CN110341275B - Environment-friendly composite material capable of classifying and recycling matrix materials and preparation method thereof - Google Patents

Environment-friendly composite material capable of classifying and recycling matrix materials and preparation method thereof Download PDF

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Publication number
CN110341275B
CN110341275B CN201910477406.1A CN201910477406A CN110341275B CN 110341275 B CN110341275 B CN 110341275B CN 201910477406 A CN201910477406 A CN 201910477406A CN 110341275 B CN110341275 B CN 110341275B
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adhesive layer
layer
composite material
polyamide
environment
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CN110341275A (en
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安家成
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Ruipo China Environmental Protection Technology Co ltd
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Ruipo China Environmental Protection Technology Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/74—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by welding and severing, or by joining and severing, the severing being performed in the area to be joined, next to the area to be joined, in the joint area or next to the joint area
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
    • B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
    • B29C66/45—Joining of substantially the whole surface of the articles
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2009/00—Layered products
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Wrappers (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention relates to the field of packaging materials, in particular to an environment-friendly composite material capable of classifying and recycling base materials and a preparation method thereof. The composite material of the present invention comprises: the base layer is an adhesive layer positioned between the base layers and independently selected from one or more of plastic, metal and paper; the plastic is polyester, polyolefin or nylon; the adhesive layer is formed of modified polyglycolic acid. The invention utilizes the adhesive layer formed by degradable modified polyglycolic acid to connect different matrix layers, and the adhesive layer can be degraded in a proper natural environment to ensure that the combined matrix layers lose connection to separate different matrix materials, thereby respectively carrying out classification and recovery treatment on the matrix materials. The modified polyglycolic acid serves to increase gas barrier properties in the final product.

Description

Environment-friendly composite material capable of classifying and recycling matrix materials and preparation method thereof
Technical Field
The invention relates to the field of packaging materials, in particular to an environment-friendly composite material capable of classifying and recycling base materials and a preparation method thereof.
Background
The composite material with paper, plastic and metal as base material is used mainly in packing engineering plastic, rubber material, building material, food, chemical fertilizer and other solid and liquid material, flexible article, etc. From the performance perspective, the composite packaging material composed of paper, plastic and metal has the advantages of high strength, good surface skid resistance and moisture resistance, good corrosion resistance, convenient use, convenient assembly and disassembly and the like. The composite material of paper, plastic and metal is generally made of kraft paper, aluminum, polyethylene/polypropylene and other plastics. The paper is easy to recycle, can be used for preparing cellulose or directly placed in the environment as plant nutrients, but the plastic as a 'white pollution' source is not directly discarded in the environment, and is recycled to reduce the environmental pressure, and the metal such as aluminum can permeate into the ground to influence the water quality of soil and underground water, and is not discarded at will. In the prior art, different base material components in the packaging material are combined together in a bonding mode and are difficult to separate, so that the components cannot be directly classified and recycled, and the environment is seriously polluted.
Therefore, there is a need to develop an environment-friendly composite material capable of recycling the base materials by classification, which can recycle the main base materials, such as paper, plastic, metal, etc., by classification, and then perform different treatments, thereby avoiding resource waste and environmental pollution.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an environment-friendly composite material and a preparation method thereof. The environment-friendly composite material is particularly suitable for packaging materials. The degradable modified polyglycolic acid is used as the adhesive layer, so that different matrix layers in the package can be separated after the service life is finished. The composite material can be degraded in a proper natural environment, so that the connection of the combined matrix layers is lost to separate different matrix materials, and the matrix materials are respectively classified and recycled.
The invention adopts the following technical scheme:
an environmentally friendly composite material comprising:
a base layer, a first layer and a second layer,
an adhesive layer positioned between the substrate layers,
the substrate layer is independently selected from one or more of plastic, metal and paper;
the plastic is polyester, polyolefin or nylon;
the adhesive layer is formed of modified polyglycolic acid.
Preferably, the thickness of the matrix layer is 7-500 μm, more preferably, the thickness of the matrix layer is 20-200 μm, more preferably, the thickness of the matrix layer is 50-100 μm, and the number of layers is 2-4; the thickness of the adhesive layer is 15-80 μm, more preferably, the thickness of the adhesive layer is 50-60 μm, and the number of layers is 1-3.
