CN112831121B - PVDC high-barrier co-extrusion self-adhesive film for military protection and preparation method thereof - Google Patents

PVDC high-barrier co-extrusion self-adhesive film for military protection and preparation method thereof Download PDF

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CN112831121B
CN112831121B CN202110146777.9A CN202110146777A CN112831121B CN 112831121 B CN112831121 B CN 112831121B CN 202110146777 A CN202110146777 A CN 202110146777A CN 112831121 B CN112831121 B CN 112831121B
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density polyethylene
mass
film
linear low
pvdc
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CN112831121A (en
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杨宜民
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Luoyang Shengpeng New Material Technology Co ltd
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Luoyang Shengpeng New Material Technology Co ltd
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    • C08J5/18—Manufacture of films or sheets
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00—Materials specially adapted for outerwear
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    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
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    • A41D31/00—Materials specially adapted for outerwear
    • A41D31/04—Materials specially adapted for outerwear characterised by special function or use
    • A41D31/08—Heat resistant; Fire retardant
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    • A—HUMAN NECESSITIES
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    • A41D31/24—Resistant to mechanical stress, e.g. pierce-proof
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    • A41D31/26—Electrically protective, e.g. preventing static electricity or electric shock
    • A41D31/265—Electrically protective, e.g. preventing static electricity or electric shock using layered materials
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    • A41D31/305—Antimicrobial, e.g. antibacterial using layered materials
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
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Abstract

The application relates to the technical field of military protection, in particular to a PVDC high-barrier co-extrusion self-adhesive film for the military protection and a preparation method thereof. The co-extrusion film can be used for protecting and preventing dust in the military industry, and can avoid the possibility that dust generates static electricity and a weak magnetic field is generated; the water vapor transmission capacity reaches about 1g/cm and is equal to 24 hours, and the moistureproof effect is excellent; the pressure-resistant stability is strong.

Description

PVDC high-barrier co-extrusion self-adhesive film for military protection and preparation method thereof
Technical Field
The application relates to the technical field of military protection, in particular to a PVDC high-barrier co-extrusion self-adhesive film for military protection and a preparation method thereof.
Background
In the field of military protection, electronic products such as electronic equipment, electronic devices, digital devices and the like are required to be subjected to film coating protection, a layer of PET antistatic agent is brushed on the surface of an electronic protection film, a very thin conductive layer is formed on the surface of the film, the surface conductivity is improved, generated charges leak as soon as possible, and the threat of static electricity is reduced, so that static electricity is prevented from being generated during operation, transportation and storage. As static electricity can cause damage or breakdown to electronic devices such as: the circuit is broken down after static electricity is attached by ash; discharge breakdown can cause integrated circuits and digital devices in the circuit board to directly damage precision devices, etc. However, the antistatic agent applied on the outer layer may fail with the lapse of time, and the antistatic effect is unstable.
Disclosure of Invention
Aiming at the defects in the prior art, the application provides a PVDC high-barrier co-extrusion self-adhesive film for military protection and a preparation method thereof.
The technical scheme adopted by the application for achieving the purpose is as follows: the PVDC high-barrier co-extrusion self-adhesive film for military protection consists of an outer layer, a first adhesive layer, a PVDC layer, a second adhesive layer, a secondary inner layer and an inner layer which are sequentially arranged, wherein the outer layer consists of linear low-density polyethylene, modified graphene and an additive, and the secondary inner layer consists of linear low-density polyethylene, metallocene polyethylene and the additive.
In the application, the thicknesses of the outer layer, the first adhesive layer, the barrier layer, the second adhesive layer, the secondary inner layer and the inner layer respectively account for 20%, 10%, 25% and 25% of the total thickness of the sealing film.
Wherein, the raw materials in the outer layer are as follows by mass percent: 70-75% of linear low-density polyethylene, 25-30% of low-density polyethylene, 5-10% of modified graphene by mass of the total mass of the linear low-density polyethylene and the low-density polyethylene, and 1-31% of additive by mass of the total mass of the linear low-density polyethylene and the low-density polyethylene.
Preferably, the additive in the outer layer is formed by combining one or more of flame retardant master batch, plasticizer, boron nitride, diatomite and hydrophobic silica.
