CN112876762B - Pesticide bottle and preparation method thereof - Google Patents

Pesticide bottle and preparation method thereof Download PDF

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Publication number
CN112876762B
CN112876762B CN202110119455.5A CN202110119455A CN112876762B CN 112876762 B CN112876762 B CN 112876762B CN 202110119455 A CN202110119455 A CN 202110119455A CN 112876762 B CN112876762 B CN 112876762B
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parts
layer
mixing
agent
pesticide bottle
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CN112876762A (en
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代人委
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
    • C08L23/06—Polyethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C08K3/34—Silicon-containing compounds
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • 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 other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • C08L23/0861—Saponified vinylacetate
    • 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
    • C09J103/00—Adhesives based on starch, amylose or amylopectin or on their derivatives or degradation products
    • C09J103/02—Starch; Degradation products thereof, e.g. dextrin
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • 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
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils

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  • Chemical & Material Sciences (AREA)
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  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The application relates to the technical field of pesticide packaging, and particularly discloses a pesticide bottle and a preparation method thereof, wherein the pesticide bottle comprises the following raw materials in parts by weight: the inner layer, the first bonding layer, the middle layer, the second bonding layer and the outer layer are respectively arranged from the inner layer to the outer layer; the inner layer comprises the following raw materials in parts by weight: 20-25 parts of HDPE, 3-5 parts of PE, 2-3 parts of reinforcing agent, 3-5 parts of anti-cracking agent, 0.5-1 part of wollastonite, 0.1-0.2 part of dispersing agent, 1-2 parts of calcium carbonate and 0.3-0.5 part of titanate coupling agent; the reinforcing agent consists of titanium dioxide, alginate fiber and coconut shell fiber; the preparation method comprises the following steps: respectively mixing the raw materials of the inner layer, the middle layer, the first bonding layer, the second bonding layer and the outer layer, and uniformly mixing to obtain an inner layer material, a middle layer material, a first bonding layer material, a second bonding layer material and an outer layer material; respectively carrying out melt extrusion on the raw materials of each layer, and then carrying out blow molding, cooling and shaping and external renovation to obtain pesticide bottles; the pesticide bottle in this application has the advantage that intensity is high.

Description

Pesticide bottle and preparation method thereof
Technical Field
The application relates to the technical field of pesticide packaging, in particular to a pesticide bottle and a preparation method thereof.
Background
China is a big agricultural country, and the annual demand of pesticides is very large; for a long time, liquid pesticides are mainly packaged by glass bottles; however, the glass bottles also have several problems: 1. the pesticide bottle made of glass is used from factory to farmer, the breakage rate generally reaches 10-20%, and the pesticide bottle is easy to damage; 2. the glass bottle has heavier tare weight, which increases the transportation cost; in order to improve the problems of pesticide bottles, after the 90 s of the 20 th century, glass packaging bottles are gradually replaced by plastic materials.
At present, most of pesticide plastic bottles are mainly produced by adopting a multilayer coextrusion blow molding method, and the prepared pesticide bottles are multilayer coextrusion bottles; common three-layer co-extrusion bottles, five-layer co-extrusion bottles and the like are provided; wherein the three-layer co-extrusion bottle has three layers, and consists of PA plastic, a bonding layer and PE plastic from the inner layer to the outer layer; an EVOH five-layer co-extrusion bottle comprises a PE layer, a first bonding layer, an EVOH layer, a second bonding layer and a PE layer from the inner layer to the outer layer.
To the correlation technique among the above-mentioned, multilayer is crowded bottle altogether and is constituteed through multiple resin that has barrier property, has better separation effect, but in the transportation, the pesticide bottle receives too big or fall under pressure, causes the pesticide bottle damaged easily, and intensity remains to improve.
Disclosure of Invention
In order to improve the strength of the pesticide bottle, the application provides the pesticide bottle and the preparation method thereof.
In a first aspect, the application provides a pesticide bottle, which adopts the following technical scheme:
an agricultural medicine bottle comprises an inner layer, a first bonding layer, a middle layer, a second bonding layer and an outer layer from the inner layer to the outer layer; the inner layer comprises the following raw materials in parts by weight:
20-25 parts of HDPE;
3-5 parts of PE;
2-3 parts of a reinforcing agent;
3-5 parts of an anti-cracking agent;
0.5-1 part of wollastonite;
0.1-0.2 part of dispersant;
1-2 parts of calcium carbonate;
0.3-0.5 part of titanate coupling agent;
the reinforcing agent consists of titanium dioxide, alginate fibers and coconut shell fibers.
