CN109096593B - EVA rubber-plastic composite foaming material used as sole and preparation method thereof - Google Patents

EVA rubber-plastic composite foaming material used as sole and preparation method thereof Download PDF

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CN109096593B
CN109096593B CN201811016055.6A CN201811016055A CN109096593B CN 109096593 B CN109096593 B CN 109096593B CN 201811016055 A CN201811016055 A CN 201811016055A CN 109096593 B CN109096593 B CN 109096593B
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plastic composite
sole
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CN109096593A (en
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蔡杰
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GUANGDONG HENGJUN INDUSTRY AND TRADE DEVELOPMENT Co.,Ltd.
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Guangdong Hengjun Industry And Trade Development Co ltd
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—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
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide
    • 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
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    • 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
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    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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    • 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
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    • C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
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    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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Abstract

The invention belongs to the technical field of rubber-plastic composite sole materials, and provides an EVA rubber-plastic composite foaming material used as a sole and a preparation method thereof. The raw materials and the weight portions are as follows: 59.8-71.9 parts of ethylene-vinyl acetate copolymer, 10-15 parts of high styrene rubber, 5-10 parts of atactic polypropylene, 4-8 parts of tetrapod-like zinc oxide whisker, 2-4 parts of nylon 66 short fiber, 3-5 parts of calcium carbonate, 2-4 parts of tungsten-cobalt alloy, 0.5-1 part of cross-linking agent, 0.5-1 part of foaming agent, 0.3-0.7 part of zinc oxide, 0.3-0.5 part of stearic acid and 0.5-1 part of anti-aging agent. The prepared rubber-plastic composite foaming material effectively overcomes the defects that the EVA foaming material is easy to slip, hard at low temperature and not puncture-resistant, has higher porosity, smaller average pore diameter and light and breathable wearing property while having higher elasticity, strength, skid resistance and wear resistance, and can be widely used in sole materials.

Description

EVA rubber-plastic composite foaming material used as sole and preparation method thereof
Technical Field
The invention belongs to the technical field of rubber-plastic composite sole materials, and provides an EVA rubber-plastic composite foaming material used as a sole and a preparation method thereof.
Background
The sole is an important component of the shoe material, and the quality of the sole greatly determines the safety, reliability and comfort of the shoe. Common characteristics of common sole materials are wear resistance, water resistance, oil resistance, heat resistance, pressure resistance, impact resistance, good elasticity, easy adaptation to foot shapes, difficult deformation after shaping, heat preservation, easy moisture absorption and the like, and the foamed sole is popular due to the excellent elasticity and comfort and is also the most commonly used material in the manufacture of various soles.
At present, the main foaming sole materials on the market are as follows: polyvinyl chloride (PVC) foamed shoe soles, Polyethylene (PE) foamed shoe soles, ethylene-vinyl acetate copolymer (EVA) foamed shoe soles, styrene-butadiene-styrene copolymer (SBS) foamed shoe soles, Polyurethane (PU) foamed shoe soles, and the like. Among them, the most commonly used is EVA foam, which is a thermoplastic plastic with rubber elasticity, having the advantages of heat insulation, shock resistance, excellent resilience, small compression deformation, large weather resistance, etc., and meeting the requirements of sole materials.
Although a large number of EVA foamed shoe soles are applied, the mechanical strength, tear resistance, peeling resistance and other properties of the EVA foamed shoe soles are not good enough, and further development and application of the EVA foamed shoe soles are limited to a certain extent. The rubber-plastic foam material has the advantages of light weight, shock absorption, good comfort and high mechanical strength, so that the EVA rubber-plastic composite foam material appears in the field of vision of people, and has wide market prospect when being used as a sole material.
Chinese patent application No. 201611012275.2 discloses a sole foam material, which comprises: 100 parts of ethylene-vinyl acetate copolymer EVA, 10-30 parts of nitrile rubber, 10-30 parts of ethylene propylene diene monomer, 2-10 parts of azodicarbonamide, 20-30 parts of calcium carbonate filler and 5-15 parts of graphene fiber. The formula of the invention not only obtains good foaming performance, but also obtains good strength, but also has the defect that the performances of skid resistance, wear resistance, low temperature resistance, puncture resistance and the like of the foaming material are not ideal.
