CN113183579B - Cold-resistant PE composite film, preparation method thereof and prepared packaging film - Google Patents

Cold-resistant PE composite film, preparation method thereof and prepared packaging film Download PDF

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CN113183579B
CN113183579B CN202110462139.8A CN202110462139A CN113183579B CN 113183579 B CN113183579 B CN 113183579B CN 202110462139 A CN202110462139 A CN 202110462139A CN 113183579 B CN113183579 B CN 113183579B
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modified
resin
cold
resistant
composite film
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CN113183579A (en
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林灿洪
刘长来
殷杰
周健刚
谭声隆
叶顺祥
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FOSHAN SOUTHERN PACKAGING CO LTD
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FOSHAN SOUTHERN PACKAGING 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
    • 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
    • B32B15/09—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 polyesters
    • 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
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • 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
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • 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
    • 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
    • B32B2307/7244—Oxygen 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
    • B32B2439/70—Food packaging
    • 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
    • C08J2423/08—Copolymers of ethene
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2244—Oxides; Hydroxides of metals of zirconium
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • 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
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

Abstract

The invention provides a cold-resistant PE composite film, a preparation method thereof and a prepared packaging film. The cold-resistant PE composite film comprises a PE resin inner layer, a modified PE resin middle layer and an EVA resin outer layer. The cold-resistant PE composite film is prepared by modifying a middle-layer PE resin layer, adding the specifically modified nano particles and a specific processing technology, so that the prepared cold-resistant PE composite film has excellent cold resistance, especially the cold resistance at the temperature of-25 ℃. The modified inorganic nanoparticles are inorganic nanoparticles with the surfaces modified by silane coupling agents, and the inorganic nanoparticles form a core-shell structure by rigid nanoparticles and metal oxides.

Description

Cold-resistant PE composite film, preparation method thereof and prepared packaging film
Technical Field
The invention belongs to the technical field of polymer chemistry, and particularly relates to a cold-resistant PE composite film, a preparation method thereof and a prepared packaging film.
Background
The frozen food is prepared by processing qualified food materials, rapidly freezing at-30 deg.C, packaging, and storing at-18 deg.C or below. Because the whole process adopts low-temperature cold chain preservation, the frozen food has the characteristics of long shelf life, difficult decay and convenient eating. At present, common frozen food packaging bags on the market are generally prepared from materials such as PET/PE and BOPP/PE. By virtue of the characteristics of stable chemical property, no toxicity, no odor, low price and the like of PE, the PE is the most common polymer material protective film in the field of food. PE films can be generally classified into high density polyethylene, medium density polyethylene and low density polyethylene films, and are generally selected according to the application scenario and the like.
Because the PE composite film for storing frozen food needs to be stored in a low-temperature environment for a long time, the PE material is easy to be fragile, easy to break and easy to crack due to the reduction of the activity of polymer molecular chains of the PE material, and the physical performance of the PE material is sharply reduced after the PE composite film is stored for a period of time at a low temperature. If the frozen food is packaged with a packaging material having poor cold resistance, the sharp protrusions of the frozen food easily puncture the package during later transportation, loading and unloading, causing leakage problems and accelerating the deterioration of the food. Therefore, how to improve the cold resistance of the PE composite film at low temperature and reduce the embrittlement temperature of the PE composite film, so that the PE composite film is not easily brittle in the low-temperature use process, becomes one of the important points of attention in the current food packaging industry.
Therefore, it is required to develop a cold-resistant PE composite film with better low temperature resistance to prepare a packaging film with better low temperature resistance.
Disclosure of Invention
The invention aims to provide a cold-resistant PE composite film aiming at the problem that the PE composite film in the prior art is poor in low-temperature use performance. The cold-resistant PE composite film is prepared by modifying a middle-layer PE resin layer, adding the specifically modified nano particles to perform low-temperature toughening and reinforcing modification on a PE resin matrix and a specific processing technology, so that the prepared cold-resistant PE composite film has excellent cold resistance, especially the cold resistance at the temperature of-25 ℃.
The invention also aims to provide a preparation method of the cold-resistant PE composite film.
Another object of the present invention is to provide a cold-resistant packaging film prepared from the cold-resistant PE composite film.
Another object of the present invention is to provide a modified PE resin having cold resistance.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
the cold-resistant PE composite film is characterized by comprising an inner layer, a middle layer and an outer layer, wherein the inner layer is a PE resin layer, the middle layer is a modified PE resin layer, and the outer layer is an EVA resin layer;
the modified PE resin layer is prepared from the following raw materials in parts by weight:
Figure BDA0003042679980000021
wherein the modified inorganic nanoparticles are inorganic nanoparticles with surfaces modified by a silane coupling agent; the inorganic nanoparticles consist of rigid nanoparticles and metal oxides; the nano-particle has a core-shell structure which takes rigid nano-particles as a core and takes metal oxide as a shell;
and in the process of preparing the modified PE resin layer, the inorganic modified nanoparticles and the POE resin are firstly melted and blended and then are melted and blended with other raw materials.
