CN116691097B - High-barrier aluminum-plastic packaging film and preparation process thereof - Google Patents

High-barrier aluminum-plastic packaging film and preparation process thereof Download PDF

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Publication number
CN116691097B
CN116691097B CN202310826374.8A CN202310826374A CN116691097B CN 116691097 B CN116691097 B CN 116691097B CN 202310826374 A CN202310826374 A CN 202310826374A CN 116691097 B CN116691097 B CN 116691097B
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packaging film
plastic packaging
resistant
heating
dropwise adding
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CN116691097A (en
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朱巍
周海滨
蒋晓程
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Shanghai People Plastic Printing Co ltd
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Shanghai People Plastic Printing Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • 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
    • 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
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • 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
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1284—Application of adhesive
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0008—Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/164—Drying
    • 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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/164—Drying
    • B32B2038/168—Removing solvent
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/554—Wear resistance
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • 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
    • B32B2307/7246—Water vapor barrier
    • 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
    • B32B2439/00—Containers; Receptacles
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/80—Medical packaging
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/14—Gas barrier composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to the technical field of packaging materials, in particular to an aluminum-plastic packaging film with high barrier property and a preparation process thereof; the aluminum plastic packaging film with a composite structure is prepared, the wear-resistant and heat-resistant resin protective layer with high mechanical strength and wear resistance is used as the outer surface of the packaging film, the aluminum foil is used as the barrier layer, and the impact resistance and the water vapor permeability are improved through the compounding among different film layers; the invention also carries out modification treatment on the wear-resistant and heat-resistant resin protective layer; firstly, preparing an epoxy compound with siloxane and fluorine elements, and further generating fluorine-silicon modified polyamide on the basis; in the reaction process, the invention particularly limits the addition of the pentafluoropropionic acid and the 4, 4-diphenyl ether dicarboxylic acid, improves the water resistance of polyurethane and improves the film forming performance of the finally prepared polyurethane, so that the aluminum plastic packaging film prepared by the invention can have enough strength and barrier performance to water vapor.

Description

High-barrier aluminum-plastic packaging film and preparation process thereof
Technical Field
The invention relates to the technical field of packaging materials, in particular to an aluminum plastic packaging film with high barrier property and a preparation process thereof.
Background
The aluminum plastic packaging film is a packaging material formed by coating and compounding aluminum foil and plastic together singly or simultaneously, has excellent air sealing performance, and is widely applied to packaging in the fields of food, medicines, cosmetics, medical appliances and the like; however, in the use process, as the aluminum plastic packaging film is required to package and store contents in response to various working environments, higher requirements are put on strength liquid of the aluminum plastic packaging film in the situation so as to avoid damage or reduction of air barrier performance in the use process.
Disclosure of Invention
The invention aims to provide an aluminum plastic packaging film with high barrier property and a preparation process thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: the high-barrier aluminum plastic packaging film has the following technical characteristics: the high-barrier aluminum-plastic packaging film consists of a wear-resistant and heat-resistant resin protective layer, an aluminum foil layer and a PE film layer;
wherein, polyurethane bonding layers are arranged on two sides of the aluminum foil layer;
the wear-resistant heat-resistant resin protective layer comprises the following components in parts by weight: 86-90 parts of fluorosilicone modified polyamide, 3-8 parts of nano silicon dioxide and 1-2.5 parts of hydrolysis inhibitor.
Further, the thickness of the aluminum foil layer is 40-80 microns; the thickness of the wear-resistant and heat-resistant resin protective layer is 25-50 microns; the thickness of the PET film layer is 15-30 microns.
Further, the thickness of the polyurethane bonding layer is 2-6 microns.
Further, the hydrolysis resistance agent is carbodiimide.
