CN109096593A - A kind of EVA rubber and plastic composite foam material and preparation method as sole - Google Patents
A kind of EVA rubber and plastic composite foam material and preparation method as sole Download PDFInfo
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- CN109096593A CN109096593A CN201811016055.6A CN201811016055A CN109096593A CN 109096593 A CN109096593 A CN 109096593A CN 201811016055 A CN201811016055 A CN 201811016055A CN 109096593 A CN109096593 A CN 109096593A
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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
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
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- 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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- C08J9/06—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
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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
- C08J2323/04—Homopolymers or copolymers of ethene
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- C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2409/06—Copolymers with styrene
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- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
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Abstract
The invention belongs to the technical fields of rubber and plastic composite sole material, provide a kind of EVA rubber and plastic composite foam material and preparation method as sole.Raw material and parts by weight are as follows: 59.8 ~ 71.9 parts of ethylene-vinyl acetate copolymer, 10 ~ 15 parts of high styrene rubber, 5 ~ 10 parts of random polypropylene, 4 ~ 8 parts of four acicular type zinc oxide crystal whisker, 2 ~ 4 parts of nylon66 fiber staple fiber, 3 ~ 5 parts of calcium carbonate, 2 ~ 4 parts of tungsten-cobalt alloy, 0.5 ~ 1 part of crosslinking agent, 0.5 ~ 1 part of foaming agent, 0.3 ~ 0.7 part of zinc oxide, 0.3 ~ 0.5 part of stearic acid, 0.5 ~ 1 part of anti-aging agent.Rubber and plastic composite foam material obtained, effectively overcome that EVA foamed material easily skids, low temperature is hardened, the defect of not puncture-resistant, while having higher elasticity, intensity, skid resistance, wearability, porosity with higher, average pore size is smaller, light air ventilation is worn, can be widely used in sole material.
Description
Technical field
The invention belongs to the technical fields of rubber and plastic composite sole material, and it is compound to provide a kind of EVA rubber and plastic as sole
Foamed material and preparation method.
Background technique
Sole is the important component of material for shoes, and the superiority and inferiority of quality is largely fixed the safe and reliable of shoes
Property and comfort.The general common characteristic of sole material should have wear-resisting, water-fast, oil resistant, heat-resisting, pressure-resistant, impact resistance, elasticity
It is good, be easy after suitable foot type, sizing not flexible type, heat preservation, easily absorb moisture etc., and foamed shoe sole with its excellent elasticity with it is easypro
Adaptive and most commonly used material in the manufacture of very popular and all kinds of soles.
Currently, main foaming sole material has in the market: polyvinyl chloride (PVC) class foamed shoe sole, polyethylene (PE) class
Foamed shoe sole, ethylene-vinyl acetate copolymer (EVA) class foamed shoe sole, styrene-butadiene-styrene (SBS)
Class foamed shoe sole, polyurethane (PU) class foamed shoe sole etc..Wherein, the most commonly used is EVA foamed material, EVA is a kind of with rubber
The thermoplastic of glue elasticity has many advantages, such as that heat-insulated, shockproof, resilience is excellent, compressive deformation is small, weatherability is big, meets shoes
The requirement of bottom material.
Although EVA foamed shoe sole has been widely applied, the performances such as its mechanical strength, tear resistance and stripper-resistance are inadequate
It is good, its further development and application is constrained to a certain extent.Rubber plastic foam material has light, damping, comfort good, mechanical strong
High advantage is spent, thus EVA rubber and plastic composite foam material appears in the people visual field, is used for sole material, has wide
Market prospects.
Chinese invention patent application number 201611012275.2 discloses a kind of Foamed Sole Materials comprising: ethylene-vinegar
Sour 100 parts by weight of ethylene copolymer EVA, 10 ~ 30 parts by weight of nitrile rubber, 10 ~ 30 parts by weight of ethylene propylene diene rubber, azo two
2 ~ 10 parts by weight of formamide, 20 ~ 30 parts by weight of pearl filler, 5 ~ 15 parts by weight of graphene fiber.The formula of the invention both obtained
To good foam performance, good intensity of getting back, but have a defect that the skid resistance of foamed material, wearability, resistance to low
The performances such as warm nature, puncture-resistant are undesirable.
