CN111485447B - Cellulose paper/dynamic covalent polymer composite packaging material and preparation method and application thereof - Google Patents

Cellulose paper/dynamic covalent polymer composite packaging material and preparation method and application thereof Download PDF

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CN111485447B
CN111485447B CN202010305839.1A CN202010305839A CN111485447B CN 111485447 B CN111485447 B CN 111485447B CN 202010305839 A CN202010305839 A CN 202010305839A CN 111485447 B CN111485447 B CN 111485447B
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packaging material
cellulose paper
dynamic covalent
covalent polymer
polymer composite
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CN111485447A (en
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王小慧
苏治平
张伟
金英华
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South China University of Technology SCUT
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South China University of Technology SCUT
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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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/47—Condensation polymers of aldehydes or ketones
    • D21H17/49—Condensation polymers of aldehydes or ketones with compounds containing hydrogen bound to nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B32B29/002—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B29/005—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material next to another layer of paper or cardboard layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B32B29/06—Layered products comprising a layer of paper or cardboard specially treated, e.g. surfaced, parchmentised
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C08G12/06—Amines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/26—All layers being made of paper or paperboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/12—Coating on the layer surface on paper layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/028—Paper layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/716—Degradable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/02—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/04—Time
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/12—Pressure
    • 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
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging

Abstract

The invention belongs to the field of material chemistry, and particularly discloses a cellulose paper/dynamic covalent polymer composite packaging material as well as a preparation method and application thereof. The preparation method of the cellulose paper/dynamic covalent polymer composite packaging material comprises the following steps: preparing dynamic covalent polymer, compounding the dynamic covalent polymer and cellulose paper to obtain a cellulose paper/dynamic covalent polymer composite material, and then carrying out hot pressing treatment on the cellulose paper/dynamic covalent polymer composite material to obtain the cellulose paper/dynamic covalent polymer composite packaging material. The polymer matrix-polyimine used in the invention can be rapidly synthesized at room temperature by using cheap reaction monomers. Meanwhile, the polyimide has good thermal processing property, self-healing property, chemical degradation property and recycling property. In addition, the cellulose paper and the polyimide can be compounded only by simple dipping, spraying or coating and assisted hot pressing treatment to obtain the cellulose paper-based packaging material.

Description

Cellulose paper/dynamic covalent polymer composite packaging material and preparation method and application thereof
Technical Field
The invention belongs to the field of material chemistry, and particularly relates to a cellulose paper/dynamic covalent polymer composite packaging material, and a preparation method and application thereof.
Background
Plastics are indispensable synthetic polymer materials in modern life. The composite material has the characteristics of low price, light weight, high transparency, good mechanical strength and the like, and has the advantages of excellent gas barrier, water resistance, high chemical stability and the like. Therefore, a large number of plastic articles are used as packaging materials for various industrial products. By 2018, the production of global plastic packaging materials has reached as high as 15 hundred million tons, which accounts for 40% of the total global plastic production. In addition, it is estimated that the total yield of global packaging plastic will exceed 25 hundred million tons in 2050. However, due to the non-degradability of conventional petroleum-based plastics and the high cost of plastic recovery, the current recovery of waste packaging plastics is less than 10%. A large amount of packaging plastic waste is buried in soil or discharged into the sea and will exist in nature for hundreds of years without being degraded, thereby posing a serious threat to the ecological environment. Although some degradable biomass-based plastics, such as polylactic acid (PLA), thermoplastic starch and PHAs (polyhydroxyalkanoates), have been put into production and applied as packaging materials. However, compared with the traditional petroleum-based plastics, the biomass-based plastics still have the defects of high production cost, poor mechanical property, insufficient toughness, low water stability, low gas barrier capability and the like. Therefore, further research and development of new biomass-based packaging plastics with high performance and low cost are needed.
Cellulose paper is a cheap biomass-based material consisting of plant fibres. The composite material not only has good mechanical property, flexibility, thermal stability and chemical stability, but also can be completely biodegraded and recycled. However, the porosity and hydrophilic nature of cellulose paper does not provide the high gas barrier and water resistance characteristics required for packaging materials. In addition, the cellulose paper does not have the thermal fusion and plastic processing properties of the traditional plastics due to the strong hydrogen bonding acting force among the cellulose molecular chains. Although cellulose paper composites with the possibility of replacing traditional plastics are currently obtained by methods and technologies of chemical vapor deposition, graphene composite, paper-plastic composite, natural polymer coating, these composites still have the disadvantages of high production cost, poor degradation performance, low water resistance, poor hot workability, etc. Therefore, it is necessary and meaningful to develop a low-cost technology for converting cellulose paper into bio-based packaging materials.
