CN109054126A - A kind of high-low temperature resistant sizing material for rubber shoe sole and preparation method thereof - Google Patents
A kind of high-low temperature resistant sizing material for rubber shoe sole and preparation method thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
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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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention discloses a kind of high-low temperature resistant sizing material for rubber shoe sole and preparation method thereof, are prepared from the following raw materials: nitrile rubber, butadiene rubber, rubber and plastic alloy, modified vinyl resin, modified RE oxide, vulcanizing agent, penta methylene thiuram of tetra-sulfurized pair, cumyl peroxide, maleic anhydride grafted polyethylene, zinc methacrylate, dibutyl phthalate, pentaerythritol stearate, modified Nano wear resistant filler, zinc ricinate, activator, softening agent, rubber accelerator, anti-aging agent.High-low temperature resistant sizing material for rubber shoe sole of the invention has high and low temperature resistance, high resiliency, high abrasion, tension, compression without being damaged, and the advantages of corrosion resistance, good weatherability.
Description
Technical field
The present invention relates to technical field of shoe making, and in particular to a kind of high-low temperature resistant sizing material for rubber shoe sole and its preparation side
Method.
Background technique
With the continuous improvement of people's living standards, being proposed to the quality of rubber overshoes, comfort level, wholesomeness, safety in utilization
Higher requirement.It is comfortable and easy to wear that this does not require nothing more than rubber overshoes, and to have high-low temperature resistant, high resiliency, high abrasion, tension, pressure
Contracting is without being damaged, the advantages of corrosion resistance, good weatherability.This just has higher requirement to the sizing material of rubber sole.
Therefore, it is badly in need of developing one kind with high-low temperature resistant, high resiliency, high abrasion, tension, compression without being damaged, and
Corrosion resistance, good weatherability high-low temperature resistant sizing material for rubber shoe sole be just very necessary.
In view of the above-mentioned problems, being retrieved to the prior art, in Chinese invention (application number: in 201510778597.7)
Disclose a kind of corrosion-and high-temp-resistant sizing material for rubber shoe sole and its preparation process, including following component: nitrile rubber；Coal tar
Resin；Fluorine silicone rubber；Dithiocar-bamate；- 4 methylphenol of 2,6- tert-butyl；2- mercapto imidazoline；Dual-tert-butyl mistake
Aoxidize diisopropyl benzene；Aramid fiber；Carbon black；Nano zine oxide；Vaseline and anti-aging agent.Sole material system provided by the invention
Standby sole has high temperature resistant, and corrosion-resistant, wear-resisting, the performances such as light softness apply pressure to raw stock in preparation process, make
Sole foaming continuous uniform obtained, sole are not easy to deform.Although the high-low temperature resistant sizing material for rubber shoe sole of the patent is certain
The problems such as the corrosion-resistant, wear-resisting of rubber boots, weatherability are improved in degree, but the nitrile rubber and fluorine silicone rubber added in raw material
Between there are problems that poor compatibility, cause obtained high-low temperature resistant sizing material for rubber shoe sole tension, compression without being damaged, be wear-resisting
The performances such as property are difficult to meet actual demand.
Summary of the invention
The present invention provides a kind of high-low temperature resistant sizing material for rubber shoe sole and preparation method thereof, solve in above-mentioned background technique
Deficiency, the high-low temperature resistant sizing material for rubber shoe sole has high-low temperature resistant, high resiliency, high abrasion, tension, compression without by broken
It is bad, and the advantages of corrosion resistance, good weatherability.
It is of the existing technology in order to solve the problems, such as, it adopts the following technical scheme that
A kind of high-low temperature resistant high-low temperature resistant sizing material for rubber shoe sole, is prepared from the following raw materials in parts by weight: 55 parts of nitrile rubber,
40 parts of butadiene rubber, 7.5 parts of rubber and plastic alloy, 6 parts of modified vinyl resin, 4.5 parts of modified RE oxide, 2.5 parts of vulcanizing agent,
5 parts of penta methylene thiuram of tetra-sulfurized pair, 4 parts of cumyl peroxide, 6 parts of maleic anhydride grafted polyethylene, methacrylic acid
3 parts of zinc, 7.5 parts of dibutyl phthalate, 4.5 parts of pentaerythritol stearate, 15 parts of modified Nano wear resistant filler, castor oil
5 parts of sour zinc, 3.5 parts of activator, 2 parts of softening agent, 1 part of rubber accelerator, 0.6 part of anti-aging agent；
The modified RE oxide preparation method includes: that rare earth oxide is taken to be dissolved in dehydrated alcohol, is then added and accounts for rare earth
Then the silane coupling agent of oxide mass 3-5%, ultrasonic vibration 20-30min stir 40-60min at 120-140 DEG C, will
Obtained modification material, which is placed in baking oven, dries 3h at 150 DEG C, removes extra dehydrated alcohol, the material after drying is ground
The modified RE oxide of 300-400 mesh is obtained after mill, sieving.
Preferably, the rubber and plastic alloy by weight ratio be 3:1 powder nitrile rubber and PBT high-temperature blending and
At.
Preferably, the preparation method of the modified vinyl resin includes: that vinylite is put into anhydrous second
In alcohol, the vinyltriethoxysilane for accounting for vinylite quality 0.3-0.7% is then added, ultrasonic treatment 1-3h forms mixed
Solution is closed, is subsequently placed in 90-100 DEG C of baking oven and places 1-2h, then the precuring 1-2h at 120-130 DEG C, is sent into press
Solidify 2-4h, solidification temperature is 160-180 DEG C, and solidifying pressure 1-3MPa obtains modified vinyl resin.
Preferably, the vulcanizing agent is one or more of sulphur, metal oxide and Thiourea.