A preparation method of an aluminum plastic packaging film with high barrier property comprises the following steps:
s1, preparing fluorine-silicon modified polyamide;
s11, dispersing the 1,2, 4-benzene tricarboxylic acid tri (ethylene oxide methyl) ester into DMF, stirring and dispersing for 3-5min, then protecting nitrogen atmosphere, heating to 55-75 ℃, dropwise adding 3-aminopropyl triethoxysilane, wherein the dropwise adding time is 1.5-3h, heating to 65-80 ℃ after the dropwise adding is finished, continuing to react for 2-3h, cooling to 45-55 ℃, dropwise adding sodium hydroxide solution to adjust pH to 8.5-9.5, dropwise adding DMF solution dissolved with pentafluoropropionic acid for 1-1.5h, heating to 65-70 ℃ after the dropwise adding is finished, continuing to react for 3-5h, and rotationally steaming to remove redundant solvent to obtain the fluorosilicone modified epoxy compound;
s12, dispersing the fluorosilicone modified epoxy compound prepared in the step S11 into pure DMF (dimethyl formamide), preparing fluorosilicone modified mixed solution, dropwise adding the mixed solution into DMF solution in which triphenyl triamine thiophosphate is dissolved in a nitrogen atmosphere for 2-4h, heating to 85-95 ℃, reacting for 2-4h, and removing redundant solvent by rotary evaporation to obtain fluorosilicone modified amino polymer;
s13, dispersing the fluorosilicone modified amino polymer prepared in the step S12 into dimethyl sulfoxide, adding 4, 4-diphenyl ether dicarboxylic acid, heating to 210-230 ℃, prepolymerizing for 1-2h in a nitrogen atmosphere, controlling the reaction air pressure to 150-1500Pa, heating to 275-290 ℃, continuing to react for 1-4h, cooling to normal temperature and normal pressure, washing a product with deionized water for 3-5 times, vacuum drying to constant weight, and performing melt extrusion and granulation to obtain fluorosilicone modified polyamide;
s2, mixing the fluorosilicone modified polyamide prepared in the step S1 with nano silicon dioxide and a hydrolysis inhibitor, heating to 225-235 ℃, blending for 0.5h, and extruding to form a film to obtain a wear-resistant heat-resistant resin protective layer;
s3, carrying out corona treatment on one surface of the wear-resistant and heat-resistant resin protective layer, which is combined with the aluminum foil layer, coating polyurethane adhesive on two sides of the aluminum foil layer after the treatment, drying at 80-90 ℃ for 1-3min, and stacking and pressing the polyurethane adhesive with the wear-resistant and heat-resistant resin protective layer and the PET layer to obtain the aluminum plastic packaging film.
Further, in step S11, the mass ratio of the tri (oxiranylmethyl) 1,2, 4-trimellitate, the 3-aminopropyl triethoxysilane, and the pentafluoropropionic acid is 1: (0.5-0.59): (0.4-0.44).
Further, in step S12, the mass ratio of the fluorosilicone modified epoxy compound to the triphenyl triamine thiophosphate is 1: (0.4-0.55).
Further, in step S13, the mass ratio of the fluorosilicone modified aminopolymer 1135 to the 4, 4-diphenyl ether dicarboxylic acid is 1: (0.2-0.24).
Further, in step S3, the pressing tension is 200-1500N, and the pressing pressure is 0.5-1MPa.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention prepares the aluminum-plastic packaging film with a composite structure, uses the wear-resistant and heat-resistant resin protective layer with high mechanical strength and wear resistance as the outer surface of the packaging film, uses aluminum foil as a barrier layer, and uses a high-safety PET material as an inner layer to be in direct contact with the package; the impact resistance and the water vapor permeability are improved through the compounding among different film layers;
2. in order to improve the shock resistance and wear resistance of the aluminum plastic packaging film, the wear-resistant and heat-resistant resin protective layer is modified; firstly, the invention uses a 1,2, 4-benzene tricarboxylic acid tri (oxiranylmethyl) ester component as a core grafting reactant, utilizes the ring opening reaction of amino groups and epoxy groups to graft 3-aminopropyl triethoxysilane on a single arm of the tri (oxiranylmethyl) ester component, introduces a siloxane structure, and further uses pentafluoropropionic acid to react with the epoxy groups on the basis, thereby preparing an epoxy compound with siloxane and fluorine elements, and further reacts with 4, 4-diphenyl ether dicarboxylic acid on the basis to produce fluorosilicone modified polyamide; in the course of this reaction, the invention specifically limits the addition of pentafluoropropionic acid to 4, 4-diphenyl ether dicarboxylic acid; the pentafluoropropionic acid is a compound containing