By adopting the technical scheme, the HDPE and the PE are adopted as the main raw materials of the inner layer, and the HDPE and the PE are combined, so that the anti-impact pesticide bottle has better impact resistance and better chemical resistance, and pesticide is prevented from reacting with the inner layer of the pesticide bottle, so that the blocking effect of the pesticide bottle is improved; the reinforcing agent adopts titanium dioxide, alginate fiber and coconut shell fiber, and the chemical properties of the titanium dioxide, the alginate fiber and the coconut shell fiber are extremely stable; the titanium dioxide is added and then is matched with other raw materials, so that the mechanical strength of the inner layer of the pesticide bottle is increased; the cellulose content in the seaweed fiber and the coconut fiber is high, and the seaweed fiber and the coconut fiber have good mechanical properties after being mixed with titanium dioxide; the reinforcing agent consists of titanium dioxide, alginate fiber and coconut fiber, and is matched with HDPE and PE, so that the strength of the pesticide bottle is improved, and the pesticide bottle is prevented from being damaged in the transportation process; the anti-cracking agent and the reinforcing agent act together to further improve the strength of the pesticide bottle; wollastonite and calcium carbonate are used as fillers for filling the inner layer of the pesticide bottle, so that the toughness of the inner layer is enhanced, and the strength of the inner layer is improved; the dispersing agent has better dispersing capacity, and the integral uniformity of the inner layer raw material is enhanced by mixing the dispersing agent with the raw materials such as titanium dioxide, alginate fiber, coconut shell fiber and the like; the titanate coupling agent has better coupling effect, and simultaneously treats the surfaces of wollastonite and calcium carbonate which are inorganic fillers, so that the affinity of the inorganic fillers with HDPE and PE is improved; in conclusion, HDPE and PE are used as main inner layer raw materials, and reinforcing agents, crack resistance agents and other raw materials composed of titanium dioxide, alginate fibers and coconut shell fibers are added to be matched together, so that the toughness of the pesticide bottle is enhanced, and the strength of the pesticide bottle is improved; the damage of the pesticide in the transportation process is avoided, the cost is saved, and the environment is protected.
Preferably, the anti-cracking agent is prepared from the following raw materials in parts by weight:
0.3-0.5 part of rubber powder;
0.6-0.8 part of bamboo fiber;
1-1.4 parts of maleic anhydride grafted polyolefin;
0.8-1.5 parts of acrylate emulsion;
the balance of deionized water.
By adopting the technical scheme, the rubber powder has better elasticity, generates deformation under the action of pressure and has certain impact strength; bamboo fiber is used as cellulose fiber extracted from bamboo, and is matched with rubber powder, so that the toughness of the inner layer of the pesticide bottle is enhanced, and the strength of the inner layer is improved; the maleic anhydride grafted polyolefin is used as an elastomer and is matched with rubber powder, bamboo fiber and acrylate emulsion together, so that the condition that the inner layer of the pesticide bottle is cracked is reduced; in addition, the uniformly mixed anti-cracking agent is further matched with the reinforcing agent, HDPE and PE, so that the toughness of the inner layer of the pesticide bottle is further enhanced, and the strength of the inner layer is improved.
Preferably, the preparation steps of the anti-cracking agent are as follows:
(1) mixing deionized water, bamboo fiber and rubber powder, and uniformly mixing to obtain a first mixture;
(2) mixing the acrylate emulsion with maleic anhydride grafted polyolefin, and uniformly mixing to obtain a second mixture;
(3) and mixing the first mixture and the second mixture, heating to 55-65 ℃, and uniformly mixing to obtain the anti-cracking agent.
By adopting the technical scheme, the anti-cracking agent after mixing is better in uniformity and more sufficient in mixing, so that the anti-cracking agent is matched with a reinforcing agent, the strength of the pesticide bottle is further improved, and the toughness of the pesticide bottle is enhanced.
Preferably, the dispersing agent comprises at least one of magnesium stearate and zinc stearate.
By adopting the technical scheme, the dispersing agent is preferably at least one of magnesium stearate and zinc stearate, so that the dispersing effect is better, the agglomeration of the raw materials of the inner layer is reduced, and the raw materials of the inner layer are uniformly dispersed after being mixed; in addition, the lubricating and demolding agent also has better lubricating and demolding effects, and is favorable for demolding treatment of the pesticide bottles at the later stage.
Preferably, the raw materials of the middle layer comprise 1-3 parts of elm bark powder and 5-8 parts of EVOH.
By adopting the technical scheme, the elm bark powder is used as a plant-type adhesive, and the barrier property of the middle layer is further enhanced through the action of EVOH with the barrier effect, so that the strength of the middle layer of the pesticide bottle is improved.
Preferably, the weight part ratio of the elm bark powder to the EVOH is 1 (3-4).
By adopting the technical scheme, the middle layer raw materials are preferably proportioned and have better barrier property and strength after being matched with each other.
Preferably, the first bonding layer and the second bonding layer are both composed of the following raw materials in parts by weight:
5-6 parts of acrylate emulsion;
2-4 parts of epoxy resin;
2-3 parts of cassava starch;
1-2 parts of gleditsia sinensis lam vegetable gum.
