WO2023193391A1 - Cold-resistant anti-skid rubber foam sole and preparation method therefor - Google Patents

Cold-resistant anti-skid rubber foam sole and preparation method therefor Download PDF

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Publication number
WO2023193391A1
WO2023193391A1 PCT/CN2022/115041 CN2022115041W WO2023193391A1 WO 2023193391 A1 WO2023193391 A1 WO 2023193391A1 CN 2022115041 W CN2022115041 W CN 2022115041W WO 2023193391 A1 WO2023193391 A1 WO 2023193391A1
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Prior art keywords
cold
rubber
resistant anti
rubber foam
mix
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PCT/CN2022/115041
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French (fr)
Chinese (zh)
Inventor
廖毅彬
卢鑫
庄东水
王育玲
丁思博
丁思恩
代雪玲
何清福
关玲
谭礼宏
Original Assignee
茂泰(福建)鞋材有限公司
盛泰(福建)鞋材有限公司
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Publication of WO2023193391A1 publication Critical patent/WO2023193391A1/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
    • C08J9/06—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 chemical blowing agent
    • C08J9/10—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 chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
    • C08J9/105—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof containing sulfur
    • 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
    • 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
    • C08J9/0014—Use of organic additives
    • C08J9/0028—Use of organic additives containing nitrogen
    • 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
    • C08J9/0095—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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • 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
    • C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08J2309/06—Copolymers with styrene
    • 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
    • C08J2423/06—Polyethene
    • 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
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • 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
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/02—Polyalkylene oxides
    • C08J2471/03—Polyepihalohydrins
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Definitions

  • the invention belongs to the field of rubber sole preparation, and specifically relates to a cold-resistant anti-slip rubber foam sole and a preparation method thereof.
  • the purpose of the present invention is to overcome the shortcomings of the prior art, provide a cold-resistant anti-slip rubber foam sole, and provide a method for preparing the above-mentioned rubber sole.
  • a cold-resistant anti-slip rubber foam sole including the following raw materials by weight:
  • the accelerator is composed of ethanolamine, zinc oxide, and phthalic acid in a mass ratio of 1:1.8-2.7:0.54-0.72.
  • the filler is composed of sepiolite powder and diatomite in a mass ratio of 1:2-3.
  • antioxidant 4020 is antioxidant 4020.
  • dispersant is dispersant AT-B.
  • the active agent is polyethylene glycol.
  • the plasticizer is diethylene glycol.
  • a preparation method for cold-resistant anti-slip rubber foam soles including the following steps:
  • Step 1 Mix the required weight portions of solution-polymerized styrene-butadiene rubber, acrylate rubber, and chloroether rubber in an internal mixer for 10-15 minutes to obtain a premix;
  • Step 2 Mix the premix prepared in Step 1 and other raw materials except diphenyl sulfonyl hydrazine ether and accelerator, and remove the glue at 115-120°C, and leave it at room temperature for more than 24 hours;
  • Step 3 Mix the internally mixed mixture on an open mill, add accurately weighed diphenylsulfonyl hydrazine ether and accelerator, and mix the mixture into uniform sheets to obtain foamed tablets;
  • Step 4 Cut the foam sheet into a shoe sole shape and put it into a rubber shoe mold for vulcanization and molding to obtain the rubber foam shoe sole.
  • the internal mixing process specifically includes: adding the premix prepared in step one and other raw materials except diphenylsulfonyl hydrazine ether and accelerator into the internal mixer, mixing and internal mixing for 5-10 minutes; then Adjust the internal mixing temperature to 90°C, keep it for 3 minutes and then turn the materials once; wait until the internal mixing temperature rises to 95°C, turn the materials twice; wait until the internal mixing temperature rises to 104°C, turn the materials three times; wait until the internal mixing temperature rises to 110°C , turn the materials four times; wait for the internal mixing temperature to rise to 115-120°C, turn the materials five times, mix again for 1 minute, discharge the glue, and leave it at room temperature for more than 24 hours.
  • step four the vulcanization molding temperature is 145-160°C.
  • this application limits solution-polymerized styrene-butadiene rubber, acrylic rubber, and chloroether rubber to be mixed with each other and matched with other raw materials to complement each other in performance, so that the rubber soles produced have cold resistance and anti-slip properties, and can be used in Maintain appropriate softness, elasticity and bending properties in a cold environment of (-30)°C to meet the sole comfort required in cold environments; among them, ethanolamine, zinc oxide, and phthalic acid are limited as accelerators, and diphenylsulfonyl Hydrazine ether is used as a foaming agent, combined with chloroether rubber to improve the cold resistance and elasticity of acrylic rubber, so as to improve the cold resistance and elasticity of the blended rubber, so that the prepared rubber sole is suitable for cold environments of (-30) °C; At the same time, the accelerator compounded with ethanolamine, zinc oxide, and phthalic acid can roughly synchronize the vulcanization speed of the mixed rubber with the foaming speed to obtain a good hole structure
  • adding polyethylene wax and magnesium stearate can enhance the diffusion of diatomite, sepiolite powder, diphenylsulfonyl hydrazine ether and accelerator, so that the above raw materials can be evenly diffused in the overall system, and at the same time can improve the
  • the molding speed facilitates demoulding and improves the brightness and smoothness of the surface of the demoulded product; among them, the diatomite and sepiolite powder used have low shrinkage, increase the wall thickness of the cells, and are combined with accelerators to stabilize development. bubble velocity to obtain a uniform closed-cell structure and better mechanical properties;
  • porous materials such as diatomaceous earth and sepiolite powder are used as fillers. With the cooperation of polyethylene wax and magnesium stearate, they are evenly diffused in the overall system. During vulcanization and molding, diphenylsulfonylhydrazine ether decomposes. Gas can be filled in the overall system through evenly dispersed diatomite and sepiolite powder to form a uniform closed-cell structure, and the closed-cell structure is independent of each other, and the bubbles are not connected to each other, ensuring that the produced Mechanical properties of rubber soles.
  • a cold-resistant anti-slip rubber foam sole including the following raw materials by weight:
  • the accelerator is composed of ethanolamine, zinc oxide, and phthalic acid in a mass ratio of 1:1.8-2.7:0.54-0.72;
  • the filler is composed of sepiolite powder and diatomite in a mass ratio of 1:2-3;
  • the antioxidant is antioxidant 4020;
  • the dispersant is dispersant AT-B;
  • the active agent is polyethylene glycol;
  • the plasticizer is diethylene glycol.