Disclosure of Invention
The invention aims at providing a preparation method of a cellulose paper/dynamic covalent polymer composite packaging material, which compounds dynamic covalent polymer in a porous network of cellulose paper so as to prepare a high-performance cellulose paper-based packaging material. The cellulose paper-based packaging material has the advantages of simple production process, low production cost and easy large-scale production.
Another object of the present invention is to provide a cellulose paper/dynamic covalent polymer composite packaging material obtained by the above preparation method, wherein the plastic product has the advantages of high strength, high modulus, high gas barrier capability, high water resistance, high chemical stability, degradability, recyclability, etc.
The invention further aims to provide application of the cellulose paper/dynamic covalent polymer composite packaging material in a bio-based packaging material.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a cellulose paper/dynamic covalent polymer composite packaging material comprises the following steps:
preparing dynamic covalent polymer, then compounding the dynamic covalent polymer and the cellulose paper to obtain a cellulose paper/dynamic covalent polymer composite material, and then carrying out hot pressing treatment on the obtained cellulose paper/dynamic covalent polymer composite material to obtain the cellulose paper/dynamic covalent polymer composite packaging material.
Preferably, the dynamic covalent polymer is at least one of polyimine, polyhydrazone, polyoxime, polyborate, polysilicone, and polydioxanilide.
Preferably, the preparation method of the dynamic covalent polymer comprises the following steps: the preparation method comprises the following steps of carrying out Schiff base reaction, transesterification reaction, Diels-Alder reaction, disulfide bond exchange reaction, ketoamine polycondensation reaction, Thiol-Michael reaction, transthioesterification reaction, boric acid condensation reaction, silicon ether bond exchange reaction, transcarbamylation reaction, aldol condensation reaction, phenolic aldehyde condensation reaction, Friedel-Crafts alkylation reaction, Strecker reaction, olefin metathesis reaction, alkyne metathesis reaction or dynamic urea bond formation on reaction monomers.
More preferably, the dynamic covalent polymer is prepared by mixing aldehyde and amine in an organic solvent, then carrying out a condensation reaction, and removing the organic solvent after the reaction is completed. Wherein the aldehyde is at least one of an aromatic aldehyde and an aliphatic aldehyde; the amine is at least one of aliphatic amine and aromatic amine; the molar ratio of the aldehyde to the amine is 1: 0.5-1, and more preferably 1: 0.77; the polycondensation reaction is carried out at normal temperature for 4-8 h.
Wherein the aromatic aldehyde is at least one of terephthalaldehyde, o-phthalaldehyde, m-phthalaldehyde, 2, 5-dihydroxy-1, 4-phthalaldehyde, 2, 5-dimethoxy-1, 4-phthalaldehyde, 2, 5-dicyano-1, 4-phthalaldehyde, 2, 5-dimethyl-1, 4-phthalaldehyde, 2, 5-diethyl-1, 4-benzenedimethanol, 4' -biphenyldicarboxaldehyde, trimesic aldehyde and furandicarboxaldehyde; the aliphatic aldehyde is at least one of glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, adipaldehyde and suberaldehyde; the aliphatic amine is at least one of ethylenediamine, butanediamine, pentanediamine, hexanediamine, heptanediamine, octanediamine, nonanediamine, decanediamine, 1, 12-diaminododecane, diethylenetriamine, N 'N-bis (3-aminopropyl) methylamine and 3,3' -diaminodipropylamine tris (2-aminoethyl) amine; the aromatic amine is at least one of p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, 3, 5-diaminonitrobenzene, 4, 6-dimethoxy-3, 5-phenylenediamine and m-xylylenediamine.
Preferably, the cellulose paper is paper made by a paper making method using plant fiber as a raw material, such as printing paper, newspaper, paper towel, and the like. More preferably, the plant is needle-leaved wood, broad-leaved wood, gramineous plant, grass, bamboo, cotton or hemp.
Preferably, the method used to incorporate the dynamic covalent polymer into the cellulose paper is dipping, spraying or coating.