Chinese invention patent application number 201510785329.8 discloses a kind of EVA rubber and plastic composite sole material, by following
The raw material of mass fraction form: 43 ~ 52 parts by weight of EVAUE631,22 ~ 32 parts by weight of nitrile rubber, 4 ~ 8 weight of inorganic fire retardants
Measure part, 8 ~ 10 parts by weight of white carbon black, 1 ~ 2 parts by weight of stearic acid, 1 ~ 4 parts by weight of filler, 1 ~ 3 parts by weight of lubricant, promotor 1
~ 4 parts by weight, sole made of this kind of scheme has elasticity strong, wear-resistant, and density is low after expanding, light weight, and has good
Good flame retardant property is worn light comfortable in addition, production cost low feature simple with formula.The invention there are the shortcomings that
It is that mechanical property, skid resistance, lower temperature resistance, the paracentesis resistance etc. of composite sole material needs to be further increased.
In conclusion being used for the EVA foamed material of sport shoe sole material, mechanical strength, tear-proof in the prior art
The performances such as property and stripper-resistance are not good enough, and that there are skid resistances is poor, wears no resistance, the defects of lower temperature resistance is poor, puncture-resistant is poor, therefore
The EVA rubber and plastic composite foam material as sole for developing a kind of excellent combination property, has great significance.
Summary of the invention
As it can be seen that the foaming EVA material for sole of the prior art that there are skid resistances is poor, wear no resistance, lower temperature resistance is poor,
The disadvantages of puncture-resistant is poor.In response to this, the present invention proposes a kind of EVA rubber and plastic composite foam material as sole and preparation
Method improves the mechanical property of composite foam material, while skid resistance, wearability, lower temperature resistance, puncture-resistant etc. are preferable.
To achieve the above object, specific technical solution of the present invention is as follows:
A kind of EVA rubber and plastic composite foam material as sole, the raw material and proportion of the rubber and plastic composite foam material preparation are as follows:
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 random polypropylene；
4 ~ 8 parts by weight of four acicular type zinc oxide crystal whisker；
2 ~ 4 parts by weight of nylon66 fiber staple fiber；
3 ~ 5 parts by weight of calcium carbonate；
2 ~ 4 parts by weight of tungsten-cobalt alloy；
0.5 ~ 1 parts by weight of crosslinking agent；
0.5 ~ 1 parts by weight of 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 parts by weight of anti-aging agent.
Preferably, in the tungsten-cobalt alloy, 80 ~ 90 parts by weight of tungsten carbide, 10 ~ 20 parts by weight of cobalt.
Preferably, the crosslinking agent is cumyl peroxide, benzoyl peroxide, di-isopropylbenzene hydroperoxide, 2,5-
At least one of -2,5 di-t-butyl hexane peroxide of dimethyl.
Preferably, the foaming agent is at least one of azodicarbonamide, azodiisobutyronitrile, urea.
The present invention also provides a kind of preparation method of above-mentioned EVA rubber and plastic composite foam material as sole, the systems
Standby process the following steps are included:
(1) diamond dust high speed is ejected into tungsten-cobalt alloy particle surface, and constantly shake overturning alloying pellet, keeps particle surface thick
It is rough, alloying pellet surface is then heated to 1100 ~ 1200 DEG C using laser, then rapidly quenching makes tungsten carbide particle precipitate into conjunction
Gold surface, then in particle surface trowelling polymeric isocyanate glue, dry, obtained modified tungsten-cobalt alloy particle；
(2) high speed is carried out with four acicular type zinc oxide crystal whisker, nylon66 fiber staple fiber, calcium carbonate respectively using silane coupling agent to be blended,
Modified four acicular type zinc oxide crystal whisker, 66 staple fiber of modification of nylon and modified calcium carbonate is made；
(3) by ethylene-vinyl acetate copolymer, high styrene rubber, random polypropylene, modified tungsten-cobalt alloy particle, modified four
Needle-shape zinc oxide crystal whisker, 66 staple fiber of modification of nylon and modified calcium carbonate are uniformly mixed, and foaming agent, zinc oxide, stearic acid is added
And anti-aging agent, mill packet roller add crosslinking agent and are kneaded, slice, cut-parts, are placed in hot-pressing and foaming in mold and are cooled to
Type, then sanction sample is carried out, the EVA rubber and plastic composite foam material as sole is made.
Preferably, the partial size of step (1) described diamond dust is 0.3 ~ 0.5mm, and injection pressure is 0.4 ~ 0.8MPa.