Preferably, the modified Nano wear resistant filler is made from the following raw materials in parts by weight: nanometer silicon carbide 15-
20 parts, 10-15 parts of nm-class boron nitride, 4-8 parts of nano molybdenum disulfide, 0.4-0.8 parts of silane coupling agent, anhydrous sorbitol list oleic acid
3-5 parts of ester, 2-4 parts of methyltriethoxysilane, 1-3 parts of stearic acid, 4-6 parts of sodium silicate；
The preparation method of the modified Nano wear resistant filler includes: (1) by nanometer silicon carbide, nm-class boron nitride and nanometer curing
Molybdenum is added in solvent, and 5-10min is sufficiently stirred at 60-80 DEG C, is filtered to remove filtrate, and filter cake is carried out washing 2-3 times, dry
Arrive mixed powder；
(2) mixed powder is made in step (1) and suitable water grinding is added, crossed 300-400 mesh, 8-13% hydrochloric acid is then added
Solution tune pH is 4-6, and repeated hydrogenation sodium oxide molybdena is adjusted to neutrality, then by sorbitan monooleate, methyltriethoxysilane,
Stearic acid, sodium silicate are added thereto, and heating stirring reacts 60-80min, and heating temperature is 90-100 DEG C, mixing speed 500-
700rpm obtains mixed slurry；
(3) silane coupling agent is added in mixed slurry in step (2), ultrasonic disperse 30-40min is filtered, dry, grinding, mistake
Up to modified Nano wear resistant filler after 100-200 mesh.
Preferably, the activator is zinc oxide, stearic acid or zinc stearate；The softening agent is hydroxyl
Silicone oil.
Preferably, it is 1:1:1 that the rubber accelerator is captax, diphenylguanidine and altax by weight
The mixture of composition；The anti-aging agent presses any weight ratio by anti-aging agent RD, antioxidant 4020, antioxidant MB and anti-aging agent 445
Composition.
Preferably, the present invention also provides the preparation methods of above-mentioned high-low temperature resistant sizing material for rubber shoe sole, including
Following steps:
(1) each raw material is weighed by weight；
(2) first nitrile rubber and butadiene rubber are added in mixer, temperature control adds after 100-110 DEG C, mixing 3-5min
Enter rubber and plastic alloy and maleic anhydride grafted polyethylene, continue mixing 5-10min, then addition modified vinyl resin, modification are dilute
Native oxide and modified Nano wear resistant filler, mixing 3-5min, then dumping, smash conjunction, tabletting, bottom sheet, be cooled to room temperature after stop
It puts 2-4h and obtains rubber compound 1；
(3) rubber compound 1 made from step (1) is put into open mill, is warming up to 130-150 DEG C, zinc methacrylate, neighbour is added
Vulcanizing agent, tetra-sulfurized pair penta is added after being kneaded 3-5min in dibatyl phithalate, pentaerythritol stearate and zinc ricinate
Methylene thiuram, cumyl peroxide and rubber accelerator are kneaded 5-10min, are eventually adding activator and softening agent, mix
2-4min is refined, then slice, it is cooling, obtain rubber compound 2；
(4) rubber compound 2 made from step (3) is put into the mold of vulcanizer, is vulcanized, room is cooled to after vulcanization
Temperature, demoulding obtain the high-low temperature resistant sizing material for rubber shoe sole.
Compared with prior art, the present invention it has the advantages that
(1) present invention can by using high-low temperature resistant sizing material for rubber shoe sole made from nitrile rubber and butadiene rubber blending method
The wearability of nitrile rubber and the corrosion resistance and cold resistance of heat resistance and butadiene rubber are had both, the two synergistic effect changes jointly
Into performances such as the high and low temperature resistance of high-low temperature resistant sizing material for rubber shoe sole, wearability, corrosion resistance, weatherabilities, while altogether
Maleic anhydride grafted polyethylene is added during mixed, solves nitrile rubber and butadiene rubber inconsistent problem and rubber and plastic closes
Gold and the problem of rubber compatibility difference so that nitrile rubber, butadiene rubber, rubber and plastic alloy triplicity it is even closer, thus
Improve the mechanical property of sizing material.
(2) the penta methylene thiuram of tetra-sulfurized pair and cumyl peroxide that the present invention is added can be realized with vulcanizing agent
Collaboration sulfurization to nitrile rubber and butadiene rubber, improves the curingprocess rate and vulcanization effect of Blend rubber；Add simultaneously
Enter activator and zinc ricinate cooperates, there is activation to the crosslinking of Blend rubber, accelerate the speed of vulcanization, improve
The mechanical property of sizing material；In addition addition modified Nano reinforced filling and sizing material have preferable compatibility, can be dispersed in
In sizing material, to improve the high and low temperature resistance of sizing material, wearability, corrosion resistance, mechanical property and weatherability；And what is be added changes
Sex ethylene base resin has stronger activity, may be homogenously dispersed in sizing material, and have using its own by modification
Adhesive property, so that the binding force of each component in sizing material is improved, to enhance the wearability of sizing material, mechanical property.
(3) modified RE oxide of the invention can form chemical bond between the organic molecule in paste system, improve
The mechanical property and weatherability of sizing material；And dibutyl phthalate and pentaerythritol stearate, improve the toughness of sizing material
Its thermal stability is improved simultaneously.
(4) the characteristics of present invention is according to component, optimizes preparation process, defines the sequence of charging during the preparation process simultaneously
Different smelting temperature and conditions of vulcanization are selected, high and low temperature resistance, wearability, corrosion resistance, the mechanical property of sizing material are improved
Energy and weatherability.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, technical solution of the present invention will be carried out below
Clear, complete description.Obviously, the described embodiment is only a part of the embodiment of the present invention, instead of all the embodiments.
Based on the embodiments of the present invention, those of ordinary skill in the art obtained institute without making creative work
There are other embodiments, belongs to the range that the present invention is protected.
Embodiment 1
The high-low temperature resistant sizing material for rubber shoe sole of the present embodiment, is prepared from the following raw materials in parts by weight: 45 parts of nitrile rubber, suitable
35 parts of buna, 5 parts of rubber and plastic alloy, 4 parts of modified vinyl resin, 3 parts of modified RE oxide, 1 part of vulcanizing agent, tetra-sulfurized pair
Penta 3 parts of methylene thiuram, 2 parts of cumyl peroxide, 4 parts of maleic anhydride grafted polyethylene, 2 parts of zinc methacrylate, neighbour
5 parts of dibatyl phithalate, 3 parts of pentaerythritol stearate, 10 parts of modified Nano wear resistant filler, 3 parts of zinc ricinate, activation
2 parts of agent, 1 part of softening agent, 0.5 part of rubber accelerator, 0.4 part of anti-aging agent.
