CN112157969A - Polyethylene heat shrinkable film and preparation method thereof - Google Patents
Polyethylene heat shrinkable film and preparation method thereof Download PDFInfo
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- B32B27/00—Layered products comprising a layer of synthetic resin
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Abstract
The invention is suitable for the technical field of materials, and provides a polyethylene heat shrinkable film, which comprises an outer film layer, a middle film layer and an inner film layer; the outer film layer and the inner film layer are respectively prepared from the following raw materials in parts by weight: 60-70 parts of high-pressure low-density polyethylene, 35-45 parts of high-density polyethylene, 85-95 parts of polypropylene resin, 4-6 parts of modified montmorillonite, 3-5 parts of flame-retardant synergist, 2-4 parts of compatilizer and 0.2-0.4 part of antioxidant; the intermediate film layer is prepared from the following raw materials in parts by weight: 35-45 parts of high-pressure low-density polyethylene, 40-50 parts of high-density polyethylene, 85-95 parts of polypropylene resin, 8-13 parts of modified nano-montmorillonite, 2-4 parts of compatilizer and 0.2-0.4 part of antioxidant; because each film layer is made of nontoxic raw materials with wide sources, the polyethylene heat shrinkable film has better flame retardant effect, good physical and mechanical properties such as heat shrinkage, tensile property, tearing strength and the like, is suitable for packaging and transporting articles such as but not limited to foods, electronic products and the like, and has good development prospect.
Description
Technical Field
The invention relates to the technical field of packaging films, in particular to a polyethylene heat shrinkable film and a preparation method thereof.
Background
With the improvement of living standard of people, people pay more attention to their living quality, which is to be satisfied by various products, but in order to ensure that various articles on the market can be delivered to users safely and completely, various packages are needed to protect the safety of the articles, the plastic packaging films are diversified, wherein the growth speed of the market demand of the heat shrinkable film is astonishing and becomes a hot spot in the plastic packaging industry, the shrinkage mechanism of the heat shrinkable film is based on the heat movement of a high polymer molecular chain, and the heat shrinkable film is mainly used for the sale and transportation of various products to achieve the purposes of stabilizing, covering and protecting the products, so the heat shrinkable film is required to have higher puncture resistance, good shrinkability and shrinkage stress.
At present, the flame retardant is added into the raw material of the heat shrinkable film to improve the flame retardant performance, but the common halogen-containing flame retardant can generate harmful chemical substances when the product is at high temperature or is burnt, so that the environment is polluted, and the health of human bodies and animals is also harmed. In addition, in order to improve the flame retardant effect, the addition amount of the flame retardant is usually not small, and other properties of the heat shrinkable film may be affected, so how to obtain a heat shrinkable film with good flame retardant performance and good comprehensive properties while using a small amount of flame retardant in the field is a technical problem to be solved in the field.
Disclosure of Invention
The embodiment of the invention provides a polyethylene heat shrinkable film, aiming at solving the problems that the flame retardant property of the heat shrinkable film is improved by adding a flame retardant into the raw material of the heat shrinkable film, but the common halogen-containing flame retardant can generate harmful chemical substances when the product is at high temperature or is burnt, pollutes the environment and has harm to the health of human bodies and animals, and the addition of the flame retardant is not small usually so as to improve the flame retardant effect and possibly influence the change of other properties of the heat shrinkable film.