Preferably, the polyester is polyethylene terephthalate (PET), Polycarbonate (PC), Polyhydroxyalkanoate (PHA), polybutylene terephthalate (PBT) or polyethylene naphthalate (PEN), and the polyester has good impact resistance, multiple solvent resistance, high transparency and good glossiness, and provides good performance for composite materials;
preferably, the polyolefin is one or two of polyethylene and polypropylene, has heat sealing performance, and is used for the composite material to seal when packaging materials;
preferably, the nylon is polyamide-6, i.e. polycaprolactam (PA6), polyamide-66, i.e. polyhexamethyleneadipamide (PA66), polyamide-1010, i.e. polyhexamethylenesebacamide (PA1010), polyamide-1414, i.e. polyparaphenyleneterephthalamide (PA1414), polyamide-610, i.e. polyhexamethylenesebacamide (PA610), polyamide-11, i.e. polyundecanolactam (PA-11), polyamide-612, i.e. polyhexamethylenedodecanoyldiamine (PA612), polyamide-12, i.e. polydodecanoylamide (PA-12), polyamide-46, i.e. polytetramethyleneadipamide (PA-46), polyamide-6T, i.e. polyhexamethyleneterephthalamide (PA-6T), polyamide-9T, i.e. polynonamethyleneterephthalamide (PA-9T), polyamide-10T, namely poly (p-phenylene terephthalamide) (PA-10T), the nylon adopted in the invention has biaxial stretching performance, and the strength and the hardness of the composite material are effectively improved.
Preferably, the metal is one or more of aluminum, tin and iron, which is used in the composite material, and can effectively protect the product from oxygen, moisture, smell and light; the metal is preferably aluminum from the viewpoint of practicality and cost;
the paper is selected from one or more of kraft paper, glass paper, plant parchment paper, asphalt paper, oil paper, wax paper, board paper and corrugated paper, has good elasticity and toughness, and can provide good protection effect for packaged objects.
Preferably, the modified polyglycolic acid comprises the following components in parts by weight: 80-100 parts of polyglycolic acid, 0.2-1 part of a mouth-opening agent, 0.05-2 parts of a slipping agent, 1-7 parts of a toughening agent, 0.5-4 parts of a tackifier and 66-111 parts of an auxiliary material.
The modified polyglycolic acid of the present invention may be in the form of particles having an average particle diameter of 1 to 5mm, an intrinsic viscosity [. eta. ] of 0.8 to 2dl/g, and a molecular weight of 10 to 15 ten thousand.
The modified polyglycolic acid of the present invention is obtained by modifying polyglycolic acid. Polyglycolic Acid (PGA), also known as Polyglycolic Acid, is derived from an alpha-hydroxy Acid, i.e., glycolic Acid. Polyglycolic acid is a high molecular material with good biocompatibility and biodegradability, and has wide application in biomedical fields such as medical absorbable suture lines, drug sustained-release carriers, fracture fixation materials, tissue engineering scaffold materials, suture reinforcement materials and the like. Polyglycolic acid forms unique polygonal crystals in the crystallization process, has stable crystal lattices, higher crystallinity and higher melting point, is difficult to process and form and is easy to absorb water and degrade when being placed in the natural environment, and the defects limit the further application of the polyglycolic acid in the industry. The polyglycolic acid is modified to adjust the molecular chain structure, the length, the crystallinity and the hydrophilicity of the polyglycolic acid and endow the polyglycolic acid with the functions of bacteriostasis, antioxidation and the like, so that the degradation rate and the mechanical strength of the polyglycolic acid are regulated, and the modified polyglycolic acid has a flexible molecular chain structure and high crystallinity and is insoluble in common organic solvents; in addition, the composite material has the characteristics of easy processing and forming, high mechanical strength, excellent gas barrier property and the like, and can be used for industrial processing.
Preferably, the opening agent can be one or more of flake graphite, talcum powder, diatomite and silicon dioxide, and is further preferably flake graphite, so that the lubricating property of the surface of the film is improved, and the composite film is prevented from being stuck when stacked or in long-term direct contact.
Preferably, the slip agent may be one or more of oleamide, stearamide and erucamide, for reducing the coefficient of friction of the film surface, thereby ensuring good subsequent processability, such as runnability on a packaging machine; the slipping agent has polar groups, so that the fatty acid amide with interface polarity difference with the modified polyglycolic acid can migrate to the surface layer of the film, and form a smooth surface after solidification and crystallization, thereby reducing the friction coefficient of the film.
