CN111231470A - Multilayer co-extruded polyethylene heat shrinkable film and preparation method thereof - Google Patents
Multilayer co-extruded polyethylene heat shrinkable film and preparation method thereof Download PDFInfo
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- CN111231470A CN111231470A CN202010260221.8A CN202010260221A CN111231470A CN 111231470 A CN111231470 A CN 111231470A CN 202010260221 A CN202010260221 A CN 202010260221A CN 111231470 A CN111231470 A CN 111231470A
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0017—Combinations of extrusion moulding with other shaping operations combined with blow-moulding or thermoforming
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
- B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/91—Heating, e.g. for cross linking
- B29C48/9105—Heating, e.g. for cross linking of hollow articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
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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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- 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
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/54—Yield strength; Tensile strength
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- 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
- B32B2307/582—Tearability
- B32B2307/5825—Tear resistant
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- 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
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- 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
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Abstract
The invention is suitable for the technical field of materials, and provides a multilayer co-extruded polyethylene heat shrinkable film and a preparation method thereof, wherein the multilayer co-extruded polyethylene heat shrinkable film comprises at least three film layers; each film layer is prepared by compounding nontoxic and widely available raw materials of high-pressure low-density polyethylene, high-density polyethylene, modified nano-montmorillonite, epoxidized soybean oil and ethylene bis-stearamide, namely, the film layers are the same material layers formed by mixing the same raw materials, so that the film layers can be recycled without mechanically stripping the film materials after use, the recycling rate is high, and the recycling cost is low; the prepared multilayer polyethylene heat-shrinkable co-extruded film not only has good physical and mechanical properties such as heat shrinkage, tensile property, tearing strength and the like, but also has good transparency, is suitable for packaging and transporting articles such as but not limited to food, electronic products and the like, and has good development prospect.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a multilayer co-extruded polyethylene heat shrinkable film and a preparation method thereof.
Background
POF (oriented polypropylene) is a heat shrinkable film, is called a multilayer co-extruded polyolefin heat shrinkable film, is prepared by plasticizing and extruding linear low-density polyethylene (LLDPE) serving as an intermediate layer and copolymerized propylene (pp) serving as an inner layer and an outer layer by three extruders, and then carrying out die head molding, bubble inflation and other special processes, and is the most widely used environment-friendly heat shrinkable film at present.
In order to meet the daily living needs of people, a large amount of packaging materials are consumed everyday, for example, heat shrinkable films are used for external packaging of foods, goods and the like, a large amount of packaging waste is generated when the packaging materials are used in large amount, and the input waste treatment cost is increased. In order to reduce the amount of waste, the reduction, harmlessness, and recycling of plastic products have become major targets for sustainable development.
At present, the recycling of the plastic products of the heat shrinkable film is generally classified recycling, i.e. the plastic products of the same kind are classified into one kind for recycling. However, since the POF heat shrinkable film has a PP/LLDPE/PP three-layer co-extrusion composite structure, and the materials between the layers interact and are firmly bonded, it is very difficult to "cleanly" peel the middle layer from the inner layer and the outer layer in the POF, and thus it is difficult to realize the classified recycling of the films of the POF heat shrinkable film.
Disclosure of Invention
The embodiment of the invention provides a multilayer co-extruded polyethylene heat shrinkable film, and aims to solve the problems that the inner layer material and the outer layer material of the existing heat shrinkable film are different, the interlayer materials are firmly combined, and the mutual peeling is difficult to carry out classification and recycling.
The embodiment of the invention is realized in such a way that the multilayer co-extruded polyethylene heat shrinkable film comprises an outer layer, at least one middle layer and an inner layer; the outer layer, the middle layer and the inner layer are all prepared from the following raw materials in parts by weight: 60-95 parts of high-pressure low-density polyethylene, 4-7 parts of high-density polyethylene, 6-15 parts of modified nano montmorillonite, 0-3 parts of epoxidized soybean oil and 0-2 parts of ethylene bis stearamide.
The embodiment of the invention also provides a preparation method of the multilayer co-extruded polyethylene heat shrinkable film, which comprises the following steps: weighing various raw materials according to the raw material formula of the film layer, mixing, adding into a plurality of film layer extruders respectively, plasticizing, and extruding in a co-extrusion die head to obtain a first film bubble; the first film bubble is drawn by a drawing device and is subjected to water cooling forming to obtain a preliminarily formed multilayer co-extruded polyethylene heat shrinkage film; wherein the water cooling temperature is 18-20 ℃, and the cooling time is 5-10 seconds. And carrying out infrared radiation heating on the preliminarily formed multilayer co-extruded polyethylene heat shrinkable film, simultaneously inflating to blow the film to form a second bubble film, and carrying out cold air circulation cooling to obtain the multilayer co-extruded polyethylene heat shrinkable film.