Preferably, the hot pressing method is flat plate hot pressing, the temperature of the hot pressing is 80-150 ℃, the pressure is 0.1-10 MPa, and the time is 1-30 min. More preferably, the pressure of the hot pressing is 1-10MPa, and the time is 5-30 min.
The invention further provides the cellulose paper/dynamic covalent polymer composite packaging material obtained by the preparation method.
The invention further provides the application of the cellulose paper/dynamic covalent polymer composite packaging material in a bio-based packaging material.
The applications include 3D structural shaping, self-healing, multi-layer compounding, degradation and recycling of cellulosic paper/dynamic covalent polymer composite packaging materials.
The invention further provides a 3D structure shaping method of the cellulose paper/dynamic covalent polymer composite packaging material, in particular to a method for shaping the stress relaxation temperature (T) of the cellulose paper/dynamic covalent polymer composite packaging materialv) The cellulose-based packaging material is heated and softened for 1-10 min and molded into different 3D shapes.
The invention further provides a self-repairing method of the cellulose paper/dynamic covalent polymer composite packaging material, which is to package the surface damaged cellulose paper/dynamic covalent polymer composite at the stress relaxation temperature (T) of the dynamic covalent polymerv) Hot pressing for 1-5 min under the pressure of 0.5 Ma-5 MPa.
The invention further provides a multilayer composite method of the cellulose paper/dynamic covalent polymer composite packaging material, wherein the cellulose paper/dynamic covalent polymer composite packaging material is stacked between two pieces of hot-pressing cloth and is at the stress relaxation temperature (T) of the materialv) Hot pressing under the pressure of 0.5-10 MPa for 1-10 min.
The invention further provides a degradation and recovery method of the cellulose paper/dynamic covalent polymer composite packaging material, which comprises the steps of soaking the cellulose paper/dynamic covalent polymer composite packaging material to be degraded into a diamine monomer solution to completely degrade polyimide; the recovered reactive monomers are then repolymerized to polyimines and the recovered cellulose paper is compounded to produce a recyclable cellulose paper-based packaging material.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the cellulose paper-based packaging material prepared by the existing cellulose paper functionalization technology, such as chemical vapor deposition, graphene compounding, paper-plastic compounding, natural polymer coating and the like, has the defects of poor stability, low water resistance, poor mechanical property, difficulty in realizing hot shaping processing, complex and long time-consuming preparation process, high production cost, difficulty in realizing 100% recycling and the like. The polymer matrix-polyimine used in the invention can be rapidly synthesized at room temperature by using cheap reaction monomers without a catalyst. Meanwhile, the polyimide has good thermal processing property, self-healing property, chemical degradation property and recycling property. In addition, the cellulose paper and the polyimide can be compounded only by simple dipping, spraying or coating and auxiliary short-time hot-pressing treatment to obtain the cellulose paper-based packaging material. The polyimide not only enables the cellulose paper-based packaging material to have good mechanical, gas barrier and water and organic solvent resistance, but also enables the final composite material to show excellent reprocessing, self-healing, degradability and recoverability. The cellulose paper-based packaging material prepared by the invention has the advantages of excellent comprehensive performance, simple production process, low cost, environmental protection and the like.
Drawings
FIG. 1 is a diagram of the preparation of polyimines;
FIG. 2 is a flow chart of the preparation of a cellulose paper/dynamic covalent polymer composite packaging material;
FIG. 3 is an infrared spectrum of a polyimide and the packaging material 1 prepared in example 1;
FIG. 4 is a plot of dynamic thermodynamic (DMA) tests of polyimines and three cellulose paper-based packaging materials (packaging material 1, packaging material 2, and packaging material 3) prepared in examples 1-3;
FIG. 5 is a tensile stress-strain curve of three cellulose paper/dynamic covalent polymer composite packaging materials (packaging material 1, packaging material 2 and packaging material 3) prepared in examples 1-3;
FIG. 6 is a tensile stress strain curve of the cellulose paper-based packaging material prepared in examples 4 to 5 at hot pressing temperatures of 80 ℃ and 150 ℃;
FIG. 7 is a tensile stress-strain curve of the cellulose paper-based packaging material prepared in examples 6 to 7 at hot pressing pressures of 0.1MPa and 10 MPa;
FIG. 8 is a tensile stress-strain curve of the cellulose paper-based packaging material prepared in examples 8 to 9 at hot pressing times of 1min and 30 min;
fig. 9 is a 3D shaping view of wrapping materials 1, 2, and 3 in example 10;
FIG. 10 is a graph comparing the tensile properties of the repaired wrapping material 1 and the original wrapping material 1 of example 11;
FIG. 11 is a graph comparing the tensile properties of the multi-layer compounded packaging material 1 and the single-layer packaging material 1 of example 12;
fig. 12 is a graph comparing the stretch properties of the recovered packaging material 1 and the original packaging material 1 in example 13.