The secondary inner layer comprises the following raw materials in percentage by mass: 50-70% of linear low-density polyethylene, 20-25% of low-density polyethylene and 10-25% of metallocene polyethylene, wherein the mass of the additive accounts for 1-31% of the total mass of the linear low-density polyethylene, the low-density polyethylene and the metallocene polyethylene.
Preferably, the additive in the secondary inner layer is formed by combining one or more of antistatic master batch, flame retardant master batch, boron nitride and plasticizer.
The anti-static master batch is added into the co-extrusion film, so that the high barrier property of the PVDC film can be effectively utilized, oxygen and water vapor in air are blocked from oxidizing corrosion on military precision equipment, and static charges in plastic packaging products can be effectively uniformly dispersed on the products, so that dust adsorption caused by static charge concentration is avoided, barrier among lines is changed, and functions and service life of the military equipment are influenced.
According to one of the preferred modes, the raw materials in the inner layer are as follows in percentage by mass: 50-55% of linear low-density polyethylene, 22-25% of low-density polyethylene and 23-25% of metallocene polyethylene, wherein the mass of the additive accounts for 2.5-32.5% of the total mass of the linear low-density polyethylene, the low-density polyethylene and the metallocene polyethylene.
Preferably, the additive in the inner layer is formed by combining one or more of antistatic master batch, flame retardant master batch, boron nitride, an opening slipping auxiliary agent, aluminum oxide and a plasticizer.
In a second preferred mode, the raw materials in the inner layer are as follows by mass percent: 45-50% of linear low-density polyethylene, 50-55% of self-adhesive master batch, and the mass of the added plasticizer and antirust agent respectively accounts for 1-1.5% and 3-7.5% of the total mass of the linear low-density polyethylene and the self-adhesive master batch.
Preferably, the secondary inner layer and the inner layer are both added with flame retardant master batches, the PVDC co-extrusion film has self-extinguishing performance, and the PVDC co-extrusion film added with the flame retardant master batches has high barrier property of the PVDC co-extrusion film and ensures that the flame retardant grade of the PVDC co-extrusion film reaches V 0 The grade is suitable for the use of military protective clothing.
A preparation method of a PVDC high-barrier co-extrusion self-adhesive film for military protection comprises the following steps:
(1) Heating a film blowing die and six extruders 3 hours before starting, and starting after the temperatures of the die and the extruders reach the set temperature and preserving heat for 0.5-1.0 hours; (2) After the raw materials of the six film layers are respectively and evenly mixed, the raw materials are respectively sucked into corresponding extruders through a suction machine, the rotating speeds of the six extruders are adjusted, and when the film surface of the stretched film meets the quality requirement, operators measure thickness, width and corona and adjust the thickness, the width and the corona to the set requirements.
The military protective clothing is characterized in that a layer of impermeable film is added on the surface of the non-woven protective clothing, the waterproof, impermeable and antibacterial effects are achieved, the covering film of the existing protective clothing is generally a polyethylene film, the co-extrusion film is applied to the protective clothing, the barrier property, comfort and wear resistance of the co-extrusion film are far higher than those of the polyethylene film, and the high-barrier co-extrusion self-adhesive film produced by the application passes the GB19082-2009 and ASTMF1671 antibacterial third party test.
The high-barrier co-extrusion self-adhesive film can be used for protecting and preventing dust in the military industry, and can avoid the possibility that dust generates static electricity and a weak magnetic field; the water vapor transmission capacity reaches about 1g/cm and is reduced to 24 hours, and the moistureproof effect is excellent; because of the special use environment of the military industry, the requirements on electronic equipment are strict, particularly, good circuit performance is still required to be kept under the conditions of rapid pressurization and depressurization, and the co-extrusion film has strong pressure-resistant stability and can meet the requirements of the military industry.
According to the application, the modified graphene is added in the outer layer, so that the electromagnetic shielding effect of the high-barrier co-extrusion self-adhesive film is improved; the flame-retardant master batch and the antistatic master batch are internally added instead of externally coated, so that the film is subjected to crosslinking reaction in the processing process, the flame retardant property and the antistatic property of the film are greatly improved, and the surface impedance of the film can reach 10 6 -10 10 Omega, flame retardant grade reaches V 0 The service life of the product is longer than three months.
Drawings
FIG. 1 is a comparison of PVDC films of the present application with EVOH films of the prior art.