The cold-resistant PE composite film is prepared by modifying a middle-layer PE resin layer and adding the specifically modified nanoparticles, so that the prepared cold-resistant PE composite film has excellent cold resistance, and a specific processing technology is used for toughening and enhancing the PE resin matrix at low temperature, so that the prepared cold-resistant PE composite film has excellent cold resistance, especially the cold resistance at-25 ℃.
The POE resin can obviously improve the low-temperature toughness of the PE resin layer, and meanwhile, the inorganic nanoparticles are added to reinforce the PE resin layer, so that the PE resin layer can have certain mechanical strength on the basis of having certain toughness at low temperature. However, since the surface of the inorganic nanoparticles contains hydrophilic groups, the compatibility of the inorganic nanoparticles with plastics such as PE is poor, the degree of combination between the particles and the base material is affected, a large number of cavities are generated in the base material, and the base material plastic is more easily subjected to brittle fracture; in addition, since the particle size of the inorganic nano particles is too small, agglomeration is easily generated in the substrate, so that small cracks are generated on the substrate, and the substrate is more easily fragile when used at low temperature.
According to the invention, researches show that inorganic rigid nanoparticles and metal oxides are prepared into a nano dispersion with a core-shell structure, then the dispersion is subjected to surface hydrophobic modification, and then the dispersion is subjected to melt blending with POE (polyolefin elastomer) resin, a hydrophobic modified layer on the surface of the modified inorganic nanoparticles can better interact with the POE resin, and the POE resin and the modified inorganic nanoparticles have stronger interaction, so that a multilayer buffering effect can be generated in a PE resin matrix, and when the modified inorganic nanoparticles are impacted at low temperature, the stress state of the PE resin can be changed, shear yielding is initiated, small cracks are prevented from further expanding, and energy loss is reduced; in addition, the inorganic nanoparticles are prepared into the core-shell structure, so that the impact strength can be improved, and the tensile strength cannot be obviously reduced; the silane coupling agent is selected to carry out surface hydrophobic modification on the inorganic nanoparticles, so that the compatibility of the inorganic nanoparticles and the polymer can be improved, and the performance of the composite material at low temperature is further improved.
Preferably, the modified PE resin layer is prepared from the following components in parts by weight:
Figure BDA0003042679980000031
preferably, the rigid nanoparticles are SiO 2 Or CaCO 3 Or a combination of both.
Preferably, the rigid nanoparticles have a particle size of 20 to 25nm.
Preferably, the metal oxide is ZrO 2 Or ZnO or a combination of the two. The metal oxide selected for use in the application has the advantages of high hardness, small particle size and the like, and can well improve the impact property of the PE resin.
Preferably, the inorganic nanoparticles are SiO 2 /ZnO and SiO 2 /ZrO 2 A mixture consisting of 1.
Preferably, the silane coupling agent is one or a combination of more of 3-aminopropyltriethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltriethoxysilane and 3- (2,3-glycidoxy) propyltriethoxysilane.
Preferably, the plasticizer is one or a combination of more of citrate compounds and epoxy compounds.
Preferably, the citrate compound is one or a combination of triethyl citrate, tributyl citrate and acetyl triethyl citrate.
Preferably, the epoxy compound is one or a combination of several of epoxidized soybean oil, epoxidized corn oil and epoxy acetyl castor oil.
The preparation method of the cold-resistant PE composite film comprises the following steps:
s1, preparing modified inorganic nanoparticles:
s11, uniformly mixing the rigid nanoparticles with the metal oxide precursor solution, refluxing for 0.5-1 h, cooling, washing, drying, and calcining at 400-600 ℃ to obtain inorganic nanoparticles with a core-shell structure;
s12, mixing the inorganic nanoparticles with the core-shell structure obtained in the step S11 with a silane coupling agent at 90-150 ℃ for 5-15 min to obtain the modified inorganic nanoparticles;
s2, preparing modified PE resin:
after the modified inorganic nanoparticles and the POE resin are melted and blended, the modified inorganic nanoparticles and the POE resin are melted, blended and granulated with the PE resin and the plasticizer to obtain the modified PE resin;
s3. Preparation of cold-resistant PE composite membrane
And (3) carrying out co-extrusion film blowing on the PE resin, the modified PE resin obtained from the S2 and the EVA resin to obtain the cold-resistant PE composite film.