The Chinese patent application No. 201510785329.8 discloses an EVA rubber-plastic composite sole material, which is composed of the following raw materials in parts by weight: EVAUE 63143-52 parts by weight, nitrile rubber 22-32 parts by weight, inorganic flame retardant 4-8 parts by weight, white carbon black 8-10 parts by weight, stearic acid 1-2 parts by weight, filler 1-4 parts by weight, lubricant 1-3 parts by weight and accelerator 1-4 parts by weight. The invention has the defects that the mechanical property, the skid resistance, the low temperature resistance, the puncture resistance and the like of the composite sole material need to be further improved.
In summary, the EVA foam material used as the sole material of the sports shoes in the prior art has the defects of poor mechanical strength, tear resistance, peeling resistance and the like, poor slip resistance, poor wear resistance, poor low temperature resistance, poor puncture resistance and the like, so the development of the EVA rubber-plastic composite foam material used as the sole with excellent comprehensive performance has important significance.
Disclosure of Invention
It can be seen that the foamed EVA material for shoe soles in the prior art has the defects of poor skid resistance, poor wear resistance, poor low temperature resistance, poor puncture resistance and the like. Aiming at the situation, the invention provides the EVA rubber-plastic composite foaming material used as the sole and the preparation method thereof, so that the mechanical property of the composite foaming material is improved, and the composite foaming material has better skid resistance, wear resistance, low temperature resistance, puncture resistance and the like.
In order to achieve the purpose, the invention relates to the following specific technical scheme:
an EVA rubber-plastic composite foaming material used as a sole comprises the following raw materials in parts by weight:
59.8-71.9 parts by weight of ethylene-vinyl acetate copolymer;
10-15 parts by weight of high styrene rubber;
5-10 parts by weight of atactic polypropylene;
4-8 parts of tetrapod-like zinc oxide whiskers;
2-4 parts of nylon 66 short fibers;
3-5 parts by weight of calcium carbonate;
2-4 parts of a tungsten-cobalt alloy;
0.5-1 part by weight of a crosslinking agent;
0.5-1 part by weight of a foaming agent;
0.3-0.7 parts by weight of zinc oxide;
0.3-0.5 parts by weight of stearic acid;
0.5-1 part of anti-aging agent.
Preferably, in the tungsten-cobalt alloy, 80-90 parts by weight of tungsten carbide and 10-20 parts by weight of cobalt are used.
Preferably, the cross-linking agent is at least one of dicumyl peroxide, benzoyl peroxide, dicumyl hydroperoxide and 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide.
Preferably, the foaming agent is at least one of azodicarbonamide, azodiisobutyronitrile and urea.
The invention also provides a preparation method of the EVA rubber-plastic composite foaming material used as the sole, and the preparation process comprises the following steps:
(1) spraying carborundum on the surface of the tungsten-cobalt alloy particles at a high speed, shaking and overturning the alloy particles continuously to roughen the surfaces of the particles, heating the surfaces of the alloy particles to 1100-1200 ℃ by adopting laser, rapidly quenching to separate out tungsten carbide particles on the surfaces of the alloy particles, smearing polyisocyanate adhesive on the surfaces of the particles, and drying to obtain modified tungsten-cobalt alloy particles;
(2) silane coupling agent is adopted to respectively carry out high-speed blending with the tetrapod-like zinc oxide crystal whisker, the nylon 66 short fiber and the calcium carbonate to prepare modified tetrapod-like zinc oxide crystal whisker, modified nylon 66 short fiber and modified calcium carbonate;
(3) mixing ethylene-vinyl acetate copolymer, high styrene rubber, atactic polypropylene, modified tungsten-cobalt alloy particles, modified tetrapod-like zinc oxide whiskers, modified nylon 66 short fibers and modified calcium carbonate uniformly, adding a foaming agent, zinc oxide, stearic acid and an anti-aging agent, opening a roll, adding a crosslinking agent, mixing, taking out pieces, cutting into pieces, placing the pieces into a mold, carrying out hot-pressing foaming and cooling forming, and cutting into samples to obtain the EVA rubber-plastic composite foaming material used as the sole.
