CN115260645B - Environment-friendly elastic EVA sole and preparation method thereof - Google Patents

Environment-friendly elastic EVA sole and preparation method thereof Download PDF

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Publication number
CN115260645B
CN115260645B CN202211048340.2A CN202211048340A CN115260645B CN 115260645 B CN115260645 B CN 115260645B CN 202211048340 A CN202211048340 A CN 202211048340A CN 115260645 B CN115260645 B CN 115260645B
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antibacterial
foaming
peba
eva
parts
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CN115260645A (en
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陈德芳
郑启春
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Jinjiang Youfu Shoes Co ltd
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Jinjiang Youfu Shoes Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00—Soles; Sole-and-heel integral units
    • A43B13/02—Soles; Sole-and-heel integral units characterised by the material
    • A43B13/04—Plastics, rubber or vulcanised fibre
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00—Soles; Sole-and-heel integral units
    • A43B13/14—Soles; Sole-and-heel integral units characterised by the constructive form
    • A43B13/18—Resilient soles
    • A43B13/187—Resiliency achieved by the features of the material, e.g. foam, non liquid materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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    • C08J9/0014—Use of organic additives
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/009—Use of pretreated compounding ingredients
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • C08J9/42—Impregnation with macromolecular compounds
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    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/06—CO2, N2 or noble gases
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/08—Supercritical fluid
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)

Abstract

The invention relates to an environment-friendly elastic EVA sole and a preparation method thereof, wherein the EVA sole comprises the following components in parts by weight: EVA, EVA waste, modified thermoplastic granules, active zinc oxide, zinc stearate, stearic acid, a flow aid, a cross-linking agent and a foaming agent; the modified thermoplastic granules are PEBA/TPS antibacterial elastic master batches. The environment-friendly EVA sole prepared by foaming EVA waste materials, EVA, modified thermoplastic granules and the like has good rebound resilience, tensile strength and elongation at break, and has excellent antibacterial performance. According to the modified thermoplastic granules, the PEBA/TPS antibacterial elastic master batch is adopted, a supercritical foaming process is adopted to prepare thermoplastic starch foaming particles with rich foaming micropore networks, and the PEBA wraps the thermoplastic starch foaming particles loaded with the antibacterial agent, so that the antibacterial elastic master batch and other components such as EVA are mixed to achieve unexpected mechanical property enhancement effect and high rebound.

Description

Environment-friendly elastic EVA sole and preparation method thereof
Technical Field
The invention relates to the technical field of shoe materials, in particular to an environment-friendly elastic EVA sole and a preparation method thereof.
Background
Along with the continuous expansion of the application surface of EVA raw materials in recent years, the quantity of EVA waste materials is continuously increased, and various auxiliary materials including filling materials, pigments and rubber additives are contained in the waste materials, so that how to apply regenerated EVA raw materials to rubber-plastic synthetic cross-linked bodies on the premise of ensuring that the technical indexes of products are not influenced is a difficult problem in the industry, and the method is beneficial to resource regeneration, pollution reduction and product cost reduction.
The PEBAX is a block copolymer formed by polyamide and polyether, is a thermoplastic elastomer material, and a foamed product of the PEBAX is light, soft, excellent in rebound resilience, environment-friendly and recyclable, and is one of the most popular elastomers at present, but has some disadvantages in tensile strength and tearing property.
At present, no technical direction research on how to utilize PEBAX to modify EVA shoe materials to obtain excellent mechanical properties and high rebound is available.
Disclosure of Invention
The invention aims to provide an environment-friendly elastic EVA sole and a preparation method thereof, waste materials are recycled, and the EVA sole with high rebound resilience and good mechanical property is prepared.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the environment-friendly elastic EVA sole comprises the following components in parts by weight: 60-80 parts of EVA, 8-12 parts of EVA waste, 15-25 parts of modified thermoplastic granules, 1-2 parts of active zinc oxide, 0.5-1.0 part of zinc stearate, 1.0-1.5 parts of stearic acid, 0.2-0.8 part of flow aid, 0.5-2.0 parts of cross-linking agent and 1.5-2.0 parts of foaming agent.