Preferably, the mass molar ratio of the rigid nanoparticles to the metal ions in the metal oxide precursor solution is 1.
Preferably, the concentration of the metal ions in the metal oxide precursor solution is 0.05 to 0.40mol/L.
The cold-resistant packaging film prepared from the cold-resistant PE composite film is also within the protection scope of the invention, and is formed by compounding the cold-resistant PE composite film, an aluminum film layer and a PET resin layer.
It should be noted that, the method (step S11) of the present invention is adopted to coat the rigid nanoparticles, and the coating (metal oxide) is deposited on the suspended core (rigid nanoparticles) to form the shell through direct surface reaction and deposition, so as to obtain the inorganic nanoparticles having the core-shell structure in which the rigid nanoparticles are coated with the metal oxide. The method is a method for preparing metal oxide coated nano particles, and is also reported in documents (She Xiaoyun, she Xiaoyun. Preparation and performance of silicon dioxide/zirconium dioxide core-shell composite material [ J ]. Chemical engineering progress, 2010,29 (9): 1710-1714) and the like.
The invention also discloses a modified PE resin which is prepared from the following raw materials in parts by weight:
Figure BDA0003042679980000041
wherein the modified inorganic nanoparticles are inorganic nanoparticles with the surface modified by a silane coupling agent; the inorganic nanoparticles consist of rigid nanoparticles and metal oxides, and have a core-shell structure with the rigid nanoparticles as a core and the metal oxides as a shell;
and in the process of preparing the modified PE resin layer, the inorganic modified nanoparticles and the POE resin are firstly melted and blended and then are melted and blended with other raw materials.
Compared with the prior art, the invention has the following beneficial effects:
the cold-resistant PE composite film is prepared by modifying a middle-layer PE resin layer and adding the specifically modified nanoparticles, so that the prepared cold-resistant PE composite film has excellent cold resistance, and a specific processing technology is used for toughening and enhancing the PE resin matrix at low temperature, so that the prepared cold-resistant PE composite film has excellent cold resistance, especially the cold resistance at-25 ℃.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
SiO used in the examples of the present invention 2 Purchased from Jiangsu Xiancheng nano material science and technology limited (particle size 20-25 nm).
Example 1
The embodiment provides a cold-resistant PE composite film, which comprises an inner layer, a middle layer and an outer layer, wherein the inner layer is a PE resin layer, the middle layer is a modified PE resin layer, and the outer layer is an EVA resin layer; the modified PE resin layer is prepared from the following raw materials in parts by weight: 40 parts of PE resin, 5 parts of POE resin, 0.5 part of modified inorganic nanoparticles and 0.1 part of epoxidized soybean oil; wherein the modified inorganic nano particles are SiO with surface modification and core-shell structure 2 /ZrO 2 And (3) particles.
The preparation method of the cold-resistant PE composite film comprises the following steps:
s1, preparation of modified inorganic nanoparticles:
S11.5g SiO 2 dispersing nanoparticles in 100mL of absolute ethanol, adding a zirconium isopropoxide solution (16.38 g of zirconium isopropoxide is dispersed in 200mL of propanol), refluxing for 1h, cooling, standing for 5min, washing with water and ethanol alternately for 3 times, centrifuging, drying the centrifuged product at 80 ℃, and calcining at 600 ℃ for 3h to obtain SiO with a core-shell structure 2 /ZrO 2 ；
S12, siO obtained in S11 2 /ZrO 2 Adding into a high-speed stirrer, stirring at 90 deg.C, dropwise adding 1wt% 3-aminopropyltriethoxysilane coupling agent, stirring at 800r/min for 5min, taking out, and oven drying to obtain the modified inorganic nanoparticles, surface hydrophobic modified SiO with core-shell structure 2 /ZrO 2 Particles;
s2, preparing modified PE resin:
adding the modified inorganic nanoparticles obtained from S1 into POE resin according to the formula proportion, carrying out melt blending at 180 ℃, then carrying out melt blending with PE resin and a plasticizer at 185 ℃, and carrying out granulation to obtain the modified PE resin;
s3. Preparation of cold-resistant PE composite membrane
And (3) putting the PE resin, the modified PE resin obtained from the S2 and the EVA resin into a three-layer co-extrusion film blowing machine set, blowing the film at 150 ℃, and rolling to obtain the cold-resistant PE composite film.
The embodiment also provides a packaging film containing the cold-resistant PE composite film, which is formed by compounding the cold-resistant PE composite film, the aluminum film layer and the PET resin layer in the embodiment 1.
