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CN109575410B - High-barrier pesticide packaging bottle and preparation method thereof - Google Patents

High-barrier pesticide packaging bottle and preparation method thereof Download PDF

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Publication number
CN109575410B
CN109575410B CN201811401089.7A CN201811401089A CN109575410B CN 109575410 B CN109575410 B CN 109575410B CN 201811401089 A CN201811401089 A CN 201811401089A CN 109575410 B CN109575410 B CN 109575410B
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barrier
packaging bottle
parts
layer
pesticide
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CN109575410A (en
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冯建水
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Hangzhou Puxin Plastic Packing Co ltd
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Hangzhou Puxin Plastic Packing Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0853—Ethene vinyl acetate copolymers
    • C08L23/0861—Saponified copolymers, e.g. ethene vinyl alcohol copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C09J123/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C09J123/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/10—Applications used for bottles

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Wrappers (AREA)

Abstract

The invention discloses a high-barrier pesticide packaging bottle and a preparation method thereof. The high-barrier pesticide packaging bottle is formed by sequentially bonding a barrier layer, a bonding layer and a base layer from inside to outside, wherein two sides of the bonding layer are respectively tightly attached to the barrier layer and the base layer, and the thickness ratio of the barrier layer to the bonding layer to the base layer is 1:0.5-0.8: 2-2.5; the preparation method comprises the following steps: s1, melting the raw materials; s2, carrying out double-screw extrusion molding; s3, blow molding; s4, blowing the barrier layer. The high-barrier pesticide packaging bottle has the advantages of excellent mechanical property and pesticide permeation resistance and better barrier property; in addition, the pesticide packaging bottle prepared by the preparation method is integrally formed, excellent in mechanical property and pesticide permeation resistance and good in barrier property.

Description

High-barrier pesticide packaging bottle and preparation method thereof
Technical Field
The invention relates to the technical field of packaging containers, in particular to a high-barrier pesticide packaging bottle and a preparation method thereof.
Background
Liquid pesticide adopts aluminium bottle and glass bottle packing always, and the aluminium bottle is expensive, and the main shortcoming of glass bottle is: 1. the breakage rate is high, the breakage rate of the glass bottles from delivery to use by farmers is generally up to 10-20%, the environment is polluted, and the cost is increased; 2. the sealing of the inner plug of the glass bottle is not tight, so that leakage is easily caused; 3. the glass bottle is heavy, so that the transportation cost is increased; 4. the bottle is difficult to recycle, and is easy to cause accidental poisoning and environmental pollution; 5. export shipping requires the use of a wood overwrap that has been effectively fumigated or heat treated.
In 1992, the plastic packaging industry was rapidly developed after the development strategy of "replacing glass with plastic" was proposed by the department of original chemistry, in which PET (polyester) bottles and hdpe (hdpe) bottles are widely used as ordinary plastic bottles in pesticide packaging.
In the prior art, reference may be made to chinese patent application No. CN201711499598.3, which discloses a PET bottle for containing pesticides and a preparation method thereof, wherein the inner wall of the PET bottle for containing pesticides is provided with a silica hydrophobic coating. Although the existing PET bottle for containing the pesticide can pour over 99.5% of liquid at one time, the PET bottle cannot block the penetration of water, because some pesticides deteriorate due to hydrolysis and cause the seepage of some pesticides.
Among the prior art, can refer to the chinese utility model patent document of application number CN201320344863.1, it discloses a take pesticide bottle on HDPE layer, the bottle comprises a bottle body, the bottle outside is equipped with a metal level, the bottle comprises the HDPE layer, the dog-ear of bottle is the circular arc transition, the bottom of bottle is equipped with places the strip. Although the existing pesticide bottle with the HDPE layer has a simple structure, good chemical resistance, water resistance and mechanical property and can achieve the purposes of being completely suitable for long-distance transportation and high-strength use, toluene, xylene and other common pesticide diluent components can easily permeate through the bottle wall.
Therefore, the problem to be solved is to prepare the high-barrier pesticide packaging bottle with good mechanical property and excellent pesticide permeation resistance.
Disclosure of Invention
Aiming at the defects in the prior art, the first purpose of the invention is to provide a pesticide packaging bottle with high barrier property, which has the advantages of good mechanical property and excellent pesticide penetration resistance.
The second purpose of the invention is to provide a preparation method of a high-barrier pesticide packaging bottle, which has the advantages that the prepared pesticide packaging bottle has good mechanical properties and excellent pesticide permeation resistance.
In order to achieve the first object, the invention provides the following technical scheme: a high-barrier pesticide packaging bottle is formed by sequentially bonding a barrier layer, a bonding layer and a base layer from inside to outside, wherein two sides of the bonding layer are respectively tightly attached to the barrier layer and the base layer; the barrier layer is formed by melt blow molding of a barrier material, and the barrier material comprises the following components in parts by weight: 2-2.5 parts of EVOH, 1-3 parts of lotus leaf hydrophobing agent, 2-4 parts of modified montmorillonite, 12-15 parts of N, N-dimethylformamide solution, 1-3 parts of nano silicon dioxide and 1-5 parts of waterborne polyurethane-acrylate emulsion.
