CN114805900A - Method for improving gas barrier property of film substrate, film and application - Google Patents
Method for improving gas barrier property of film substrate, film and application Download PDFInfo
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Abstract
The invention discloses a method for improving the barrier property of matrix gas, belonging to the technical field of biological plastic packaging. The technical scheme is as follows: preparing a cellulose acetate film from Cellulose Acetate (CA) and a glycerol solution with a certain mass fraction by a tape casting method, combining with Graphene Oxide (GO) nanosheets under the action of molecular glue to form a compact composite film material (CA/GO), and then riveting transition metal oxide Nanoparticles (NPs) prepared by a room-temperature rapid reduction method on the surface of the CA/GO film by a hydrogen bond to realize precise repairing of GO defect sites, so as to block a gas transmission channel, thereby obtaining the high-gas-barrier CA/GO-NPs nano composite film. The invention has low energy consumption and simple process flow, is easy for mass and large-area production, effectively reduces the permeability of oxygen and water vapor molecules, and is expected to be widely applied to the fields of food preservation, drug packaging, electronic product packaging, agricultural packaging and other bioplastic-based packaging.
Description
Technical Field
The invention belongs to the technical field of a gas-resistant film of bioplastic, and particularly relates to a method for improving the gas barrier property of a matrix.
Background
In recent years, with the issue of "plastic forbidden" and the growing concern of people about environmental issues, natural materials as bioplastic packaging have attracted more and more attention due to their advantages of biocompatibility, biodegradability, renewability, low cost, and the like. In particular, cellulose is the most abundant and renewable natural polysaccharide that can be efficiently separated from a variety of lignocellulosic biomass, including wood or agricultural residues. In addition, Cellulose Acetate (CA), one of the most promising derivatives of cellulose, has been widely used in various everyday consumer products such as cigarette filters, textiles, and packaging film materials. However, the high gas permeability of pure CA films severely limits their practical application in the field of bioplastic packaging to protect oxygen and moisture sensitive objects, especially under high humidity conditions. An effective strategy to overcome this disadvantage is to add suitable nanofillers such as montmorillonite, inorganic oxides and carbonaceous nanomaterials (such as carbon nanotubes, reduced graphene oxide (rGO) and Graphene Oxide (GO) nanoplatelets). Among them, two-dimensional (2D) graphene materials involving stacked GO and rGO nanoplates are considered new stars in gas barrier materials due to the highly sp2 hybridized aligned carbon backbone structure and small lattice parameter of 0.246 nm. Theoretically, defect-free single-layer graphene nanoplatelets are impermeable to all gases, liquids and corrosive chemicals. However, various defects such as Stone-Wales defects, grain boundaries, vacancies, and macro defects are inevitably generated in the substrate surface during the exfoliation of the original graphite and the subsequent reduction, which results in many microscopic gas transmission channels and short gas permeation paths, thereby resulting in poor gas barrier properties.
To date, various GO and derivatives have been synthesized and incorporated into CA film matrices to improve barrier properties through physical mixing. However, this treatment method limits the progress to further optimize the basic physicochemical properties of the nanocomposite film. Furthermore, dispersion of rGO typically involves the use of toxic organic solvents, contaminating the surrounding environment. Thus, it is practical to apply GO or rGO as a multi-layer coating on different substrate surfaces, rather than as a separate film, by spray coating, rod coating or dipping techniques. However, poor interfacial interactions can easily lead to the GO or rGO layers falling off the substrate under external physical forces (e.g., bending, stretching and folding), limiting practical applications. Therefore, it is highly desirable to produce strong bio-plastic films with high gas resistance.
Disclosure of Invention
Based on this, it was an object of the present invention to provide a method for improving the barrier properties of a matrix gas.
In order to achieve the purpose, the invention adopts the technical scheme that:
preparing a cellulose acetate film from cellulose acetate and a glycerol solution with a certain mass fraction by a tape casting method, combining the cellulose acetate film with GO nanosheets under the action of molecular glue to form a compact composite film material (CA/GO), and then riveting transition metal oxide Nanoparticles (NPs) prepared by a room-temperature rapid reduction method on the surface of the CA/GO film by a hydrogen bond to realize precise repairing of GO defect sites, so as to block a gas transmission channel, thus obtaining the CA/GO-NPs nano composite film material with high gas barrier performance.