Example 2
The embodiment provides a cold-resistant PE composite film, which comprises an inner layer, a middle layer and an outer layer, wherein the inner layer is a PE resin layer, the middle layer is a modified PE resin layer, and the outer layer is an EVA resin layer; the modified PE resin layer is composed of the following raw materials in parts by weight: 90 parts of PE resin and 20 parts of POE resin5 parts of modified inorganic nanoparticles and 10 parts of triethyl citrate, wherein the modified inorganic nanoparticles are SiO with surface modification and a core-shell structure 2 a/ZnO particle.
The preparation method of the cold-resistant PE composite film comprises the following steps:
s1, preparation of modified inorganic nanoparticles:
S11.2g SiO 2 dispersing nanoparticles in 80mL of absolute ethanol, adding zinc sulfate solution (3.88 g of zinc sulfate is dispersed in 100mL of water), refluxing for 1h, cooling, standing for 10min, alternately washing with water and ethanol for 6 times, centrifuging, drying the centrifuged product at 60 ℃, and calcining at 400 ℃ for 6h to obtain SiO with a core-shell structure 2 /ZnO；
S12, preparing SiO obtained in S11 2 Adding ZnO into a high-speed stirrer, stirring at 90 ℃, dropwise adding 5wt% of vinyl triethoxysilane coupling agent, stirring at 2000r/min for 5min, taking out, and drying to obtain the modified inorganic nano particle-surface hydrophobic modified SiO with core-shell structure 2 /ZnO particles;
s2, preparing modified PE resin:
adding the modified inorganic nanoparticles obtained from the step S1 into POE resin according to the formula proportion, melting and blending at 200 ℃, then melting and blending with PE resin and a plasticizer at 190 ℃, and granulating to obtain the modified PE resin;
s3. Preparation of cold-resistant PE composite membrane
And (3) putting the PE resin, the modified PE resin obtained from the S2 and the EVA resin into a three-layer co-extrusion film blowing unit, blowing the film at 200 ℃, and rolling to obtain the cold-resistant PE composite film.
The embodiment also provides a packaging film containing the cold-resistant PE composite film, which is formed by compounding the cold-resistant PE composite film, the aluminum film layer and the PET resin layer in the embodiment 2.
Example 3
The embodiment provides a cold-resistant PE composite film, cold-resistant PE composite film includes inlayer, middle level and skin, the inlayer is the PE resin layer, the middle level is the modified PE resin layer, the skin is the EVA resin layer(ii) a The modified PE resin layer is composed of the following raw materials in parts by weight: 50 parts of PE resin, 8 parts of POE resin, 1.5 parts of modified inorganic nanoparticles and 0.5 part of acetyl triethyl citrate, wherein the modified inorganic nanoparticles are SiO with surface modification and core-shell structure 2 /ZnO particles and SiO 2 /ZrO 2 The particles are a composition consisting of 1.
The preparation method of the cold-resistant PE composite film comprises the following steps:
s1, preparation of modified inorganic nanoparticles:
S11.1g SiO 2 dispersing nano particles in 50mL of absolute ethyl alcohol, adding a zirconium isopropoxide solution (4.91 g of zirconium isopropoxide is dispersed in 150mL of propyl alcohol), refluxing for 1h, cooling, standing for 20min, washing with water and ethyl alcohol alternately for 4 times, centrifuging, drying a centrifuged product at 60 ℃, and calcining at 400 ℃ for 6h to obtain SiO with a core-shell structure 2 /ZrO 2 ；
Similarly, the zirconium isopropoxide solution was replaced with a zinc sulfate solution (2 g zinc sulfate dispersed in 60mL water) to prepare SiO with a core-shell structure 2 /ZnO；
S12, preparing SiO obtained in S11 2 /ZnO and SiO 2 /ZrO 2 Adding the mixture into a high-speed stirrer according to the weight ratio of 1.5 to 1.5, stirring the mixture at 120 ℃, dropwise adding 2wt% of 3- (2,3-epoxypropoxy) propyl triethoxysilane coupling agent, stirring the mixture for 10min at the rotating speed of 1500r/min, taking out the mixture and drying the mixture to obtain the modified inorganic nano particles, namely the SiO with the core-shell structure and the hydrophobically modified surface 2 /ZnO particles and SiO 2 /ZrO 2 A particle composition;
s2, preparing modified PE resin:
adding the modified inorganic nanoparticle composition obtained in the step S1 into POE resin according to the formula ratio, carrying out melt blending at 170 ℃, and then carrying out melt blending and granulation with PE resin and a plasticizer at 190 ℃ to obtain the modified PE resin;
s3. Preparation of cold-resistant PE composite membrane
And (3) putting the PE resin, the modified PE resin obtained from the S2 and the EVA resin into a three-layer coextrusion film blowing unit, blowing the film at 150 ℃, and rolling to obtain the cold-resistant PE composite film.