By adopting the technical scheme, the EVOH combines the processability of the ethylene polymer and the barrier effect of the vinyl alcohol polymer, so the EVOH not only has excellent barrier effect on gas, smell, solvent and the like, but also has hydrophilicity and hygroscopicity because hydroxyl exists in the molecular structure of the EVOH, and the modified montmorillonite and the EVOH can form a diaphragm with excellent hydrophobic property when being dissolved in N, N-dimethylformamide solution, so that the barrier property of a packaging bottle can be improved, and the mechanical property and the chemical resistance of the packaging bottle can also be improved; the montmorillonite has the characteristics of good heat resistance, good barrier property, aging resistance, excellent flame retardance and the like, the surface of the montmorillonite has hydrophilicity and is not beneficial to improving the anti-permeability performance, the surface of the modified montmorillonite is hydrophobic, and has stronger interface bonding with EVOH, so that the performance of the diaphragm can be improved; the lotus leaf hydrophobizing agent is nonionic emulsion, and a hydrophobic surface is formed in the barrier layer, so that water, toluene or xylene and other easily exuded molecules in the packaging bottle are not easy to exude, and the anti-seepage effect of the packaging bottle is improved; the nano silicon dioxide has lower surface energy, the waterborne polyurethane-acrylate emulsion integrates the advantages of polyurethane emulsion and polyacrylic acid value emulsion, the waterborne polyurethane-acrylate emulsion has excellent surface coating performance, the nano silicon dioxide particles are introduced into the waterborne polyurethane-acrylate emulsion, the surface hydrophobic performance of the diaphragm can be obviously improved, multiple diaphragms are formed in the barrier layer, the toughness and the mechanical strength of a packaging bottle can be improved, the compatibility of the nano silicon dioxide and EVOH is good, and the nano silicon dioxide and EVOH are matched with each other, so that the moisture permeability coefficient and the air permeability coefficient of the barrier layer can be reduced, and the impermeability performance of the barrier layer is improved.
Further, the barrier material is prepared by the following method: dissolving EVOH: adding EVOH and 2/3N, N-dimethylformamide into a reactor, heating while stirring, and heating to 180-190 ℃ to fully dissolve the EVOH;
dissolving modified montmorillonite: dissolving the modified montmorillonite in the rest N, N-dimethylformamide solution, and mixing uniformly;
mixing: uniformly mixing the nano silicon dioxide and the waterborne polyurethane-acrylate emulsion, adding the dissolved EVOH and the modified montmorillonite, stirring at 80-100 ℃, adding the lotus leaf hydrophobing agent while stirring, and uniformly mixing.
By adopting the technical scheme, EVOH and montmorillonite are respectively dissolved by N, N-dimethylformamide so as to completely dissolve EVOH and montmorillonite, then nano-silica is mixed with the aqueous polyurethane-acrylate emulsion to improve the surface hydrophobic property of the aqueous polyurethane-acrylate emulsion, and finally the aqueous polyurethane-acrylate emulsion is mixed with a lotus leaf hydrophobic agent to prepare the barrier material with good anti-permeability performance.
Further, the modified montmorillonite is prepared by the following method:
(1) mixing 2-5 parts of sodium montmorillonite with 5-10 parts of deionized water to prepare montmorillonite suspension, adjusting the pH to 1 by using HCl solution, and stirring at 80-85 ℃ for 2-3 h;
(2) adding 1-3 parts of dioctadecyl ammonium dichloride, continuously stirring for 2-3h at 80-85 ℃, filtering, washing with deionized water at 40-50 ℃ for repeated washing, and then drying in a thermostat at 80-85 ℃ to prepare organic montmorillonite;
(3) dispersing organic montmorillonite in deionized water, stirring well to obtain 0.2-0.5% solution, adding 1-3 parts of coupling agent into the solution, stirring at 40-45 deg.C for 4-5h, drying, grinding, and sieving with 200 mesh sieve.
By adopting the technical scheme, the surface of the montmorillonite is modified by adopting dioctadecyl ammonium dichloride, the interface environment is improved, the interface property of the montmorillonite is changed from hydrophilicity to hydrophobicity, the interlayer spacing of the montmorillonite is increased, the intercalation reaction with the EVOH is facilitated, the organic montmorillonite is treated by using a coupling agent, the compatibility of the EVOH and the montmorillonite can be improved, the tensile strength of the barrier layer is improved, the modified montmorillonite can be well dispersed between the EVOH, the permeation of gas molecules or moisture can be effectively prevented, and the air permeability coefficient and the water permeability coefficient of the barrier layer are improved.
Further, the coupling agent is a silane coupling agent KH550, and the mass fraction of the silane coupling agent KH is 5-8%.
By adopting the technical scheme, the silane coupling agent is used as a bridge between the EVOH and the montmorillonite, one end of the silane coupling agent is connected with the EVOH, and the other end of the silane coupling agent is connected with the montmorillonite, so that the compatibility between the EVOH and the montmorillonite is improved, the diaphragm prepared by mixing the EVOH and the montmorillonite has excellent compactness, the anti-permeability performance is improved, and the anti-tensile strength and the anti-permeability effect of the barrier layer can be obviously improved by using the montmorillonite modified by the silane coupling agent KH550 again.
Furthermore, the barrier layer accounts for 7-9% of the total wall thickness of the high-barrier pesticide packaging bottle, the adhesive layer accounts for 9-11% of the total wall thickness of the high-barrier pesticide packaging bottle, and the base layer accounts for 80-84% of the total wall thickness of the high-barrier pesticide packaging bottle.
By adopting the technical scheme, the bonding layer, the barrier layer and the base layer which are mutually attached are adopted, the barrier layer is thinner than the bonding layer, the base layer is thicker than the barrier layer, and the three are mutually matched, so that the pesticide penetration resistance is excellent, the thickness of the base layer is larger, and the pesticide penetration resistance and the waterproof performance are excellent.
Furthermore, the bonding layer is formed by melt blow molding of a bonding material, and the bonding material is formed by mixing a bonding agent, HDPE and LLDPE in a mass ratio of 1:2-3: 2-3.
By adopting the technical scheme, the HDPE has the advantages of wear resistance, toughness and chemical stability, small permeability to water vapor and air, low water absorption, good aging resistance, and capability of improving the defects of easy embrittlement, stress cracking, low surface hardness and the like of the HDPE by mixing with the LLDPE, so that the bonding layer has the advantages of good toughness, high strength, and excellent heat resistance and cold resistance.
