Preparation method of damp-proof and anti-static corrugated board based on graphene composite film

Abstract

The invention relates to a preparation method of a damp-proof and anti-static corrugated board based on a graphene composite film, and belongs to the technical field of corrugated boards. Graphene is added into a paper pulp raw material; coating a layer of base glue on the surface of the corrugated board; coating a layer of anti-static coating after the substrate glue is aired; compounding the graphene composite film onto the corrugated board in a hot pressing manner; and after coating and compounding are completed, drying, sizing, line pressing and cooling are conducted, and the dampproof and antistatic corrugated board with the graphene composite film is obtained. The preparation method comprises the following steps: preparing aminated graphene from an amino silane coupling agent, graphene and water; the preparation method comprises the following steps: preparing triquinyl graphene from castor oil maleate, aminated graphene, 2, 4, 6-triallyloxy-1, 3, 5-triazine, amino-terminated hyperbranched polyamide, dimethylamine and methylbenzene; the moisture-proof and anti-static corrugated board based on the graphene composite film prepared by the invention has excellent moisture-proof and anti-static performance.

Description

Technical Field

[0001] The invention relates to the technical field of corrugated paperboards, in particular to a method for preparing moisture-proof and antistatic corrugated paperboards based on a graphene composite film. Background Art

[0002] Corrugated cardboard occupies an extremely important position among all packaging paper container materials. This is because corrugated boxes not only have a variety of shapes, are suitable for automated high-speed production, and have good appearance display effects, but also can effectively protect products. They are also inexpensive, easy to recycle, and do not cause pollution to the environment. They are environmentally friendly packaging materials.

[0003] Chinese patent CN222251535U: A corrugated cardboard, comprising a first side paper and a second side paper, wherein at least one layer of core paper assembly is provided between the first side paper and the second side paper, wherein the core paper assembly is formed by two corrugated core papers buckled together and resting against each other on the inner side wall so that the corrugated core paper and the corrugated core paper, the first side paper or the second side paper have a buffer cavity to meet the buffering requirements.

[0004] Chinese patent CN119162866A: relates to the field of papermaking technology, specifically a high-pressure corrugated cardboard base paper and its production process; the present invention first uses 3-glycidyloxypropyltriethoxysilane to graft-modify diatomaceous earth, then uniformly disperses the diatomaceous earth in a polyhexamethyleneguanidine salt aqueous solution, mixes and stirs to uniformly disperse the polyhexamethyleneguanidine salt and adheres to the surface of the diatomaceous earth and its porous structure, and finally the antibacterial agent is successfully "grafted" onto the surface of the diatomaceous earth through 3-glycidyloxypropyltriethoxysilane, and forms a three-dimensional antibacterial network on the surface of the diatomaceous earth. The synergistic cooperation of diatomaceous earth, polyhexamethyleneguanidine salt and antibacterial agent effectively ensures the antibacterial performance of the functional additive. The use of the diatomaceous earth as a raw material for corrugated cardboard base paper significantly improves its antibacterial performance and extends its service life to a certain extent.

[0005] Chinese patent CN222205877U: discloses a reinforced corrugated cardboard, including outer cardboards, a support core and a buffer core are installed between the outer cardboards, the support core includes a support plate and a support frame installed between the support plates, the inner surface of the outer cardboard is fixedly installed with a reinforcing plate frame, the outer surface of the support plate is provided with a positioning slot, and the reinforcing plate frame is engaged with the positioning slot; the cross-sectional shape of the support frame is set to be X-shaped, and the two ends of the support frame are fixedly connected to the support plate; through the designed support core and reinforcing plate frame, when in use, the support is supported between the outer cardboards by the support core, and the strength and supporting capacity of the corrugated cardboard are strengthened by the support core, and the reinforcing plate frame is installed on the inner side of the outer cardboard, and cooperates with the positioning slot to make the reinforcing plate frame engaged with the support core, while the outer cardboard is reinforced by the reinforcing plate frame and the connection between the outer cardboard and the support core is stable, thereby making the strength of the corrugated cardboard higher.