The embodiment also provides a packaging film containing the cold-resistant PE composite film, which is formed by compounding the cold-resistant PE composite film, the aluminum film layer and the PET resin layer in the embodiment 3.
Example 4
The embodiment provides a cold-resistant PE composite film, which comprises an inner layer, a middle layer and an outer layer, wherein the inner layer is a PE resin layer, the middle layer is a modified PE resin layer, and the outer layer is an EVA resin layer; the modified PE resin layer is composed of the following raw materials in parts by weight: 80 parts of PE resin, 12 parts of POE resin, 7 parts of modified inorganic nanoparticles and 5 parts of epoxy corn oil, wherein the modified inorganic nanoparticles are SiO with surface modification and core-shell structure 2 /ZnO particles and SiO 2 /ZrO 2 The particles are 5:2 by weight.
The preparation method of the cold-resistant PE composite film comprises the following steps:
s1, preparing modified inorganic nanoparticles:
S11.8g SiO 2 dispersing nano particles in 170mL of absolute ethyl alcohol, adding a zirconium isopropoxide solution (28.8 g of zirconium isopropoxide is dispersed in 300mL of propyl alcohol), refluxing for 1h, cooling, standing for 10min, washing with water and ethyl alcohol alternately for 4 times, centrifuging, drying a centrifuged product at 70 ℃, and calcining at 500 ℃ for 6h to obtain SiO with a core-shell structure 2 /ZrO 2 ；
Similarly, by replacing the zirconium isopropoxide solution with a zinc sulfate solution (14.2 g zinc sulfate dispersed in 100mL water), siO with a core-shell structure was prepared 2 /ZnO；
S12, preparing SiO obtained in S11 2 /ZnO and SiO 2 /ZrO 2 Adding 5:2 in a weight ratio into a high-speed stirrer, stirring at 150 ℃, dropwise adding 1.5wt% of silane coupling agent compound, wherein the silane coupling agent compound is prepared by mixing vinyl triethoxysilane and 3-methacryloxypropyl triethoxysilane in a weight ratio of 1:3, stirring for 15min at the rotating speed of 1500r/min, taking out and drying to obtain the modified inorganic nano particle-surface hydrophobic modified toolSiO with core-shell structure 2 /ZnO particles and SiO 2 /ZrO 2 A particle composition;
s2, preparing modified PE resin:
adding the modified inorganic nanoparticle composition obtained from S1 into POE resin according to the formula ratio, carrying out melt blending at 185 ℃, then carrying out melt blending with PE resin and a plasticizer at 190 ℃, and carrying out granulation to obtain the modified PE resin;
s3. Preparation of cold-resistant PE composite membrane
And (3) putting the PE resin, the modified PE resin obtained from the S2 and the EVA resin into a three-layer co-extrusion film blowing machine set, blowing the film at 150 ℃, and rolling to obtain the cold-resistant PE composite film.
The embodiment also provides a packaging film containing the cold-resistant PE composite film, which is formed by compounding the cold-resistant PE composite film, the aluminum film layer and the PET resin layer in the embodiment 4.
Example 5
The embodiment provides a cold-resistant PE composite film, which comprises an inner layer, a middle layer and an outer layer, wherein the inner layer is a PE resin layer, the middle layer is a modified PE resin layer, and the outer layer is an EVA resin layer; the modified PE resin layer is composed of the following raw materials in parts by weight: 75 parts of PE resin, 10 parts of POE resin, 3 parts of modified inorganic nanoparticles and 2.2 parts of tributyl citrate, wherein the modified inorganic nanoparticles are surface-modified SiO with a core-shell structure 2 /ZnO particles and SiO 2 /ZrO 2 The particles are 2:1 by weight.