Preferably, the toughening agent may be DuPont of DuPontTM
Figure BDA0002082722910000031
One or more of Strong 120, polyolefin thermoplastic elastomer, ethylene propylene diene monomer, methyl methacrylate-butadiene-styrene copolymer, which is used for improving the toughness of the modified polyglycolic acid material and reducing the brittleness of the modified polyglycolic acid material; in addition, the adhesive capacity between the modified polyglycolic acid and the matrix layer can be improved. The toughening agent may also beSo as to be a composite toughening agent, wherein the composite toughening agent can be nano calcite, nano talcum powder and sub-nano fatty acid rare earth salt, and the weight ratio of the nano calcite to the nano talcum powder is 30-50: 10-20: 1-5 parts by weight, and further preferably 35-45: 13-18: 2-3 parts by weight.
Preferably, the tackifier is Ethylene-Acrylic Acid copolymer (EAA), Ethylene-Vinyl Acetate copolymer (EVA), Ethylene-Methyl Acrylate copolymer (EMA), Ethylene-Ethyl Acrylate copolymer (EEA), Ethylene-Methacrylic Acid copolymer (EMAA), and Polyvinyl Butyral (Polyvinyl Butyral), which can improve the adhesion between the modified polyglycolic Acid and the substrate layer.
Preferably, the auxiliary materials comprise the following components in parts by weight: 45-60 parts of polycaprolactone, 2-5 parts of poly (L-lactide-epsilon-caprolactone), 0.03-0.2 part of antioxidant, 2-6 parts of antibacterial agent, 15-35 parts of starch and 1-5 parts of reinforcing fiber.
Preferably, the molecular weight of the polycaprolactone is 4-10 ten thousand, and the polycaprolactone has good compatibility and biodegradability, can improve the flexibility and extensibility of the composite material, is favorable for low-temperature forming, delays the biodegradation time of a single modified polyglycolic acid material, and improves the durability of the material.
Preferably, poly (L-lactide-co-epsilon-caprolactone), PLLCA, has a weight average molecular weight (Mw) of 20 to 50 ten thousand and a mole percentage of epsilon-caprolactone units of 20 to 25% in poly (L-lactide-epsilon-caprolactone) for significantly increasing the elongation and tensile strength.
Preferably, the antioxidant is one or more of pentaerythritol tetraphenylpropionate, n-octadecyl propionate, phenyl triphosphite, dioctadecyl thiodipropionate and didodecyl thiodipropionate, and is used for improving the oxidation resistance of the composite material, particularly the thermal durability in the process of processing and forming, preventing the yellowing of the product and prolonging the service life of the product.
Preferably, the antibacterial agent is one or more of chitosan, sodium alginate, bacteriocin, lysozyme, geraniol and tea tree essential oil extracted from animals and plants or synthesized by microorganisms, and the antibacterial agent has good biocompatibility and biodegradability, and degradation products are nontoxic, so that the quality of the contents in a package can be guaranteed, the microbial pollution is reduced, the antibacterial activity of the composite material is improved, the degradation rate of the modified polyglycolic acid is reduced, and the service life of the product is prolonged.
Preferably, the starch is one or more of corn starch, soybean starch, sweet potato starch and potato starch, is used as a biodegradation agent for polycaprolactone, and is safe and non-toxic.
Preferably, the reinforced fiber is one or more of various natural polymer plant fibers such as wood fiber, hemp fiber, cotton fiber, bamboo fiber and the like, the fiber has better strength and rigidity and small specific gravity, can be degraded in a natural environment, has no pollution to the environment, and improves the bending resistance of the product.
In the invention, the modified polyglycolic acid is obtained by mixing polyglycolic acid, a mouth-opening agent, a slipping agent, a toughening agent, a tackifier and auxiliary materials.
Preferably, the modified polyglycolic acid is placed into a die-cutting machine for die-cutting pressing at the pressure of 50-150T for 2-10s, and the adhesive layer is prepared by cooling after film pressing.
The preparation method of the environment-friendly composite material comprises the following steps:
hot melting the adhesive layer;
applying an adhesive layer between the substrate layers;
and cooling the adhesive layer to obtain the environment-friendly composite material.