Further, the adhesive is one or a mixture of more of epoxy resin adhesive, vinyl acetate resin adhesive or polyurethane adhesive.
Further, the base layer is formed by melting and blow molding of a base layer material, and the base layer material is formed by mixing 1-5 parts of HDPE, 0.6-1.0 part of color master batch, 2-5 parts of nano zinc oxide and 1-5 parts of polyimide emulsion.
Through adopting above-mentioned technical scheme, the look female has good anti-oxidant and ultraviolet resistance, nanometer zinc oxide can shield ultraviolet ray, and nanometer zinc oxide and look female all have bactericidal ability, avoid the packing bottle to arrange in humid environment, breed the bacterium, polyimide emulsion and nanometer zinc oxide are mutually supported, can improve polyimide emulsion to ultraviolet radiation's resistance, reduce the sensitivity of packing bottle to humid environment, improve ageing resistance, nanometer zinc oxide can improve the intensity of basic unit simultaneously, prevent that the crackle from appearing in the basic unit.
In order to achieve the second object, the invention provides the following technical scheme: a preparation method of a high-barrier pesticide packaging bottle comprises the following steps:
s1, melting raw materials: heating and melting the base material at 180-190 ℃ to obtain a base material melt, adding the bonding material at 160-170 ℃ to melt to obtain a bonding material melt, and melting the barrier material at 180-190 ℃ to obtain a barrier material melt;
s2, extrusion molding: compressing and compacting the base material melt by a screw A, compressing and compacting the bonding material by a screw B, compressing and compacting the barrier material melt by a screw C, simultaneously extruding A, B, C three screws at a constant speed, compounding a material blank by a die head, simultaneously working a left die and a right die, blowing by an inserted rod, and cooling and shaping.
By adopting the technical scheme, the base material, the bonding material and the barrier material are melted and extruded together, the base material, the bonding material and the barrier material are compounded through the die head to form a material blank, and a finished product is prepared through air blowing, cooling and shaping, so that the process is simple and the operation is convenient.
Further, in the step S2, the rotating speed of the screw A is 40-60r/min, the rotating speed of the screw B is 20-30r/min, and the rotating speed of the screw C is 10-20 r/min.
By adopting the technical scheme, the rotating speeds of the three screws are different, so that the speeds of the base material, the bonding material and the barrier material are different when the base material, the bonding material and the barrier material are extruded, and the thicknesses of the three layers of materials in the prepared pesticide packaging bottle are different.
In conclusion, the invention has the following beneficial effects:
firstly, because the invention adopts the base layer, the adhesive layer and the barrier layer which are mutually adhered from outside to inside, and the barrier layer is made of materials such as EVOH, modified montmorillonite, lotus leaf hydrophobing agent and the like, the surface of the modified montmorillonite has hydrophobicity after being modified, and the modified montmorillonite is mutually matched with EVOH, so that a diaphragm with hydrophobicity can be obtained, and the anti-permeability performance and the mechanical performance of the barrier layer are improved; meanwhile, the lotus leaf hydrophobizing agent is nonionic emulsion, and a hydrophobic surface is formed in the barrier layer, so that molecules such as water, xylene and the like which are easy to leak in the packaging bottle are not easy to leak in the packaging bottle, and the impermeability and the barrier property of the packaging bottle are improved;
secondly, the nano silicon dioxide and the aqueous polyurethane-acrylate emulsion are adopted, the nano silicon dioxide has lower surface energy, the aqueous polyurethane-acrylate emulsion integrates the advantages of polyurethane emulsion and polyacrylic acid value emulsion, the surface coating performance is excellent, nano silicon dioxide particles are introduced into the aqueous polyurethane-acrylate emulsion, the surface hydrophobic performance of the diaphragm can be obviously improved, multiple diaphragms are formed in the barrier layer, the toughness and the mechanical strength of a packaging bottle can be improved, the compatibility of the nano silicon dioxide and EVOH is good, the nano silicon dioxide and EVOH are matched with each other, the moisture permeability coefficient and the air permeability coefficient of the barrier layer can be reduced, and the impermeability and the barrier property of the barrier layer are improved.
And the modified montmorillonite can be well dispersed among the EVOH, and can effectively block gas molecules or moisture from permeating, so that the air permeability coefficient and the water permeability coefficient of the barrier layer are improved.
Fourthly, in the invention, the silane coupling agent KH550 is preferably adopted as the silane coupling agent, the silane coupling agent is used as a bridge between EVOH and montmorillonite, one end of the silane coupling agent is connected with EVOH, and the other end of the silane coupling agent is connected with montmorillonite, so that the compatibility between EVOH and montmorillonite is improved, the diaphragm prepared by mixing EVOH and montmorillonite has excellent compactness, the anti-permeability performance is improved, and the montmorillonite modified by the silane coupling agent KH550 can obviously improve the tensile strength and the anti-permeability effect of the barrier layer.
Fifth, the color master batch, the nano zinc oxide and the polyimide emulsion are used as base materials, the color master batch and the nano zinc oxide have excellent oxidation resistance and ultraviolet resistance, the action time is long, the packaging bottle is prevented from being damaged by ultraviolet rays, meanwhile, the color master batch and the nano zinc oxide also have sterilization capability, the situation that the packaging bottle is placed in a humid environment and bacteria are bred is avoided, the nano zinc oxide and the polyimide emulsion are matched with each other, the resistance of the polyimide emulsion to ultraviolet radiation can be improved, the sensitivity of the packaging bottle to the humid environment is reduced, the aging resistance is improved, meanwhile, the strength of the base layer can be improved through the nano zinc oxide, and cracks of the base layer are prevented.
Sixth, the method of the invention is easy and convenient to operate, the pesticide packaging bottle prepared has good mechanical properties and excellent anti-permeability effect, and the bottle bottom is prevented from separating from the package due to thermal expansion to cause environmental pollution.