[0006] The corrugated paperboards prepared by the above patents and prior art have unsatisfactory moisture-proof and anti-static properties. Summary of the Invention

[0007] In order to solve the above problems, the present invention provides a method for preparing moisture-proof and anti-static corrugated cardboard based on a graphene composite film, which comprises face paper, lining paper, corrugated paper and a graphene composite film; the face paper and lining paper are bonded to both sides of the corrugated paper by an adhesive; the preparation method is as follows: S1: Add 1-5% graphene to the pulp raw material to improve the compressive strength and moisture resistance of the paperboard; S2: Apply a layer of base glue on the surface of the corrugated cardboard to enhance the adsorption of the antistatic agent on the paper surface; ‌S3: After the base glue is dry, apply a layer of anti-static coating to form an effective anti-static layer; S4: The graphene composite film is laminated to the corrugated cardboard by hot pressing to enhance its moisture resistance and form an effective moisture barrier; ‌S5‌: After coating and lamination, drying, shaping, pressing and cooling are carried out to obtain moisture-proof and anti-static corrugated cardboard with graphene composite film.

[0008] The preparation method of the base glue is as follows: Add 80-100 parts of water, 10-20 parts of corn starch, 1-5 parts of carrageenan, 0.1-1 parts of bentonite, 0.1-1 parts of citric acid, and 1-5 parts of polylactic acid (PLA4032D), heat to 30-40°C, and stir for 15-25 minutes to obtain a base glue.

[0009] The preparation method of the antistatic coating is: 2-5 parts of triquinoline graphene, 8-14 parts of ethoxylated alkyl ammonium sulfate, 22-36 parts of epoxy resin E-44, and 14-26 parts of polyacrylamide NPAM-910 are stirred for 10-20 minutes to obtain an antistatic coating.

[0010] The preparation method of the triquinoline graphene is: K1: Add 3-6 parts of aminosilane coupling agent, 100-150 parts of graphene, and 1200-1500 parts of water to reactor 1, stir and react at room temperature for 100-120 minutes, filter, and dry to obtain amino-treated graphene; K2: Add 5-10 parts of castor oil maleate, 100-150 parts of amino graphene, 0.6-2.6 parts of 2,4,6-tripropyleneoxy-1,3,5-triazine, 0.5-2 parts of amino-terminated hyperbranched polyamide with a molecular weight of 350-2200 g / mol, 1.5-3.6 parts of dimethylamine, and 1200-1500 parts of toluene to reactor 2, stir and react at room temperature for 120-160 minutes, filter, and dry to obtain triquinoline graphene.

[0011] The hot pressing temperature of S4 is 160-180° C. and the time is 5-10 minutes.

[0012] Reaction mechanism Amine-olefin addition reaction: Amino groups on the surface of ammoniated graphene react with olefin groups in 2,4,6-tripropyleneoxy-1,3,5-triazine (TAT) and castor oil maleate (COE) to form covalently linked complexes. This reaction not only increases the chemical stability of the material but also introduces a variety of functional groups, expanding its diversity and application range.

[0013] Technical Effects The present invention provides a method for preparing moisture-proof and antistatic corrugated paperboard based on a graphene composite film. Compared with the prior art, the present invention has the following significant effects: 1. Enhance moisture-proof performance: Through molecular design and structural optimization, the composite material exhibits excellent moisture-proof properties and is suitable for packaging, construction and other fields.

[0014] The introduction of hyperbranched polyamide increases the material's hydrophobicity, which is further enhanced by the addition of triazine groups and castor oil esters; these groups work together to form an effective moisture barrier.

[0015] The graphene composite film is laminated to the corrugated cardboard by hot pressing to form a dense structure that effectively prevents moisture penetration; this structural design enables the composite material to maintain its performance even in a humid environment.

[0016] 2. Improve mechanical strength: The combination of graphene and hyperbranched polymer makes the composite material exhibit better resistance to deformation when subjected to external force.

[0017] 3. Improve thermal stability: Composite materials can remain stable at high temperatures and are suitable for use in various extreme conditions.

[0018] In summary, the graphene composite material grafted with hyperbranched polyamide, triazine, and castor oil ester, prepared through an amine-olefin addition reaction, is not only innovative in its molecular structure but also exhibits excellent thermal properties and moisture-proofing mechanisms. This material, when laminated to corrugated cardboard via hot pressing, significantly enhances its moisture-proof properties, forming an effective moisture barrier. DETAILED DESCRIPTION

[0019] In order to further illustrate the technical means and effects adopted by the present invention to achieve the predetermined invention object, the following is a detailed description in conjunction with examples and comparative examples: 1. Moisture Rejection Rate Test: Measured using a moisture resistivity tester; 2. Antistatic rate test: Measured using an electrostatic tester.