Preferably, the modified thermoplastic pellets are PEBA/TPS antibacterial elastic master batches. The PEBA/TPS antibacterial elastic master batch is prepared from thermoplastic starch, a cell stabilizer, an antibacterial agent and PEBA, wherein the mass ratio of the thermoplastic starch to the antibacterial agent to the cell stabilizer is 25-35:3-10:0-0.6, and the PEBA dosage is 4-10% of the PEBA/TPS antibacterial elastic master batch.
Preferably, the preparation method of the PEBA/TPS antibacterial elastic master batch comprises the following steps: s11, preparing antibacterial porous foaming particles by supercritical foaming of thermoplastic starch, a cell stabilizer and an antibacterial agent; s12, respectively soaking the antibacterial porous foaming particles prepared in the step S11 in a PEBA solution, wrapping PEBA slurry outside the antibacterial porous foaming particles, and then drying to remove the solvent of the PEBA slurry to obtain the PEBA/TPS antibacterial elastic master batch.
Preferably, the preparation method of the antibacterial porous foaming particles in the step S12 comprises the following steps: s111, adding 25-35 parts of thermoplastic starch and 0-0.6 part of cell stabilizer into an internal mixer, banburying at 115-125 ℃ for 20-30 min, then opening the mixer to thin out sheets, soaking to saturation under the supercritical fluid atmosphere, maintaining the pressure at 10-20 MPa for 40-60 min, then rapidly decompressing, and taking out to obtain thermoplastic starch foaming particles through crushing; s112, placing the thermoplastic starch foaming particles in the step S111 in an organic solvent, adding 3-10 parts of an antibacterial agent, carrying out ultrasonic dispersion to uniformly load the antibacterial agent on the surfaces of the thermoplastic starch foaming particles and the inner walls of cells, and then drying to obtain the antibacterial porous foaming particles.
Preferably, the antibacterial agent is an inorganic antibacterial agent or a plant antibacterial agent.
Preferably, the cell stabilizer is poly (isobutyl methacrylate).
Preferably, the supercritical fluid is carbon dioxide or nitrogen.
Preferably, the sizing amount of PEBA in the step S12 is 4% -10% of PEBA/TPS antibacterial elastic master batch.
The invention also provides a preparation method of the environment-friendly elastic EVA sole, which specifically comprises the following steps: s1, preparing PEBA/TPS antibacterial elastic master batches; s2, mixing EVA, EVA waste, zinc stearate, stearic acid, a flow aid and activated zinc oxide, adding the PEBA/TPS antibacterial elastic master batch, a foaming agent and a cross-linking agent in the step S1 when the temperature reaches 118-123 ℃, continuously banburying, discharging when the temperature is increased to 130-135 ℃, carrying out open milling, and granulating to obtain foaming master batch; s3, spraying a release agent on a mold of a foaming machine, adding foaming master batch for compression molding foaming, wherein the foaming temperature is 150-160 ℃, the foaming pressure is 10-15 Mpa, and the foaming time is 300-500S.
Compared with the prior art, the invention has the following beneficial effects:
the environment-friendly EVA sole prepared by foaming EVA waste materials, EVA, modified thermoplastic granules and the like has good rebound resilience, tensile strength and elongation at break, and has excellent antibacterial performance. The modified thermoplastic granules adopt PEBA/TPS antibacterial elastic master batch, and thermoplastic starch foaming particles with abundant foaming micropore networks are prepared by a supercritical foaming process, so that uniform loading of the antibacterial agent and delayed release and long-term antibacterial effect in use are facilitated, and the thermoplastic starch foaming particles loaded with the antibacterial agent are wrapped by PEBA, so that the antibacterial elastic master batch and other components such as EVA are mixed to achieve unexpected mechanical property enhancement effect and high rebound.
Detailed Description
Example 1
The embodiment provides an environment-friendly elastic EVA sole, which comprises the following components in parts by weight: 80 parts of EVA, 8 parts of EVA waste, 25 parts of PEBA/TPS antibacterial elastic master batch, 1 part of active zinc oxide, 1.0 part of zinc stearate, 1.5 parts of stearic acid, 0.2 part of flow aid, 2.0 parts of cross-linking agent and 2.0 parts of foaming agent.