Preferably, the heating rate of step (1) the laser heating is 800 ~ 1000 DEG C/s, the cooling rate rapidly quenched
For 80 ~ 100 DEG C/s.
Preferably, step (1) the polymeric isocyanate glue trowelling with a thickness of 20 ~ 40mm.
Preferably, step (2) silane coupling agent is gamma-aminopropyl-triethoxy-silane, γ-(2,3- the third oxygen of epoxy)
Propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane, in γ-aminopropyltrimethoxysilane
At least one, usage amount are the 2 ~ 3% of packing quality.
Preferably, the temperature that step (2) high speed is blended is 100 ~ 120 DEG C, and revolving speed is 80 ~ 150r/min, when mixing
Between be 10 ~ 30min.
The present invention provides a kind of EVA rubber and plastic composite foam material and preparation method as sole, with prior art phase
Than the feature and excellent effect protruded is:
1. EVA rubber and plastic composite foam material prepared by the present invention, joined high styrene rubber in EVA, EVA can be overcome to send out
Foam material easily skids, low temperature is hardened, the defect of not puncture-resistant.
2. preparation method of the invention can improve point of the high styrene rubber in EVA by adding random polypropylene
Property is dissipated, improves uniform in foaming, and improve the elasticity and skid resistance of foamed material.
3. preparation method of the invention improves the non-skid property of EVA by adding four acicular type zinc oxide crystal whisker.
4. preparation method of the invention, using nylon66 fiber staple fiber and calcium carbonate as reinforcing agent, the compound hair of rubber and plastic obtained
Foam material can maintain higher intensity while keeping high porosity.
5. preparation method of the invention can by the way that tungsten-cobalt alloy successively to be carried out to sandblasting, laser modified and trowelling binder
It is well compatible with matrix, hence it is evident that improve the wearability and skid resistance of EVA foamed material.
6. EVA rubber and plastic composite foam material prepared by the present invention, not only comprehensive mechanical property is excellent, but also with higher
Porosity, average pore size is smaller, wears light air ventilation, can be widely used in sole material.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
Raw material and proportion are as follows:
62 parts by weight of ethylene-vinyl acetate copolymer；
13 parts by weight of high styrene rubber；
7 parts by weight of random polypropylene；
5 parts by weight of four acicular type zinc oxide crystal whisker；
3 parts by weight of nylon66 fiber staple fiber；
4 parts by weight of calcium carbonate；
3 parts by weight of tungsten-cobalt alloy；
0.7 parts by weight of crosslinking agent；
0.7 parts by weight of foaming agent；
0.5 parts by weight of zinc oxide；
0.4 parts by weight of stearic acid；
0.7 parts by weight of anti-aging agent；
In tungsten-cobalt alloy, 86 parts by weight of tungsten carbide, 14 parts by weight of cobalt；Crosslinking agent is cumyl peroxide；Foaming agent is azo
Diformamide；
Preparation process are as follows:
(1) diamond dust high speed is ejected into tungsten-cobalt alloy particle surface, and constantly shake overturning alloying pellet, keeps particle surface thick
It is rough, alloying pellet surface is then heated to 1160 DEG C using laser, then rapidly quenching makes tungsten carbide particle precipitate into alloy table
Face, then in particle surface trowelling polymeric isocyanate glue, dry, obtained modified tungsten-cobalt alloy particle；The average grain diameter of diamond dust is
0.4mm, injection pressure are 0.7MPa；Laser heating heating rate be 890 DEG C/s, the cooling rate rapidly quenched be 88 DEG C/
s；The average thickness of polymeric isocyanate glue trowelling is 28mm；
(2) high speed is carried out with four acicular type zinc oxide crystal whisker, nylon66 fiber staple fiber, calcium carbonate respectively using silane coupling agent to be blended,
Modified four acicular type zinc oxide crystal whisker, 66 staple fiber of modification of nylon and modified calcium carbonate is made；Silane coupling agent is γ-aminopropyl three
Ethoxysilane, usage amount are the 2.6% of packing quality；The temperature that high speed is blended is 108 DEG C, revolving speed 110r/min, when mixing
Between be 22min；
(3) by ethylene-vinyl acetate copolymer, high styrene rubber, random polypropylene, modified tungsten-cobalt alloy particle, modified four
Needle-shape zinc oxide crystal whisker, 66 staple fiber of modification of nylon and modified calcium carbonate are uniformly mixed, and foaming agent, zinc oxide, stearic acid is added
And anti-aging agent, mill packet roller add crosslinking agent and are kneaded, slice, cut-parts, are placed in hot-pressing and foaming in mold and are cooled to
Type, then sanction sample is carried out, the EVA rubber and plastic composite foam material as sole is made.