[0020] Example 1 A method for preparing moisture-proof and anti-static corrugated cardboard based on a graphene composite film, comprising face paper, lining paper, corrugated paper, and the graphene composite film; the face paper and lining paper are bonded to both sides of the corrugated paper by an adhesive; the preparation method is as follows: S1: Adding 1% by weight of graphene to the pulp raw material to improve the compressive strength and moisture resistance of the paperboard; S2: Apply a layer of base glue on the surface of the corrugated cardboard to enhance the adsorption of the antistatic agent on the paper surface; ‌S3: After the base glue is dry, apply a layer of anti-static coating to form an effective anti-static layer; S4: The graphene composite film is laminated to the corrugated cardboard by hot pressing to enhance its moisture resistance and form an effective moisture barrier; ‌S5‌: After coating and lamination, drying, shaping, pressing and cooling are carried out to obtain moisture-proof and anti-static corrugated cardboard with graphene composite film.

[0021] The preparation method of the base glue is as follows: 80 g of water, 10 g of corn starch, 1 g of carrageenan, 0.1 g of bentonite, 0.1 g of citric acid, and 1 g of polylactic acid (PLA4032D) were heated to 30°C and stirred for 15 min to obtain a base glue.

[0022] The preparation method of the antistatic coating is: 2 g of triquinoline graphene, 8 g of ethoxylated alkyl ammonium sulfate, 22 g of epoxy resin E-44, and 14 g of polyacrylamide NPAM-910 were stirred for 10 min to obtain an antistatic coating.

[0023] The preparation method of the triquinoline graphene is: K1: Add 3 g of aminosilane coupling agent, 100 g of graphene, and 1200 g of water to reactor 1, stir and react at room temperature for 100 minutes, filter, and dry to obtain amino-modified graphene; K2: Add 5 g of castor oil maleate, 100 g of amino-modified graphene, 0.6 g of 2,4,6-tripropyleneoxy-1,3,5-triazine, 0.5 g of amino-terminated hyperbranched polyamide with a molecular weight of 350 g / mol, 1.5 g of dimethylamine, and 1200 g of toluene to reactor 2. After stirring at room temperature for 120 minutes, filter and dry to obtain triquinoline graphene.

[0024] The hot pressing temperature of S4 is 160° C. and the time is 5 minutes.

[0025] Example 2 A method for preparing moisture-proof and anti-static corrugated cardboard based on a graphene composite film, comprising face paper, lining paper, corrugated paper, and the graphene composite film; the face paper and lining paper are bonded to both sides of the corrugated paper by an adhesive; the preparation method is as follows: S1: Add 2% by weight of graphene to the pulp raw material to improve the compressive strength and moisture resistance of the paperboard; S2: Apply a layer of base glue on the surface of the corrugated cardboard to enhance the adsorption of the antistatic agent on the paper surface; ‌S3: After the base glue is dry, apply a layer of anti-static coating to form an effective anti-static layer; S4: The graphene composite film is laminated to the corrugated cardboard by hot pressing to enhance its moisture resistance and form an effective moisture barrier; ‌S5‌: After coating and lamination, drying, shaping, pressing and cooling are carried out to obtain moisture-proof and anti-static corrugated cardboard with graphene composite film.

[0026] The preparation method of the base glue is as follows: 85 g of water, 13 g of corn starch, 2 g of carrageenan, 0.5 g of bentonite, 0.5 g of citric acid, and 2 g of polylactic acid (PLA4032D) were heated to 35°C and stirred for 18 min to obtain a base glue.

[0027] The preparation method of the antistatic coating is: 3 g of triquinoline graphene, 10 g of ethoxylated alkyl ammonium sulfate, 28 g of epoxy resin E-44, and 18 g of polyacrylamide NPAM-910 were stirred for 15 min to obtain an antistatic coating.

[0028] The preparation method of the triquinoline graphene is: K1: 4 g of aminosilane coupling agent, 110 g of graphene, and 1300 g of water were added to reactor 1. The mixture was stirred at room temperature for 105 minutes, filtered, and dried to obtain amino-modified graphene. K2: Add 6 g of castor oil maleate, 110 g of amino-modified graphene, 1.2 g of 2,4,6-tripropyleneoxy-1,3,5-triazine, 1 g of amino-terminated hyperbranched polyamide with a molecular weight of 1000 g / mol, 2 g of dimethylamine, and 1300 g of toluene to reactor 2. After stirring at room temperature for 130 minutes, filter and dry to obtain triquinoline graphene.

