CN117183520A - Co-extrusion stretch film for packaging and preparation process thereof - Google Patents
Co-extrusion stretch film for packaging and preparation process thereof Download PDFInfo
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- 238000001125 extrusion Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920006302 stretch film Polymers 0.000 title abstract description 13
- 238000012858 packaging process Methods 0.000 title description 2
- 239000000463 material Substances 0.000 claims abstract description 83
- 229920000092 linear low density polyethylene Polymers 0.000 claims abstract description 69
- 239000004707 linear low-density polyethylene Substances 0.000 claims abstract description 69
- 229920001526 metallocene linear low density polyethylene Polymers 0.000 claims abstract description 54
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 29
- 238000004806 packaging method and process Methods 0.000 claims abstract description 27
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 claims abstract description 27
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims description 37
- 239000004698 Polyethylene Substances 0.000 claims description 36
- -1 polyethylene Polymers 0.000 claims description 36
- 229920000573 polyethylene Polymers 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 31
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 30
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- 230000008569 process Effects 0.000 claims description 26
- JVVRCYWZTJLJSG-UHFFFAOYSA-N 4-dimethylaminophenol Chemical compound CN(C)C1=CC=C(O)C=C1 JVVRCYWZTJLJSG-UHFFFAOYSA-N 0.000 claims description 20
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 13
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 12
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims description 11
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 10
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 10
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 9
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- 229910052740 iodine Inorganic materials 0.000 claims description 9
- 239000011630 iodine Substances 0.000 claims description 9
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 8
- QWMJEUJXWVZSAG-UHFFFAOYSA-N (4-ethenylphenyl)boronic acid Chemical compound OB(O)C1=CC=C(C=C)C=C1 QWMJEUJXWVZSAG-UHFFFAOYSA-N 0.000 claims description 7
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 claims description 4
- 229910021590 Copper(II) bromide Inorganic materials 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000004708 Very-low-density polyethylene Substances 0.000 abstract description 21
- 229920001866 very low density polyethylene Polymers 0.000 abstract description 21
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 239000011347 resin Substances 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 4
- 239000000428 dust Substances 0.000 abstract description 2
- 229920005610 lignin Polymers 0.000 abstract description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 23
- 238000001291 vacuum drying Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 238000009998 heat setting Methods 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 7
- 238000010025 steaming Methods 0.000 description 7
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- 239000000853 adhesive Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
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- 239000003208 petroleum Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
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- 238000000071 blow moulding Methods 0.000 description 4
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- 239000000203 mixture Substances 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000006872 improvement Effects 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical group CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XZRMXDPWEPRYMF-UHFFFAOYSA-N (4-ethenylphenoxy)boronic acid Chemical compound OB(O)OC1=CC=C(C=C)C=C1 XZRMXDPWEPRYMF-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 230000001788 irregular Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- MDCWDBMBZLORER-UHFFFAOYSA-N triphenyl borate Chemical compound C=1C=CC=CC=1OB(OC=1C=CC=CC=1)OC1=CC=CC=C1 MDCWDBMBZLORER-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Laminated Bodies (AREA)
Abstract
The invention relates to the technical field of stretch films, in particular to a coextrusion stretch film for packaging and a preparation process thereof, which sequentially comprise the following steps: the stretching film is obtained by co-extrusion of an inner layer material, a middle layer material and an outer layer material; the outer layer material comprises 15 to 25 parts of linear low density polyethylene, 35 to 45 parts of metallocene ultralow density polyethylene, 35 to 45 parts of metallocene linear low density polyethylene, 8 to 12 parts of sodium lignin sulfonate, 15 to 20 parts of modified LLDPE and 1 to 2 parts of PPA processing aid. The stretched film is obtained by co-extrusion of an inner layer material, a middle layer material and an outer layer material, wherein LLDPE, m-VLDPE and m-LLDPE are taken as basic resins in the outer layer material, and the prepared outer layer has good toughness and mechanical properties under the synergistic effect, and phenolic lignin and modified LLDPE are added for modification, so that the mechanical properties, dust resistance and wear resistance of the stretched film are further improved.
Description
Technical Field
The invention relates to the technical field of stretch films, in particular to a coextrusion stretch film for packaging and a preparation process thereof.
Background
The stretching film, also called a winding film, has higher stretching strength, tearing strength and good self-adhesion, can wrap various products with regular or irregular shapes to form a whole, can protect goods, prevent the goods from falling off and collapsing during transportation, reduces economic loss caused by improper packaging, and is widely used for packaging goods trays, such as wrapping and packaging in industries of building materials, chemical industry, electronics, metal fittings, wires and cables, food, papermaking and the like. Polyethylene, which is currently one of the most widely used materials in the field of plastic materials, occupies about 45% of the film application market, and is the most important packaging material. However, some existing stretch films have poor strength and are prone to frictional breakage during use and transportation. Therefore, we propose a co-extruded stretch film for packaging and a process for preparing the same.
Disclosure of Invention
The invention aims to provide a coextrusion stretched film for packaging and a preparation process thereof, which are used for solving the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: a coextruded stretched film for packaging comprising, in order from top to bottom: the stretch film is obtained by coextrusion of an inner layer material, a middle layer material and an outer layer material.
