CN109096651A - A kind of preparation method of antibacterial wear-resisting foaming sole material - Google Patents

A kind of preparation method of antibacterial wear-resisting foaming sole material Download PDF

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CN109096651A
CN109096651A CN201810943381.5A CN201810943381A CN109096651A CN 109096651 A CN109096651 A CN 109096651A CN 201810943381 A CN201810943381 A CN 201810943381A CN 109096651 A CN109096651 A CN 109096651A
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parts
sole material
graphite
preparation
resisting
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刘菊花
章红英
王素香
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Foshan Chao Hung New Mstar Technology Ltd
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Foshan Chao Hung New Mstar Technology Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06Working-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
    • C08J9/10Working-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
    • C08J9/102Azo-compounds
    • C08J9/103Azodicarbonamide
    • AHUMAN NECESSITIES
    • A43FOOTWEAR
    • A43BCHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00Soles; Sole-and-heel integral units
    • A43B13/02Soles; Sole-and-heel integral units characterised by the material
    • A43B13/04Plastics, rubber or vulcanised fibre
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00Foams characterized by the expanding agent
    • C08J2203/04N2 releasing, ex azodicarbonamide or nitroso compound
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00Characterised 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 at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02Characterised 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 at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04Characterised 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 at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06Homopolymers or copolymers of vinyl chloride
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2409/00Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08J2409/02Copolymers with acrylonitrile
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/09Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098Metal salts of carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/22Expanded, porous or hollow particles
    • C08K7/24Expanded, porous or hollow particles inorganic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/02Ingredients treated with inorganic substances
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/04Ingredients treated with organic substances

Abstract

The invention discloses a kind of preparation methods of antibacterial wear-resisting foaming sole material, belong to sole material preparation technical field.The present invention is by expansible graphite microwave treatment, the thrust of the inter-layer bonding force much larger than graphite particle is formed by concussion dispersion, cause nano-graphite lamella fully dispersed in rubber, and the insulation crystalline region of rubber can be destroyed, nano zine oxide is the anti-biotic material haveing excellent performance, when being contacted with bacterium, zinc ion, which will be slow, to be released, the present invention fills nanometer silicon carbide in polyvinyl-chloride foam material, since nanometer silicon carbide density is low, hardness is high, compatibility between nanometer silicon carbide and PVC base system is poor, therefore the present invention passes through addition titanate coupling agent isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, make nanometer silicon carbide in PVC base system dispersibility be improved significantly, to reduce the abrasion loss and friction factor of sole material, significantly improve its wear-resisting property, before wide application Scape.

Description

A kind of preparation method of antibacterial wear-resisting foaming sole material
Technical field
The invention discloses a kind of preparation methods of antibacterial wear-resisting foaming sole material, belong to sole material technology of preparing neck Domain.
Background technique
The construction of sole is considerably complicated, just in the broadest sense, it may include all materials for constituting bottom such as outer bottom, indsole and heel Material.For narrow sense, then for only referring to outer bottom, the common characteristic of general sole material should have it is wear-resisting, water-fast, oil resistant, it is heat-resisting, Pressure resistance, impact resistance, elasticity is good, is easy after suitable foot type, sizing not flexible type, heat preservation, easily absorption moisture etc., while more to cooperate Indsole has braking action to be not the stop Deng terms and conditions that slip and be easy in the change of feet on foot.There are many type of sole materials, Two kinds of class bottom material of natural class bottom material and synthesis can be divided into.Natural class bottom material includes natural bottom leather, bamboo and wood material etc., synthesizes class bottom material Including rubber, plastics, rubber and plastic suitable materials, regenerated leather, elastic hardboard etc..
Shoes are the essential daily necessities of people's daily life, and the comfort level and wearability of sole determine the practical of shoes Property and its service life.Foamed shoe sole is comfortable, light because of its, has the characteristics that certain functionality, so that it is in shoes Using more and more extensive.
Since foamed shoe sole is made of homogenous material foaming, the soft or hard degree of entire sole different parts is one Sample.But the sole of people be not it is flat, arch of the foot position all be arch, generally all cannot directly be contacted with foamed shoe sole; Furthermore when people walk, the stress degree of foamed shoe sole different location be it is different, the heel position of general foamed shoe sole by Power is maximum, and maximum with floor frictional force, and arch of the foot position sole absolutely not stress, and tiptoe position sole stress degree is slightly It is small.Therefore, shoes are broken down because heel position sole abrasion is serious.
