CN116922909B - Easy-to-uncover film with barrier property and preparation method thereof - Google Patents

Easy-to-uncover film with barrier property and preparation method thereof Download PDF

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Publication number
CN116922909B
CN116922909B CN202310801262.7A CN202310801262A CN116922909B CN 116922909 B CN116922909 B CN 116922909B CN 202310801262 A CN202310801262 A CN 202310801262A CN 116922909 B CN116922909 B CN 116922909B
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layer
middle layer
easy
ethylene
terminated
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CN116922909A (en
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徐涛
李鹏
朱雷
韩亚胜
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Anhui Zijin New Material Science & Technology Co ltd
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Anhui Zijin New Material Science & Technology Co ltd
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    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin 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
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • 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
    • 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
    • B65D53/00—Sealing or packing elements; Sealings formed by liquid or plastics material
    • B65D53/08—Flexible adhesive strips adapted to seal filling or discharging apertures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • B29L2007/00—Flat articles, e.g. films or sheets
    • B29L2007/008—Wide strips, e.g. films, webs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • 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
    • B32B2307/31—Heat sealable
    • 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
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B32B2307/7145—Rot proof, resistant to bacteria, mildew, mould, fungi
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2553/00—Packaging equipment or accessories not otherwise provided for
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2477/06—Polyamides derived from polyamines and polycarboxylic acids
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C08J2479/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Laminated Bodies (AREA)

Abstract

The invention discloses an easy-to-tear film with barrier property, which comprises the following components: a heat sealing layer, a middle layer and a surface layer; the raw materials of the heat sealing layer comprise: polyethylene, ethylene-vinyl acetate, ethylene-methyl acrylate, polyphthalamide, modified amino-terminated tougheners, graphene oxide, and the like; the mass ratio of polyethylene, ethylene-vinyl acetate, ethylene-methyl acrylate, polyphthalamide, modified amino-terminated toughening agent, graphene oxide, nano alumina powder, sodium sulfamate, polybutene and anti-fog master batch is 20-40:10-30:5-20:1-2:1-3:1-5:0.1-1:0.1-1:1-5:1-2; the middle layer raw materials comprise: the mass ratio of the low-density polyethylene resin to the high-density polyethylene resin is 30-50:10-30:1-3; the surface layer is polyester elastomer.

Description

Easy-to-uncover film with barrier property and preparation method thereof
Technical Field
The invention relates to the technical field of easy-to-tear films, in particular to an easy-to-tear film with barrier property and a preparation method thereof.
Background
Along with the continuous development and change of the packaging market, the special requirements of people on packaging are also increasing, and the easy-to-tear film is used as a film which can be conveniently torn off and is mainly used for sealing the mouth part of a container, and when the medium in the container needs to be taken, the easy-to-tear film on the container is torn off to open the mouth part of the container.
The appearance of the easy-to-tear film package breaks through the traditional concept of people, and the package is required at present, particularly the package of the convenient food commodity, so that the packaged content can be protected from spilling and deteriorating, and the package is convenient to open when in use. The easy-to-tear film is a functional packaging material developed from the viewpoint of facilitating the use of the masses, has sealing performance, prevents the volatilization and pollution of the content of the product, and has no odor precipitation. Along with the rapid expansion of the application surface of the easy-to-tear packaging material, the easy-to-tear packaging material is widely used as a cover material of plastic containers such as jam, beverage, microwave food, bottled medicine and the like.
At present, the easy-to-tear film generally comprises a heat sealing layer with heat sealing and easy-to-tear properties, a middle layer with blocking and supporting functions and a surface layer with decorating and thickening blocking functions, wherein the heat sealing layer of the easy-to-tear film is heat sealed on a container, so that the sealing of the container opening is realized.
At present, the food field is full of packing materials and packing forms of tourmaline for attracting a plurality of consumers, but the existing easy-to-tear film has poor barrier property and lower strength, and influences the use experience of the easy-to-tear film.
The graphene is used as an inorganic two-dimensional nano lamellar material, has high aspect ratio, large specific surface area and excellent mechanical property, and is widely applied to preparing composite materials with mechanical reinforcement, excellent barrier, flame retardance, corrosion resistance and the like. If graphene is added into the film-uncovering system, the uniform mixing of the graphene serving as the inorganic reinforcing phase and polyethylene is difficult, and the graphene is easy to agglomerate in a polyethylene matrix and cannot be uniformly dispersed, so that the barrier property cannot be improved, and the comprehensive performance of the film-uncovering system is reduced. At present, a cover-uncovering film with high barrier property and better safety performance is needed to be provided, and the cover-uncovering film can meet the strict sealing property and mechanical flexibility of package and can be conveniently opened.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides an easy-to-tear film with barrier property and a preparation method thereof.
An easy-to-tear film having barrier properties, comprising: the heat sealing layer, the middle layer and the surface layer are respectively attached to two sides of the middle layer; the raw materials of the heat sealing layer comprise: polyethylene, ethylene-vinyl acetate, ethylene-methyl acrylate, polyphthalamide, modified amine-terminated toughener, graphene oxide, nano alumina powder, sodium sulfamate, polybutene and anti-fog master batch; the mass ratio of polyethylene, ethylene-vinyl acetate, ethylene-methyl acrylate, polyphthalamide, modified amino-terminated toughening agent, graphene oxide, nano alumina powder, sodium sulfamate, polybutene and anti-fog master batch is 20-40:10-30:5-20:1-2:1-3:1-5:0.1-1:0.1-1:1-5:1-2; the middle layer raw materials comprise: the mass ratio of the low-density polyethylene resin to the high-density polyethylene resin is 30-50:10-30:1-3; the surface layer adopts polyester elastomer as raw material.
Preferably, the total thickness of the easy-to-tear film is 60-70 μm, and the thickness ratio of the heat sealing layer, the middle layer and the surface layer is 7-10:50-55:3-5.
Preferably, the modified amino-terminated toughening agent takes n-hexylamine as an initiator, and methyl acrylate and ethylenediamine are used for alternating reaction to obtain dendritic molecules.