Embodiment 2
Raw material and proportion 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 random polypropylene；
5 parts by weight of four acicular type zinc oxide crystal whisker；
3 parts by weight of nylon66 fiber staple fiber；
3 parts by weight of calcium carbonate；
3 parts by weight of tungsten-cobalt alloy；
0.6 parts by weight of crosslinking agent；
0.6 parts by weight of foaming agent；
0.4 parts by weight of zinc oxide；
0.4 parts by weight of stearic acid；
0.6 parts by weight of anti-aging agent；
In tungsten-cobalt alloy, 82 parts by weight of tungsten carbide, 18 parts by weight of cobalt；Crosslinking agent is benzoyl peroxide；Foaming agent is azo two
Isobutyronitrile；
Preparation process are as follows:
(1) diamond dust high speed is ejected into tungsten-cobalt alloy particle surface, and constantly shake overturning alloying pellet, keeps particle surface thick
It is rough, alloying pellet surface is then heated to 1120 DEG C using laser, then rapidly quenching makes tungsten carbide particle precipitate into alloy table
Face, then in particle surface trowelling polymeric isocyanate glue, dry, obtained modified tungsten-cobalt alloy particle；The average grain diameter of diamond dust is
0.3mm, injection pressure are 0.5MPa；Laser heating heating rate be 850 DEG C/s, the cooling rate rapidly quenched be 85 DEG C/
s；The average thickness of polymeric isocyanate glue trowelling is 25mm；
(2) high speed is carried out with four acicular type zinc oxide crystal whisker, nylon66 fiber staple fiber, calcium carbonate respectively using silane coupling agent to be blended,
Modified four acicular type zinc oxide crystal whisker, 66 staple fiber of modification of nylon and modified calcium carbonate is made；Silane coupling agent is γ-(2,3- ring
The third oxygen of oxygen) propyl trimethoxy silicane, usage amount is the 2% of packing quality；The temperature that high speed is blended is 105 DEG C, and revolving speed is
90r/min, incorporation time 25min；
(3) by ethylene-vinyl acetate copolymer, high styrene rubber, random polypropylene, modified tungsten-cobalt alloy particle, modified four
Needle-shape zinc oxide crystal whisker, 66 staple fiber of modification of nylon and modified calcium carbonate are uniformly mixed, and foaming agent, zinc oxide, stearic acid is added
And anti-aging agent, mill packet roller add crosslinking agent and are kneaded, slice, cut-parts, are placed in hot-pressing and foaming in mold and are cooled to
Type, then sanction sample is carried out, the EVA rubber and plastic composite foam material as sole is made.
Embodiment 3
Raw material and proportion are as follows:
65.3 parts by weight of ethylene-vinyl acetate copolymer；
14 parts by weight of high styrene rubber；
8 parts by weight of random polypropylene；
7 parts by weight of four acicular type zinc oxide crystal whisker；
4 parts by weight of nylon66 fiber staple fiber；
5 parts by weight of calcium carbonate；
3 parts by weight of tungsten-cobalt alloy；
0.8 parts by weight of crosslinking agent；
0.9 parts by weight of foaming agent；
0.6 parts by weight of zinc oxide；
0.5 parts by weight of stearic acid；
0.9 parts by weight of anti-aging agent；
In tungsten-cobalt alloy, 88 parts by weight of tungsten carbide, 12 parts by weight of cobalt；Crosslinking agent is di-isopropylbenzene hydroperoxide；Foaming agent is urine
Element；
Preparation process are as follows:
(1) diamond dust high speed is ejected into tungsten-cobalt alloy particle surface, and constantly shake overturning alloying pellet, keeps particle surface thick
It is rough, alloying pellet surface is then heated to 1180 DEG C using laser, then rapidly quenching makes tungsten carbide particle precipitate into alloy table
Face, then in particle surface trowelling polymeric isocyanate glue, dry, obtained modified tungsten-cobalt alloy particle；The average grain diameter of diamond dust is
0.5mm, injection pressure are 0.7MPa；Laser heating heating rate be 950 DEG C/s, the cooling rate rapidly quenched be 95 DEG C/