five fluorine atoms and a carboxyl functional group, belongs to fluorocarboxylic acid compounds, and has carboxyl groups and five fluorine atoms in a pentafluoropropionic acid molecule respectively connected to a propyl skeleton through a C-F bond and a C=O bond, wherein the five fluorine atoms can attract electrons, but the C-F bond still has poor nucleophilic reaction capability on a nucleophilic reagent compared with a C-H bond, and an amino group is a weak nucleophilic reagent, and in addition, the five fluorine atoms in the pentafluoropropionic acid molecule greatly increase the molecular electron density of the pentafluoropropionic acid, so that the pentafluoropropionic acid is not easy to attack by the nucleophilic reagent, and the possibility of the pentafluoropropionic acid to react with the amino group is inhibited; in order to avoid the influence of molecular structure on the film forming performance of finally prepared polyamide, the invention uses 4, 4-diphenyl ether dicarboxylic acid as a reactant and introduces ether groups, thereby improving the film forming performance of finally prepared polyurethane.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The tris (oxiranylmethyl) 1,2, 4-benzenetricarboxylic acid used in the present application is supplied by Shaanxi, inc. of New Material, inc.; the 3-aminopropyl triethoxysilane is provided by Nanjing Nandina-Tian-Yi chemical industry Co., ltd; the pentafluoropropionic acid used was supplied by Shanghai Ala Biochemical technologies Co., ltd; the triphenyl triamine thiophosphate used is supplied by the Hangzhou Brown biomedical technology Co., ltd; the 4, 4-diphenyl ether dicarboxylic acid used is supplied by synephora physical and chemical technologies, inc.; the nano silicon dioxide is DK-SiO2-60 nano silicon dioxide of Beijing De island gold technology Co., ltd;
example 1.
A preparation process of an aluminum plastic packaging film with high barrier property comprises the following steps:
s1, preparing fluorine-silicon modified polyamide;
s11, dispersing 1 part of 1,2, 4-benzene tricarboxylic acid tri (ethylene oxide methyl) ester into DMF (dimethyl formamide), stirring and dispersing for 3min, then, protecting in nitrogen atmosphere, heating to 55 ℃, dropwise adding 0.5 part of 3-aminopropyl triethoxysilane, wherein the dropwise adding time is 1.5h, heating to 65 ℃ after the dropwise adding is finished, continuously reacting for 2h, cooling to 45 ℃, dropwise adding sodium hydroxide solution to adjust the pH to 8.5, dropwise adding DMF solution with 0.4 part of pentafluoropropionic acid, wherein the dropwise adding time is 1h, heating to 65 ℃ after the dropwise adding is finished, continuously reacting for 3h, and rotationally steaming to remove redundant solvent to obtain a fluorosilicone modified epoxy compound;
s12, dispersing 1 part of the fluorosilicone modified epoxy compound prepared in the step S11 into pure DMF (dimethyl formamide) according to parts by weight, preparing fluorosilicone modified mixed solution, dropwise adding the mixed solution into DMF solution dissolved with 0.4 part of triphenyl triamine thiophosphate in a nitrogen atmosphere for 2 hours, heating to 85 ℃, reacting for 2 hours, and removing redundant solvent by rotary evaporation to obtain fluorosilicone modified amino polymer;
s13, dispersing 1 part of the fluorosilicone modified amino polymer prepared in the step S12 into dimethyl sulfoxide according to parts by weight, adding 0.2 part of 4, 4-diphenyl ether dicarboxylic acid, heating to 210-230 ℃, prepolymerizing for 1-2 hours in a nitrogen atmosphere, controlling the reaction air pressure to be 150Pa, heating to 275 ℃, continuing to react for 1 hour, cooling to normal temperature and normal pressure, washing a product with deionized water for 3 times, vacuum drying to constant weight, and performing melt extrusion and granulation to obtain the fluorosilicone modified polyamide;
s2, mixing 86 parts of the fluorosilicone modified polyamide prepared in the step S1 with 3 parts of nano silicon dioxide and 1 part of carbodiimide hydrolysis resistance agent according to parts by weight, heating to 225 ℃, blending for 0.5h, and extruding to form a film to obtain a wear-resistant and heat-resistant resin protective layer;
s3, carrying out corona treatment on one surface of the wear-resistant and heat-resistant resin protective layer combined with the aluminum foil layer, coating polyurethane adhesive on two sides of the aluminum foil layer after finishing treatment, and stacking and pressing the polyurethane adhesive with the wear-resistant and heat-resistant resin protective layer and the PET layer after drying at 80 ℃ for 1min to obtain the aluminum plastic packaging film.
Example 2.