Detailed Description
The present invention will be described in further detail with reference to examples.
Preparation examples 1 to 3 of Barrier layer Material
In the following preparation examples, the aqueous polyurethane-acrylate emulsion is selected from JAZO type aqueous polyurethane-acrylate emulsion of Nanjing Jiazhong chemical technology Co., Ltd, the lotus leaf hydrophobing agent is purchased from Zhengzhou yu chemical product Co., Ltd, the sodium-based montmorillonite is selected from SM-P sodium-based montmorillonite sold by Zhejiang Fenghong new material Co., Ltd, and each component can also adopt other similar products.
Preparation example 1: dissolving EVOH: according to the proportion in the table 1, 2 kg of EVOH and 8 kg of N, N-dimethylformamide are added into a reactor, and the mixture is heated to 180 ℃ while stirring to fully dissolve the EVOH, wherein the ethylene content in RVOH is 38%;
dissolving modified montmorillonite: dissolving 2 kg of modified montmorillonite in 4 kg of N, N-dimethylformamide solution, and uniformly mixing; mixing: after 1 kg of nano silicon dioxide and 1 kg of waterborne polyurethane-acrylate emulsion are uniformly mixed, adding dissolved EVOH and modified montmorillonite, stirring at 80 ℃, adding 1 kg of lotus leaf hydrophobing agent while stirring, and uniformly mixing.
The preparation method of the modified montmorillonite comprises the following steps: (1) mixing 2 parts of sodium montmorillonite and 5 parts of deionized water according to the proportion in the table 2 to prepare montmorillonite suspension, adjusting the pH to 1 by using HCl solution, and stirring for 2 hours at 80 ℃;
(2) adding 1 part of dioctadecyl ammonium dichloride, continuously stirring for 2 hours at 80 ℃, filtering, washing with deionized water at 40 ℃ for repeated washing, and then drying in a thermostat at 80 ℃ to prepare organic montmorillonite;
(3) dispersing organic montmorillonite in deionized water, stirring uniformly to prepare a solution with the mass fraction of 0.2%, adding 1 part of silane coupling agent KH550 with the mass fraction of 5% into the solution, stirring for 4 hours at 40 ℃, drying, grinding and sieving with a 200-mesh sieve.
TABLE 1 raw material ratios of barrier materials in preparation examples 1 to 3
Figure BDA0001876325940000061
TABLE 2 raw material ratios of modified montmorillonite in preparation examples 1-3
Figure BDA0001876325940000062
Preparation example 2: dissolving EVOH: according to the proportion in Table 1, 2.3 kg of EVOH and 9 kg of N, N-dimethylformamide are added into a reactor, and the mixture is heated to 1850 ℃ while stirring to fully dissolve the EVOH, wherein the ethylene content in RVOH is 38%;
dissolving modified montmorillonite: dissolving 3 kg of modified montmorillonite in 4.5 kg of N, N-dimethylformamide solution, and uniformly mixing;
mixing: after 2 kg of nano silicon dioxide and 3 kg of waterborne polyurethane-acrylate emulsion are uniformly mixed, adding the dissolved EVOH and the modified montmorillonite, stirring at 90 ℃, adding 2 kg of lotus leaf hydrophobing agent while stirring, and uniformly mixing.
The preparation method of the modified montmorillonite comprises the following steps: (1) mixing 3.5 parts of sodium montmorillonite and 7.5 parts of deionized water according to the proportion in the table 2 to prepare montmorillonite suspension, adjusting the pH to 1 by using HCl solution, and stirring for 2.5 hours at 83 ℃;
(2) adding 2 parts of dioctadecyl ammonium dichloride, continuously stirring for 2.5 hours at 83 ℃, filtering, washing with deionized water at 45 ℃ for repeated washing, and then drying in a thermostat at 83 ℃ to prepare organic montmorillonite;
(3) dispersing organic montmorillonite in deionized water, stirring uniformly to prepare a solution with the mass fraction of 0.3%, adding 2 parts of silane coupling agent KH550 with the mass fraction of 6% into the solution, stirring for 4.5h at 43 ℃, drying, grinding and sieving with a 200-mesh sieve.
Preparation example 3: dissolving EVOH: according to the proportion in the table 1, 2.5 kg of EVOH and 10 kg of N, N-dimethylformamide are added into a reactor, the mixture is heated to 190 ℃ while stirring, so that the EVOH is fully dissolved, wherein the ethylene content in RVOH is 38%;
dissolving modified montmorillonite: dissolving 4 kg of modified montmorillonite in 5 kg of N, N-dimethylformamide solution, and uniformly mixing; mixing: after 3 kg of nano silicon dioxide and 5 kg of waterborne polyurethane-acrylate emulsion are uniformly mixed, adding dissolved EVOH and modified montmorillonite, stirring at 100 ℃, adding 3 kg of lotus leaf hydrophobing agent while stirring, and uniformly mixing.
The preparation method of the modified montmorillonite comprises the following steps: (1) mixing 5 parts of sodium montmorillonite and 10 parts of deionized water according to the proportion in the table 2 to prepare montmorillonite suspension, adjusting the pH to 1 by using HCl solution, and stirring for 3 hours at 85 ℃;
(2) adding 3 parts of dioctadecyl ammonium dichloride, continuously stirring for 3 hours at 85 ℃, filtering, washing with deionized water at 50 ℃ for repeated washing, and then drying in a thermostat at 85 ℃ to prepare organic montmorillonite;
(3) dispersing organic montmorillonite in deionized water, stirring uniformly to prepare a solution with the mass fraction of 0.5%, adding 3 parts of silane coupling agent KH550 with the mass fraction of 8% into the solution, stirring for 5 hours at 45 ℃, drying, grinding and sieving with a 200-mesh sieve.
