CN113698640A - Preparation method of nano calcium carbonate/bio-based film - Google Patents
Preparation method of nano calcium carbonate/bio-based film Download PDFInfo
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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
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- 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
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- 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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Abstract
The invention belongs to a film preparation method, and particularly relates to a preparation method of a nano calcium carbonate/bio-based film, which comprises the following steps: dissolving tetrabutyl titanate in ethanol, and mixing the ethanol with acetic acid and deionized water; obtaining sol through the two solutions, adding zinc acetate, stirring, adding nano calcium carbonate, drying a product, and calcining to obtain antibacterial particles @ nano calcium carbonate catalytic particles; preparing a chitosan acid solution; preparing a carboxymethyl cellulose solution; adding the chitosan acid solution into the carboxymethyl cellulose solution, and then adding sodium phytate to obtain a mixed solution; adding the antibacterial particles @ nano calcium carbonate catalytic particles into the mixed solution, and finally drying to form a film; according to the invention, an antibacterial metal compound is loaded on the surface of nano calcium carbonate to prepare a heterostructure compound with antibacterial and barrier functions, and antibacterial particles @ nano calcium carbonate catalytic particles are introduced into a bio-based film, so that the antibacterial and barrier properties of the bio-based film are enhanced.
Description
Technical Field
The invention belongs to a film preparation method, and particularly relates to a preparation method of a nano calcium carbonate/bio-based film.
Background
At present, with social progress and scientific and technological development, film materials play an important role in people's lives, such as shopping, preservation, packaging and other corners, but most film products do not have the defects of degradability, poor antibacterial and barrier properties and the like, so that two important fields of antibacterial and barrier become the focus of increasing attention of people.
The Chinese invention patent with the publication number of CN113003596A provides a light calcium carbonate in-situ filled biomacromolecule film and application thereof in packaging oily food and medicines, wherein Ca is firstly added into a mixed solution of N-hydroxypropyl-3-trimethyl chitosan HTCC and carboxymethyl cellulose CMC2+Wait for Ca2+Adding CO after fully reacting with carboxylic acid and ions in CMC3 2-Preparing light calcium carbonate in situ; and adding a plasticizer to form a film to obtain the biological macromolecular film. Although the antibacterial property of the biological macromolecular membrane is integrally improved, the barrier property of the biological macromolecular membrane is still to be improved.
Disclosure of Invention
The invention aims to provide a preparation method of a nano calcium carbonate/bio-based film with good antibacterial and barrier effects.
The nano calcium carbonate/bio-based film is prepared from a carrier, an antibacterial metal compound, a bio-based material, deionized water and the like according to mass fractions under certain conditions. Wherein the carrier is nano calcium carbonate; the antibacterial metal compound is a mixture of metal oxides with antibacterial effect, such as tetrabutyl titanate, zinc acetate and the like; the bio-based material is hydroxyl cellulose, chitosan, sodium phytate and the like.
The method for preparing the nano calcium carbonate/bio-based film specifically comprises the following steps:
step S1, preparation of the antibacterial particle @ nano calcium carbonate catalytic particle:
(1) dissolving tetrabutyl titanate in ethanol to obtain a solution A; mixing ethanol with acetic acid and deionized water to obtain a solution B; dripping the solution B into the solution A, stirring to obtain sol, and aging;
(2) adding zinc acetate into the aged sol, stirring, adding nano calcium carbonate, stirring, performing suction filtration, drying, and calcining the dried product to obtain antibacterial particles @ nano calcium carbonate catalytic particles;
step S2, preparation of mixed solution:
(1) dissolving chitosan in an acid solution, and stirring to obtain a chitosan acid solution;
(2) dispersing carboxymethyl cellulose in deionized water, stirring, and adjusting the pH to be more than 7 to obtain a carboxymethyl cellulose solution;
(3) adding the chitosan acid solution into the carboxymethyl cellulose solution, adding the sodium phytate solution, and stirring to obtain a mixed solution;
step S3, preparing the nano calcium carbonate/bio-based film:
adding the antibacterial particles @ nano calcium carbonate catalytic particles into the mixed solution, stirring to obtain a composite solution, pouring the composite solution into a mold, and drying to obtain the nano calcium carbonate/bio-based film.