More preferably, the reaction solvent is methanol.
More preferably, the mass ratio of methyl acrylate, ethylenediamine and n-hexylamine is 4-6:5-10:1-2.
More preferably, the modified amino-terminated toughener is prepared by: dropwise adding n-hexylamine methanol solution into methyl acrylate methanol solution in ice bath, regulating the temperature to 40-50 ℃, stirring for 10-20h, rotary steaming, vacuum drying, dissolving a solid product in methanol, dropwise adding the solid product into ethylenediamine methanol solution in ice bath, regulating the temperature to 30-35 ℃, stirring for 50-150h, rotary steaming, and vacuum drying to obtain the modified amino-terminated toughener.
The preparation method of the easy-to-tear film with the barrier property comprises the following steps:
s1, adding graphene oxide, nano alumina powder and sodium sulfamate into absolute ethyl alcohol, stirring at a high speed for 1-2h, adding a modified amino-terminated toughening agent, continuously stirring for 10-30min in an ice water bath, adjusting the temperature to 30-50 ℃, continuously stirring for 5-15min, filtering, and spray drying to obtain reinforced graphene oxide;
s2, uniformly mixing polyethylene, ethylene-vinyl acetate, ethylene-methyl acrylate, polyphthalamide, polybutene, anti-fog master batch and reinforced graphene oxide to obtain a heat sealing layer mixture; uniformly mixing the middle layer raw materials to obtain a middle layer mixture;
and S3, sequentially adding the heat seal layer mixture, the middle layer mixture and the polyester elastomer into an extruder hopper, respectively putting into three single screw extruders of a three-layer Co-extrusion film blowing machine for melting, blowing films, cooling and shaping, and performing Co60 irradiation sterilization to obtain the easy-to-tear film with barrier property.
Preferably, in the three-layer co-extrusion film blowing machine, the extrusion temperature of the heat seal layer is 150-165 ℃, the extrusion temperature of the middle layer is 140-152 ℃, and the extrusion temperature of the surface layer is 170-210 ℃.
Preferably, the cooling and shaping temperature is 10-30 ℃.
Preferably, the Co60 irradiation dose is 10-40kGy.
The technical effects of the invention are as follows:
according to the invention, graphene oxide is reacted with sodium sulfamate in a heat sealing layer, sodium sulfamate is grafted on the graphene oxide so as to introduce epoxy groups, and the modified amino-terminated toughening agent has an amphiphilic characteristic, so that the nano alumina powder can be effectively promoted to be fully dispersed in a grafted graphene oxide lamellar structure, and also has active amino groups, can be combined with epoxy groups on the surface of the graphene oxide, and the bonding strength of the nano alumina powder on the graphene lamellar is coated and enhanced.
The middle layer adopts low-density polyethylene resin and high-density polyethylene resin to be matched with modified amino-terminated toughening agent, the modified amino-terminated toughening agent has excellent affinity with the low-density polyethylene resin and the high-density polyethylene resin in terms of structural hydrophobic alkyl chain, and the modified amino-terminated toughening agent is fully dispersed in the modified amino-terminated toughening agent after being subjected to melt treatment. Meanwhile, the obtained modified amino-terminated toughening agent is discharged along with a solvent in a spray drying process to form a porous structure in the structure, active groups in the porous structure are easier to expose, the obtained product has good compatibility with low-density polyethylene resin and high-density polyethylene resin, the low-density polyethylene resin and the high-density polyethylene resin can fully enter the porous structure in a melting process, and the bonding strength of the graphene lamellar structure in the middle layer is extremely high.
The invention adopts the easy-to-uncover film formed by compounding the surface layer, the middle layer and the heat sealing layer, and in the hot pressing process, as the middle layer contains the modified amino-terminated toughening agent and has a large amount of active amino groups, the modified amino-terminated toughening agent can interact with groups such as active hydroxyl groups, carboxyl groups and the like of the reinforced graphene lamellar structure in the heat sealing layer structure to generate hydrogen bonds, and the easy-to-uncover film is difficult to form microscopic layering, so that the invention has better uncover effect.
According to the invention, co60 is adopted for irradiation sterilization after shaping, so that the antibacterial effect is remarkable, the irradiation treatment promotes the alumina powder to be further and fully dispersed on the surface of the graphene lamellar structure, and as the unstable alumina powder can generate phase change when being subjected to the irradiation treatment, all crystal forms of alumina can form a high-temperature stable alpha-alumina phase on the surface of the graphene lamellar structure, and the crystal forms of alumina are matched with the graphene lamellar structure, so that the radiation resistance stability of the easy-to-uncover film can be effectively enhanced, and the mechanical property is good.
The applicant finds through experiments that the irradiation treatment can influence the barrier property of the easy-to-tear film, the moisture permeability of the application is hardly changed, but the oxygen permeability is in a descending trend, and the barrier property of the system is enhanced probably due to the combination of the generated high-temperature resistant alpha-alumina phase and the graphene sheet layer. However, when the irradiation dose exceeds 40kGy, the barrier property is greatly reduced, and the moisture resistance and the oxygen resistance are both reduced due to the fact that a large number of molecular chains are broken by irradiation.
The invention can ensure the heat sealing strength and the uncovering effect by compounding and modifying the heat sealing layer and the middle layer, has excellent toughness and barrier property, improves the application adaptability of the easy-uncovering packaging film, and has excellent effect especially in fresh preservation.
Drawings
FIG. 1 is a graph showing the heat seal strength and hot press temperature of the easy-release film obtained in example 5.
Fig. 2 is a thermogravimetric analysis curve of graphene oxide, the enhanced graphene oxide obtained in comparative example 2, and the enhanced graphene oxide obtained in example 5.
FIG. 3 is a graph comparing the barrier properties of the release films obtained in example 5 and comparative examples 1-4.
FIG. 4 is a graph showing the comparison of mechanical properties of the easy-release films obtained in example 5 and comparative examples 1 to 4.
Detailed Description
The invention is further illustrated below in connection with specific embodiments.
