CN114575186B - Cellulose-based composite barrier film and preparation method thereof - Google Patents

Cellulose-based composite barrier film and preparation method thereof Download PDF

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CN114575186B
CN114575186B CN202210197681.XA CN202210197681A CN114575186B CN 114575186 B CN114575186 B CN 114575186B CN 202210197681 A CN202210197681 A CN 202210197681A CN 114575186 B CN114575186 B CN 114575186B
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boron nitride
cellulose
barrier film
coating
hydroxylated
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CN114575186A (en
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陈枫
谢康
刘锴
韩咚林
王帅鹏
傅强
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Sichuan University
Sichuan Sanlian New Material Co Ltd
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Sichuan University
Sichuan Sanlian New Material Co Ltd
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/52—Cellulose; Derivatives thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents
    • 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 the technical field of barrier films, and particularly relates to a modified boron nitride/cellulose-based composite efficient barrier film and a preparation method thereof. The invention provides a preparation method of a cellulose-based barrier film, which comprises the following steps: uniformly mixing modified boron nitride and cellulose ether to form a coating, coating the coating on the surface of a matrix, and drying to obtain the cellulose-based barrier film; wherein the modified boron nitride is prepared by the following method: heating the hydroxylated boron nitride, the alcohol solvent and the aminopropyltriethoxysilane at 40-70 ℃ for 15-36 h, then carrying out vacuum filtration, and finally washing and drying to obtain the modified boron nitride. The modified boron nitride/cellulose-based composite efficient barrier film disclosed by the invention has excellent mechanical properties and excellent oxygen and water vapor barrier properties.

Description

Cellulose-based composite barrier film and preparation method thereof
Technical Field
The invention belongs to the technical field of barrier films, and particularly relates to a modified boron nitride/cellulose-based composite efficient barrier film and a preparation method thereof.
Background
The barrier film is capable of effectively isolating water vapor and oxygen, and has excellent physical and mechanical properties, and can be used for a long time at 120 ℃. In food packaging, the storage time of food can be reduced by oxygen and water vapor, the storage time of the food can be effectively prolonged by the high-efficiency barrier film, the common polymer film is used as the barrier film, and the renewable resources are selected for substitution in consideration of the limitation of petroleum-based high polymer resources, so that the high-efficiency barrier film has very important value. To prevent water vapor and oxygen from entering food packaging, it is known to incorporate inorganic fillers with oxygen and water vapor barrier properties into polymeric films and coatings as barrier additives to enhance barrier performance.
Disclosure of Invention
Aiming at the defects, the invention provides a modified boron nitride/cellulose-based composite efficient barrier film and a preparation method thereof, which can effectively reduce the dependence on petroleum-based macromolecules.
The technical scheme of the invention is as follows:
the first technical problem to be solved by the invention is to provide a preparation method of a cellulose-based barrier film, which comprises the following steps: uniformly mixing modified boron nitride and cellulose ether to form a coating, coating the coating on the surface of a matrix, and drying to obtain the cellulose-based barrier film;
wherein the modified boron nitride is prepared by the following method: heating the hydroxylated boron nitride, the alcohol solvent and the aminopropyltriethoxysilane at 40-70 ℃ for 15-36 h, then carrying out vacuum filtration, and finally washing and drying to obtain the modified boron nitride.
Further, the ratio of the modified boron nitride to the cellulose ether is as follows: 90-98 parts of modified boron nitride and 2-10 parts of cellulose ether.
Further, the cellulose ether is selected from: at least one of cellulose acetate butyrate, ethyl cellulose, hydroxypropyl cellulose, or cellulose acetate.
Further, the matrix is selected from: one of book paper, coated paper, matt powder paper, grey card paper, white card paper or special paper; the properties of each paper are different, and the mechanical strength of the prepared composite film is different.
Further, the method for uniformly mixing the modified boron nitride and the cellulose ether to form the coating comprises the following steps: uniformly stirring and mixing cellulose ether and modified boron nitride in an alcohol solvent, wherein the dissolving mass ratio of the total mass of the modified boron nitride and the cellulose ether in the alcohol solvent is controlled to be 10-40%.
Preferably, in the preparation method of the coating, the solvent is ethanol with a purity of more than 95%.