According to the multilayer co-extruded polyethylene heat shrinkable film provided by the embodiment of the invention, each film layer is made of the same material layer formed by mixing the same raw materials, so that the film layers can be recycled without mechanically peeling the film materials after use, the recycling rate is high, and the recycling cost is low. The multi-layer polyethylene heat-shrinkable co-extruded film prepared by compounding the nontoxic and widely available raw materials of high-pressure low-density polyethylene, high-density polyethylene, modified nano-montmorillonite, epoxidized soybean oil and ethylene bis-stearamide not only has good physical and mechanical properties such as heat shrinkage, tensile property and tearing strength, but also has good transparency, is suitable for packaging and transporting articles such as but not limited to food, electronic products and the like, and has good development prospect.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
According to the multilayer co-extruded polyethylene heat shrinkable film provided by the embodiment of the invention, each film layer is made of the same material layer formed by mixing the same raw materials, so that the film layers can be recycled without mechanically peeling the film materials after use, the recycling rate is high, and the recycling cost is low. The multi-layer polyethylene heat-shrinkable co-extruded film prepared by compounding the nontoxic and widely available raw materials of high-pressure low-density polyethylene, high-density polyethylene, modified nano-montmorillonite, epoxidized soybean oil and ethylene bis-stearamide not only has good physical and mechanical properties such as heat shrinkage, tensile property and tearing strength, but also has good transparency, is suitable for packaging and transporting articles such as but not limited to food, electronic products and the like, and has good development prospect.
The embodiment of the invention provides a multilayer co-extruded polyethylene heat shrinkable film, which comprises at least three film layers;
wherein each film layer is prepared from the following raw materials in parts by weight: 60-95 parts of high-pressure low-density polyethylene, 4-7 parts of high-density polyethylene, 6-15 parts of modified nano montmorillonite, 0-3 parts of epoxidized soybean oil and 0-2 parts of ethylene bis stearamide.
Preferably, the modified nano-montmorillonite is a mixture of cetyl trimethyl ammonium bromide modified nano-montmorillonite and magnesium salt modified nano-montmorillonite.
More preferably, the mixing weight ratio of the hexadecyl trimethyl ammonium bromide modified nanometer montmorillonite to the magnesium salt modified nanometer montmorillonite is 2.5-3: 1.
High pressure Low Density Polyethylene (LDPE) is generally a thermoplastic produced by a high pressure process, the reaction pressure is generally 110 to 350MPa, the reaction temperature is generally 160 to 350 ℃, and the polymerization reaction time is very short, generally 15 seconds to 2 minutes. The LDPE has good chemical stability, no obvious damage effect of general acid and alkali, good dielectric property, thermal stability, toughness, impact resistance, high transparency and other properties. High Density Polyethylene (HDPE) has fewer molecular branches and is easily crystallized.
The montmorillonite has unique layered one-dimensional nano structure characteristic, morphological characteristic, designable reactivity among layers and ultra-large specific surface area (750 m)2/g) and a diameter/thickness ratio of up to 200 or more. The method comprises the steps of treating the montmorillonite by cetyl trimethyl ammonium bromide to enable the montmorillonite to generate cation exchange reaction, and enabling organic groups to cover the surface of the montmorillonite or be inserted into the interlayer of the montmorillonite, so that the surface energy of the montmorillonite is changed, the interlayer spacing is increased, the montmorillonite is changed from hydrophilicity to lipophilicity, and the cetyl trimethyl ammonium bromide modified nano montmorillonite is prepared.
Under the action of interlayer solvent, by adding magnesium salt to treat the montmorillonite, the montmorillonite can be peeled and dispersed into thinner single crystal chips, and the magnesium salt modified nanometer montmorillonite with average chip thickness less than 25nm is prepared.