Preferably, the temperature for hot-melting the adhesive is 250-350 ℃.
More specifically, the preparation method of the environment-friendly composite material comprises the following steps:
s1: putting the modified polyglycolic acid into a die-cutting machine, performing die-cutting pressing at the pressure of 50-150T for 2-10s, and cooling to obtain an adhesive layer after pressing to form a film;
s2: and (4) carrying out hot melting on the adhesive layer obtained in the step (S1), putting the adhesive layer and the substrate layer into a die cutting machine in a stacking mode for bonding, and cooling the adhesive layer after bonding. Wherein the adhesive layer obtained in S1 is located between two substrate layers.
S3: if the three or more matrixes are compounded in a multi-layer mode, the operation of S1 is repeated to prepare the adhesive layer, then the die cutting and the pressing are continuously carried out, and finally the environment-friendly composite material is prepared.
The invention has the advantages of
(1) The modified polyglycolic acid obtained by modifying polyglycolic acid has natural degradability, can be decomposed into low molecular compounds by microorganisms (bacteria, fungi, algae and the like) under a natural environment with proper or indicative period, and is finally completely decomposed into water and carbon dioxide; meanwhile, the composite material has good biocompatibility, gas barrier property, water resistance, strength and thermoplasticity, and can be effectively used for processing composite materials;
(2) the invention utilizes the adhesive layer formed by degradable modified polyglycolic acid to connect different matrix layers, and when the degradable modified polyglycolic acid is degraded in natural environment, the composite matrix layers can lose connection to obtain different matrix materials, so that the different matrix materials are respectively classified and recycled;
(3) the composite material has the advantages of excellent comprehensive performance, low preparation cost and simple process.
Drawings
FIG. 1 is a schematic structural view of a composite material of example 1;
FIG. 2 is a schematic structural view of the composite material of example 2;
FIG. 3 is a schematic structural view of the composite material of example 3;
FIG. 4 is a schematic structural view of the composite material of example 6;
FIG. 5 is a schematic structural view of a composite material of example 7.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments.
Example 1
An environment-friendly composite material comprises a kraft paper layer, an adhesive layer and a polyethylene layer in sequence; the thickness of the kraft paper layer is 30 μm, the thickness of the adhesive layer is 15 μm, and the thickness of the polyethylene layer is 60 μm.
The adhesive layer was formed from modified polyglycolic acid, and the components of the modified polyglycolic acid are shown in table 1.
The preparation method of the environment-friendly composite material comprises the following steps:
s1: putting the modified polyglycolic acid into a die-cutting machine, performing die-cutting pressing at the pressure of 50-150T for 2-10s, and cooling to obtain an adhesive layer after pressing to form a film;
s2: and (3) carrying out hot melting on the adhesive layer obtained in the step (S1), placing the adhesive layer, the kraft paper layer and the polyethylene layer into a die cutting machine in a stacking mode for adhesion, wherein the adhesive layer is positioned between the kraft paper layer and the polyethylene layer, and cooling the adhesive layer after adhesion to obtain the environment-friendly composite material.
Example 2
An environment-friendly composite material comprises a polyethylene terephthalate layer, an adhesive layer and a polyethylene layer in sequence; the thickness of the polyethylene terephthalate layer is 60 micrometers, the thickness of the adhesive layer is 20 micrometers, and the thickness of the polyethylene layer is 80 micrometers.
The adhesive layer was formed from modified polyglycolic acid, and the components of the modified polyglycolic acid are shown in table 1.
The preparation method of the environment-friendly composite material comprises the following steps:
s1: putting the modified polyglycolic acid into a die-cutting machine, performing die-cutting pressing at the pressure of 50-150T for 2-10s, and cooling to obtain an adhesive layer after pressing to form a film;
s2: and melting the adhesive layer obtained in the step S1, putting the adhesive layer, the polyethylene terephthalate layer and the polyethylene layer into a die cutting machine in a stacking mode for bonding, wherein the adhesive layer is positioned between the polyethylene terephthalate layer and the polyethylene layer, and cooling the adhesive layer after bonding to obtain the environment-friendly composite material.