Detailed Description
The application is further illustrated below in connection with specific examples.
Example 1
The PVDC high-barrier co-extrusion self-adhesive film for military protection consists of an outer layer, a first adhesive layer, a PVDC layer, a second adhesive layer, a secondary inner layer and an inner layer which are sequentially arranged, wherein the outer layer comprises 70% of linear low-density polyethylene and 30% of low-density polyethylene, the modified graphene is 5% of the total mass of the linear low-density polyethylene and the low-density polyethylene, the mass of a plasticizer is 1% of the total mass of the linear low-density polyethylene and the low-density polyethylene, and the mass of a flame-retardant master batch is 30% of the total mass of the linear low-density polyethylene and the low-density polyethylene. The secondary inner layer comprises 70% of linear low-density polyethylene, 20% of low-density polyethylene and 10% of metallocene polyethylene, wherein the mass of the plasticizer is 1% of the total mass of the linear low-density polyethylene, the low-density polyethylene and the metallocene polyethylene, and the mass of the boron nitride is 15% of the total mass of the linear low-density polyethylene, the low-density polyethylene and the metallocene polyethylene. The inner layer consists of 50% of linear low-density polyethylene and 50% of self-adhesive master batch, and the plasticizer is 1% of the total mass of the linear low-density polyethylene and the self-adhesive master batch. The first adhesive layer and the second adhesive layer are both TIE.
The PVDC co-extrusion film has self-extinguishing property, and the PVDC co-extrusion film added with the flame-retardant master batch has high barrier property of the PVDC co-extrusion film and ensures that the flame-retardant grade of the PVDC co-extrusion film reaches V 0 The grade is suitable for military protection.
In the application, the mass ratio is 1:10, adding graphene and ferric nitrate into ethylene glycol, stirring to form a stable suspension, adding sodium acetate to be homogeneous, adding polyethylene glycol to form a mixed solution, pouring into a high-pressure reaction kettle, reacting for 6-10h at 150-200 ℃, cooling, taking out, washing reactants with ethanol and distilled water for multiple times in sequence, filtering, and airing to obtain the modified graphene.
In the application, PVDC resin is prepared from 80-90 parts of vinylidene chloride monomer, 5-15 parts of methyl acrylate monomer, 1-2 parts of plasticizer, 3-4 parts of heat stabilizer, 0.3 part of dispersing agent and 0.2 part of chelating agent, then PVDC layer is prepared correspondingly by using the PVDC resin, and the PVDC layer is molded correspondingly with other film layers of PVDC co-extrusion film, wherein the specific preparation process and principle of PVDC resin are known techniques and are not repeated herein. In order to reduce thermal decomposition in PVDC layer processing and improve ageing resistance, dioctyl sebacate plasticizer and epoxy resin stabilizer are added in the PVDC resin preparation process, and stearic acid amide is adopted as a lubricant, wherein the plasticizer, the stabilizer, the dispersing agent, the chelating agent and other auxiliary agents are added before the PVDC resin is processed, and the lubricant is mixed into the PVDC resin during coextrusion to generate a PVDC core film layer. The PVDC layer has a thickness of 25-35 microns.
The antirust agent is prepared by the following preparation process:
(1) The mass ratio is 1-2:3-5, adding an emulsifier into the linseed oil, and stirring the mixture in a constant-temperature water bath at the temperature of 60 ℃ until the emulsifier is uniformly dispersed to prepare a mixture A; the mass of the emulsifier is 1-3% of that of the linseed oil; adding starch into a sodium hydroxide solution with the mass percent of 1%, uniformly stirring, adding a mixed solution of sodium phosphate with the mass percent of 4% and sodium hydroxide with the mass percent of 1%, and uniformly stirring to prepare a mixture B, wherein the mass-volume ratio of the starch to the sodium hydroxide solution to the mixed solution is 1-3g:10mL:5-15mL; adding the mixture B into the mixture A, stirring and reacting for 4-6h to obtain a mixture C, and spray-freeze-drying the mixture C to obtain an antirust agent I for later use;
(2) Mixing vinyl silicone oil and porous corn starch, and stirring uniformly to obtain an antirust agent II for later use;
(3) The rust inhibitor I and the rust inhibitor II are mixed according to the following ratio of 1: and mixing uniformly in a mass ratio of 1-1.5 to obtain the antirust agent.