Examples
The epoxy resin adhesive is selected from 2058A/B type epoxy resin crystal glue sold by Seiensi industries, Inc. of Dongguan city, the vinyl acetate resin adhesive is selected from PVACS3343T type polyvinyl acetate adhesive sold by Nitai Nuda new material technology, Inc., the polyurethane adhesive is selected from J-2105 type sold by Jule electronic materials, Inc. of Dongguan city, the color master is selected from 6711-30 type anti-aging white master batch sold by Ziboding morning plastic technology, Inc., the polyimide emulsion is selected from PPA-2 type polyimide emulsion sold by Changzhou Furun plastic technology, HDPE is new material 5502 type HDPE produced by Korean Dalin, LLDPE is selected from 1018 type produced by Dutch DSM, and each component can also adopt other similar type products.
Example 1: the utility model provides a high barrier nature pesticide bottle, is formed by barrier layer, bond line and basic unit from interior to exterior bonding in proper order, and barrier layer and basic unit are hugged closely respectively to the both sides of bond line, and the barrier layer accounts for high barrier nature pesticide packing bottle total wall thickness 7%, the bond line accounts for high barrier nature pesticide packing bottle total wall thickness 9%, the basic unit accounts for high barrier nature pesticide packing bottle total wall thickness 84%. The barrier layer is formed by melt blow molding of barrier materials, the adhesive layer is formed by melt blow molding of adhesive materials, and the base layer is formed by melt blow molding of base layer materials.
The preparation method of the high-barrier pesticide packaging bottle comprises the following steps:
s1, melting raw materials: heating and melting a base material at 180 ℃ to obtain a base material melt, adding and melting an adhesive material at 160 ℃ to obtain an adhesive material melt, and melting an barrier material at 180 ℃ to obtain a barrier material melt, wherein the barrier material is prepared by preparation example 1;
wherein the base material is prepared by mixing 1 part of HDPE, 0.6 part of color master, 2 parts of nano zinc oxide and 1 part of polyimide emulsion; the bonding material is formed by mixing a bonding agent, HDPE and LLDPE in a mass ratio of 1:2:2, wherein the bonding agent is an epoxy resin bonding agent;
s2: and (3) extrusion molding: compressing and compacting a base material melt by a screw A, extruding by a screw A at a rotating speed of 45r/min, compressing and compacting an adhesive material by a screw B, compressing and compacting a barrier material melt by a screw C, extruding at a constant speed by A, B, C three screws at the same time, simultaneously working by a left die and a right die through a die head composite material blank, blowing by an inserted rod, cooling and shaping, wherein the rotating speed of the screw A is 40r/min, the rotating speed of the screw B is 20r/min, and the rotating speed of the screw C is 10 r/min.
Example 2: the high-barrier pesticide bottle is different from the pesticide bottle in embodiment 1 in that the barrier layer accounts for 8% of the total wall thickness of the high-barrier pesticide packaging bottle, the adhesive layer accounts for 10% of the total wall thickness of the high-barrier pesticide packaging bottle, and the base layer accounts for 82% of the total wall thickness of the high-barrier pesticide packaging bottle.
Example 3: the high-barrier pesticide bottle is different from the pesticide bottle in embodiment 1 in that the barrier layer accounts for 9% of the total wall thickness of the high-barrier pesticide packaging bottle, the adhesive layer accounts for 11% of the total wall thickness of the high-barrier pesticide packaging bottle, and the base layer accounts for 80% of the total wall thickness of the high-barrier pesticide packaging bottle.
Example 4: a high-barrier pesticide packaging bottle is different from that in the embodiment 1, in the step S1, a base material is heated and melted at 185 ℃, an adhesive material is heated and melted at 165 ℃, a barrier material is heated and melted at 185 ℃, and the base material is formed by mixing 3 parts of HDPE, 0.8 part of color master batch, 4 parts of nano zinc oxide and 3 parts of polyimide emulsion; wherein the rotating speed of the screw A is 50r/min, the rotating speed of the screw B is 25r/min, and the rotating speed of the screw C is 15 r/min.
Example 5: a high-barrier pesticide packaging bottle is different from the packaging bottle in the embodiment 1 in that in the step S1, a base material is heated and melted at 190 ℃, an adhesive material is heated and melted at 170 ℃, a barrier material is heated and melted at 190 ℃, and the base material is formed by mixing 5 parts of HDPE, 1.0 part of color master batch, 5 parts of nano zinc oxide and 5 parts of polyimide emulsion; wherein the rotating speed of the screw A is 60r/min, the rotating speed of the screw B is 30r/min, and the rotating speed of the screw C is 20 r/min.
Example 6: a high-barrier pesticide packaging bottle is different from that in example 1 in that an adhesive material is formed by mixing an adhesive, HDPE and LLDPE in a mass ratio of 1:2.5:2.5, wherein the adhesive is a vinyl acetate resin adhesive.
Example 7: a high-barrier pesticide packaging bottle is different from that in the embodiment 1 in that an adhesive material is formed by mixing an adhesive, HDPE and LLDPE in a mass ratio of 1:3:3, wherein the adhesive is a polyurethane adhesive.
Comparative example
Comparative example 1: the high-barrier pesticide bottle is different from the pesticide bottle in embodiment 1 in that the barrier layer accounts for 6% of the total wall thickness of the high-barrier pesticide packaging bottle, the adhesive layer accounts for 8% of the total wall thickness of the high-barrier pesticide packaging bottle, and the base layer accounts for 86% of the total wall thickness of the high-barrier pesticide packaging bottle.
Comparative example 2: the high-barrier pesticide bottle is different from the pesticide bottle in embodiment 1 in that the barrier layer accounts for 10% of the total wall thickness of the high-barrier pesticide packaging bottle, the adhesive layer accounts for 12% of the total wall thickness of the high-barrier pesticide packaging bottle, and the base layer accounts for 78% of the total wall thickness of the high-barrier pesticide packaging bottle.