Example 3
An environment-friendly composite material comprises a kraft paper layer, an adhesive layer, an aluminum layer, an adhesive layer and a polyethylene layer in sequence; the thickness of the kraft paper layer is 30 μm, the thickness of the adhesive layer is 50 μm, the thickness of the aluminum layer is 6 μm, and the thickness of the polyethylene layer is 100 μm.
The adhesive layer was formed from modified polyglycolic acid, and the components of the modified polyglycolic acid are shown in table 1.
The preparation method of the environment-friendly composite material comprises the following steps:
s1: putting the modified polyglycolic acid into a die-cutting machine, performing die-cutting pressing at the pressure of 50-150T for 2-10s, and cooling to obtain an adhesive layer after pressing to form a film;
s2: and (4) carrying out hot melting on the adhesive layer obtained in the step (S1), and putting the adhesive layer, the kraft paper layer and the aluminum layer into a die cutting machine in a stacking mode for bonding, wherein the adhesive layer is positioned between the kraft paper layer and the aluminum layer. And cooling the adhesive layer after bonding.
S3: and repeating the operation of S1 to prepare an adhesive layer, carrying out hot melting on the adhesive layer, adhering the adhesive layer with the material obtained in the step S2 and the polyethylene layer in the same form, and cooling the adhesive layer after adhesion to obtain the environment-friendly composite material.
Example 4
An environment-friendly composite material comprises an oil paper layer, an adhesive layer, an aluminum layer, an adhesive layer and a polyethylene layer in sequence; the thickness of the oil paper layer is 100 micrometers, the thickness of the adhesive layer is 15 micrometers, the thickness of the aluminum layer is 7 micrometers, and the thickness of the polyethylene layer is 80 micrometers.
The adhesive layer was formed from modified polyglycolic acid, and the components of the modified polyglycolic acid are shown in table 1.
The preparation method of the environment-friendly composite material comprises the following steps:
s1: putting the modified polyglycolic acid into a die-cutting machine, performing die-cutting pressing at the pressure of 50-150T for 2-10s, and cooling to obtain an adhesive layer after pressing to form a film;
s2: and (4) hot melting the adhesive layer obtained in the step (S1), and putting the adhesive layer, the oil paper layer and the aluminum layer into a die cutting machine in a stacking mode for bonding, wherein the adhesive layer is positioned between the oil paper layer and the aluminum layer. And cooling the adhesive layer after bonding.
S3: and repeating the operation of S1 to prepare an adhesive layer, carrying out hot melting on the adhesive layer, adhering the adhesive layer with the material obtained in the step S2 and the polyethylene layer in the same form, and cooling the adhesive layer after adhesion to obtain the environment-friendly composite material.
Example 5
An environment-friendly composite material comprises a cellophane layer, an adhesive layer, an aluminum layer, an adhesive layer and a polyethylene layer in sequence; the thickness of the cellophane layer is 200 μm, the thickness of the adhesive layer is 30 μm, the thickness of the aluminum layer is 9 μm, and the thickness of the polyethylene layer is 140 μm.
The adhesive layer was formed from modified polyglycolic acid, and the components of the modified polyglycolic acid are shown in table 1.
The preparation method of the environment-friendly composite material comprises the following steps:
s1: putting the modified polyglycolic acid into a die-cutting machine, performing die-cutting pressing at the pressure of 50-150T for 2-10s, and cooling to obtain an adhesive layer after pressing to form a film;
s2: and (4) carrying out hot melting on the adhesive layer obtained in the step (S1), and putting the adhesive layer, the cellophane layer and the aluminum layer into a die cutting machine in a stacking mode for bonding, wherein the adhesive layer is positioned between the cellophane layer and the aluminum layer. And cooling the adhesive layer after bonding.
S3: and repeating the operation of S1 to prepare an adhesive layer, carrying out hot melting on the adhesive layer, adhering the adhesive layer with the material obtained in the step S2 and the polyethylene layer in the same form, and cooling the adhesive layer after adhesion to obtain the environment-friendly composite material.
Example 6
An environment-friendly composite material comprises a polybutylene terephthalate layer, an adhesive layer, an aluminum layer, an adhesive layer and a polyethylene layer in sequence; the thickness of the polybutylene terephthalate layer is 12 micrometers, the thickness of the adhesive layer is 15 micrometers, the thickness of the aluminum layer is 6 micrometers, and the thickness of the polyethylene layer is 50 micrometers.