The modified nano-montmorillonite formed by the mixture of the hexadecyl trimethyl ammonium bromide modified nano-montmorillonite and the magnesium salt modified nano-montmorillonite is uniformly dispersed in a nano-level manner in the process of preparing the multilayer co-extruded polyethylene heat shrinkage film, and has a good enhancement effect on the mechanical property of the shrinkage film; meanwhile, due to the sheet structure, the mechanical property of the shrink film can be improved uniquely; and the physical and mechanical properties of the shrink film can be obviously improved by compounding the shrink film with raw materials such as high-pressure low-density polyethylene, high-density polyethylene and the like in a certain proportion, so that the shrink film has good elongation at break, toughness and tensile strength. The added epoxidized soybean oil can improve the stability of the shrink film to light and heat; the ethylene bis stearamide is added, so that the lubricating property of the shrink film can be improved, the friction generated during the rolling of the shrink film is reduced, and the heat shrinkage rate of the shrink film is kept.
In the embodiment of the present invention, it is preferable to use a high-pressure low-density polyethylene having a melt index (MFR) of 0.2 to 0.3 g/(10 min). High pressure low density polyethylene having a melt index in this range has good processability.
In a preferred embodiment of the invention, the film layer is prepared from the following raw materials in parts by weight: 95 parts of high-pressure low-density polyethylene, 4 parts of high-density polyethylene, 10 parts of modified nano-montmorillonite, 1 part of epoxidized soybean oil and 1 part of ethylene bis-stearamide.
In practical production, the multilayer coextruded polyethylene heat shrinkable film can be prepared into a three-layer or five-layer film structure according to the transportation requirements of packaged objects.
The embodiment of the invention also provides a preparation method of the multilayer co-extruded polyethylene heat shrinkable film, which comprises the following steps:
step 101, weighing various raw materials according to the raw material formula of the film layer, mixing, adding into a plurality of film layer extruders respectively, plasticizing, and extruding through a co-extrusion die head to obtain a first film bubble.
102, drawing the first film bubble by a drawing device and performing water-cooling forming to obtain a preliminarily formed multilayer co-extruded polyethylene heat shrinkage film; wherein the water cooling temperature is 18-20 ℃, and the cooling time is 5-10 seconds.
103, heating the preliminarily formed multilayer co-extruded polyethylene heat shrinkable film by infrared radiation, inflating the film to blow the film to form a second bubble film, and cooling the second bubble film by cold air circulation to obtain the multilayer co-extruded polyethylene heat shrinkable film.
In step 101, in order to mix the raw materials uniformly, the weighed raw materials may be put into a high-speed kneader to be mixed, and then the mixed materials are added into a plurality of film layer extruders respectively. For example, to prepare a three-layer co-extruded polyethylene heat shrinkable film, the mixed materials are fed into three extruders, an outer layer extruder, a middle layer extruder and an inner layer extruder. For another example, to prepare a five-layer co-extruded polyethylene heat shrinkable film, the mixed materials are respectively fed into five extruders, namely an outer layer extruder, an intermediate layer 1 extruder, an intermediate layer 2 extruder and an inner layer extruder.
In step 102, in the step of heating the preliminarily formed multilayer coextruded polyethylene heat shrinkable film by infrared radiation and simultaneously inflating the film to blow the film to form a second bubble film, the blow-up ratio of the die is controlled to be 2-3. When the blow-up ratio is controlled to be 2-3, the transverse shrinkage rate and the light transmittance of the multilayer co-extruded polyethylene heat shrinkable film can be improved.
In the embodiment of the invention, the water cooling temperature is controlled to be 18-20 ℃, the cooling time is 5-10 seconds, the first bubble film forming is accelerated, and the shrinkage rate and the light transmittance of the prepared multilayer co-extruded polyethylene heat shrinkable film product are improved.
Preferably, in the blowing process of the second bubble film, the first bubble film is properly softened by two-section infrared radiation heating, the temperature of the first section infrared radiation heating is controlled to be 180-200 ℃, the temperature of the second section infrared radiation heating is controlled to be 150-165 ℃ to form the second bubble film, the second bubble film is favorably subjected to inflation and blowing to realize bidirectional stretching of polyolefin molecules, and the stretching performance, the transverse shrinkage rate and the longitudinal shrinkage rate of the second bubble film are improved.
The technical solution and the technical effect of the present invention will be further described by specific examples.