Further, the stretching film comprises 15-25% of inner layer material, 50-70% of middle layer material and 15-25% of outer layer material according to mass fraction.
Further, the inner layer material comprises the following components in parts by mass: 35 to 45 parts of Linear Low Density Polyethylene (LLDPE), 25 to 35 parts of ultra low density polyethylene (VLDPE), 25 to 35 parts of metallocene linear low density polyethylene (m-LLDPE), 2 to 4 parts of opening agent and 2 to 4 parts of PPA processing aid.
Further, the middle layer material comprises the following components in parts by mass: 40 to 50 parts of Linear Low Density Polyethylene (LLDPE), 50 to 60 parts of metallocene linear low density polyethylene (m-LLDPE), 10 to 20 parts of POSS modified polyethylene and 0.5 to 1.5 parts of PPA processing aid.
Further, the POSS modified polyethylene is prepared by the following process:
placing vinyl POSS, divinylbenzene and LLDPE in a double-screw extruder for melt extrusion, wherein the barrel temperature is as follows: the POSS modified polyethylene is obtained by melt blending for 5-6 min at 150 ℃, 160 ℃, 175 ℃, 170 ℃, 190-195 ℃ of the temperature of the machine head and 60-180 rpm of the rotating speed.
Further, the POSS modified polyethylene is prepared from the following components in parts by mass: 10-18 parts of vinyl POSS, 12-20 parts of divinylbenzene and 100 parts of LLDPE.
Further, the linear low-density polyethylene is subjected to irradiation pretreatment, and the specific process steps are as follows:
LLDPE is taken and placed in an electron accelerator for pre-irradiation, and the technological parameters are as follows: the power is 10000-120000W, the accelerating voltage is 27000-30000V, the beam length is 68-75 mm, the scanning width is 120cm, the transmission speed is 0.06-0.08 m/s, and the pre-irradiation dose is 12-15 kGy.
Further, the outer layer material comprises the following components in mass percent: 15 to 25 parts of Linear Low Density Polyethylene (LLDPE), 35 to 45 parts of metallocene ultra-low density polyethylene (m-VLDPE), 35 to 45 parts of metallocene linear low density polyethylene (m-LLDPE), 8 to 12 parts of sodium lignin sulfonate, 15 to 20 parts of modified LLDPE and 1 to 2 parts of PPA processing aid.
Further, the modified LLDPE is prepared by the following process:
taking methacryloyl chloride, 4-dimethylaminophenol and triethylamine, and reacting for 150-200 min at 58-65 ℃; adding 37% concentrated hydrochloric acid and absolute ethyl alcohol, mixing, reacting for 25-30 min at 23-27 ℃, heating to 43-47 ℃, regulating the pH of the system to 7.5-8.0, slowly adding epichlorohydrin, and reacting for 7-8 h at a constant temperature of 40-48 ℃; spin steaming, removing solvent, and vacuum drying to obtain quaternary ammonium compound;
heating linear low-density polyethylene and dimethylbenzene to 80-100 ℃ and stirring and mixing, adding initiator dicumyl peroxide under the protection of nitrogen atmosphere, mixing, then adding iodine simple substance and divinylbenzene, mixing uniformly, and reacting for 4-8 hours at constant temperature; after the reaction is finished, rapidly cooling in ice water, adding petroleum ether for precipitation, washing, filtering, and vacuum drying at 24-27 ℃ for 12 hours to obtain branched polyethylene;
mixing branched polyethylene, 4-vinylphenylboronic acid, a quaternary ammonium compound, methyl methacrylate, cuprous bromide and copper bromide, adding dimethylbenzene, and heating to 98-105 ℃ for reaction for 4-8 h under the protection of nitrogen atmosphere; adding n-hexane, standing, taking the precipitate, and vacuum drying to constant weight to obtain the modified LLDPE.
Further, the mol ratio of the methacryloyl chloride, the 4-dimethylaminophenol and the epichlorohydrin is 1:1 (1.0-1.1);
the ratio of the methacryloyl chloride to the triethylamine to the concentrated hydrochloric acid to the absolute ethyl alcohol is 10g (21-24 g) (3.0-3.5 g) to 100mL.
Further, the proportion of the linear low density polyethylene, the divinylbenzene, the initiator dicumyl peroxide, the iodine simple substance and the dimethylbenzene is (43-49) g (2.6-5.2) g (0.27-0.64) g (0.13-0.25) g and 100mL;
further, the proportions of the branched polyethylene, the 4-vinylphenylboronic acid, the quaternary ammonium compound, the methyl methacrylate, the cuprous bromide, the cupric bromide and the xylene are (46-57) g (1.5-3.0) g (0.14-0.28) g (0.10-0.20) g (0.14-0.28) g (0.01-0.02) g and 100mL.
Linear Low Density Polyethylene (LLDPE): HS7001 is derived from China petrochemical Yangzi petrochemical industry Co., ltd;
ultra low density polyethylene (VLDPE): 4501, available from the american dow chemical company;
metallocene linear low density polyethylene (m-LLDPE): SP1520, from mitsubishi chemical corporation;
metallocene ultra low density polyethylene (m-VLDPE): VL0003, derived from Korean large forest industries, inc.;
the opening agent is stearic acid amide; PPA processing aid: from Shanghai robust Polymer technologies Co., ltd;
vinyl POSS: from Shanghai Michelin chemical Co.