Detailed Description
The present invention will be described in further detail with reference to specific examples and drawings, but the embodiments of the present invention are not limited thereto, and may be performed with reference to conventional techniques for process parameters not particularly noted. In the embodiment, the normal temperature is 20-35 ℃.
Example 1
This embodiment provides a method for producing a printed paper-based packaging material (packaging material 1).
The preparation method of the packaging material 1 comprises the following steps:
(1) preparing polyimide: according to the Schiff base reaction mechanism shown in figure 1, according to the mole ratio of dialdehyde (terephthalaldehyde), diamine (diethylenetriamine) and triamine (tris (2-aminoethyl) amine) of 1:0.3:0.47, 3.46g of terephthalaldehyde, 0.8g of diethylenetriamine and 1.76g of tris (2-aminoethyl) amine are dissolved in 170ml of ethanol and reacted for 6h at normal temperature to obtain a polyimide solution, and the organic solvent is further volatilized to obtain the polyimide film. The infrared spectrum (fig. 3) shows that the synthesized polymer has a strong imine absorption peak, which proves that the polyimide is successfully synthesized. Dynamic mechanical analysis testing (DMA) showed that the glass transition temperature (Tg) of the polyimide was 115 ℃ (fig. 4);
(2) according to fig. 2, the printing paper is immersed in the polyimide solution for 40 min;
(3) volatilizing a large amount of ethanol at room temperature to solidify the polyimide inside and on the surface of the paper;
(4) and (3) carrying out hot pressing on the obtained paper-polyimide composite material for 5min at the temperature of 120 ℃ and under the pressure of 1.54MPa by utilizing a flat hot press to obtain the packaging material 1. Fig. 5 shows that the tensile strength of the packaging material 1 was 75MPa and the elongation at break was 4.6%. The packaging material 1 has a water vapor transmission rate, an oxygen transmission rate and a water flux of<0.01g·mm·m-2·day-1，<1.0×10- 4Barrer and 0 ml. m-2·min-1·KPa-1。
Example 2
This example provides a method of preparing a newspaper-based packaging material (packaging material 2).
The preparation method of the packaging material 2 is as follows:
(1) preparing polyimide: according to the Schiff base reaction mechanism shown in figure 1, 3.46g of terephthalaldehyde, 0.8g of diethylenetriamine and 1.76g of tris (2-aminoethyl) amine are dissolved in 170ml of ethanol according to the molar ratio of dialdehyde (terephthalaldehyde), diamine (diethylenetriamine) and triamine (tris (2-aminoethyl) amine) of 1:0.3:0.47, and reacted at normal temperature for 6h to obtain a polyimide solution. Further volatilizing the organic solvent to obtain a polyimide film, and an infrared spectrum (figure 3) shows that the synthesized polymer has a strong imine absorption peak, which proves that the polyimide is successfully synthesized. Dynamic mechanical analysis testing (DMA) showed that the glass transition temperature (Tg) of the polyimide was 115 ℃ (fig. 4);
(2) according to FIG. 2, the newspaper is dipped in the polyimide solution for 80 min;
(3) volatilizing a large amount of ethanol at room temperature to solidify the polyimide inside and on the surface of the paper;
(4) and (3) carrying out hot pressing on the obtained paper-polyimide composite material for 5min at the temperature of 120 ℃ and under the pressure of 1.54MPa by utilizing a flat hot press to obtain the packaging material 2. Fig. 5 shows that the tensile strength of the packaging material 2 was 62MPa and the elongation at break was 2.8%. The packaging material 2 has a water vapor transmission rate, an oxygen transmission rate and a water flux of<0.006g·mm·m-2·day-1，<7.0×10- 5Barrer and 0 ml. m-2·min-1·KPa-1。
Example 3
This example provides a method for producing a packaging material (packaging material 3) based on a paper towel.