[0029] The hot pressing temperature of S4 is 165° C. and the time is 6 minutes.

[0030] Example 3 A method for preparing moisture-proof and anti-static corrugated cardboard based on a graphene composite film, comprising face paper, lining paper, corrugated paper, and the graphene composite film; the face paper and lining paper are bonded to both sides of the corrugated paper by an adhesive; the preparation method is as follows: S1: Adding 4% by weight of graphene to the pulp raw material to improve the compressive strength and moisture resistance of the paperboard; S2: Apply a layer of base glue on the surface of the corrugated cardboard to enhance the adsorption of the antistatic agent on the paper surface; ‌S3: After the base glue is dry, apply a layer of anti-static coating to form an effective anti-static layer; S4: The graphene composite film is laminated to the corrugated cardboard by hot pressing to enhance its moisture resistance and form an effective moisture barrier; ‌S5‌: After coating and lamination, drying, shaping, pressing and cooling are carried out to obtain moisture-proof and anti-static corrugated cardboard with graphene composite film.

[0031] The preparation method of the base glue is as follows: 95 g of water, 18 g of corn starch, 4 g of carrageenan, 0.8 g of bentonite, 0.8 g of citric acid, and 4 g of polylactic acid (PLA4032D) were heated to 35°C and stirred for 23 min to obtain a base glue.

[0032] The preparation method of the antistatic coating is: 4 g of triquinoline graphene, 12 g of ethoxylated alkyl ammonium sulfate, 32 g of epoxy resin E-44, and 23 g of polyacrylamide NPAM-910 were stirred for 15 min to obtain an antistatic coating.

[0033] The preparation method of the triquinoline graphene is: K1: 5 g of aminosilane coupling agent, 140 g of graphene, and 1400 g of water were added to reactor 1. The mixture was stirred at room temperature for 115 minutes, filtered, and dried to obtain amino-modified graphene. K2: 8 g of castor oil maleate, 140 g of amino-modified graphene, 2 g of 2,4,6-tripropyleneoxy-1,3,5-triazine, 1.5 g of amino-terminated hyperbranched polyamide with a molecular weight of 1500 g / mol, 3 g of dimethylamine, and 1400 g of toluene were added to reactor 2. The mixture was stirred at room temperature for 150 minutes, filtered, and dried to obtain triquinoline graphene.

[0034] The hot pressing temperature of S4 is 175° C. and the time is 8 minutes.

[0035] Example 4 A method for preparing moisture-proof and anti-static corrugated cardboard based on a graphene composite film, comprising face paper, lining paper, corrugated paper, and the graphene composite film; the face paper and lining paper are bonded to both sides of the corrugated paper by an adhesive; the preparation method is as follows: S1: Add 5% by weight of graphene to the pulp raw material to improve the compressive strength and moisture resistance of the paperboard; S2: Apply a layer of base glue on the surface of the corrugated cardboard to enhance the adsorption of the antistatic agent on the paper surface; ‌S3: After the base glue is dry, apply a layer of anti-static coating to form an effective anti-static layer; S4: The graphene composite film is laminated to the corrugated cardboard by hot pressing to enhance its moisture resistance and form an effective moisture barrier; ‌S5‌: After coating and lamination, drying, shaping, pressing and cooling are carried out to obtain moisture-proof and anti-static corrugated cardboard with graphene composite film.

[0036] The preparation method of the base glue is as follows: 100 g of water, 20 g of corn starch, 5 g of carrageenan, 1 g of bentonite, 1 g of citric acid, and 5 g of polylactic acid (PLA4032D) were heated to 40°C and stirred for 25 min to obtain a base glue.

[0037] The preparation method of the antistatic coating is: 5 g of triquinoline graphene, 14 g of ethoxylated alkyl ammonium sulfate, 36 g of epoxy resin E-44, and 26 g of polyacrylamide NPAM-910 were stirred for 20 min to obtain an antistatic coating.

[0038] The preparation method of the triquinoline graphene is: K1: Add 6 g of aminosilane coupling agent, 150 g of graphene, and 1500 g of water to reactor 1, stir and react at room temperature for 120 minutes, filter, and dry to obtain amino-treated graphene; K2: 10 g of castor oil maleate, 150 g of amino-modified graphene, 2.6 g of 2,4,6-tripropyleneoxy-1,3,5-triazine, 2 g of amino-terminated hyperbranched polyamide with a molecular weight of 2200 g / mol, 3.6 g of dimethylamine, and 1500 g of toluene were added to reactor 2. The mixture was stirred at room temperature for 160 minutes, filtered, and dried to obtain triquinoline graphene.