Preferably, the carborundum in the step (1) has the grain diameter of 0.3-0.5 mm and the injection pressure of 0.4-0.8 MPa.
Preferably, the temperature rise speed of the laser heating in the step (1) is 800-1000 ℃/s, and the temperature drop speed of the rapid quenching is 80-100 ℃/s.
Preferably, the thickness of the coating of the polyisocyanate adhesive in the step (1) is 20-40 mm.
Preferably, the silane coupling agent in the step (2) is at least one of gamma-aminopropyltriethoxysilane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane and gamma-aminopropyltrimethoxysilane, and the using amount of the silane coupling agent is 2-3% of the mass of the filler.
Preferably, the high-speed blending in the step (2) is performed at the temperature of 100-120 ℃, the rotating speed of 80-150 r/min and the mixing time of 10-30 min.
The invention provides an EVA rubber-plastic composite foaming material used as a sole and a preparation method thereof, compared with the prior art, the EVA rubber-plastic composite foaming material has the outstanding characteristics and excellent effects that:
1. according to the EVA rubber-plastic composite foaming material prepared by the invention, the high styrene rubber is added into the EVA, so that the defects of easy slipping, low-temperature hardening and poor puncture resistance of the EVA foaming material can be overcome.
2. According to the preparation method disclosed by the invention, the random polypropylene is added, so that the dispersity of the high styrene rubber in the EVA can be improved, the foaming uniformity is improved, and the elasticity and the skid resistance of the foaming material are improved.
3. According to the preparation method, the tetrapod-like zinc oxide whiskers are added, so that the anti-skid property of the EVA is improved.
4. According to the preparation method, nylon 66 short fibers and calcium carbonate are used as reinforcing agents, and the prepared rubber-plastic composite foaming material can maintain high strength while high porosity is maintained.
5. According to the preparation method, the tungsten-cobalt alloy is subjected to sand blasting, laser modification and adhesive smearing in sequence, so that the tungsten-cobalt alloy is well compatible with a matrix, and the wear resistance and the skid resistance of the EVA foam material are obviously improved.
6. The EVA rubber-plastic composite foaming material prepared by the invention has excellent comprehensive mechanical properties, higher porosity, smaller average pore diameter, light and breathable wearing, and can be widely used in sole materials.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
The raw materials and the mixture ratio are as follows:
62 parts of ethylene-vinyl acetate copolymer;
13 parts by weight of high styrene rubber;
7 parts by weight of atactic polypropylene;
5 parts of tetrapod-like zinc oxide whisker;
3 parts of nylon 66 short fibers;
4 parts by weight of calcium carbonate;
3 parts of tungsten-cobalt alloy;
0.7 part by weight of a crosslinking agent;
0.7 part by weight of foaming agent;
0.5 part by weight of zinc oxide;
0.4 part by weight of stearic acid;
0.7 part of anti-aging agent;
in the tungsten-cobalt alloy, 86 parts by weight of tungsten carbide and 14 parts by weight of cobalt; the cross-linking agent is dicumyl peroxide; the foaming agent is azodicarbonamide;
the preparation process comprises the following steps:
(1) spraying carborundum on the surface of the tungsten-cobalt alloy particles at a high speed, shaking and overturning the alloy particles continuously to roughen the surfaces of the particles, heating the surfaces of the alloy particles to 1160 ℃ by adopting laser, rapidly quenching to separate out tungsten carbide particles on the surfaces of the alloy particles, smearing polyisocyanate adhesive on the surfaces of the particles, and drying to obtain modified tungsten-cobalt alloy particles; the average grain diameter of the carborundum is 0.4mm, and the injection pressure is 0.7 MPa; the temperature rising speed of laser heating is 890 ℃/s, and the temperature reducing speed of rapid quenching is 88 ℃/s; the average thickness of the coating of the polyisocyanate adhesive is 28 mm;
(2) silane coupling agent is adopted to respectively carry out high-speed blending with the tetrapod-like zinc oxide crystal whisker, the nylon 66 short fiber and the calcium carbonate to prepare modified tetrapod-like zinc oxide crystal whisker, modified nylon 66 short fiber and modified calcium carbonate; the silane coupling agent is gamma-aminopropyl triethoxysilane, and the using amount of the silane coupling agent is 2.6 percent of the mass of the filler; the high-speed blending temperature is 108 ℃, the rotating speed is 110r/min, and the mixing time is 22 min;
(3) mixing ethylene-vinyl acetate copolymer, high styrene rubber, atactic polypropylene, modified tungsten-cobalt alloy particles, modified tetrapod-like zinc oxide whiskers, modified nylon 66 short fibers and modified calcium carbonate uniformly, adding a foaming agent, zinc oxide, stearic acid and an anti-aging agent, opening a roll, adding a crosslinking agent, mixing, taking out pieces, cutting into pieces, placing the pieces into a mold, carrying out hot-pressing foaming and cooling forming, and cutting into samples to obtain the EVA rubber-plastic composite foaming material used as the sole.