With the development of social economy and the raising of living standards of the people, people pay more attention in the comfort and safety of shoes Property, such as the performance requirements such as the damping, on-slip and lightweight of shoes are continuously improved.Usually increase the service life of shoes, foaming Expansion ratio can be reduced in sole preparation process, promote the wearability of sole, although the service life of shoes can be promoted in this way, Sole is heavier, shoes degree of comfort decreased, and arch of the foot position still can not directly be contacted with sole, directly affects shoes feel.At present The internal layer specific surface area of foaming sole material is larger, soaks rear bacterium easy to breed, the antistatic effect of foaming sole material by sweat Fruit is poor, and wear-resisting property is bad.
Therefore, inventing the antibacterial wear-resisting foaming sole material of one kind has positive effect to sole material preparation technical field.
Summary of the invention
Present invention mainly solves the technical issues of, it is larger for the internal layer specific surface area of current foaming sole material, by sweat Liquid soaks rear bacterium easy to breed, and foaming sole material antistatic effect is poor, and the bad defect of wear-resisting property provides a kind of suppression The preparation method of the wear-resisting foaming sole material of bacterium.
In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is that:
A kind of preparation method of antibacterial wear-resisting foaming sole material, it is characterised in that specific preparation step are as follows:
(1) it weighs 20~30g expansible graphite to be placed in a vacuum drying oven, 100~120g, five oxygen is put into vacuum oven Change two phosphorus, it is dry, the expansible graphite after drying is put into beaker, then beaker is placed in microwave treater and is handled, is taken out Beaker is cooled to room temperature, and expands expansible graphite, and such microwave treatment heating expansion 3~5 times obtains expanded graphite;
(2) 20~25g lauryl sodium sulfate, 4~5g nano zine oxide, 200~220mL deionized water are mixed, stirring 10 ~15min, obtains emulsion, and 10~15g expanded graphite is impregnated in emulsion, suspension is obtained, is surpassed to suspension Sonication obtains the water slurry of nano-graphite lamella after ultrasonic treatment;
(3) 100~110g acrylonitrile and 90~100g butadiene are added in the three-necked flask with blender and thermometer, to 100~120mL sodium hydroxide solution, 30~40g polyvinyl alcohol and 100~110mL nano-graphite lamella are added in three-necked flask Water slurry, start blender, after 80~90r/min revolving speed stirring and emulsifying, 10~15min, be added 1~3g potassium peroxydisulfate, Heat temperature raising, insulation reaction obtain nanometer enhancing nitrile rubber;
(4) according to parts by weight, 10~15 parts of nanometer enhancing nitrile rubbers, 20~30 parts of polyvinyl chloride resins are placed in double roll mill In, it plasticates 2~3 times, then 10~12 parts of nanometer silicon carbides, 4~5 parts of (dioctyl cokes of isopropyls three are added into double roll mill Phosphoric acid acyloxy) titanate esters, it mixes and plasticates 2~3 times, obtain mixing rubber;
(5) according to parts by weight, by 4~5 parts of azodicarbonamides, 0.7~1.0 part of cumyl peroxide, 0.4~0.5 part Sulphur, 0.2~0.3 part of benzothiazole disulfide, 2~3 parts of zinc stearates, 30~35 parts of mixing rubber are added to open type dual-roller It is pressed into sheet material on kneading machine, vulcanizer is embedded into mold heating in advance, sheet material obtained is put into vulcanizer and is embedded in mold, The molding of pressing mold crosslinked foaming is carried out, slice obtains antibacterial wear-resisting foaming sole material after cooled to room temperature.
Vacuum oven temperature is set described in step (1) as 100~110 DEG C, drying time is 8~10h, microwave treatment Device sets power as 700~800W, and the processing time is 40~45s.
Ultrasonic frequency is set as 30~32kHz when ultrasonic treatment described in step (2).
The mass fraction of sodium hydroxide solution described in step (3) is 5%, after three-necked flask heat temperature raising temperature be 45~ 48 DEG C, the insulation reaction time is 3~4h.
When double roll mill described in step (4) is kneaded, preceding roll temperature is 55~60 DEG C, and rear roll temperature is 50~55 DEG C, Roll spacing is 6~8mm.
Sheet thickness described in step (5) is 3~4mm, and temperature is 180~200 DEG C after vulcanizer embeds mold preheating, pressure Pressure is 1.4~1.5MPa when mould crosslinked foaming forms.