Vinyl silicone oil and porous corn starch according to 1:3, by utilizing the characteristics of large specific surface area of porous corn starch and cellular holes of porous starch particles, vinyl silicone oil is adsorbed and embedded in the starch particles, the adsorption embedding rate can reach more than 96.7%, and the self-adhesive master batch can be partially adsorbed on the surfaces of the multi-hollow starch particles, so that the surface area of the self-adhesive master batch is increased, the adhesive force of a co-extrusion film is improved, and consumable materials required by military equipment packaging can be reduced. Meanwhile, when the co-extruded film is used for packaging military equipment and the film is damaged in the storage and transportation process, the oil quality in the rust inhibitor can extend to the extruded part of the packaging film, so that internal packages are prevented from being exposed in the air, and the surface oxidation of the equipment is avoided.
The co-extrusion film has good barrier property, and has very high barrier property on oxygen, nitrogen, carbon dioxide and water vapor; its barrier properties are several times or even hundreds of times that of other materials. And the PVDC high-barrier film has no change in barrier performance along with the change of the environmental humidity, and can still exert the high barrier performance even in high-humidity environments such as high-humidity areas, southern plum rains and the like.
Determining production time according to the set requirements; heating the die set of the film blowing machine 3 hours before starting; the temperature of the first zone, the second zone, the third zone and the fourth zone of the first heating die set is set to 150 ℃, when the temperature of the die reaches 150 ℃, the second temperature setting is carried out, the temperature of the die is set to 184 ℃, and the heating is continued to the set temperature; simultaneously, setting the temperature of each extruder for the first time and starting heating; the temperatures of the first area, the second area, the third area, the fourth area and the fifth area of the No. 1 extruder, the No. 3 extruder and the No. 5 extruder are set to be 130 ℃, and the temperatures of the second area, the third area, the fourth area and the fifth area are all set to be 140 ℃; the temperature of the first area of the No. 2 extruder is set to be 100 ℃, and the temperature of the second area, the third area, the fourth area and the fifth area are all set to be 110 ℃; the temperature of the first zone of the No. 4 extruder and the temperature of the second zone, the third zone, the fourth zone and the fifth zone of the No. 6 extruder are all set to be 100 ℃; when the temperatures of all the extruders reach the set temperature, setting the temperature of each extruder for the second time, wherein the set temperature of a first area of the No. 1 extruder is 170 ℃, 180 ℃ of a second area, 185 ℃ of a third area and 185 ℃ of a fourth area, and 186 ℃ of a fifth area; the first zone of the No. 2 extruder is set to be 130 ℃, the second zone and the third zone are 140 ℃, and the fourth zone and the fifth zone are 142 ℃; the first zone of the No. 3 extruder is set at 172 ℃, the second zone is 180 ℃, the third zone and the fourth zone are 185 ℃, and the fifth zone is 186 ℃; the first zone of the No. 5 extruder is set to be at 174 ℃, the second zone is 182 ℃, the third zone is 184 ℃, the fourth zone is 184 ℃, and the fifth zone is 186 ℃; the first area of the No. 4 extruder and the No. 6 extruder is set to 120 ℃, and the second area, the third area, the fourth area and the fifth area are set to 130 ℃; when the temperature of the die and the temperature of the extruder reach the set temperatures, the die is started after heat preservation for 0.5 hour. The temperature of each extruder is adjusted in a small range appropriately according to the condition of the film surface after the extruder is started.