The adhesive layer was formed from modified polyglycolic acid, and the components of the modified polyglycolic acid are shown in table 1.
The preparation method of the environment-friendly composite material comprises the following steps:
s1: putting the modified polyglycolic acid into a die-cutting machine, performing die-cutting pressing at the pressure of 50-150T for 2-10s, and cooling to obtain an adhesive layer after pressing to form a film;
s2: and (3) carrying out hot melting on the adhesive layer obtained in the step (S1), and putting the adhesive layer, the polybutylene terephthalate layer and the aluminum layer into a die cutting machine in a stacking mode for bonding, wherein the adhesive layer is positioned between the polybutylene terephthalate layer and the aluminum layer. Cooling the adhesive layer after bonding;
s3: and repeating the operation of S1 to prepare an adhesive layer, carrying out hot melting on the adhesive layer, adhering the adhesive layer with the material obtained in the step S2 and the polyethylene layer in the same form, and cooling the adhesive layer after adhesion to obtain the environment-friendly composite material.
Example 7
An environment-friendly composite material comprises a polyhydroxyalkanoate layer, an adhesive layer, an aluminum layer, an adhesive layer, a polyamide-6 layer, an adhesive layer and a polyethylene layer in sequence; the thickness of the polyhydroxyalkanoate layer is 12 micrometers, the thickness of the adhesive layer is 15 micrometers, the thickness of the aluminum layer is 7 micrometers, the thickness of the polyamide-6 layer is 15 micrometers, and the thickness of the polyethylene layer is 60 micrometers.
The adhesive layer was formed from modified polyglycolic acid, and the components of the modified polyglycolic acid are shown in table 1.
The preparation method of the environment-friendly composite material comprises the following steps:
s1: putting the modified polyglycolic acid into a die-cutting machine, performing die-cutting pressing at the pressure of 50-150T for 2-10s, and cooling to obtain an adhesive layer after pressing to form a film;
s2: hot melting the adhesive layer obtained in the step S1, placing the adhesive layer, the polyhydroxylated fatty acid ester layer and the aluminum layer into a die cutting machine in a stacking mode for bonding, wherein the adhesive layer is positioned between the polyhydroxylated fatty acid ester layer and the aluminum layer, and cooling the adhesive layer after bonding;
s3: repeating the operation of S1 to prepare an adhesive layer, carrying out hot melting on the adhesive layer, bonding the adhesive layer with the material obtained in the step S2 and the polyamide-6 layer in the same form, and cooling the adhesive layer after bonding;
s4: and repeating the operation of S1 to prepare an adhesive layer, carrying out hot melting on the adhesive layer, adhering the adhesive layer with the material obtained in the step S3 and the polyethylene layer in the same form, and cooling the adhesive layer after adhesion to obtain the environment-friendly composite material.
Example 8
An environment-friendly composite material comprises a polyethylene terephthalate layer, an adhesive layer, an aluminum layer, an adhesive layer, a polyamide-66 layer, an adhesive layer and a polyethylene layer in sequence; the thickness of the polyethylene terephthalate layer is 12 micrometers, the thickness of the adhesive layer is 15 micrometers, the thickness of the aluminum layer is 9 micrometers, the thickness of the polyamide-66 layer is 15 micrometers, and the thickness of the polyethylene layer is 90 micrometers.
The adhesive layer was formed from modified polyglycolic acid, and the components of the modified polyglycolic acid are shown in table 1.
The preparation method of the environment-friendly composite material comprises the following steps:
s1: putting the modified polyglycolic acid into a die-cutting machine, performing die-cutting pressing at the pressure of 50-150T for 2-10s, and cooling to obtain an adhesive layer after pressing to form a film;
s2: hot melting the adhesive layer obtained in the step S1, placing the adhesive layer, the polyethylene terephthalate layer and the aluminum layer into a die cutting machine in a stacking mode for bonding, wherein the adhesive layer is positioned between the polyethylene terephthalate layer and the aluminum layer, and cooling the adhesive layer after bonding;
s3: repeating the operation of S1 to prepare an adhesive layer, carrying out hot melting on the adhesive layer, bonding the adhesive layer with the material obtained in the step S2 and the polyamide-66 layer in the same form, and cooling the adhesive layer after bonding;
s4: and repeating the operation of S1 to prepare an adhesive layer, carrying out hot melting on the adhesive layer, adhering the adhesive layer with the material obtained in the step S3 and the polyethylene layer in the same form, and cooling the adhesive layer after adhesion to obtain the environment-friendly composite material.