Example 2
The raw materials and the mixture ratio are as follows:
65.4 parts by weight of ethylene-vinyl acetate copolymer;
12 parts by weight of high styrene rubber;
6 parts by weight of atactic polypropylene;
5 parts of tetrapod-like zinc oxide whisker;
3 parts of nylon 66 short fibers;
3 parts by weight of calcium carbonate;
3 parts of tungsten-cobalt alloy;
0.6 part by weight of a crosslinking agent;
0.6 part by weight of foaming agent;
0.4 part by weight of zinc oxide;
0.4 part by weight of stearic acid;
0.6 part of anti-aging agent;
in the tungsten-cobalt alloy, 82 parts by weight of tungsten carbide and 18 parts by weight of cobalt; the cross-linking agent is benzoyl peroxide; the foaming agent is azodiisobutyronitrile;
the preparation process comprises the following steps:
(1) spraying carborundum on the surface of the tungsten-cobalt alloy particles at a high speed, shaking and overturning the alloy particles continuously to roughen the surfaces of the particles, heating the surfaces of the alloy particles to 1120 ℃ by adopting laser, rapidly quenching to separate out tungsten carbide particles on the surfaces of the alloy particles, smearing polyisocyanate adhesive on the surfaces of the particles, and drying to obtain modified tungsten-cobalt alloy particles; the average grain diameter of the carborundum is 0.3mm, and the injection pressure is 0.5 MPa; the temperature rising speed of laser heating is 850 ℃/s, and the temperature lowering speed of rapid quenching is 85 ℃/s; the average thickness of the coating of the polyisocyanate adhesive is 25 mm;
(2) silane coupling agent is adopted to respectively carry out high-speed blending with the tetrapod-like zinc oxide crystal whisker, the nylon 66 short fiber and the calcium carbonate to prepare modified tetrapod-like zinc oxide crystal whisker, modified nylon 66 short fiber and modified calcium carbonate; the silane coupling agent is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, and the using amount of the silane coupling agent is 2 percent of the mass of the filler; the high-speed blending temperature is 105 ℃, the rotating speed is 90r/min, and the mixing time is 25 min;
(3) mixing ethylene-vinyl acetate copolymer, high styrene rubber, atactic polypropylene, modified tungsten-cobalt alloy particles, modified tetrapod-like zinc oxide whiskers, modified nylon 66 short fibers and modified calcium carbonate uniformly, adding a foaming agent, zinc oxide, stearic acid and an anti-aging agent, opening a roll, adding a crosslinking agent, mixing, taking out pieces, cutting into pieces, placing the pieces into a mold, carrying out hot-pressing foaming and cooling forming, and cutting into samples to obtain the EVA rubber-plastic composite foaming material used as the sole.
