CN114805900B - Method for improving gas barrier property of film substrate, film and application - Google Patents
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Abstract
The invention discloses a method for improving the gas barrier property of a matrix, and belongs to the technical field of bio-plastic packaging. The technical scheme adopted is as follows: cellulose Acetate (CA) and glycerol solution with certain mass fraction are prepared into a cellulose acetate film through a tape casting method, the cellulose acetate film is combined with Graphene Oxide (GO) nanosheets under the action of molecular glue to form a compact composite film material (CA/GO), and then transition metal oxide Nanoparticles (NPs) prepared by a room temperature rapid reduction method are riveted on the surface of the CA/GO film under the action of hydrogen bonds to realize accurate repair of GO defect positions, block gas transmission channels and further obtain the high-gas-barrier CA/GO-NPs nanocomposite film. The invention has low energy consumption and simple process flow, is easy for mass production 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 fresh-keeping, medicine packaging, electronic product packaging, agricultural packaging and other bio-plastic-based packaging.
Description
Technical Field
The invention belongs to the technical field of gas-resistant films 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 increasing attention of people to environmental problems, natural materials as bioplastic packaging have attracted more and more attention due to the advantages of biocompatibility, biodegradability, reproducibility, low cost and the like. In particular, cellulose is the most abundant and renewable natural polysaccharide that can be effectively separated from various lignocellulosic biomass, including wood or agricultural residues. In addition, cellulose Acetate (CA) has been widely used as one of the most promising derivatives of cellulose in various consumer products for daily use, such as cigarette filters, textiles, and packaging film materials. However, the high gas permeability of pure CA films severely limits their practical use 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 (e.g. carbon nanotubes, reduced graphene oxide (rGO) and Graphene Oxide (GO) nanoplatelets). Among these, two-dimensional (2D) graphene materials involving stacked GO and rGO nanoplatelets are considered to be novels in gas barrier materials due to the highly sp2 hybridized aligned carbon framework structure and small lattice parameters of 0.246 nm. Theoretically, defect-free monolayer graphene nanoplatelets are impermeable to all gases, liquids, and corrosive chemicals. However, various defects such as Stone-Wales defects, grain boundaries, vacancies, and macroscopic defects are inevitably generated in the basal plane during the exfoliation process of the original graphite and the subsequent reduction process, 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 by physical mixing. However, this treatment method limits the progress of further optimizing the basic physicochemical properties of the nanocomposite film. In addition, the dispersion of rGO typically involves the use of toxic organic solvents, which can cause environmental pollution. Therefore, it is practical to apply GO or rGO as a multilayer coating to different substrate surfaces, rather than as a separate film, by spraying, bar 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 bioplastic films with high gas resistance.
Disclosure of Invention
Based on this, it is an object of the present invention to provide a method for improving the gas barrier properties of a substrate.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
and (3) preparing a cellulose acetate film from a certain mass fraction of cellulose acetate and glycerol solution by a tape casting method, combining the cellulose acetate film with GO nano sheets under the action of molecular glue to form a compact composite film material (CA/GO), and then accurately repairing GO defect positions of rivets prepared by a room temperature rapid reduction method on the surface of the CA/GO film under the action of hydrogen bonds to block a gas transmission channel, so that the CA/GO-NPs nano composite film material with high gas barrier property can be obtained.
The cellulose acetate film is prepared by a tape casting method through a certain mass fraction of cellulose acetate and glycerol solution, wherein 6-18 wt.% of cellulose acetate and 3-12 wt.% of plasticizer are dispersed in the acetic acid solution, and the mixture is stirred uniformly, and 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) nano sheets under the action of molecular glue to form a compact composite film material (CA/GO);
3) And then, in a solution, the transition metal oxide Nano Particles (NPs) prepared by a rapid reduction method at room temperature are riveted on the surface of the CA/GO film under the action of hydrogen bonds containing oxygen groups on the surface of the GO, so that the high-gas-barrier CA/GO-NPs composite film is obtained.