The polyethylenes used in the following examples and comparative examples had a melt flow index (190 ℃ C., 2.16 kg) of 0.3g/10min, a melting point of 90 ℃ C., and a density of 0.89g/cm 3 。
The melt flow index (190 ℃,2.16 kg) of ethylene-vinyl acetate used in the following examples and comparative examples was 0.5g/10min, and the vinyl acetate content was 5%;
the melt flow index (190 ℃,2.16 kg) of the ethylene-methyl acrylate used in the following examples and comparative examples was 0.5g/10min, and the methyl acrylate content was 10%;
the melt flow index (190 c) of the polyester elastomers used in the examples and comparative examples described below,2.16 kg) is 2g/10min, the melting point is 180 ℃, and the density is 1.0g/cm 3 ；
Example 1
An easy-to-tear film having barrier properties, comprising: the heat sealing layer, the middle layer and the surface layer made of polyester elastomer are respectively attached to two sides of the middle layer.
The raw materials of the heat sealing layer comprise: 20g of polyethylene, 10g of ethylene-vinyl acetate, 5g of ethylene-methyl acrylate, 1g of polyphthalamide, 1g of modified terminal amino toughening agent, 3g of graphene oxide, 0.1g of nano alumina powder, 0.1g of sodium sulfamate, 1g of polybutene and 1g of anti-fog master batch.
The middle layer raw materials comprise: 30g of low-density polyethylene resin, 10g of high-density polyethylene resin and 1g of modified amino-terminated toughening agent.
The modified amino-terminated toughening agent is prepared by the following steps: and (3) dropwise adding a methanol solution containing 1g of n-hexylamine into a methanol solution containing 4g of methyl acrylate in an ice bath, regulating the temperature to 40 ℃, stirring for 10 hours, performing rotary evaporation, vacuum drying, dissolving a solid product in methanol, dropwise adding the solid product into a methanol solution containing 5g of ethylenediamine in the ice bath, regulating the temperature to 30 ℃, stirring for 50 hours, performing rotary evaporation, and vacuum drying to obtain the modified amino-terminated toughener.
The preparation method of the easy-to-tear film with the barrier property comprises the following steps:
s1, adding graphene oxide, nano alumina powder and sodium sulfamate into absolute ethyl alcohol, stirring for 1h at a high speed of 1000r/min, adding a modified amino-terminated toughening agent, continuously stirring for 10min in an ice water bath, adjusting the temperature to 30 ℃, continuously stirring for 5min, filtering, and spray-drying to obtain reinforced graphene oxide;
s2, uniformly mixing polyethylene, ethylene-vinyl acetate, ethylene-methyl acrylate, polyphthalamide, polybutene, anti-fog master batch and reinforced graphene oxide to obtain a heat sealing layer mixture; uniformly mixing the middle layer raw materials to obtain a middle layer mixture;
and S3, sequentially adding the heat seal layer mixture, the middle layer mixture and the polyester elastomer into hoppers of an extruder, respectively adding into three single-screw extruders of a three-layer Co-extrusion film blowing machine for melting, wherein the extrusion temperature of the heat seal layer is 150 ℃, the extrusion temperature of the middle layer is 140 ℃, the extrusion temperature of the surface layer is 170 ℃, blowing the film by a die head, cooling and shaping the film by a sheet casting machine at 10 ℃, and carrying out Co60 irradiation sterilization with the irradiation dose of 10kGy to obtain the easy-to-tear film with barrier property.
Example 2
An easy-to-tear film having barrier properties, comprising: the heat sealing layer, the middle layer and the surface layer made of polyester elastomer are respectively attached to two sides of the middle layer.
The raw materials of the heat sealing layer comprise: 40g of polyethylene, 30g of ethylene-vinyl acetate, 20g of ethylene-methyl acrylate, 2g of polyphthalamide, 3g of modified terminal amino toughening agent, 5g of graphene oxide, 1g of nano alumina powder, 1g of sodium sulfamate, 5g of polybutene and 2g of anti-fog master batch.
The middle layer raw materials comprise: 50g of low-density polyethylene resin, 30g of high-density polyethylene resin and 3g of modified amino-terminated toughening agent.
The modified amino-terminated toughening agent is prepared by the following steps: and (3) dropwise adding a methanol solution containing 2g of n-hexylamine into a methanol solution containing 6g of methyl acrylate in an ice bath, regulating the temperature to 50 ℃, stirring for 20 hours, performing rotary evaporation, vacuum drying, dissolving a solid product in methanol, dropwise adding the solid product into a methanol solution containing 10g of ethylenediamine in the ice bath, regulating the temperature to 35 ℃, stirring for 150 hours, performing rotary evaporation, and vacuum drying to obtain the modified amino-terminated toughener.
The preparation method of the easy-to-tear film with the barrier property comprises the following steps:
s1, adding graphene oxide, nano alumina powder and sodium sulfamate into absolute ethyl alcohol, stirring for 2 hours at a high speed of 2000r/min, adding a modified amino-terminated toughening agent, continuously stirring for 30min in an ice water bath, adjusting the temperature to 50 ℃, continuously stirring for 15min, filtering, and spray-drying to obtain reinforced graphene oxide;
s2, uniformly mixing polyethylene, ethylene-vinyl acetate, ethylene-methyl acrylate, polyphthalamide, polybutene, anti-fog master batch and reinforced graphene oxide to obtain a heat sealing layer mixture; uniformly mixing the middle layer raw materials to obtain a middle layer mixture;
and S3, sequentially adding the heat seal layer mixture, the middle layer mixture and the polyester elastomer into hoppers of an extruder, respectively adding into three single-screw extruders of a three-layer Co-extrusion film blowing machine for melting, wherein the extrusion temperature of the heat seal layer is 165 ℃, the extrusion temperature of the middle layer is 152 ℃, the extrusion temperature of the surface layer is 210 ℃, blowing the film by a die head, cooling and shaping the film by a sheet casting machine at 30 ℃, and carrying out Co60 irradiation sterilization with the irradiation dose of 40kGy to obtain the easy-to-tear film with barrier property.
Example 3
An easy-to-tear film having barrier properties, comprising: the heat sealing layer, the middle layer and the surface layer made of polyester elastomer are respectively attached to two sides of the middle layer.