The embodiment of the invention is realized in such a way that the polyethylene heat shrinkable film comprises an outer film layer, an intermediate film layer and an inner film layer; the thickness of the heat shrinkable film is 60-80 mu m, and the heat shrinkable film is composed of three layers of co-extruded and bonded films, namely an outer film layer, a middle layer and an inner film layer;
the outer film layer and the inner film layer are respectively prepared from the following raw materials in parts by weight:
60-70 parts of high-pressure low-density polyethylene, 35-45 parts of high-density polyethylene, 85-95 parts of polypropylene resin, 4-6 parts of modified montmorillonite, 3-5 parts of flame-retardant synergist, 2-4 parts of compatilizer and 0.2-0.4 part of antioxidant;
the intermediate film layer is prepared from the following raw materials in parts by weight:
35-45 parts of high-pressure low-density polyethylene, 40-50 parts of high-density polyethylene, 85-95 parts of polypropylene resin, 8-13 parts of modified nano-montmorillonite, 2-4 parts of compatilizer and 0.2-0.4 part of antioxidant;
a method for manufacturing a polyethylene heavy-duty heat shrinkable film comprises the following steps: and mixing and stirring the raw materials of each layer uniformly, and then extruding the mixture through three-layer co-extrusion equipment.
The montmorillonite composite flame-retardant material and the preparation method thereof provided by the invention have the following beneficial effects:
(1) the montmorillonite is mainly composed of montmorillonite which is a layered silicate crystal consisting of two layers of Si-O tetrahedrons and one layer of Al-O octahedron and has a large width-thickness ratio, but the montmorillonite and polypropylene are difficult to mix, the function of the montmorillonite is difficult to play, and the interlayer of the montmorillonite can be changed from hydrophilic oleophobic to oleophilic hydrophobic through modifying the montmorillonite, so that the compatibility with organic matters is enhanced, therefore, the montmorillonite can be well dispersed in the polymer to play a role, has good flame retardant effect and anti-dripping effect, and can enhance the smoke suppression effect.
(2) The composite material prepared by the invention is added with the inorganic flame-retardant synergist, can further play a synergistic effect with the modified montmorillonite and the phosphorus-containing flame retardant, has better flame-retardant effect, and can further improve the mechanical property of the composite material.
(3) The composite material is composed of specific components, all the components play a role in a synergistic mode, no toxic or harmful gas is generated after combustion, no harm is caused to human bodies, no environment pollution is caused, the preparation process is simple and convenient, the cost is low, and the composite material is suitable for industrial production.
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 an outer film layer and an inner film layer of the polyethylene heat shrinkable film compounded by adopting nontoxic and widely available raw materials of high-pressure low-density polyethylene, high-density polyethylene, polypropylene resin, modified montmorillonite, a flame-retardant synergist, a compatilizer and an antioxidant, and simultaneously, the high-pressure low-density polyethylene, the high-density polyethylene, the polypropylene resin, the modified nano-montmorillonite, the compatilizer and the antioxidant are compounded to form a middle film layer of the polyethylene heat shrinkable film.
In the embodiment of the invention, the outer film layer and the inner film layer are both prepared from the following raw materials in parts by weight:
60-70 parts of high-pressure low-density polyethylene, 35-45 parts of high-density polyethylene, 85-95 parts of polypropylene resin, 4-6 parts of modified montmorillonite, 3-5 parts of flame-retardant synergist, 2-4 parts of compatilizer and 0.2-0.4 part of antioxidant;
the intermediate film layer is prepared from the following raw materials in parts by weight:
35-45 parts of high-pressure low-density polyethylene, 40-50 parts of high-density polyethylene, 85-95 parts of polypropylene resin, 8-13 parts of modified nano-montmorillonite, 2-4 parts of compatilizer and 0.2-0.4 part of antioxidant;
in the embodiment of the invention, the high-pressure low-density polyethylene has a melt index of 0.3-0.5 g/10min and a density of 0.92-0.94 g/cm 3; the high-density polyethylene has a melt index of 0.2-0.6 g/10min and a density of 0.96-0.98 g/cm 3.