The cellulose acetate film prepared from the cellulose acetate and the glycerol solution with certain mass fractions through a tape casting method is prepared by dispersing 6-18 wt.% of cellulose acetate and 3-12 wt.% of plasticizer in the acetic acid solution, and uniformly stirring, wherein the plasticizer is glycerol.
The preparation method comprises the following steps: 1) preparing a cellulose acetate film from a Cellulose Acetate (CA) solution and a glycerol solution by a tape casting method;
2) combining with Graphene Oxide (GO) nanosheets under the action of molecular glue to form a compact composite thin film material (CA/GO);
3) and then riveting transition metal oxide Nanoparticles (NPs) prepared by a rapid reduction method at room temperature on the surface of the CA/GO film in a solution under the action of hydrogen bonds of oxygen-containing groups on the surface of GO so as to obtain the high-gas-barrier CA/GO-NPs composite film.
The preparation method comprises the following steps of (1) preparing a cellulose acetate film from cellulose acetate and a glycerol solution by a tape casting method, wherein the tape casting raw materials are prepared by dispersing 6-18 wt% (preferably 10-13 wt%) cellulose acetate and 3-12 wt% (preferably 4-7 wt%) plasticizer in the acetic acid solution, and uniformly stirring, wherein the plasticizer is glycerol; the thickness of the cellulose acetate film prepared by the tape casting method is 80-100 mu m.
The step (2) is combined with GO nano sheets with the thickness of 1-2nm under the action of molecular glue to form a compact composite film material, and the operation process is as follows:
1) soaking a cellulose acetate film in a chitosan aqueous solution, wherein the mass of the film is 2-8g (preferably 4-6 g), the volume of the solution is 10-30mL (preferably 20-25mL), the action temperature of molecular glue is 40-100 ℃ (preferably 50-70 ℃), the action time is 5-48 h (preferably 20-26h), the type of the molecular glue is one or more of chitosan, polyvinyl alcohol, polyethyleneimine and ethylenediamine tetraacetic acid, and the concentration is 1.0-5 wt.% (preferably 2-4 wt.%);
2) taking out the film, washing with water to remove unreacted molecular glue, and then immersing in a GO aqueous solution at the temperature of 40-100 ℃ (preferably 50-70 ℃) for 5-48 h (preferably 20-26 h); taking out the film, washing with water to remove unfixed GO, and drying at room temperature to obtain a CA/GO film; the GO concentration in the water solution is 0.1-2mg/mL (preferably 0.8-1.2mg/mL), and the volume of the GO solution is 10-30mL (preferably 20-25 mL).
The transition metal oxide Nanoparticles (NPs) prepared by the room-temperature fast reduction method in the step (3) are transition metal oxide nanoparticle solutions obtained by fast reducing transition metal salt ions in a solvent by using sodium borohydride at room temperature, wherein the solvent is ethylene glycol, and the obtained nanoparticles are one or more of iron oxide, cobalt oxide and nickel oxide.
The anion of the transition metal salt is one or more of acetate ion, chloride ion, nitrate ion, etc. The concentration of transition metal ions in 10mL of the solvent is 10-120mM (preferably 40-60mM), the amount of sodium borohydride added is 50-300mg (preferably 80-120mg), and the reaction temperature is 20-30 deg.C (preferably 24-28 deg.C). The rivet can realize precise repair of GO defect sites on the surface of a CA/GO film under the action of hydrogen bonds, and the specific process is that the prepared CA/GO composite film is soaked in a prepared NPs solution, the soaking time is 1-10h (preferably 1.5-3h) when the film mass is 3-9g (preferably 5-7g) and the solution volume is 5-30mL (preferably 10-15mL), and the temperature is 20-30 ℃ and preferably 24-28 ℃.
The prepared product has the advantages of simple operation, low energy consumption, good repeatability among batches, easy large-area production, excellent gas barrier property and the like, and effectively reduces the permeability of oxygen and water vapor molecules.
