CN117209863A - PEBA/TPS antibacterial elastic master batch, preparation method thereof and EVA sole - Google Patents

PEBA/TPS antibacterial elastic master batch, preparation method thereof and EVA sole Download PDF

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Publication number
CN117209863A
CN117209863A CN202311276753.0A CN202311276753A CN117209863A CN 117209863 A CN117209863 A CN 117209863A CN 202311276753 A CN202311276753 A CN 202311276753A CN 117209863 A CN117209863 A CN 117209863A
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peba
antibacterial
tps
master batch
foaming
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Inventor
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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Priority to CN202311276753.0A priority Critical patent/CN117209863A/en
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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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • 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
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
    • 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
    • C08J9/0061—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
    • 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
    • C08J9/009—Use of pretreated compounding ingredients
    • 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
    • C08J9/0095—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
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/06—CO2, N2 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/08—Supercritical fluid
    • 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
    • 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
    • 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
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Abstract

The application relates to a PEBA/TPS antibacterial elastic master batch and a preparation method thereof, and an EVA sole, wherein the PEBA/TPS antibacterial elastic master batch is prepared from thermoplastic starch, a cell stabilizer, an antibacterial agent and PEBA, 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; the antibacterial porous foaming particles are prepared by supercritical foaming, and then are immersed and coated with PEBA. 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

PEBA/TPS antibacterial elastic master batch, preparation method thereof and EVA sole
The application discloses a divisional application of an application application with the name of environment-friendly elastic EVA sole and a preparation method thereof, wherein the application number of the divisional application is 202211048340.2, and the application date of the divisional application is as follows: 2022.08.30.
Technical Field
The application relates to the technical field of shoe materials, in particular to a PEBA/TPS antibacterial elastic master batch, a preparation method thereof and an EVA sole.
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 application aims to provide a PEBA/TPS antibacterial elastic master batch and a preparation method thereof, which delay release, resist bacteria for a long time and help to improve the mechanical property and rebound resilience of EVA materials.
In order to achieve the aim of the application, the application adopts the following technical scheme:
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 antibacterial agent is an inorganic antibacterial agent or a plant antibacterial agent.
Preferably, the cell stabilizer is poly (isobutyl methacrylate).
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, wherein the sizing amount of PEBA is 4-10% of that of the PEBA/TPS antibacterial elastic master batch, and then drying to remove the solvent of the PEBA slurry to obtain the 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 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.
The application further aims to provide an EVA sole, which is prepared by recycling waste materials and foaming an auxiliary agent, EVA waste materials and PEBA/TPS antibacterial elastic master batch prepared by the preparation method, and has high rebound resilience and good mechanical property.
Preferably, the EVA sole comprises the following components in parts by weight: 60 parts of EVA, 12 parts of EVA waste, 20 parts of PEBA/TPS antibacterial elastic master batch, 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.
Compared with the prior art, the application 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 application and advantages of the application have been shown and described, it will be understood by those skilled in the art that the present application is not limited by the foregoing embodiments, which are described in the foregoing description merely illustrate the principles of the application, and various changes and modifications may be made therein without departing from the spirit and scope of the application as defined in the appended claims and their equivalents.

Claims (9)

  1. The PEBA/TPS antibacterial elastic master batch is characterized by being 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.
  2. 2. The PEBA/TPS antibacterial elastic master batch of claim 1, wherein: the antibacterial agent is an inorganic antibacterial agent or a plant antibacterial agent.
  3. 3. The PEBA/TPS antibacterial elastic master batch of claim 1, wherein: the cell stabilizer is poly (isobutyl methacrylate).
  4. The preparation method of the PEBA/TPS antibacterial elastic master batch is characterized by comprising the following steps of:
    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, wherein the sizing amount of PEBA is 4-10% of that of the PEBA/TPS antibacterial elastic master batch, and then drying to remove the solvent of the PEBA slurry to obtain the 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 the antibacterial porous foaming particles.
  5. 5. The method for preparing the PEBA/TPS antibacterial elastic master batch according to claim 4, wherein: the antibacterial agent is an inorganic antibacterial agent or a plant antibacterial agent.
  6. 6. The method for preparing the PEBA/TPS antibacterial elastic master batch according to claim 4, wherein: the cell stabilizer is poly (isobutyl methacrylate).
  7. 7. The method for preparing the PEBA/TPS antibacterial elastic master batch according to claim 4, wherein: the supercritical fluid is carbon dioxide or nitrogen.
  8. EVA sole, its characterized in that: the PEBA/TPS antibacterial elastic master batch prepared by the preparation method of any one of claims 4 to 7 is foamed by an auxiliary agent, EVA waste material and the preparation method.
  9. 9. The EVA sole according to claim 8, wherein: comprises the following components in parts by weight: 60 parts of EVA, 12 parts of EVA waste, 20 parts of PEBA/TPS antibacterial elastic master batch, 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.
CN202311276753.0A 2022-08-30 2022-08-30 PEBA/TPS antibacterial elastic master batch, preparation method thereof and EVA sole Pending CN117209863A (en)

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US9957386B2 (en) * 2013-09-10 2018-05-01 Arkema Inc. Antistatic thermoplastic starch alloys
TWI656169B (en) * 2018-03-16 2019-04-11 加久企業股份有限公司 Elastic composite process and its finished products
US10843429B2 (en) * 2018-05-21 2020-11-24 O2 Partners, Llc Biodegradable, industrially compostable, and recyclable injection molded microcellular flexible foams
CN112300481A (en) * 2020-11-18 2021-02-02 董启林 Foaming material applied to sports shoe soles
CN113414928A (en) * 2021-06-21 2021-09-21 福建省泉州市金奇宝鞋塑有限责任公司 Foaming anti-puncture sole forming process and sports shoes

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