The raw materials of the heat sealing layer comprise: 25g of polyethylene, 25g of ethylene-vinyl acetate, 10g of ethylene-methyl acrylate, 1.7g of polyphthalamide, 1.5g of modified amino-terminated toughening agent, 4.5g of graphene oxide, 0.2g of nano alumina powder, 0.8g of sodium sulfamate, 2g of polybutene and 1.7g of anti-fog master batch.
The middle layer raw materials comprise: 35g of low-density polyethylene resin, 25g of high-density polyethylene resin and 1.5g of modified amino-terminated toughening agent.
The modified amino-terminated toughening agent is prepared by the following steps: and (3) dropwise adding a methanol solution containing 1.7g of n-hexylamine into a methanol solution containing 4.5g of methyl acrylate in an ice bath, regulating the temperature to 48 ℃, stirring for 13h, performing rotary evaporation, vacuum drying, dissolving a solid product in methanol, dropwise adding the solid product into a methanol solution containing 8g of ethylenediamine in the ice bath, regulating the temperature to 32 ℃, stirring for 120h, performing rotary evaporation, and vacuum drying to obtain the modified amino-terminated toughener.
The preparation method of the easy-to-tear film with the barrier property comprises the following steps:
s1, adding graphene oxide, nano alumina powder and sodium sulfamate into absolute ethyl alcohol, stirring at a high speed of 1200r/min for 1.3h, adding a modified amino-terminated toughening agent, continuously stirring for 25min in an ice water bath, adjusting the temperature to 35 ℃, continuously stirring for 12min, filtering, and spray drying to obtain reinforced graphene oxide;
s2, uniformly mixing polyethylene, ethylene-vinyl acetate, ethylene-methyl acrylate, polyphthalamide, polybutene, anti-fog master batch and reinforced graphene oxide to obtain a heat sealing layer mixture; uniformly mixing the middle layer raw materials to obtain a middle layer mixture;
and S3, sequentially adding the heat seal layer mixture, the middle layer mixture and the polyester elastomer into hoppers of an extruder, respectively adding into three single-screw extruders of a three-layer Co-extrusion film blowing machine for melting, wherein the extrusion temperature of the heat seal layer is 155 ℃, the extrusion temperature of the middle layer is 149 ℃, the extrusion temperature of the surface layer is 180 ℃, blowing the film by a die head, cooling and shaping the film by a sheet casting machine at 25 ℃, and carrying out Co60 irradiation sterilization with the irradiation dose of 20kGy to obtain the easy-to-tear film with barrier property.
Example 4
An easy-to-tear film having barrier properties, comprising: the heat sealing layer, the middle layer and the surface layer made of polyester elastomer are respectively attached to two sides of the middle layer.
The raw materials of the heat sealing layer comprise: 35g of polyethylene, 15g of ethylene-vinyl acetate, 15g of ethylene-methyl acrylate, 1.3g of polyphthalamide, 2.5g of modified amino-terminated toughening agent, 3.5g of graphene oxide, 0.8g of nano alumina powder, 0.2g of sodium sulfamate, 4g of polybutene and 1.3g of anti-fog master batch.
The middle layer raw materials comprise: 45g of low-density polyethylene resin, 15g of high-density polyethylene resin and 2.5g of modified amino-terminated toughening agent.
The modified amino-terminated toughening agent is prepared by the following steps: and (3) dropwise adding a methanol solution containing 1.3g of n-hexylamine into a methanol solution containing 5.5g of methyl acrylate in an ice bath, regulating the temperature to 42 ℃, stirring for 17 hours, performing rotary evaporation, vacuum drying, dissolving a solid product in methanol, dropwise adding the solid product into a methanol solution containing 6g of ethylenediamine in the ice bath, regulating the temperature to 34 ℃, stirring for 80 hours, performing rotary evaporation, and vacuum drying to obtain the modified amino-terminated toughener.
The preparation method of the easy-to-tear film with the barrier property comprises the following steps:
s1, adding graphene oxide, nano alumina powder and sodium sulfamate into absolute ethyl alcohol, stirring at a high speed for 1.7h, wherein the stirring speed is 1800r/min, adding a modified amino-terminated toughening agent, continuously stirring for 15min in an ice water bath, adjusting the temperature to 45 ℃, continuously stirring for 8min, filtering, and spray drying to obtain reinforced graphene oxide;
s2, uniformly mixing polyethylene, ethylene-vinyl acetate, ethylene-methyl acrylate, polyphthalamide, polybutene, anti-fog master batch and reinforced graphene oxide to obtain a heat sealing layer mixture; uniformly mixing the middle layer raw materials to obtain a middle layer mixture;
and S3, sequentially adding the heat seal layer mixture, the middle layer mixture and the polyester elastomer into hoppers of an extruder, respectively adding into three single-screw extruders of a three-layer Co-extrusion film blowing machine for melting, wherein the extrusion temperature of the heat seal layer is 160 ℃, the extrusion temperature of the middle layer is 143 ℃, the extrusion temperature of the surface layer is 200 ℃, blowing the film by a die head, cooling and shaping the film by a sheet casting machine at 15 ℃, and carrying out Co60 irradiation sterilization with the irradiation dose of 30kGy to obtain the easy-to-tear film with barrier property.
Example 5
An easy-to-tear film having barrier properties, comprising: the heat sealing layer, the middle layer and the surface layer made of polyester elastomer are respectively attached to two sides of the middle layer.
The raw materials of the heat sealing layer comprise: 30g of polyethylene, 20g of ethylene-vinyl acetate, 12g of ethylene-methyl acrylate, 1.5g of polyphthalamide, 2g of modified amino-terminated toughening agent, 4g of graphene oxide, 0.5g of nano alumina powder, 0.5g of sodium sulfamate, 3g of polybutene and 1.5g of anti-fog master batch.
The middle layer raw materials comprise: 40g of low-density polyethylene resin, 20g of high-density polyethylene resin and 2g of modified amino-terminated toughening agent.