s；The average thickness of polymeric isocyanate glue trowelling is 35mm；
(2) high speed is carried out with four acicular type zinc oxide crystal whisker, nylon66 fiber staple fiber, calcium carbonate respectively using silane coupling agent to be blended,
Modified four acicular type zinc oxide crystal whisker, 66 staple fiber of modification of nylon and modified calcium carbonate is made；Silane coupling agent is γ-metering system
Acryloxypropylethoxysilane trimethoxy silane, usage amount are the 2.8% of packing quality；The temperature that high speed is blended is 115 DEG C, and revolving speed is
130r/min, incorporation time 25min；
(3) by ethylene-vinyl acetate copolymer, high styrene rubber, random polypropylene, modified tungsten-cobalt alloy particle, modified four
Needle-shape zinc oxide crystal whisker, 66 staple fiber of modification of nylon and modified calcium carbonate are uniformly mixed, and foaming agent, zinc oxide, stearic acid is added
And anti-aging agent, mill packet roller add crosslinking agent and are kneaded, slice, cut-parts, are placed in hot-pressing and foaming in mold and are cooled to
Type, then sanction sample is carried out, the EVA rubber and plastic composite foam material as sole is made.
Embodiment 4
Raw material and proportion are as follows:
71.9 parts by weight of ethylene-vinyl acetate copolymer；
10 parts by weight of high styrene rubber；
5 parts by weight of random polypropylene；
4 parts by weight of four acicular type zinc oxide crystal whisker；
2 parts by weight of nylon66 fiber staple fiber；
3 parts by weight of calcium carbonate；
2 parts by weight of tungsten-cobalt alloy；
0.5 parts by weight of crosslinking agent；
0.5 parts by weight of foaming agent；
0.3 parts by weight of zinc oxide；
0.3 parts by weight of stearic acid；
0.5 parts by weight of anti-aging agent；
In tungsten-cobalt alloy, 80 parts by weight of tungsten carbide, 20 parts by weight of cobalt；Crosslinking agent is -2,5 di-t-butyl peroxide of 2,5- dimethyl
Change hexane；Foaming agent is azodicarbonamide；
Preparation process are as follows:
(1) diamond dust high speed is ejected into tungsten-cobalt alloy particle surface, and constantly shake overturning alloying pellet, keeps particle surface thick
It is rough, alloying pellet surface is then heated to 1100 DEG C using laser, then rapidly quenching makes tungsten carbide particle precipitate into alloy table
Face, then in particle surface trowelling polymeric isocyanate glue, dry, obtained modified tungsten-cobalt alloy particle；The average grain diameter of diamond dust is
0.3mm, injection pressure are 0.4MPa；Laser heating heating rate be 800 DEG C/s, the cooling rate rapidly quenched be 80 DEG C/
s；The average thickness of polymeric isocyanate glue trowelling is 20mm；
(2) high speed is carried out with four acicular type zinc oxide crystal whisker, nylon66 fiber staple fiber, calcium carbonate respectively using silane coupling agent to be blended,
Modified four acicular type zinc oxide crystal whisker, 66 staple fiber of modification of nylon and modified calcium carbonate is made；Silane coupling agent is γ-aminopropyl three
Methoxy silane, usage amount are the 2% of packing quality；The temperature that high speed is blended is 100 DEG C, revolving speed 80r/min, incorporation time
For 30min；
(3) by ethylene-vinyl acetate copolymer, high styrene rubber, random polypropylene, modified tungsten-cobalt alloy particle, modified four
Needle-shape zinc oxide crystal whisker, 66 staple fiber of modification of nylon and modified calcium carbonate are uniformly mixed, and foaming agent, zinc oxide, stearic acid is added
And anti-aging agent, mill packet roller add crosslinking agent and are kneaded, slice, cut-parts, are placed in hot-pressing and foaming in mold and are cooled to
Type, then sanction sample is carried out, the EVA rubber and plastic composite foam material as sole is made.