  • a preparation method for cold-resistant anti-slip rubber foam soles including the following steps:
  • Step 1 Mix the required weight portions of solution-polymerized styrene-butadiene rubber, acrylate rubber, and chloroether rubber in an internal mixer for 10-15 minutes to obtain a premix;
  • Step 2 Add the premix prepared in Step 1 and other raw materials except diphenylsulfonyl hydrazine ether and accelerator into the internal mixer, mix and mix for 5-10 minutes; then adjust the internal mixing temperature to 90°C and maintain for 3 minutes. Turn the materials for the last time; wait for the internal mixing temperature to rise to 95°C, turn the materials for the second time; wait for the internal mixing temperature to rise to 104°C, turn the materials for the third time; wait for the internal mixing temperature to rise to 110°C, turn the materials for the fourth time; wait for the internal mixing temperature to rise to 110°C, turn the materials for the fourth time. Raise to 115-120°C, turn the materials over five times, mix again for 1 minute, discharge the glue, and leave it at room temperature for more than 24 hours;
  • Step 3 Mix the internally mixed mixture on an open mill, add the above-mentioned amounts of diphenylsulfonyl hydrazine ether and accelerator, and mix the mixture into uniform sheets to obtain foamed tablets;
  • Step 4 Cut the foam sheet into the shape of a shoe sole and put it into a rubber shoe mold for vulcanization and molding.
  • the vulcanization temperature is 145-160°C to obtain the rubber foam shoe sole.
  • a cold-resistant anti-slip rubber foam sole including the following raw materials by weight:
  • the accelerator is composed of ethanolamine, zinc oxide, and phthalic acid in a mass ratio of 1:1.8:0.72;
  • the filler is composed of sepiolite powder and diatomite in a mass ratio of 1:2.
  • a preparation method for cold-resistant anti-slip rubber foam soles including the following steps:
  • Step 1 Mix the required weight portions of solution-polymerized styrene-butadiene rubber, acrylate rubber, and chloroether rubber in an internal mixer for 15 minutes to obtain a premix;
  • Step 2 Add the premix prepared in step 1 and other raw materials except diphenylsulfonyl hydrazine ether and accelerator into the internal mixer, mix and mix for 5 minutes; then adjust the internal mixing temperature to 90°C and keep it for 3 minutes. Turn over the materials; wait for the internal mixing temperature to rise to 95°C, turn over the materials twice; wait for the internal mixing temperature to rise to 104°C, turn over the materials three times; wait for the internal mixing temperature to rise to 110°C, turn over the materials four times; wait until the internal mixing temperature rises to 115°C, turn the materials five times, mix again for 1 minute, drain the glue, and leave it at room temperature for more than 24 hours;
  • Step 3 Mix the internally mixed mixture on an open mill, add diphenyl sulfonyl hydrazine ether and accelerator weighed in the above proportions, and mix the mixture into uniform sheets to obtain foamed tablets;
  • Step 4 Cut the foam sheet into the shape of a shoe sole and put it into a rubber shoe mold for vulcanization and molding.
  • the vulcanization temperature is 145°C to obtain the rubber foam shoe sole.
  • a cold-resistant anti-slip rubber foam sole including the following raw materials by weight:
  • the accelerator is composed of ethanolamine, zinc oxide, and phthalic acid in a mass ratio of 1:2.7:0.54;
  • the filler is composed of sepiolite powder and diatomite in a mass ratio of 1:3.
  • a preparation method for cold-resistant anti-slip rubber foam soles including the following steps:
  • Step 1 Mix the required weight portions of solution-polymerized styrene-butadiene rubber, acrylate rubber, and chloroether rubber in a high internal mixer for 10 minutes to obtain a premix;
  • Step 2 Add the premix prepared in Step 1 and other raw materials except diphenylsulfonyl hydrazine ether and accelerator into the internal mixer, mix and mix for 10 minutes; then adjust the internal mixing temperature to 90°C and keep it for 3 minutes. Turn over the materials; wait for the internal mixing temperature to rise to 95°C, turn over the materials twice; wait for the internal mixing temperature to rise to 104°C, turn over the materials three times; wait for the internal mixing temperature to rise to 110°C, turn over the materials four times; wait until the internal mixing temperature rises to 120°C, turn the materials five times, mix again for 1 minute, drain the glue, and leave it at room temperature for more than 24 hours;
  • Step 3 Mix the internally mixed mixture on an open mill, add diphenyl sulfonyl hydrazine ether and accelerator determined according to the above ratio, and mix the mixture into uniform sheets to obtain foamed tablets;
  • Step 4 Cut the foam sheet into the shape of a shoe sole and put it into a rubber shoe mold for vulcanization and molding.
  • the vulcanization temperature is 160°C to obtain the rubber foam shoe sole.
  • a cold-resistant anti-slip rubber foam sole including the following raw materials by weight:
  • the accelerator is composed of ethanolamine, zinc oxide, and phthalic acid in a mass ratio of 1:2.3:0.65;
  • the filler is composed of sepiolite powder and diatomite in a mass ratio of 1:2.5.
  • a preparation method for cold-resistant anti-slip rubber foam soles including the following steps:
  • Step 1 Mix the required weight portions of solution-polymerized styrene-butadiene rubber, acrylate rubber, and chloroether rubber in an internal mixer for 12 minutes to obtain a premix;
  • Step 2 Add the premix prepared in Step 1 and other raw materials except diphenylsulfonyl hydrazine ether and accelerator into the internal mixer, mix and mix for 8 minutes; then adjust the internal mixing temperature to 90°C and keep it for 3 minutes. Turn over the materials; wait for the internal mixing temperature to rise to 95°C, turn over the materials twice; wait for the internal mixing temperature to rise to 104°C, turn over the materials three times; wait for the internal mixing temperature to rise to 110°C, turn over the materials four times; wait until the internal mixing temperature rises to 118°C, turn the materials five times, mix again for 1 minute, drain the glue, and leave it at room temperature for more than 24 hours;
  • Step 3 Mix the internally mixed mixture on an open mill, add the required amount of diphenylsulfonyl hydrazine ether and accelerator, and mix the mixture into uniform sheets to obtain foamed tablets;
  • Step 4 Cut the foam sheet into the shape of a shoe sole and put it into a rubber shoe mold for vulcanization and molding.