By adopting the technical scheme, the acrylate emulsion and the epoxy resin are matched, so that the adhesive has better bonding and anti-permeability performance; cassava starch and gleditsia sinensis plant gum are used as excellent binders, and are matched with the acrylate emulsion and the epoxy resin together to enhance the binding power and toughness of the first bonding layer and the second bonding layer, so that the inner layer, the middle layer and the outer layer are tightly bonded, and the blocking effect and the toughening strength are improved.
Preferably, the outer layer comprises the following raw materials in parts by weight:
4-5 parts of HDPE;
0.5-0.8 part of glass fiber;
0.3-0.5 part of talcum powder.
By adopting the technical scheme, HDPE is used as an excellent wear-resistant high-toughness material, and is combined with glass fiber and talcum powder with higher strength, so that the strength of the outer layer is improved; in the transportation, pesticide bottle's skin at first receives the impact, through HDPE, glass fiber, talcum powder cooperation, improves outer shock strength, and then the damage problem appears in the protection pesticide bottle transportation.
In a second aspect, the application provides a method for preparing pesticide bottles, which adopts the following technical scheme:
a preparation method of a pesticide bottle comprises the following steps:
s1, mixing HDPE, PE, a reinforcing agent, an anti-cracking agent, wollastonite, a dispersing agent, calcium carbonate and a titanate coupling agent, and uniformly mixing to obtain an inner layer material; mixing elm bark powder and EVOH, and uniformly mixing to obtain a middle-layer material; mixing the acrylate emulsion, the epoxy resin, the cassava starch and the gleditsia sinensis lam vegetable gum uniformly to obtain a first bonding layer material and a second bonding layer material; mixing HDPE, glass fiber and talcum powder, and uniformly mixing to obtain an outer layer material;
s2, respectively melting and extruding the inner layer material, the middle layer material, the first bonding layer material, the second bonding layer material and the outer layer material;
and S3, performing blow molding after extrusion, cooling and shaping, and performing external renovation to obtain the pesticide bottle.
By adopting the technical scheme, the raw materials of each layer are firstly uniformly mixed, and then are subjected to melt extrusion, blow molding, cooling and shaping and external renovation to obtain the pesticide bottle.
Preferably, the temperature in the melt extrusion of the step S2 is controlled to be 180-220 ℃, and the heating time is 8-12 min.
By adopting the technical scheme, when a lower temperature is adopted, the raw materials of each layer cannot form a molten state, so that the mixing effect is poor; when the temperature is higher, more power is consumed, and the cost is higher; by adopting the temperature and the heating time, the cost is saved and the production efficiency is improved while the raw materials of each layer are uniformly mixed.
In summary, the present application has the following beneficial effects:
1. the HDPE and the PE are used as main raw materials of the inner layer, and the reinforcing agent, the anti-cracking agent and other auxiliaries are added and matched together, so that the toughness of the pesticide bottle is enhanced, and the strength of the pesticide bottle is improved; the reinforcing agent preferably adopts titanium dioxide, alginate fiber and coconut shell fiber, and the titanium dioxide, the alginate fiber and the coconut shell fiber have stable chemical properties and have higher mechanical strength after being matched, so that the reinforcing agent is matched with HDPE and PE to reinforce the toughness of the pesticide bottle and improve the strength of the pesticide bottle; the damage of the pesticide in the transportation process is avoided, the cost is saved, and the environment is protected.
2. In the application, an anti-cracking agent consisting of rubber powder, bamboo fiber, maleic anhydride grafted polyolefin and acrylic emulsion is preferably adopted, and various raw materials are matched with each other, so that the toughness of the inner layer of the pesticide bottle is enhanced, the strength of the inner layer is improved, and the pesticide bottle is prevented from cracking; the dispersing agent preferably adopts at least one of magnesium stearate and zinc stearate, so that the agglomeration of the inner layer raw material is reduced; the middle layer is made of elm bark powder and EVOH, so that the barrier property of the middle layer is enhanced, and the strength of the middle layer of the pesticide bottle is improved; the first bonding layer and the second bonding layer are both composed of acrylate emulsion, epoxy resin, cassava starch and gleditsia sinensis gum, so that the inner layer, the middle layer and the outer layer are tightly bonded, and the barrier effect and the toughening strength are improved; HDPE, glass fiber and talcum powder are selected for use to the outer layer to constitute, and the cooperation between the five layers strengthens pesticide bottle's toughness jointly, improves pesticide bottle's intensity.
3. The method comprises the steps of uniformly mixing raw materials of all layers, performing melt extrusion, blow molding, cooling and shaping, and performing external renovation to obtain the pesticide bottle; the preparation method ensures that the toughness and the strength of the prepared pesticide bottle are uniformly distributed, and has the advantages of simple process, higher efficiency and cost saving.
Detailed Description
The present application is described in further detail below.