The preparation method of the cold-resistant PE composite film comprises the following steps:
s1, preparation of modified inorganic nanoparticles:
S11.3g SiO 2 dispersing nano particles in 80mL of absolute ethanol, adding a zirconium isopropoxide solution (12.77 g of zirconium isopropoxide is dispersed in 200mL of propanol), refluxing for 1h, cooling, standing for 8min, washing with water and ethanol for 4 times alternately, centrifuging, drying a centrifuged product at 80 ℃, and calcining at 500 ℃ for 6h to obtain SiO with a core-shell structure 2 /ZrO 2 ；
Similarly, replacement of zirconium isopropoxide solution with zinc sulfate solution (6.30 g zinc sulfate dispersed in 200mL water) produced SiO with a core-shell structure 2 /ZnO；
S12, preparing SiO obtained in S11 2 /ZnO and SiO 2 /ZrO 2 Adding 2:1 in weight ratio into a high-speed stirrer, stirring at 150 ℃, dropwise adding 1.5wt% of silane coupling agent compound, mixing the silane coupling agent compound with 3-methacryloxypropyltriethoxysilane at a weight ratio of 2.5 2 /ZnO particles and SiO 2 /ZrO 2 A particle composition;
s2, preparing modified PE resin:
adding the modified inorganic nanoparticle composition obtained in the step S1 into POE resin according to the formula ratio, carrying out melt blending at 180 ℃, then carrying out melt blending with PE resin and a plasticizer at 190 ℃, and carrying out granulation to obtain the modified PE resin;
s3. Preparation of cold-resistant PE composite membrane
And (3) putting the PE resin, the modified PE resin obtained from the S2 and the EVA resin into a three-layer co-extrusion film blowing machine set, blowing the film at 150 ℃, and rolling to obtain the cold-resistant PE composite film.
The embodiment also provides a packaging film containing the cold-resistant PE composite film, which is formed by compounding the cold-resistant PE composite film, the aluminum film layer and the PET resin layer in the embodiment 5.
Comparative example 1
This comparative example provides a PE composite film using unmodified SiO 2 The particles, other formulas and proportions of the modified PE resin, the cold-resistant PE composite film, the preparation method of the cold-resistant PE composite film and the structure of the cold-resistant PE composite film packaging film are consistent with those in example 1.
Comparative example 2
This comparative example provides a PE composite film with inorganic nanoparticles not selected from metal oxide-SiO pairs 2 The particles are modified (i.e. step S11 is not included) by using only silane coupling agent for SiO 2 ParticlesThe surface modification is carried out, and other formulas and proportions of the modified PE resin, the cold-resistant PE composite film, the preparation method of the cold-resistant PE composite film and the structure of the cold-resistant PE composite film packaging film are all consistent with those of the embodiment 1.
Comparative example 3
This comparative example provides a PE composite film, inorganic nanoparticles not selected from silane coupling agent to SiO 2 The surface of the particles is modified by hydrophobicity (namely no silane coupling agent is added in the step S12), and SiO is only selected from metal oxides 2 The particles are modified, and other formulas and proportions of the modified PE resin, the cold-resistant PE composite film, the preparation method of the cold-resistant PE composite film and the structure of the cold-resistant PE composite film packaging film are consistent with those of example 1.
Comparative example 4
The comparative example provides a PE composite film, POE resin is not added to the modified PE resin, the remaining formulation and ratio, the preparation method of the cold-resistant PE composite film, and the structure of the packaging film comprising the cold-resistant PE composite film, consistent with example 1.
Comparative example 5
The present comparative example provides a PE composite film, in which a plasticizer tributyl citrate is not added to the modified PE resin, and the remaining formulation and ratio, the preparation method of the cold-resistant PE composite film, and the structure of the packaging film comprising the cold-resistant PE composite film are all the same as those in example 1.
Comparative example 6
Compared with the embodiment 1, the PE composite film is different in that the modified inorganic nanoparticles and the POE resin are not blended when the PE composite film is prepared, but the modified inorganic nanoparticles, the POE resin, the PE resin and the plasticizer are directly subjected to melt blending and granulation at 185 ℃.
The performance test of the (cold-resistant) PE composite film/packaging bag prepared in the above examples and comparative examples is carried out, and the test items and methods are as follows:
1. impact testing
The PE composite film formulas of examples 1-5 and comparative examples 1-6 of the invention were injection molded into samples for impact performance testing. The impact performance test was performed according to the method specified in the national standard GB/T1843-2008. The sample size was: 80mm 10mm 4mm, notch depth of 2mm, using a cantilever beam impact tester for testing, test temperature of 23 degrees, 0 degrees, 25 degrees, each test point of each example/test example for 10 times of parallel test, its arithmetic mean value as the final test results (see Table 1).
During the test, the cantilever beam impact tester tries to raise the pendulum bob to a specified height position, then releases the pendulum bob, freely swings downwards, and impacts and supports the cantilever beam type sample at the moment when the pendulum bob swings to the lowest point. Calculating the capacity loss value of the pendulum bob in the impact process according to the falling height and the swinging height of the pendulum bob, and taking the energy consumed by the unit original cross-sectional area at the notch when the sample is broken as the impact strength in kJ/m 2 That is, the larger the value, the stronger the impact resistance, the better the toughness of the material, and the less brittle fracture at low temperature.