Wherein, the rubber and plastic alloy is formed by the powder nitrile rubber that weight ratio is 3:1 with PBT high-temperature blending.
Wherein, the preparation method of the modified vinyl resin includes: that vinylite is put into dehydrated alcohol, then
The vinyltriethoxysilane for accounting for vinylite quality 0.3% is added, ultrasonic treatment 1h forms mixed solution, is subsequently placed in
1h is placed in 90 DEG C of baking ovens, then the precuring 1h at 120 DEG C, be sent into press and solidify 2h, solidification temperature is 160 DEG C, solidification
Pressure is 1MPa, obtains modified vinyl resin.
Wherein, the modified RE oxide preparation method includes: that rare earth oxide is taken to be dissolved in dehydrated alcohol, then plus
Enter to account for the silane coupling agent of rare-earth oxidation amount of substance 3%, then ultrasonic vibration 20min stirs 40min at 120 DEG C, will obtain
Modification material be placed in baking oven and dry 3h at 150 DEG C, extra dehydrated alcohol is removed, by the material grinding after drying, mistake
The modified RE oxide of 300-400 mesh is obtained after sieve.
Wherein, the vulcanizing agent is one or more of sulphur, metal oxide and Thiourea.
Wherein, the modified Nano wear resistant filler is made from the following raw materials in parts by weight: 15 part, nanometer nitrogen of nanometer silicon carbide
Change 10 parts of boron, 4 parts of nano molybdenum disulfide, 0.4 part of silane coupling agent, 3 parts of sorbitan monooleate, methyltriethoxy silane
2 parts of alkane, 1 part of stearic acid, 4 parts of sodium silicate；
The preparation method of the modified Nano wear resistant filler includes: (1) by nanometer silicon carbide, nm-class boron nitride and nanometer curing
Molybdenum is added in solvent, and 5min is sufficiently stirred at 60 DEG C, is filtered to remove filtrate, filter cake is carried out washing 2-3 times, dry arriving is mixed
Close powder；
(2) mixed powder is made in step (1) and suitable water grinding is added, crossed 300-400 mesh, 8-13% hydrochloric acid is then added
Solution tune pH is 4-6, and repeated hydrogenation sodium oxide molybdena is adjusted to neutrality, then by sorbitan monooleate, methyltriethoxysilane,
Stearic acid, sodium silicate are added thereto, and heating stirring reacts 60min, and heating temperature is 90 DEG C, and mixing speed 500rpm is obtained
Mixed slurry；
(3) silane coupling agent is added in mixed slurry in step (2), ultrasonic disperse 30min is filtered, dry, grinding, mistake
Up to modified Nano wear resistant filler after 100-200 mesh.
Wherein, the activator is zinc oxide, stearic acid or zinc stearate；The softening agent is hydroxy silicon oil.
Wherein, it is the mixed of 1:1:1 composition that the rubber accelerator is captax, diphenylguanidine and altax by weight
Close object；The anti-aging agent is made of anti-aging agent RD, antioxidant 4020, antioxidant MB and anti-aging agent 445 by any weight ratio.
Wherein, the present invention also provides the preparation methods of above-mentioned high-low temperature resistant sizing material for rubber shoe sole, comprising the following steps:
(1) each raw material is weighed by weight；
(2) first nitrile rubber and butadiene rubber are added in mixer, rubber and plastic is added after 100 DEG C, mixing 3min in temperature control
Alloy and maleic anhydride grafted polyethylene, continue mixing 5min, then be added modified vinyl resin, modified RE oxide and
Modified Nano wear resistant filler, mixing 3min, then dumping, smash conjunction, tabletting, bottom sheet, be cooled to after room temperature and park 2h and be kneaded
Glue 1；
(3) rubber compound 1 made from step (1) is put into open mill, is warming up to 130 DEG C, zinc methacrylate, adjacent benzene two is added
Vulcanizing agent, penta methylene of tetra-sulfurized pair is added after being kneaded 3min in formic acid dibutyl ester, pentaerythritol stearate and zinc ricinate
Thiuram, cumyl peroxide and rubber accelerator are kneaded 5min, are eventually adding activator and softening agent, are kneaded 2min, so
Slice afterwards, it is cooling, obtain rubber compound 2；
(4) rubber compound 2 made from step (3) is put into the mold of vulcanizer, is vulcanized, room is cooled to after vulcanization
Temperature, demoulding obtain the high-low temperature resistant sizing material for rubber shoe sole.
Embodiment 2
The high-low temperature resistant sizing material for rubber shoe sole of the present embodiment, is prepared from the following raw materials in parts by weight: 65 parts of nitrile rubber, suitable
45 parts of buna, 10 parts of rubber and plastic alloy, 8 parts of modified vinyl resin, 6 parts of modified RE oxide, 4 parts of vulcanizing agent, four vulcanizations
Double 7 parts of penta methylene thiurams, 6 parts of cumyl peroxide, 8 parts of maleic anhydride grafted polyethylene, 4 parts of zinc methacrylate,
10 parts of dibutyl phthalate, 6 parts of pentaerythritol stearate, 20 parts of modified Nano wear resistant filler, 7 parts of zinc ricinate,
5 parts of activator, 3 parts of softening agent, 1.5 parts of rubber accelerator, 0.8 part of anti-aging agent.
Wherein, the rubber and plastic alloy is formed by the powder nitrile rubber that weight ratio is 3:1 with PBT high-temperature blending.
Wherein, the preparation method of the modified vinyl resin includes: that vinylite is put into dehydrated alcohol, then
The vinyltriethoxysilane for accounting for vinylite quality 0.7% is added, ultrasonic treatment 3h forms mixed solution, is subsequently placed in
2h is placed in 100 DEG C of baking ovens, then the precuring 2h at 130 DEG C, be sent into press and solidify 4h, solidification temperature is 180 DEG C, solidification
Pressure is 3MPa, obtains modified vinyl resin.