Furthermore, in the preparation method of the coating, the stirring speed is 100-1000 r/min, and the stirring time is more than 3 min.
Further, in the preparation method of the modified boron nitride, the mass ratio of the alcohol solvent to the hydroxylated boron nitride is 1: 1-5, the mass ratio of Aminopropyltriethoxysilane (APS) to hydroxylated boron nitride is 1-100: 1000.
further, in the preparation method of the modified boron nitride, the hydroxylated boron nitride is prepared by the following method: adding urea and deionized water into boron nitride to obtain a mixture, then carrying out ball milling treatment at room temperature until the mixture is uniformly dispersed and the hexagonal layered boron nitride is completely hydroxylated, and finally removing the residual urea and impurities and drying to obtain the edge-hydroxylated modified hexagonal layered boron nitride.
Further, in the preparation method of the hydroxylated boron nitride, the mass ratio of the raw materials is as follows: urea: boron nitride: water =30 to 90:1:10 to 30.
Further, in the preparation method of the hydroxylated boron nitride, the ball milling process comprises the following steps: ball milling is carried out for 5 to 36 hours at a speed of 100 to 800 r/min.
Further, in the above method for manufacturing a cellulose-based barrier film, the coating film has a thickness of 10 to 500 μm.
The second technical problem to be solved by the present invention is to provide a cellulose-based barrier film, which is manufactured by the above method.
The invention has the beneficial effects that:
the modified boron nitride/cellulose-based composite efficient barrier film has excellent mechanical property and excellent oxygen and water vapor barrier property, the composite film main body is made of cellulose-based materials, only a small amount of inorganic filler is contained, no toxic and harmful reagents or medicines are used in the preparation process, the preparation process is completely green, the characteristics of environmental protection, simple flow and low cost are realized, the modified boron nitride/cellulose-based composite efficient barrier film can be used in the food packaging film industry, and the modified boron nitride/cellulose-based composite efficient barrier film has wide development prospect and industrial application value.
Description of the drawings:
FIG. 1 is a graph showing the results of water vapor barrier properties of the composite films obtained in examples 1 to 5 and comparative examples 1 to 2.
FIG. 2 is the results of mechanical properties of the composite films obtained in examples 1 to 5 and comparative example 1.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Example 1
Step one, preparing mixed slurry of urea, boron nitride and water, wherein the mass ratio of the urea to the boron nitride to the water is 60:1:24, ball milling at the rotating speed of 500r/min, and centrifuging at 5000r/min for 30min to obtain hydroxylated boron nitride; then adding the hydroxylated boron nitride into ethanol, wherein the mass ratio of the ethanol to the hydroxylated boron nitride is 1:1, then adding Aminopropyltriethoxysilane (APS), wherein the mass ratio of the added Aminopropyltriethoxysilane (APS) to the hydroxylated boron nitride is 1:1000 Heating for 15h at the temperature of 60 ℃, then filtering in vacuum, mixing and washing with ethanol and water, and then drying to obtain the modified boron nitride.
Step two, according to the mass part ratio of 2.5:97.5 mixing the modified boron nitride and the cellulose acetate butyrate into ethanol, wherein the total mass fraction is 30% (the mass fraction of the total weight of the boron nitride and the cellulose acetate butyrate in the ethanol), and stirring at a high speed of 500r/min for 5min by using a stirring rod to obtain the mixed coating.
Step three, coating the mixed paint in the step two on cellulose paper with the thickness of 50 microns in a blade mode, and drying in an oven at the temperature of 50 ℃ for 3min to obtain a composite film; the film is labeled BNNS-2.5.
Example 2
Step one, preparing mixed slurry of urea, boron nitride and water, wherein the mass ratio of the mixed slurry to the water is 60:1:24, ball milling at the rotating speed of 500r/min, and centrifuging at 5000r/min for 30min to obtain hydroxylated boron nitride; then adding the hydroxylated boron nitride into ethanol, wherein the mass ratio of the ethanol to the hydroxylated boron nitride is 1:1, then adding Aminopropyltriethoxysilane (APS), wherein the mass ratio of the added Aminopropyltriethoxysilane (APS) to the hydroxylated boron nitride is 1:1000, heating for 15h at the temperature of 60 ℃, then filtering in vacuum, mixing and washing by using ethanol and water, and then drying to obtain the modified boron nitride.