The beneficial effects of the present invention are:
(1) for the present invention by expansible graphite microwave treatment, heat expandable graphite obtains expanded graphite, then expanded graphite is placed in It is ultrasonically treated in surface activating solution, forms the thrust of the inter-layer bonding force much larger than graphite particle by concussion dispersion, Make nano zine oxide intercalation in nano graphite flakes interlayer, nano-graphite lamella during acrylonitrile and butadiene copolymer, due to Nano-graphite lamella can trigger the cross-linking reaction of rubber there may be some active reaction points, improve nano-graphite lamella with The compatibility of rubber, under the conditions of emulsion blending, graphite flake layer has reached nano-dispersed in rubber matrix, while there are also certain Intercalation configuration exist, potential active site and rubber molecule, which have occurred, on nano-graphite lamella sufficient contact and thus occurs Autovulcanization, causes nano-graphite lamella fully dispersed in rubber, and can destroy the insulation crystalline region of rubber, forms conductive mesh Network reduces the resistivity of sole material, so as to improve the electric conductivity of sole material, mentions the antistatic property of sole material Height, nano zine oxide is the anti-biotic material haveing excellent performance, and when contacting with bacterium, zinc ion, which will be slow, to be released, due to zinc Ion has oxidation-reduction quality, thus can in conjunction with cell membrane and memebrane protein, and with the sulfydryl of organic matter in its structure, carboxyl, Hydroxyl reaction destroys after its structure enters cell and destroys the enzyme of electron transport system, and reacts with-SH base, reaches the mesh of antibacterial , and after killing bacterium, zinc ion can come out from endocellular liberation, repeat the above process, and nano zine oxide Intercalation is acted in nano-graphite sheet material by electrostatic attraction, and washability is preferable, to reach more lasting anti-microbial property;
(2) present invention fills nanometer silicon carbide in polyvinyl-chloride foam material, since nanometer silicon carbide density is low, hardness is high, It is good with excellent thermodynamic stability, wear-resisting property, therefore the compression strength, hardness and creep resistance of sole material can be improved Can, and with other substances rub when, nanometer silicon carbide can play the role of carrying, therefore improve the wear-resisting of this sole material Performance, the compatibility between nanometer silicon carbide and PVC base system is poor, and interface bond strength is lower, therefore the present invention passes through Titanate coupling agent isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters are added, make nanometer silicon carbide in PVC base system In dispersibility be improved significantly, so that nanometer silicon carbide reunion volume is become smaller and is evenly distributed, and change its intrinsic parent It is aqueous, significantly improve the interface bond strength of nanometer silicon carbide and polyvinyl chloride, in friction process, nanometer silicon carbide is not easy It falls off from resin, reduces the abrasive wear of sole material, to reduce the abrasion loss and friction factor of sole material, significantly Its wear-resisting property is improved, is had broad application prospects.
Specific embodiment
It weighs 20~30g expansible graphite to be placed in a vacuum drying oven, sets vacuum oven temperature as 100~110 DEG C, 100~120g phosphorus pentoxide is put into vacuum oven, the expansible graphite after drying is put into beaker by dry 8~10h In, then beaker is placed on 40~45s of Power Processing in microwave treater with 700~800W, it takes out beaker and is cooled to room temperature, make Expansible graphite expands, and such microwave treatment heating expansion 3~5 times obtains expanded graphite;By 20~25g dodecyl Sodium sulphate, 4~5g nano zine oxide, the mixing of 200~220mL deionized water, stir 10~15min, obtain emulsion, by 10~ 15g expanded graphite is impregnated in emulsion, obtains suspension, is ultrasonically treated to suspension, sets ultrasonic frequency as 30 ~32kHz obtains the water slurry of nano-graphite lamella after ultrasonic treatment;By 100~110g acrylonitrile and 90~100g fourth two Alkene is added in the three-necked flask with blender and thermometer, and it is 5% that 100~120mL mass fraction is added into three-necked flask The water slurry of sodium hydroxide solution, 30~40g polyvinyl alcohol and 100~110mL nano-graphite lamella starts blender, with After 80~90r/min revolving speed stirring and emulsifying, 10~15min, 1~3g potassium peroxydisulfate is added, is heated to 45~48 DEG C, heat preservation 3~4h is reacted, nanometer enhancing nitrile rubber is obtained;According to parts by weight, 10~15 parts of nanometers are enhanced into nitrile rubber, 20~30 Part polyvinyl chloride resin is placed in double roll mill, is 55~60 DEG C in preceding roll temperature, and rear roll temperature is 50~55 DEG C, and roll spacing is 6~ It plasticates under conditions of 8mm 2~3 times, then 10~12 parts of nanometer silicon carbides, 4~5 parts of isopropyls three is added into double roll mill (dioctylphyrophosphoric acid acyloxy) titanate esters, mixing are plasticated 2~3 times, and mixing rubber is obtained;According to parts by weight, by 4~5 parts Azodicarbonamide, 0.7~1.0 part of cumyl peroxide, 0.4~0.5 part of sulphur, 0.2~0.3 part of curing benzo thiophene Azoles, 2~3 parts of zinc stearates, 30~35 parts of mixing rubber are added to being pressed into a thickness of 3~4mm on open type dual-roller kneading machine Sheet material, vulcanizer is embedded into mold in advance and is heated to 180~200 DEG C, by sheet material obtained be put into vulcanizer embed mold in, The molding of pressing mold crosslinked foaming is carried out with the pressure of 1.4~1.5MPa, and slice obtains antibacterial wear-resisting foaming after cooled to room temperature Sole material.