The modified amino-terminated toughening agent is prepared by the following steps: and (3) dropwise adding a methanol solution containing 1.5g of n-hexylamine into a methanol solution containing 5g of methyl acrylate in an ice bath, regulating the temperature to 45 ℃, stirring for 15h, performing rotary evaporation, vacuum drying, dissolving a solid product in methanol, dropwise adding the solid product into a methanol solution containing 7g of ethylenediamine in the ice bath, regulating the temperature to 33 ℃, stirring for 100h, performing rotary evaporation, and vacuum drying to obtain the modified amino-terminated toughener.
The preparation method of the easy-to-tear film with the barrier property comprises the following steps:
s1, adding graphene oxide, nano alumina powder and sodium sulfamate into absolute ethyl alcohol, stirring at a high speed for 1.5h, wherein the stirring speed is 1500r/min, adding a modified amino-terminated toughening agent, continuously stirring for 20min in an ice water bath, adjusting the temperature to 40 ℃, continuously stirring for 10min, filtering, and spray drying to obtain reinforced graphene oxide;
s2, uniformly mixing polyethylene, ethylene-vinyl acetate, ethylene-methyl acrylate, polyphthalamide, polybutene, anti-fog master batch and reinforced graphene oxide to obtain a heat sealing layer mixture; uniformly mixing the middle layer raw materials to obtain a middle layer mixture;
and S3, sequentially adding the heat seal layer mixture, the middle layer mixture and the polyester elastomer into hoppers of an extruder, respectively adding into three single-screw extruders of a three-layer Co-extrusion film blowing machine for melting, wherein the extrusion temperature of the heat seal layer is 158 ℃, the extrusion temperature of the middle layer is 146 ℃, the extrusion temperature of the surface layer is 190 ℃, blowing the film by a die head, cooling and shaping the film by a sheet casting machine at 20 ℃, and carrying out Co60 irradiation sterilization with an irradiation dose of 25kGy to obtain the easy-to-tear film with barrier property.
The polypropylene (PP) cup material was used as a test, and the easy-to-tear film obtained in example 5 was used for heat sealing, the pressure was 0.2MPa, and the heat pressing time was 1s. As shown in FIG. 1, the heat seal strength of the easy-to-tear film is generally 5-10N/15mm, while the heat seal strength of the easy-to-tear film obtained in the embodiment 5 is always in the range of easy-to-tear (5-10N/15 mm) under the condition that the hot press temperature is 140-195 ℃, namely, the heat press temperature range corresponding to the easy-to-tear film obtained in the embodiment 5 is wide, the control requirement on heat press during production can be reduced, and the heat seal quality of a finished product is stable and reliable.
Comparative example 1
An easy-to-tear film having barrier properties, comprising: the heat sealing layer, the middle layer and the surface layer made of polyester elastomer are respectively attached to two sides of the middle layer.
The raw materials of the heat sealing layer comprise: 30g of polyethylene, 20g of ethylene-vinyl acetate, 12g of ethylene-methyl acrylate, 1.5g of polyphthalamide, 2g of modified amino-terminated toughening agent, 4g of graphene oxide, 0.5g of nano alumina powder, 0.5g of sodium sulfamate, 3g of polybutene and 1.5g of anti-fog master batch.
The middle layer raw materials comprise: 40g of low-density polyethylene resin and 20g of high-density polyethylene resin.
The modified amino-terminated toughening agent is prepared by the following steps: and (3) dropwise adding a methanol solution containing 1.5g of n-hexylamine into a methanol solution containing 5g of methyl acrylate in an ice bath, regulating the temperature to 45 ℃, stirring for 15h, performing rotary evaporation, vacuum drying, dissolving a solid product in methanol, dropwise adding the solid product into a methanol solution containing 7g of ethylenediamine in the ice bath, regulating the temperature to 33 ℃, stirring for 100h, performing rotary evaporation, and vacuum drying to obtain the modified amino-terminated toughener.
The preparation method of the easy-to-tear film with the barrier property comprises the following steps:
s1, adding graphene oxide, nano alumina powder and sodium sulfamate into absolute ethyl alcohol, stirring at a high speed for 1.5h, wherein the stirring speed is 1500r/min, adding a modified amino-terminated toughening agent, continuously stirring for 20min in an ice water bath, adjusting the temperature to 40 ℃, continuously stirring for 10min, filtering, and spray drying to obtain reinforced graphene oxide;
s2, uniformly mixing polyethylene, ethylene-vinyl acetate, ethylene-methyl acrylate, polyphthalamide, polybutene, anti-fog master batch and reinforced graphene oxide to obtain a heat sealing layer mixture; uniformly mixing the middle layer raw materials to obtain a middle layer mixture;
and S3, sequentially adding the heat seal layer mixture, the middle layer mixture and the polyester elastomer into hoppers of an extruder, respectively adding into three single-screw extruders of a three-layer Co-extrusion film blowing machine for melting, wherein the extrusion temperature of the heat seal layer is 158 ℃, the extrusion temperature of the middle layer is 146 ℃, the extrusion temperature of the surface layer is 190 ℃, blowing the film by a die head, cooling and shaping the film by a sheet casting machine at 20 ℃, and carrying out Co60 irradiation sterilization with an irradiation dose of 25kGy to obtain the easy-to-tear film with barrier property.
Comparative example 2
An easy-to-tear film having barrier properties, comprising: the heat sealing layer, the middle layer and the surface layer made of polyester elastomer are respectively attached to two sides of the middle layer.
The raw materials of the heat sealing layer comprise: 30g of polyethylene, 20g of ethylene-vinyl acetate, 12g of ethylene-methyl acrylate, 1.5g of polyphthalamide, 4g of graphene oxide, 0.5g of nano alumina powder, 0.5g of sodium sulfamate, 3g of polybutene and 1.5g of anti-fog master batch.
The middle layer raw materials comprise: 40g of low-density polyethylene resin, 20g of high-density polyethylene resin and 2g of modified amino-terminated toughening agent.