The preparation process of the cellulose acetate film prepared by a casting method through the cellulose acetate and glycerin solution and adopting a casting raw material comprises the steps of dispersing 6-18 wt% (preferably 10-13 wt%) of cellulose acetate and 3-12 wt% (preferably 4-7 wt%) of plasticizer in the acetic acid solution according to the mass fraction, uniformly stirring, wherein the plasticizer is glycerin; 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) Immersing a cellulose acetate film in a chitosan aqueous solution, wherein the mass of the film is 2-8g (preferably 4-6), the volume of the solution is 10-30mL (preferably 20-25 mL), the action temperature of molecular glue is 40-100 ℃ (preferably 50-70 ℃), the action time is 5-48 h (preferably 20-26 h), 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, then immersing in GO aqueous solution, and reacting for 5-48 h (preferably 20-26 h) at 40-100deg.C (preferably 50-70deg.C); taking out the film, washing with water to remove unfixed GO, and drying at room temperature to obtain a CA/GO film; the concentration of GO in the aqueous solution is 0.1-2mg/mL (preferably 0.8-1.2 mg/mL), and the volume of GO solution is 10-30mL (preferably 20-25 mL).
The transition metal oxide Nano Particles (NPs) prepared by adopting a rapid reduction method at room temperature in the step (3) are transition metal oxide nano particle solutions obtained by rapidly reducing transition metal salt ions in a solvent at room temperature by adopting sodium borohydride, wherein one or more than two of transition metal iron, cobalt and nickel are obtained, the solvent is ethylene glycol, and the obtained nano particles are one or more than two of ferric oxide, cobalt oxide and nickel oxide.
The anions of the transition metal salt are one or more than two of acetate ions, chloride ions, nitrate ions and the like. The concentration of transition metal ion in 10mL solvent is 10-120mM (preferably 40-60 mM), the dosage of sodium borohydride is 50-300mg (preferably 80-120 mg), and the reaction temperature is 20-30deg.C (preferably 24-28deg.C). The rivet can realize GO defect level accurate repair on the surface of the CA/GO film under the action of hydrogen bond, and the specific process is that the prepared CA/GO composite film is soaked in the prepared NPs solution, the mass of the film is 3-9g (preferably 5-7 g), the volume of the solution is 5-30mL (preferably 10-15 mL), the soaking time is 1-10h (preferably 1.5-3 h), and the temperature is 20-30 ℃ and preferably 24-28 ℃.
The prepared product has the advantages of simple operation, low energy consumption, good batch-to-batch repeatability, 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 the bioplastic film with stable structure and high barrier property by adopting molecular glue and a nano repair strategy for the first time, and is expected to be widely applied to the field 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 bio-plastic film has low energy consumption and simple flow, and is easy for mass production and large-area production.
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and are all performed in accordance with the operation or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagents available commercially without the manufacturer's knowledge.
Example 1
1) 12g of cellulose acetate and 5mL of glycerol were accurately weighed and dissolved in 95mL of acetic acid solution, and stirred well until all dissolved. And (3) adopting a tape casting method to obtain a cellulose acetate film, and naturally drying at room temperature to obtain a CA film, wherein the thickness of the CA film is 100 mu m.
2) 5g of cellulose acetate film was immersed in 20mL of an aqueous solution of chitosan having a concentration of 3wt.% and incubated at 60℃for 24h.
Taking out the film, flushing with deionized water, and removing unreacted molecular glue; then immersing in 20mL of GO (thickness 1-2 nm) aqueous solution with concentration of 1mg/mL, and preserving the temperature at 60 ℃ for 24h. Taking out the film, washing with deionized water to remove unfixed GO, and drying at room temperature to obtain the CA/GO film.
3) Accurately weighing 0.18g of cobalt acetate tetrahydrate, dissolving in 10mL of glycol, slowly adding 100mg of sodium borohydride in a stirring state, and obtaining a glycol solution with cobalt nanoparticles (particle size of 2-3 nm) uniformly dispersed.
