CN113698640B - 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
- 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
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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
- 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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- 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
- 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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- 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
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- 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
Abstract
The invention belongs to a film preparation method, in particular 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, and calcining a dried product to obtain antibacterial particles @ nano calcium carbonate catalytic particles; preparing chitosan acid solution; preparing a carboxymethyl cellulose solution; adding chitosan acid solution into carboxymethyl cellulose solution, and then adding sodium phytate to obtain mixed solution; adding 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 the development of society and technology, film materials have important roles in life of people, such as shopping, fresh-keeping, packaging and the like, but most film products have no defects of degradability, poor antibacterial and barrier properties and the like, so that two important fields of antibacterial and barrier are the focus of increasing attention.
The Chinese patent publication No. CN113003596A provides a biological macromolecular membrane filled with light calcium carbonate in situ and application thereof in oily food and medicine packaging, wherein Ca is firstly added into a mixed solution of N-hydroxypropyl-3-trimethyl chitosan HTCC and carboxymethyl cellulose CMC 2+ To be Ca 2+ Fully reacts with the carboxylate ions in CMC and then adds CO 3 2- Preparing light calcium carbonate in situ; and adding a plasticizer to form a film, thereby obtaining the biological macromolecule film. The biological macromolecular membrane has the advantages that the antibacterial property is improved as a whole, but the barrier property 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 hydroxy 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, preparing antibacterial particles @ nano calcium carbonate catalytic particles:
(1) Tetrabutyl titanate is dissolved in ethanol to obtain a solution A; mixing ethanol, acetic acid and deionized water to obtain a solution B; dropwise adding the solution B into the solution A, stirring to obtain sol, and aging;
(2) Taking the aged sol, adding zinc acetate, stirring, adding nano calcium carbonate, stirring, carrying out suction filtration, drying, and calcining a dried product to obtain antibacterial particles @ nano calcium carbonate catalytic particles;
step S2, preparing a 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 carboxymethyl cellulose solution;
(3) Adding chitosan acid solution into carboxymethyl cellulose solution, adding sodium phytate solution, and stirring to obtain mixed solution;
step S3, preparing a nano calcium carbonate/bio-based film:
adding 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 ethanol, acetic acid and deionized water is 18:2:5.
Further, in the step S1, the weight ratio of the sol to the zinc acetate to the nano calcium carbonate is 30:3:2.
Further, the acid solution used in the step S2 is an acetic acid solution.
Further, in the step S2, the volume weight ratio of the acetic acid solution to the chitosan is 100ml:0.1-0.9g.
Further, in the step S2, the pH of the carboxymethyl cellulose solution is adjusted to 10.
Further, in the step S2, the volume ratio of the chitosan acidic solution to the carboxymethyl cellulose solution is 1:2.
further, in the step S2, the volume weight ratio of the mixed solution to the antibacterial particles @ nano calcium carbonate catalytic particles is 150ml:0.01-0.3g.
The preparation method has the beneficial effects that the antibacterial metal compound is loaded on the surface of the nano calcium carbonate by a coprecipitation method, then the heterostructure compound with antibacterial and blocking functions, namely antibacterial particles@nano calcium carbonate catalytic particles, is prepared by high-temperature calcination, and 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 the corresponding blocking and antibacterial effects, meanwhile, the antibacterial catalytic particles and the nano calcium carbonate play the synergistic effects, the blocking and antibacterial effects are improved, and then the antibacterial particles@nano calcium carbonate catalytic particles are introduced into the biological-based film, so that the antibacterial and blocking performances of the biological-based film are enhanced.
Drawings
FIG. 1 is a schematic diagram of the infrared spectrum of the antibacterial particles @ nano calcium carbonate catalytic particles of the present invention.
Detailed Description
Example 1
The preparation method of the nano calcium carbonate/bio-based film comprises the following steps:
step S1, preparing antibacterial particles @ nano calcium carbonate catalytic particles:
(1) 8g of tetrabutyl titanate is dissolved in 36g of ethanol and stirred for 30min to obtain a solution A; mixing 36g of ethanol with 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) 60g of the aged sol is taken, 6g of zinc acetate is added, and the mixture is stirred for 30mAfter in, 4g of nano calcium carbonate is added, stirred for 12 hours at 40 ℃, filtered and dried for 9 hours. Calcining the dried product in a muffle furnace at 400 ℃ for 2 hours to obtain the antibacterial@nano calcium carbonate catalytic particles. As shown in figure 1, the modified product antibacterial particles @ nano calcium carbonate catalytic particles (Zn@TiO) 2 @CaCO 3 ) At 1100-500cm -1 Relative to CaCO 3 Has obvious change and shows ZnO and TiO 2 Is characterized by the peak of CaCO 3 The characteristic peaks themselves also vary significantly.
Step S2, preparing a mixed solution:
(1) Preparing chitosan acid solution: weighing 5mL of glacial acetic acid, dissolving in deionized water, preparing 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 for 1h at room temperature to obtain 1mg/mL of chitosan acid solution;
(2) Preparing a cellulose solution: dispersing 2g of carboxymethyl cellulose in deionized water, stirring strongly to prepare carboxymethyl cellulose solution with concentration of 2%, and regulating the pH value of the system to 10 by using sodium hydroxide solution for later use;
(3) Taking 100mL of carboxymethyl cellulose solution with the pH value adjusted to 10 in the step (2), slowly adding 50mL of chitosan acid solution in a beaker during stirring, then adding 0.02g of sodium phytate solution (PA-Na) with the concentration of 10%, and stirring at 40 ℃;
step S3, preparing a nano calcium carbonate/bio-based film:
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, continuously 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, and the temperature is controlled to be 45 ℃.