  • the vulcanization temperature is 155°C to obtain the rubber foam shoe sole.
  • the raw material composition and preparation method are basically the same as those in Example 3, except that in the raw material composition, diphenylsulfonyl hydrazine ether is replaced by the foaming agent AC.
  • the raw material composition and preparation method are basically the same as those in Example 3, except that in the raw material composition, the accelerator is dicumyl peroxide.
  • the raw material composition and preparation method are basically the same as those in Example 3. The difference is that in the raw material composition, the accelerator is ethanolamine and zinc oxide in a mass ratio of 1:1.8-2.7.
  • the raw material composition and preparation method are basically the same as those in Example 3. The difference is that in the raw material composition, the accelerator is ethanolamine and phthalic acid in a mass ratio of 1:0.54-0.72.
  • the raw material composition and preparation method are basically the same as those in Example 3. The difference is that in the raw material composition, the filler is talc powder.
  • the rubber foam soles prepared in this application can maintain appropriate softness, elasticity and bending properties in a cold environment of (-30)°C, and meet the required sole comfort in cold environments; where the solution is limited Polystyrene-butadiene rubber, acrylic rubber, and chloroether rubber are mixed with each other and matched with other raw materials to complement each other in performance, so that the rubber soles produced have cold resistance and anti-slip properties; ethanolamine, zinc oxide, and phthalic acid are limited As an accelerator, diphenylsulfonyl hydrazine ether is used as a foaming agent, and is combined with chloroether rubber to improve the cold resistance and elasticity of acrylic rubber to improve the cold resistance and elasticity of the blended rubber so that the prepared rubber sole is suitable for ( -30)°C cold environment; at the same time, the accelerator compounded with ethanolamine, zinc oxide, and phthalic acid can make the vulcanization speed of the mixed rubber roughly synchronized with the foaming speed to obtain a
  • the invention discloses a cold-resistant anti-slip rubber foam sole and a preparation method thereof.
  • the rubber foam sole includes the following raw materials: solution-polymerized styrene-butadiene rubber, acrylate rubber, chloroether rubber, paraffin oil, diphenylsulfonylhydrazine ether, accelerator Agent, filler, polyethylene wax, magnesium stearate, silane coupling agent, antioxidant, plasticizer, dispersant, active agent. This application limits the mixing of solution-polymerized styrene-butadiene rubber, acrylate rubber, and chloroether rubber.
  • the rubber soles produced When combined with other raw materials, they can be complementary in performance, so that the rubber soles produced have cold resistance and anti-slip properties, and can maintain appropriate softness, elasticity and bending properties in a cold environment of (-30)°C, meeting the requirements
  • the sole comfort required in cold environments has industrial practicality.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)

Abstract

A cold-resistant anti-skid rubber foam sole and a preparation method therefor. The rubber foam sole comprises the following raw materials: solution polymerized styrene-butadiene rubber, acrylate rubber, epichlorohydrin rubber, paraffin oil, bis(benzenesulfonyl hydrazide)ether, an accelerator, a filler, polyethylene wax, magnesium stearate, a silane coupling agent, an antioxidant, a plasticizer, a dispersing agent, and an active agent. According to the present application, the solution polymerized styrene-butadiene rubber, the acrylate rubber, and epichlorohydrin rubber are defined to be used in combination with each other, and are used in combination with other raw materials to implement complementarity in performance, so that a prepared rubber sole has cold resistance and anti-skid performance, and can maintain proper softness, elasticity, and bending performance in a cold environment of (-30)°C, thereby meeting the comfort of a sole required in a cold environment.

Description

一种耐寒防滑橡胶发泡鞋底及其制备方法A cold-resistant anti-slip rubber foam sole and its preparation method 技术领域Technical field
本发明属于橡胶鞋底制备领域，具体涉及一种耐寒防滑橡胶发泡鞋底及其制备方法。The invention belongs to the field of rubber sole preparation, and specifically relates to a cold-resistant anti-slip rubber foam sole and a preparation method thereof.
背景技术Background technique
由于近年来户外运动、探险运动等活动的兴起，以及地区条件差异等，为了适应极端恶劣的低温环境的需要，对鞋类的某些特殊功能提出了新的要求。目前，大多数户外产品只能满足一般寒冷程度的需求，在极端寒冷的条件下，对鞋底的耐寒性能要求更高。然而，普通橡胶鞋底在-15℃冷冻24小时候，硬度将上升15-20度，硬度上升，任性和柔韧性都会大打折扣，导致鞋底断裂，有待进一步改进。Due to the rise of outdoor sports, adventure sports and other activities in recent years, as well as differences in regional conditions, new requirements have been put forward for certain special functions of footwear in order to adapt to extremely harsh low-temperature environments. At present, most outdoor products can only meet the needs of general cold levels. Under extremely cold conditions, the cold resistance performance of the soles is required to be higher. However, if ordinary rubber soles are frozen at -15°C for 24 hours, the hardness will increase by 15-20 degrees. As the hardness increases, the willfulness and flexibility will be greatly reduced, resulting in the soles breaking, which needs further improvement.
发明内容Contents of the invention
本发明的目的是克服现有技术的缺点，提供一种耐寒防滑橡胶发泡鞋底，及提供一种制备上述橡胶鞋底的方法。The purpose of the present invention is to overcome the shortcomings of the prior art, provide a cold-resistant anti-slip rubber foam sole, and provide a method for preparing the above-mentioned rubber sole.
本发明采用如下技术方案：The present invention adopts the following technical solutions:
一种耐寒防滑橡胶发泡鞋底，包括以下重量份的原料：A cold-resistant anti-slip rubber foam sole, including the following raw materials by weight:
Figure PCTCN2022115041-appb-000001
Figure PCTCN2022115041-appb-000001
Figure PCTCN2022115041-appb-000002
Figure PCTCN2022115041-appb-000002
进一步的，所述促进剂由乙醇胺、氧化锌、苯二甲酸按质量比1:1.8-2.7:0.54-0.72的比例组成。Further, the accelerator is composed of ethanolamine, zinc oxide, and phthalic acid in a mass ratio of 1:1.8-2.7:0.54-0.72.
进一步的，所述填料由海泡石粉与硅藻土按质量比1：2-3的比例组成。Further, the filler is composed of sepiolite powder and diatomite in a mass ratio of 1:2-3.
进一步的，所述防老剂为防老剂4020。Further, the antioxidant is antioxidant 4020.