The preparation method of the environment-friendly elastic EVA sole specifically comprises the following steps:
s1, preparing PEBA/TPS antibacterial elastic master batch: s11, preparing antibacterial porous foaming particles by supercritical foaming of thermoplastic starch, a cell stabilizer and an antibacterial agent; s12, respectively soaking the antibacterial porous foaming particles prepared in the step S11 in a PEBA solution, wrapping PEBA slurry outside the antibacterial porous foaming particles, stirring and dissolving the PEBA slurry in a DMF solvent by PEBA powder, and then drying to remove the solvent of the PEBA slurry to obtain the PEBA/TPS antibacterial elastic master batch, wherein the sizing amount of the PEBA is 8+/-0.2% of that of the PEBA/TPS antibacterial elastic master batch.
S2, mixing EVA, EVA waste, zinc stearate, stearic acid, a flow aid and activated zinc oxide for 25min, adding the PEBA/TPS antibacterial elastic master batch, the foaming agent and the cross-linking agent in the step S1 when the temperature reaches 118 ℃, continuously banburying, discharging when the temperature rises to 130 ℃, carrying out open milling, and granulating to obtain foaming master batch; s3, spraying a release agent on a mold of a foaming machine, adding foaming master batch for compression molding foaming, wherein the foaming temperature is 155 ℃, the foaming pressure is 15Mpa, and the foaming time is 300S.
The preparation method of the antibacterial porous foaming particles in the step S12 comprises the following steps: s111, adding 25 parts of thermoplastic starch and 0.1 part of poly (isobutyl methacrylate) into an internal mixer, banburying at 115 ℃ for 30min, then open milling to form sheets, soaking to saturation under the supercritical fluid carbon dioxide atmosphere, maintaining the pressure at 15MPa for 50min, then rapidly decompressing, and taking out to obtain thermoplastic starch foaming particles through crushing; s112, placing the thermoplastic starch foaming particles in the step S111 in an organic solvent, adding 5 parts of an antibacterial agent which is silver ions, carrying out ultrasonic dispersion to uniformly load the antibacterial agent on the surfaces of the thermoplastic starch foaming particles and the inner walls of cells, and then drying to obtain the antibacterial porous foaming particles.
Example 2
The embodiment provides an environment-friendly elastic EVA sole, which comprises the following components in parts by weight: 70 parts of EVA, 10 parts of EVA waste, 15 parts of PEBA/TPS antibacterial elastic master batch, 2 parts of active zinc oxide, 0.8 part of zinc stearate, 1.0 part of stearic acid, 0.5 part of flow aid, 0.5 part of cross-linking agent and 1.5 parts of foaming agent.
The preparation method of the environment-friendly elastic EVA sole specifically comprises the following steps:
s1, preparing PEBA/TPS antibacterial elastic master batch: s11, preparing antibacterial porous foaming particles by supercritical foaming of thermoplastic starch, a cell stabilizer and an antibacterial agent; s12, respectively soaking the antibacterial porous foaming particles prepared in the step S11 in a PEBA solution, wrapping PEBA slurry outside the antibacterial porous foaming particles, stirring and dissolving the PEBA slurry in a DMF solvent by PEBA powder, and then drying to remove the solvent of the PEBA slurry to obtain the PEBA/TPS antibacterial elastic master batch, wherein the sizing amount of the PEBA is 4.5+/-0.2% of that of the PEBA/TPS antibacterial elastic master batch.
S2, mixing EVA, EVA waste, zinc stearate, stearic acid, a flow aid and activated zinc oxide for 20min, adding the PEBA/TPS antibacterial elastic master batch, the foaming agent and the cross-linking agent in the step S1 when the temperature reaches 120 ℃, continuously banburying, discharging when the temperature rises to 130 ℃, carrying out open milling, and granulating to obtain foaming master batch; s3, spraying a release agent on a mold of a foaming machine, adding foaming master batch for compression molding foaming, wherein the foaming temperature is 150 ℃, the foaming pressure is 10Mpa, and the foaming time is 400S.