It weighs 20g expansible graphite to be placed in a vacuum drying oven, sets vacuum oven temperature as 100 DEG C, done to vacuum It is put into 100g phosphorus pentoxide in dry case, the expansible graphite after drying is put into beaker by dry 8h, then beaker is placed on micro- With the Power Processing 40s of 700W in wave processor, takes out beaker and be cooled to room temperature, expand expansible graphite, it is so micro- Wave processing heating expansion 3 times, obtains expanded graphite;By 20g lauryl sodium sulfate, 4g nano zine oxide, 200mL deionized water Mixing stirs 10min, obtains emulsion, 10g expanded graphite is impregnated in emulsion, suspension is obtained, and carries out to suspension Ultrasonic treatment, sets ultrasonic frequency as 30kHz, the water slurry of nano-graphite lamella is obtained after ultrasonic treatment;By 100g third Alkene nitrile and 90g butadiene are added in the three-necked flask with blender and thermometer, and 100mL mass point is added into three-necked flask The water slurry of sodium hydroxide solution, 30g polyvinyl alcohol and 100mL nano-graphite lamella that number is 5%, starts blender, with After 80r/min revolving speed stirring and emulsifying 10min, 1g potassium peroxydisulfate is added, is heated to 45 DEG C, insulation reaction 3h obtains nanometer Enhance nitrile rubber;According to parts by weight, 10 parts of nanometer enhancing nitrile rubbers, 20 parts of polyvinyl chloride resins are placed in double roll mill, It is 55 DEG C in preceding roll temperature, rear roll temperature is 50 DEG C, and roll spacing is plasticated 2 times under conditions of being 6mm, then is added into double roll mill 10 parts of nanometer silicon carbides, 4 parts of isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, mixing are plasticated 2 times, obtain being kneaded rubber Glue;According to parts by weight, by 4 parts of azodicarbonamides, 0.7 part of cumyl peroxide, 0.4 part of sulphur, 0.2 part of curing benzene And thiazole, 2 parts of zinc stearates, 30 parts of mixing rubber are added to the sheet material being pressed on open type dual-roller kneading machine with a thickness of 3mm, Vulcanizer is embedded into mold in advance and is heated to 180 DEG C, sheet material obtained is put into vulcanizer and is embedded in mold, with the pressure of 1.4MPa Power carries out the molding of pressing mold crosslinked foaming, and slice obtains antibacterial wear-resisting foaming sole material after cooled to room temperature.