Further, in the step S1, the weight ratio of tetrabutyl titanate to ethanol is 2: 9.
Further, in the step S1, the weight ratio of the ethanol to the acetic acid to the deionized water is 18:2: 5.
Further, in the step S1, the weight ratio of the sol, the zinc acetate and the nano calcium carbonate is 30:3: 2.
Further, the acid solution used in step S2 is an acetic acid solution.
Further, in the step S2, the volume-to-weight ratio of the acetic acid solution to the chitosan is 100 ml: 0.1-0.9 g.
Further, in the step S2, the pH of the carboxymethyl cellulose solution is adjusted to 10.
Further, in step S2, the volume ratio of the chitosan acid solution to the carboxymethyl cellulose solution is 1: 2.
further, in the step S2, the volume-to-weight ratio of the mixed solution to the bacteriostatic particles @ nano calcium carbonate catalytic particles is 150 ml: 0.01-0.3 g.
The method has the beneficial effects that through a coprecipitation method, the antibacterial metal compound is loaded on the surface of the nano calcium carbonate, and then the mixture is calcined at high temperature to prepare the heterostructure compound with antibacterial and barrier functions, namely the antibacterial particles @ nano calcium carbonate catalytic particles, the antibacterial particles @ nano calcium carbonate catalytic particles are used as carriers of the antibacterial catalytic particles, so that the antibacterial catalytic particles can effectively play corresponding barrier and antibacterial functions, meanwhile, the antibacterial catalytic particles and the nano calcium carbonate play a synergistic effect, the barrier and antibacterial effects are improved, and then the antibacterial particles @ nano calcium carbonate catalytic particles are introduced into the bio-based film, so that the antibacterial and barrier properties of the bio-based film are enhanced.
Drawings
FIG. 1 is a schematic infrared spectrum diagram of the bacteriostatic particle @ nano calcium carbonate catalytic particle of the invention.
Detailed Description
Example 1
A preparation method of a nano calcium carbonate/bio-based film comprises the following steps:
step S1, preparation of the antibacterial particle @ nano calcium carbonate catalytic particle:
(1) dissolving 8g of tetrabutyl titanate in 36g of ethanol, and stirring for 30min to obtain a solution A; mixing 36g of ethanol, 4g of acetic acid and 10g of deionized water, and stirring for 30min to obtain a solution B; dropwise adding the solution B into the solution A, stirring for 2 hours to obtain transparent milky white sol, and aging for 2 hours at room temperature;
(2) and (3) adding 6g of zinc acetate into 60g of the aged sol, stirring for 30min, adding 4g of nano calcium carbonate, stirring for 12h at 40 ℃, performing suction filtration, and drying for 9 h. And calcining the dried product in a muffle furnace at 400 ℃ for 2h to obtain the bacteriostatic @ nano calcium carbonate catalytic particles. As shown in figure 1, the modified product bacteriostatic particle @ nano calcium carbonate catalytic particle (Zn @ TiO)2@CaCO3) At 1100--1Relative to CaCO3With obvious changes, showing ZnO and TiO2Characteristic peak of (C), CaCO3The characteristic peak of the material also has obvious change.
Step S2, preparation of mixed solution:
(1) preparing a chitosan acid solution: measuring 5mL of glacial acetic acid, dissolving in deionized water to prepare 2mg/mL of acetic acid solution, and storing in a volumetric flask for later use; dissolving 0.1g of chitosan in 100mL of acetic acid solution, and stirring at room temperature for 1h to obtain 1mg/mL of chitosan acid solution;
(2) preparing a cellulose solution: taking 2g of carboxymethyl cellulose, dispersing the carboxymethyl cellulose in deionized water, strongly stirring, preparing a carboxymethyl cellulose solution with the concentration of 2%, and adjusting the pH of the system to 10 by using a sodium hydroxide solution for later use;
(3) adding 100mL (2) of carboxymethyl cellulose solution with the pH value adjusted to 10 into a beaker, slowly adding 50mL of chitosan acid solution in the stirring process, then adding 0.02g of 10% sodium phytate solution (PA-Na), and stirring at 40 ℃;
step S3, preparing the nano calcium carbonate/bio-based film:
and (3) weighing 0.1g of antibacterial particles @ nano calcium carbonate catalytic particles, adding the antibacterial particles @ nano calcium carbonate catalytic particles into the mixed solution obtained in the step S2, continuing stirring for half an hour to obtain a composite solution, pouring the composite solution into a polytetrafluoroethylene mold, and drying in a constant temperature and humidity box to obtain the nano calcium carbonate/bio-based film. Wherein the humidity of the constant temperature and humidity box is controlled to be 70RH percent, and the temperature is controlled to be 45 ℃.