The raw materials are taken according to the production formula, the raw materials are weighed according to the formula proportion and then are sequentially filled into a mixer for mixing, the mixing time is 15 minutes after all the raw materials enter the mixer, and the uniform mixing of all the raw materials is ensured; the raw materials used by all the extruders are different and are respectively mixed in sequence. The evenly mixed raw materials are transferred to a film blowing machine by a stainless steel transfer basket; when the die temperature of the film blowing unit and the extruder temperature reach the set degree, raw materials required by each group of extruders are sucked into a hopper through a suction machine, then the rotating speeds of the extruders are respectively adjusted on a central control, the rotating speeds of the No. 1, the No. 3 and the No. 5 are 30Hz, the positions of the No. 2 are 20 Hz, the positions of the No. 4 and the No. 6 are 15 Hz, after the raw materials in the extruders reach a die opening through the die, an operator pulls out films from the die opening, sequentially passes through a bubble stabilizer, a lambdoidal deck, one pull and one upper rotate, sequentially passes through each roller, a corona machine, a correction, two pulls and finally reaches a winding shaft, and at the moment, the rotating speeds of the extruders are respectively adjusted: no. 1, no. 3 and No. 5 are 50 hz, no. 2 is 30hz, no. 4 and No. 6 are 25 Hz; setting the first traction speed as 10 Hz, the second traction speed as 30Hz, the external wind 36, the air inlet 13, the air outlet 25 and the winding speed as 11m/min; when the co-extrusion film surface meets the quality requirement, an operator measures the thickness, the width and the corona and adjusts the thickness, the width and the corona to the order requirement; in the production process, operators carry out self-checking on the specification, model, appearance quality and the like of the product according to the quality requirement of the product; the defective products are marked obviously, and remarks are made on production records; after the production of the product, packaging, transferring the product to a semi-finished product storage area, and placing the semi-finished product on a tray for standby; and is covered by a black film to avoid direct light to the product.
Removing black spots, crystal spots and impurities generated in the production process by operators during slitting; carrying out internal packaging on the cut products according to the packaging requirements, boxing and labeling; the product is cut and the vanning in-process detection room detects according to this batch of product quantity random sampling, and the detection item is: indexes such as sense, specification and size, mechanical indexes, optical performance, barrier performance and the like; the packaged products are consistently stacked on a tray according to the requirements and timely transferred to a finished product warehouse, and the inspection data of the finished products are shown in the following table 1.
TABLE 1 product test data from example 1
Example 2
A PVDC high-barrier co-extrusion self-adhesive film for military protection consists of an outer layer, a first bonding layer, a PVDC layer, a second bonding layer, a secondary inner layer and an inner layer which are sequentially arranged,
the outer layer consisted of 75% linear low density polyethylene, 25% low density polyethylene, 7% modified graphene, 20% flame retardant masterbatch, 1% plasticizer, 1.5% boron nitride, 4% diatomaceous earth, 4% hydrophobic silica. The secondary inner layer consisted of 55% linear low density polyethylene, 22% low density polyethylene, 23% metallocene polyethylene, 1.5% antistatic masterbatch, 2.0% boron nitride, 22% flame retardant masterbatch, and 1% plasticizer. The inner layer consisted of 50% linear low density polyethylene, 25% metallocene polyethylene, 1.5% open slip agent, 3% boron nitride, 2% alumina, 18% antistatic masterbatch, and 1% plasticizer. The first adhesive layer and the second adhesive layer are both TIE. The addition of boron nitride makes the inner layer of the co-extrusion film have excellent friction resistance.
The special structure of the diatomite, the boron nitride and the hydrophobic silica can be adsorbed in the pores of the diatomite and the nano-pores of the diatomite for quality inspection, and the synergistic effect of the boron nitride and the hydrophobic silica ensures that the outer layer of the co-extrusion film has excellent hydrophobic property and the synergistic effect of the boron nitride and the diatomite ensures that the outer layer of the co-extrusion film has excellent friction resistance and oxidation resistance. The inner layer is added with boron nitride, aluminum oxide and antistatic master batch, and the synergistic effect of the three enables the co-extrusion film to have excellent antistatic property, and simultaneously improves the heat conduction capability of the co-extrusion film, wherein the heat conductivity can reach more than 1.8W/(m.K), so that when the co-extrusion film is used for military protective clothing, the heat dissipation capability of the protective clothing is improved, and meanwhile, the sheet-shaped structure of the boron nitride and the granular structure of the aluminum oxide are mutually intersected, and the tearing resistance capability of the co-extrusion film is improved.
Finished products were prepared according to the procedure of example 1, and the test data are shown in Table 2 below.