In the embodiment of the invention:
1) adding montmorillonite into water at 82-88 ℃, ultrasonically dispersing for 0.6-1.2 h to prepare montmorillonite dispersion liquid with the concentration of 6-12 wt%, then adding an intercalating agent and a protonating agent, controlling the temperature to be 82-88 ℃, continuing to ultrasonically disperse for 0.6-1.2 h, then filtering to obtain first precipitate, placing the first precipitate in a beaker, adding water at 82-88 ℃, stirring for 0.6-1.2 h, filtering to obtain second precipitate, placing the second precipitate in the beaker, adding water at 82-88 ℃, stirring for 0.6-1.2 h, filtering to obtain third precipitate, placing the third precipitate in the beaker, adding water at 82-88 ℃, stirring for 0.6-1.2 h, filtering, and finally drying to prepare the modified montmorillonite.
Preferably, the intercalating agent is one or more of cetyl ammonium bromide, cetyl trimethyl ammonium bromide, stearyl ammonium bromide, dimethyl phenethyldodecyl ammonium chloride and methacryloyloxyethyl-benzyl-dimethyl ammonium chloride.
Preferably, the protonating agent is one or a mixture of sulfuric acid, hydrochloric acid, phosphoric acid, isophthalic acid and phthalic acid.
Preferably, the weight ratio of the montmorillonite to the intercalating agent to the protonating agent is 15-25: 0.4-0.6.
Preferably, the weight ratio of montmorillonite, intercalating agent and protonating agent is 30:25: 1.
Preferably, the flame retardant synergist is zinc borate or zinc oxide.
Preferably, the compatibilizer is maleic anhydride grafted polypropylene.
Preferably, the antioxidant is one or a mixture of several of antioxidant 1010, antioxidant 1076, antioxidant 1024 and antioxidant 300.
2) The modified montmorillonite and tetrahydrofuran are mixed according to the weight ratio of 6-9: 1-4, ultrasonically dispersing for 1.2-1.8 h at 105-115 ℃, and drying for 1.2-1.8 h at 45-65 ℃.
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 2-3: 1.5.
The montmorillonite has unique layered one-dimensional nano structure characteristics, morphological characteristics, designable reactivity among layers, ultra-large specific surface area (750m2/g) and diameter/thickness ratio of more than 200. 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.
In a preferred embodiment of the invention, the outer membrane layer and the inner membrane layer are both prepared from the following raw materials in parts by weight:
60-65 parts of high-pressure low-density polyethylene, 35-40 parts of high-density polyethylene, 85-90 parts of polypropylene resin, 4-5 parts of modified montmorillonite, 3-4 parts of flame-retardant synergist, 2-3 parts of compatilizer and 0.2-0.3 part of antioxidant;
the intermediate film layer is prepared from the following raw materials in parts by weight:
36-40 parts of high-pressure low-density polyethylene, 42-56 parts of high-density polyethylene, 87-90 parts of polypropylene resin, 9-11 parts of modified nano-montmorillonite, 2-3 parts of a compatilizer and 0.2-0.3 part of an antioxidant;
in another preferred embodiment of the present invention, the outer membrane layer and the inner membrane layer are made of the following raw materials by weight:
66 parts of high-pressure low-density polyethylene, 40 parts of high-density polyethylene, 90 parts of polypropylene resin, 4 parts of modified montmorillonite, 3 parts of flame-retardant synergist, 2 parts of compatilizer and 0.2 part of antioxidant;
the intermediate film layer is prepared from the following raw materials in parts by weight:
40 parts of high-pressure low-density polyethylene, 44 parts of high-density polyethylene, 90 parts of polypropylene resin, 11 parts of modified nano-montmorillonite, 3 parts of compatilizer and 0.3 part of antioxidant;
adding montmorillonite into 88 ℃ water, performing ultrasonic dispersion for 1.2h to prepare montmorillonite dispersion liquid with the concentration of 8 wt%, then adding an intercalating agent and a protonating agent, controlling the temperature to be 88 ℃, continuing the ultrasonic dispersion for 1.2h, then filtering to obtain a first precipitate, placing the first precipitate in a beaker, adding 88 ℃ water, stirring for 0.5h, filtering to obtain a second precipitate, placing the second precipitate in the beaker, adding 88 ℃ water, stirring for 0.5h, filtering to obtain a third precipitate, placing the third precipitate in the beaker, adding 88 ℃ water, stirring for 0.5h, filtering, and finally drying to prepare modified montmorillonite, wherein the intercalating agent is hexadecyl ammonium bromide; the protonating agent is sulfuric acid; the weight ratio of the montmorillonite to the intercalating agent to the protonating agent is 25:20: 0.55.