Embodiment 5
Raw material and proportion are as follows:
59.8 parts by weight of ethylene-vinyl acetate copolymer；
15 parts by weight of high styrene rubber；
10 parts by weight of random polypropylene；
8 parts by weight of four acicular type zinc oxide crystal whisker；
4 parts by weight of nylon66 fiber staple fiber；
5 parts by weight of calcium carbonate；
4 parts by weight of tungsten-cobalt alloy；
1 parts by weight of crosslinking agent；
1 parts by weight of foaming agent；
0.7 parts by weight of zinc oxide；
0.5 parts by weight of stearic acid；
1 parts by weight of anti-aging agent；
In tungsten-cobalt alloy, 90 parts by weight of tungsten carbide, 10 parts by weight of cobalt；Crosslinking agent is cumyl peroxide；Foaming agent is azo
Bis-isobutyronitrile；
Preparation process are as follows:
(1) diamond dust high speed is ejected into tungsten-cobalt alloy particle surface, and constantly shake overturning alloying pellet, keeps particle surface thick
It is rough, alloying pellet surface is then heated to 1200 DEG C using laser, then rapidly quenching makes tungsten carbide particle precipitate into alloy table
Face, then in particle surface trowelling polymeric isocyanate glue, dry, obtained modified tungsten-cobalt alloy particle；The average grain diameter of diamond dust is
0.5mm, injection pressure are 0.8MPa；The heating rate of laser heating is 1000 DEG C/s, and the cooling rate rapidly quenched is 100
℃/s；The average thickness of polymeric isocyanate glue trowelling is 40mm；
(2) high speed is carried out with four acicular type zinc oxide crystal whisker, nylon66 fiber staple fiber, calcium carbonate respectively using silane coupling agent to be blended,
Modified four acicular type zinc oxide crystal whisker, 66 staple fiber of modification of nylon and modified calcium carbonate is made；Silane coupling agent is γ-aminopropyl three
Ethoxysilane, usage amount are the 3% of packing quality；The temperature that high speed is blended is 120 DEG C, revolving speed 150r/min, incorporation time
For 10min；
(3) by ethylene-vinyl acetate copolymer, high styrene rubber, random polypropylene, modified tungsten-cobalt alloy particle, modified four
Needle-shape zinc oxide crystal whisker, 66 staple fiber of modification of nylon and modified calcium carbonate are uniformly mixed, and foaming agent, zinc oxide, stearic acid is added
And anti-aging agent, mill packet roller add crosslinking agent and are kneaded, slice, cut-parts, are placed in hot-pressing and foaming in mold and are cooled to
Type, then sanction sample is carried out, the EVA rubber and plastic composite foam material as sole is made.
Embodiment 6
Raw material and proportion are as follows:
60.9 parts by weight of ethylene-vinyl acetate copolymer；
12 parts by weight of high styrene rubber；
8 parts by weight of random polypropylene；
6 parts by weight of four acicular type zinc oxide crystal whisker；
3 parts by weight of nylon66 fiber staple fiber；
4 parts by weight of calcium carbonate；
3 parts by weight of tungsten-cobalt alloy；
0.8 parts by weight of crosslinking agent；
0.7 parts by weight of foaming agent；
0.5 parts by weight of zinc oxide；
0.4 parts by weight of stearic acid；
0.7 parts by weight of anti-aging agent；
In tungsten-cobalt alloy, 85 parts by weight of tungsten carbide, 15 parts by weight of cobalt；Crosslinking agent is cumyl peroxide；Foaming agent is urea；
Preparation process are as follows:
(1) diamond dust high speed is ejected into tungsten-cobalt alloy particle surface, and constantly shake overturning alloying pellet, keeps particle surface thick
It is rough, alloying pellet surface is then heated to 1150 DEG C using laser, then rapidly quenching makes tungsten carbide particle precipitate into alloy table
Face, then in particle surface trowelling polymeric isocyanate glue, dry, obtained modified tungsten-cobalt alloy particle；The average grain diameter of diamond dust is
0.4mm, injection pressure are 0.6MPa；Laser heating heating rate be 900 DEG C/s, the cooling rate rapidly quenched be 90 DEG C/
s；The average thickness of polymeric isocyanate glue trowelling is 30mm；
(2) high speed is carried out with four acicular type zinc oxide crystal whisker, nylon66 fiber staple fiber, calcium carbonate respectively using silane coupling agent to be blended,
Modified four acicular type zinc oxide crystal whisker, 66 staple fiber of modification of nylon and modified calcium carbonate is made；Silane coupling agent is γ-(2,3- ring
The third oxygen of oxygen) propyl trimethoxy silicane, usage amount is the 2.5% of packing quality；The temperature that high speed is blended is 110 DEG C, and revolving speed is
120r/min, incorporation time 20min；
(3) by ethylene-vinyl acetate copolymer, high styrene rubber, random polypropylene, modified tungsten-cobalt alloy particle, modified four
Needle-shape zinc oxide crystal whisker, 66 staple fiber of modification of nylon and modified calcium carbonate are uniformly mixed, and foaming agent, zinc oxide, stearic acid is added
And anti-aging agent, mill packet roller add crosslinking agent and are kneaded, slice, cut-parts, are placed in hot-pressing and foaming in mold and are cooled to
Type, then sanction sample is carried out, the EVA rubber and plastic composite foam material as sole is made.