进一步的，所述分散剂为分散剂AT-B。Further, the dispersant is dispersant AT-B.
进一步的，所述活性剂为聚乙二醇。Further, the active agent is polyethylene glycol.
进一步的，所述增塑剂为二甘醇。Further, the plasticizer is diethylene glycol.
一种耐寒防滑橡胶发泡鞋底的制备方法，包括以下步骤：A preparation method for cold-resistant anti-slip rubber foam soles, including the following steps:
步骤一，将所需重量份的溶聚丁苯橡胶、丙烯酸酯橡胶、氯醚橡胶在密炼机中密炼10-15min，得预混物；Step 1: Mix the required weight portions of solution-polymerized styrene-butadiene rubber, acrylate rubber, and chloroether rubber in an internal mixer for 10-15 minutes to obtain a premix;
步骤二，将步骤一制备的预混物和除二苯磺酰肼醚、促进剂外的其 他原料，混合密炼，115-120℃排胶，室温放置24h以上；Step 2: Mix the premix prepared in Step 1 and other raw materials except diphenyl sulfonyl hydrazine ether and accelerator, and remove the glue at 115-120°C, and leave it at room temperature for more than 24 hours;
步骤三，将密炼后的混合物在开炼机上混炼，并加入准确称量的二苯磺酰肼醚、促进剂，混料均匀片状出片，得发泡片；Step 3: Mix the internally mixed mixture on an open mill, add accurately weighed diphenylsulfonyl hydrazine ether and accelerator, and mix the mixture into uniform sheets to obtain foamed tablets;
步骤四，将发泡片裁成鞋底形状放入橡胶鞋模中硫化成型，得所述橡胶发泡鞋底。Step 4: Cut the foam sheet into a shoe sole shape and put it into a rubber shoe mold for vulcanization and molding to obtain the rubber foam shoe sole.
进一步的，步骤二中，密炼过程具体包括：往密炼机中加入步骤一制备的预混物和除二苯磺酰肼醚、促进剂外的其他原料，混合密炼5-10min；然后调整密炼温度到90℃，保持3min后一次翻料；待密炼温度升至95℃，二次翻料；待密炼温度升至104℃，三次翻料；待密炼温度升至110℃，四次翻料；待密炼温度升至115-120℃，五次翻料，再密炼1min，排胶，室温放置24h以上。Further, in step two, the internal mixing process specifically includes: adding the premix prepared in step one and other raw materials except diphenylsulfonyl hydrazine ether and accelerator into the internal mixer, mixing and internal mixing for 5-10 minutes; then Adjust the internal mixing temperature to 90℃, keep it for 3 minutes and then turn the materials once; wait until the internal mixing temperature rises to 95℃, turn the materials twice; wait until the internal mixing temperature rises to 104℃, turn the materials three times; wait until the internal mixing temperature rises to 110℃ , turn the materials four times; wait for the internal mixing temperature to rise to 115-120°C, turn the materials five times, mix again for 1 minute, discharge the glue, and leave it at room temperature for more than 24 hours.
进一步的，步骤四中，硫化成型的温度为145-160℃。Further, in step four, the vulcanization molding temperature is 145-160°C.
由上述对本发明的描述可知，与现有技术相比，本发明的有益效果是：From the above description of the present invention, it can be seen that compared with the prior art, the beneficial effects of the present invention are:
第一，本申请限定溶聚丁苯橡胶、丙烯酸酯橡胶、氯醚橡胶相互混用，与其他原料配合，在性能上能够做到互补，以使制得的橡胶鞋底具有耐寒、防滑性能，能够在(-30)℃的寒冷环境下保持相适宜的柔软性、弹性及弯曲性能，满足寒冷环境下要求的鞋底舒适度；其中，限定乙醇胺、氧化锌、苯二甲酸作为促进剂，二苯磺酰肼醚作为发泡剂，配合氯醚橡胶改善丙烯酸酯橡胶的耐寒性、弹性，以提高共混胶的耐寒性和弹性，以使制得的橡胶鞋底适用于(-30)℃的寒冷环境；同时，以乙醇胺、 氧化锌、苯二甲酸复配的促进剂，可使混合胶的硫化速度与发泡速度大致同步，以获得良好的孔眼结构，保证制得的橡胶鞋底的力学性能；First, this application limits solution-polymerized styrene-butadiene rubber, acrylic rubber, and chloroether rubber to be mixed with each other and matched with other raw materials to complement each other in performance, so that the rubber soles produced have cold resistance and anti-slip properties, and can be used in Maintain appropriate softness, elasticity and bending properties in a cold environment of (-30)℃ to meet the sole comfort required in cold environments; among them, ethanolamine, zinc oxide, and phthalic acid are limited as accelerators, and diphenylsulfonyl Hydrazine ether is used as a foaming agent, combined with chloroether rubber to improve the cold resistance and elasticity of acrylic rubber, so as to improve the cold resistance and elasticity of the blended rubber, so that the prepared rubber sole is suitable for cold environments of (-30) ℃; At the same time, the accelerator compounded with ethanolamine, zinc oxide, and phthalic acid can roughly synchronize the vulcanization speed of the mixed rubber with the foaming speed to obtain a good hole structure and ensure the mechanical properties of the rubber sole produced;
第二，加入聚乙烯蜡与硬脂酸镁配合，可增强硅藻土、海泡石粉、二苯磺酰肼醚与促进剂的扩散，以使上述原料均匀扩散在整体体系中，同时可提高成型的速率，便于脱模，提高脱模后的产品表面的光亮度及光滑度；其中，采用的硅藻土和海泡石粉收缩率低，增加泡孔的壁厚，配合促进剂，稳定发泡速度，以获得均匀的闭孔结构，获得较好的力学性能；Second, adding polyethylene wax and magnesium stearate can enhance the diffusion of diatomite, sepiolite powder, diphenylsulfonyl hydrazine ether and accelerator, so that the above raw materials can be evenly diffused in the overall system, and at the same time can improve the The molding speed facilitates demoulding and improves the brightness and smoothness of the surface of the demoulded product; among them, the diatomite and sepiolite powder used have low shrinkage, increase the wall thickness of the cells, and are combined with accelerators to stabilize development. bubble velocity to obtain a uniform closed-cell structure and better mechanical properties;
第三，采用硅藻土、海泡石粉等多孔的物质作为填料，在聚乙烯蜡与硬脂酸镁的配合下，均匀扩散在整体体系中，硫化成型时，二苯磺酰肼醚分解的气体能通过均匀分散的硅藻土、海泡石粉填充在整体体系中，以形成均匀地闭孔结构，且闭孔结构呈相互独立的状态，气泡与气泡之间相互不连通，保证制得的橡胶鞋底的力学性能。Third, porous materials such as diatomaceous earth and sepiolite powder are used as fillers. With the cooperation of polyethylene wax and magnesium stearate, they are evenly diffused in the overall system. During vulcanization and molding, diphenylsulfonylhydrazine ether decomposes. Gas can be filled in the overall system through evenly dispersed diatomite and sepiolite powder to form a uniform closed-cell structure, and the closed-cell structure is independent of each other, and the bubbles are not connected to each other, ensuring that the produced Mechanical properties of rubber soles.