Step two, according to the mass part ratio of 5:95 mixing the modified boron nitride and the cellulose acetate butyrate into ethanol, wherein the total mass fraction is 30%, and stirring at a high speed of 500r/min for 5min by using a stirring rod to obtain the mixed coating.
And step three, coating the coating obtained in the step two on cellulose paper by blade coating with the thickness of 50 microns, and drying in an oven at 50 ℃ for 3min to obtain a composite film, wherein the film is marked as BNNS-5.
Example 3
Step one, preparing mixed slurry of urea, boron nitride and water, wherein the mass ratio is 60; then adding the hydroxylated boron nitride into ethanol, wherein the mass ratio of the ethanol to the hydroxylated boron nitride is 1:1, adding Aminopropyltriethoxysilane (APS) and hydroxylated boron nitride in a mass ratio of 1:1000, heating for 15h at the temperature of 60 ℃, then filtering in vacuum, washing by mixing ethanol and water, and drying to obtain the modified boron nitride.
Step two, according to the mass part ratio of 7.5:92.5 mixing the modified boron nitride and the cellulose acetate butyrate into ethanol, wherein the total mass fraction is 30%, and stirring at a high speed of 500r/min for 5min by using a stirring rod to obtain the mixed coating.
And step three, coating the coating obtained in the step two on cellulose paper by blade coating with the thickness of 50 microns, and drying in an oven at 50 ℃ for 3min to obtain a composite film, wherein the film is marked as BNNS-7.5.
Example 4
Step one, preparing mixed slurry of urea, boron nitride and water, wherein the mass ratio is 60; then adding the hydroxylated boron nitride into ethanol, wherein the mass ratio of the ethanol to the hydroxylated boron nitride is 1:1, adding Aminopropyltriethoxysilane (APS) and hydroxylated boron nitride in a mass ratio of 1:1000, heating for 15h at the temperature of 60 ℃, then filtering in vacuum, washing by mixing ethanol and water, and drying to obtain the modified boron nitride.
Step two, according to the mass part ratio of 10:90, mixing the modified boron nitride and the cellulose acetate butyrate into ethanol, wherein the total mass fraction is 30%, and stirring the mixture for 5min at a high speed of 500r/min by using a stirring rod to obtain the mixed coating.
And step three, coating the coating in the step two on cellulose paper by a blade of 50 micrometers, and drying in an oven at 50 ℃ for 3min to obtain a composite film, wherein the film is marked as BNNS-10.
Example 5
Step one, preparing mixed slurry of urea, boron nitride and water, wherein the mass ratio of the urea to the boron nitride to the water is 60:1, adding Aminopropyltriethoxysilane (APS) and hydroxylated boron nitride in a mass ratio of 1:1000, heating for 15h at the temperature of 60 ℃, then filtering in vacuum, mixing and washing by using ethanol and water, and then drying to obtain the modified boron nitride.
Step two, according to the mass part ratio of 12.5:87.5 mixing the modified boron nitride and the cellulose acetate butyrate into the ethanol, wherein the total mass fraction is 30%, and stirring the mixture for 5min at a high speed of 500r/min by using a stirring rod to obtain the mixed coating.
And step three, coating the coating obtained in the step two on cellulose paper by blade coating with the thickness of 50 microns, and drying in an oven at 50 ℃ for 3min to obtain a composite film, wherein the film is marked as BNNS-12.5.
Comparative example 1
Step one, dissolving cellulose acetate butyrate in ethanol according to the mass fraction of 30%, and stirring at a high speed of 500r/min for 5min by using a stirring rod to obtain the mixed coating.
And step two, coating the coating of the step one on cellulose paper by blade coating with a thickness of 50 μm, and drying in an oven at 50 ℃ for 3min to obtain a composite film, wherein the film is marked as P-CAB.
Comparative example 2
Step one, preparing mixed slurry of urea, boron nitride and water, wherein the mass ratio is 60.
Step two, according to the mass part ratio of 12.5:87.5 mixing the modified hydroxylated boron nitride and the cellulose acetate butyrate into ethanol, wherein the total mass fraction is 30%, and stirring at a high speed of 500r/min for 5min by using a stirring rod to obtain the mixed coating.