Compared with example 1, this example increases the addition amount of 3-aminopropyl triethoxysilane in step S11;
a preparation process of an aluminum plastic packaging film with high barrier property comprises the following steps:
s1, preparing fluorine-silicon modified polyamide;
s11, dispersing 1 part of 1,2, 4-benzene tricarboxylic acid tri (ethylene oxide methyl) ester into DMF (dimethyl formamide), stirring and dispersing for 3min, then, protecting in nitrogen atmosphere, heating to 55 ℃, dropwise adding 0.59 part of 3-aminopropyl triethoxysilane, wherein the dropwise adding time is 1.5h, heating to 65 ℃ after the dropwise adding is finished, continuously reacting for 2h, cooling to 45 ℃, dropwise adding sodium hydroxide solution to adjust the pH to 8.5, dropwise adding DMF solution with 0.4 part of pentafluoropropionic acid, wherein the dropwise adding time is 1h, heating to 65 ℃ after the dropwise adding is finished, continuously reacting for 3h, and rotationally steaming to remove redundant solvent to obtain a fluorosilicone modified epoxy compound;
s12, dispersing 1 part of the fluorosilicone modified epoxy compound prepared in the step S11 into pure DMF (dimethyl formamide) according to parts by weight, preparing fluorosilicone modified mixed solution, dropwise adding the mixed solution into DMF solution dissolved with 0.4 part of triphenyl triamine thiophosphate in a nitrogen atmosphere for 2 hours, heating to 85 ℃, reacting for 2 hours, and removing redundant solvent by rotary evaporation to obtain fluorosilicone modified amino polymer;
s13, dispersing 1 part of the fluorosilicone modified amino polymer prepared in the step S12 into dimethyl sulfoxide according to parts by weight, adding 0.2 part of 4, 4-diphenyl ether dicarboxylic acid, heating to 210-230 ℃, prepolymerizing for 1-2 hours in a nitrogen atmosphere, controlling the reaction air pressure to be 150Pa, heating to 275 ℃, continuing to react for 1 hour, cooling to normal temperature and normal pressure, washing a product with deionized water for 3 times, vacuum drying to constant weight, and performing melt extrusion and granulation to obtain the fluorosilicone modified polyamide;
s2, mixing 86 parts of the fluorosilicone modified polyamide prepared in the step S1 with 3 parts of nano silicon dioxide and 1 part of carbodiimide hydrolysis resistance agent according to parts by weight, heating to 225 ℃, blending for 0.5h, and extruding to form a film to obtain a wear-resistant and heat-resistant resin protective layer;
s3, carrying out corona treatment on one surface of the wear-resistant and heat-resistant resin protective layer combined with the aluminum foil layer, coating polyurethane adhesive on two sides of the aluminum foil layer after finishing treatment, and stacking and pressing the polyurethane adhesive with the wear-resistant and heat-resistant resin protective layer and the PET layer after drying at 80 ℃ for 1min to obtain the aluminum plastic packaging film.
Example 3.
Compared with example 1, this example increases the addition amount of pentafluoropropionic acid in step S11;
a preparation process of an aluminum plastic packaging film with high barrier property comprises the following steps:
s1, preparing fluorine-silicon modified polyamide;
s11, dispersing 1 part of 1,2, 4-benzene tricarboxylic acid tri (ethylene oxide methyl) ester into DMF (dimethyl formamide), stirring and dispersing for 3min, then, protecting in nitrogen atmosphere, heating to 55 ℃, dropwise adding 0.5 part of 3-aminopropyl triethoxysilane, wherein the dropwise adding time is 1.5h, heating to 65 ℃ after the dropwise adding is finished, continuously reacting for 2h, cooling to 45 ℃, dropwise adding sodium hydroxide solution to adjust the pH to 8.5, dropwise adding DMF solution with 0.44 part of pentafluoropropionic acid, wherein the dropwise adding time is 1h, heating to 65 ℃ after the dropwise adding is finished, continuously reacting for 3h, and rotationally steaming to remove redundant solvent to obtain a fluorosilicone modified epoxy compound;
s12, dispersing 1 part of the fluorosilicone modified epoxy compound prepared in the step S11 into pure DMF (dimethyl formamide) according to parts by weight, preparing fluorosilicone modified mixed solution, dropwise adding the mixed solution into DMF solution dissolved with 0.4 part of triphenyl triamine thiophosphate in a nitrogen atmosphere for 2 hours, heating to 85 ℃, reacting for 2 hours, and removing redundant solvent by rotary evaporation to obtain fluorosilicone modified amino polymer;