Example 1
Weighing the components according to the following formula for later use: 60 parts of high-pressure low-density polyethylene, 7 parts of high-density polyethylene, 8 parts of modified nano-montmorillonite, 1 part of epoxidized soybean oil and 0.5 part of ethylene bis-stearamide;
the multilayer coextruded polyethylene heat shrinkable film (three-layer coextruded film) of the embodiment is prepared by the following steps:
the weighed raw materials are put into a high-speed kneader to be kneaded at a high speed, are mixed uniformly and then are respectively added into a plurality of film layer extruders, and are plasticized and then enter a co-extrusion die head to be extruded to obtain a first film bubble;
the first film bubble is drawn by a drawing device and is subjected to water cooling forming to obtain a preliminarily formed multilayer co-extruded polyethylene heat shrinkage film; wherein the water cooling temperature is 18 ℃, and the cooling time is 5 seconds;
and carrying out two-stage infrared radiation heating on the preliminarily formed multilayer co-extruded polyethylene heat shrinkable film, controlling the temperature of the first-stage infrared radiation heating to be 180 ℃, controlling the temperature of the second-stage infrared radiation heating to be 150 ℃, simultaneously inflating and blowing the film, controlling the blow-up ratio of a die to be 2, forming a second bubble film, and carrying out cold air circulation cooling to obtain the multilayer co-extruded polyethylene heat shrinkable film.
Example 2
Weighing the components according to the following formula for later use: 70 parts of high-pressure low-density polyethylene, 6 parts of high-density polyethylene, 10 parts of modified nano-montmorillonite and 2 parts of ethylene bis-stearamide;
the multilayer coextruded polyethylene heat shrinkable film (three-layer coextruded film) of the embodiment is prepared by the following steps:
the weighed raw materials are put into a high-speed kneader to be kneaded at a high speed, are mixed uniformly and then are respectively added into a plurality of film layer extruders, and are plasticized and then enter a co-extrusion die head to be extruded to obtain a first film bubble;
the first film bubble is drawn by a drawing device and is subjected to water cooling forming to obtain a preliminarily formed multilayer co-extruded polyethylene heat shrinkage film; wherein the water cooling temperature is 20 ℃, and the cooling time is 8 seconds;
and carrying out two-stage infrared radiation heating on the preliminarily formed multilayer co-extruded polyethylene heat shrinkable film, controlling the temperature of the first-stage infrared radiation heating to be 200 ℃, controlling the temperature of the second-stage infrared radiation heating to be 160 ℃, simultaneously inflating and blowing the film, controlling the blow-up ratio of a die to be 2.5 to form a second bubble film, and carrying out cold air circulation cooling to obtain the multilayer co-extruded polyethylene heat shrinkable film.
Example 3
Weighing the components according to the following formula for later use: 80 parts of high-pressure low-density polyethylene, 4 parts of high-density polyethylene, 15 parts of modified nano-montmorillonite and 3 parts of epoxidized soybean oil;
the multilayer coextruded polyethylene heat shrinkable film (three-layer coextruded film) of the embodiment is prepared by the following steps:
the weighed raw materials are put into a high-speed kneader to be kneaded at a high speed, are mixed uniformly and then are respectively added into a plurality of film layer extruders, and are plasticized and then enter a co-extrusion die head to be extruded to obtain a first film bubble;
the first film bubble is drawn by a drawing device and is subjected to water cooling forming to obtain a preliminarily formed multilayer co-extruded polyethylene heat shrinkage film; wherein the water cooling temperature is 18 ℃, and the cooling time is 10 seconds;
and carrying out two-stage infrared radiation heating on the preliminarily formed multilayer co-extruded polyethylene heat shrinkable film, controlling the temperature of the first-stage infrared radiation heating to be 195 ℃ and the temperature of the second-stage infrared radiation heating to be 165 ℃, simultaneously inflating and blowing the film, controlling the blow-up ratio of a die to be 3 to form a second bubble film, and carrying out cold air circulation cooling to obtain the multilayer co-extruded polyethylene heat shrinkable film.