A process for preparing a co-extruded stretch film for packaging, comprising the following steps:
taking linear low density polyethylene, ultra-low density polyethylene, metallocene linear low density polyethylene, an opening agent and PPA processing aid as inner layer materials;
linear low density polyethylene, metallocene linear low density polyethylene, POSS modified polyethylene and PPA processing aid are used as middle layer materials;
linear low density polyethylene, metallocene ultra low density polyethylene, metallocene linear low density polyethylene, sodium lignin sulfonate, modified LLDPE and PPA processing aid are used as outer layer materials;
and (3) placing the film into a three-layer coextrusion blown film machine, coextrusion blown film and stretching to obtain a stretched film.
Further, the extrusion temperature is 150-170 ℃;
the stretching process conditions are as follows: longitudinal stretching is carried out at the temperature of 105-120 ℃, the stretching ratio is 2.0-3.0, transverse stretching is carried out at the temperature of 95-115 ℃, and the stretching ratio is 1.5-2.0;
and (3) carrying out heat setting after stretching, wherein the process conditions are as follows: the heat setting temperature is 85-105 ℃, and the heat setting time is 30-100 s.
Compared with the prior art, the invention has the following beneficial effects:
in the above technical solution, the stretched film comprises the following laminate structure: the inner layer, the middle layer and the outer layer are sequentially formed by co-extrusion of an inner layer material, a middle layer material and an outer layer material, the main resin raw material is Linear Low Density Polyethylene (LLDPE), the mechanical property is good, the strength is high, the toughness is good, the rigidity is strong, the heat resistance and the cold resistance are realized, and the blow molding is easy. The ultra-low density polyethylene (VLDPE) is added into the inner layer material as a self-adhesive material, and meanwhile, when the self-adhesive material is blended, the interface adhesive force is strong, and the performance advantages of the Linear Low Density Polyethylene (LLDPE) and the ultra-low density polyethylene (VLDPE) can be integrated after the self-adhesive material is blended, so that the toughness and the processing performance of the prepared inner layer are improved. Ultra low density polyethylene (VLDPE) has long chain branches with more short chain branches than LLDPE, impairing the formation of crystalline regions on the polymer molecular backbone, which are deformed to cause defects when formed, and therefore metallocene linear low density polyethylene (m-LLDPE) needs to be added to improve its mechanical properties.
In the middle layer material component, linear Low Density Polyethylene (LLDPE) and metallocene linear low density polyethylene (m-LLDPE) are used as base resin materials, and POSS modified polyethylene is added for compound modification. The POSS modified polyethylene is obtained by grafting irradiated LLDPE and vinyl POSS, and a large amount of peroxide is generated on a molecular chain of the irradiated LLDPE; when the peroxide is contacted with vinyl POSS, the system temperature is raised, and the peroxide is decomposed to generate free radicals, so that the free radicals are grafted with the peroxide, the POSS is grafted onto a polymer molecular chain, and a crosslinked network structure is formed, so that the obtained POSS modified polyethylene can improve the processability, mechanical property, strong hardness and thermal stability of the prepared middle layer.
In the outer layer material components, linear Low Density Polyethylene (LLDPE), metallocene ultra low density polyethylene (m-VLDPE) and metallocene linear low density polyethylene (m-LLDPE) are taken as base resins, and the synergistic effect ensures that the prepared outer layer has good toughness and mechanical properties, and phenolized lignin and modified LLDPE are added for modification. Firstly, preparing polydivinylbenzene-polyethylene (branched polyethylene) with iodine-containing end groups by taking diiso-base as a monomer under the initiation action of azodiisobutyronitrile, then taking the obtained product as an initiator, taking copper bromide and cuprous bromide as catalysts, initiating grafting of 4-vinylphenylboric acid, quaternary ammonium compounds and methyl methacrylate on the branched polyethylene end groups, reacting phenolic hydroxyl groups in sodium lignin sulfonate with boric acid in the modified LLDPE under the alkaline action provided by quaternary ammonium salts to generate phenyl borate, improving the crosslinking degree of the prepared outer layer, forming a three-dimensional network structure, and obtaining the modified polyethylene (sodium lignin sulfonate+modified LLDP) with amphipathy, which improves the polarity and hydrophilicity of the prepared outer layer, and can improve the adhesive capacity and antistatic capacity of the prepared stretched film; the rigidity of the outer layer can be improved to a certain extent, the combination of the tough middle layer and the rigid outer layer of the prepared stretched film is realized, the mechanical property and the heat resistance of the stretched film are further improved, the adsorption of dust is prevented, and the resistance to friction is improved.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clearly and completely described, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following embodiments, linear Low Density Polyethylene (LLDPE): HS7001 is derived from China petrochemical Yangzi petrochemical industry Co., ltd;
ultra low density polyethylene (VLDPE): 4501, available from the american dow chemical company;
metallocene linear low density polyethylene (m-LLDPE): SP1520, from mitsubishi chemical corporation;
metallocene ultra low density polyethylene (m-VLDPE): VL0003, derived from Korean large forest industries, inc.;
the opening agent is stearic acid amide; PPA processing aid: from Shanghai robust Polymer technologies Co., ltd;
vinyl POSS: from Shanghai Michelin chemical Co., ltd;
the number of parts is mass part.