Example 2
A preparation method of a nano calcium carbonate/bio-based film comprises the following steps:
steps S1 and S2 in this embodiment 2 are the same as steps S1 and S2 in embodiment 1.
Step S3, preparing the nano calcium carbonate/bio-based film:
and (3) weighing 0.15g of antibacterial particles @ nano calcium carbonate catalytic particles, adding the antibacterial particles @ nano calcium carbonate catalytic particles into the mixed solution obtained in the step S2, continuing stirring for half an hour to obtain a composite solution, pouring the composite solution into a polytetrafluoroethylene mold, and drying in a constant temperature and humidity box to obtain the nano calcium carbonate/bio-based film. Wherein the humidity of the constant temperature and humidity box is controlled to be 70RH percent, and the temperature is controlled to be 45 ℃.
Example 3
A preparation method of a nano calcium carbonate/bio-based film comprises the following steps:
steps S1 and S2 in this embodiment 3 are the same as steps S1 and S2 in embodiment 1.
Step S3, preparing the nano calcium carbonate/bio-based film:
and (3) weighing 0.2g of antibacterial particles @ nano calcium carbonate catalytic particles, adding the antibacterial particles @ nano calcium carbonate catalytic particles into the mixed solution obtained in the step S2, continuing stirring for half an hour to obtain a composite solution, pouring the composite solution into a polytetrafluoroethylene mold, and drying in a constant temperature and humidity box to obtain the nano calcium carbonate/bio-based film. Wherein the humidity of the constant temperature and humidity box is controlled to be 70RH percent, and the temperature is controlled to be 45 ℃.
Comparative example 1
A method for preparing a bio-based film, comprising the steps of:
step S1, preparation of antibacterial catalytic particles:
(1) dissolving 8g of tetrabutyl titanate in 36g of ethanol, and stirring for 30min to obtain a solution A; mixing 36g of ethanol, 4g of acetic acid and 10g of deionized water, and stirring for 30min to obtain a solution B; dropwise adding the solution B into the solution A, stirring for 2 hours to obtain transparent milky white sol, and aging for 2 hours at room temperature;
(2) and (3) adding 6g of zinc acetate into 60g of the aged sol, stirring for 30min, stirring for 12h at 40 ℃, performing suction filtration, and drying for 9 h. And calcining the dried product in a muffle furnace at 400 ℃ for 2h to obtain the antibacterial catalytic particles.
Comparative example 1, step S2 and step S3 are the same as steps S2 and S3 of examples 1 to 3, except that 0.2g of bacteriostatic particles @ nanocalcium carbonate catalytic particles are replaced with 0.2g of bacteriostatic catalytic particles in step S3.
Comparative example 2
A method for preparing a bio-based film, comprising the steps of:
step S1, preparation of mixed solution: this step S1 is the same as step S2 of examples 1-3.
Step S2, preparing a bio-based film: this step S1 is the same as step S3 of example 3, except that 0.2g of bacteriostatic particles @ nanocalcium carbonate catalytic particles were replaced with 0.2g of unmodified calcium carbonate.
Comparative example 3
Comparative example 3, step S1, step S2 and step S3 are the same as example 3, step S1, step S2 and step S3, except that the sodium phytate solution is not added in step S2 of comparative example 4.
The film materials obtained in the above examples 1 to 3 and comparative examples 1 to 3 were subjected to performance tests, respectively, the performance tests including:
(1) and (3) testing antibacterial performance: the measurement is carried out according to the test method disclosed in GB/T31402-2015/ISO22196:2007 method for testing the antibacterial property of the surface of plastic.
(2) And (3) testing antiviral performance: the determination is carried out according to the test method disclosed in ISO21702:2019 determination of antiviral activity on plastics and other non-porous surfaces.