Wherein, the modified RE oxide preparation method includes: that rare earth oxide is taken to be dissolved in dehydrated alcohol, then plus
Enter to account for the silane coupling agent of rare-earth oxidation amount of substance 5%, then ultrasonic vibration 30min stirs 60min at 140 DEG C, will obtain
Modification material be placed in baking oven and dry 3h at 150 DEG C, extra dehydrated alcohol is removed, by the material grinding after drying, mistake
The modified RE oxide of 300-400 mesh is obtained after sieve.
Wherein, the vulcanizing agent is one or more of sulphur, metal oxide and Thiourea.
Wherein, the modified Nano wear resistant filler is made from the following raw materials in parts by weight: 20 part, nanometer nitrogen of nanometer silicon carbide
Change 15 parts of boron, 8 parts of nano molybdenum disulfide, 0.8 part of silane coupling agent, 5 parts of sorbitan monooleate, methyltriethoxy silane
4 parts of alkane, 3 parts of stearic acid, 6 parts of sodium silicate；
The preparation method of the modified Nano wear resistant filler includes: (1) by nanometer silicon carbide, nm-class boron nitride and nanometer curing
Molybdenum is added in solvent, and 10min is sufficiently stirred at 80 DEG C, is filtered to remove filtrate, filter cake is carried out washing 2-3 times, dry arrives
Mixed powder；
(2) mixed powder is made in step (1) and suitable water grinding is added, crossed 300-400 mesh, 8-13% hydrochloric acid is then added
Solution tune pH is 4-6, and repeated hydrogenation sodium oxide molybdena is adjusted to neutrality, then by sorbitan monooleate, methyltriethoxysilane,
Stearic acid, sodium silicate are added thereto, and heating stirring reacts 80min, and heating temperature is 100 DEG C, and mixing speed 700rpm is obtained
Mixed slurry；
(3) silane coupling agent is added in mixed slurry in step (2), ultrasonic disperse 40min is filtered, dry, grinding, mistake
Up to modified Nano wear resistant filler after 100-200 mesh.
Wherein, the activator is zinc oxide, stearic acid or zinc stearate；The softening agent is hydroxy silicon oil.
Wherein, it is the mixed of 1:1:1 composition that the rubber accelerator is captax, diphenylguanidine and altax by weight
Close object；The anti-aging agent is made of anti-aging agent RD, antioxidant 4020, antioxidant MB and anti-aging agent 445 by any weight ratio.
Wherein, the present invention also provides the preparation methods of above-mentioned high-low temperature resistant sizing material for rubber shoe sole, comprising the following steps:
(1) each raw material is weighed by weight；
(2) first nitrile rubber and butadiene rubber are added in mixer, rubber and plastic is added after 110 DEG C, mixing 5min in temperature control
Alloy and maleic anhydride grafted polyethylene continue mixing 10min, and modified vinyl resin, modified RE oxide is then added
With modified Nano wear resistant filler, mixing 5min, then dumping, smash conjunction, tabletting, bottom sheet, be cooled to after room temperature and park 4h and mixed
Refining glue 1；
(3) rubber compound 1 made from step (1) is put into open mill, is warming up to 150 DEG C, zinc methacrylate, adjacent benzene two is added
Vulcanizing agent, penta methylene of tetra-sulfurized pair is added after being kneaded 5min in formic acid dibutyl ester, pentaerythritol stearate and zinc ricinate
Thiuram, cumyl peroxide and rubber accelerator are kneaded 10min, are eventually adding activator and softening agent, are kneaded 4min,
Then slice, it is cooling, obtain rubber compound 2；
(4) rubber compound 2 made from step (3) is put into the mold of vulcanizer, is vulcanized, room is cooled to after vulcanization
Temperature, demoulding obtain the high-low temperature resistant sizing material for rubber shoe sole.
Embodiment 3
The high-low temperature resistant sizing material for rubber shoe sole of the present embodiment, is prepared from the following raw materials in parts by weight: 55 parts of nitrile rubber, suitable
40 parts of buna, 7.5 parts of rubber and plastic alloy, 6 parts of modified vinyl resin, 4.5 parts of modified RE oxide, 2.5 parts of vulcanizing agent, four
Vulcanize double 5 parts of penta methylene thiuram, 4 parts of cumyl peroxide, 6 parts of maleic anhydride grafted polyethylenes, zinc methacrylate 3
Part, 7.5 parts of dibutyl phthalate, 4.5 parts of pentaerythritol stearate, 15 parts of modified Nano wear resistant filler, ricinoleic acid
5 parts of zinc, 3.5 parts of activator, 2 parts of softening agent, 1 part of rubber accelerator, 0.6 part of anti-aging agent.
Wherein, the rubber and plastic alloy is formed by the powder nitrile rubber that weight ratio is 3:1 with PBT high-temperature blending.
Wherein, the preparation method of the modified vinyl resin includes: that vinylite is put into dehydrated alcohol, then
The vinyltriethoxysilane for accounting for vinylite quality 0.5% is added, ultrasonic treatment 2h forms mixed solution, is subsequently placed in
1.5h to be placed in 95 DEG C of baking ovens, then the precuring 1.5h at 125 DEG C, is sent into press and solidifies 3h, solidification temperature is 170 DEG C,
Solidifying pressure is 2MPa, obtains modified vinyl resin.
Wherein, the modified RE oxide preparation method includes: that rare earth oxide is taken to be dissolved in dehydrated alcohol, then plus
Enter to account for the silane coupling agent of rare-earth oxidation amount of substance 4%, then ultrasonic vibration 25min stirs 50min at 130 DEG C, will obtain
Modification material be placed in baking oven and dry 3h at 150 DEG C, extra dehydrated alcohol is removed, by the material grinding after drying, mistake
The modified RE oxide of 300-400 mesh is obtained after sieve.
Wherein, the vulcanizing agent is one or more of sulphur, metal oxide and Thiourea.