Compared with the prior art, the preparation method provided by the invention has the following advantages:
1. the invention provides a method for preparing a bioplastic film with stable structure and high barrier property by simultaneously adopting molecular glue and a nano-repairing strategy for the first time, and the bioplastic film is expected to be widely applied to the fields of bioplastic-based packaging such as food preservation, medicine packaging, electronic product packaging, agricultural packaging and the like.
2. The production process for preparing the bioplastic film has low energy consumption and simple flow, and is easy for mass production and large-area production.
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The specific experimental procedures or conditions not specified in the examples were performed according to the procedures or conditions of the conventional experimental procedures described in the literature in the field. The reagents or apparatus used are not indicated by the manufacturer, and are all conventional reagents which are commercially available.
Example 1
1) Accurately weighed 12g of cellulose acetate and 5mL of glycerol were dissolved in 95mL of acetic acid solution and stirred well until all dissolved. And obtaining a cellulose acetate film by adopting a tape casting method, and naturally drying at room temperature to obtain a CA film with the film thickness of 100 mu m.
2) 5g of cellulose acetate film was soaked in 20mL of a 3 wt.% aqueous chitosan solution and incubated at 60 ℃ for 24 h.
Taking out the film, washing with deionized water, and removing unreacted molecular glue; then immersed in 20mL of 1mg/mL GO (1-2 nm thick) aqueous solution and incubated at 60 ℃ for 24 h. And taking out the film, washing with deionized water to remove the unfixed GO, and drying at room temperature to obtain the CA/GO film.
3) 0.18g of cobalt acetate tetrahydrate is accurately weighed and dissolved in 10mL of glycol, and 100mg of sodium borohydride is slowly added under the stirring state, so that the glycol solution with uniformly dispersed cobalt nanoparticles (the particle size is 2-3nm) can be obtained.
And (3) soaking the 6gCA/GO film in 10mL of the reacted ethylene glycol solution, taking out after 8h, washing with deionized water to remove non-riveted nano particles, and thus obtaining the CA/GO-NPs composite film.
Example 2
1) Accurately weighing 15g of cellulose acetate and 5mL of glycerol, dissolving in 95mL of acetic acid solution, and stirring thoroughly until all is dissolved. Adopting a tape casting method to obtain a cellulose acetate film, and naturally drying at room temperature to obtain a CA film with the film thickness of 100 mu m.
2) 4g of cellulose acetate film was immersed in 20mL of a 2 wt.% aqueous polyvinyl alcohol solution and incubated at 90 ℃ for 12 h. The film was removed, rinsed with deionized water to remove unreacted molecular glue, and then immersed in 20mL of 2mg/mL GO (1-2 nm thick) aqueous solution at 60 deg.C for 10 h. And (3) taking out the film, washing with deionized water to remove unfixed GO, and drying at room temperature to obtain the CA/GO film.
3) 0.18g of nickel acetate tetrahydrate is accurately weighed and dissolved in 10mL of glycol, and 150mg of sodium borohydride is slowly added under the stirring state, so that the glycol solution with uniformly dispersed nickel nanoparticles (the particle size is 2-3nm) can be obtained.
And (3) soaking the 6gCA/GO film in 10mL of the reacted ethylene glycol solution, taking out after 2h, washing with deionized water to remove non-riveted nano particles, and thus obtaining the CA/GO-NPs composite film.
Example 3
1) 6g of cellulose acetate and 10mL of glycerol were weighed out accurately and dissolved in 90mL of acetic acid solution, and the mixture was stirred well until the solution was completely dissolved. And obtaining a cellulose acetate film by adopting a tape casting method, and naturally drying at room temperature to obtain a CA film with the film thickness of 90 mu m.
2) 5g of cellulose acetate film was immersed in 20mL of a 2 wt.% aqueous polyethyleneimine solution and incubated at 40 ℃ for 5 h. The film was removed, rinsed with deionized water to remove unreacted molecular glue, and then immersed in 20mL of 2mg/mL GO (1-2 nm thick) aqueous solution and incubated at 50 ℃ for 6 h. And taking out the film, washing with deionized water to remove the unfixed GO, and drying at room temperature to obtain the CA/GO film.