具体实施方式Detailed ways
以下通过具体实施方式对本发明作进一步的描述。The present invention will be further described below through specific embodiments.
一种耐寒防滑橡胶发泡鞋底，包括以下重量份的原料：A cold-resistant anti-slip rubber foam sole, including the following raw materials by weight:
Figure PCTCN2022115041-appb-000003
Figure PCTCN2022115041-appb-000003
Figure PCTCN2022115041-appb-000004
Figure PCTCN2022115041-appb-000004
其中，促进剂由乙醇胺、氧化锌、苯二甲酸按质量比1:1.8-2.7:0.54-0.72的比例组成；填料由海泡石粉与硅藻土按质量比1：2-3的比例组成；防老剂为防老剂4020；分散剂为分散剂AT-B；活性剂为聚乙二醇；增塑剂为二甘醇。Among them, the accelerator is composed of ethanolamine, zinc oxide, and phthalic acid in a mass ratio of 1:1.8-2.7:0.54-0.72; the filler is composed of sepiolite powder and diatomite in a mass ratio of 1:2-3; The antioxidant is antioxidant 4020; the dispersant is dispersant AT-B; the active agent is polyethylene glycol; the plasticizer is diethylene glycol.
一种耐寒防滑橡胶发泡鞋底的制备方法，包括以下步骤：A preparation method for cold-resistant anti-slip rubber foam soles, including the following steps:
步骤一，将所需重量份的溶聚丁苯橡胶、丙烯酸酯橡胶、氯醚橡胶在密炼机中密炼10-15min，得预混物；Step 1: Mix the required weight portions of solution-polymerized styrene-butadiene rubber, acrylate rubber, and chloroether rubber in an internal mixer for 10-15 minutes to obtain a premix;
步骤二，往密炼机中加入步骤一制备的预混物和除二苯磺酰肼醚、促进剂外的其他原料，混合密炼5-10min；然后调整密炼温度到90℃，保持3min后一次翻料；待密炼温度升至95℃，二次翻料；待密炼温度升 至104℃，三次翻料；待密炼温度升至110℃，四次翻料；待密炼温度升至115-120℃，五次翻料，再密炼1min，排胶，室温放置24h以上；Step 2: Add the premix prepared in Step 1 and other raw materials except diphenylsulfonyl hydrazine ether and accelerator into the internal mixer, mix and mix for 5-10 minutes; then adjust the internal mixing temperature to 90°C and maintain for 3 minutes. Turn the materials for the last time; wait for the internal mixing temperature to rise to 95℃, turn the materials for the second time; wait for the internal mixing temperature to rise to 104℃, turn the materials for the third time; wait for the internal mixing temperature to rise to 110℃, turn the materials for the fourth time; wait for the internal mixing temperature to rise to 110℃, turn the materials for the fourth time. Raise to 115-120°C, turn the materials over five times, mix again for 1 minute, discharge the glue, and leave it at room temperature for more than 24 hours;
步骤三，将密炼后的混合物在开炼机上混炼，并加入上述份量的二苯磺酰肼醚、促进剂，混料均匀片状出片，得发泡片；Step 3: Mix the internally mixed mixture on an open mill, add the above-mentioned amounts of diphenylsulfonyl hydrazine ether and accelerator, and mix the mixture into uniform sheets to obtain foamed tablets;
步骤四，将发泡片裁成鞋底形状放入橡胶鞋模中硫化成型，硫化温度为145-160℃，得所述橡胶发泡鞋底。Step 4: Cut the foam sheet into the shape of a shoe sole and put it into a rubber shoe mold for vulcanization and molding. The vulcanization temperature is 145-160°C to obtain the rubber foam shoe sole.
实施例1Example 1
一种耐寒防滑橡胶发泡鞋底，包括以下重量份的原料：A cold-resistant anti-slip rubber foam sole, including the following raw materials by weight:
Figure PCTCN2022115041-appb-000005
Figure PCTCN2022115041-appb-000005
Figure PCTCN2022115041-appb-000006
Figure PCTCN2022115041-appb-000006
其中，促进剂由乙醇胺、氧化锌、苯二甲酸按质量比1:1.8:0.72的比例组成；填料由海泡石粉与硅藻土按质量比1：2的比例组成。Among them, the accelerator is composed of ethanolamine, zinc oxide, and phthalic acid in a mass ratio of 1:1.8:0.72; the filler is composed of sepiolite powder and diatomite in a mass ratio of 1:2.