The preparation method of the packaging material 3 is as follows:
(1) preparing polyimide: according to the Schiff base reaction mechanism shown in figure 1, 3.46g of terephthalaldehyde, 0.8g of diethylenetriamine and 1.76g of tris (2-aminoethyl) amine are dissolved in 170ml of ethanol according to the molar ratio of dialdehyde (terephthalaldehyde), diamine (diethylenetriamine) and triamine (tris (2-aminoethyl) amine) of 1:0.3:0.47, and reacted at normal temperature for 6h to obtain a polyimide solution. Further volatilizing the organic solvent to obtain a polyimide film, and an infrared spectrum (figure 3) shows that the synthesized polymer has a strong imine absorption peak, which proves that the polyimide is successfully synthesized. Dynamic mechanical analysis testing (DMA) showed that the glass transition temperature (Tg) of the polyimide was 115 ℃ (fig. 4);
(2) according to FIG. 2, the paper towel is immersed in the polyimide solution for 20 min;
(3) volatilizing a large amount of ethanol at room temperature to solidify the polyimide inside and on the surface of the paper;
(4) and (3) carrying out hot pressing on the obtained paper-polyimide composite material for 5min at the temperature of 120 ℃ and under the pressure of 1.54MPa by utilizing a flat hot press to obtain a packaging material 3. Fig. 5 shows that the tensile strength of the wrapping material 3 was 55MPa and the elongation at break was 3.8%. The packaging material 3 has a water vapor transmission rate, an oxygen transmission rate and a water flux of<0.006g·mm·m-2·day-1，<7.0×10- 5Barrer and 0 ml. m-2·min-1·KPa-1。
Example 4
This example provides a method for preparing a packaging material by hot pressing at 80 ℃ at 1-80 ℃.
The preparation method of the packaging material at 1-80 ℃ comprises the following steps:
(1) preparing polyimide: according to the Schiff base reaction mechanism shown in figure 1, 3.46g of terephthalaldehyde, 0.8g of diethylenetriamine and 1.76g of tris (2-aminoethyl) amine are dissolved in 170ml of ethanol according to the molar ratio of dialdehyde (terephthalaldehyde), diamine (diethylenetriamine) and triamine (tris (2-aminoethyl) amine) of 1:0.3:0.47, and reacted at normal temperature for 6h to obtain a polyimide solution. Further volatilizing the organic solvent to obtain a polyimide film, and an infrared spectrum (figure 3) shows that the synthesized polymer has a strong imine absorption peak, which proves that the polyimide is successfully synthesized. Dynamic mechanical analysis testing (DMA) showed that the glass transition temperature (Tg) of the polyimide was 115 ℃ (fig. 4);
(2) according to fig. 2, the printing paper is immersed in the polyimide solution for 40 min;
(3) volatilizing a large amount of ethanol at room temperature to solidify the polyimide inside and on the surface of the paper;
(4) and hot-pressing the obtained paper-polyimide composite material for 5min at 80 ℃ and 1.54MPa by using a flat hot press to obtain the packaging material at 1-80 ℃. FIG. 6 shows that the tensile strength of the packaging material at 1-80 ℃ is 68MPa and the elongation at break is 3.7%.
Example 5
This example provides a method for preparing a packaging material by hot pressing at 150 ℃ at 1-150 ℃.
The preparation method of the packaging material at 1-150 ℃ comprises the following steps:
(1) preparing polyimide: according to the Schiff base reaction mechanism shown in figure 1, 3.46g of terephthalaldehyde, 0.8g of diethylenetriamine and 1.76g of tris (2-aminoethyl) amine are dissolved in 170ml of ethanol according to the molar ratio of dialdehyde (terephthalaldehyde), diamine (diethylenetriamine) and triamine (tris (2-aminoethyl) amine) of 1:0.3:0.47, and reacted at normal temperature for 6h to obtain a polyimide solution. Further volatilizing the organic solvent to obtain a polyimide film, and an infrared spectrum (figure 3) shows that the synthesized polymer has a strong imine absorption peak, which proves that the polyimide is successfully synthesized. Dynamic mechanical analysis testing (DMA) showed that the glass transition temperature (Tg) of the polyimide was 115 ℃ (fig. 4);
(2) according to fig. 2, the printing paper is immersed in the polyimide solution for 40 min;
(3) volatilizing a large amount of ethanol at room temperature to solidify the polyimide inside and on the surface of the paper;
(4) and hot-pressing the obtained paper-polyimide composite material for 5min at 150 ℃ and 1.54MPa by using a flat hot press to obtain the packaging material at 1-150 ℃. FIG. 6 shows that the tensile strength of the packaging material at 1-150 ℃ is 70MPa and the elongation at break is 3.5%.