2. Tensile Property test
The PE composite film formulas of the examples 1-5 and the comparative examples 1-6 are injected into samples for tensile property test, the tensile property test is carried out according to the national standard GB/T1040.1-2006, the cold-resistant PE composite film formulas of the examples 1-5 and the comparative examples 1-5 are injected through an injection molding machine to obtain dumbbell-shaped samples for the tensile property test, a universal testing machine is used for testing the tensile strength and the elongation at break of the dumbbell-shaped samples, the sizes of the samples are 120mm multiplied by 6mm multiplied by 1mm, each example/comparative example is subjected to 5 times of parallel tests, and the arithmetic mean value of the parallel tests is taken as the final test result. The elongation at break is expressed in% and the tensile strength is the maximum tensile stress to which the sample is subjected, expressed in Mpa (see table 1).
3. Oxygen permeability test
The packaging bags prepared by compounding the PE composite films of examples 1-5 and comparative examples 1-6 with the aluminum film layer and the PET resin layer are subjected to oxygen permeability test, an oxygen permeability instrument is adopted for testing, and the samples are cut into the packaging bags with the effective area of 10cm 2 The packaging bag of (1). The temperature and humidity are adjusted for 48 hours under the conditions that the temperature is 23 ℃ and the relative humidity is 50 +/-10%. In the testing process, the oxygen pressure is set to be 101KPa, the flow rates of nitrogen and oxygen are respectively 10 mL/min and 20mL/min, and the pressure is controlled at-18 ℃, 0 ℃, 15 ℃ and 30 DEGThe oxygen transmission rate was measured at DEG C, and 3 parallel tests were carried out for each example/comparative example, and the arithmetic mean value thereof was taken as the final test result, and the result was expressed in units of mL/m 2 D (see Table 1).
Table 1 (cold-resistant) PE composite film performance test results prepared in examples and comparative examples
Figure BDA0003042679980000111
Figure BDA0003042679980000121
From the test results in table 1, the specific modified inorganic nanoparticles, POE resin and plasticizer of the present invention have the effect of synergistically enhancing the impact performance of the cold-resistant PE composite film, and can better improve the cold resistance of the composite film at low temperature.
Comparative example 1 is different from example 1 in that inorganic nanoparticles used in the preparation of pellets of a modified PE resin layer are not modified at all, as can be seen from the test results in Table 1, and the impact strength at different temperatures is greatly reduced; comparative example 2 is different from example 1 in that inorganic nanoparticles used in preparing pellets of a modified PE resin layer only employ a silane coupling agent for SiO 2 The particles were modified individually, and the impact properties were also reduced as can be seen from the test results in Table 1; comparative example 3 is different from example 1 in that modified inorganic nanoparticles used in preparing pellets of a modified PE resin layer are not surface-hydrophobically modified and as can be seen from the test results of Table 1, impact properties thereof are higher than those obtained by adding SiO alone 2 Comparative example 1 of the particles is worse, probably because of SiO 2 /ZnO particles and SiO 2 /ZrO 2 Caused by agglomeration of the particle composition; the difference between the comparative example 4 and the example 1 is that when modified PE resin layer granules are prepared, POE resin is not added for modification, the impact strength is the worst in all the examples and the comparative examples, and the influence of the addition of POE on the mechanical property of the cold-resistant PE composite film is larger; comparative example 5 differs from example 1 in the preparation of the modificationWhen the PE resin layer pellets are used, the impact performance of the PE resin layer pellets is slightly reduced compared with that of the PE resin layer pellets in example 1 without adding the plasticizer tributyl citrate; the difference between the comparative example 6 and the example 1 is that the modified inorganic nanoparticles and POE are not mixed in advance, and the mechanical strength of the prepared PE composite film is slightly reduced, which is probably because when POE and modified inorganic nanoparticles are mixed in advance, the hydrophobic modified layer on the surface of the modified inorganic nanoparticles can interact with POE resin better, and the stronger interaction between POE resin and the modified inorganic nanoparticles can generate multilayer buffering effect in the PE resin matrix, so that the prepared PE film has good mechanical properties (such as impact property), especially the mechanical properties at low temperature, and the cold resistance of the material is improved.
Elongation at break is the ratio of the displacement value of the specimen at break to the original length, expressed in%; tensile strength refers to the maximum tensile stress in Mpa that a specimen is subjected to during a tensile test. Comparative example 4 is different from example 1 in that, when pellets of a modified PE resin layer were prepared, modification was carried out without adding POE resin, and the elongation at break and tensile strength were lower than those of example 1. Generally, the material is modified by adding the POE resin, so that the impact strength is improved and the tensile property is obviously reduced, but the invention adds the modified nano particles for specific modification during modification and adopts a specific processing technology to form multilayer interaction in the material, so that the materials are combined more tightly and the mechanical property is more excellent.