一种耐寒防滑橡胶发泡鞋底的制备方法，包括以下步骤：A preparation method for cold-resistant anti-slip rubber foam soles, including the following steps:
步骤一，将所需重量份的溶聚丁苯橡胶、丙烯酸酯橡胶、氯醚橡胶在密炼机中密炼15min，得预混物；Step 1: Mix the required weight portions of solution-polymerized styrene-butadiene rubber, acrylate rubber, and chloroether rubber in an internal mixer for 15 minutes to obtain a premix;
步骤二，往密炼机中加入步骤一制备的预混物和除二苯磺酰肼醚、促进剂外的其他原料，混合密炼5min；然后调整密炼温度到90℃，保持3min后一次翻料；待密炼温度升至95℃，二次翻料；待密炼温度升至104℃，三次翻料；待密炼温度升至110℃，四次翻料；待密炼温度升至115℃，五次翻料，再密炼1min，排胶，室温放置24h以上；Step 2: Add the premix prepared in step 1 and other raw materials except diphenylsulfonyl hydrazine ether and accelerator into the internal mixer, mix and mix for 5 minutes; then adjust the internal mixing temperature to 90°C and keep it for 3 minutes. Turn over the materials; wait for the internal mixing temperature to rise to 95℃, turn over the materials twice; wait for the internal mixing temperature to rise to 104℃, turn over the materials three times; wait for the internal mixing temperature to rise to 110℃, turn over the materials four times; wait until the internal mixing temperature rises to 115℃, turn the materials five times, mix again for 1 minute, drain the glue, and leave it at room temperature for more than 24 hours;
步骤三，将密炼后的混合物在开炼机上混炼，并加入上述比例称量的二苯磺酰肼醚、促进剂，混料均匀片状出片，得发泡片；Step 3: Mix the internally mixed mixture on an open mill, add diphenyl sulfonyl hydrazine ether and accelerator weighed in the above proportions, and mix the mixture into uniform sheets to obtain foamed tablets;
步骤四，将发泡片裁成鞋底形状放入橡胶鞋模中硫化成型，硫化温度为145℃，得所述橡胶发泡鞋底。Step 4: Cut the foam sheet into the shape of a shoe sole and put it into a rubber shoe mold for vulcanization and molding. The vulcanization temperature is 145°C to obtain the rubber foam shoe sole.
实施例2Example 2
一种耐寒防滑橡胶发泡鞋底，包括以下重量份的原料：A cold-resistant anti-slip rubber foam sole, including the following raw materials by weight:
Figure PCTCN2022115041-appb-000007
Figure PCTCN2022115041-appb-000007
Figure PCTCN2022115041-appb-000008
Figure PCTCN2022115041-appb-000008
其中，促进剂由乙醇胺、氧化锌、苯二甲酸按质量比1:2.7:0.54的比例组成；填料由海泡石粉与硅藻土按质量比1：3的比例组成。Among them, the accelerator is composed of ethanolamine, zinc oxide, and phthalic acid in a mass ratio of 1:2.7:0.54; the filler is composed of sepiolite powder and diatomite in a mass ratio of 1:3.
一种耐寒防滑橡胶发泡鞋底的制备方法，包括以下步骤：A preparation method for cold-resistant anti-slip rubber foam soles, including the following steps:
步骤一，将所需重量份的溶聚丁苯橡胶、丙烯酸酯橡胶、氯醚橡胶在高密炼机中密炼10min，得预混物；Step 1: Mix the required weight portions of solution-polymerized styrene-butadiene rubber, acrylate rubber, and chloroether rubber in a high internal mixer for 10 minutes to obtain a premix;
步骤二，往密炼机中加入步骤一制备的预混物和除二苯磺酰肼醚、促进剂外的其他原料，混合密炼10min；然后调整密炼温度到90℃，保持3min后一次翻料；待密炼温度升至95℃，二次翻料；待密炼温度升至104℃，三次翻料；待密炼温度升至110℃，四次翻料；待密炼温度升至 120℃，五次翻料，再密炼1min，排胶，室温放置24h以上；Step 2: Add the premix prepared in Step 1 and other raw materials except diphenylsulfonyl hydrazine ether and accelerator into the internal mixer, mix and mix for 10 minutes; then adjust the internal mixing temperature to 90°C and keep it for 3 minutes. Turn over the materials; wait for the internal mixing temperature to rise to 95℃, turn over the materials twice; wait for the internal mixing temperature to rise to 104℃, turn over the materials three times; wait for the internal mixing temperature to rise to 110℃, turn over the materials four times; wait until the internal mixing temperature rises to 120℃, turn the materials five times, mix again for 1 minute, drain the glue, and leave it at room temperature for more than 24 hours;
步骤三，将密炼后的混合物在开炼机上混炼，并加入按上述比例确定的二苯磺酰肼醚、促进剂，混料均匀片状出片，得发泡片；Step 3: Mix the internally mixed mixture on an open mill, add diphenyl sulfonyl hydrazine ether and accelerator determined according to the above ratio, and mix the mixture into uniform sheets to obtain foamed tablets;
步骤四，将发泡片裁成鞋底形状放入橡胶鞋模中硫化成型，硫化温度为160℃，得所述橡胶发泡鞋底。Step 4: Cut the foam sheet into the shape of a shoe sole and put it into a rubber shoe mold for vulcanization and molding. The vulcanization temperature is 160°C to obtain the rubber foam shoe sole.
实施例3Example 3
一种耐寒防滑橡胶发泡鞋底，包括以下重量份的原料：A cold-resistant anti-slip rubber foam sole, including the following raw materials by weight:
Figure PCTCN2022115041-appb-000009
Figure PCTCN2022115041-appb-000009
Figure PCTCN2022115041-appb-000010
Figure PCTCN2022115041-appb-000010
其中，促进剂由乙醇胺、氧化锌、苯二甲酸按质量比1:2.3:0.65的比例组成；填料由海泡石粉与硅藻土按质量比1：2.5的比例组成。Among them, the accelerator is composed of ethanolamine, zinc oxide, and phthalic acid in a mass ratio of 1:2.3:0.65; the filler is composed of sepiolite powder and diatomite in a mass ratio of 1:2.5.
一种耐寒防滑橡胶发泡鞋底的制备方法，包括以下步骤：A preparation method for cold-resistant anti-slip rubber foam soles, including the following steps:
步骤一，将所需重量份的溶聚丁苯橡胶、丙烯酸酯橡胶、氯醚橡胶在密炼机中密炼12min，得预混物；Step 1: Mix the required weight portions of solution-polymerized styrene-butadiene rubber, acrylate rubber, and chloroether rubber in an internal mixer for 12 minutes to obtain a premix;
步骤二，往密炼机中加入步骤一制备的预混物和除二苯磺酰肼醚、促进剂外的其他原料，混合密炼8min；然后调整密炼温度到90℃，保持3min后一次翻料；待密炼温度升至95℃，二次翻料；待密炼温度升至104℃，三次翻料；待密炼温度升至110℃，四次翻料；待密炼温度升至118℃，五次翻料，再密炼1min，排胶，室温放置24h以上；Step 2: Add the premix prepared in Step 1 and other raw materials except diphenylsulfonyl hydrazine ether and accelerator into the internal mixer, mix and mix for 8 minutes; then adjust the internal mixing temperature to 90°C and keep it for 3 minutes. Turn over the materials; wait for the internal mixing temperature to rise to 95℃, turn over the materials twice; wait for the internal mixing temperature to rise to 104℃, turn over the materials three times; wait for the internal mixing temperature to rise to 110℃, turn over the materials four times; wait until the internal mixing temperature rises to 118℃, turn the materials five times, mix again for 1 minute, drain the glue, and leave it at room temperature for more than 24 hours;
步骤三，将密炼后的混合物在开炼机上混炼，并加入所需量的二苯磺酰肼醚、促进剂，混料均匀片状出片，得发泡片；Step 3: Mix the internally mixed mixture on an open mill, add the required amount of diphenylsulfonyl hydrazine ether and accelerator, and mix the mixture into uniform sheets to obtain foamed tablets;
步骤四，将发泡片裁成鞋底形状放入橡胶鞋模中硫化成型，硫化温度为155℃，得所述橡胶发泡鞋底。Step 4: Cut the foam sheet into the shape of a shoe sole and put it into a rubber shoe mold for vulcanization and molding. The vulcanization temperature is 155°C to obtain the rubber foam shoe sole.