The modified amino-terminated toughening agent is prepared by the following steps: and (3) dropwise adding a methanol solution containing 1.5g of n-hexylamine into a methanol solution containing 5g of methyl acrylate in an ice bath, regulating the temperature to 45 ℃, stirring for 15h, performing rotary evaporation, vacuum drying, dissolving a solid product in methanol, dropwise adding the solid product into a methanol solution containing 7g of ethylenediamine in the ice bath, regulating the temperature to 33 ℃, stirring for 100h, performing rotary evaporation, and vacuum drying to obtain the modified amino-terminated toughener.
The preparation method of the easy-to-tear film with the barrier property comprises the following steps:
s1, adding graphene oxide, nano alumina powder and sodium sulfamate into absolute ethyl alcohol, stirring at a high speed for 1.5h, wherein the stirring speed is 1500r/min, filtering, and spray drying to obtain reinforced graphene oxide;
s2, uniformly mixing polyethylene, ethylene-vinyl acetate, ethylene-methyl acrylate, polyphthalamide, polybutene, anti-fog master batch and reinforced graphene oxide to obtain a heat sealing layer mixture; uniformly mixing the middle layer raw materials to obtain a middle layer mixture;
and S3, sequentially adding the heat seal layer mixture, the middle layer mixture and the polyester elastomer into hoppers of an extruder, respectively adding into three single-screw extruders of a three-layer Co-extrusion film blowing machine for melting, wherein the extrusion temperature of the heat seal layer is 158 ℃, the extrusion temperature of the middle layer is 146 ℃, the extrusion temperature of the surface layer is 190 ℃, blowing the film by a die head, cooling and shaping the film by a sheet casting machine at 20 ℃, and carrying out Co60 irradiation sterilization with an irradiation dose of 25kGy to obtain the easy-to-tear film with barrier property.
Thermogravimetric analysis was performed on graphene oxide, the enhanced graphene oxide obtained in comparative example 2 and the enhanced graphene oxide obtained in example 5, with gas: n (N) 2 Temperature: 50-800 ℃, and the temperature rising rate is as follows: 10 ℃/min.
As shown in fig. 2, the mass loss of the three components is roughly divided into three stages, the first stage: the quality starts to be obviously reduced at about 100 ℃, which belongs to the evaporation of water; and a second stage: quality loss at 100-350 DEG COxygen-containing functional groups such as hydroxyl, carboxyl and epoxy groups are not decomposed to generate CO 2 And H 2 O; and a third stage: the decomposition of carbon skeleton at 350-800 deg.c.
Whereas the enhanced graphene oxide obtained in example 5 and comparative example 2 had higher carbon residue than graphene oxide, due to grafting both on the graphene oxide surface; however, the carbon residue amount of the reinforced graphene oxide obtained in example 5 is higher than that of comparative example 2, which shows that the surface grafting group content of the reinforced graphene oxide obtained in example 5 is higher than that of comparative example 2, and the modified amino-terminated toughening agent is indeed effectively grafted on the graphene oxide from the side.
Comparative example 3
An easy-to-tear film having barrier properties, comprising: the heat sealing layer, the middle layer and the surface layer made of polyester elastomer are respectively attached to two sides of the middle layer.
The raw materials of the heat sealing layer comprise: 30g of polyethylene, 20g of ethylene-vinyl acetate, 12g of ethylene-methyl acrylate, 1.5g of polyphthalamide, 2g of modified amino-terminated toughening agent, 4g of graphene oxide, 0.5g of nano alumina powder, 0.5g of sodium sulfamate, 3g of polybutene and 1.5g of anti-fog master batch.
The middle layer raw materials comprise: 40g of low-density polyethylene resin, 20g of high-density polyethylene resin and 2g of modified amino-terminated toughening agent.
The modified amino-terminated toughening agent is prepared by the following steps: and (3) dropwise adding a methanol solution containing 1.5g of n-hexylamine into a methanol solution containing 5g of methyl acrylate in an ice bath, regulating the temperature to 45 ℃, stirring for 15h, performing rotary evaporation, vacuum drying, dissolving a solid product in methanol, dropwise adding the solid product into a methanol solution containing 7g of ethylenediamine in the ice bath, regulating the temperature to 33 ℃, stirring for 100h, performing rotary evaporation, and vacuum drying to obtain the modified amino-terminated toughener.
The preparation method of the easy-to-tear film with the barrier property comprises the following steps:
s1, adding graphene oxide, nano alumina powder and sodium sulfamate into absolute ethyl alcohol, stirring at a high speed for 1.5h, wherein the stirring speed is 1500r/min, adding a modified amino-terminated toughening agent, continuously stirring for 20min in an ice water bath, adjusting the temperature to 40 ℃, continuously stirring for 10min, filtering, and spray drying to obtain reinforced graphene oxide;
s2, uniformly mixing polyethylene, ethylene-vinyl acetate, ethylene-methyl acrylate, polyphthalamide, polybutene, anti-fog master batch and reinforced graphene oxide to obtain a heat sealing layer mixture; uniformly mixing the middle layer raw materials to obtain a middle layer mixture;
and S3, sequentially adding the mixture of the heat sealing layer, the mixture of the middle layer and the polyester elastomer into hoppers of an extruder, respectively putting the three single-screw extruders of a three-layer co-extrusion film blowing machine into the extruder for melting, wherein the extrusion temperature of the heat sealing layer is 158 ℃, the extrusion temperature of the middle layer is 146 ℃, the extrusion temperature of the surface layer is 190 ℃, blowing the film by a die head, and cooling and shaping the film at 20 ℃ by a sheet casting machine to obtain the easy-to-tear film with barrier property.
Comparative example 4
An easy-to-tear film having barrier properties, comprising: the heat sealing layer, the middle layer and the surface layer made of polyester elastomer are respectively attached to two sides of the middle layer.
The raw materials of the heat sealing layer comprise: 30g of polyethylene, 20g of ethylene-vinyl acetate, 12g of ethylene-methyl acrylate, 1.5g of polyphthalamide, 2g of modified amino-terminated toughening agent, 4g of graphene oxide, 0.5g of nano alumina powder, 0.5g of sodium sulfamate, 3g of polybutene and 1.5g of anti-fog master batch.