Example 3
The raw materials and the mixture ratio are as follows:
65.3 parts by weight of an ethylene-vinyl acetate copolymer;
14 parts by weight of high styrene rubber;
8 parts by weight of atactic polypropylene;
7 parts of tetrapod-like zinc oxide whisker;
4 parts of nylon 66 short fibers;
5 parts by weight of calcium carbonate;
3 parts of tungsten-cobalt alloy;
0.8 part by weight of a crosslinking agent;
0.9 part by weight of foaming agent;
0.6 part by weight of zinc oxide;
0.5 part by weight of stearic acid;
0.9 part of anti-aging agent;
88 parts of tungsten carbide and 12 parts of cobalt in the tungsten-cobalt alloy; the cross-linking agent is hydrogen peroxide diisopropylbenzene; the foaming agent is urea;
the preparation process comprises the following steps:
(1) spraying carborundum on the surface of the tungsten-cobalt alloy particles at a high speed, shaking and overturning the alloy particles continuously to roughen the surfaces of the particles, heating the surfaces of the alloy particles to 1180 ℃ by adopting laser, rapidly quenching to separate out tungsten carbide particles on the surfaces of the alloy particles, smearing polyisocyanate adhesive on the surfaces of the particles, and drying to obtain modified tungsten-cobalt alloy particles; the average grain diameter of the carborundum is 0.5mm, and the injection pressure is 0.7 MPa; the temperature rising speed of laser heating is 950 ℃/s, and the temperature lowering speed of rapid quenching is 95 ℃/s; the average thickness of the coating of the polyisocyanate adhesive is 35 mm;
(2) silane coupling agent is adopted to respectively carry out high-speed blending with the tetrapod-like zinc oxide crystal whisker, the nylon 66 short fiber and the calcium carbonate to prepare modified tetrapod-like zinc oxide crystal whisker, modified nylon 66 short fiber and modified calcium carbonate; the silane coupling agent is gamma-methacryloxypropyltrimethoxysilane, and the using amount of the silane coupling agent is 2.8 percent of the mass of the filler; the high-speed blending temperature is 115 ℃, the rotating speed is 130r/min, and the mixing time is 25 min;
(3) mixing ethylene-vinyl acetate copolymer, high styrene rubber, atactic polypropylene, modified tungsten-cobalt alloy particles, modified tetrapod-like zinc oxide whiskers, modified nylon 66 short fibers and modified calcium carbonate uniformly, adding a foaming agent, zinc oxide, stearic acid and an anti-aging agent, opening a roll, adding a crosslinking agent, mixing, taking out pieces, cutting into pieces, placing the pieces into a mold, carrying out hot-pressing foaming and cooling forming, and cutting into samples to obtain the EVA rubber-plastic composite foaming material used as the sole.
Example 4
The raw materials and the mixture ratio are as follows:
71.9 parts of ethylene-vinyl acetate copolymer;
10 parts by weight of high styrene rubber;
5 parts by weight of atactic polypropylene;
4 parts of tetrapod-like zinc oxide whisker;
2 parts of nylon 66 short fibers;
3 parts by weight of calcium carbonate;
2 parts of tungsten-cobalt alloy;
0.5 part by weight of a crosslinking agent;
0.5 part by weight of foaming agent;
0.3 part by weight of zinc oxide;
0.3 part by weight of stearic acid;
0.5 part of anti-aging agent;
in the tungsten-cobalt alloy, 80 parts by weight of tungsten carbide and 20 parts by weight of cobalt; the cross-linking agent is 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide; the foaming agent is azodicarbonamide;
the preparation process comprises the following steps:
(1) spraying carborundum on the surface of the tungsten-cobalt alloy particles at a high speed, shaking and overturning the alloy particles continuously to roughen the surfaces of the particles, heating the surfaces of the alloy particles to 1100 ℃ by adopting laser, rapidly quenching to separate out tungsten carbide particles on the surfaces of the alloy particles, smearing polyisocyanate adhesive on the surfaces of the particles, and drying to obtain modified tungsten-cobalt alloy particles; the average grain diameter of the carborundum is 0.3mm, and the injection pressure is 0.4 MPa; the temperature rising speed of laser heating is 800 ℃/s, and the temperature reducing speed of rapid quenching is 80 ℃/s; the average thickness of the coating of the polyisocyanate adhesive is 20 mm;
(2) silane coupling agent is adopted to respectively carry out high-speed blending with the tetrapod-like zinc oxide crystal whisker, the nylon 66 short fiber and the calcium carbonate to prepare modified tetrapod-like zinc oxide crystal whisker, modified nylon 66 short fiber and modified calcium carbonate; the silane coupling agent is gamma-aminopropyl trimethoxy silane, and the using amount of the silane coupling agent is 2 percent of the mass of the filler; the high-speed blending temperature is 100 ℃, the rotating speed is 80r/min, and the mixing time is 30 min;
(3) mixing ethylene-vinyl acetate copolymer, high styrene rubber, atactic polypropylene, modified tungsten-cobalt alloy particles, modified tetrapod-like zinc oxide whiskers, modified nylon 66 short fibers and modified calcium carbonate uniformly, adding a foaming agent, zinc oxide, stearic acid and an anti-aging agent, opening a roll, adding a crosslinking agent, mixing, taking out pieces, cutting into pieces, placing the pieces into a mold, carrying out hot-pressing foaming and cooling forming, and cutting into samples to obtain the EVA rubber-plastic composite foaming material used as the sole.