The invention also tests the oxygen passing rate of the packaging bag prepared from the cold-resistant PE composite film, and the result shows that the packaging bag prepared from the cold-resistant PE composite film has lower oxygen passing rate than the packaging bags prepared according to comparative examples 1-6, which indicates that the inorganic nanoparticles are specifically modified by the invention, so that the dispersion of the inorganic nanoparticles in the materials can be well improved, and the materials can be more tightly combined by adopting a specific processing technology, the prepared PE film is more compact, the oxygen passing rate is lower, and the packaging bag is beneficial to fresh keeping.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (8)

1. The cold-resistant PE composite film is characterized by comprising an inner layer, a middle layer and an outer layer, wherein the inner layer is a PE resin layer, the middle layer is a modified PE resin layer, and the outer layer is an EVA resin layer;
the modified PE resin layer is prepared from the following raw materials in parts by weight:
Figure FDA0003840039230000011
wherein the modified inorganic nanoparticles are inorganic nanoparticles with the surface modified by a silane coupling agent; the inorganic nanoparticles consist of rigid nanoparticles and metal oxides, and have a core-shell structure with the rigid nanoparticles as a core and the metal oxides as a shell; the rigid nano particles are SiO 2 Or CaCO 3 One or a combination of both; the metal oxide is ZrO 2 Or ZnO or a combination of the two;
and in the process of preparing the modified PE resin layer, the inorganic modified nanoparticles and the POE resin are firstly melted and blended and then are melted and blended with other raw materials.
2. The cold-resistant PE composite film according to claim 1, wherein the silane coupling agent is one or a combination of 3-aminopropyltriethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltriethoxysilane and 3- (2,3-epoxypropoxy) propyltriethoxysilane.
3. The cold-resistant PE composite film according to claim 1, wherein the plasticizer is one or a combination of citrate compounds and epoxy compounds.
4. The cold-resistant PE composite film according to claim 3, wherein the citrate compound is one or a combination of triethyl citrate, tributyl citrate and acetyl triethyl citrate.
5. The cold-resistant PE composite film according to claim 3, wherein the epoxy compound is one or a combination of epoxy soybean oil, epoxy corn oil and epoxy acetyl castor oil.
6. The preparation method of the cold-resistant PE composite film as claimed in any one of claims 1 to 5, which is characterized by comprising the following steps:
s1, preparation of modified inorganic nanoparticles:
s11, uniformly mixing the rigid nanoparticles with a metal oxide precursor solution, refluxing for 0.5-1 h, cooling, washing, drying, and calcining at 400-600 ℃ to obtain inorganic nanoparticles;
s12, mixing the inorganic nanoparticles obtained in the step S11 with a silane coupling agent at 90-150 ℃ for 5-15 min to obtain modified inorganic nanoparticles;
s2, preparing modified PE resin:
after the modified inorganic nanoparticles and the POE resin are melted and blended, the modified inorganic nanoparticles and the POE resin are melted, blended and granulated with the PE resin and the plasticizer to obtain the modified PE resin;
s3. Preparation of cold-resistant PE composite membrane
And (3) carrying out co-extrusion film blowing on the PE resin, the modified PE resin obtained from the S2 and the EVA resin to obtain the cold-resistant PE composite film.
7. The modified PE resin is characterized by being prepared from the following raw materials in parts by weight:
Figure FDA0003840039230000021
wherein the modified inorganic nanoparticles are inorganic nanoparticles with the surface modified by a silane coupling agent; the inorganic nanoparticles consist of rigid nanoparticles and metal oxides, and have a core-shell structure with the rigid nanoparticles as a core and the metal oxides as a shell; the rigid nano particles are SiO 2 Or CaCO 3 One or a combination of two; the metal oxide is ZrO 2 Or ZnO or a combination of the two;
and in the process of preparing the modified PE resin layer, the inorganic modified nanoparticles and the POE resin are firstly melted and blended and then are melted and blended with other raw materials.
8. A cold-resistant packaging film, which is prepared from the cold-resistant PE composite film as claimed in any one of claims 1 to 5.
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CN1322773A (en) * 2001-05-24 2001-11-21 宁波信高塑化有限公司 Inorganic nanometer particle modified optical cable protecting casing material and its prepn
CN102909925A (en) * 2012-10-31 2013-02-06 安徽省科汇恒达包装材料科技有限公司 Multilayer frozen polyethylene film
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CN1322773A (en) * 2001-05-24 2001-11-21 宁波信高塑化有限公司 Inorganic nanometer particle modified optical cable protecting casing material and its prepn
CN102909925A (en) * 2012-10-31 2013-02-06 安徽省科汇恒达包装材料科技有限公司 Multilayer frozen polyethylene film
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