The preparation method of the antibacterial porous foaming particles in the step S12 comprises the following steps: s111, adding 35 parts of thermoplastic starch and 0.6 part of poly (isobutyl methacrylate) into an internal mixer, banburying at 120 ℃ for 30min, then open milling to form sheets, soaking to saturation under the supercritical fluid carbon dioxide atmosphere, maintaining the pressure at 10MPa for 60min, then rapidly decompressing, and taking out to obtain thermoplastic starch foaming particles through crushing; s112, placing the thermoplastic starch foaming particles in the step S111 in an organic solvent, adding 3 parts of an antibacterial agent which is zinc oxide, carrying out ultrasonic dispersion to uniformly load the antibacterial agent on the surfaces of the thermoplastic starch foaming particles and the inner walls of cells, and then drying to obtain the antibacterial porous foaming particles.
Example 3
The embodiment provides an environment-friendly elastic EVA sole, which comprises the following components in parts by weight: 60 parts of EVA, 12 parts of EVA waste, 20 parts of modified thermoplastic granules, 1.5 parts of active zinc oxide, 0.5 part of zinc stearate, 1.0 part of stearic acid, 0.8 part of flow aid, 1.0 part of cross-linking agent and 1.5 parts of foaming agent, wherein the modified thermoplastic granules are PEBA/TPS antibacterial elastic master batches.
The preparation method of the environment-friendly elastic EVA sole specifically comprises the following steps:
s1, preparing PEBA/TPS antibacterial elastic master batch: s11, preparing antibacterial porous foaming particles by supercritical foaming of thermoplastic starch, a cell stabilizer and an antibacterial agent; s12, respectively soaking the antibacterial porous foaming particles prepared in the step S11 in a PEBA solution, wrapping PEBA slurry outside the antibacterial porous foaming particles, stirring and dissolving the PEBA slurry in a DMF solvent by PEBA powder, and then drying to remove the solvent of the PEBA slurry to obtain the PEBA/TPS antibacterial elastic master batch, wherein the sizing amount of the PEBA is 6+/-0.2% of that of the PEBA/TPS antibacterial elastic master batch.
S2, mixing EVA, EVA waste, zinc stearate, stearic acid, a flow aid and activated zinc oxide for 30min, adding the PEBA/TPS antibacterial elastic master batch, the foaming agent and the cross-linking agent in the step S1 when the temperature reaches 120 ℃, continuously banburying, discharging when the temperature rises to 135 ℃, carrying out open milling, and granulating to obtain foaming master batch; s3, spraying a release agent on a mold of a foaming machine, adding foaming master batch for compression molding foaming, wherein the foaming temperature is 160 ℃, the foaming pressure is 12.5Mpa, and the foaming time is 500S.
The preparation method of the antibacterial porous foaming particles in the step S12 comprises the following steps: s111, adding 30 parts of thermoplastic starch and 0.25 part of poly (isobutyl methacrylate) into an internal mixer, banburying at 125 ℃ for 20min, then open milling to form sheets, soaking to saturation under the atmosphere of supercritical fluid nitrogen, maintaining the pressure at 20MPa for 40min, then rapidly decompressing, and taking out to obtain thermoplastic starch foaming particles through crushing; s112, placing the thermoplastic starch foaming particles in the step S111 in an organic solvent, adding 8 parts of an antibacterial agent which is lavender plant extract, carrying out ultrasonic dispersion to uniformly load the antibacterial agent on the surface of the thermoplastic starch foaming particles and the inner wall of cells, and then drying to obtain the antibacterial porous foaming particles.
Comparative example 1
This comparative example 1 differs from example 3 only in that: the step S12 is not performed when PEBA is not added to the modified thermoplastic pellets and the modified thermoplastic pellets are prepared.
Comparative example 2
This comparative example 2 differs from example 3 only in that: the modified thermoplastic pellets were not added PEBA and were prepared without step S12, but there was a substantial amount of the individual component PEBA in the sole formulation components as in example 3, which was compounded with EVA, EVA scrap, zinc stearate, stearic acid, flow aid and activated zinc oxide in step S2.