The components and manufacturers in the examples are shown in Table 1.
TABLE 1 Components and manufacturers
Components/apparatus Model/specification Manufacturer of the product
HDPE DMDH-6400NT7 Super Wang Plastic Material Co Ltd of Dongguan City
PE MG12 Suzhouxinyuan plastics Co Ltd
Titanium white powder R-996 Jinan Baoli gold chemical Co Ltd
Alginate fiber 40HZ Fushan City Zhencai textile Co Ltd
Coconut shell fiber 188 Qingdao Onyang International Logistics Ltd
Wollastonite 6531 Shijiazhuang Ruina mineral products Co Ltd
Paraffin wax Number 64 Cangzhou bee wing wax company Ltd
Calcium carbonate / Ling shou county Tulin mineral processing factory
Titanate coupling agent NDZ-201 Dongguan city Dinghai plastic chemical Co., Ltd
Bamboo fiber 29 Shandong Aoyun clothing Co Ltd
Maleic anhydride grafted polyolefins -VA-1202 Dongguan City plastics Material Co Ltd
Acrylic ester emulsion 602 Qingdao Zhuandida architecture science and technology Co Ltd
Magnesium stearate kang666 Shaanxi Yuanyu Biotech Co Ltd
Calcium stearate sxcfd Hubei hongtao bioengineering Limited
Elm bark powder ysx Gansu Probiotics Biotech Ltd
EVOH G176B Dongguan city Jintian Plastic Material Co., Ltd
Epoxy resin E-44 Hebei Onsheng building materials Ltd
Cassava starch 54769 Chengdu Viention Hongrun Biotech Co., Ltd
Gleditsia sinensis plant gum 123-41-1 Shanghai Crane-Shikusho Co Ltd
Glass fiber 002 Shandong Rentai New energy GmbH
Talcum powder 600 mesh, whiteness 85 Guishou county Jiashuo building materials processing Co Ltd
Glyceryl monostearate 31566-31-1 Hubeixin run de chemical Co., Ltd
Stirring tank 2000 One sail machine, Inc. of Laizhou
Screw extruder SJ4520 Shanghai Xiangchun electric appliances Co Ltd
Blow molding machine 45L Dongguang county Jincheng machinery manufacturing Co., Ltd
Preparation example
Preparation example 1 an anti-cracking agent comprising the specific components and weights shown in table 2 was prepared by the following steps:
(1) adding deionized water and rubber powder into a stirring tank and stirring at the stirring speed of 800 r/min; uniformly stirring to obtain a first mixture;
(2) and mixing the first mixture with acrylic emulsion, controlling the temperature to be 55 ℃, stirring at the stirring speed of 1000r/min, and uniformly stirring to obtain the anti-cracking agent.
Preparation example 2 an anti-cracking agent, comprising the specific components and weights shown in table 2, was prepared by the following steps:
(1) adding deionized water, bamboo fiber and rubber powder into a stirring tank for stirring at the stirring speed of 900r/min, and uniformly stirring to obtain a first mixture;
(2) mixing and stirring the acrylate emulsion and the maleic anhydride grafted polyolefin in another stirring tank at the stirring speed of 900r/min to obtain a second mixture after uniform stirring;
(3) and mixing and stirring the first mixture and the second mixture, heating to 55 ℃, controlling the stirring speed to be 1200r/min, and uniformly stirring to obtain the anti-cracking agent.
Preparation example 3 an anti-cracking agent was distinguished from preparation example 2 in that the weight of each component was different, and the specific components and weights included were as shown in table 2.
TABLE 2 specific compositions and weights of preparation examples 1-3
Figure BDA0002921451260000061
Preparation example 4 an anti-cracking agent, which is different from example 2 in that the temperature was raised to 65 ℃ in step (3).
Examples
Example 1:
a pesticide bottle comprises the following specific components by weight as shown in Table 3, and is prepared by the following steps:
s1, stirring HDPE, PE, a reinforcing agent, the anti-cracking agent prepared in the preparation example 1, wollastonite, a dispersant glyceryl monostearate, calcium carbonate and a titanate coupling agent in a stirring tank at the stirring speed of 1000r/min, and uniformly stirring to obtain an inner layer material; the middle layer material consists of EVOH; mixing and stirring the acrylate emulsion, the epoxy resin, the cassava starch and the gleditsia sinensis lam vegetable gum at the stirring speed of 1200r/min, and respectively obtaining a first bonding layer material and a second bonding layer material after uniformly stirring; mixing and stirring HDPE, glass fiber and talcum powder at the stirring speed of 1000r/min, and uniformly stirring to obtain an outer layer material;
s2, respectively carrying out melt extrusion on the obtained inner layer material, middle layer material, first bonding layer material, second bonding layer material and outer layer material in corresponding screw extruders; wherein the melting temperature of the inner layer is 220 ℃, the melting temperatures of the first bonding layer and the second bonding layer are both 180 ℃, the melting temperature of the barrier layer is 200 ℃, the melting temperature of the outer layer is 200 ℃, and the heating time is 8 min; wherein the thickness ratio of the layers is 1:1.5:4:1.5:6, and the thickness of the inner layer is 0.35 mm;
and S3, performing blow molding by a blow molding machine under the air pressure of 6kg after extrusion, cooling and shaping, and finishing the outer corners to obtain the pesticide bottles.