s13, dispersing 1 part of the fluorosilicone modified amino polymer prepared in the step S12 into dimethyl sulfoxide according to parts by weight, adding 0.2 part of 4, 4-diphenyl ether dicarboxylic acid, heating to 210-230 ℃, prepolymerizing for 1-2 hours in a nitrogen atmosphere, controlling the reaction air pressure to be 150Pa, heating to 275 ℃, continuing to react for 1 hour, cooling to normal temperature and normal pressure, washing a product with deionized water for 3 times, vacuum drying to constant weight, and performing melt extrusion and granulation to obtain the fluorosilicone modified polyamide;
s2, mixing 86 parts of the fluorosilicone modified polyamide prepared in the step S1 with 3 parts of nano silicon dioxide and 1 part of carbodiimide hydrolysis resistance agent according to parts by weight, heating to 225 ℃, blending for 0.5h, and extruding to form a film to obtain a wear-resistant and heat-resistant resin protective layer;
s3, carrying out corona treatment on one surface of the wear-resistant and heat-resistant resin protective layer combined with the aluminum foil layer, coating polyurethane adhesive on two sides of the aluminum foil layer after finishing treatment, and stacking and pressing the polyurethane adhesive with the wear-resistant and heat-resistant resin protective layer and the PET layer after drying at 80 ℃ for 1min to obtain the aluminum plastic packaging film.
Example 4.
Compared with example 1, this example increases the addition amount of triphenyl triamine thiophosphate in step S12;
a preparation process of an aluminum plastic packaging film with high barrier property comprises the following steps:
s1, preparing fluorine-silicon modified polyamide;
s11, dispersing 1 part of 1,2, 4-benzene tricarboxylic acid tri (ethylene oxide methyl) ester into DMF (dimethyl formamide), stirring and dispersing for 3min, then, protecting in nitrogen atmosphere, heating to 55 ℃, dropwise adding 0.5 part of 3-aminopropyl triethoxysilane, wherein the dropwise adding time is 1.5h, heating to 65 ℃ after the dropwise adding is finished, continuously reacting for 2h, cooling to 45 ℃, dropwise adding sodium hydroxide solution to adjust the pH to 8.5, dropwise adding DMF solution with 0.4 part of pentafluoropropionic acid, wherein the dropwise adding time is 1h, heating to 65 ℃ after the dropwise adding is finished, continuously reacting for 3h, and rotationally steaming to remove redundant solvent to obtain a fluorosilicone modified epoxy compound;
s12, dispersing 1 part of the fluorosilicone modified epoxy compound prepared in the step S11 into pure DMF (dimethyl formamide) according to parts by weight, preparing fluorosilicone modified mixed solution, dropwise adding the mixed solution into DMF solution dissolved with 0.55 part of triphenyl triamine thiophosphate in a nitrogen atmosphere for 2 hours, heating to 85 ℃, reacting for 2 hours, and removing redundant solvent by rotary evaporation to obtain fluorosilicone modified amino polymer;
s13, dispersing 1 part of the fluorosilicone modified amino polymer prepared in the step S12 into dimethyl sulfoxide according to parts by weight, adding 0.2 part of 4, 4-diphenyl ether dicarboxylic acid, heating to 210-230 ℃, prepolymerizing for 1-2 hours in a nitrogen atmosphere, controlling the reaction air pressure to be 150Pa, heating to 275 ℃, continuing to react for 1 hour, cooling to normal temperature and normal pressure, washing a product with deionized water for 3 times, vacuum drying to constant weight, and performing melt extrusion and granulation to obtain the fluorosilicone modified polyamide;
s2, mixing 86 parts of the fluorosilicone modified polyamide prepared in the step S1 with 3 parts of nano silicon dioxide and 1 part of carbodiimide hydrolysis resistance agent according to parts by weight, heating to 225 ℃, blending for 0.5h, and extruding to form a film to obtain a wear-resistant and heat-resistant resin protective layer;
s3, carrying out corona treatment on one surface of the wear-resistant and heat-resistant resin protective layer combined with the aluminum foil layer, coating polyurethane adhesive on two sides of the aluminum foil layer after finishing treatment, and stacking and pressing the polyurethane adhesive with the wear-resistant and heat-resistant resin protective layer and the PET layer after drying at 80 ℃ for 1min to obtain the aluminum plastic packaging film.
Example 5.