Comparative example 3
This comparative example 3 differs from example 3 only in that: the preparation methods of PEBA/TPS antibacterial elastic master batches are different, and specifically comprise the following steps: the thermoplastic starch, cell stabilizer, antimicrobial agent and PEBA in amounts comparable to example 3 were co-extruded through a twin screw extruder and pelletized.
The EVA soles obtained in examples 1 to 3 (hereinafter referred to as L1 to L3) and comparative examples 1 to 3 (hereinafter referred to as D1 to D3) were subjected to physical property tests, respectively, and the test results are shown in Table 1.
While the basic principles and main features of the invention and advantages of the invention have been shown and described, it will be understood by those skilled in the art that the present invention is not limited by the foregoing embodiments, which are described in the foregoing description merely illustrate the principles of the invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined in the appended claims and their equivalents.

Claims (5)

1. The environment-friendly elastic EVA sole is characterized by comprising the following components in parts by weight: 60-80 parts of EVA, 8-12 parts of EVA waste, 15-25 parts of modified thermoplastic granules, 1-2 parts of active zinc oxide, 0.5-1.0 part of zinc stearate, 1.0-1.5 parts of stearic acid, 0.2-0.8 part of flow aid, 0.5-2.0 parts of cross-linking agent and 1.5-2.0 parts of foaming agent;
the modified thermoplastic granules are PEBA/TPS antibacterial elastic master batches, and the preparation method of the PEBA/TPS antibacterial elastic master batches comprises the following steps: s11, preparing antibacterial porous foaming particles by supercritical foaming of thermoplastic starch, a cell stabilizer and an antibacterial agent; s12, respectively soaking the antibacterial porous foaming particles prepared in the step S11 in a PEBA solution, wrapping PEBA slurry outside the antibacterial porous foaming particles, and then drying to remove a solvent of the PEBA slurry to obtain PEBA/TPS antibacterial elastic master batch;
the preparation method of the antibacterial porous foaming particles in the step S11 comprises the following steps: s111, adding 25-35 parts of thermoplastic starch and 0-0.6 part of cell stabilizer into an internal mixer, banburying at 115-125 ℃ for 20-30 min, then opening the mixer to thin out sheets, soaking to saturation under the supercritical fluid atmosphere, maintaining the pressure at 10-20 MPa for 40-60 min, then rapidly decompressing, and taking out to obtain thermoplastic starch foaming particles through crushing; s112, placing the thermoplastic starch foaming particles in the step S111 in an organic solvent, adding 3-10 parts of an antibacterial agent, carrying out ultrasonic dispersion to uniformly load the antibacterial agent on the surfaces of the thermoplastic starch foaming particles and the inner walls of cells, and then drying to obtain antibacterial porous foaming particles;
the sizing amount of PEBA is 4% -10% of the PEBA/TPS antibacterial elastic master batch.
2. The environmentally friendly elastic EVA sole according to claim 1, characterized in that: the antibacterial agent is an inorganic antibacterial agent or a plant antibacterial agent.
3. The environmentally friendly elastic EVA sole according to claim 1, characterized in that: the cell stabilizer is poly (isobutyl methacrylate).
4. The environmentally friendly elastic EVA sole according to claim 1, characterized in that: the supercritical fluid is carbon dioxide or nitrogen.
5. A method for preparing an environment-friendly elastic EVA sole according to any one of claims 1 to 4, characterized in that: the method specifically comprises the following steps: s1, preparing PEBA/TPS antibacterial elastic master batches; s2, mixing EVA, EVA waste, zinc stearate, stearic acid, a flow aid and activated zinc oxide, adding the PEBA/TPS antibacterial elastic master batch, a foaming agent and a cross-linking agent in the step S1 when the temperature reaches 120 ℃, continuously banburying, discharging when the temperature is increased to 130-135 ℃, carrying out open milling, and granulating to obtain foaming master batch; s3, spraying a release agent on a mold of the foaming machine, and adding foaming master batches for compression molding foaming.
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