TABLE 2 product test data from example 2
Example 3
A PVDC high-barrier co-extrusion self-adhesive film for military protection consists of an outer layer, a first bonding layer, a PVDC layer, a second bonding layer, a secondary inner layer and an inner layer which are sequentially arranged. The outer layer comprises 73% of linear low-density polyethylene and 22% of low-density polyethylene, the flame-retardant master batch is 17% of the total mass of the linear low-density polyethylene, the low-density polyethylene and the modified graphene, the antistatic master batch is 13% of the total mass of the linear low-density polyethylene, the low-density polyethylene and the modified graphene, the plasticizer is 1% of the total mass of the linear low-density polyethylene, the low-density polyethylene and the modified graphene, and the modified graphene is 7% of the total mass of the linear low-density polyethylene, the low-density polyethylene and the modified graphene. The secondary inner layer consists of 52% of linear low-density polyethylene, 24% of metallocene polyethylene, antistatic master batch, flame retardant master batch and plasticizer, wherein the plasticizer is 1% of the total mass of the linear low-density polyethylene, the low-density polyethylene and the metallocene polyethylene, the flame retardant master batch is 10% of the total mass of the linear low-density polyethylene, the low-density polyethylene and the metallocene polyethylene, and the antistatic master batch is 10% of the total mass of the linear low-density polyethylene, the low-density polyethylene and the metallocene polyethylene. The inner layer consists of 51% of linear low-density polyethylene, 25% of low-density polyethylene, 24% of metallocene polyethylene, an opening slipping agent, an antistatic master batch, a flame-retardant master batch and a plasticizer, wherein the plasticizer is 1% of the total mass of the linear low-density polyethylene, the low-density polyethylene and the metallocene polyethylene, the flame-retardant master batch is 14% of the total mass of the linear low-density polyethylene, the low-density polyethylene and the metallocene polyethylene, the antistatic master batch is 16% of the total mass of the linear low-density polyethylene, the low-density polyethylene and the metallocene polyethylene, and the opening slipping agent is 1.5% of the total mass of the linear low-density polyethylene, the low-density polyethylene and the metallocene polyethylene. The first adhesive layer and the second adhesive layer are both TIE. Finished products were prepared according to the procedure of example 1, and the test data are shown in Table 3 below.
TABLE 3 product test data from example 3
The sealing film prepared by the application is detected according to GB/T28117-2011, 10 rolls are randomly sampled for detection, and the detection results are shown in the following table 4:
TABLE 4 detection report of Co-extruded films of the application
The PVDC co-extrusion film has strong intermolecular cohesive force and high crystallinity, chlorine atoms in molecules of the PVDC co-extrusion film have hydrophobicity, hydrogen bonds are not formed, and oxygen molecules and water molecules are difficult to move in PVDC molecules, so that the PVDC co-extrusion film has excellent oxygen resistance and water resistance, and the oxygen resistance is not influenced by the humidity of the surrounding environment.
The PVDC co-extrusion film has self-extinguishing performance, and the PVDC co-extrusion film added with the flame-retardant master batch has high barrier property of the PVDC co-extrusion film, ensures that the flame-retardant level of the PVDC co-extrusion film reaches V0 level, and is suitable for use in military protective clothing. During the processing of plastic packaging films, static charges exist on a certain part of the surface of the product, and the static charges can adsorb dust to pollute the product; the PVDC co-extrusion film is added with the antistatic master batch, so that the high barrier property of the PVDC film can be effectively utilized, the oxidation corrosion of oxygen and water vapor in air to the precise electronic component can be blocked, and the static charge in the plastic packaging product can be effectively uniformly dispersed on the product, so that dust adsorption caused by static charge concentration is avoided, the barrier between circuits is changed, and the functions and the service life of the precise electronic component are influenced.
The PVDC film of the present application is compared to EVOH films of the prior art, as shown in FIG. 1. As can be seen from fig. 1, the PVDC high barrier film barrier properties do not change with changes in ambient humidity. Even in high humidity areas and in high humidity environments such as the southern plum rainy season, the high barrier property can be exerted. The PVDC co-extrusion film has strong intermolecular cohesive force and high crystallinity, chlorine atoms in molecules of the PVDC co-extrusion film have hydrophobicity, hydrogen bonds are not formed, and oxygen molecules and water molecules are difficult to move in PVDC molecules, so that the PVDC co-extrusion film has excellent oxygen resistance and water resistance, and the oxygen resistance is not influenced by the humidity of the surrounding environment.
The above embodiments are only examples of the present application, and are not limited to the scope of the present application, and all equivalent molecular structures or equivalent synthetic preparation process changes made by the present application, or direct or indirect application in other related technical fields are included in the scope of the present application.