Comparative example 1
In preparation process, it is not added with high styrene rubber, other preparation conditions and embodiment 6 are consistent.
Comparative example 2
In preparation process, it is not added with random polypropylene, other preparation conditions and embodiment 6 are consistent.
Comparative example 3
In preparation process, it is not added with four acicular type zinc oxide crystal whisker, other preparation conditions and embodiment 6 are consistent.
Comparative example 4
In preparation process, it is not added with tungsten-cobalt alloy, other preparation conditions and embodiment 6 are consistent.
Performance test:
(1) it does, the kinematics and static friction coefficient under wet condition: referring to HG/T 2729-1995 standard, being rubbed using Jinan daylight MX-01A
It wipes coefficient instrument and tests composite foam material produced by the present invention in kinematics and static friction coefficient dry, under wet condition, moisture state is spread
Water is sample having a size of 63mm × 63mm × 2mm, and tensile speed 150mm/min, test sliding distance is 140mm, test 5
Secondary calculating average value；
(2) abrasion test abrasion loss: according to ISO4649 standard, sanction sample first is carried out to composite foam material produced by the present invention, so
Abrasion test is carried out using GT-7012-D DIN Abrasion Tester afterwards；Diameter of cylinder is 150mm, revolving speed 40r/min, friction
Distance is 40m；The diameter of test sample is 16mm, and with a thickness of 6mm, the load of test is 10N, tests and calculates abrasion loss: A=
(△ m × 200mg)/(Q × S), wherein A is abrasion loss, and △ m is the of poor quality of sample friction front and back, and Q is Standard erosion value, S
For the density of sample；
(3) it porosity: directlys adopt JF-2900V foamed plastics porosity test instrument and measures composite foamed material produced by the present invention
The porosity of material；
(4) tensile strength: tensile strength test is carried out referring to GB/T 6344-2008 standard, by composite foam material of the invention
Standard batten is made, is tested using electronic universal tester, test speed 500mm/min measures tensile strength；
(5) elastic: to carry out resilience test referring to GB/T 1681-2009 standard, mark is made in composite foam material of the invention
Quasi- sample is tested using resiliency test machine, measures resilience；
(6) brittleness temperature: directlying adopt rubber black brittleness temperature measuring device and tested, and it is multiple to test rubber and plastic produced by the present invention
Close the black brittleness temperature of foamed material；
(7) puncture-resistant intensity: directlying adopt puncture strength tester and tested, by the composite foamed material of rubber and plastic produced by the present invention
The sample that average thickness is 1cm is made in material, using the steel needle that diameter is 1.0mm, spherical tips radius is 0.5mm, with 50 ±
The speed of 5mm/min goes to top to pierce, and measures puncture-resistant intensity.
The data obtained is as shown in table 1.
Table 1:
Claims (10)
1. a kind of EVA rubber and plastic composite foam material as sole, which is characterized in that the rubber and plastic composite foam material preparation
Raw material and proportion are as follows:
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 random polypropylene；
4 ~ 8 parts by weight of four acicular type zinc oxide crystal whisker；
2 ~ 4 parts by weight of nylon66 fiber staple fiber；
3 ~ 5 parts by weight of calcium carbonate；
2 ~ 4 parts by weight of tungsten-cobalt alloy；
0.5 ~ 1 parts by weight of crosslinking agent；
0.5 ~ 1 parts by weight of 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 parts by weight of anti-aging agent.
2. a kind of EVA rubber and plastic composite foam material as sole according to claim 1, it is characterised in that: the tungsten-cobalt
In alloy, 80 ~ 90 parts by weight of tungsten carbide, 10 ~ 20 parts by weight of cobalt.