And (3) soaking the 6gCA/GO film in 10mL of the reacted glycol solution, taking out after 8h, and washing with deionized water to remove the non-riveted nano particles, thereby obtaining the CA/GO-NPs composite film.
Example 2
1) 15g of cellulose acetate and 5mL of glycerol were accurately weighed and dissolved in 95mL of acetic acid solution, and stirred well until all dissolved. And (3) adopting a tape casting method to obtain a cellulose acetate film, and naturally drying at room temperature to obtain a CA film, wherein the thickness of the CA film is 100 mu m.
2) 4g of cellulose acetate film was immersed in 20mL of an aqueous solution of polyvinyl alcohol having a concentration of 2wt.% and incubated at 90℃for 12 hours. The film was removed, rinsed with deionized water to remove unreacted molecular glue, then immersed in 20mL of aqueous solution of GO (thickness 1-2 nm) at a concentration of 2mg/mL, and incubated at 60℃for 10h. Taking out the film, washing with deionized water to remove unfixed GO, and drying at room temperature to obtain the CA/GO film.
3) Accurately weighing 0.18g of nickel acetate tetrahydrate, dissolving in 10mL of ethylene glycol, slowly adding 150mg of sodium borohydride in a stirring state, and obtaining the ethylene glycol solution with uniformly dispersed nickel nanoparticles (particle size of 2-3 nm).
And immersing the 6gCA/GO film in 10mL of the reacted glycol solution, taking out after 2 hours, and washing with deionized water to remove the non-riveted nano particles, thereby obtaining the CA/GO-NPs composite film.
Example 3
1) 6g of cellulose acetate and 10mL of glycerol were accurately weighed and dissolved in 90mL of acetic acid solution, and stirred well until all dissolved. And (3) adopting a tape casting method to obtain a cellulose acetate film, and naturally drying at room temperature to obtain a CA film, wherein the thickness of the CA film is 90 mu m.
2) 5g of cellulose acetate film was immersed in 20mL of an aqueous solution of polyethylenimine having a concentration of 2wt.% and incubated at 40℃for 5h. The film was removed, rinsed with deionized water to remove unreacted molecular glue, then immersed in 20mL of aqueous solution of GO (thickness 1-2 nm) at a concentration of 2mg/mL, and incubated at 50deg.C for 6h. Taking out the film, washing with deionized water to remove unfixed GO, and drying at room temperature to obtain the CA/GO film.
3) Accurately weighing 0.18g of iron acetate tetrahydrate, dissolving in 10mL of ethylene glycol, and slowly adding 300mg of sodium borohydride in a stirring state to obtain an ethylene glycol solution with uniformly dispersed iron nanoparticles (particle size of 2-3 nm).
And immersing the 6gCA/GO film in 10mL of the reacted glycol solution, taking out after 7h, and washing with deionized water to remove the non-riveted nano particles, thus obtaining the CA/GO-NPs.
Example 4
1) 12g of cellulose acetate and 8mL of glycerol were accurately weighed and dissolved in 92mL of acetic acid solution, and stirred well until all dissolved. And (3) adopting a tape casting method to obtain a cellulose acetate film, and naturally drying at room temperature to obtain a CA film, wherein the thickness of the CA film is 100 mu m.
2) 6g of cellulose acetate film was immersed in 20mL of an aqueous solution of polyethylenimine having a concentration of 2wt.% and incubated at 70℃for 12h. The film was removed, rinsed with deionized water to remove unreacted molecular glue, then immersed in 20mL of aqueous solution of GO (thickness 1-2 nm) at a concentration of 2mg/mL, and incubated at 70℃for 12h. Taking out the film, washing with deionized water to remove unfixed GO, and drying at room temperature to obtain the CA/GO film.
3) Accurately weighing 0.09g of iron acetate tetrahydrate and 0.09g of cobalt acetate tetrahydrate, dissolving in 10mL of ethylene glycol, slowly adding 100mg of sodium borohydride in a stirring state, and obtaining the ethylene glycol solution with uniformly dispersed iron-cobalt nanoparticles (particle size of 2-3 nm).