Comparative example 3: the pesticide bottle with high barrier property is different from the pesticide bottle in the embodiment 1 in that modified montmorillonite is not added in the material of the barrier layer.
Comparative example 4: the high-barrier pesticide bottle is different from the pesticide bottle in the embodiment 1 in that no lotus leaf hydrophobing agent is added in the material of the barrier layer.
Comparative example 5: the high-barrier pesticide bottle is different from the pesticide bottle in the embodiment 1 in that nano silicon dioxide and aqueous polyurethane-acrylate emulsion are not added in the barrier layer material.
Comparative example 6: a high-barrier pesticide packaging bottle is different from that in example 1 in that an adhesive material is formed by mixing an adhesive, HDPE and LLDPE in a mass ratio of 1:1.5: 1.5.
Comparative example 7: a high-barrier pesticide packaging bottle is different from that in example 1 in that an adhesive material is formed by mixing an adhesive, HDPE and LLDPE in a mass ratio of 1:3.5: 3.5.
Comparative example 8: a high-barrier pesticide packaging bottle is different from the packaging bottle in the embodiment 1 in that a base material does not contain color masterbatch.
Comparative example 9: the high-barrier pesticide packaging bottle is different from the embodiment 1 in that the base material does not contain nano zinc oxide.
Comparative example 10: a high-barrier pesticide packaging bottle is different from the packaging bottle in the embodiment 1 in that a base material does not contain color master batch and nano zinc oxide.
Comparative example 11: the high-barrier pesticide packaging bottle is different from the packaging bottle in the embodiment 1 in that the base material does not contain nano zinc oxide and polyimide emulsion.
Performance test
Firstly, testing mechanical property and aging resistance: the high-barrier pesticide packaging bottles are prepared according to the methods in examples 1-7 and comparative examples 1-11, and the mechanical property and the aging resistance of the high-barrier pesticide packaging bottles are detected according to the following methods or standards:
1. tensile strength: the test was carried out according to ASTM D638-2003 Standard test method for tensile Properties of plastics, in which three packaging bottles were used for each of examples and comparative examples, the tensile rate was 50mm/min, and the test results are shown in Table 3;
2. impact strength: according to ASTM D256-1997 Standard test method for testing the Izod impact Property of plastics, three packaging bottles were taken for each of the examples and comparative examples, test specimens 5cm in length and 3cm in width were cut from each packaging bottle, and the test results are shown in Table 3;
3. bending strength: the test was carried out according to ASTM D790-2003 Standard test method for the flexibility of reinforced and reinforced plastics and electrically insulating materials, with a bending rate of 10mm/min and the test results shown in Table 3;
4. maximum falling height: each of the examples and comparative examples was made of three packing bottles, the packing bottles were filled with water, left to stand at room temperature (25 ℃) for 6 days, and the bottles were dropped onto a smooth cement floor from a height of every 0.305 m increasing height until the packing bottles were broken, the temperature was controlled at 15 ℃ in the experiment, and the average of the maximum heights that the three packing bottles in each example or comparative example could pass was calculated, and the test results are shown in table 3;
5. aging resistance; reference is made to GB/T16422.3-1997 part 3 of the plastics laboratory light Exposure test method: the test of the fluorescent ultraviolet lamp is carried out, after the packaging bottle is irradiated for 50 hours at 40 ℃ under a helium neon lamp, the breaking elongation retention rate of the packaging bottle is tested, the higher the breaking elongation retention rate is, the stronger the aging resistance is, and the test results are shown in Table 3.
TABLE 3 mechanical, ageing resistance test results for the bottles of examples 1 to 7 and comparative examples 1 to 11
Figure BDA0001876325940000101
Figure BDA0001876325940000111
As can be seen from the data in Table 3, the high barrier property packaging bottles for agricultural chemicals prepared according to the methods of examples 1-7 have high tensile strength, notch impact strength and bending strength, good drop resistance and excellent aging resistance.
Compared with the barrier layer, the adhesive layer and the base layer in the comparative example 1 are relatively thin, so that the packaging bottle is relatively low in tensile strength, notch impact strength and bending strength, the maximum falling height is 3.05 meters, but the breaking elongation retention rate is relatively high, and therefore the barrier layer accounts for 7-9% of the total wall thickness of the high-barrier pesticide packaging bottle, the adhesive layer accounts for 9-11% of the total wall thickness of the high-barrier pesticide packaging bottle, and the base layer accounts for 80-84% of the total wall thickness of the high-barrier pesticide packaging bottle, so that the packaging bottle has good mechanical property, and the packaging bottle has high toughness and falling resistance; in comparative example 2, the thickness of the bonding layer and the base layer is relatively larger than that of the barrier layer, and although the tensile strength, the notch impact strength, the falling-resistant height and the like of the packaging bottle are not much different from those of example 1, the bending strength of the packaging bottle is smaller due to the larger thickness of the bonding layer and the base layer of the packaging bottle, so that the barrier layer accounts for 7-9% of the total wall thickness of the high-barrier pesticide packaging bottle, the bonding layer accounts for 9-11% of the total wall thickness of the high-barrier pesticide packaging bottle, and the base layer accounts for 80-84% of the total wall thickness of the high-barrier pesticide packaging bottle, and the packaging bottle can have.
The comparative examples 3 and 4 have no obvious influence on the mechanical property and the aging resistance of the packaging bottle because the modified montmorillonite and the lotus leaf hydrophobing agent are not added in the barrier material respectively, and the data in the table shows that the modified montmorillonite and the lotus leaf hydrophobing agent are not added; in comparative example 5, as the nano-silica and the aqueous polyurethane-acrylate emulsion are not added to the barrier material, the properties of the packaging bottle, such as tensile strength, bending strength and the like, are poorer than those of the packaging bottle in example 1, but the elongation at break retention rate is not changed much compared with that of the packaging bottle in example 1, which indicates that the nano-silica and the aqueous polyurethane-acrylate emulsion are added to the barrier material, a tough diaphragm can be formed in the barrier layer, the mechanical property of the packaging bottle can be improved, and the aging resistance of the packaging bottle is not affected.