Example 2 a pesticide bottle was distinguished from example 1 in that the weight of each component was varied, and the specific components included and their weights are shown in table 3.
Example 3 a pesticide bottle, which is different from example 1 in that an anti-cracking agent was prepared according to preparation example 2.
Example 4 a pesticide bottle, which is different from example 1 in that an anti-cracking agent was prepared according to preparation example 3.
Example 5 a pesticide bottle, which is different from example 1 in that an anti-cracking agent was prepared according to preparation example 4.
Examples 6 to 7 a pesticide bottle, which is different from example 1 in the dispersant components and the weight ratio, was comprised of the specific components and weights shown in table 3.
Examples 8 to 9 a pesticide bottle, which is different from example 1 in the composition and weight of the middle layer, was comprised of the specific components and weights shown in table 3.
TABLE 3 specific compositions and weights of examples 1-2, examples 6-9
Figure BDA0002921451260000071
Figure BDA0002921451260000081
Examples 10 to 11A pesticide bottle is different from example 9 in that the weight of each component in the middle layer is different and the specific components and weights included are shown in Table 4.
Examples 12 to 13A pesticide bottle, which is different from example 1 in that the first adhesive layer and the second adhesive layer have different compositions and weights, and specific compositions and weights thereof are contained as shown in Table 4.
Examples 14 to 15 a pesticide bottle, which is different from example 1 in the composition and weight of the outer layer, was comprised of the specific components and weights shown in table 4.
Examples 16 to 17A pesticide bottle is different from example 5 in that each component and weight are different, and the specific components and weights are included as shown in Table 4.
TABLE 4 specific compositions and weights of examples 10-17
Figure BDA0002921451260000082
Figure BDA0002921451260000091
Example 18A pesticide bottle as distinguished from example 17 in that the inner layer had a melting temperature of 210 deg.C, the first and second adhesive layers had melting temperatures of 180 deg.C, the barrier layer had a melting temperature of 210 deg.C, the outer layer had a melting temperature of 220 deg.C, and the heating time was 8 min.
Comparative example
Comparative example 1 a pesticide bottle, which is different from example 1 in that the reinforcing agent does not contain titanium dioxide.
Comparative example 2 a pesticide bottle was distinguished from example 1 in that the reinforcing agent did not contain titanium dioxide powder and coconut shell fiber.
Comparative example 3 a pesticide bottle was different from example 1 in that the reinforcing agent did not contain titanium dioxide and alginate fibers.
Comparative example 4 a pesticide bottle was distinguished from example 1 in that it did not contain an anti-cracking agent.
Comparative example 5 a pesticide bottle was distinguished from example 1 in that it did not contain reinforcing agent and anti-cracking agent.
Comparative example 6 a pesticide bottle was made by the following steps:
(1) preparing modified titanium dioxide: uniformly mixing titanium dioxide, a melt strength enhancer, namely tripropyl citrate and a lubricant, namely stearic acid, according to a mass ratio of 21:5:1, heating to completely melt, and uniformly stirring to obtain modified titanium dioxide;
(2) preparing a color change preventing agent: adding polyoxyethylene stearate and polycaprolactam powder into a ball mill according to the ratio of 2:1, and performing ball milling treatment for 35min to obtain a color change preventing agent;
(3) manufacturing a bottle blank mold: the bottle blank mold is prepared by injecting a melting material into a mold by using an injection machine, 70kg of PET powder, 13kg of modified titanium dioxide and 3kg of anti-color-change agent are sent into a heated charging barrel from a hopper of the injection machine, after heating, melting and plasticizing, the material is compressed and moves forwards by virtue of the thrust of a plunger or a screw, the material is injected into a closed mold cavity through a nozzle at the front end of the charging barrel, and after cooling and shaping, the mold is opened to obtain a product;
(4) the bottle blanks are sequenced and then sequentially enter an integrated bottle blowing machine, a bottle blank star wheel is arranged on the integrated bottle blowing machine, and workpieces are sequentially transmitted to a conveying chain wheel through the bottle blank star wheel; conveying the bottle blanks to a heating mechanism by a conveying chain wheel to heat the bottle blanks, wherein the bottle blanks are conveyed to a bottle blowing machine after being heated by the heating mechanism which adopts a drying oven;
(5) step five: carrying out bottle blowing operation, namely placing the preheated bottle blank into a prepared mould, carrying out high-pressure inflation on the bottle blank, and carrying out blowing and drawing on the bottle blank into a required bottle, wherein the blowing process of a bottle blowing machine is a bidirectional stretching process, and PET chains are bidirectionally extended, oriented and arranged in the bidirectional stretching process; and taking out the bottle body after blowing from the bottle blowing machine.