3. a kind of EVA rubber and plastic composite foam material as sole according to claim 1, it is characterised in that: the crosslinking
Agent is cumyl peroxide, benzoyl peroxide, di-isopropylbenzene hydroperoxide, -2,5 di-t-butyl peroxide of 2,5- dimethyl
Change at least one of hexane.
4. a kind of EVA rubber and plastic composite foam material as sole according to claim 1, it is characterised in that: the foaming
Agent is at least one of azodicarbonamide, azodiisobutyronitrile, urea.
5. a kind of preparation method of EVA rubber and plastic composite foam material as sole, feature exist according to claim 1 ~ 4
In, the preparation process the following steps are included:
(1) diamond dust high speed is ejected into tungsten-cobalt alloy particle surface, and constantly shake overturning alloying pellet, keeps particle surface thick
It is rough, alloying pellet surface is then heated to 1100 ~ 1200 DEG C using laser, then rapidly quenching makes tungsten carbide particle precipitate into conjunction
Gold surface, then in particle surface trowelling polymeric isocyanate glue, dry, obtained modified tungsten-cobalt alloy particle；
(2) high speed is carried out with four acicular type zinc oxide crystal whisker, nylon66 fiber staple fiber, calcium carbonate respectively using silane coupling agent to be blended,
Modified four acicular type zinc oxide crystal whisker, 66 staple fiber of modification of nylon and modified calcium carbonate is made；
(3) by ethylene-vinyl acetate copolymer, high styrene rubber, random polypropylene, modified tungsten-cobalt alloy particle, modified four
Needle-shape zinc oxide crystal whisker, 66 staple fiber of modification of nylon and modified calcium carbonate are uniformly mixed, and foaming agent, zinc oxide, stearic acid is added
And anti-aging agent, mill packet roller add crosslinking agent and are kneaded, slice, cut-parts, are placed in hot-pressing and foaming in mold and are cooled to
Type, then sanction sample is carried out, the EVA rubber and plastic composite foam material as sole is made.
6. a kind of preparation method of the EVA rubber and plastic composite foam material as sole, feature exist according to claim 5
In: the partial size of step (1) described diamond dust is 0.3 ~ 0.5mm, and injection pressure is 0.4 ~ 0.8MPa.
7. a kind of preparation method of the EVA rubber and plastic composite foam material as sole, feature exist according to claim 5
It is 800 ~ 1000 DEG C/s in the heating rate of: step (1) the laser heating, the cooling rate rapidly quenched is 80 ~ 100 DEG C/
s。
8. a kind of preparation method of the EVA rubber and plastic composite foam material as sole, feature exist according to claim 5
In: step (1) the polymeric isocyanate glue trowelling with a thickness of 20 ~ 40mm.
9. a kind of preparation method of the EVA rubber and plastic composite foam material as sole, feature exist according to claim 5
In: step (2) silane coupling agent is gamma-aminopropyl-triethoxy-silane, γ-(the third oxygen of 2,3- epoxy) propyl trimethoxy
At least one of base silane, γ-methacryloxypropyl trimethoxy silane, γ-aminopropyltrimethoxysilane, make
Dosage is the 2 ~ 3% of packing quality.
10. a kind of preparation method of the EVA rubber and plastic composite foam material as sole, feature exist according to claim 5
In: the temperature that step (2) high speed is blended is 100 ~ 120 DEG C, and revolving speed is 80 ~ 150r/min, and incorporation time is 10 ~ 30min.
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| CN115368666B (en) * | 2021-12-07 | 2024-03-26 | 河北穿着不累医疗科技有限公司 | Ray protection shoe material and preparation method thereof |
| CN114773658B (en) * | 2022-05-24 | 2023-09-08 | 安踏（中国）有限公司 | Wear-resistant, light and anti-slip high-soft-elasticity cushioning EVA (ethylene-vinyl acetate) foam sole material and preparation method and application thereof |
| CN114773658A (en) * | 2022-05-24 | 2022-07-22 | 安踏（中国）有限公司 | Wear-resistant, light and anti-slip high-softness-elasticity cushioning EVA (ethylene-vinyl acetate copolymer) foamed sole material and preparation method and application thereof |
| CN116102806A (en) * | 2022-11-29 | 2023-05-12 | 惠州市广润环保科技有限公司 | High-toughness heat-resistant foamed plastic |
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