Comparative example 6 shows that the packaging bottle has lower toughness and poor drop resistance due to the fact that the content of HDPE and LLDPE in the adhesive material is relatively less than that of the adhesive, and the packaging bottle has no great influence on various performances compared with example 1 due to the fact that the content of HDPE and LLDPE in the adhesive material is relatively more than that of the adhesive, and the mechanical performance of the packaging bottle can be improved when the mass ratio of the adhesive to HDPE and LLDPE in the adhesive material is 1:2-3: 2-3.
In the comparative example 8, no color master is added into the base material, so that the mechanical property of the packaging bottle is not greatly influenced, but the breaking elongation retention rate of the packaging bottle is low, which indicates that the color master can improve the aging resistance of the packaging bottle; compared with the prior art, the nano zinc oxide is added into the base material in the comparative example 9, so that the strength and toughness of the packaging bottle are poor, the falling-resistant height is only 2.44 meters, and the breaking elongation retention rate is only 60.6%, which shows that the nano zinc oxide can improve the strength and toughness of the packaging bottle, improve the falling-resistant performance of the packaging bottle and enable the packaging bottle to have excellent aging-resistant performance; the base material in the comparative example 10 is not added with the color master and the nano zinc oxide, and the data in the table show that the performance of the packaging bottle prepared by the comparative example 10 is poorer than that of the packaging bottle prepared by the comparative example 8 and the packaging bottle prepared by the comparative example 9, which shows that the color master and the nano zinc oxide are added simultaneously, and can be coordinated with each other, so that the strength and the aging resistance of the packaging bottle are improved; the data show that the packaging bottle has poor tensile strength, bending strength and notch impact strength, small drop-resistant height and poor aging resistance, so that the nano zinc oxide and the polyimide emulsion are mutually matched, and the mechanical property and the aging resistance of the packaging bottle can be improved.
And secondly, testing the anti-permeability barrier property: the high-barrier pesticide packaging bottles are prepared according to the methods in the examples 1 to 7 and the comparative examples 1 to 11, and the anti-barrier property of the high-barrier pesticide packaging bottles is detected according to the following methods or standards:
1. testing of toluene Barrier Properties: the test was conducted in accordance with ASTM D2684/D2684M-2015 penetration test method for thermoplastic containers for packaging reagents or patent products, in which three packaging bottles were used as samples for each of examples and comparative examples, the test results were averaged, the packaging bottles were filled with xylene, sealed, and the weight m of the packaging bottles was weighed1(g) The measuring temperature is 50 ℃, and the weight m of the packaging bottle is tested after 14 days2(g) And testing the weight loss percentage of the packaging bottle to obtain the permeability, which is shown as the following formula: permeability (%) ═ m1-m2)/m1The x is 100%, the smaller the permeability is, the better the barrier property is shown, and the test result is shown in table 4;
2. gasoline or gasoline containing 10% methanol barrier performance test: the test was carried out according to ASTM D2684/D2684M-2015 test method for permeability of thermoplastic containers for packaging reagents or patent products, in which three packaging bottles were used as samples for each of the examples and comparative examples, the test results were averaged, and the mass m of each packaging bottle was measured by sealing 1/2 of the volume of a gasoline package or a gasoline package containing 10% methanol3(g) Standing at 40 deg.C for 14 days, pouring out, adding new gasoline or gasoline containing 10% methanol to 1/2 of the volume of the packaging bottle, sealing, placing into an explosion-proof thermostat at 40 deg.C for 8 weeks, taking out, and measuring the mass m of the packaging bottle4(g) The amount of permeation per day was measured as shown in the following formula: penetration (g/d) ═ m3-m4) 14+ 8X 7, the test results are shown in Table 4.
TABLE 4 Barrier Performance test of high-Barrier pesticide packaging bottles in examples 1-7 and comparative examples 1-11
Figure BDA0001876325940000121
Figure BDA0001876325940000131
As can be seen from the data in Table 4, the high-barrier pesticide packaging bottles prepared according to the methods in examples 1 to 7 have excellent permeation resistance to xylene, the permeation rate is only 0.116 to 0.123%, the permeation amount to gasoline is only 0.0021 to 0.0032g/d, and the permeation amount to gasoline containing 10% of methanol is only 0.014 to 0.017%, so that the high-barrier pesticide packaging bottles prepared according to the invention have excellent permeation resistance and barrier property.
The adhesive layer and the base layer of comparative example 1 have relatively thin thicknesses compared to the barrier layer, so that the thickness of the entire packaging bottle is thin and the permeation resistance of the packaging bottle is poor, thereby illustrating that the thickness ratio of the barrier layer, the adhesive layer and the base layer is 1:0.5-0.8:2-2.5, the packaging bottle has good anti-permeability and barrier properties; in comparative example 2, the thickness of the adhesive layer and the base layer is relatively larger than that of the barrier layer, and the three layers are not tightly matched, so that the anti-permeability performance of the packaging bottle for p-xylene, gasoline and gasoline containing 10% of methanol is poor, which indicates that the thickness ratio of the barrier layer to the adhesive layer to the base layer is 1:0.5-0.8:2-2.5, the packaging bottle has good barrier property.