The middle layer raw materials comprise: 40g of low-density polyethylene resin, 20g of high-density polyethylene resin and 2g of modified amino-terminated toughening agent.
The modified amino-terminated toughening agent is prepared by the following steps: and (3) dropwise adding a methanol solution containing 1.5g of n-hexylamine into a methanol solution containing 5g of methyl acrylate in an ice bath, regulating the temperature to 45 ℃, stirring for 15h, performing rotary evaporation, vacuum drying, dissolving a solid product in methanol, dropwise adding the solid product into a methanol solution containing 7g of ethylenediamine in the ice bath, regulating the temperature to 33 ℃, stirring for 100h, performing rotary evaporation, and vacuum drying to obtain the modified amino-terminated toughener.
The preparation method of the easy-to-tear film with the barrier property comprises the following steps:
s1, adding graphene oxide, nano alumina powder and sodium sulfamate into absolute ethyl alcohol, stirring at a high speed for 1.5h, wherein the stirring speed is 1500r/min, adding a modified amino-terminated toughening agent, continuously stirring for 20min in an ice water bath, adjusting the temperature to 40 ℃, continuously stirring for 10min, filtering, and spray drying to obtain reinforced graphene oxide;
s2, uniformly mixing polyethylene, ethylene-vinyl acetate, ethylene-methyl acrylate, polyphthalamide, polybutene, anti-fog master batch and reinforced graphene oxide to obtain a heat sealing layer mixture; uniformly mixing the middle layer raw materials to obtain a middle layer mixture;
and S3, sequentially adding the heat seal layer mixture, the middle layer mixture and the polyester elastomer into hoppers of an extruder, respectively adding into three single-screw extruders of a three-layer Co-extrusion film blowing machine for melting, wherein the extrusion temperature of the heat seal layer is 158 ℃, the extrusion temperature of the middle layer is 146 ℃, the extrusion temperature of the surface layer is 190 ℃, blowing the film by a die head, cooling and shaping the film by a sheet casting machine at 20 ℃, and carrying out Co60 irradiation sterilization with the irradiation dose of 45kGy to obtain the easy-to-tear film with barrier property.
The thickness of each layer of the easy-release films obtained in example 5 and comparative examples 1 to 4 was measured as follows:
total thickness, μm Heat sealing layer, μm Middle layer, μm Surface layer, μm
Example 5 65.7 8.5 53.3 3.9
Comparative example 1 66.8 8.7 53.9 4.2
Comparative example 2 67.4 9.2 53.5 4.7
Comparative example 3 64.4 7.9 53.2 3.3
Comparative example 4 63.9 8.8 51.5 3.6
The barrier properties of the easy-release films obtained in example 5 and comparative examples 1 to 4 were measured, and the barrier properties of the materials were characterized by the water vapor transmission rate and the oxygen transmission rate. The water vapor permeation quantity test is carried out by referring to a weight increasing method in GB/T1037-2021 method for measuring the water vapor permeation properties of plastic films and thin sheets, wherein the test temperature is 38 ℃, the humidity is 90% RH, the preheating time is 2h, the rotation interval is 10min, and 3 groups are arranged in parallel. Reference is made to GB/T1038.1-2022 section 1, method for testing the gas permeability of films and sheets for Plastic products: the differential pressure method is used for testing the oxygen transmittance, the testing temperature is 23 ℃, the humidity is 50% RH, and the vacuumizing time is 4 hours. The surface of the sample is ensured to be pollution-free and scratch-free, and each group is provided with 3 parallel parts.
As shown in fig. 3, the water vapor transmission rate and the oxygen transmission rate of the easy-to-tear film obtained in example 5 are very close to those of the easy-to-tear film obtained in comparative example 1, so that the barrier properties of the easy-to-tear film obtained in example 5 are basically consistent with those of the easy-to-tear film obtained in comparative example 1, i.e. the barrier properties of the easy-to-tear film are not affected by the layer change between the two films.
The barrier property of the easy-to-tear film obtained in example 5 is superior to that of comparative example 2, and the applicant believes that the modification of the heat sealing layer by adopting the modified amino-terminated toughening agent in example 5 promotes the full dispersion of the nano alumina powder in the grafted graphene oxide lamellar structure, and can be combined with the epoxy groups on the surface of the graphene oxide to coat and enhance the bonding strength of the nano alumina powder on the graphene lamellar, so that the barrier property of the easy-to-tear film obtained in example 5 is excellent.
The vapor permeability of the easy-to-tear film obtained in example 5 is very close to that of comparative example 3, and the oxygen permeability is higher than that of comparative example 3, which shows that the application adopts irradiation sterilization, although the moisture permeability is hardly changed, the oxygen permeability is reduced, and the applicant considers that the irradiation treatment promotes the alumina powder to be fully dispersed on the surface of the graphene lamellar structure, meanwhile, the alumina powder is unstable to generate phase change in the irradiation treatment process, and all crystal forms of alumina can form a high-temperature stable alpha-alumina phase on the surface of the graphene lamellar structure, so that the high-temperature stable alpha-alumina phase is combined with the graphene lamellar structure, and the barrier performance of the system is effectively enhanced.
The barrier properties of the easy-to-tear film obtained in example 5 were superior to those of comparative example 4, because irradiation generates a large amount of radicals when the irradiation dose is too high, causing molecular chain rearrangement to cause chain scission and crosslinking reaction to interrupt the chain reaction to take precedence, thus causing molecular chains to be broken in a large amount, which is manifested as a decrease in moisture and oxygen barrier properties.
The mechanical properties of the easy-release films obtained in example 5 and comparative examples 1 to 4 were measured and the tensile strength and elongation at break were used to characterize the mechanical properties of the materials. Determination of tensile Properties of plastics section 1, see GB/T1040.1-2018: the general rule is that a strip-shaped sampler is adopted for sampling, the length of a rectangular sample is 150+/-0.5 mm, the width of the rectangular sample is 15+/-0.5 mm, the original gauge length is set to be 50mm, the stretching rate is set to be 50mm/min, the samples are ensured to be free from wrinkles and damage, the samples are vertically clamped, and each group of samples are parallel.
