西省石油化工研究设计院 | Synthesis method of propanol zinc |
| KR20130094991A (en) * | 2012-02-17 | 2013-08-27 | 동국대학교 산학협력단 | Water-resistant oxygen indicator using gel-forming natural polymer and manufacturing method the same |
| CN105837865A (en) * | 2016-03-25 | 2016-08-10 | 同济大学 | Chitosan/ZnO antibacterial preservative film, preparation method and application thereof |
| KR20160119453A (en) * | 2015-04-06 | 2016-10-14 | 동국대학교 산학협력단 | Manufacturing method of functional food packaging film for preventing greening of potato |
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2017
- 2017-12-11 CN CN201711307526.4A patent/CN107936581B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008076339A3 (en) * | 2006-12-15 | 2008-12-18 | Univ Drexel | Multilayer films |
| CN102060665A (en) * | 2011-01-07 | 2011-05-18 | 陕西省石油化工研究设计院 | Synthesis method of propanol zinc |
| KR20130094991A (en) * | 2012-02-17 | 2013-08-27 | 동국대학교 산학협력단 | Water-resistant oxygen indicator using gel-forming natural polymer and manufacturing method the same |
| KR20160119453A (en) * | 2015-04-06 | 2016-10-14 | 동국대학교 산학협력단 | Manufacturing method of functional food packaging film for preventing greening of potato |
| CN105837865A (en) * | 2016-03-25 | 2016-08-10 | 同济大学 | Chitosan/ZnO antibacterial preservative film, preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| ZnO nanoparticles induced effects on nanomechanical behavior and cell viability of chitosan films;Ambalangodage C. Jayasuriya et al.;《Materials Science and Engineering C》;20130504;第33卷;2.2节 * |
| 壳聚糖水果保鲜膜的应用探讨;李继维;《北方环境》;20041231;第29卷(第6期);第61-63页 * |
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