And immersing the 6gCA/GO film in 10mL of the reacted glycol solution, taking out after 3 hours, and washing with deionized water to remove the non-riveted nano particles, thus obtaining the CA/GO-NPs.
Example 5
1) 14g of cellulose acetate and 8mL of glycerol were accurately weighed and dissolved in 92mL of acetic acid solution, and stirred well until all dissolved. And (3) adopting a tape casting method to obtain a cellulose acetate film, and naturally drying at room temperature to obtain a CA film, wherein the thickness of the CA film is 100 mu m.
2) 5g of cellulose acetate film was immersed in 20mL of an aqueous solution of polyethylenimine having a concentration of 2wt.% and incubated at 80℃for 10h. The film was removed, rinsed with deionized water to remove unreacted molecular glue, then immersed in 20mL of aqueous solution of GO (thickness 1-2 nm) at a concentration of 1mg/mL, and incubated at 80℃for 10h. Taking out the film, washing with deionized water to remove unfixed GO, and drying at room temperature to obtain the CA/GO film.
3) Accurately weighing 0.18g of iron acetate tetrahydrate, dissolving in 10mL of ethylene glycol, and slowly adding 50mg of sodium borohydride in a stirring state to obtain an ethylene glycol solution with uniformly dispersed iron nanoparticles (particle size of 2-3 nm).
And (3) immersing the 7gCA/GO film in 10mL of the reacted glycol solution, taking out after 5 hours, and washing with deionized water to remove the non-riveted nano particles, thus obtaining the CA/GO-NPs.
Test of gas barrier and stability properties of the composite film:
1. laboratory evaluation method:
1) Measuring Oxygen Transmission Rate (OTR) with a differential pressure gas permeameter (BASIC 201, china) according to ASTM D3985 at an ambient temperature of 23±2 ℃ and a relative humidity of 50±5%;
2) The Water Vapor Permeability (WVP) was measured by a water vapor permeation tester (PERMEW 3/010, LABTHINK, china) at 38.+ -. 0.5 ℃ and 90.+ -. 1% relative humidity according to the standard method (ASTM E398).
2. Performance detection
The results of the comparison of the effects of the three films prepared in example 1 above are shown in Table 1.
Table 1 example 1 effect comparison
As can be seen from Table 1, the barrier effect of the obtained CA/GO-NPs composite film is superior to that of other comparative examples, and the oxygen and water vapor transmission rates are obviously lower than those of other comparative examples.
The barrier effect of the CA/GO-NPs composite films prepared in the various examples above were compared and the results are shown in Table 2.
TABLE 2 Barrier Effect comparison 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 superior to that of other examples, and the oxygen and water vapor transmission rates are significantly lower than those of other examples. However, the composite films prepared in examples 2 to 5 are superior to the original CA film in gas barrier property, and the oxygen and water vapor transmission rates are significantly lower than those of the original CA film, so that the gas barrier property of the CA film can be significantly improved by the method of the invention.
3. Product stability test
The stability of the product was examined using the CA/GO-NPs composite film prepared in example 1, and the results are shown in Table 3.
TABLE 3 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 bioplastic film. The films prepared in examples 2-5 also had good stability and showed no significant delamination after repeated and sustained bending for 100 times.
The invention relates to a method for improving the gas barrier property of a matrix, belonging to the technical field of bio-plastic packaging. Experimental results show that the oxygen and water vapor barrier properties of the prepared composite film are comprehensively superior to those of the same type of products, the cost is lower, and the system is stable and has no layering and falling phenomenon.
Claims (13)
1. A method for 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) nano sheets under the action of molecular glue to form a compact composite film material (CA/GO);
3) And then, in a solution, the transition metal oxide Nano Particles (NPs) prepared by a rapid reduction method at room temperature are riveted on the surface of the CA/GO film under the action of hydrogen bonds containing oxygen groups on the surface of the GO, so that the high-gas-barrier CA/GO-NPs composite film is obtained.