Example 4
Weighing the components according to the following formula for later use: 90 parts of high-pressure low-density polyethylene, 5 parts of high-density polyethylene, 6 parts of modified nano-montmorillonite, 2 parts of epoxidized soybean oil and 1 part of ethylene bis-stearamide;
the multilayer coextruded polyethylene heat shrinkable film (three-layer coextruded film) of the embodiment is prepared by the following steps:
the weighed raw materials are put into a high-speed kneader to be kneaded at a high speed, are mixed uniformly and then are respectively added into a plurality of film layer extruders, and are plasticized and then enter a co-extrusion die head to be extruded to obtain a first film bubble;
the first film bubble is drawn by a drawing device and is subjected to water cooling forming to obtain a preliminarily formed multilayer co-extruded polyethylene heat shrinkage film; wherein the water cooling temperature is 20 ℃, and the cooling time is 5 seconds;
and carrying out two-stage infrared radiation heating on the preliminarily formed multilayer co-extruded polyethylene heat shrinkable film, controlling the temperature of the first-stage infrared radiation heating to be 200 ℃, controlling the temperature of the second-stage infrared radiation heating to be 165 ℃, simultaneously inflating and blowing the film, controlling the blow-up ratio of a die to be 2.8 to form a second bubble film, and carrying out cold air circulation cooling to obtain the multilayer co-extruded polyethylene heat shrinkable film.
Example 5
Weighing the components according to the following formula for later use: 95 parts of high-pressure low-density polyethylene, 4 parts of high-density polyethylene, 10 parts of modified nano-montmorillonite, 1 part of epoxidized soybean oil and 1 part of ethylene bis-stearamide;
the multilayer coextruded polyethylene heat shrinkable film (three-layer coextruded film) of the embodiment is prepared by the following steps:
the weighed raw materials are put into a high-speed kneader to be kneaded at a high speed, are mixed uniformly and then are respectively added into a plurality of film layer extruders, and are plasticized and then enter a co-extrusion die head to be extruded to obtain a first film bubble;
the first film bubble is drawn by a drawing device and is subjected to water cooling forming to obtain a preliminarily formed multilayer co-extruded polyethylene heat shrinkage film; wherein the water cooling temperature is 18 ℃, and the cooling time is 10 seconds;
and carrying out two-stage infrared radiation heating on the preliminarily formed multilayer co-extruded polyethylene heat shrinkable film, controlling the temperature of the first-stage infrared radiation heating to be 195 ℃ and the temperature of the second-stage infrared radiation heating to be 165 ℃, simultaneously inflating and blowing the film, controlling the blow-up ratio of a die to be 3 to form a second bubble film, and carrying out cold air circulation cooling to obtain the multilayer co-extruded polyethylene heat shrinkable film.
The following performance tests were performed on the multilayer coextruded polyethylene heat shrinkable films of examples 1 to 5 of the present invention and the conventional polyethylene heat shrinkable films, to further describe the technical effects of the present invention in detail.
Test I,
1. Thickness: the multilayer coextruded polyethylene heat shrinkable films prepared in examples 1 to 5 were measured to have a thickness of 12 to 15 μm by weighing 100 square meters in area and weighing mass, calculating the thickness according to density, measuring three times, and averaging.
2. The tensile properties were tested according to GB/T13022-.
3. The shrinkage was measured according to GB/T13519-.
Note: the single-layer polyethylene heat shrinkable film was made of the same material as in example 5, except that the single-layer polyethylene heat shrinkable film had one film layer and three film layers in example 5.
As can be seen from table 1 above, the multilayer coextruded polyethylene heat shrinkable film prepared by the double-bubble coextrusion process in embodiments 1 to 5 of the present invention has excellent physical properties, and is significantly superior to the physical properties of the existing heat shrinkable film and the existing single-layer coextruded polyethylene heat shrinkable film.
Test II,
By adopting a single-factor test, only the addition ratio of the modified nano-montmorillonite in the formula of the raw materials is changed, the addition amount of the rest raw materials and the preparation process conditions are the same as those in the example 5, the multilayer co-extruded polyethylene heat-shrinkable film is prepared, various physical properties of each group of prepared multilayer co-extruded polyethylene heat-shrinkable films are tested, and the test results are detailed in table 2.
From the above table 2, it can be seen that the physical properties, especially the tensile properties, of the multilayer coextruded polyethylene heat shrinkable film can be significantly improved by adding the modified nano montmorillonite into the system, but the influence on the heat shrinkage rate is not great. The results in table 2 show that the addition amount of the modified nano-montmorillonite is preferably 6-15 parts by weight, the physical properties of the multilayer coextruded polyethylene heat shrinkable film prepared by the method are excellent, and the addition amount is preferably 10 parts by weight.