The modified montmorillonite and tetrahydrofuran are mixed according to the weight ratio of 8: 1, mixing, performing ultrasonic dispersion for 1.8h at the temperature of 115 ℃, and drying for 1.8h at the temperature of 65 ℃.
The raw materials are produced according to the conventional process of three-layer co-extrusion equipment, and the polyethylene repackaging heat shrinkable film is obtained.
Example 1
Weighing the raw materials according to the following raw material formulas of the outer membrane layer, the intermediate membrane layer and the inner membrane layer, wherein the outer membrane layer and the inner membrane layer are respectively prepared from the following raw materials in parts by weight:
60 parts of high-pressure low-density polyethylene, 35 parts of high-density polyethylene, 85 parts of polypropylene resin, 4 parts of modified montmorillonite, 3 parts of flame-retardant synergist, 2 parts of compatilizer and 0.2 part of antioxidant;
the intermediate film layer is prepared from the following raw materials in parts by weight:
35 parts of high-pressure low-density polyethylene, 40 parts of high-density polyethylene, 85 parts of polypropylene resin, 8 parts of modified nano-montmorillonite, 2 parts of compatilizer and 0.2 part of antioxidant;
adding montmorillonite into 82 ℃ water, performing ultrasonic dispersion for 0.6h to prepare montmorillonite dispersion liquid with the concentration of 6 wt%, then adding an intercalating agent and a protonating agent, controlling the temperature to be 82 ℃, continuing to perform ultrasonic dispersion for 0.6h, then filtering to obtain a first precipitate, placing the first precipitate in a beaker, adding 82 ℃ water, stirring for 0.6h, filtering to obtain a second precipitate, placing the second precipitate in the beaker, adding 82 ℃ water, stirring for 0.6h, filtering to obtain a third precipitate, placing the third precipitate in the beaker, adding 82 ℃ water, stirring for 0.6h, filtering, and finally drying to prepare modified montmorillonite, wherein the intercalating agent is hexadecyl ammonium bromide; the protonating agent is sulfuric acid; the weight ratio of the montmorillonite to the intercalating agent to the protonating agent is 10:10: 0.4.
The modified montmorillonite and tetrahydrofuran are mixed according to the weight ratio of 6: 1, mixing, performing ultrasonic dispersion at 105 ℃ for 1.8h, and drying at 45 ℃ for 1.8 h.
The raw materials are produced according to the conventional process of three-layer co-extrusion equipment, and the polyethylene repackaging heat shrinkable film is obtained.
Example 2
Weighing the raw materials according to the following raw material formulas of the outer membrane layer, the intermediate membrane layer and the inner membrane layer, wherein the outer membrane layer and the inner membrane layer are respectively prepared from the following raw materials in parts by weight:
65 parts of high-pressure low-density polyethylene, 40 parts of high-density polyethylene, 90 parts of polypropylene resin, 5 parts of modified montmorillonite, 4 parts of flame-retardant synergist, 3 parts of compatilizer and 0.3 part of antioxidant;
the intermediate film layer is prepared from the following raw materials in parts by weight:
40 parts of high-pressure low-density polyethylene, 45 parts of high-density polyethylene, 90 parts of polypropylene resin, 10 parts of modified nano-montmorillonite, 3 parts of compatilizer and 0.3 part of antioxidant;
adding montmorillonite into 88 ℃ water, performing ultrasonic dispersion for 1.2h to prepare a montmorillonite dispersion liquid with the concentration of 12 wt%, then adding an intercalating agent and a protonating agent, controlling the temperature to be 88 ℃, continuing the ultrasonic dispersion for 1.2h, then filtering to obtain a first precipitate, placing the first precipitate in a beaker, adding 88 ℃ water, stirring for 0.6h, filtering to obtain a second precipitate, placing the second precipitate in the beaker, adding 88 ℃ water, stirring for 0.6h, filtering to obtain a third precipitate, placing the third precipitate in the beaker, adding 88 ℃ water, stirring for 0.6h, filtering, and finally drying to prepare modified montmorillonite, wherein the intercalating agent is hexadecyl ammonium bromide; the protonating agent is sulfuric acid; the weight ratio of the montmorillonite to the intercalating agent to the protonating agent is 15:15: 0.6.