3) 0.18g of ferric acetate tetrahydrate is accurately weighed and dissolved in 10mL of glycol, and 300mg of sodium borohydride is slowly added under the stirring state, so that the glycol solution with uniformly dispersed iron nanoparticles (the particle size is 2-3nm) can be obtained.
And (3) soaking the 6gCA/GO film in 10mL of the reacted ethylene glycol solution, taking out after 7h, and washing with deionized water to remove the non-riveted nano particles to obtain the CA/GO-NPs.
Example 4
1) Accurately weighed 12g of cellulose acetate and 8mL of glycerol were dissolved in 92mL of acetic acid solution and stirred well until all dissolved. And obtaining a cellulose acetate film by adopting a tape casting method, and naturally drying at room temperature to obtain a CA film with the film thickness of 100 mu m.
2) 6g of cellulose acetate film was immersed in 20mL of a 2 wt.% aqueous polyethyleneimine solution and incubated at 70 ℃ for 12 h. Taking out the film, washing with deionized water to remove unreacted molecular glue, then soaking in 20mL of 2mg/mL GO (1-2 nm in thickness) aqueous solution, and keeping the temperature at 70 ℃ for 12 h. And taking out the film, washing with deionized water to remove the unfixed GO, and drying at room temperature to obtain the CA/GO film.
3) 0.09g of ferric acetate tetrahydrate and 0.09g of cobalt acetate tetrahydrate are accurately weighed and dissolved in 10mL of glycol, and 100mg of sodium borohydride is slowly added under the stirring state, so that the glycol solution with uniformly dispersed iron-cobalt nanoparticles (the particle size is 2-3nm) can be obtained.
And (3) soaking the 6gCA/GO film in 10mL of the reacted ethylene glycol solution, taking out after 3h, and washing with deionized water to remove the non-riveted nano particles to obtain the CA/GO-NPs.
Example 5
1) Accurately weighed 14g of cellulose acetate and 8mL of glycerol were dissolved in 92mL of acetic acid solution and stirred well until all dissolved. And obtaining a cellulose acetate film by adopting a tape casting method, and naturally drying at room temperature to obtain a CA film with the film thickness of 100 mu m.
2) 5g of cellulose acetate film was immersed in 20mL of a 2 wt.% aqueous polyethyleneimine solution and incubated at 80 ℃ for 10 h. Taking out the film, washing with deionized water to remove unreacted molecular glue, then soaking in 20mL of 1mg/mL GO (1-2 nm in thickness) aqueous solution, and keeping the temperature at 80 ℃ for 10 h. And taking out the film, washing with deionized water to remove the unfixed GO, and drying at room temperature to obtain the CA/GO film.
3) 0.18g of ferric acetate tetrahydrate is accurately weighed and dissolved in 10mL of glycol, and 50mg of sodium borohydride is slowly added under the stirring state, so that the glycol solution with uniformly dispersed iron nanoparticles (the particle size is 2-3nm) can be obtained.
And (3) soaking the 7gCA/GO film in 10mL of the reacted ethylene glycol solution, taking out after 5h, washing with deionized water to remove non-riveted nano particles, and thus obtaining the CA/GO-NPs.
Testing the gas barrier and stability performance of the composite film:
1. laboratory evaluation methods:
1) oxygen Transmission Rate (OTR) was measured with a differential pressure gas permeameter (BASIC201, China) at an ambient temperature of 23 + -2 deg.C and a relative humidity of 50 + -5% according to ASTM D3985;
2) water Vapor Permeability (WVP) is determined by a water vapor permeability tester (PERMEW3/010, LABTHINK, China) at 38 + -0.5 deg.C and 90 + -1% relative humidity according to standard methods (ASTM E398).
2. Performance detection
The results of comparing the effects of the three films prepared in example 1 above are shown in table 1.