Example 1: a process for preparing a co-extruded stretch film for packaging, comprising the following steps:
s1, taking 35 parts of Linear Low Density Polyethylene (LLDPE), 25 parts of ultra low density polyethylene (VLDPE), 25 parts of metallocene linear low density polyethylene (m-LLDPE), 2 parts of an opening agent and 2 parts of PPA processing aid as inner layer materials;
s2, placing LLDPE in an electron accelerator for pre-irradiation, wherein the technological parameters are as follows: the power is 120000W, the accelerating voltage is 30000V, the beam length is 75mm, the scanning width is 120cm, the transmission speed is 0.08m/s, and the pre-irradiation dose is 15kGy;
10 parts of vinyl POSS, 12 parts of divinylbenzene and 100 parts of LLDPE are placed in a double-screw extruder for melt extrusion, and the barrel temperature is as follows: melt blending at 150 ℃, 160 ℃, 175 ℃, 170 ℃, 190 ℃ at the machine head temperature and 60rpm to obtain POSS modified polyethylene;
taking 40 parts of Linear Low Density Polyethylene (LLDPE), 50 parts of metallocene linear low density polyethylene (m-LLDPE), 10 parts of POSS modified polyethylene and 0.5 part of PPA processing aid as middle layer materials;
s3, the modified LLDPE is specifically prepared by the following process:
10.4g of methacryloyl chloride, 13.7g of 4-dimethylaminophenol and 21.8g of triethylamine are taken and reacted at 58 ℃ for 150min; adding 3.1g of 37% concentrated hydrochloric acid and 100mL of absolute ethyl alcohol, mixing, reacting for 25min at 23 ℃, heating to 43 ℃, adjusting the pH of the system to 7.5, slowly adding 9.2g of epichlorohydrin, and reacting for 7h at a constant temperature of 40 ℃; spin steaming, removing solvent, and vacuum drying to obtain quaternary ammonium compound;
taking 43g of linear low-density polyethylene and 100mL of dimethylbenzene, heating to 80 ℃ and stirring and mixing, adding 0.27g of initiator dicumyl peroxide under the protection of nitrogen atmosphere, mixing, then adding 0.13g of iodine simple substance and 2.6g of divinylbenzene, uniformly mixing, and reacting for 4 hours at constant temperature; after the reaction is finished, rapidly cooling in ice water, adding petroleum ether for precipitation, washing, filtering, and vacuum drying at 24 ℃ for 12 hours to obtain branched polyethylene;
mixing 46g of branched polyethylene, 1.5g of 4-vinylphenylboronic acid, 0.14g of quaternary ammonium compound, 0.10g of methyl methacrylate, 0.14g of cuprous bromide and 0.01g of copper bromide, adding 100mL of dimethylbenzene, and heating to 98 ℃ for reaction for 4 hours under the protection of nitrogen atmosphere; adding n-hexane, standing, taking the precipitate, and vacuum drying to constant weight to obtain modified LLDPE;
15 parts of Linear Low Density Polyethylene (LLDPE), 35 parts of metallocene ultra-low density polyethylene (m-VLDPE), 35 parts of metallocene linear low density polyethylene (m-LLDPE), 8 parts of sodium lignin sulfonate, 15 parts of modified LLDPE and 1 part of PPA processing aid are taken as outer layer materials;
15% of inner layer material, 70% of middle layer material and 15% of outer layer material in the stretched film;
s4, placing the mixture in a three-layer coextrusion blown film machine, and carrying out coextrusion blow molding, wherein the extrusion temperature is 160 ℃; stretching, wherein the stretching process conditions are as follows: stretching at 112 deg.c in longitudinal direction at a stretching ratio of 2.5 and stretching at 105 deg.c in transverse direction at a stretching ratio of 1.8;
and (3) carrying out heat setting after stretching, wherein the process conditions are as follows: the heat setting temperature is 85 ℃, the heat setting time is 100s, and the stretched film is obtained.