2. A method according to claim 1, characterized in that: the preparation process of the cellulose acetate film prepared by a casting method through the cellulose acetate and glycerol solution and adopting the casting raw material comprises the steps of dispersing 6-18 wt.% of cellulose acetate and 3-12 wt wt.% of plasticizer in the acetic acid solution according to mass fraction, 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. A method according to claim 2, characterized in that: the preparation process of the cellulose acetate film prepared by the casting method through the cellulose acetate and glycerol solution and adopting the casting raw material comprises the steps of dispersing 10-13% by mass of wt% of cellulose acetate and 4-7% by mass of wt% of plasticizer in the acetic acid solution, and uniformly stirring.
4. A method according to claim 1, characterized in that:
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 cellulose acetate film inIn the chitosan aqueous solution, the film mass is 2-8g, the solution volume is 10-30mL molecules, and the glue action temperature is 40-100 o C, the acting time is 5-48 h, the molecular glue is one or more of chitosan, polyvinyl alcohol, polyethyleneimine and ethylenediamine tetraacetic acid, and the concentration is 1.0-5 wt%;
2) Taking out the film, washing with water to remove unreacted molecular glue, then immersing in GO aqueous solution at 40-100 DEG C o C, the acting time is 5-48 hours; taking out the film, washing with water to remove unfixed GO, and drying at room temperature to obtain a CA/GO film; the concentration of GO in the aqueous solution is 0.1-2mg/mL, and the volume of the GO solution is 10-30 mL.
5. The method of claim 4, 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 cellulose acetate film in chitosan water solution at a film mass of 4-6g, a solution volume of 20-25mL molecules and a glue action temperature of 50-70 o C, the acting time is 20-26h, the molecular glue is one or more of chitosan, polyvinyl alcohol, polyethyleneimine and ethylenediamine tetraacetic acid, and the concentration is 2-4 wt%;
2) Taking out the film, washing with water to remove unreacted molecular glue, then immersing in GO aqueous solution at 50-70 deg.C o C, the acting time is 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 concentration of GO in the aqueous solution is 0.8-1.2mg/mL, and the volume of the GO solution is 20-25 mL.
6. A method according to claim 1, characterized in that:
the transition metal oxide Nano Particles (NPs) prepared by adopting a rapid reduction method at room temperature in the step (3) are transition metal oxide nano particle solutions obtained by rapidly reducing transition metal salt ions in a solvent at room temperature by adopting sodium borohydride, wherein one or more than two of transition metal iron, cobalt and nickel are obtained, the solvent is ethylene glycol, and the obtained nano particles are one or more than two of ferric oxide, cobalt oxide and nickel oxide.
7. The method of claim 6, wherein: 10 The concentration of transition metal ion in the mL solvent is 10-120mM, the dosage of sodium borohydride is 50-300mg, and the reaction temperature is 20-30 o C。
8. The method of claim 7, wherein: 10 The concentration of transition metal ions in the mL solvent is 40-60mM, the dosage of sodium borohydride added is 80-120mg, and the reaction temperature is 24-28 o C。
9. The method of claim 6, wherein:
the anions of the transition metal salt are one or more than two of acetate ions, chloride ions and nitrate ions.
10. A method according to claim 1, characterized in that: the rivet can realize GO defect level accurate repair on the surface of the CA/GO film under the action of hydrogen bond, and the specific process comprises the steps of soaking the prepared CA/GO composite film in the prepared NPs solution, wherein the mass of the film is 3-9g, the volume of the solution is 5-30mL, the soaking time is 1-10h, and the temperature is 20-30 o C。
11. The method of claim 10, wherein: the rivet can realize GO defect level accurate repair on the surface of the CA/GO film under the action of hydrogen bond, and the specific process comprises the steps of soaking the prepared CA/GO composite film in the prepared NPs solution, wherein the mass of the film is 5-7g, the volume of the solution is 10-15mL, the soaking time is 1.5-3h, and the temperature is 24-28 o C。
12. A film prepared by the method of any one of claims 1-11.
13. Use of the film of claim 12 as a packaging film in food preservation, pharmaceutical packaging, electronic product packaging or agricultural product packaging.
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| 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 |
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