Example 6
This example provides a method for preparing a packaging material at 1-0.1MPa by hot pressing under 0.1 MPa.
The preparation method of the packaging material with 1-0.1MPa comprises the following steps:
(1) preparing polyimide: according to the Schiff base reaction mechanism shown in figure 1, 3.46g of terephthalaldehyde, 0.8g of diethylenetriamine and 1.76g of tris (2-aminoethyl) amine are dissolved in 170ml of ethanol according to the molar ratio of dialdehyde (terephthalaldehyde), diamine (diethylenetriamine) and triamine (tris (2-aminoethyl) amine) of 1:0.3:0.47, and reacted at normal temperature for 6h to obtain a polyimide solution. Further volatilizing the organic solvent to obtain a polyimide film, and an infrared spectrum (figure 3) shows that the synthesized polymer has a strong imine absorption peak, which proves that the polyimide is successfully synthesized. Dynamic mechanical analysis testing (DMA) showed that the glass transition temperature (Tg) of the polyimide was 115 ℃ (fig. 4);
(2) according to fig. 2, the printing paper is immersed in the polyimide solution for 40 min;
(3) volatilizing a large amount of ethanol at room temperature to solidify the polyimide inside and on the surface of the paper;
(4) and hot-pressing the obtained paper-polyimide composite material for 5min at 120 ℃ and 0.1MPa by using a flat hot press to obtain the packaging material with the pressure of 1-0.1 MPa. FIG. 7 shows that the tensile strength of the packaging material 1-0.1MPa is 53MPa and the elongation at break is 3.3%.
Example 7
This example provides a method for hot pressing a packaging material at 10MPa to produce a packaging material at 1-10 MPa.
The preparation method of the packaging material with 1-10MPa comprises the following steps:
(1) preparing polyimide: according to the Schiff base reaction mechanism shown in figure 1, 3.46g of terephthalaldehyde, 0.8g of diethylenetriamine and 1.76g of tris (2-aminoethyl) amine are dissolved in 170ml of ethanol according to the molar ratio of dialdehyde (terephthalaldehyde), diamine (diethylenetriamine) and triamine (tris (2-aminoethyl) amine) of 1:0.3:0.47, and reacted at normal temperature for 6h to obtain a polyimide solution. Further volatilizing the organic solvent to obtain a polyimide film, and an infrared spectrum (figure 3) shows that the synthesized polymer has a strong imine absorption peak, which proves that the polyimide is successfully synthesized. Dynamic mechanical analysis testing (DMA) showed that the glass transition temperature (Tg) of the polyimide was 115 ℃ (fig. 4);
(2) according to fig. 2, the printing paper is immersed in the polyimide solution for 40 min;
(3) volatilizing a large amount of ethanol at room temperature to solidify the polyimide inside and on the surface of the paper;
(4) and hot-pressing the obtained paper-polyimide composite material for 5min at 120 ℃ and 10MPa by using a flat hot press to obtain the packaging material with the pressure of 1-10 MPa. FIG. 7 shows that the tensile strength of the packaging material 1-10MPa is 72MPa and the elongation at break is 4.4%.
Example 8
This example provides a method for preparing a packaging material by hot pressing for 1-1min under a hot pressing time of 1 min.
The preparation method of the packaging material for 1-1min comprises the following steps:
(1) preparing polyimide: according to the Schiff base reaction mechanism shown in figure 1, 3.46g of terephthalaldehyde, 0.8g of diethylenetriamine and 1.76g of tris (2-aminoethyl) amine are dissolved in 170ml of ethanol according to the molar ratio of dialdehyde (terephthalaldehyde), diamine (diethylenetriamine) and triamine (tris (2-aminoethyl) amine) of 1:0.3:0.47, and reacted at normal temperature for 6h to obtain a polyimide solution. Further volatilizing the organic solvent to obtain a polyimide film, and an infrared spectrum (figure 3) shows that the synthesized polymer has a strong imine absorption peak, which proves that the polyimide is successfully synthesized. Dynamic mechanical analysis testing (DMA) showed that the glass transition temperature (Tg) of the polyimide was 115 ℃ (fig. 4);
(2) according to fig. 2, the printing paper is immersed in the polyimide solution for 40 min;
(3) volatilizing a large amount of ethanol at room temperature to solidify the polyimide inside and on the surface of the paper;
(4) and carrying out hot pressing on the obtained paper-polyimide composite material for 1min by using a flat hot press at the temperature of 120 ℃ and under the pressure of 1.54MPa to obtain the packaging material for 1-1 min. FIG. 8 shows that the tensile strength of the packaging material at 1-1min is 48MPa and the elongation at break is 2.5%.