It weighs 25g expansible graphite to be placed in a vacuum drying oven, sets vacuum oven temperature as 105 DEG C, done to vacuum It is put into 110g phosphorus pentoxide in dry case, the expansible graphite after drying is put into beaker by dry 9h, then beaker is placed on micro- With the Power Processing 42s of 750W in wave processor, takes out beaker and be cooled to room temperature, expand expansible graphite, it is so micro- Wave processing heating expansion 4 times, obtains expanded graphite;By 22g lauryl sodium sulfate, 4g nano zine oxide, 210mL deionized water Mixing stirs 12min, obtains emulsion, 12g expanded graphite is impregnated in emulsion, suspension is obtained, and carries out to suspension Ultrasonic treatment, sets ultrasonic frequency as 31kHz, the water slurry of nano-graphite lamella is obtained after ultrasonic treatment;By 105g third Alkene nitrile and 95g butadiene are added in the three-necked flask with blender and thermometer, and 110mL mass point is added into three-necked flask The water slurry of sodium hydroxide solution, 35g polyvinyl alcohol and 105mL nano-graphite lamella that number is 5%, starts blender, with After 85r/min revolving speed stirring and emulsifying 12min, 2g potassium peroxydisulfate is added, is heated to 47 DEG C, insulation reaction 3.5h is received Meter Zeng Qiang nitrile rubber;According to parts by weight, 12 parts of nanometer enhancing nitrile rubbers, 25 parts of polyvinyl chloride resins are placed in double roll mill In, it is 57 DEG C in preceding roll temperature, rear roll temperature is 52 DEG C, and roll spacing is plasticated 2 times under conditions of being 7mm, then into double roll mill 11 parts of nanometer silicon carbides, 4 parts of isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters are added, mixing is plasticated 2 times, is kneaded Rubber;According to parts by weight, by 4 parts of azodicarbonamides, 0.9 part of cumyl peroxide, 0.4 part of sulphur, 0.2 part of curing Benzothiazole, 2 parts of zinc stearates, 32 parts of mixing rubber are added to the piece being pressed on open type dual-roller kneading machine with a thickness of 3mm Vulcanizer is embedded mold in advance and is heated to 190 DEG C by material, and sheet material obtained is put into vulcanizer and is embedded in mold, with 1.4MPa Pressure carry out the molding of pressing mold crosslinked foaming, slice obtains antibacterial wear-resisting foaming sole material after cooled to room temperature.
It weighs 30g expansible graphite to be placed in a vacuum drying oven, sets vacuum oven temperature as 110 DEG C, done to vacuum 120g phosphorus pentoxide is put into dry case, the expansible graphite after drying is put into beaker, then beaker is placed on by dry 10h With the Power Processing 45s of 800W in microwave treater, takes out beaker and be cooled to room temperature, expand expansible graphite, so Microwave treatment heating expansion 5 times, obtain expanded graphite;By 25g lauryl sodium sulfate, 5g nano zine oxide, 220mL deionization Water mixing, stir 15min, obtain emulsion, 15g expanded graphite be impregnated in emulsion, suspension is obtained, to suspension into Row ultrasonic treatment, sets ultrasonic frequency as 32kHz, the water slurry of nano-graphite lamella is obtained after ultrasonic treatment;By 110g Acrylonitrile and 100g butadiene are added in the three-necked flask with blender and thermometer, and 120mL matter is added into three-necked flask The sodium hydroxide solution that score is 5%, the water slurry of 40g polyvinyl alcohol and 110mL nano-graphite lamella are measured, blender is started, After 90r/min revolving speed stirring and emulsifying 15min, 3g potassium peroxydisulfate is added, is heated to 48 DEG C, insulation reaction 4h is received Meter Zeng Qiang nitrile rubber;According to parts by weight, 15 parts of nanometer enhancing nitrile rubbers, 30 parts of polyvinyl chloride resins are placed in double roll mill In, it is 60 DEG C in preceding roll temperature, rear roll temperature is 55 DEG C, and roll spacing is plasticated 3 times under conditions of being 8mm, then into double roll mill 12 parts of nanometer silicon carbides, 5 parts of isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters are added, mixing is plasticated 3 times, is kneaded Rubber;According to parts by weight, by 5 parts of azodicarbonamides, 1.0 parts of cumyl peroxides, 0.5 part of sulphur, 0.3 part of curing Benzothiazole, 3 parts of zinc stearates, 35 parts of mixing rubber are added to the piece being pressed on open type dual-roller kneading machine with a thickness of 4mm Vulcanizer is embedded mold in advance and is heated to 200 DEG C by material, and sheet material obtained is put into vulcanizer and is embedded in mold, with 1.5MPa Pressure carry out the molding of pressing mold crosslinked foaming, slice obtains antibacterial wear-resisting foaming sole material after cooled to room temperature.
The antibacterial wear-resisting foaming sole material that comparative example is produced with Xuzhou company is as a comparison case to produced by the present invention Antibacterial wear-resisting foaming sole material in antibacterial wear-resisting foaming sole material and comparative example carries out performance detection, testing result such as table Shown in 1:
Test method:
Hardness test is detected using LX-A hardometer.
DIN wear test is detected by GB/ T3903.2 standard using XK-3018 sole wear-resistance testing machine.
The test of compression set rate is detected by HG/T2876-2009.
The test of dimensional contraction rate is detected by GB/T3903.13-2005.
Sheet resistance test is detected by GB_T 11210-2014 standard.
Escherichia coli be averaged bacterium number test by JC/T897-2002 regulation progress bacteriostasis property detection.