As shown in fig. 4, the peel-off film obtained in example 5 had the highest tensile strength. The applicant believes that: the invention promotes the nano alumina powder to be fully dispersed in the grafted graphene oxide lamellar structure through the modified amino-terminated toughening agent in the heat sealing layer, can be combined with the epoxy groups on the surface of the graphene oxide, and coats and enhances the bonding strength of the nano alumina powder on the graphene lamellar; on the other hand, the middle layer adopts the low-density polyethylene resin, the high-density polyethylene resin and the modified amino-terminated toughener to be matched, and the modified amino-terminated toughener has a special branch structure, so that the middle layer is not easy to tangle, and the formed three-dimensional network structure can effectively enhance the toughness of the middle layer structure and has excellent mechanical property; and the modified amino-terminated toughening agent is discharged along with a solvent in a spray drying process to form a porous structure in the structure, so that active groups in the porous structure are easier to expose, the obtained product has good compatibility with a polyester elastomer, the polyester elastomer can fully enter the porous structure in a melting process, the bonding strength of a graphene lamellar structure in the polyester elastomer structure is extremely high, and the tensile strength of the obtained easy-to-tear film is further improved. Meanwhile, the alumina powder is further fully dispersed on the surface of the graphene lamellar structure through irradiation sterilization, the alumina powder is further stabilized in alpha-alumina phase at high temperature, and the alumina powder is matched with the graphene lamellar structure, so that the mechanical property of the easy-to-uncover film can be effectively enhanced.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.

Claims (7)

1. An easy-to-tear film having barrier properties, comprising: the heat sealing layer, the middle layer and the surface layer are respectively attached to two sides of the middle layer;
the raw materials of the heat sealing layer comprise: polyethylene, ethylene-vinyl acetate, ethylene-methyl acrylate, polyphthalamide, modified amine-terminated toughener, graphene oxide, nano alumina powder, sodium sulfamate, polybutene and anti-fog master batch; the mass ratio of polyethylene, ethylene-vinyl acetate, ethylene-methyl acrylate, polyphthalamide, modified amino-terminated toughening agent, graphene oxide, nano alumina powder, sodium sulfamate, polybutene and anti-fog master batch is 20-40:10-30:5-20:1-2:1-3:1-5:0.1-1:0.1-1:1-5:1-2;
the middle layer raw materials comprise: the mass ratio of the low-density polyethylene resin to the high-density polyethylene resin is 30-50:10-30:1-3;
the modified amino-terminated toughening agent takes n-hexylamine as an initiator, and adopts methyl acrylate and ethylenediamine to react alternately to obtain dendritic molecules;
the surface layer adopts polyester elastomer as raw material;
the preparation method of the easy-to-tear film comprises the following steps:
s1, adding graphene oxide, nano alumina powder and sodium sulfamate into absolute ethyl alcohol, stirring at a high speed for 1-2h, adding a modified amino-terminated toughening agent, continuously stirring for 10-30min in an ice water bath, adjusting the temperature to 30-50 ℃, continuously stirring for 5-15min, filtering, and spray drying to obtain reinforced graphene oxide;
s2, uniformly mixing polyethylene, ethylene-vinyl acetate, ethylene-methyl acrylate, polyphthalamide, polybutene, anti-fog master batch and reinforced graphene oxide to obtain a heat sealing layer mixture; uniformly mixing the middle layer raw materials to obtain a middle layer mixture;
and S3, sequentially adding the heat seal layer mixture, the middle layer mixture and the polyester elastomer into an extruder hopper, respectively putting into three single screw extruders of a three-layer Co-extrusion film blowing machine for melting, blowing films, cooling and shaping, and performing Co60 irradiation sterilization to obtain the easy-to-tear film with barrier property.
2. The release film with barrier properties according to claim 1, wherein the total thickness of the release film is 60-70 μm and the thickness ratio of the heat sealing layer, middle layer and surface layer is 7-10:50-55:3-5.
3. The easy release film of claim 1 wherein the modified terminal amino toughener is methanol as the reaction solvent.
4. The easy-to-tear film with barrier property according to claim 1, wherein the mass ratio of methyl acrylate, ethylenediamine and n-hexylamine in the modified amino-terminated toughening agent is 4-6:5-10:1-2.
5. The film of claim 1, wherein the heat seal layer extrusion temperature is 150-165 ℃, the middle layer extrusion temperature is 140-152 ℃, and the skin layer extrusion temperature is 170-210 ℃ in the three-layer co-extrusion film blowing machine.
6. The release film of claim 1 having barrier properties, wherein the cooling set temperature is from 10 ℃ to 30 ℃.
7. The release film with barrier properties of claim 1, wherein the Co60 irradiation dose is 10-40kGy.
CN202310801262.7A 2023-06-30 2023-06-30 Easy-to-uncover film with barrier property and preparation method thereof Active CN116922909B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105619981A (en) * 2015-12-22 2016-06-01 湖北恒泰橡塑有限公司 Medical packing easy-to-tear-off film and preparation method thereof
CN113736344A (en) * 2021-09-26 2021-12-03 鞠慧 Water-based epoxy anticorrosive paint and preparation method thereof
CN115010855A (en) * 2022-05-27 2022-09-06 昕亮科技（深圳）有限公司 Nylon toughening agent with high toughening efficiency
CN116080191A (en) * 2023-02-15 2023-05-09 浙江鹏远新材料科技集团股份有限公司 High-barrier packaging material and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105619981A (en) * 2015-12-22 2016-06-01 湖北恒泰橡塑有限公司 Medical packing easy-to-tear-off film and preparation method thereof
CN113736344A (en) * 2021-09-26 2021-12-03 鞠慧 Water-based epoxy anticorrosive paint and preparation method thereof
CN115010855A (en) * 2022-05-27 2022-09-06 昕亮科技（深圳）有限公司 Nylon toughening agent with high toughening efficiency
CN116080191A (en) * 2023-02-15 2023-05-09 浙江鹏远新材料科技集团股份有限公司 High-barrier packaging material and preparation method thereof

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