Example 2
The preparation method of the nano calcium carbonate/bio-based film comprises the following steps:
step S1 and step S2 in this embodiment 2 are the same as step S1 and step S2 in embodiment 1.
Step S3, preparing a nano calcium carbonate/bio-based film:
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, continuously 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, and the temperature is controlled to be 45 ℃.
Example 3
The preparation method of the nano calcium carbonate/bio-based film comprises the following steps:
step S1 and step S2 in this embodiment 3 are the same as step S1 and step S2 in embodiment 1.
Step S3, preparing a nano calcium carbonate/bio-based film:
and (2) 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), continuously 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, 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, preparing antibacterial catalytic particles:
(1) 8g of tetrabutyl titanate is dissolved in 36g of ethanol and stirred for 30min to obtain a solution A; mixing 36g of ethanol with 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) Taking 60g of the aged sol, adding 6g of zinc acetate, stirring for 30min, stirring for 12h at 40 ℃, carrying out suction filtration, and drying for 9h. Calcining the dried product in a muffle furnace at 400 ℃ for 2 hours to obtain the antibacterial catalytic particles.
Step S2 and step S3 of this comparative example 1 are the same as step S2 and step S3 of examples 1 to 3, except that 0.2g of antibacterial particles @ nano calcium carbonate catalytic particles in step S3 are replaced with 0.2g of antibacterial catalytic particles.
Comparative example 2
A method for preparing a bio-based film, comprising the steps of:
step S1, preparing a mixed solution: this step S1 is identical to step S2 of examples 1-3.
Step S2, preparing a bio-based film: this step S1 is identical to step S3 of example 3, except that 0.2g of bacteriostatic particles @ nano-calcium carbonate catalytic particles are replaced by 0.2g of unmodified calcium carbonate.
Comparative example 3
Step S1, step S2 and step S3 of comparative example 3 are the same as step S1, step S2 and step S3 of example 3, except that the sodium phytate solution is not added to step S2 of comparative example 4.
For the film materials obtained in examples 1 to 3 and comparative examples 1 to 3 described above, performance tests were conducted, respectively, and the performance tests included:
(1) Antibacterial performance test: the detection is carried out according to the test method disclosed in GB/T31402-2015/ISO22196:2007 test method for antibacterial Property of Plastic surface.
(2) Antiviral performance test: the determination was carried out according to the test method disclosed in ISO21702:2019 determination of antiviral Activity of plastics and other non-porous surfaces.
(3) Barrier performance test: the measurement was carried out according to the test method disclosed in GB/T1038-2000 "test method for permeability to gases of Plastic films and sheets-differential pressure method".
The performance results are shown in Table 1.
Table 1: bio-based film performance detection
| Antibacterial rate% | Antiviral Activity Rate% | Oxygen inhibition 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 detection data, the antibacterial rate, antiviral activity rate and oxygen inhibition rate of examples 1 to 3 were all superior to those of comparative examples 1 to 3. Compared with comparative example 1 in which bacteriostatic catalytic particles are directly added, the bacteriostatic catalytic particles in examples 1-3 can effectively exert the corresponding blocking and bacteriostatic effects by using the nano calcium carbonate as the carrier of the bacteriostatic catalytic particles, and can also exert the synergistic effect with the nano calcium carbonate, so that the blocking and bacteriostatic effects of the film material are better.
Claims (9)
1. The preparation method of the nano calcium carbonate/bio-based film is characterized by comprising the following steps of:
step S1, preparing antibacterial particles @ nano calcium carbonate catalytic particles:
(1) Tetrabutyl titanate is dissolved in ethanol to obtain a solution A; mixing ethanol, acetic acid and deionized water to obtain a solution B; dropwise adding the solution B into the solution A, stirring to obtain sol, and aging;
(2) Taking the aged sol, adding zinc acetate, stirring, adding nano calcium carbonate, stirring, carrying out suction filtration, drying, and calcining a dried product to obtain antibacterial particles @ nano calcium carbonate catalytic particles;
step S2, preparing a 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 carboxymethyl cellulose solution;
(3) Adding chitosan acid solution into carboxymethyl cellulose solution, adding sodium phytate solution, and stirring to obtain mixed solution;
step S3, preparing a nano calcium carbonate/bio-based film:
adding 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 for preparing a nano calcium carbonate/bio-based film according to claim 1, wherein in the step S1, the weight ratio of tetrabutyl titanate to ethanol is 2:9.
3. The method for preparing a 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 a nano calcium carbonate/bio-based film according to claim 1, wherein in the step S1, the weight ratio of the sol to the zinc acetate to the nano calcium carbonate is 30:3:2.
5. The method for preparing nano calcium carbonate/bio-based film according to claim 1, wherein the acid solution used in the step S2 is an acetic acid solution.
6. The method for preparing a nano calcium carbonate/bio-based film according to claim 5, wherein in the step S2, the volume weight ratio of the acetic acid solution to the chitosan is 100ml:0.1-0.9g.
7. The method for preparing a nano calcium carbonate/bio-based film according to claim 1, wherein the pH value of the carboxymethyl cellulose solution is adjusted to 10 in the step S2.
8. The method for preparing a nano calcium carbonate/bio-based film according to claim 1, wherein in the step S2, the volume ratio of the chitosan acid solution to the carboxymethyl cellulose solution is 1:2.
9. the method for preparing a nano calcium carbonate/bio-based film according to claim 1, wherein in the step S3, the volume weight ratio of the mixed solution to the antibacterial particles @ nano calcium carbonate catalytic particles is 150ml:0.01-0.3g.
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