Table 1 comparison of the effects of example 1
As can be seen from Table 1, the barrier effect of the obtained CA/GO-NPs composite film is better than that of other comparative examples, and the oxygen and water vapor transmission rate is obviously lower than that of other comparative examples.
The barrier effect of the CA/GO-NPs composite films prepared in the different examples is compared, and the results are shown in Table 2.
TABLE 2 comparison of Barrier Effect of CA/GO-NPs composite films prepared in different examples
As can be seen from Table 2, the barrier effect of the CA/GO-NPs composite film obtained in example 1 is better than that of other examples, and the oxygen and water vapor transmission rate is obviously lower than that of other examples. However, the gas barrier properties of the composite films prepared in examples 2 to 5 were all superior to those of the original CA film, and the oxygen and water vapor transmission rates were significantly lower than those of the original CA film.
3. Product stability test
The stability of the product was examined using the CA/GO-NPs composite film prepared in best mode example 1, and the results are shown in Table 3.
TABLE 3 EXAMPLE 1 preparation of CA/GO-NPs film stability
As can be seen from Table 3, the product has excellent structural stability and meets the practical application requirements of the bio-plastic film. The films prepared in examples 2-5 also have good stability, and no obvious delamination phenomenon exists after repeated and continuous bending for 100 times.
The invention discloses a method for improving the barrier property of matrix gas, belonging to the technical field of biological plastic packaging. The experimental result shows that the prepared composite film has better oxygen and water vapor barrier property than the same type of products, lower cost and stable system without layering and falling off.
Claims (9)
1. A method of improving the gas barrier properties of a film substrate, comprising:
1) preparing a cellulose acetate film from a Cellulose Acetate (CA) solution and a glycerol solution by a tape casting method;
2) combining with Graphene Oxide (GO) nanosheets under the action of molecular glue to form a compact composite thin film material (CA/GO);
3) and then riveting transition metal oxide Nanoparticles (NPs) prepared by a rapid reduction method at room temperature on the surface of the CA/GO film in a solution under the action of hydrogen bonds of oxygen-containing groups on the surface of GO so as to obtain the high-gas-barrier CA/GO-NPs composite film.
2. The method of claim 1, wherein: the preparation method comprises the following steps of (1) preparing a cellulose acetate film from cellulose acetate and a glycerol solution by a tape casting method, wherein the tape casting raw materials are prepared by dispersing 6-18 wt% (preferably 10-13 wt%) cellulose acetate and 3-12 wt% (preferably 4-7 wt%) plasticizer in the acetic acid solution, and uniformly stirring, wherein the plasticizer is glycerol; the thickness of the cellulose acetate film prepared by the tape casting method is 80-100 mu m.
3. The method of claim 1, wherein:
the step (2) is combined with GO nano sheets with the thickness of 1-2nm under the action of molecular glue to form a compact composite film material, and the operation process is as follows:
1) soaking a cellulose acetate film in a chitosan aqueous solution, wherein the mass of the film is 2-8g (preferably 4-6 g), the volume of the solution is 10-30mL (preferably 20-25mL), the action temperature of molecular glue is 40-100 ℃ (preferably 50-70 ℃), the action time is 5-48 h (preferably 20-26h), the type of the molecular glue is one or more of chitosan, polyvinyl alcohol, polyethyleneimine and ethylenediamine tetraacetic acid, and the concentration is 1.0-5 wt.% (preferably 2-4 wt.%);
2) taking out the film, washing with water to remove unreacted molecular glue, and then immersing in a GO aqueous solution at the temperature of 40-100 ℃ (preferably 50-70 ℃) for 5-48 h (preferably 20-26 h); taking out the film, washing with water to remove unfixed GO, and drying at room temperature to obtain a CA/GO film; the GO concentration in the water solution is 0.1-2mg/mL (preferably 0.8-1.2mg/mL), and the volume of the GO solution is 10-30mL (preferably 20-25 mL).
4. The method of claim 1, wherein:
the transition metal oxide Nanoparticles (NPs) prepared by the room-temperature fast reduction method in the step (3) are transition metal oxide nanoparticle solutions obtained by fast reducing transition metal salt ions in a solvent by using sodium borohydride at room temperature, wherein the solvent is ethylene glycol, and the obtained nanoparticles are one or more of iron oxide, cobalt oxide and nickel oxide.