Test III,
By adopting a single-factor test, only changing the mixing ratios of the hexadecyl trimethyl ammonium bromide modified nano gliadine and the magnesium salt modified nano gliadine to be 1:1, 2:1, 2.5:1, 3:1, 3.5:1 and 1:3 respectively, and the other raw materials and preparation process conditions are the same as those of the example 5, preparing a multilayer coextruded polyethylene heat-shrinkable film, and testing the physical properties of each group of prepared multilayer coextruded polyethylene heat-shrinkable films, the results show that when the mixing ratio of the hexadecyl trimethyl ammonium bromide modified nano gliadine and the magnesium salt modified nano gliadine is 1:1 or 1:3 or 2:1, the prepared multilayer coextruded polyethylene heat-shrinkable film has obviously reduced tensile strength and tear strength compared with the multilayer coextruded polyethylene heat-shrinkable film prepared by adopting other groups of mixing ratios, and the thermal shrinkage ratio is obviously reduced, The change in transparency was not significant. The ratio of the hexadecyl trimethyl ammonium bromide modified nanometer montmorillonite to the magnesium salt modified nanometer montmorillonite is 3:1, and the prepared multilayer co-extruded polyethylene heat shrinkage film has the best tensile strength, tearing strength and heat shrinkage;
through a large number of experimental researches, the modified nano-montmorillonite in the raw material is a mixture of hexadecyl trimethyl ammonium bromide modified nano-montmorillonite and magnesium salt modified nano-montmorillonite, and the physical performance of the prepared multilayer co-extruded polyethylene heat-shrinkable film is superior to that of the multilayer co-extruded polyethylene heat-shrinkable film prepared by singly adopting hexadecyl trimethyl ammonium bromide modified nano-montmorillonite or magnesium salt modified nano-montmorillonite;
in addition, on the basis of example 5, the modified nano-montmorillonite is equivalently replaced by unmodified montmorillonite, which is consistent with raw materials and a preparation process, and the physical properties of the prepared multilayer coextruded polyethylene heat shrinkable film are tested, wherein the test results comprise that the tensile strength (TD/MD) is 25/31 MPa, the elongation at break (TD/MD) is 255%/489%, the tear strength (TD/MD) is 53/57 kN/m, and the heat shrinkage (TD/MD) is 14%/65%. Therefore, compared with the multilayer co-extruded polyethylene heat shrinkage film prepared by adding the unmodified nano montmorillonite, the multilayer co-extruded polyethylene heat shrinkage film prepared by adding the modified montmorillonite has the advantages that the tensile strength, the elongation at break and the tearing strength are obviously improved, and the influence on the heat shrinkage rate is not obvious. Namely, the addition of the modified montmorillonite is beneficial to improving the tensile strength, the elongation at break and the tearing strength of the multilayer co-extruded polyethylene heat shrinkable film.
Test four,
By adopting a single-factor test, the water-cooling forming cooling time of the first foam film is changed to be 1, 5, 8, 10 and 15 seconds respectively, the rest raw materials and the process conditions are the same as those of the example 5, each group of multilayer co-extruded polyethylene heat shrinkage films corresponding to the water-cooling forming cooling time are prepared, and each physical property of each group of prepared multilayer co-extruded polyethylene heat shrinkage films is tested, and the results are detailed in the following table 3.
TABLE 3
As can be seen from table 3, when the cooling time of the first foam film is 1 second, the first foam film is difficult to form due to too short cooling time, and normal operation of subsequent processes is directly affected, so that the multilayer co-extruded polyethylene heat shrinkable film cannot be prepared. When the cooling time of the first foam film is 5-10 seconds, the first foam film can be normally formed, and the heat shrinkage rates of the prepared multilayer coextruded polyethylene heat shrinkable film are obviously better than those of the multilayer coextruded polyethylene heat shrinkable film prepared by the cooling time of 15 seconds, and the influence on the stretching performance is not obvious.
In addition, the multilayer coextruded polyethylene heat shrinkable film prepared by heating the preliminarily formed multilayer coextruded polyethylene heat shrinkable film by two-stage infrared radiation is obviously improved in heat shrinkage rate and is not remarkably changed in stretching performance compared with the multilayer coextruded polyethylene heat shrinkable film prepared by heating by single-stage infrared radiation (for example, the temperature is controlled to be 180-200 ℃).