Wherein, the modified Nano wear resistant filler is made from the following raw materials in parts by weight: 18 part, nanometer nitrogen of nanometer silicon carbide
Change 12 parts of boron, 6 parts of nano molybdenum disulfide, 0.6 part of silane coupling agent, 4 parts of sorbitan monooleate, methyltriethoxy silane
3 parts of alkane, 2 parts of stearic acid, 5 parts of sodium silicate；
The preparation method of the modified Nano wear resistant filler includes: (1) by nanometer silicon carbide, nm-class boron nitride and nanometer curing
Molybdenum is added in solvent, and 8min is sufficiently stirred at 70 DEG C, is filtered to remove filtrate, filter cake is carried out washing 2-3 times, dry arriving is mixed
Close powder；
(2) mixed powder is made in step (1) and suitable water grinding is added, crossed 300-400 mesh, 8-13% hydrochloric acid is then added
Solution tune pH is 4-6, and repeated hydrogenation sodium oxide molybdena is adjusted to neutrality, then by sorbitan monooleate, methyltriethoxysilane,
Stearic acid, sodium silicate are added thereto, and heating stirring reacts 70min, and heating temperature is 95 DEG C, and mixing speed 600rpm is obtained
Mixed slurry；
(3) silane coupling agent is added in mixed slurry in step (2), ultrasonic disperse 35min is filtered, dry, grinding, mistake
Up to modified Nano wear resistant filler after 100-200 mesh.
Wherein, the activator is zinc oxide, stearic acid or zinc stearate；The softening agent is hydroxy silicon oil.
Wherein, it is the mixed of 1:1:1 composition that the rubber accelerator is captax, diphenylguanidine and altax by weight
Close object；The anti-aging agent is made of anti-aging agent RD, antioxidant 4020, antioxidant MB and anti-aging agent 445 by any weight ratio.
Wherein, the present invention also provides the preparation methods of above-mentioned high-low temperature resistant sizing material for rubber shoe sole, comprising the following steps:
(1) each raw material is weighed by weight；
(2) first nitrile rubber and butadiene rubber are added in mixer, rubber and plastic is added after 105 DEG C, mixing 4min in temperature control
Alloy and maleic anhydride grafted polyethylene continue mixing 7.5min, and modified vinyl resin, modified RE oxide is then added
With modified Nano wear resistant filler, mixing 4min, then dumping, smash conjunction, tabletting, bottom sheet, be cooled to after room temperature and park 3h and mixed
Refining glue 1；
(3) rubber compound 1 made from step (1) is put into open mill, is warming up to 140 DEG C, zinc methacrylate, adjacent benzene two is added
Vulcanizing agent, penta methylene of tetra-sulfurized pair is added after being kneaded 4min in formic acid dibutyl ester, pentaerythritol stearate and zinc ricinate
Thiuram, cumyl peroxide and rubber accelerator are kneaded 7.5min, are eventually adding activator and softening agent, are kneaded 3min,
Then slice, it is cooling, obtain rubber compound 2；
(4) rubber compound 2 made from step (3) is put into the mold of vulcanizer, is vulcanized, room is cooled to after vulcanization
Temperature, demoulding obtain the high-low temperature resistant sizing material for rubber shoe sole.
Embodiment 4
The high-low temperature resistant sizing material for rubber shoe sole of the present embodiment, is prepared from the following raw materials in parts by weight: 50 parts of nitrile rubber, suitable
38 parts of buna, 6 parts of rubber and plastic alloy, 5 parts of modified vinyl resin, 4 parts of modified RE oxide, 2 parts of vulcanizing agent, tetra-sulfurized pair
Penta 4 parts of methylene thiuram, 3 parts of cumyl peroxide, 5 parts of maleic anhydride grafted polyethylene, 2.5 parts of zinc methacrylate,
6 parts of dibutyl phthalate, 13 parts of modified Nano wear resistant filler, 4 parts of zinc ricinate, is lived at 4 parts of pentaerythritol stearate
3 parts of agent, 1.5 parts of softening agent, 0.8 part of rubber accelerator, 0.5 part of anti-aging agent.
Wherein, the rubber and plastic alloy is formed by the powder nitrile rubber that weight ratio is 3:1 with PBT high-temperature blending.
Wherein, the preparation method of the modified vinyl resin includes: that vinylite is put into dehydrated alcohol, then
The vinyltriethoxysilane for accounting for vinylite quality 0.4% is added, ultrasonic treatment 1.5h forms mixed solution, then sets
1.2h is placed in 92 DEG C of baking ovens, then the precuring 1.3h at 123 DEG C, is sent into press and solidifies 2.5h, solidification temperature 165
DEG C, solidifying pressure 1.5MPa obtains modified vinyl resin.
Wherein, the modified RE oxide preparation method includes: that rare earth oxide is taken to be dissolved in dehydrated alcohol, then plus
Entering to account for the silane coupling agent of rare-earth oxidation amount of substance 3.5%, then ultrasonic vibration 23min stirs 45min at 125 DEG C, will
To modification material be placed in baking oven and dry 3h at 150 DEG C, remove extra dehydrated alcohol, by after drying material grinding,
The modified RE oxide of 300-400 mesh is obtained after sieving.
Wherein, the vulcanizing agent is one or more of sulphur, metal oxide and Thiourea.
Wherein, the modified Nano wear resistant filler is made from the following raw materials in parts by weight: 16 part, nanometer nitrogen of nanometer silicon carbide
Change 12 parts of boron, 5 parts of nano molybdenum disulfide, 0.5 part of silane coupling agent, 3.5 parts of sorbitan monooleate, methyl triethoxy
2.5 parts of silane, 1.5 parts of stearic acid, 4.5 parts of sodium silicate；
The preparation method of the modified Nano wear resistant filler includes: (1) by nanometer silicon carbide, nm-class boron nitride and nanometer curing
Molybdenum is added in solvent, and 6min is sufficiently stirred at 65 DEG C, is filtered to remove filtrate, filter cake is carried out washing 2-3 times, dry arriving is mixed
Close powder；
(2) mixed powder is made in step (1) and suitable water grinding is added, crossed 300-400 mesh, 8-13% hydrochloric acid is then added
Solution tune pH is 4-6, and repeated hydrogenation sodium oxide molybdena is adjusted to neutrality, then by sorbitan monooleate, methyltriethoxysilane,
Stearic acid, sodium silicate are added thereto, and heating stirring reacts 65min, and heating temperature is 93 DEG C, and mixing speed 550rpm is obtained
Mixed slurry；
(3) silane coupling agent is added in mixed slurry in step (2), ultrasonic disperse 33min is filtered, dry, grinding, mistake
Up to modified Nano wear resistant filler after 100-200 mesh.