Detection method
Experiment one: impact strength test experimental samples: samples of 80X 10X 4mm are manufactured according to examples 1-18 and comparative examples 1-6, a notch with the depth of 2mm is manufactured at the edge of the middle position of the length of the sample, the notch is 45 degrees, and the radius of the bottom of the notch is 0.25 mm; notched bar specimens produced in examples 1 to 18 were designated as test samples 1 to 18, respectively, and notched bar specimens produced in comparative examples 1 to 6 were designated as comparative samples 1 to 6, respectively; there were 5 for each experimental sample.
An experimental instrument: cantilever beam impact tester (model FR-1809B-22, Shanghai hair instruments science and technology Co., Ltd.).
The experimental method comprises the following steps: the impact strength performance of the experimental samples 1-18 and the comparative samples 1-6 is tested according to the determination of the plastic cantilever beam impact strength of the national standard GB/T1843-2008;
firstly, lifting and locking a pendulum bob, installing an experimental sample, wherein a notch is arranged on one side of an impact edge of the pendulum bob; releasing the pendulum bob and recording the impact energy absorbed by the experimental sample; and necessary correction is made for the friction loss and the like.
Taking the average value of the shock resistance of each experimental sample as the final data of the shock resistance of the experimental sample; for example, after 5 test samples 1 are tested, the average of 5 data is taken as the final impact resistance data of the test sample 1.
The experimental results are as follows: the results of the test impact strength tests of the test samples 1 to 18 and the comparative samples 1 to 6 are shown in Table 5.
Experiment two: tensile strength test experimental samples: examples 1 to 18 and comparative examples 1 to 6 were cut into a shape prescribed in GB1039, and samples cut from examples 1 to 18 were designated as experimental samples 1 to 18, respectively, and samples cut from comparative examples 1 to 6 were designated as comparative samples 1 to 6, respectively; there were 5 for each experimental sample.
An experimental instrument: tensile strength tester (Hecheng brand, model HS-3004B-S).
The experimental method comprises the following steps: the tensile strength of the experimental samples 1-18 and the comparative samples 1-6 is tested by referring to the tensile strength test in the plastic tensile property test method of the national standard GB 1040-92;
firstly, adjusting an experimental sample according to the regulation of GB 2918, and then measuring the width and the thickness of a test; and after the test is finished, clamping the experimental sample by using a clamp, selecting the test speed to be 10mm/min, and recording the maximum tensile strength of the experimental sample until the experimental sample is broken.
Taking the average value of the tensile strength of each experimental sample as the final data of the tensile strength of the experimental sample; for example, after 5 test samples 1 are tested, the average of the 5 data is taken as the final tensile strength data of the test sample 1.
The experimental results are as follows: the results of the tensile strength tests for the test samples 1-18 and the comparative samples 1-6 are shown in Table 5.
Experiment three: experimental sample of Barrier Property: the pesticide bottles of examples 1 to 18 and comparative examples 1 to 6 are consistent in size and 500mL in volume; the pesticide bottles of examples 1 to 18 were respectively named as experimental samples 1 to 18, and the pesticide bottles of comparative examples 1 to 6 were respectively named as comparative samples 1 to 6; there were 5 for each experimental sample.
An experimental instrument: balance (goods number JTS-A-precision electronic balance; the manufacturer is Qingdao Yu constant weighing apparatus Co., Ltd.) the experimental method: the experimental samples 1-18 and the comparative sample 1-6, filling gasoline with the height of 2/3 of the pesticide bottle, and sealing; weighing the pesticide bottle filled with gasoline by a balance to obtain m1(ii) a Standing at 50 deg.C for 20 days, weighing pesticide bottle again to weight m2(ii) a The permeability is calculated as (m)1-m2)/m1X 100%. Taking the average value of the permeability of each experimental sample as the final data of the permeability of the experimental sample; for example, after 5 test samples 1 are tested, the average of the 5 data is taken as the final barrier performance data of the test sample 1.
The experimental results are as follows: the results of the barrier performance tests for test samples 1-18 and comparative samples 1-6 are shown in table 5.
TABLE 5 impact strength, tensile strength, and barrier performance results for experimental samples 1-18 and comparative samples 1-6
Figure BDA0002921451260000111
As can be seen from Table 5, the impact strengths of the experimental samples 1 to 18 were 36.3 to 39.8kJ/m2While the impact strength of the comparative sample is only 15.8-31.4kJ/m2The experimental samples 1-18 demonstrated better impact strength than the comparative samples 1-6; the tensile strengths of the experimental samples 1-18 were 38.1-41.4MPa, while the tensile strength of the comparative samples was only 16.9-33.5MPa, indicating that the tensile strengths of the experimental samples 1-18 were better than the tensile strengths of the comparative samples 1-6; the experimental samples 1-18 have better strength, and are not easy to break in the transportation process; the permeability of experimental samples 1-18 is lower compared to comparative examples 1-6, indicating that the barrier properties of experimental samples 1-18 are better.