[0039] The hot pressing temperature of S4 is 180° C. and the time is 10 minutes.

[0040] Comparative Example 1 Without adding triquinoline graphene, the other steps were the same as in Example 1.

[0041] Comparative Example 2 The same procedures as in Example 1 were followed except that castor oil maleate was not added.

[0042] Comparative Example 3 The other steps were the same as in Example 1 except that 2,4,6-tripropyleneoxy-1,3,5-triazine was not added.

[0043] The test results are shown in Table 1: Table 1 Moisture rejection rate / % Antistatic rate / % Example 1 4.8 99.69 Example 2 4.5 99.73 Example 3 4.1 99.81 Example 4 3.9 99.85 Comparative Example 1 8.3 82.37 Comparative Example 2 6.7 93.77 Comparative Example 3 6.2 95.46 Through the data analysis of the above examples and comparative examples, the moisture-proof and antistatic corrugated paperboard based on the graphene composite film prepared by the present invention has excellent moisture-proof and antistatic properties.

[0044] The above description is merely a preferred embodiment of the present invention and does not constitute any form of limitation to the present invention. Although the present invention has been disclosed as above in terms of a preferred embodiment, it is not intended to limit the present invention. Any person skilled in the art can, without departing from the scope of the technical solution of the present invention, make some changes or modifications to equivalent embodiments using the technical contents disclosed above. However, any brief modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. A method for preparing moisture-proof and anti-static corrugated paperboard based on a graphene composite film, comprising face paper, lining paper, corrugated paper, and a graphene composite film; the face paper and lining paper are bonded to both sides of the corrugated paper by an adhesive; Its preparation method is: S1: Add 1-5% graphene to the pulp raw material to improve the compressive strength and moisture resistance of the paperboard; S2: Apply a layer of base glue on the surface of the corrugated cardboard to enhance the adsorption of the antistatic agent on the paper surface; ‌S3: After the base glue is dry, apply a layer of anti-static coating to form an effective anti-static layer; S4: The graphene composite film is laminated to the corrugated cardboard by hot pressing to enhance its moisture resistance and form an effective moisture barrier; S5: After coating and lamination, the product is dried, shaped, pressed, and cooled to obtain moisture-proof and anti-static corrugated cardboard with graphene composite film. The antistatic coating is prepared by reacting triquinoline graphene, ethoxylated alkyl ammonium sulfate, epoxy resin and polyacrylamide.

2. The method for preparing moisture-proof and antistatic corrugated cardboard based on graphene composite film according to claim 1, characterized in that: The preparation method of the base glue is as follows: Add 80-100 parts of water, 10-20 parts of corn starch, 1-5 parts of carrageenan, 0.1-1 parts of bentonite, 0.1-1 parts of citric acid, and 1-5 parts of polylactic acid, heat to 30-40°C and stir for 15-25 minutes to obtain a base glue.

3. The method for preparing moisture-proof and antistatic corrugated paperboard based on graphene composite film according to claim 1, characterized in that: The preparation method of the antistatic coating is: 2-5 parts of triquinoline graphene, 8-14 parts of ethoxylated alkyl ammonium sulfate, 22-36 parts of epoxy resin, and 14-26 parts of polyacrylamide are stirred for 10-20 minutes to obtain an antistatic coating.

4. The method for preparing moisture-proof and antistatic corrugated paperboard based on graphene composite film according to claim 3, characterized in that: The preparation method of the triquinoline graphene is: K1: Add 3-6 parts of aminosilane coupling agent, 100-150 parts of graphene, and 1200-1500 parts of water to reactor 1, stir and react at room temperature for 100-120 minutes, filter, and dry to obtain amino-treated graphene; K2: Add 5-10 parts of castor oil maleate, 100-150 parts of amino graphene, 0.6-2.6 parts of 2,4,6-tripropyleneoxy-1,3,5-triazine, 0.5-2 parts of amino-terminated hyperbranched polyamide, 1.5-3.6 parts of dimethylamine, and 1200-1500 parts of toluene to reactor 2, stir and react at room temperature for 120-160 minutes, filter, and dry to obtain triquinoline graphene.

5. The method for preparing moisture-proof and antistatic corrugated paperboard based on graphene composite film according to claim 1, characterized in that: The hot pressing temperature of S4 is 160-180° C. and the time is 5-10 minutes.