Example 5
The raw materials and the mixture ratio are as follows:
59.8 parts by weight of ethylene-vinyl acetate copolymer;
15 parts of high styrene rubber;
10 parts by weight of atactic polypropylene;
8 parts of tetrapod-like zinc oxide whisker;
4 parts of nylon 66 short fibers;
5 parts by weight of calcium carbonate;
4 parts of tungsten-cobalt alloy;
1 part by weight of a crosslinking agent;
1 part by weight of foaming agent;
0.7 part by weight of zinc oxide;
0.5 part by weight of stearic acid;
1 part of anti-aging agent;
in the tungsten-cobalt alloy, 90 parts by weight of tungsten carbide and 10 parts by weight of cobalt are added; the cross-linking agent is dicumyl peroxide; the foaming agent is azodiisobutyronitrile;
the preparation process comprises the following steps:
(1) spraying carborundum on the surface of the tungsten-cobalt alloy particles at a high speed, shaking and overturning the alloy particles continuously to roughen the surfaces of the particles, heating the surfaces of the alloy particles to 1200 ℃ by adopting laser, rapidly quenching to separate out tungsten carbide particles on the surfaces of the alloy particles, smearing polyisocyanate adhesive on the surfaces of the particles, and drying to obtain modified tungsten-cobalt alloy particles; the average grain diameter of the carborundum is 0.5mm, and the injection pressure is 0.8 MPa; the temperature rising speed of laser heating is 1000 ℃/s, and the temperature reducing speed of rapid quenching is 100 ℃/s; the average thickness of the coating of the polyisocyanate adhesive is 40 mm;
(2) silane coupling agent is adopted to respectively carry out high-speed blending with the tetrapod-like zinc oxide crystal whisker, the nylon 66 short fiber and the calcium carbonate to prepare modified tetrapod-like zinc oxide crystal whisker, modified nylon 66 short fiber and modified calcium carbonate; the silane coupling agent is gamma-aminopropyl triethoxysilane, and the using amount of the silane coupling agent is 3 percent of the mass of the filler; the high-speed blending temperature is 120 ℃, the rotating speed is 150r/min, and the mixing time is 10 min;
(3) mixing ethylene-vinyl acetate copolymer, high styrene rubber, atactic polypropylene, modified tungsten-cobalt alloy particles, modified tetrapod-like zinc oxide whiskers, modified nylon 66 short fibers and modified calcium carbonate uniformly, adding a foaming agent, zinc oxide, stearic acid and an anti-aging agent, opening a roll, adding a crosslinking agent, mixing, taking out pieces, cutting into pieces, placing the pieces into a mold, carrying out hot-pressing foaming and cooling forming, and cutting into samples to obtain the EVA rubber-plastic composite foaming material used as the sole.