Example 2: a process for preparing a co-extruded stretch film for packaging, comprising the following steps:
s1, taking 40 parts of Linear Low Density Polyethylene (LLDPE), 30 parts of ultra low density polyethylene (VLDPE), 30 parts of metallocene linear low density polyethylene (m-LLDPE), 3 parts of an opening agent and 3 parts of PPA processing aid as inner layer materials;
s2, placing LLDPE in an electron accelerator for pre-irradiation, wherein the technological parameters are as follows: the power is 120000W, the accelerating voltage is 30000V, the beam length is 75mm, the scanning width is 120cm, the transmission speed is 0.08m/s, and the pre-irradiation dose is 15kGy;
14 parts of vinyl POSS, 16 parts of divinylbenzene and 100 parts of LLDPE are placed in a twin-screw extruder for melt extrusion, the barrel temperature being: melt blending at 150 ℃, 160 ℃, 175 ℃, 170 ℃, 192 ℃ at the head temperature and the rotation speed of 120rpm for 5.5min to obtain POSS modified polyethylene;
45 parts of Linear Low Density Polyethylene (LLDPE), 55 parts of metallocene linear low density polyethylene (m-LLDPE), 15 parts of POSS modified polyethylene and 1.0 part of PPA processing aid are taken as middle layer materials;
s3, the modified LLDPE is specifically prepared by the following process:
10.4g of methacryloyl chloride, 13.7g of 4-dimethylaminophenol and 23.3g of triethylamine are taken and reacted at 61 ℃ for 180min; adding 3.3g of 37% concentrated hydrochloric acid and 100mL of absolute ethyl alcohol, mixing, reacting for 27min at 25 ℃, heating to 45 ℃, adjusting the pH of the system to 7.8, slowly adding 9.7g of epichlorohydrin, and reacting for 7.5h at the constant temperature of 45 ℃; spin steaming, removing solvent, and vacuum drying to obtain quaternary ammonium compound;
taking 46g of linear low-density polyethylene and 100mL of dimethylbenzene, heating to 90 ℃ and stirring and mixing, adding 0.45g of initiator dicumyl peroxide under the protection of nitrogen atmosphere, mixing, then adding 0.20g of iodine simple substance and 3.9g of divinylbenzene, uniformly mixing, and reacting for 6 hours at constant temperature; after the reaction is finished, rapidly cooling in ice water, adding petroleum ether for precipitation, washing, filtering, and vacuum drying at 25 ℃ for 12 hours to obtain branched polyethylene;
51g of branched polyethylene, 2.2g of 4-vinylphenylboronic acid, 0.21g of quaternary ammonium compound, 0.15g of methyl methacrylate, 0.21g of cuprous bromide and 0.015g of copper bromide are taken and mixed, 100mL of dimethylbenzene is added, and the temperature is raised to 102 ℃ for reaction for 6 hours under the protection of nitrogen atmosphere; adding n-hexane, standing, taking the precipitate, and vacuum drying to constant weight to obtain modified LLDPE;
taking 20 parts of Linear Low Density Polyethylene (LLDPE), 40 parts of metallocene ultra-low density polyethylene (m-VLDPE), 40 parts of metallocene linear low density polyethylene (m-LLDPE), 10 parts of sodium lignin sulfonate, 18 parts of modified LLDPE and 1.5 parts of PPA processing aid as outer layer materials;
the stretching film comprises 20% of inner layer material, 60% of middle layer material and 20% of outer layer material;
s4, placing the mixture in a three-layer coextrusion blown film machine, and carrying out coextrusion blow molding, wherein the extrusion temperature is 160 ℃; stretching, wherein the stretching process conditions are as follows: stretching at 112 deg.c in longitudinal direction at a stretching ratio of 2.5 and stretching at 105 deg.c in transverse direction at a stretching ratio of 1.8;
and (3) carrying out heat setting after stretching, wherein the process conditions are as follows: the heat setting temperature is 85 ℃, the heat setting time is 60s, and the stretched film is obtained.
Example 3: a process for preparing a co-extruded stretch film for packaging, comprising the following steps:
s1, taking 45 parts of Linear Low Density Polyethylene (LLDPE), 35 parts of ultra low density polyethylene (VLDPE), 35 parts of metallocene linear low density polyethylene (m-LLDPE), 4 parts of an opening agent and 4 parts of PPA processing aid as inner layer materials;
s2, placing LLDPE in an electron accelerator for pre-irradiation, wherein the technological parameters are as follows: the power is 120000W, the accelerating voltage is 30000V, the beam length is 75mm, the scanning width is 120cm, the transmission speed is 0.08m/s, and the pre-irradiation dose is 15kGy;
18 parts of vinyl POSS, 20 parts of divinylbenzene and 100 parts of LLDPE are placed in a twin-screw extruder for melt extrusion, and the barrel temperature is: melt blending at 150 ℃, 160 ℃, 175 ℃, 170 ℃, head temperature 195 ℃ and rotating speed 180rpm for 5min to obtain POSS modified polyethylene;
50 parts of Linear Low Density Polyethylene (LLDPE), 60 parts of metallocene linear low density polyethylene (m-LLDPE), 20 parts of POSS modified polyethylene and 1.5 parts of PPA processing aid are taken as middle layer materials;