Comparing the experimental sample 1 with the comparative sample 1, it can be seen that after the titanium dioxide is added, the impact strength and the tensile strength of the experimental sample 1 are both improved, and the permeability is also lower, which indicates that the titanium dioxide has better capability of improving the impact strength and the tensile strength of the pesticide bottle, and is also helpful for improving the barrier effect of the pesticide bottle. The titanium dioxide has better hardness and stability, and is matched with HDPE and PE, so that the problem of poor strength of the inner layer of the pesticide bottle is solved; the alginate fiber and the coconut fiber have high cellulose content and a multicellular aggregation structure, so that the alginate fiber and the coconut fiber have excellent mechanical properties, and the impact strength and the tensile strength of the inner layer of the pesticide bottle are improved together by matching with titanium dioxide.
As can be seen from comparison of the experimental sample 1 and the comparative samples 2 to 3, when the reinforcing agent contains only the alginate fiber, the impact strength and the tensile strength are poor; when the reinforcing agent only contains the coconut fibers, the impact strength and the tensile strength are poor; the larger the amplitude of improving the impact strength and the tensile strength of the pesticide bottle is after the titanium dioxide, the alginate fiber and the coconut shell fiber are matched together; the alginate fiber and the coconut fiber have high cellulose content and a multicellular aggregation structure, so that the alginate fiber and the coconut fiber have excellent mechanical properties, and the impact strength and the tensile strength of the inner layer of the pesticide bottle are improved together by matching with titanium dioxide.
Comparing the experimental sample 1 and the comparative sample 4, it can be known that the impact strength and the tensile strength of the pesticide bottle are reduced to a certain extent after the anti-cracking agent is not added; compared with the experimental sample 1 and the comparative sample 5, the impact strength, the tensile strength and the barrier property of the pesticide bottle are improved to a certain extent after the pesticide bottle does not contain the reinforcing agent and the anti-cracking agent, and the matching effect of the two is more obvious;
comparing the experimental sample 1 and the comparative sample 6 shows that the pesticide bottle manufactured by using the formulation of the application has better toughness and impact resistance than the pesticide bottle of the comparative sample 6, which indicates that the pesticide bottle is not easy to break in the transportation process.
Comparing the experimental sample 1 with the experimental samples 3-5, the anti-cracking agent is beneficial to improving the impact strength and the tensile strength of the pesticide bottle after adopting a complete formula; the rubber powder has good elasticity and certain impact resistance under the action of pressure, the bamboo fiber has good wear resistance, and the toughness of the inner layer of the pesticide bottle is enhanced and the strength of the inner layer is improved by matching with the rubber powder; the maleic anhydride grafted polyolefin can improve the compatibility of the coconut shell fiber, the alginate fiber and the HDPE, so that the impact strength and the tensile strength of the inner layer are improved; comparing the experimental sample 1 and the comparative samples 6 to 7, it can be seen that after the dispersing agent is preferably magnesium stearate or calcium stearate, the impact strength and the tensile strength of the pesticide bottle are partially improved; the dispersing agents magnesium stearate and calcium stearate have the dual characteristics of metal salt and stearic acid, are suitable for the inner layer of the pesticide bottle and are beneficial to improving the dispersibility of the inner layer. Comparing the experimental sample 1 with the comparative samples 8-9, it can be seen that after the elm bark powder and the EVOH are preferably adopted for the middle layer to be mixed, the impact strength and the tensile strength of the pesticide bottle are partially improved, and meanwhile, the permeability is low, so that the barrier property of the pesticide bottle is also good; EVOH is used as a high-barrier material and has strong oil resistance and organic solvent resistance; the elm bark powder is used as a plant processing product, the main component of the polypentaose polymer chain contains a plurality of hydroxyl groups, and the adsorption capacity is very strong, so that the polypentaose polymer chain is matched with EVOH to form a high-viscoelasticity middle layer, further the impact strength and the tensile strength of the middle layer of the pesticide bottle are improved, and the barrier property is enhanced. Comparing the experimental samples 9-11, it can be seen that the ratio of the middle layer raw material, i.e. the weight ratio of elm bark powder to EVOH, is 1 (3-4), the greater the increase of the impact strength and tensile strength of the pesticide bottle; comparing the experimental sample 1 with the experimental samples 12-13, the first bonding layer and the second bonding layer are preferably composed of acrylate emulsion, epoxy resin, tapioca starch and gleditsia sinensis plant gum, and the impact strength and the tensile strength of the pesticide bottle are partially improved; the acrylic ester emulsion and the epoxy resin both have good viscosity, the cassava starch and the gleditsia sinensis lam gum are used as plant substances, the ratio of amylopectin to amylose in the cassava starch is high, and the cassava starch has good viscosity; the gleditsia sinensis gum is a polysaccharide polymer, belongs to a high-molecular complex compound, and can form a colloidal solution, so that the gleditsia sinensis gum has good viscosity; the first adhesive layer and the second adhesive layer which are made of acrylate emulsion, epoxy resin, cassava starch and gleditsia sinensis plant gum have good adhesive capacity with the inner layer, the middle layer and the outer layer, so that the tensile strength of the pesticide bottle is improved.