Wherein, the activator is zinc oxide, stearic acid or zinc stearate；The softening agent is hydroxy silicon oil.
Wherein, it is the mixed of 1:1:1 composition that the rubber accelerator is captax, diphenylguanidine and altax by weight
Close object；The anti-aging agent is made of anti-aging agent RD, antioxidant 4020, antioxidant MB and anti-aging agent 445 by any weight ratio.
Wherein, the present invention also provides the preparation methods of above-mentioned high-low temperature resistant sizing material for rubber shoe sole, comprising the following steps:
(1) each raw material is weighed by weight；
(2) first nitrile rubber and butadiene rubber are added in mixer, rubber is added after 103 DEG C, mixing 3.5min in temperature control
Alloy and maleic anhydride grafted polyethylene are moulded, mixing 6min is continued, modified vinyl resin, modified RE oxide is then added
With modified Nano wear resistant filler, mixing 3-5min, then dumping, smash conjunction, tabletting, bottom sheet, be cooled to after room temperature and park 2.5h and obtain
To rubber compound 1；
(3) rubber compound 1 made from step (1) is put into open mill, is warming up to 135 DEG C, zinc methacrylate, adjacent benzene two is added
Vulcanizing agent, penta methylene of tetra-sulfurized pair is added after being kneaded 3.5min in formic acid dibutyl ester, pentaerythritol stearate and zinc ricinate
Base thiuram, cumyl peroxide and rubber accelerator are kneaded 6min, are eventually adding activator and softening agent, are kneaded
2.5min, then slice, cooling, obtains rubber compound 2；
(4) rubber compound 2 made from step (3) is put into the mold of vulcanizer, is vulcanized, room is cooled to after vulcanization
Temperature, demoulding obtain the high-low temperature resistant sizing material for rubber shoe sole.
Embodiment 5
The high-low temperature resistant sizing material for rubber shoe sole of the present embodiment, is prepared from the following raw materials in parts by weight: 60 parts of nitrile rubber, suitable
42 parts of buna, 9 parts of rubber and plastic alloy, 7 parts of modified vinyl resin, 5 parts of modified RE oxide, 3 parts of vulcanizing agent, tetra-sulfurized pair
Penta 6 parts of methylene thiuram, 5 parts of cumyl peroxide, 7 parts of maleic anhydride grafted polyethylene, 3.5 parts of zinc methacrylate,
9 parts of dibutyl phthalate, 18 parts of modified Nano wear resistant filler, 6 parts of zinc ricinate, is lived at 5 parts of pentaerythritol stearate
4 parts of agent, 2.5 parts of softening agent, 1.2 parts of rubber accelerator, 0.78 part of anti-aging agent.
Wherein, the rubber and plastic alloy is formed by the powder nitrile rubber that weight ratio is 3:1 with PBT high-temperature blending.
Wherein, the preparation method of the modified vinyl resin includes: that vinylite is put into dehydrated alcohol, then
The vinyltriethoxysilane for accounting for vinylite quality 0.6% is added, ultrasonic treatment 2.5h forms mixed solution, then sets
1.8h is placed in 98 DEG C of baking ovens, then the precuring 1.8h at 128 DEG C, is sent into press and solidifies 3.5h, solidification temperature 175
DEG C, solidifying pressure 2.5MPa obtains modified vinyl resin.
Wherein, the modified RE oxide preparation method includes: that rare earth oxide is taken to be dissolved in dehydrated alcohol, then plus
Entering to account for the silane coupling agent of rare-earth oxidation amount of substance 4.5%, then ultrasonic vibration 28min stirs 55min at 135 DEG C, will
To modification material be placed in baking oven and dry 3h at 150 DEG C, remove extra dehydrated alcohol, by after drying material grinding,
The modified RE oxide of 300-400 mesh is obtained after sieving.
Wherein, the vulcanizing agent is one or more of sulphur, metal oxide and Thiourea.
Wherein, the modified Nano wear resistant filler is made from the following raw materials in parts by weight: 18 part, nanometer nitrogen of nanometer silicon carbide
Change 14 parts of boron, 7 parts of nano molybdenum disulfide, 0.7 part of silane coupling agent, 4.5 parts of sorbitan monooleate, methyl triethoxy
3.5 parts of silane, 2.5 parts of stearic acid, 5.5 parts of sodium silicate；
The preparation method of the modified Nano wear resistant filler includes: (1) by nanometer silicon carbide, nm-class boron nitride and nanometer curing
Molybdenum is added in solvent, and 9min is sufficiently stirred at 75 DEG C, is filtered to remove filtrate, filter cake is carried out washing 2-3 times, dry arriving is mixed
Close powder；
(2) mixed powder is made in step (1) and suitable water grinding is added, crossed 300-400 mesh, 8-13% hydrochloric acid is then added
Solution tune pH is 4-6, and repeated hydrogenation sodium oxide molybdena is adjusted to neutrality, then by sorbitan monooleate, methyltriethoxysilane,
Stearic acid, sodium silicate are added thereto, and heating stirring reacts 75min, and heating temperature is 98 DEG C, and mixing speed 650rpm is obtained
Mixed slurry；
(3) silane coupling agent is added in mixed slurry in step (2), ultrasonic disperse 38min is filtered, dry, grinding, mistake
Up to modified Nano wear resistant filler after 100-200 mesh.
Wherein, the activator is zinc oxide, stearic acid or zinc stearate；The softening agent is hydroxy silicon oil.
Wherein, it is the mixed of 1:1:1 composition that the rubber accelerator is captax, diphenylguanidine and altax by weight
Close object；The anti-aging agent is made of anti-aging agent RD, antioxidant 4020, antioxidant MB and anti-aging agent 445 by any weight ratio.