A preparation process of an aluminum plastic packaging film with high barrier property comprises the following steps:
s1, preparing fluorine-silicon modified polyamide;
s11, dispersing 1 part of 1,2, 4-benzene tricarboxylic acid tri (ethylene oxide methyl) ester into DMF (dimethyl formamide), stirring and dispersing for 5min, then protecting in nitrogen atmosphere, heating to 55 ℃, dropwise adding 0.59 part of 3-aminopropyl triethoxysilane, wherein the dropwise adding time is 1.5h, heating to 65 ℃ after the dropwise adding is finished, continuously reacting for 2h, cooling to 45 ℃, dropwise adding sodium hydroxide solution to adjust the pH to 9.5, dropwise adding DMF solution with 0.44 part of pentafluoropropionic acid, wherein the dropwise adding time is 1h, heating to 65 ℃ after the dropwise adding is finished, continuously reacting for 3h, and rotationally steaming to remove redundant solvent to obtain a fluorosilicone modified epoxy compound;
s12, dispersing 1 part of the fluorosilicone modified epoxy compound prepared in the step S11 into pure DMF (dimethyl formamide) according to parts by weight, preparing fluorosilicone modified mixed solution, dropwise adding the mixed solution into DMF solution dissolved with 0.55 part of triphenyl triamine thiophosphate in a nitrogen atmosphere for 2 hours, heating to 85 ℃, reacting for 2 hours, and removing redundant solvent by rotary evaporation to obtain fluorosilicone modified amino polymer;
s13, dispersing 1 part of the fluorosilicone modified amino polymer prepared in the step S12 into dimethyl sulfoxide according to parts by weight, adding 0.24 part of 4, 4-diphenyl ether dicarboxylic acid, heating to 210-230 ℃, prepolymerizing for 1-2h under nitrogen atmosphere, controlling the reaction air pressure to 150Pa, heating to 275 ℃, continuing to react for 1h, cooling to normal temperature and normal pressure, washing a product with deionized water for 3 times, vacuum drying to constant weight, and performing melt extrusion and granulation to obtain the fluorosilicone modified polyamide;
s2, mixing 86 parts of the fluorosilicone modified polyamide prepared in the step S1 with 3 parts of nano silicon dioxide and 1 part of carbodiimide hydrolysis resistance agent according to parts by weight, heating to 225 ℃, blending for 0.5h, and extruding to form a film to obtain a wear-resistant and heat-resistant resin protective layer;
s3, carrying out corona treatment on one surface of the wear-resistant and heat-resistant resin protective layer combined with the aluminum foil layer, coating polyurethane adhesive on two sides of the aluminum foil layer after finishing treatment, and stacking and pressing the polyurethane adhesive with the wear-resistant and heat-resistant resin protective layer and the PET layer after drying at 80 ℃ for 1min to obtain the aluminum plastic packaging film.
Comparative example 1.
In comparison with example 1, the present comparative example did not produce a fluorosilicone-modified polyamide, but reacted only diamine in an equivalent amount with 4, 4-diphenylether dicarboxylic acid;
a preparation process of an aluminum plastic packaging film with high barrier property comprises the following steps:
s1, preparing polyamide;
dispersing 0.45 part of 1, 6-hexamethylenediamine into dimethyl sulfoxide according to parts by weight, adding 1 part of 4, 4-diphenyl ether dicarboxylic acid, heating to 210-230 ℃, prepolymerizing for 1-2 hours in nitrogen atmosphere, controlling the reaction air pressure to 150Pa, heating to 275 ℃, continuing to react for 1 hour, cooling to normal temperature and normal pressure, washing a product with deionized water for 3 times, vacuum drying to constant weight, and carrying out melt extrusion and pelleting to obtain polyamide;
s2, mixing 86 parts of polyamide prepared in the step S1 with 3 parts of nano silicon dioxide and 1 part of carbodiimide hydrolysis-resistant agent according to parts by weight, heating to 225 ℃, blending for 0.5h, and extruding to form a film to obtain a wear-resistant and heat-resistant resin protective layer;
s3, carrying out corona treatment on one surface of the wear-resistant and heat-resistant resin protective layer combined with the aluminum foil layer, coating polyurethane adhesive on two sides of the aluminum foil layer after finishing treatment, and stacking and pressing the polyurethane adhesive with the wear-resistant and heat-resistant resin protective layer and the PET layer after drying at 80 ℃ for 1min to obtain the aluminum plastic packaging film.