The modified montmorillonite and tetrahydrofuran are mixed according to the weight ratio of 9: 4, mixing, performing ultrasonic dispersion at 115 ℃ for 1.2h, and drying at 65 ℃ for 1.2 h.
The raw materials are produced according to the conventional process of three-layer co-extrusion equipment, and the polyethylene repackaging heat shrinkable film is obtained.
Example 3
Weighing the raw materials according to the following raw material formulas of the outer membrane layer, the intermediate membrane layer and the inner membrane layer, wherein the outer membrane layer and the inner membrane layer are respectively prepared from the following raw materials in parts by weight:
70 parts of high-pressure low-density polyethylene, 45 parts of high-density polyethylene, 95 parts of polypropylene resin, 6 parts of modified montmorillonite, 5 parts of flame-retardant synergist, 4 parts of compatilizer and 0.4 part of antioxidant;
the intermediate film layer is prepared from the following raw materials in parts by weight:
45 parts of high-pressure low-density polyethylene, 50 parts of high-density polyethylene, 95 parts of polypropylene resin, 13 parts of modified nano-montmorillonite, 4 parts of compatilizer and 0.4 part of antioxidant;
adding montmorillonite into 88 ℃ water, performing ultrasonic dispersion for 1.2h to prepare montmorillonite dispersion liquid with the concentration of 8 wt%, then adding an intercalating agent and a protonating agent, controlling the temperature to be 88 ℃, continuing the ultrasonic dispersion for 1.2h, then filtering to obtain a first precipitate, placing the first precipitate in a beaker, adding 88 ℃ water, stirring for 0.6h, filtering to obtain a second precipitate, placing the second precipitate in the beaker, adding 88 ℃ water, stirring for 0.6h, filtering to obtain a third precipitate, placing the third precipitate in the beaker, adding 88 ℃ water, stirring for 0.6h, filtering, and finally drying to prepare modified montmorillonite, wherein the intercalating agent is hexadecyl ammonium bromide; the protonating agent is sulfuric acid; the weight ratio of the montmorillonite to the intercalating agent to the protonating agent is 20:20: 0.45.
The modified montmorillonite and tetrahydrofuran are mixed according to the weight ratio of 8: 2, mixing, performing ultrasonic dispersion for 1.8h at the temperature of 115 ℃, and drying for 1.8h at the temperature of 65 ℃.
The raw materials are produced according to the conventional process of three-layer co-extrusion equipment, and the polyethylene repackaging heat shrinkable film is obtained.