Comparing the experimental sample 1 with the comparative samples 14-15, it can be known that the addition of the glass fiber and the talcum powder to the outer layer component is helpful to improve the impact strength and the tensile strength of the pesticide bottle; the strength of the glass fiber is far higher than that of natural plant fiber, so that the glass fiber is matched with talcum powder and HDPE to improve the hardness of the outer layer of the pesticide bottle; comparing the experimental sample 5 with the experimental samples 16-17, it can be seen that after the raw materials of each layer of the pesticide bottle are optimized, the impact strength, the tensile strength and the barrier property of the pesticide bottle are improved to a certain extent; comparing the experimental sample 1 and the experimental sample 18, it can be seen that controlling the melting temperature of each layer also helps to improve the impact strength and tensile strength of the pesticide bottle.
The present embodiment is only for explaining the present application, and it is not limited to the present application, 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 application.

Claims (3)

1. A pesticide bottle is characterized in that an inner layer, a first bonding layer, a middle layer, a second bonding layer and an outer layer are respectively arranged from the inner layer to the outer layer;
the inner layer comprises the following raw materials in parts by weight:
20-25 parts of HDPE;
3-5 parts of PE;
2-3 parts of a reinforcing agent;
3-5 parts of an anti-cracking agent;
0.5-1 part of wollastonite;
0.1-0.2 part of dispersant;
1-2 parts of calcium carbonate;
0.3-0.5 part of titanate coupling agent;
the reinforcing agent consists of titanium dioxide, alginate fibers and coconut shell fibers;
the anti-cracking agent is prepared from the following raw materials in parts by weight:
0.3-0.5 part of rubber powder;
0.6-0.8 part of bamboo fiber;
1-1.4 parts of maleic anhydride grafted polyolefin;
0.8-1.5 parts of acrylate emulsion;
the balance of deionized water;
the preparation steps of the anti-cracking agent are as follows:
(1) mixing deionized water, bamboo fiber and rubber powder, and uniformly mixing to obtain a first mixture;
(2) mixing the acrylate emulsion with maleic anhydride grafted polyolefin, and uniformly mixing to obtain a second mixture;
(3) mixing the first mixture and the second mixture, heating to 55-65 ℃, and uniformly mixing to obtain the anti-cracking agent;
the dispersing agent comprises at least one of magnesium stearate and zinc stearate;
the middle layer is made of 1-3 parts of elm bark powder and 5-8 parts of EVOH;
the weight part ratio of the elm bark powder to the EVOH is 1 (3-4);
the first bonding layer and the second bonding layer are respectively composed of the following raw materials in parts by weight:
5-6 parts of acrylate emulsion;
2-4 parts of epoxy resin;
2-3 parts of cassava starch;
1-2 parts of gleditsia sinensis lam vegetable gum;
the outer layer comprises the following raw materials in parts by weight:
4-5 parts of HDPE;
0.5-0.8 part of glass fiber;
0.3-0.5 part of talcum powder;
the model of the HDPE is DMDH-6400NT7;
the PE is MG 12.
2. The method of manufacturing a pesticide bottle as set forth in claim 1, comprising the steps of:
s1, mixing HDPE, PE, a reinforcing agent, an anti-cracking agent, wollastonite, a dispersing agent, calcium carbonate and a titanate coupling agent, and uniformly mixing to obtain an inner layer material; mixing elm bark powder and EVOH, and uniformly mixing to obtain a middle-layer material; mixing the acrylate emulsion, the epoxy resin, the cassava starch and the gleditsia sinensis lam vegetable gum uniformly to obtain a first bonding layer material and a second bonding layer material; mixing HDPE, glass fiber and talcum powder, and uniformly mixing to obtain an outer layer material;
s2, respectively melting and extruding the inner layer material, the middle layer material, the first bonding layer material, the second bonding layer material and the outer layer material;
and S3, performing blow molding after extrusion, cooling and shaping, and performing external renovation to obtain the pesticide bottle.
3. The method as claimed in claim 2, wherein the temperature of the melt extrusion of step S2 is controlled at 220 ℃ for 8-12 min.
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