Wherein, the present invention also provides the preparation methods of above-mentioned high-low temperature resistant sizing material for rubber shoe sole, comprising the following steps:
(1) each raw material is weighed by weight；
(2) first nitrile rubber and butadiene rubber are added in mixer, rubber is added after 108 DEG C, mixing 4.5min in temperature control
Alloy and maleic anhydride grafted polyethylene are moulded, mixing 9min is continued, modified vinyl resin, modified RE oxide is then added
With modified Nano wear resistant filler, mixing 4.5min, then dumping, smash conjunction, tabletting, bottom sheet, be cooled to after room temperature and park 2-4h and obtain
To rubber compound 1；
(3) rubber compound 1 made from step (1) is put into open mill, is warming up to 145 DEG C, zinc methacrylate, adjacent benzene two is added
Vulcanizing agent, penta methylene of tetra-sulfurized pair is added after being kneaded 4.5min in formic acid dibutyl ester, pentaerythritol stearate and zinc ricinate
Base thiuram, cumyl peroxide and rubber accelerator are kneaded 9min, are eventually adding activator and softening agent, are kneaded
3.5min, then slice, cooling, obtains rubber compound 2；
(4) rubber compound 2 made from step (3) is put into the mold of vulcanizer, is vulcanized, room is cooled to after vulcanization
Temperature, demoulding obtain the high-low temperature resistant sizing material for rubber shoe sole.
Comparative example 1
Using corrosion-and high-temp-resistant high-low temperature resistant rubber boots made from the method in Chinese Patent Application No. 201510778597.7
Bottom sizing material.
Comparative example 2
In addition to no butadiene rubber, material content and preparation step are consistent with embodiment 1.
Comparative example 3
In addition to no modified vinyl resin, material content and preparation step are consistent with embodiment 1.
Comparative example 4
In addition to no modified RE oxide, material content and preparation step are consistent with embodiment 1.
Comparative example 5
In addition to no modified Nano wear resistant filler, material content and preparation step are consistent with embodiment 1.
Comparative example 6
In addition to no maleic anhydride grafted polyethylene, other preparation steps are consistent with embodiment 1 with method.
Experimental example
Following performance test, tool are carried out to high-low temperature resistant sizing material for rubber shoe sole embodiment 1-5 obtained above, comparative example 1-6
The results are shown in Table 1 for body.
Table 1
As shown in Table 1, the wearability, mechanical property of high-low temperature resistant sizing material for rubber shoe sole of the present invention, high and low temperature resistance and resistance to
Ageing properties are superior to comparative example 1-6, and according to high-low temperature resistant rubber soles made from 3 preparation process of embodiment and material content
With sizing material mechanical property, high and low temperature resistance and ageing-resistant performance be better than other embodiments, and by comparative example 2-6 it is found that
Comparative example 2 disappears due to eliminating butadiene rubber, such nitrile rubber and organic siliconresin coordinated, causes high-low temperature resistant rubber
Wearability, mechanical property, high and low temperature resistance and the ageing-resistant performance decline of rubber sole sizing material；And comparative example 3 is due to saving
Modified vinyl resin, the combination dynamics decline in sizing material between each ingredient, causes high-low temperature resistant sizing material for rubber shoe sole
Wearability, mechanical property, high and low temperature resistance and ageing-resistant performance decline；And comparative example 4 is due to saving modified RE oxide
It goes, causes wearability, mechanical property, high and low temperature resistance and the ageing-resistant performance decline of high-low temperature resistant sizing material for rubber shoe sole；
Comparative example 5 is due to eliminating modified Nano nanofiller, so that the wear-resisting property of high-low temperature resistant sizing material for rubber shoe sole, high temperature resistant
Performance decline；So that and comparative example 6 eliminates expanding material maleic anhydride grafted polyethylene, nitrile rubber and butadiene rubber compatibility
Be deteriorated, blending optimization function can not be played, cause the mechanical property of high-low temperature resistant sizing material for rubber shoe sole, high and low temperature resistance and
Ageing-resistant performance decline.
In conclusion creativeness of the invention is concentrated mainly on the following aspects:
(1) present invention can by using high-low temperature resistant sizing material for rubber shoe sole made from nitrile rubber and butadiene rubber blending method
The wearability of nitrile rubber and the corrosion resistance and weatherability of heat resistance and butadiene rubber are had both, the two synergistic effect changes jointly
The performances such as wearability, corrosion resistance, weatherability into high-low temperature resistant sizing material for rubber shoe sole, while horse being added in the blending process
Maleic anhydride grafted polyethylene solves nitrile rubber and butadiene rubber inconsistent problem and rubber and plastic alloy and rubber compatibility
Difference problem so that nitrile rubber, butadiene rubber, rubber and plastic alloy triplicity it is even closer, to improve the power of sizing material
Learn performance.
(2) the penta methylene thiuram of tetra-sulfurized pair and cumyl peroxide that the present invention is added can be realized with vulcanizing agent
Collaboration sulfurization to nitrile rubber and butadiene rubber, improves the curingprocess rate and vulcanization effect of Blend rubber；Add simultaneously
Enter activator and zinc ricinate cooperates, there is activation to the crosslinking of Blend rubber, accelerate the speed of vulcanization, improve
The mechanical property of sizing material；In addition the present invention has preferable compatibility by addition modified Nano reinforced filling and sizing material, can
It is dispersed in sizing material, to improve the wearability of sizing material, corrosion resistance, mechanical property and weatherability；And the modification being added
Vinylite has stronger activity, may be homogenously dispersed in sizing material by modification, and have using its own
Adhesive property, so that the binding force of each component in sizing material is improved, to enhance the wearability of sizing material, mechanical property.
(3) modified RE oxide of the invention can form chemical bond between the organic molecule in paste system, improve
The mechanical property and weatherability of sizing material；And dibutyl phthalate and pentaerythritol stearate, improve the toughness of sizing material
Its thermal stability is improved simultaneously.