Example 9
This example provides a method for preparing a packaging material by hot pressing for 1-30min under the condition of a hot pressing time of 30 min.
The preparation method of the packaging material for 1-30min comprises the following steps:
(1) preparing polyimide: according to the Schiff base reaction mechanism shown in figure 1, 3.46g of terephthalaldehyde, 0.8g of diethylenetriamine and 1.76g of tris (2-aminoethyl) amine are dissolved in 170ml of ethanol according to the molar ratio of dialdehyde (terephthalaldehyde), diamine (diethylenetriamine) and triamine (tris (2-aminoethyl) amine) of 1:0.3:0.47, and reacted at normal temperature for 6h to obtain a polyimide solution. Further volatilizing the organic solvent to obtain a polyimide film, and an infrared spectrum (figure 3) shows that the synthesized polymer has a strong imine absorption peak, which proves that the polyimide is successfully synthesized. Dynamic mechanical analysis testing (DMA) showed that the glass transition temperature (Tg) of the polyimide was 115 ℃ (fig. 4);
(2) according to fig. 2, the printing paper is immersed in the polyimide solution for 40 min;
(3) volatilizing a large amount of ethanol at room temperature to solidify the polyimide inside and on the surface of the paper;
(4) and carrying out hot pressing on the obtained paper-polyimide composite material for 30min by using a flat hot press under the conditions of 120 ℃ and 1.54MPa to obtain the packaging material for 1-30 min. FIG. 8 shows that the tensile strength of the packaging material is 68MPa and the elongation at break is 4.4% for 1-30 min.
Example 10
The present embodiment provides a method of 3D shaping a packaging material 1, a packaging material 2 and a packaging material 3.
The preparation method comprises the following steps:
(1) heating and softening the plane packaging material 1, the packaging material 2 and the packaging material 3 in an oven at 120 ℃ for 5 min;
(2) shaping while hot, then cooling to room temperature to obtain 3D shape 1 (fig. 9);
(3) heating and softening the 3D shape 1 in a 120 ℃ oven for 5min to restore the shape to the original plane for packaging;
(4) the recovered flat package is reshaped into 3D shape 2 (fig. 9) using the same thermoforming process.
Example 11
This example provides a self-healing method for a cellulosic paper/dynamic covalent polymer composite packaging material.
The preparation method comprises the following steps:
(1) scratching a flaw on the packaging material 1 by using a blade to obtain a damaged packaging material 1;
(2) and (3) carrying out hot pressing on the damaged packaging material 1 for 3min at the temperature of 120 ℃ and under the pressure of 1.5MPa by utilizing a flat hot press to obtain the repaired packaging material 1. Fig. 10 shows that the mechanical properties of the repaired packaging material 1 can be recovered by more than 95% compared with the original packaging material 1.
Example 12
This example provides a multilayer composite method for cellulosic paper/dynamic covalent polymer composite packaging materials.
The preparation method comprises the following steps:
(1) stacking two or three layers of the plane packaging materials 1 together;
(2) and (3) carrying out hot pressing on the damaged part for 5min at 120 ℃ and 2.0MPa by using a flat hot press to obtain the double-layer or three-layer composite packaging material 1. Figure 11 the double and triple layer composite packaging material 1 has a higher tensile strength than the original single layer packaging material 1.
Example 13
The embodiment provides a method for degrading and recycling a cellulose paper/dynamic covalent polymer composite packaging material.
The preparation method comprises the following steps:
(1) soaking the packaging material 1 in 0.08M ethanol solution of diamine (diethylenetriamine) for 8h to completely degrade the polyimide in the packaging material 1;
(2) the recovered cellulose paper and the reactive monomer solution are separated.
(3) According to the chemical dialdehyde: diamine (b): the stoichiometric ratio of triamine is 1:0.3:0.47, the corresponding amount of dialdehyde and diamine are supplemented in the recovered reaction monomer, and the recovered polyimine solution is prepared by polymerization;
(4) the recovered cellulose paper was compounded with the polyimide solution in accordance with the method for preparing a cellulose paper packaging material in example 1 to prepare a recovered cellulose paper-based packaging material. Figure 12 shows that the recycled cellulose paper based packaging material and the virgin cellulose paper based packaging material have the same mechanical properties.