Comparative example 3 no modified montmorillonite is added in the barrier material, the permeability of the packaging bottle to xylene is 1.287%, the permeability to gasoline is 0.123g/d, and the permeability to gasoline containing 10% methanol is 0.245g/d, compared with example 1, the permeability to xylene is large, the permeability to gasoline is high, which shows that the modified montmorillonite can improve the permeability resistance and the barrier property of the packaging bottle; comparative example 4 no lotus leaf hydrophobing agent is added in the barrier material, the permeability of the packaging bottle to the dimethylbenzene and the permeability to the gasoline are both large, which shows that the lotus leaf hydrophobing agent can improve the anti-permeability performance and the barrier property of the packaging bottle; in the comparative example 5, because the nano silicon dioxide and the aqueous polyurethane-acrylate emulsion are not added to the barrier material, compared with the example 1, the permeation amount of the paraxylene and the gasoline is larger, which shows that the nano silicon dioxide and the aqueous polyurethane-acrylate emulsion are added to the barrier material, a diaphragm with an anti-permeation function can be formed in the barrier layer, and the anti-permeation performance and the barrier performance of the packaging bottle can be improved.
In comparative example 6, the barrier property of the packaging bottle was poor because the contents of HDPE and LLDPE in the adhesive material were relatively small compared to the adhesive, and the barrier property of the packaging bottle was poor because the contents of HDPE and LLDPE in comparative example 7 were relatively large compared to the adhesive, indicating that the barrier property and barrier property of the packaging bottle could be improved only when the mass ratio of the adhesive, HDPE and LLDPE in the adhesive material was 1:2-3: 2-3.
The data show that the leakage rate of the packaging bottle to xylene, the leakage rate to gasoline and the leakage resistance to the packaging bottle containing 10% of methanol are not much better than those of the packaging bottle in example 1, so that the color master, the nano zinc oxide and the polyimide emulsion do not have great influence on the leakage resistance of the packaging bottle.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.

Claims (7)

1. A high-barrier pesticide packaging bottle is characterized in that the high-barrier pesticide packaging bottle is formed by sequentially bonding a barrier layer, a bonding layer and a base layer from inside to outside, wherein two sides of the bonding layer are respectively tightly attached to the barrier layer and the base layer;
the barrier layer is formed by melt blow molding of a barrier material, and the barrier material comprises the following components in parts by weight: 2-2.5 parts of EVOH, 1-3 parts of lotus leaf hydrophobing agent, 2-4 parts of modified montmorillonite, 12-15 parts of N, N-dimethylformamide, 1-3 parts of nano silicon dioxide and 1-5 parts of waterborne polyurethane-acrylate emulsion;
the modified montmorillonite is prepared by the following method: (1) mixing 2-5 parts of sodium montmorillonite with 5-10 parts of deionized water to prepare montmorillonite suspension, adjusting the pH to 1 by using HCl solution, and stirring at 80-85 ℃ for 2-3 h; (2) adding 1-3 parts of dioctadecyl ammonium dichloride, continuously stirring for 2-3h at 80-85 ℃, filtering, washing with deionized water at 40-50 ℃ for repeated washing, and then drying in a thermostat at 80-85 ℃ to prepare organic montmorillonite; (3) dispersing organic montmorillonite in deionized water, stirring uniformly to obtain a solution with the mass fraction of 0.2-0.5%, adding 1-3 parts of coupling agent into the solution, stirring at 40-45 ℃ for 4-5h, drying, grinding and sieving with a 200-mesh sieve;
the bonding layer is formed by melting and blow molding of a bonding material, and the bonding material is formed by mixing a bonding agent, HDPE and LLDPE in a mass ratio of 1:2-3: 2-3;
the base layer is formed by melting and blow molding of a base layer material, and the base layer material is formed by mixing 1-5 parts of HDPE, 0.6-1.0 part of color master, 2-5 parts of nano zinc oxide and 1-5 parts of polyimide emulsion.
2. The high-barrier pesticide packaging bottle as claimed in claim 1, wherein the barrier material is prepared by the following method: dissolving EVOH: adding EVOH and 2/3N, N-dimethylformamide into a reactor, heating while stirring, and heating to 180-190 ℃ to fully dissolve the EVOH;
dissolving modified montmorillonite: dissolving the modified montmorillonite in the rest N, N-dimethylformamide, and mixing uniformly;
mixing: uniformly mixing the nano silicon dioxide and the waterborne polyurethane-acrylate emulsion, adding the dissolved EVOH and the modified montmorillonite, stirring at 80-100 ℃, adding the lotus leaf hydrophobing agent while stirring, and uniformly mixing.
3. The high-barrier pesticide packaging bottle as claimed in claim 1, wherein the coupling agent is a silane coupling agent KH550 with a mass fraction of 5-8%.
4. The high-barrier pesticide packaging bottle as claimed in claim 1, wherein the barrier layer accounts for 7-9% of the total wall thickness of the high-barrier pesticide packaging bottle, the adhesive layer accounts for 9-11% of the total wall thickness of the high-barrier pesticide packaging bottle, and the base layer accounts for 80-84% of the total wall thickness of the high-barrier pesticide packaging bottle.
5. The high-barrier pesticide packaging bottle as claimed in claim 1, wherein the adhesive is one or a mixture of epoxy resin adhesive, vinyl acetate resin adhesive or polyurethane adhesive.
6. The preparation method of the high-barrier pesticide packaging bottle according to any one of claims 1 to 5, characterized by comprising the following steps:
s1, melting raw materials: heating and melting the base material at 180-190 ℃ to obtain a base material melt, adding the bonding material at 160-170 ℃ to melt to obtain a bonding material melt, and melting the barrier material at 180-190 ℃ to obtain a barrier material melt;
s2, extrusion molding: compressing and compacting the base material melt by a screw A, compressing and compacting the bonding material by a screw B, compressing and compacting the barrier material melt by a screw C, simultaneously extruding A, B, C three screws at a constant speed, compounding a material blank by a die head, simultaneously working a left die and a right die, blowing by an inserted rod, and cooling and shaping.
7. The preparation method of the high-barrier pesticide packaging bottle according to claim 6, wherein in the step S2, the rotating speed of the screw A is 40-60r/min, the rotating speed of the screw B is 20-30r/min, and the rotating speed of the screw C is 10-20 r/min.
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