And step three, coating the coating in the step two on cellulose paper by blade coating with the thickness of 50 microns, and drying in an oven at 50 ℃ for 3min to obtain a composite film, wherein the mark of the film is BN-12.5.
And (3) carrying out barrier property test and mechanical property test on the composite films obtained in the above embodiments and comparative examples, wherein the test methods respectively comprise: using Mocon
Figure BDA0003526546880000051
W3/31 (Modern Controls Inc.), the moisture resistance of the composite coated paper was verified as Water Vapor Transmission (WVTR), in accordance with GB/T1037-1988 (38 ℃ and 90% relative humidity); briefly, a sample of about 100 mm in diameter is prepared and mounted in a cylindrical cup containing distilled water, reported as [ g/(m) m 2 ·24h)]Results of (a) are from at least 3 independent samples; the composite material was processed using a FAVIGRAPH semi-automatic machine (Textech Company, germany) at room temperature for 20mm min -1 Tensile Strength (σ) b ) And strain (. Epsilon.) values.
The results of the barrier property test and the mechanical property test are respectively shown in fig. 1 and fig. 2, and it can be seen from fig. 1 that the composite film obtained by the invention has better water vapor barrier property, and it can be seen from fig. 2 that the composite film obtained by the invention has excellent mechanical property. In addition, most of the invention is cellulose-based material, has wide sources, is completely green and nontoxic in the production process, meets the requirement of current environmental protection, and has wide development prospect and industrial application value.
The scope of the present invention is not limited to the embodiments described above, and any modifications or substitutions within the scope of the present invention will be apparent to those skilled in the art.

Claims (8)

1. A method of making a cellulose-based barrier film, the method comprising: uniformly mixing modified boron nitride and cellulose ether to form a coating, coating the coating on the surface of a matrix, and drying to obtain the cellulose-based barrier film; the proportion of the modified boron nitride to the cellulose ether is as follows: 2.5:97.5,5:95,7.5:92.5, 10:90 or 12.5:87.5;
wherein the modified boron nitride is prepared by the following method: heating the hydroxylated boron nitride, the alcohol solvent and the aminopropyltriethoxysilane at 40-70 ℃ for 15-36 h, then carrying out vacuum filtration, and finally washing and drying to obtain modified boron nitride; the mass ratio of the alcohol solvent to the hydroxylated boron nitride is 1: 1-5, the mass ratio of aminopropyltriethoxysilane to hydroxylated boron nitride is 1-100: 1000;
and, the hydroxylated boron nitride is prepared by the following method: adding urea and deionized water into boron nitride to obtain a mixture, then carrying out ball milling treatment at room temperature until the mixture is uniformly dispersed and the boron nitride is completely hydroxylated, and finally removing the residual urea and impurities and drying to obtain edge-hydroxylated modified boron nitride; wherein the mass ratio of the raw materials is as follows: urea: boron nitride: water =30 to 90:1:10 to 30 parts; the ball milling process is to perform ball milling for 5 to 36 hours at a speed of between 100 and 800 r/min.
2. The method of preparing a cellulose-based barrier film according to claim 1, wherein the cellulose ether is selected from the group consisting of: at least one of cellulose acetate butyrate, ethyl cellulose, hydroxypropyl cellulose, or cellulose acetate.
3. A method of manufacturing a cellulose-based barrier film as in claim 1 or 2, wherein the substrate is selected from the group consisting of: one of book paper, coated paper, matt powder paper, grey card paper, white card paper or special paper.
4. The method for preparing the cellulose-based barrier film according to claim 1 or 2, wherein the method for uniformly mixing the modified boron nitride and the cellulose ether to form the coating comprises the following steps: and stirring and uniformly mixing cellulose ether and modified boron nitride in an alcohol solvent, wherein the dissolving mass ratio of the total mass of the modified boron nitride to the total mass of the cellulose ether in the alcohol solvent is controlled within 10-40%.
5. The method of claim 4, wherein the solvent is ethanol with a purity of greater than 95%.
6. The method of claim 4, wherein the stirring speed is 100-1000 r/min, and the stirring time is 3min or more.
7. The method of manufacturing a cellulose-based barrier film according to claim 1 or 2, wherein a coating film thickness is between 10 and 500 μm.
8. A cellulose-based barrier film, characterized in that the barrier film is produced using the method of any one of claims 1 to 7.
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