Claims (6)

1. A preparation method of a cellulose paper/dynamic covalent polymer composite packaging material is characterized by comprising the following steps:
preparing a dynamic covalent polymer, then compounding the dynamic covalent polymer and cellulose paper to obtain a cellulose paper/dynamic covalent polymer composite material, and carrying out hot-pressing treatment on the obtained cellulose paper/dynamic covalent polymer composite material to obtain a cellulose paper/dynamic covalent polymer composite packaging material;
the dynamic covalent polymer is polyimide, and is prepared by mixing aldehyde and amine in an organic solvent, then carrying out condensation reaction, and removing the organic solvent after the reaction is finished; wherein the aldehyde is at least one of an aromatic aldehyde and an aliphatic aldehyde; the amine is at least one of aliphatic amine and aromatic amine; the molar ratio of the aldehyde to the amine is 1: 0.5-1; the condensation reaction temperature is normal temperature, and the time is 4-8 h; the aromatic aldehyde is at least one of terephthalaldehyde, o-phthalaldehyde, m-phthalaldehyde, 2, 5-dihydroxy-1, 4-phthalaldehyde, 2, 5-dimethoxy-1, 4-phthalaldehyde, 2, 5-dicyano-1, 4-phthalaldehyde, 2, 5-dimethyl-1, 4-phthalaldehyde, 2, 5-diethyl-1, 4-benzenedimethanol, 4' -phthalaldehyde, trimesic aldehyde and furandicarboxaldehyde, and the aliphatic aldehyde is at least one of glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, hexanedial and octanedial;
the aliphatic amine is at least one of ethylenediamine, butanediamine, pentanediamine, hexanediamine, heptanediamine, octanediamine, nonanediamine, decanediamine, 1, 12-diaminododecane, diethylenetriamine, N 'N-bis (3-aminopropyl) methylamine, 3' -diaminodipropylamine and tris (2-aminoethyl) amine; the aromatic amine is at least one of p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, 3, 5-diaminonitrobenzene, 4, 6-dimethoxy-3, 5-phenylenediamine and m-xylylenediamine.
2. The method of preparing a cellulose paper/dynamic covalent polymer composite packaging material according to claim 1, characterized in that: the cellulose paper is made from plant fibers by a paper making method; the method used to incorporate the dynamic covalent polymer into the cellulose paper is dipping, spraying or coating; the hot pressing method is flat plate hot pressing.
3. The method of preparing a cellulose paper/dynamic covalent polymer composite packaging material according to claim 2, characterized in that: the temperature of the hot pressing treatment in the flat plate hot pressing is 80-150 ℃, the pressure is 0.1-10 MPa, and the time is 1-30 min.
4. A cellulose paper/dynamic covalent polymer composite packaging material prepared according to the method of any one of claims 1 to 3.
5. Use of the cellulose paper/dynamic covalent polymer composite packaging material according to claim 4 in bio-based packaging materials.
6. Use of the cellulose paper/dynamic covalent polymer composite packaging material according to claim 4 in bio-based packaging material, characterized in that: the applications include 3D structural shaping, self-repair, multi-layer compounding, degradation and recovery of cellulose paper/dynamic covalent polymer composite packaging materials;
the self-repairing of the cellulose paper/dynamic covalent polymer composite packaging material is specifically as follows: hot-pressing the surface damaged cellulose-based packaging material for 1-5 min at the stress relaxation temperature of the dynamic covalent polymer or above and under the pressure of 0.5 Ma-5 MPa;
the multilayer compounding of the cellulose paper/dynamic covalent polymer composite packaging material is specifically as follows: stacking the cellulose-based packaging material between two pieces of hot-pressing cloth, and carrying out hot-pressing treatment under the conditions of the stress relaxation temperature of the material and the pressure of 0.5-10 MPa, wherein the hot-pressing time is 1-10 min;
the degradation and recovery of the cellulose paper/dynamic covalent polymer composite packaging material are specifically as follows: soaking a cellulose-based packaging material to be degraded in a solution of diamine monomers to completely degrade polyimide; the recovered reactive monomers are then repolymerized to polyimines and the recovered cellulose paper is compounded to produce a recyclable cellulose paper-based packaging material.
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