对比例1Comparative example 1
其原料组成与制备方法与实施例3基本一致，其区别在于：原料组成中，二苯磺酰肼醚替换为发泡剂AC。The raw material composition and preparation method are basically the same as those in Example 3, except that in the raw material composition, diphenylsulfonyl hydrazine ether is replaced by the foaming agent AC.
对比例2Comparative example 2
其原料组成与制备方法与实施例3基本一致，其区别在于：原料组成中，促进剂为过氧化二异丙苯。The raw material composition and preparation method are basically the same as those in Example 3, except that in the raw material composition, the accelerator is dicumyl peroxide.
对比例3Comparative example 3
其原料组成与制备方法与实施例3基本一致，其区别在于：原料组成中，促进剂为乙醇胺、氧化锌按质量比1:1.8-2.7的比例组成。The raw material composition and preparation method are basically the same as those in Example 3. The difference is that in the raw material composition, the accelerator is ethanolamine and zinc oxide in a mass ratio of 1:1.8-2.7.
对比例4Comparative example 4
其原料组成与制备方法与实施例3基本一致，其区别在于：原料组成中，促进剂为乙醇胺、苯二甲酸按质量比1:0.54-0.72的比例组成。The raw material composition and preparation method are basically the same as those in Example 3. The difference is that in the raw material composition, the accelerator is ethanolamine and phthalic acid in a mass ratio of 1:0.54-0.72.
对比例5Comparative example 5
其原料组成与制备方法与实施例3基本一致，其区别在于：原料组成中，填料为滑石粉。The raw material composition and preparation method are basically the same as those in Example 3. The difference is that in the raw material composition, the filler is talc powder.
将实施例1-3与对比例1-5制备的橡胶发泡鞋底进行相应测试，获得如下数据：The rubber foam soles prepared in Examples 1-3 and Comparative Examples 1-5 were tested accordingly, and the following data were obtained:
表1各实施例数据表Table 1 Data table of each embodiment
Figure PCTCN2022115041-appb-000011
Figure PCTCN2022115041-appb-000011
Figure PCTCN2022115041-appb-000012
Figure PCTCN2022115041-appb-000012
通过上述表格可知，本申请制备的橡胶发泡鞋底能够在(-30)℃的寒冷环境下保持相适宜的柔软性、弹性及弯曲性能，满足寒冷环境下要求的鞋底舒适度；其中，限定溶聚丁苯橡胶、丙烯酸酯橡胶、氯醚橡胶相互混用，与其他原料配合，在性能上能够做到互补，以使制得的橡胶鞋底具有耐寒、防滑性能；限定乙醇胺、氧化锌、苯二甲酸作为促进剂，二苯磺酰肼醚作为发泡剂，配合氯醚橡胶改善丙烯酸酯橡胶的耐寒性、弹性，以提高共混胶的耐寒性和弹性，以使制得的橡胶鞋底适用于(-30)℃的寒冷环境；同时，以乙醇胺、氧化锌、苯二甲酸复配的促进剂，可使混合胶的硫化速度与发泡速度大致同步，以获得良好的孔眼结构，保证制得的橡胶鞋底的力学性能。It can be seen from the above table that the rubber foam soles prepared in this application can maintain appropriate softness, elasticity and bending properties in a cold environment of (-30)°C, and meet the required sole comfort in cold environments; where the solution is limited Polystyrene-butadiene rubber, acrylic rubber, and chloroether rubber are mixed with each other and matched with other raw materials to complement each other in performance, so that the rubber soles produced have cold resistance and anti-slip properties; ethanolamine, zinc oxide, and phthalic acid are limited As an accelerator, diphenylsulfonyl hydrazine ether is used as a foaming agent, and is combined with chloroether rubber to improve the cold resistance and elasticity of acrylic rubber to improve the cold resistance and elasticity of the blended rubber so that the prepared rubber sole is suitable for ( -30)℃ cold environment; at the same time, the accelerator compounded with ethanolamine, zinc oxide, and phthalic acid can make the vulcanization speed of the mixed rubber roughly synchronized with the foaming speed to obtain a good hole structure and ensure the obtained Mechanical properties of rubber soles.
以上所述，仅为本发明的较佳实施例而已，故不能以此限定本发明实施的范围，即依本发明申请专利范围及说明书内容所作的等效变化与 修饰，皆应仍属本发明专利涵盖的范围内。The above are only preferred embodiments of the present invention, and therefore cannot be used to limit the scope of the present invention. That is, equivalent changes and modifications made based on the patent scope of the present invention and the content of the specification shall still belong to the present invention. within the scope covered by the patent.
工业实用性Industrial applicability
本发明公开了一种耐寒防滑橡胶发泡鞋底及其制备方法，橡胶发泡鞋底包括以下原料：溶聚丁苯橡胶、丙烯酸酯橡胶、氯醚橡胶、石蜡油、二苯磺酰肼醚、促进剂、填料、聚乙烯蜡、硬脂酸镁、硅烷偶联剂、防老剂、增塑剂、分散剂、活性剂，本申请限定溶聚丁苯橡胶、丙烯酸酯橡胶、氯醚橡胶相互混用，与其他原料配合，在性能上能够做到互补，以使制得的橡胶鞋底具有耐寒、防滑性能，能够在(-30)℃的寒冷环境下保持相适宜的柔软性、弹性及弯曲性能，满足寒冷环境下要求的鞋底舒适度,具有工业实用性。The invention discloses a cold-resistant anti-slip rubber foam sole and a preparation method thereof. The rubber foam sole includes the following raw materials: solution-polymerized styrene-butadiene rubber, acrylate rubber, chloroether rubber, paraffin oil, diphenylsulfonylhydrazine ether, accelerator Agent, filler, polyethylene wax, magnesium stearate, silane coupling agent, antioxidant, plasticizer, dispersant, active agent. This application limits the mixing of solution-polymerized styrene-butadiene rubber, acrylate rubber, and chloroether rubber. When combined with other raw materials, they can be complementary in performance, so that the rubber soles produced have cold resistance and anti-slip properties, and can maintain appropriate softness, elasticity and bending properties in a cold environment of (-30)°C, meeting the requirements The sole comfort required in cold environments has industrial practicality.