Comparative example 2.
In comparison with example 1, this example does not use 4, 4-diphenyl ether dicarboxylic acid, but instead only terephthalic acid in an equal amount of material;
a preparation process of an aluminum plastic packaging film with high barrier property comprises the following steps:
s1, preparing fluorine-silicon modified polyamide;
s11, dispersing 1 part of 1,2, 4-benzene tricarboxylic acid tri (ethylene oxide methyl) ester into DMF (dimethyl formamide), stirring and dispersing for 3min, then, protecting in nitrogen atmosphere, heating to 55 ℃, dropwise adding 0.5 part of 3-aminopropyl triethoxysilane, wherein the dropwise adding time is 1.5h, heating to 65 ℃ after the dropwise adding is finished, continuously reacting for 2h, cooling to 45 ℃, dropwise adding sodium hydroxide solution to adjust the pH to 8.5, dropwise adding DMF solution with 0.4 part of pentafluoropropionic acid, wherein the dropwise adding time is 1h, heating to 65 ℃ after the dropwise adding is finished, continuously reacting for 3h, and rotationally steaming to remove redundant solvent to obtain a fluorosilicone modified epoxy compound;
s12, dispersing 1 part of the fluorosilicone modified epoxy compound prepared in the step S11 into pure DMF (dimethyl formamide) according to parts by weight, preparing fluorosilicone modified mixed solution, dropwise adding the mixed solution into DMF solution dissolved with 0.4 part of triphenyl triamine thiophosphate in a nitrogen atmosphere for 2 hours, heating to 85 ℃, reacting for 2 hours, and removing redundant solvent by rotary evaporation to obtain fluorosilicone modified amino polymer;
s13, dispersing 1 part of the fluorosilicone modified amino polymer prepared in the step S12 into dimethyl sulfoxide according to parts by weight, adding 0.15 part of terephthalic acid, heating to 210-230 ℃, pre-polymerizing for 1-2 hours in a nitrogen atmosphere, controlling the reaction air pressure to be 150Pa, heating to 275 ℃, continuing to react for 1 hour, cooling to normal temperature and normal pressure, washing a product with deionized water for 3 times, vacuum drying to constant weight, and performing melt extrusion and granulation to obtain fluorosilicone modified polyamide;
s2, mixing 86 parts of the fluorosilicone modified polyamide prepared in the step S1 with 3 parts of nano silicon dioxide and 1 part of carbodiimide hydrolysis resistance agent according to parts by weight, heating to 225 ℃, blending for 0.5h, and extruding to form a film to obtain a wear-resistant and heat-resistant resin protective layer;
s3, carrying out corona treatment on one surface of the wear-resistant and heat-resistant resin protective layer combined with the aluminum foil layer, coating polyurethane adhesive on two sides of the aluminum foil layer after finishing treatment, and stacking and pressing the polyurethane adhesive with the wear-resistant and heat-resistant resin protective layer and the PET layer after drying at 80 ℃ for 1min to obtain the aluminum plastic packaging film.
And (3) detection: samples prepared in examples 1-5 and comparative examples 1-2 were prepared to have a wear-resistant heat-resistant resin protective layer thickness of 30 microns; aluminum foil layer thickness is 50 micrometers, and aluminum plastic packaging film is 20 micrometers behind PET film layer; the water vapor permeability coefficient of the aluminum plastic packaging film samples prepared in the examples 1-5 and the comparative examples 1-2 is detected by using a water vapor permeability tester; examples 1 to 5 and examples according to GB/T8808Peel strength of the abrasion-resistant heat-resistant resin protective layer and the aluminum foil layer in the aluminum-plastic packaging film samples prepared in comparative examples 1-2; abrasion-resistant and heat-resistant resin protective layers of the aluminum plastic packaging film samples prepared in examples 1 to 5 and comparative examples 1 to 2 were rubbed 10 times with #0000 steel wool, and the friction force was 150g/cm 2 Detecting the surface scratch condition of the glass; the detection results are shown in the following table:
finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (9)

1. The preparation method of the high-barrier aluminum plastic packaging film is characterized by comprising the following steps of:
s1, preparing fluorine-silicon modified polyamide;