Example 4
Weighing the raw materials according to the following raw material formulas of the outer membrane layer, the intermediate membrane layer and the inner membrane layer, wherein the outer membrane layer and the inner membrane layer are respectively prepared from the following raw materials in parts by weight:
68 parts of high-pressure low-density polyethylene, 42 parts of high-density polyethylene, 92 parts of polypropylene resin, 5 parts of modified montmorillonite, 4 parts of flame-retardant synergist, 3 parts of compatilizer and 0.3 part of antioxidant;
the intermediate film layer is prepared from the following raw materials in parts by weight:
42 parts of high-pressure low-density polyethylene, 46 parts of high-density polyethylene, 92 parts of polypropylene resin, 13 parts of modified nano-montmorillonite, 4 parts of compatilizer and 0.4 part of antioxidant;
adding montmorillonite into 88 ℃ water, performing ultrasonic dispersion for 1.2h to prepare 9 wt% montmorillonite dispersion liquid, then adding an intercalating agent and a protonating agent, controlling the temperature to be 88 ℃, continuing to perform ultrasonic dispersion for 1.2h, then filtering to obtain a first precipitate, placing the first precipitate in a beaker, adding 88 ℃ water, stirring for 0.6h, filtering to obtain a second precipitate, placing the second precipitate in the beaker, adding 88 ℃ water, stirring for 0.6h, filtering to obtain a third precipitate, placing the third precipitate in the beaker, adding 88 ℃ water, stirring for 0.6h, filtering, and finally drying to prepare modified montmorillonite, wherein the intercalating agent is hexadecyl ammonium bromide; the protonating agent is sulfuric acid; the weight ratio of the montmorillonite to the intercalating agent to the protonating agent is 25:25: 0.5.
The modified montmorillonite and tetrahydrofuran are mixed according to the weight ratio of 8: 3, mixing, performing ultrasonic dispersion for 1.8 hours at the temperature of 115 ℃, and drying for 1.8 hours at the temperature of 65 ℃.
Example 5
Weighing the raw materials according to the following raw material formulas of the outer membrane layer, the intermediate membrane layer and the inner membrane layer, wherein the outer membrane layer and the inner membrane layer are respectively prepared from the following raw materials in parts by weight:
66 parts of high-pressure low-density polyethylene, 40 parts of high-density polyethylene, 90 parts of polypropylene resin, 4 parts of modified montmorillonite, 3 parts of flame-retardant synergist, 2 parts of compatilizer and 0.2 part of antioxidant;
the intermediate film layer is prepared from the following raw materials in parts by weight:
40 parts of high-pressure low-density polyethylene, 44 parts of high-density polyethylene, 90 parts of polypropylene resin, 11 parts of modified nano-montmorillonite, 3 parts of compatilizer and 0.3 part of antioxidant;
adding montmorillonite into 88 ℃ water, performing ultrasonic dispersion for 1.2h to prepare montmorillonite dispersion liquid with the concentration of 8 wt%, then adding an intercalating agent and a protonating agent, controlling the temperature to be 88 ℃, continuing the ultrasonic dispersion for 1.2h, then filtering to obtain a first precipitate, placing the first precipitate in a beaker, adding 88 ℃ water, stirring for 0.5h, filtering to obtain a second precipitate, placing the second precipitate in the beaker, adding 88 ℃ water, stirring for 0.5h, filtering to obtain a third precipitate, placing the third precipitate in the beaker, adding 88 ℃ water, stirring for 0.5h, filtering, and finally drying to prepare modified montmorillonite, wherein the intercalating agent is hexadecyl ammonium bromide; the protonating agent is sulfuric acid; the weight ratio of the montmorillonite to the intercalating agent to the protonating agent is 25:20: 0.55.
The modified montmorillonite and tetrahydrofuran are mixed according to the weight ratio of 8: 1, mixing, performing ultrasonic dispersion for 1.8h at the temperature of 115 ℃, and drying for 1.8h at the temperature of 65 ℃.
The raw materials are produced according to the conventional process of three-layer co-extrusion equipment, and the polyethylene repackaging heat shrinkable film is obtained.
The polyethylene heat shrinkable films prepared in the embodiments 1 to 5 of the present invention and the existing polyethylene heat shrinkable films were subjected to performance test analysis, wherein a weighing method was used to measure an area of 100 square meters, weigh the area to obtain a mass, calculate a thickness according to a density, test the thickness three times, and take an average value thereof, thereby measuring that the thickness of the polyethylene heat shrinkable films prepared in the embodiments 1 to 7 was 11 to 14 μm; tensile strength was measured according to GB/T1040-2006, shrinkage was measured according to GB/T13519-1992, oxygen index was measured according to GB/T8924, and vertical burn was measured according to ASTM, the results of which are given in Table 1 below.