s3, the modified LLDPE is specifically prepared by the following process:
10.4g of methacryloyl chloride, 13.7g of 4-dimethylaminophenol and 24.9g of triethylamine are taken and reacted for 200min at 65 ℃; adding 3.6g of 37% concentrated hydrochloric acid and 100mL of absolute ethyl alcohol, mixing, reacting for 30min at 27 ℃, heating to 47 ℃, adjusting the pH of the system to 8.0, slowly adding 10.1g of epichlorohydrin, and reacting for 8h at the constant temperature of 48 ℃; spin steaming, removing solvent, and vacuum drying to obtain quaternary ammonium compound;
taking 49g of linear low-density polyethylene and 100mL of dimethylbenzene, heating to 100 ℃ and stirring and mixing, adding 0.64g of initiator dicumyl peroxide under the protection of nitrogen atmosphere, mixing, then adding 0.25g of iodine simple substance and 5.2g of divinylbenzene, uniformly mixing, and reacting for 8 hours at constant temperature; after the reaction is finished, rapidly cooling in ice water, adding petroleum ether for precipitation, washing, filtering, and vacuum drying at 27 ℃ for 12 hours to obtain branched polyethylene;
57g of branched polyethylene, 3.0g of 4-vinylphenylboronic acid, 0.28g of quaternary ammonium compound, 0.20g of methyl methacrylate, 0.28g of cuprous bromide and 0.02g of copper bromide are taken and mixed, 100mL of dimethylbenzene is added, and the temperature is raised to 105 ℃ for reaction for 8 hours under the protection of nitrogen atmosphere; adding n-hexane, standing, taking the precipitate, and vacuum drying to constant weight to obtain modified LLDPE;
taking 25 parts of Linear Low Density Polyethylene (LLDPE), 45 parts of metallocene ultra-low density polyethylene (m-VLDPE), 45 parts of metallocene linear low density polyethylene (m-LLDPE), 12 parts of sodium lignin sulfonate, 20 parts of modified LLDPE and 2 parts of PPA processing aid as outer layer materials;
the stretching film comprises 25% of inner layer material, 50% of middle layer material and 25% of outer layer material;
s4, placing the mixture in a three-layer coextrusion blown film machine, and carrying out coextrusion blow molding, wherein the extrusion temperature is 160 ℃; stretching, wherein the stretching process conditions are as follows: stretching at 112 deg.c in longitudinal direction at a stretching ratio of 2.5 and stretching at 105 deg.c in transverse direction at a stretching ratio of 1.8;
and (3) carrying out heat setting after stretching, wherein the process conditions are as follows: and (5) heat setting at 105 ℃ for 30s to obtain the stretched film.
Comparative example 1: a preparation process of a coextrusion stretching film for packaging,
s2, taking 50 parts of Linear Low Density Polyethylene (LLDPE), 50 parts of metallocene linear low density polyethylene (m-LLDPE) and 0.5 part of PPA processing aid as a middle layer material;
steps S1, S3 and S4 were the same as in example 1, resulting in a stretched film.
Comparative example 2: a preparation process of a coextrusion stretching film for packaging,
s3, the modified LLDPE is specifically prepared by the following process:
10.4g of methacryloyl chloride, 13.7g of 4-dimethylaminophenol and 21.8g of triethylamine are taken and reacted at 58 ℃ for 150min; adding 3.1g of 37% concentrated hydrochloric acid and 100mL of absolute ethyl alcohol, mixing, reacting for 25min at 23 ℃, heating to 43 ℃, adjusting the pH of the system to 7.5, slowly adding 9.2g of epichlorohydrin, and reacting for 7h at a constant temperature of 40 ℃; spin steaming, removing solvent, and vacuum drying to obtain quaternary ammonium compound;
taking 43g of linear low-density polyethylene and 100mL of dimethylbenzene, heating to 80 ℃ and stirring and mixing, adding 0.27g of initiator dicumyl peroxide under the protection of nitrogen atmosphere, mixing, then adding 0.13g of iodine simple substance and 2.6g of divinylbenzene, uniformly mixing, and reacting for 4 hours at constant temperature; after the reaction is finished, rapidly cooling in ice water, adding petroleum ether for precipitation, washing, filtering, and vacuum drying at 24 ℃ for 12 hours to obtain branched polyethylene;
mixing 46g of branched polyethylene, 0.14g of quaternary ammonium compound, 0.10g of methyl methacrylate, 0.14g of cuprous bromide and 0.01g of copper bromide, adding 100mL of dimethylbenzene, and heating to 98 ℃ for reaction for 4 hours under the protection of nitrogen atmosphere; adding n-hexane, standing, taking the precipitate, and vacuum drying to constant weight to obtain modified LLDPE;
15 parts of Linear Low Density Polyethylene (LLDPE), 35 parts of metallocene ultra-low density polyethylene (m-VLDPE), 35 parts of metallocene linear low density polyethylene (m-LLDPE), 8 parts of sodium lignin sulfonate, 15 parts of modified LLDPE and 1 part of PPA processing aid are taken as outer layer materials;
15% of inner layer material, 70% of middle layer material and 15% of outer layer material in the stretched film;
steps S1, S2 and S4 were the same as in comparative example 1, resulting in a stretched film.