5. The method of claim 4, wherein: the concentration of transition metal ions in 10mL of the solvent is 10-120mM (preferably 40-60mM), the amount of sodium borohydride added is 50-300mg (preferably 80-120mg), and the reaction temperature is 20-30 deg.C (preferably 24-28 deg.C).
6. The method of claim 4, wherein:
the anion of the transition metal salt is one or more of acetate ion, chloride ion, nitrate ion, etc.
7. The method of claim 1, wherein: the rivet can realize precise repair of GO defect sites on the surface of a CA/GO film under the action of hydrogen bonds, and the specific process is that the prepared CA/GO composite film is soaked in a prepared NPs solution, the soaking time is 1-10h (preferably 1.5-3h) when the film mass is 3-9g (preferably 5-7g) and the solution volume is 5-30mL (preferably 10-15mL), and the temperature is 20-30 ℃ and preferably 24-28 ℃.
8. A film prepared by the method of any one of claims 1 to 7.
9. Use of the film of claim 8 as a packaging film for food preservation, pharmaceutical packaging, electronic packaging or agricultural packaging.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210400449.1A CN114805900B (en) | 2022-04-16 | 2022-04-16 | Method for improving gas barrier property of film substrate, film and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210400449.1A CN114805900B (en) | 2022-04-16 | 2022-04-16 | Method for improving gas barrier property of film substrate, film and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114805900A true CN114805900A (en) | 2022-07-29 |
| CN114805900B CN114805900B (en) | 2023-05-30 |
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| CN104817710A (en) * | 2015-04-30 | 2015-08-05 | 北京化工大学 | Transparent gas barrier film materials and production method thereof |
| US20160303518A1 (en) * | 2015-04-15 | 2016-10-20 | Korea Research Institute Of Chemical Technology | Nanocomposite ultrafiltration membrane containing graphene oxide or reduced graphene oxide and preparation method thereof |
| CN106519268A (en) * | 2016-10-28 | 2017-03-22 | 江南大学 | Preparation method for high-barrier water-resistant polyvinyl alcohol (PVA)/cellulose nanocrystal (CNC)/graphene oxide (GO) composite film |
| US20170106342A1 (en) * | 2014-03-28 | 2017-04-20 | The University Of Manchester | Reduced Graphene Oxide Barrier Materials |
| CN106700110A (en) * | 2017-01-09 | 2017-05-24 | 东北林业大学 | Preparation method of graphene oxide/nano cellulose/polyvinyl alcohol composite film |
| US20170369322A1 (en) * | 2016-06-24 | 2017-12-28 | Case Western Reserve University | Ketyl radical induced photoreduction of graphene oxide; grafting of metal nanoparticles on graphene by photoreduction |
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| US20170106342A1 (en) * | 2014-03-28 | 2017-04-20 | The University Of Manchester | Reduced Graphene Oxide Barrier Materials |
| US20160303518A1 (en) * | 2015-04-15 | 2016-10-20 | Korea Research Institute Of Chemical Technology | Nanocomposite ultrafiltration membrane containing graphene oxide or reduced graphene oxide and preparation method thereof |
| CN104817710A (en) * | 2015-04-30 | 2015-08-05 | 北京化工大学 | Transparent gas barrier film materials and production method thereof |
| US20170369322A1 (en) * | 2016-06-24 | 2017-12-28 | Case Western Reserve University | Ketyl radical induced photoreduction of graphene oxide; grafting of metal nanoparticles on graphene by photoreduction |
| CN106519268A (en) * | 2016-10-28 | 2017-03-22 | 江南大学 | Preparation method for high-barrier water-resistant polyvinyl alcohol (PVA)/cellulose nanocrystal (CNC)/graphene oxide (GO) composite film |
| CN106700110A (en) * | 2017-01-09 | 2017-05-24 | 东北林业大学 | Preparation method of graphene oxide/nano cellulose/polyvinyl alcohol composite film |
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