TABLE 1
Comparative example 1
Comparative example 1 is different from example 5 in that the flame retardant synergist is not contained in the composition, and the rest is the same as example 5.
Comparative example 2
Comparative example 2 is the same as example 5 except that the modified nanogel stone was not included in the composition.
Comparative example 3
Comparative example 3 is different from example 5 in that the components do not contain modified nano-montmorillonite and a flame retardant synergist, and the rest is the same as example 5.
Comparative example 4
Comparative example 4 is the same as example 5 except that montmorillonite was not modified.
Comparative example 5
Comparative example 5 is different from example 5 in that the nano-sized greenstone was not modified and the same as example 5 was used.
The polyethylene heat shrinkable films prepared in the above comparative examples 1 to 5 were subjected to the above-mentioned correlation performance test analysis, and the test results are detailed in the following table 2.
TABLE 2
In conclusion, it can be seen from the above table that the mechanical properties and flame retardant properties of the polyethylene heat shrinkable films prepared in examples 1 to 5 are better than those of comparative examples 1 to 5, and especially, the polyethylene heat shrinkable films prepared in examples 1 to 5 are significantly better than those of comparative examples 1 to 5 in flame retardant property. The polyethylene heat shrinkable film prepared by the invention generates little smoke after combustion, does not generate a large amount of molten drops, has no toxicity, does not bring harm to people and is environment-friendly. As can be seen from the above table, the components of the invention have synergistic effect, and the flame retardant property is obviously improved, and the mechanical property is also improved. While the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
In summary, each film layer of the multilayer coextruded polyethylene heat shrinkable film provided by the embodiment of the invention adopts the nontoxic and widely available raw materials of high-pressure low-density polyethylene, high-density polyethylene, polypropylene resin, modified montmorillonite, flame-retardant synergist, compatilizer and antioxidant to compound the outer film layer and the inner film layer of the polyethylene heat shrinkable film, and adopts the high-pressure low-density polyethylene, high-density polyethylene, polypropylene resin, modified nano-montmorillonite, compatilizer and antioxidant to compound the middle film layer of the polyethylene heat shrinkable film.
Claims (10)
1. A polyethylene heat shrinkable film comprises an outer film layer, a middle film layer and an inner film layer; the thickness of the heat shrinkable film is 60-80 mu m, and the heat shrinkable film is composed of three layers of co-extruded and bonded films, namely an outer film layer, a middle layer and an inner film layer;
the outer film layer and the inner film layer are respectively prepared from the following raw materials in parts by weight:
60-70 parts of high-pressure low-density polyethylene, 35-45 parts of high-density polyethylene, 85-95 parts of polypropylene resin, 4-6 parts of modified montmorillonite, 3-5 parts of flame-retardant synergist, 2-4 parts of compatilizer and 0.2-0.4 part of antioxidant;
the intermediate film layer is prepared from the following raw materials in parts by weight:
35-45 parts of high-pressure low-density polyethylene, 40-50 parts of high-density polyethylene, 85-95 parts of polypropylene resin, 8-13 parts of modified nano-montmorillonite, 2-4 parts of a compatilizer and 0.2-0.4 part of an antioxidant.
2. The polyethylene heat shrinkable film of claim 1, wherein the preparation method of the modified montmorillonite comprises:
adding montmorillonite into 82-88 ℃ water, performing ultrasonic dispersion for 0.6-1.2 hours to prepare montmorillonite dispersion liquid with the concentration of 6-12 wt%, then adding an intercalating agent and a protonating agent, controlling the temperature to be 82-88 ℃, continuing to perform ultrasonic dispersion for 0.6-1.2 hours, then filtering to obtain first precipitate, placing the first precipitate in a beaker, adding 82-88 ℃ water, stirring for 0.6-1.2 hours, filtering to obtain second precipitate, placing the second precipitate in the beaker, adding 82-88 ℃ water, stirring for 0.6-1.2 hours, filtering to obtain third precipitate, placing the third precipitate in the beaker, adding 82-88 ℃ water, stirring for 0.6-1.2 hours, filtering, and finally drying to prepare the modified montmorillonite.