In summary, in the multilayer coextruded polyethylene heat shrinkable film provided by the embodiment of the invention, each film layer is made of the same material layer formed by mixing the same raw materials, so that the film layers can be recycled without mechanically peeling the film layers after use, the recycling rate is high, and the recycling cost is low. The multi-layer polyethylene heat-shrinkable co-extruded film prepared by compounding the nontoxic and widely available raw materials of high-pressure low-density polyethylene, high-density polyethylene, modified nano-montmorillonite, epoxidized soybean oil and ethylene bis-stearamide not only has good physical and mechanical properties such as heat shrinkage, tensile property and tearing strength, but also has good transparency, is suitable for packaging and transporting articles such as but not limited to food, electronic products and the like, and has good development prospect.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A multilayer co-extruded polyethylene heat shrinkable film is characterized by comprising at least three film layers;
wherein each film layer is prepared from the following raw materials in parts by weight:
60-95 parts of high-pressure low-density polyethylene, 4-7 parts of high-density polyethylene, 6-15 parts of modified nano montmorillonite, 0-3 parts of epoxidized soybean oil and 0-2 parts of ethylene bis stearamide.
2. The multilayer coextruded polyethylene heat shrink film of claim 1 wherein the modified nanomicelle is a mixture of cetyl trimethyl ammonium bromide modified nanomicelle and magnesium salt modified nanomicelle.
3. The multilayer coextruded polyethylene heat shrink film of claim 2, wherein the weight ratio of the cetyl trimethyl ammonium bromide modified nanosieve stone and the magnesium salt modified nanosieve stone is 2.5-3: 1.
4. The multilayer coextruded polyethylene heat shrink film of claim 1 wherein the high pressure low density polyethylene has a melt index of 0.2 to 0.3 g/(10 min).
5. The multilayer coextruded polyethylene heat shrink film of claim 1, wherein each layer is made from the following raw materials in parts by weight:
95 parts of high-pressure low-density polyethylene, 4 parts of high-density polyethylene, 10 parts of modified nano-montmorillonite, 1 part of epoxidized soybean oil and 1 part of ethylene bis-stearamide.
6. The multilayer coextruded polyethylene heat shrink film of claim 1 wherein the multilayer coextruded polyethylene heat shrink film is a three or five layer coextruded polyethylene heat shrink film.
7. The method for preparing a multilayer coextruded polyethylene heat shrink film according to any of claims 1 to 6, comprising the steps of:
weighing various raw materials according to the raw material formula of the film layer as defined in any one of claims 1 to 6, mixing, adding into a plurality of film layer extruders respectively, plasticizing, and extruding through a co-extrusion die head to obtain a first film bubble;
the first film bubble is drawn by a drawing device and is subjected to water cooling forming to obtain a preliminarily formed multilayer co-extruded polyethylene heat shrinkage film; wherein the water cooling temperature is 18-20 ℃, and the cooling time is 5-10 seconds;
and carrying out infrared radiation heating on the preliminarily formed multilayer co-extruded polyethylene heat shrinkable film, simultaneously inflating to blow the film to form a second bubble film, and carrying out cold air circulation cooling to obtain the multilayer co-extruded polyethylene heat shrinkable film.
8. The method for preparing the multilayer co-extruded polyethylene heat shrinkable film as claimed in claim 7, wherein in the step of heating the preliminarily formed multilayer co-extruded polyethylene heat shrinkable film by infrared radiation and simultaneously inflating the film to blow the film to form the second bubble film, the blow-up ratio of the mold is controlled to be 2-3.
9. The method for preparing the multilayer co-extruded polyethylene heat shrinkable film according to claim 7, wherein the step of heating the preliminarily formed multilayer co-extruded polyethylene heat shrinkable film by infrared radiation comprises the following steps:
and carrying out two-stage infrared radiation heating on the preliminarily formed multilayer co-extruded polyethylene heat shrinkable film, wherein the temperature of the first-stage infrared radiation heating is controlled to be 180-200 ℃, and the temperature of the second-stage infrared radiation heating is controlled to be 150-165 ℃.
10. The method for preparing the multilayer coextruded polyethylene heat shrinkable film of claim 9, wherein the preliminary formed multilayer coextruded polyethylene heat shrinkable film is subjected to two-stage infrared radiation heating, the temperature of the first stage infrared radiation heating is controlled to be 180-200 ℃, and the temperature of the second stage infrared radiation heating is controlled to be 150-165 ℃, specifically:
and carrying out two-stage infrared radiation heating on the preliminarily formed multilayer co-extruded polyethylene heat shrinkable film, wherein the temperature of the first-stage infrared radiation heating is controlled at 200 ℃, and the temperature of the second-stage infrared radiation heating is controlled at 165 ℃.
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