s11, dispersing the 1,2, 4-benzene tricarboxylic acid tri (ethylene oxide methyl) ester into DMF, stirring and dispersing for 3-5min, then protecting nitrogen atmosphere, heating to 55-75 ℃, dropwise adding 3-aminopropyl triethoxysilane, wherein the dropwise adding time is 1.5-3h, heating to 65-80 ℃ after the dropwise adding is finished, continuing to react for 2-3h, cooling to 45-55 ℃, dropwise adding sodium hydroxide solution to adjust pH to 8.5-9.5, dropwise adding DMF solution dissolved with pentafluoropropionic acid for 1-1.5h, heating to 65-70 ℃ after the dropwise adding is finished, continuing to react for 3-5h, and rotationally steaming to remove redundant solvent to obtain the fluorosilicone modified epoxy compound;
s12, dispersing the fluorosilicone modified epoxy compound prepared in the step S11 into pure DMF (dimethyl formamide), preparing fluorosilicone modified mixed solution, dropwise adding the mixed solution into DMF solution in which triphenyl triamine thiophosphate is dissolved in a nitrogen atmosphere for 2-4h, heating to 85-95 ℃, reacting for 2-4h, and removing redundant solvent by rotary evaporation to obtain fluorosilicone modified amino polymer;
s13, dispersing the fluorosilicone modified amino polymer prepared in the step S12 into dimethyl sulfoxide, adding 4, 4-diphenyl ether dicarboxylic acid, heating to 210-230 ℃, prepolymerizing for 1-2h in a nitrogen atmosphere, controlling the reaction air pressure to 150-1500Pa, heating to 275-290 ℃, continuing to react for 1-4h, cooling to normal temperature and normal pressure, washing a product with deionized water for 3-5 times, vacuum drying to constant weight, and performing melt extrusion and granulation to obtain fluorosilicone modified polyamide;
s2, mixing the fluorosilicone modified polyamide prepared in the step S1 with nano silicon dioxide and a hydrolysis inhibitor, heating to 225-235 ℃, blending for 0.5-1h, and extruding to form a film to obtain a wear-resistant and heat-resistant resin protective layer;
s3, carrying out corona treatment on one surface of the wear-resistant and heat-resistant resin protective layer, which is combined with the aluminum foil layer, coating polyurethane adhesive on two sides of the aluminum foil layer after the treatment, drying at 80-90 ℃ for 1-3min, and stacking and pressing the polyurethane adhesive with the wear-resistant and heat-resistant resin protective layer and the PET layer to obtain the aluminum plastic packaging film.
2. The method for preparing the high-barrier aluminum plastic packaging film according to claim 1, which is characterized in that: the wear-resistant heat-resistant resin protective layer comprises the following components in parts by weight: 86-90 parts of fluorosilicone modified polyamide, 3-8 parts of nano silicon dioxide and 1-2.5 parts of hydrolysis inhibitor.
3. The method for preparing the high-barrier aluminum plastic packaging film according to claim 1, which is characterized in that: the thickness of the aluminum foil layer is 40-80 microns; the thickness of the wear-resistant and heat-resistant resin protective layer is 25-50 microns; the thickness of the PET film layer is 15-30 microns.
4. The method for preparing the high-barrier aluminum plastic packaging film according to claim 1, which is characterized in that: the thickness of the polyurethane bonding layer is 2-6 microns.
5. The method for preparing the high-barrier aluminum plastic packaging film according to claim 1, which is characterized in that: the hydrolysis resistance agent is carbodiimide.
6. The method for preparing the high-barrier aluminum plastic packaging film according to claim 1, which is characterized in that: in the step S11, the mass ratio of the 1,2, 4-benzene tricarboxylic acid tri (oxiranylmethyl) ester, the 3-aminopropyl triethoxysilane and the pentafluoropropionic acid is 1: (0.5-0.59): (0.4-0.44).
7. The method for preparing the high-barrier aluminum plastic packaging film according to claim 1, which is characterized in that: in the step S12, the mass ratio of the fluorosilicone modified epoxy compound to the triphenyl triamine thiophosphate is 1: (0.4-0.55).
8. The method for preparing the high-barrier aluminum plastic packaging film according to claim 1, which is characterized in that: in the step S13, the mass ratio of the fluorine-silicon modified amino polymer 1135 to the 4, 4-diphenyl ether dicarboxylic acid is 1: (0.2-0.24).
9. The method for preparing the high-barrier aluminum plastic packaging film according to claim 1, which is characterized in that: in the step S3, the lamination tension is 200-1500N, and the lamination pressure is 0.5-1MPa.
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