Staphylococcus aureus be averaged bacterium number test by JC/T897-2002 regulation progress bacteriostasis property detection.
1 foaming sole material performance measurement result of table
According to data among the above, antibacterial wear-resisting foaming sole material hardness of the invention is high, and abrasion are low, and wearability is good, deformation Rate is low, and antistatic effect is good, and bacteriostasis rate is high, and bacteria can be prevented from growing, has broad application prospects.

Claims (6)

1. a kind of preparation method of antibacterial wear-resisting foaming sole material, it is characterised in that specific preparation step are as follows:
(1) it weighs 20~30g expansible graphite to be placed in a vacuum drying oven, 100~120g, five oxygen is put into vacuum oven Change two phosphorus, it is dry, the expansible graphite after drying is put into beaker, then beaker is placed in microwave treater and is handled, is taken out Beaker is cooled to room temperature, and expands expansible graphite, and such microwave treatment heating expansion 3~5 times obtains expanded graphite;
(2) 20~25g lauryl sodium sulfate, 4~5g nano zine oxide, 200~220mL deionized water are mixed, stirring 10 ~15min, obtains emulsion, and 10~15g expanded graphite is impregnated in emulsion, suspension is obtained, is surpassed to suspension Sonication obtains the water slurry of nano-graphite lamella after ultrasonic treatment;
(3) 100~110g acrylonitrile and 90~100g butadiene are added in the three-necked flask with blender and thermometer, 100~120mL sodium hydroxide solution, 30~40g polyvinyl alcohol and 100~110mL nano graphite flakes are added into three-necked flask The water slurry of layer starts blender, and after 80~90r/min revolving speed stirring and emulsifying, 10~15min, 1~3g persulfuric acid is added Potassium, heat temperature raising, insulation reaction obtain nanometer enhancing nitrile rubber;
(4) according to parts by weight, 10~15 parts of nanometer enhancing nitrile rubbers, 20~30 parts of polyvinyl chloride resins are placed in double roll mill In, it plasticates 2~3 times, then 10~12 parts of nanometer silicon carbides, 4~5 parts of (dioctyl cokes of isopropyls three are added into double roll mill Phosphoric acid acyloxy) titanate esters, it mixes and plasticates 2~3 times, obtain mixing rubber;
(5) according to parts by weight, by 4~5 parts of azodicarbonamides, 0.7~1.0 part of cumyl peroxide, 0.4~0.5 part Sulphur, 0.2~0.3 part of benzothiazole disulfide, 2~3 parts of zinc stearates, 30~35 parts of mixing rubber are added to open type dual-roller It is pressed into sheet material on kneading machine, vulcanizer is embedded into mold heating in advance, sheet material obtained is put into vulcanizer and is embedded in mold, The molding of pressing mold crosslinked foaming is carried out, slice obtains antibacterial wear-resisting foaming sole material after cooled to room temperature.
2. the preparation method of the antibacterial wear-resisting foaming sole material of one kind according to claim 1, it is characterised in that: step (1) set vacuum oven temperature as 100~110 DEG C described in, drying time is 8~10h, microwave treater set power as 700~800W, processing time are 40~45s.
3. the preparation method of the antibacterial wear-resisting foaming sole material of one kind according to claim 1, it is characterised in that: step (2) ultrasonic frequency is set as 30~32kHz when ultrasonic treatment described in.
4. the preparation method of the antibacterial wear-resisting foaming sole material of one kind according to claim 1, it is characterised in that: step (3) mass fraction of the sodium hydroxide solution described in is 5%, and temperature is 45~48 DEG C after three-necked flask heat temperature raising, insulation reaction Time is 3~4h.
5. the preparation method of the antibacterial wear-resisting foaming sole material of one kind according to claim 1, it is characterised in that: step (4) when the double roll mill described in is kneaded, preceding roll temperature is 55~60 DEG C, and rear roll temperature is 50~55 DEG C, and roll spacing is 6~8mm.
6. the preparation method of the antibacterial wear-resisting foaming sole material of one kind according to claim 1, it is characterised in that: step (5) sheet thickness described in is 3~4mm, and temperature is 180~200 DEG C after vulcanizer embeds mold preheating, pressing mold crosslinked foaming at Pressure is 1.4~1.5MPa when type.
CN201810943381.5A 2018-08-17 2018-08-17 A kind of preparation method of antibacterial wear-resisting foaming sole material Pending CN109096651A (en)

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Application publication date: 20181228