(3) And (3) testing barrier property: the measurement was carried out according to the test method disclosed in GB/T1038-2000 "test method for gas permeability of Plastic film and sheet-pressure differential method".
The performance results of the experimental tests are shown in table 1.
Table 1: bio-based film performance detection
| The antibacterial rate% | The antiviral activity% | Oxygen barrier rate/m 2 & 24h | |
| Example 1 | 87.2 | 84.3 | 39.9 |
| Example 2 | 89.5 | 87.6 | 43.5 |
| Example 3 | 92.1 | 90.2 | 45.6 |
| Comparative example 1 | 74.9 | 70.2 | 36.8 |
| Comparative example 2 | 5.7 | 4.1 | 38.1 |
| Comparative example 3 | 84.1 | 81.5 | 33.9 |
From the above test data, the antibacterial rate, antiviral activity rate and oxygen barrier rate of examples 1 to 3 are superior to those of comparative examples 1 to 3. Compared with comparative example 1 in which bacteriostatic catalytic particles are directly added, in the embodiments 1 to 3, the nano calcium carbonate is used as the carrier of the bacteriostatic catalytic particles, so that the bacteriostatic catalytic particles can effectively exert the corresponding barrier and bacteriostatic effects, and can exert the synergistic effect with the nano calcium carbonate, so that the barrier and bacteriostatic effects of the film material are also better.
Claims (9)
1. A preparation method of a nano calcium carbonate/bio-based film is characterized by comprising the following steps:
step S1, preparation of the antibacterial particle @ nano calcium carbonate catalytic particle:
(1) dissolving tetrabutyl titanate in ethanol to obtain a solution A; mixing ethanol with acetic acid and deionized water to obtain a solution B; dripping the solution B into the solution A, stirring to obtain sol, and aging;
(2) adding zinc acetate into the aged sol, stirring, adding nano calcium carbonate, stirring, performing suction filtration, drying, and calcining the dried product to obtain antibacterial particles @ nano calcium carbonate catalytic particles;
step S2, preparation of mixed solution:
(1) dissolving chitosan in an acid solution, and stirring to obtain a chitosan acid solution;
(2) dispersing carboxymethyl cellulose in deionized water, stirring, and adjusting the pH to be more than 7 to obtain a carboxymethyl cellulose solution;
(3) adding the chitosan acid solution into the carboxymethyl cellulose solution, adding the sodium phytate solution, and stirring to obtain a mixed solution;
step S3, preparing the nano calcium carbonate/bio-based film:
adding the antibacterial particles @ nano calcium carbonate catalytic particles into the mixed solution, stirring to obtain a composite solution, pouring the composite solution into a mold, and drying to obtain the nano calcium carbonate/bio-based film.
2. The method of claim 1, wherein in step S1, the weight ratio of tetrabutyl titanate to ethanol is 2: 9.
3. The method for preparing nano calcium carbonate/bio-based film according to claim 1 or 2, wherein in the step S1, the weight ratio of ethanol, acetic acid and deionized water is 18:2: 5.
4. The method for preparing nano calcium carbonate/bio-based film according to claim 1, wherein in step S1, the weight ratio of the sol, the zinc acetate and the nano calcium carbonate is 30:3: 2.
5. The method of claim 1, wherein the acid solution used in step S2 is an acetic acid solution.
6. The method for preparing nano calcium carbonate/bio-based film according to claim 5, wherein in step S2, the volume weight ratio of acetic acid solution to chitosan is 100 ml: 0.1-0.9 g.
7. The method of claim 1, wherein the carboxymethyl cellulose solution is adjusted to have a pH of 10 in step S2.
8. The method for preparing nano calcium carbonate/bio-based film according to claim 1, wherein in step S2, the volume ratio of the chitosan acid solution to the carboxymethyl cellulose solution is 1: 2.
9. the method for preparing nano calcium carbonate/bio-based film according to claim 1, wherein in step S2, the volume-to-weight ratio of the mixed solution to the bacteriostatic particles @ nano calcium carbonate catalytic particles is 150 ml: 0.01-0.3 g.
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| CN114753062A (en) * | 2022-04-01 | 2022-07-15 | 浙江工商大学 | Recyclable hand towel and preparation method thereof |
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