Example 9
An environment-friendly composite material comprises a kraft paper layer, an adhesive layer, an aluminum layer, an adhesive layer, a polyamide-46 layer, an adhesive layer and a polyethylene terephthalate layer in sequence; the thickness of the kraft paper layer is 180 μm, the thickness of the adhesive layer is 15 μm, the thickness of the aluminum layer is 12 μm, the thickness of the polyamide-46 layer is 15 μm, and the thickness of the polyethylene terephthalate layer is 50 μm.
The adhesive layer was formed from modified polyglycolic acid, and the components of the modified polyglycolic acid are shown in table 1.
The preparation method of the environment-friendly composite material comprises the following steps:
s1: putting the modified polyglycolic acid into a die-cutting machine, performing die-cutting pressing at the pressure of 50-150T for 2-10s, and cooling to obtain an adhesive layer after pressing to form a film;
s2: hot melting the adhesive layer obtained in the step S1, placing the adhesive layer, the kraft paper layer and the aluminum layer into a die cutting machine in a stacking mode for bonding, wherein the adhesive layer is positioned between the kraft paper layer and the aluminum layer, and cooling the adhesive layer after bonding;
s3: repeating the operation of S1 to prepare an adhesive layer, carrying out hot melting on the adhesive layer, bonding the adhesive layer with the material obtained in the step S2 and the polyamide-46 layer in the same form, and cooling the adhesive layer after bonding;
s4: and repeating the operation of S1 to prepare an adhesive layer, carrying out hot melting on the adhesive layer, bonding the adhesive layer with the material obtained in the step S3 and the polyethylene terephthalate layer in the same form, and cooling the adhesive layer after bonding to obtain the environment-friendly composite material.
The components of the modified polyglycolic acids of examples 1 to 9 are shown in Table 1.
TABLE 1
Figure BDA0002082722910000091
Figure BDA0002082722910000101
Examples of the experiments
The composite material is placed in a constant temperature and humidity box under the given temperature and humidity conditions for degradation performance test. In the test process, a part of samples are taken out at intervals, the oven dry mass is weighed, and the mass loss rate and the test peel strength are calculated. The mass loss rate and peel strength results of the multi-layer composite during degradation are shown in tables 2 and 3, respectively.
TABLE 2 Mass loss Rate of multilayer composites prepared from modified polyglycolic acid as adhesive layer under specific degradation conditions
When degradedWorkshop (sky) Mass loss rate (%) Degradation time (Tian) Mass loss rate (%)
15 99.98 210 99.87
30 99.93 270 99.89
60 99.75 330 99.18
120 99.74 360 96.23
150 99.86 400 86.17
Note: the degradation performance test of the composite material is carried out under the conditions of the temperature of 25 ℃ and the relative humidity (RH 93%), and the degradation environment atmosphere is air.
TABLE 3 Change in peel Strength between layers of a multilayer composite during degradation
Figure BDA0002082722910000111
Note: the peel strength test standard is referred to GB 8808-88. According to the requirements of the medicine and food packaging on the peel strength of the aluminum foil composite film, the peel strength of the inner layer is more than or equal to 2.0N/15mm, and the peel strength is the minimum value of the peel strength among the multilayer composite films.
Generally, the mass loss rate is 100% in the initial stage of degradation, i.e., the degradation rate is 0 in the initial stage, the material is gradually degraded with time, the mass loss rate gradually decreases from 100% as a starting point, and the smaller the mass loss rate value, the greater the degradation degree of the material is indicated. The results in table 2 show that the multilayer composite material prepared by using modified polyglycolic acid as the adhesive layer is not degraded within 70 days under the conditions of room temperature and high relative humidity (RH 93%), while polyglycolic acid itself is very easy to hydrolyze to degrade under the conditions of high temperature and high humidity. After further extension of the test time, it was found that modified polyglycolic acid started to degrade after 12 months as an adhesive layer. The results in Table 3 show that the peel strength between the modified polyglycolic acid and the matrix is still more than 3N/15mm in 12 months, and the peel strength meets the peel strength standard of the multilayer composite film in medicine and food packaging. The results show that the modified polyglycolic acid prepared by the invention can be used for adhesive layers of metal, plastic and paper composite materials, and can be degraded within a period of time after reaching the use period so as to classify and recycle different types of base materials in the packaging layers.