Example 6
The raw materials and the mixture ratio are as follows:
60.9 parts of ethylene-vinyl acetate copolymer;
12 parts by weight of high styrene rubber;
8 parts by weight of atactic polypropylene;
6 parts of tetrapod-like zinc oxide whisker;
3 parts of nylon 66 short fibers;
4 parts by weight of calcium carbonate;
3 parts of tungsten-cobalt alloy;
0.8 part by weight of a crosslinking agent;
0.7 part by weight of foaming agent;
0.5 part by weight of zinc oxide;
0.4 part by weight of stearic acid;
0.7 part of anti-aging agent;
in the tungsten-cobalt alloy, 85 parts by weight of tungsten carbide and 15 parts by weight of cobalt; the cross-linking agent is dicumyl peroxide; the foaming agent is urea;
the preparation process comprises the following steps:
(1) spraying carborundum on the surface of the tungsten-cobalt alloy particles at a high speed, continuously shaking and overturning the alloy particles to roughen the surfaces of the particles, then heating the surfaces of the alloy particles to 1150 ℃ by adopting laser, rapidly quenching to separate out tungsten carbide particles on the surfaces of the alloy particles, smearing polyisocyanate adhesive on the surfaces of the particles, and drying to obtain modified tungsten-cobalt alloy particles; the average grain diameter of the carborundum is 0.4mm, and the injection pressure is 0.6 MPa; the temperature rising speed of laser heating is 900 ℃/s, and the temperature reducing speed of rapid quenching is 90 ℃/s; the average thickness of the coating of the polyisocyanate adhesive is 30 mm;
(2) silane coupling agent is adopted to respectively carry out high-speed blending with the tetrapod-like zinc oxide crystal whisker, the nylon 66 short fiber and the calcium carbonate to prepare modified tetrapod-like zinc oxide crystal whisker, modified nylon 66 short fiber and modified calcium carbonate; the silane coupling agent is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, and the using amount of the silane coupling agent is 2.5 percent of the mass of the filler; the high-speed blending temperature is 110 ℃, the rotating speed is 120r/min, and the mixing time is 20 min;
(3) mixing ethylene-vinyl acetate copolymer, high styrene rubber, atactic polypropylene, modified tungsten-cobalt alloy particles, modified tetrapod-like zinc oxide whiskers, modified nylon 66 short fibers and modified calcium carbonate uniformly, adding a foaming agent, zinc oxide, stearic acid and an anti-aging agent, opening a roll, adding a crosslinking agent, mixing, taking out pieces, cutting into pieces, placing the pieces into a mold, carrying out hot-pressing foaming and cooling forming, and cutting into samples to obtain the EVA rubber-plastic composite foaming material used as the sole.
Comparative example 1
During the preparation, no high styrene rubber was added, and the other preparation conditions were the same as in example 6.
Comparative example 2
During the preparation, no atactic polypropylene was added, and the other preparation conditions were the same as in example 6.
Comparative example 3
In the preparation process, no tetrapod-like zinc oxide whiskers are added, and other preparation conditions are consistent with those of example 6.
Comparative example 4
In the preparation process, the tungsten-cobalt alloy is not added, and other preparation conditions are consistent with those of the example 6.
And (3) performance testing:
(1) dynamic and static friction coefficients in dry and wet states: according to HG/T2729-;
(2) abrasion loss of abrasion resistance test: according to the ISO4649 standard, the composite foam material prepared by the invention is cut into samples, and then a GT-7012-D DIN abrasion tester is adopted for carrying out abrasion resistance test; the diameter of the roller is 150mm, the rotating speed is 40r/min, and the friction distance is 40 m; the test specimen had a diameter of 16mm and a thickness of 6mm, the test load was 10N, and the abrasion loss was measured and calculated: a = ([ Delta ] m × 200 mg)/(Q × S), wherein A is the abrasion loss, [ Delta ] m is the mass difference of the sample before and after friction, Q is the standard abrasion value, and S is the density of the sample;
(3) porosity: directly adopting a JF-2900V foamed plastic porosity tester to measure the porosity of the composite foamed material prepared by the invention;
(4) tensile strength: the tensile strength test is carried out according to GB/T6344-;
(5) elasticity: performing resilience test according to GB/T1681-;
(6) brittle temperature: directly adopting a rubber low-temperature brittleness temperature tester to test the low-temperature brittleness temperature of the rubber-plastic composite foaming material prepared by the invention;
(7) puncture resistance strength: the puncture strength tester is directly adopted for testing, the rubber-plastic composite foaming material prepared by the invention is prepared into a sample with the average thickness of 1cm, a steel needle with the diameter of 1.0mm and the spherical top end radius of 0.5mm is utilized for removing top pricks at the speed of 50 +/-5 mm/min, and the puncture resistance strength is measured.
The data obtained are shown in Table 1.