Claims (10)

  1. 一种耐寒防滑橡胶发泡鞋底，其特征在于：包括以下重量份的原料：A kind of cold-resistant anti-slip rubber foam sole, which is characterized in that: it includes the following raw materials in parts by weight:
    Figure PCTCN2022115041-appb-100001
    Figure PCTCN2022115041-appb-100001
  2. 根据权利要求1所述的一种耐寒防滑橡胶发泡鞋底，其特征在于：所述促进剂由乙醇胺、氧化锌、苯二甲酸按质量比1:1.8-2.7:0.54-0.72的比例组成。A kind of cold-resistant anti-slip rubber foam sole according to claim 1, characterized in that: the accelerator is composed of ethanolamine, zinc oxide, and phthalic acid in a mass ratio of 1:1.8-2.7:0.54-0.72.
  3. 根据权利要求1所述的一种耐寒防滑橡胶发泡鞋底，其特征在于： 所述填料由海泡石粉与硅藻土按质量比1：2-3的比例组成。A cold-resistant anti-slip rubber foam sole according to claim 1, characterized in that: the filler is composed of sepiolite powder and diatomite in a mass ratio of 1:2-3.
  4. 根据权利要求1所述的一种耐寒防滑橡胶发泡鞋底，其特征在于：所述防老剂为防老剂4020。A kind of cold-resistant anti-slip rubber foam sole according to claim 1, characterized in that: the anti-aging agent is anti-aging agent 4020.
  5. 根据权利要求1所述的一种耐寒防滑橡胶发泡鞋底，其特征在于：所述分散剂为分散剂AT-B。A cold-resistant anti-slip rubber foam sole according to claim 1, characterized in that the dispersant is dispersant AT-B.
  6. 根据权利要求1所述的一种耐寒防滑橡胶发泡鞋底，其特征在于：所述活性剂为聚乙二醇。A cold-resistant anti-slip rubber foam sole according to claim 1, characterized in that: the active agent is polyethylene glycol.
  7. 根据权利要求1所述的一种耐寒防滑橡胶发泡鞋底，其特征在于：所述增塑剂为二甘醇。A cold-resistant anti-slip rubber foam sole according to claim 1, characterized in that: the plasticizer is diethylene glycol.
  8. 一种耐寒防滑橡胶发泡鞋底的制备方法，其特征在于：包括以下步骤：A method for preparing cold-resistant anti-slip rubber foam soles, which is characterized in that it includes the following steps:
    步骤一，将所需重量份的溶聚丁苯橡胶、丙烯酸酯橡胶、氯醚橡胶在密炼机中密炼10-15min，得预混物；Step 1: Mix the required weight portions of solution-polymerized styrene-butadiene rubber, acrylate rubber, and chloroether rubber in an internal mixer for 10-15 minutes to obtain a premix;
    步骤二，将步骤一制备的预混物和除二苯磺酰肼醚、促进剂外的其他原料，混合密炼，115-120℃排胶，室温放置24h以上；Step 2: Mix the premix prepared in Step 1 and other raw materials except diphenylsulfonyl hydrazine ether and accelerator, and mix them, debind them at 115-120°C, and leave them at room temperature for more than 24 hours;
    步骤三，将密炼后的混合物在开炼机上混炼，并加入准确称量的二苯磺酰肼醚、促进剂，混料均匀片状出片，得发泡片；Step 3: Mix the internally mixed mixture on an open mill, add accurately weighed diphenylsulfonyl hydrazine ether and accelerator, and mix the mixture into uniform sheets to obtain foamed tablets;
    步骤四，将发泡片裁成鞋底形状放入橡胶鞋模中硫化成型，得所述橡胶发泡鞋底。Step 4: Cut the foam sheet into a shoe sole shape and put it into a rubber shoe mold for vulcanization and molding to obtain the rubber foam shoe sole.
  9. 根据权利要求8所述的一种耐寒防滑橡胶发泡鞋底的制备方法，其特征在于：步骤二中，密炼过程具体包括：往密炼机中加入步骤一制 备的预混物和除二苯磺酰肼醚、促进剂外的其他原料，混合密炼5-10min；然后调整密炼温度到90℃，保持3min后一次翻料；待密炼温度升至95℃，二次翻料；待密炼温度升至104℃，三次翻料；待密炼温度升至110℃，四次翻料；待密炼温度升至115-120℃，五次翻料，再密炼1min，排胶，室温放置24h以上。A method for preparing cold-resistant anti-slip rubber foam soles according to claim 8, characterized in that: in step two, the internal mixing process specifically includes: adding the premix prepared in step one and removing diphenyl to the internal mixer. Mix other raw materials except sulfonyl hydrazine ether and accelerator for 5-10 minutes; then adjust the internal mixing temperature to 90°C, keep it for 3 minutes and then turn over once; wait until the internal mixing temperature rises to 95°C, turn over twice; wait for When the internal mixing temperature rises to 104℃, turn the materials three times; when the internal mixing temperature rises to 110℃, turn the materials four times; when the internal mixing temperature rises to 115-120℃, turn the materials five times, then mix for another 1 minute, and remove the glue. Leave at room temperature for more than 24 hours.
  10. 根据权利要求8所述的一种耐寒防滑橡胶发泡鞋底的制备方法，其特征在于：步骤四中，硫化成型的温度为145-160℃。The method for preparing cold-resistant anti-slip rubber foam soles according to claim 8, characterized in that in step four, the vulcanization molding temperature is 145-160°C.
PCT/CN2022/115041 2022-04-06 2022-08-26 Cold-resistant anti-skid rubber foam sole and preparation method therefor WO2023193391A1 (en)

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