Comparative example 3: a preparation process of a coextrusion stretching film for packaging,
s3, the modified LLDPE is specifically prepared by the following process:
10.4g of methacryloyl chloride, 13.7g of 4-dimethylaminophenol and 21.8g of triethylamine are taken and reacted at 58 ℃ for 150min; adding 3.1g of 37% concentrated hydrochloric acid and 100mL of absolute ethyl alcohol, mixing, reacting for 25min at 23 ℃, heating to 43 ℃, adjusting the pH of the system to 7.5, slowly adding 9.2g of epichlorohydrin, and reacting for 7h at a constant temperature of 40 ℃; spin steaming, removing solvent, and vacuum drying to obtain quaternary ammonium compound;
LLDPE is taken and placed in an electron accelerator for pre-irradiation, and the technological parameters are as follows: the power is 120000W, the accelerating voltage is 30000V, the beam length is 75mm, the scanning width is 120cm, the transmission speed is 0.08m/s, and the pre-irradiation dose is 15kGy;
0.14g of quaternary ammonium compound, 0.10g of methyl methacrylate, 2.6g of divinylbenzene, 43g of LLDPE were melt extruded in a twin-screw extruder at the barrel temperature: melt blending at 150 ℃, 160 ℃, 175 ℃, 170 ℃, 185 ℃ at the head temperature and 60rpm to obtain modified LLDPE;
15 parts of Linear Low Density Polyethylene (LLDPE), 35 parts of metallocene ultra-low density polyethylene (m-VLDPE), 35 parts of metallocene linear low density polyethylene (m-LLDPE), 8 parts of sodium lignin sulfonate, 15 parts of modified LLDPE and 1 part of PPA processing aid are taken as outer layer materials;
15% of inner layer material, 70% of middle layer material and 15% of outer layer material in the stretched film;
steps S1, S2 and S4 were the same as in comparative example 1, resulting in a stretched film.
Comparative example 4: a preparation process of a coextrusion stretching film for packaging,
s3, the modified LLDPE is specifically prepared by the following process:
10.4g of methacryloyl chloride, 13.7g of 4-dimethylaminophenol and 21.8g of triethylamine are taken and reacted at 58 ℃ for 150min; adding 3.1g of 37% concentrated hydrochloric acid and 100mL of absolute ethyl alcohol, mixing, reacting for 25min at 23 ℃, heating to 43 ℃, adjusting the pH of the system to 7.5, slowly adding 9.2g of epichlorohydrin, and reacting for 7h at a constant temperature of 40 ℃; spin steaming, removing solvent, and vacuum drying to obtain quaternary ammonium compound;
LLDPE is taken and placed in an electron accelerator for pre-irradiation, and the technological parameters are as follows: the power is 120000W, the accelerating voltage is 30000V, the beam length is 75mm, the scanning width is 120cm, the transmission speed is 0.08m/s, and the pre-irradiation dose is 15kGy;
0.14g of quaternary ammonium compound and 43g of LLDPE are placed in a twin-screw extruder for melt extrusion, the barrel temperature being: melt blending at 150 ℃, 160 ℃, 175 ℃, 170 ℃, 185 ℃ at the head temperature and 60rpm to obtain modified LLDPE;
15 parts of Linear Low Density Polyethylene (LLDPE), 35 parts of metallocene ultra-low density polyethylene (m-VLDPE), 35 parts of metallocene linear low density polyethylene (m-LLDPE), 8 parts of sodium lignin sulfonate, 15 parts of modified LLDPE and 1 part of PPA processing aid are taken as outer layer materials;
15% of inner layer material, 70% of middle layer material and 15% of outer layer material in the stretched film;
steps S1, S2 and S4 were the same as in comparative example 1, resulting in a stretched film.
Comparative example 5: a preparation process of a coextrusion stretching film for packaging,
s3, taking 30 parts of Linear Low Density Polyethylene (LLDPE), 35 parts of metallocene ultra-low density polyethylene (m-VLDPE), 35 parts of metallocene linear low density polyethylene (m-LLDPE), 15 parts of modified LLDPE and 1 part of PPA processing aid as outer layer materials;
15% of inner layer material, 70% of middle layer material and 15% of outer layer material in the stretched film;
steps S1, S2 and S4 were the same as in comparative example 1, resulting in a stretched film.
Experiment
The stretched films obtained in examples 1 to 3 and comparative examples 1 to 5 were 18 μm thick, and samples were prepared, and the properties thereof were examined and the results were recorded, respectively:
mechanical property experiment: using GB/T1040.3-2006 as a reference standard, and adopting an electronic universal testing machine to detect the tensile property of a sample, wherein the size of the sample is 150mm multiplied by 15mm; the stretching speed is 200mm/min;
antistatic dustproof experiment: placing the sample in an air environment for 15 days, recording the mass of the sample before and after the experiment, and calculating the difference value of the mass and the mass, wherein the size of the sample is 15mm multiplied by 15mm;
friction resistance test: the sample is taken to be contacted with 400-mesh sand paper, a 10N weight is placed, the sample is horizontally pushed for 20cm, the sample is defined as one cycle, and the sample is detected to be 10 6 After each cycle, the volumetric wear rate of the sample was used as a performance index.
From the data in the above table, the following conclusions can be clearly drawn:
the stretched films obtained in examples 1 to 3 were compared with the stretched films obtained in comparative examples 1 to 5, and it was found that,
compared with the comparative examples, the stretched films obtained in examples 1-3 have better tensile strength, dustproof performance and volumetric wear rate data, which fully demonstrate that the invention achieves improvement of mechanical properties, wear resistance and dustproof performance of the prepared stretched films.