Claims (8)

1. An environmentally friendly composite material, comprising:
a base layer, a first layer and a second layer,
an adhesive layer positioned between the substrate layers,
the substrate layer is independently selected from one or more of plastic, metal and paper;
the plastic is polyester, polyolefin or nylon;
the adhesive layer is formed by modified polyglycolic acid;
the modified polyglycolic acid comprises the following components in parts by weight: 80-100 parts of polyglycolic acid, 0.2-1 part of a mouth-opening agent, 0.05-2 parts of a slipping agent, 1-7 parts of a toughening agent, 0.5-4 parts of a tackifier and 66-111 parts of an auxiliary material;
the auxiliary materials comprise the following components in parts by weight: 45-60 parts of polycaprolactone, 2-5 parts of poly (L-lactide-epsilon-caprolactone), 0.03-0.2 part of antioxidant, 2-6 parts of antibacterial agent, 15-35 parts of starch and 1-5 parts of reinforcing fiber;
wherein the starch is one or more of corn starch, soybean starch, sweet potato starch and potato starch.
2. The environment-friendly composite material according to claim 1, wherein the substrate layers are each 7 to 500 μm thick and have 2 to 4 layers; the thickness of the adhesive layer is 15-80 μm, and the number of layers is 1-3.
3. The environment-friendly composite material according to claim 1, wherein the polyester is polyethylene terephthalate, polycarbonate, polyhydroxyalkanoate, polybutylene terephthalate, or polyethylene naphthalate;
the polyolefin is one or two of polyethylene and polypropylene;
the nylon is polyamide-6, polyamide-66, polyamide-1010, polyamide-1414, polyamide-610, polyamide-11, polyamide-612, polyamide-12, polyamide-46, polyamide-6T, polyamide-9T or polyamide-10T;
the metal is one or more of aluminum, tin and iron;
the paper is selected from one or more of kraft paper, glass paper, plant parchment paper, asphalt paper, oil paper, wax paper, board paper and corrugated paper.
4. The environment-friendly composite material according to claim 1, wherein the opening agent is one or more of flake graphite, talc, diatomaceous earth, and silica.
5. The environmentally friendly composite material of claim 1, wherein the slip agent is one or more of oleamide, stearamide, and erucamide.
6. The environmentally friendly composite material of claim 1, wherein the toughening agent is DuPont from DuPontTM
Figure FDA0002990249320000011
One or more of Strong 120, polyolefin thermoplastic elastomer, ethylene propylene diene monomer, methyl methacrylate-butadiene-styrene copolymer and composite toughening agent; the composite toughening agent is prepared by combining nano calcite, nano talcum powder and sub-nano fatty acid rare earth salt according to the weight part ratio of 30-50: 10-20: 1-5.
7. The environmentally friendly composite of claim 1, wherein the tackifier is selected from one or more of ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, and polyvinyl butyral.
8. The method for preparing the environment-friendly composite material as recited in any one of claims 1 to 7, comprising:
hot melting the adhesive layer;
applying an adhesive layer between the substrate layers;
and cooling the adhesive layer to obtain the environment-friendly composite material.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4156676A (en) * 1978-03-27 1979-05-29 Chevron Research Company Hot melt adhesives having improved thermal stability
WO2011008868A1 (en) * 2009-07-15 2011-01-20 Nerites Corporation Thin film compositions and methods of synthesis and use therefor
CN106634686A (en) * 2016-10-10 2017-05-10 上海金大塑胶有限公司 Novel environment-friendly adhesive sticker material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4156676A (en) * 1978-03-27 1979-05-29 Chevron Research Company Hot melt adhesives having improved thermal stability
WO2011008868A1 (en) * 2009-07-15 2011-01-20 Nerites Corporation Thin film compositions and methods of synthesis and use therefor
CN106634686A (en) * 2016-10-10 2017-05-10 上海金大塑胶有限公司 Novel environment-friendly adhesive sticker material

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