3. The polyethylene heat shrink film of claim 1 or 2, wherein the intercalator is one or more of cetyl ammonium bromide, cetyl trimethyl ammonium bromide, stearyl ammonium bromide, dimethyl phenethyldodecyl ammonium chloride and methacryloyloxyethyl-benzyl-dimethyl ammonium chloride.
4. The polyethylene heat shrink film as claimed in claim 1 or 2, wherein the protonating agent is one or more of sulfuric acid, hydrochloric acid, phosphoric acid, isophthalic acid and phthalic acid.
5. The polyethylene heat shrinkage film as claimed in claim 1 or 2, wherein the weight ratio of montmorillonite, intercalating agent and protonating agent is 15-25: 0.4-0.6.
6. The polyethylene heat shrinkable film of claim 1 or 2, wherein the flame retardant synergist is zinc borate or zinc oxide, the compatibilizer is maleic anhydride grafted polypropylene, and the antioxidant is one or a mixture of several of antioxidant 1010, antioxidant 1076, antioxidant 1024 and antioxidant 300.
7. The polyethylene heat shrink film as claimed in claim 1, wherein the modified nano-montmorillonite is a mixture of cetyl trimethyl ammonium bromide modified nano-montmorillonite and magnesium salt modified nano-montmorillonite.
8. The polyethylene heat shrink film as claimed in claim 1 or 7, wherein the mixing weight ratio of the cetyl trimethyl ammonium bromide modified nano montmorillonite to the magnesium salt modified nano montmorillonite is 2-3: 1.5.
9. The polyethylene heat shrinkable film of claim 1,
the outer film layer and the inner film layer are respectively prepared from the following raw materials in parts by weight:
66 parts of high-pressure low-density polyethylene, 40 parts of high-density polyethylene, 90 parts of polypropylene resin, 4 parts of modified montmorillonite, 3 parts of flame-retardant synergist, 2 parts of compatilizer and 0.2 part of antioxidant;
the intermediate film layer is prepared from the following raw materials in parts by weight:
40 parts of high-pressure low-density polyethylene, 44 parts of high-density polyethylene, 90 parts of polypropylene resin, 11 parts of modified nano-montmorillonite, 3 parts of compatilizer and 0.3 part of antioxidant.
10. The method for preparing a polyethylene heat shrinkable film according to any one of claims 1 to 7, further comprising the steps of:
1) the modified montmorillonite and tetrahydrofuran are mixed according to the weight ratio of 6-9: 1-4, ultrasonically dispersing for 1.2-1.8 h at 105-115 ℃, and drying for 1.2-1.8 h at 45-65 ℃;
2) the method comprises the following steps of treating the montmorillonite by cetyl trimethyl ammonium bromide to enable the montmorillonite to generate a 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;
3) and mixing and stirring the raw materials of each layer uniformly, and then extruding the mixture through three-layer co-extrusion equipment.
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| CN111267449A (en) * | 2020-04-14 | 2020-06-12 | 汕头市明佳热收缩膜有限公司 | PEF heat shrinkable film and preparation method thereof |
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| CN106700227A (en) * | 2015-11-12 | 2017-05-24 | 北京化工大学 | Polypropylene nanometer montmorillonite intumescent flame-retardant composite and preparation method thereof |
| CN107778663A (en) * | 2017-11-29 | 2018-03-09 | 西华大学 | A kind of montmorillonite Composite fire proofing and preparation method thereof |
| CN111231470A (en) * | 2020-04-03 | 2020-06-05 | 汕头市明佳热收缩膜有限公司 | Multilayer co-extruded polyethylene heat shrinkable film and preparation method thereof |
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