The middle layer material in comparative example 1 is different from that in example 1; the outer layer materials in comparative examples 2-5 were different from those in comparative example 1; the tensile films obtained in comparative examples 1 to 5 were deteriorated in tensile strength, dust-proof performance and bulk wear rate data, and it was found that the invention can promote improvement of mechanical properties, abrasion resistance and dust-proof performance of the resulting tensile films by setting the composition of the intermediate layer material, the outer layer material and the process thereof.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process method article or apparatus.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A coextruded stretched film for packaging, characterized in that: the method sequentially comprises the following steps from top to bottom: the stretching film is obtained by co-extrusion of an inner layer material, a middle layer material and an outer layer material;
the outer layer material comprises the following components in mass percent: 15 to 25 parts of linear low density polyethylene, 35 to 45 parts of metallocene ultralow density polyethylene, 35 to 45 parts of metallocene linear low density polyethylene, 8 to 12 parts of sodium lignin sulfonate, 15 to 20 parts of modified LLDPE and 1 to 2 parts of PPA processing aid.
2. A coextruded stretched film for packaging as set forth in claim 1, wherein: the inner layer material comprises the following components in mass percent: 35-45 parts of linear low density polyethylene, 25-35 parts of ultra-low density polyethylene, 25-35 parts of metallocene linear low density polyethylene, 2-4 parts of opening agent and 2-4 parts of PPA processing aid.
3. A coextruded stretched film for packaging as set forth in claim 1, wherein: the middle layer material comprises the following components in parts by mass: 40 to 50 parts of linear low density polyethylene, 50 to 60 parts of metallocene linear low density polyethylene, 10 to 20 parts of POSS modified polyethylene and 0.5 to 1.5 parts of PPA processing aid.
4. A coextruded stretched film for packaging as set forth in claim 1, wherein: the stretching film comprises 15-25% of inner layer material, 50-70% of middle layer material and 15-25% of outer layer material according to mass fraction.
5. A preparation process of a coextrusion stretched film for packaging is characterized by comprising the following steps: the method comprises the following steps:
taking linear low density polyethylene, ultra-low density polyethylene, metallocene linear low density polyethylene, an opening agent and PPA processing aid as inner layer materials;
linear low density polyethylene, metallocene linear low density polyethylene, POSS modified polyethylene and PPA processing aid are used as middle layer materials;
linear low density polyethylene, metallocene ultra low density polyethylene, metallocene linear low density polyethylene, sodium lignin sulfonate, modified LLDPE and PPA processing aid are used as outer layer materials;
and (3) placing the film into a three-layer coextrusion blown film machine, coextrusion blown film and stretching to obtain a stretched film.
6. The process for producing a co-extruded stretched film for packaging according to claim 5, wherein: the modified LLDPE is prepared by the following process:
taking methacryloyl chloride, 4-dimethylaminophenol and triethylamine, and reacting for 150-200 min at 58-65 ℃; adding 37% concentrated hydrochloric acid and absolute ethyl alcohol, mixing, reacting for 25-30 min at 23-27 ℃, heating to 43-47 ℃, regulating the pH of the system to 7.5-8.0, slowly adding epichlorohydrin, and reacting for 7-8 h at a constant temperature of 40-48 ℃ to obtain a quaternary ammonium compound;
taking linear low-density polyethylene and dimethylbenzene, heating to 80-100 ℃ and stirring and mixing, adding an initiator dicumyl peroxide under the protection of nitrogen atmosphere, mixing, then adding iodine simple substance and divinylbenzene, uniformly mixing, and reacting at constant temperature for 4-8 hours to obtain branched polyethylene;
mixing branched polyethylene, 4-vinylphenylboronic acid, quaternary ammonium compound, methyl methacrylate, cuprous bromide and copper bromide, adding dimethylbenzene, heating to 98-105 ℃ under the protection of nitrogen atmosphere, and reacting for 4-8 hours to obtain modified LLDPE.
7. The process for producing a co-extruded stretched film for packaging according to claim 6, wherein: the mol ratio of the methacryloyl chloride to the 4-dimethylaminophenol to the epichlorohydrin is 1:1 (1.0-1.1).
8. The process for producing a co-extruded stretched film for packaging according to claim 6, wherein: the mass ratio of the linear low density polyethylene to the divinylbenzene to the initiator dicumyl peroxide to the iodine simple substance is (43-49), 2.6-5.2, 0.27-0.64 and 0.13-0.25.
9. The process for producing a co-extruded stretched film for packaging according to claim 6, wherein: the mass ratio of the branched polyethylene to the 4-vinylphenylboronic acid to the quaternary ammonium compound to the methyl methacrylate to the cuprous bromide to the cupric bromide is (46-57) (1.5-3.0) (0.14-0.28) (0.10-0.20) (0.14-0.28) (0.01-0.02).
10. The process for producing a co-extruded stretched film for packaging according to claim 5, wherein: the POSS modified polyethylene is specifically prepared by the following process:
placing vinyl POSS, divinylbenzene and LLDPE in a double-screw extruder for melt extrusion, wherein the barrel temperature is as follows: the POSS modified polyethylene is obtained by melt blending for 5-6 min at 150 ℃, 160 ℃, 175 ℃, 170 ℃, 190-195 ℃ of the temperature of the machine head and 60-180 rpm of the rotating speed.
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