Claims (3)

1. A PVDC high barrier is crowded self-adhesive film altogether for military project protection, its characterized in that: comprises an outer layer, a first bonding layer, a PVDC layer, a second bonding layer, a secondary inner layer and an inner layer which are sequentially arranged, wherein the outer layer comprises linear low-density polyethylene, modified graphene and an additive,
the mass ratio is 1:10, adding graphene and ferric nitrate into ethylene glycol, stirring to form a stable suspension, adding sodium acetate to be homogeneous, adding polyethylene glycol to form a mixed solution, pouring into a high-pressure reaction kettle, reacting for 6-10h at 150-200 ℃, cooling, taking out, washing reactants with ethanol and distilled water for multiple times in sequence, filtering, and airing to obtain modified graphene;
the secondary inner layer consists of linear low-density polyethylene, metallocene polyethylene and an additive, and the additive in the outer layer is formed by combining one or more of flame-retardant master batch, plasticizer, boron nitride, diatomite and hydrophobic silicon dioxide; the additive in the secondary inner layer is formed by combining one or more of antistatic master batch, flame retardant master batch, boron nitride and plasticizer; the inner layer comprises the following raw materials in percentage by mass: 45-50% of linear low-density polyethylene, 50-55% of self-adhesion master batch, and the mass of an additional plasticizer and an additional antirust agent respectively accounts for 1-1.5% and 3-7.5% of the total mass of the linear low-density polyethylene and the self-adhesion master batch, wherein the antirust agent I and the antirust agent II are prepared according to the following weight ratio of 1:1 to 1.5 mass ratio, and the antirust agent is prepared;
the antirust agent is prepared by the following preparation process:
(1) The mass ratio is 1-2:3-5, adding an emulsifier into the linseed oil, and stirring the mixture in a constant-temperature water bath at the temperature of 60 ℃ until the emulsifier is uniformly dispersed to prepare a mixture A; the mass of the emulsifier is 1-3% of that of the linseed oil; adding starch into a sodium hydroxide solution with the mass percent of 1%, uniformly stirring, adding a mixed solution of sodium phosphate with the mass percent of 4% and sodium hydroxide with the mass percent of 1%, and uniformly stirring to prepare a mixture B, wherein the mass-volume ratio of the starch to the sodium hydroxide solution to the mixed solution is 1-3g:10mL:5-15mL; adding the mixture B into the mixture A, stirring and reacting for 4-6h to obtain a mixture C, and spray-freeze-drying the mixture C to obtain an antirust agent I for later use;
(2) Mixing vinyl silicone oil and porous corn starch, and stirring uniformly to obtain an antirust agent II for later use;
(3) The rust inhibitor I and the rust inhibitor II are mixed according to the following ratio of 1:1 to 1.5 mass ratio, and the antirust agent is prepared;
the raw materials in the outer layer are as follows by mass percent: 70-75% of linear low-density polyethylene, 25-30% of low-density polyethylene, 5-10% of modified graphene by mass of the linear low-density polyethylene and the low-density polyethylene, and 1-31% of additive by mass of the linear low-density polyethylene;
the secondary inner layer comprises the following raw materials in percentage by mass: 50-70% of linear low-density polyethylene, 20-25% of low-density polyethylene and 10-25% of metallocene polyethylene, wherein the mass of the additive accounts for 1-31% of the total mass of the linear low-density polyethylene, the low-density polyethylene and the metallocene polyethylene.
2. A PVDC high-barrier co-extruded self-adhesive film for military protection as set forth in claim 1, wherein: the thickness of the outer layer, the first adhesive layer, the barrier layer, the second adhesive layer, the secondary inner layer and the inner layer respectively account for 20%, 10%, 25% and 25% of the total thickness of the sealing film.
3. A method of preparing a PVDC high barrier co-extruded self-adhesive film for military protection according to claim 1, comprising the steps of:
(1) Heating a film blowing die and six extruders 3 hours before starting, and starting after the temperatures of the die and the extruders reach the set temperature and preserving heat for 0.5-1.0 hours; (2) After the raw materials of the six film layers are respectively and evenly mixed, the raw materials are respectively sucked into corresponding extruders through a suction machine, the rotating speeds of the six extruders are adjusted, and when the film surface of the stretched film meets the quality requirement, operators measure thickness, width and corona and adjust the thickness, the width and the corona to the set requirements.
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