Table 1:
Figure DEST_PATH_IMAGE001

Claims (10)

1. the EVA rubber-plastic composite foaming material used as the sole is characterized by comprising the following raw materials in parts by weight:
59.8-71.9 parts by weight of ethylene-vinyl acetate copolymer;
10-15 parts by weight of high styrene rubber;
5-10 parts by weight of atactic polypropylene;
4-8 parts of tetrapod-like zinc oxide whiskers;
2-4 parts of nylon 66 short fibers;
3-5 parts by weight of calcium carbonate;
2-4 parts of a tungsten-cobalt alloy;
0.5-1 part by weight of a crosslinking agent;
0.5-1 part by weight of a foaming agent;
0.3-0.7 parts by weight of zinc oxide;
0.3-0.5 parts by weight of stearic acid;
0.5-1 part of anti-aging agent.
2. The EVA rubber-plastic composite foam material used as a sole of a shoe as claimed in claim 1, wherein: in the tungsten-cobalt alloy, 80-90 parts by weight of tungsten carbide and 10-20 parts by weight of cobalt are used.
3. The EVA rubber-plastic composite foam material used as a sole of a shoe as claimed in claim 1, wherein: the cross-linking agent is at least one of dicumyl peroxide, benzoyl peroxide, dicumyl hydroperoxide and 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide.
4. The EVA rubber-plastic composite foam material used as a sole of a shoe as claimed in claim 1, wherein: the foaming agent is at least one of azodicarbonamide, azodiisobutyronitrile and urea.
5. The preparation method of the EVA rubber-plastic composite foaming material used as the sole according to any one of claims 1 to 4, wherein the preparation process comprises the following steps:
(1) spraying carborundum on the surface of the tungsten-cobalt alloy particles at a high speed, shaking and overturning the alloy particles continuously to roughen the surfaces of the particles, heating the surfaces of the alloy particles to 1100-1200 ℃ by adopting laser, rapidly quenching to separate out tungsten carbide particles on the surfaces of the alloy particles, smearing polyisocyanate adhesive on the surfaces of the particles, and drying to obtain modified tungsten-cobalt alloy particles;
(2) silane coupling agent is adopted to respectively carry out high-speed blending with the tetrapod-like zinc oxide crystal whisker, the nylon 66 short fiber and the calcium carbonate to prepare modified tetrapod-like zinc oxide crystal whisker, modified nylon 66 short fiber and modified calcium carbonate;
(3) mixing ethylene-vinyl acetate copolymer, high styrene rubber, atactic polypropylene, modified tungsten-cobalt alloy particles, modified tetrapod-like zinc oxide whiskers, modified nylon 66 short fibers and modified calcium carbonate uniformly, adding a foaming agent, zinc oxide, stearic acid and an anti-aging agent, opening a roll, adding a crosslinking agent, mixing, taking out pieces, cutting into pieces, placing the pieces into a mold, carrying out hot-pressing foaming and cooling forming, and cutting into samples to obtain the EVA rubber-plastic composite foaming material used as the sole.
6. The method for preparing the EVA rubber-plastic composite foaming material used as the sole according to claim 5, is characterized in that: the grain diameter of the carborundum in the step (1) is 0.3-0.5 mm, and the injection pressure is 0.4-0.8 MPa.
7. The method for preparing the EVA rubber-plastic composite foaming material used as the sole according to claim 5, is characterized in that: the temperature rising speed of the laser heating in the step (1) is 800-1000 ℃/s, and the temperature lowering speed of the rapid quenching is 80-100 ℃/s.
8. The method for preparing the EVA rubber-plastic composite foaming material used as the sole according to claim 5, is characterized in that: the thickness of the coating of the polyisocyanate adhesive in the step (1) is 20-40 mm.
9. The method for preparing the EVA rubber-plastic composite foaming material used as the sole according to claim 5, is characterized in that: the silane coupling agent in the step (2) is at least one of gamma-aminopropyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyl trimethoxysilane, gamma-methacryloxypropyl trimethoxysilane and gamma-aminopropyltrimethoxysilane, and the using amount of the silane coupling agent is 2-3% of the mass of the filler.
10. The method for preparing the EVA rubber-plastic composite foaming material used as the sole according to claim 5, is characterized in that: the temperature of the high-speed blending in the step (2) is 100-120 ℃, the rotating speed is 80-150 r/min, and the mixing time is 10-30 min.
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