(4) the characteristics of present invention is according to component, optimizes preparation process, defines the sequence of charging during the preparation process simultaneously
Different smelting temperature and conditions of vulcanization are selected, wearability, corrosion resistance, mechanical property and the weatherability of sizing material are improved.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (8)
1. a kind of high-low temperature resistant high-low temperature resistant sizing material for rubber shoe sole, which is characterized in that be prepared from the following raw materials in parts by weight:
55 parts of nitrile rubber, 40 parts of butadiene rubber, 7.5 parts of rubber and plastic alloy, 6 parts of modified vinyl resin, modified RE oxide 4.5
Part, 2.5 parts of vulcanizing agent, 5 parts of penta methylene thiuram of tetra-sulfurized pair, 4 parts of cumyl peroxide, maleic anhydride grafted polyethylene
6 parts, 3 parts of zinc methacrylate, 7.5 parts of dibutyl phthalate, 4.5 parts of pentaerythritol stearate, modified Nano it is wear-resisting
15 parts of filler, 5 parts of zinc ricinate, 3.5 parts of activator, 2 parts of softening agent, 1 part of rubber accelerator, 0.6 part of anti-aging agent；
The modified RE oxide preparation method includes: that rare earth oxide is taken to be dissolved in dehydrated alcohol, is then added and accounts for rare earth
Then the silane coupling agent of oxide mass 3-5%, ultrasonic vibration 20-30min stir 40-60min at 120-140 DEG C, will
Obtained modification material, which is placed in baking oven, dries 3h at 150 DEG C, removes extra dehydrated alcohol, the material after drying is ground
The modified RE oxide of 300-400 mesh is obtained after mill, sieving.
2. high-low temperature resistant sizing material for rubber shoe sole according to claim 1, which is characterized in that the rubber and plastic alloy is by weight
It is formed than the powder nitrile rubber for 3:1 with PBT high-temperature blending.
3. high-low temperature resistant sizing material for rubber shoe sole according to claim 1, which is characterized in that the modified vinyl resin
Preparation method include: that vinylite is put into dehydrated alcohol, then be added account for vinylite quality 0.3-0.7%'s
Vinyltriethoxysilane, ultrasonic treatment 1-3h form mixed solution, are subsequently placed in 90-100 DEG C of baking oven and place 1-2h, so
The precuring 1-2h at 120-130 DEG C afterwards is sent into press and solidifies 2-4h, and solidification temperature is 160-180 DEG C, solidifying pressure 1-
3MPa obtains modified vinyl resin.
4. high-low temperature resistant sizing material for rubber shoe sole according to claim 1, which is characterized in that the vulcanizing agent be sulphur,
One or more of metal oxide and Thiourea.
5. high-low temperature resistant sizing material for rubber shoe sole according to claim 1, which is characterized in that the modified Nano is wear-resisting to be filled out
Material is made from the following raw materials in parts by weight: 15-20 parts of nanometer silicon carbide, 10-15 parts of nm-class boron nitride, nano molybdenum disulfide 4-8
Part, 0.4-0.8 parts of silane coupling agent, 3-5 parts of sorbitan monooleate, 2-4 parts of methyltriethoxysilane, stearic acid 1-
3 parts, 4-6 parts of sodium silicate；
The preparation method of the modified Nano wear resistant filler includes: (1) by nanometer silicon carbide, nm-class boron nitride and nanometer curing
Molybdenum is added in solvent, and 5-10min is sufficiently stirred at 60-80 DEG C, is filtered to remove filtrate, and filter cake is carried out washing 2-3 times, dry
Arrive mixed powder；
(2) mixed powder is made in step (1) and suitable water grinding is added, crossed 300-400 mesh, 8-13% hydrochloric acid is then added
Solution tune pH is 4-6, and repeated hydrogenation sodium oxide molybdena is adjusted to neutrality, then by sorbitan monooleate, methyltriethoxysilane,
Stearic acid, sodium silicate are added thereto, and heating stirring reacts 60-80min, and heating temperature is 90-100 DEG C, mixing speed 500-
700rpm obtains mixed slurry；
(3) silane coupling agent is added in mixed slurry in step (2), ultrasonic disperse 30-40min is filtered, dry, grinding, mistake
Up to modified Nano wear resistant filler after 100-200 mesh.
6. high-low temperature resistant sizing material for rubber shoe sole according to claim 1, which is characterized in that the activator is oxygen
Change zinc, stearic acid or zinc stearate；The softening agent is hydroxy silicon oil.
7. high-low temperature resistant sizing material for rubber shoe sole according to claim 1, which is characterized in that the rubber accelerator is to promote
It is by weight the mixture of 1:1:1 composition into agent M, diphenylguanidine and altax；The anti-aging agent is by anti-aging agent RD, anti-old
Agent 4020, antioxidant MB and anti-aging agent 445 are formed by any weight ratio.
8. the preparation method of high-low temperature resistant sizing material for rubber shoe sole according to claim 1-7, which is characterized in that
The following steps are included:
(1) each raw material is weighed by weight；
(2) first nitrile rubber and butadiene rubber are added in mixer, temperature control adds after 100-110 DEG C, mixing 3-5min
Enter rubber and plastic alloy and maleic anhydride grafted polyethylene, continue mixing 5-10min, then addition modified vinyl resin, modification are dilute
Native oxide and modified Nano wear resistant filler, mixing 3-5min, then dumping, smash conjunction, tabletting, bottom sheet, be cooled to room temperature after stop
It puts 2-4h and obtains rubber compound 1；
(3) rubber compound 1 made from step (1) is put into open mill, is warming up to 130-150 DEG C, zinc methacrylate, neighbour is added
Vulcanizing agent, tetra-sulfurized pair penta is added after being kneaded 3-5min in dibatyl phithalate, pentaerythritol stearate and zinc ricinate
Methylene thiuram, cumyl peroxide and rubber accelerator are kneaded 5-10min, are eventually adding activator and softening agent, mix
2-4min is refined, then slice, it is cooling, obtain rubber compound 2；
(4) rubber compound 2 made from step (3) is put into the mold of vulcanizer, is vulcanized, room is cooled to after vulcanization
Temperature, demoulding obtain the high-low temperature resistant sizing material for rubber shoe sole.
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| CN112778587A (en) * | 2020-12-31 | 2021-05-11 | 莆田鸿途鞋塑有限公司 | Preparation method of oil-resistant anti-slip sole |
| CN113845716A (en) * | 2021-11-15 | 2021-12-28 | 安踏（中国）有限公司 | Modified EVA (ethylene-vinyl acetate copolymer), preparation method thereof and wide-temperature-range high-performance EVA composite foam material |
| CN114907607A (en) * | 2022-04-28 | 2022-08-16 | 茂泰(福建)鞋材有限公司 | Light cold-resistant EVA sole and preparation method thereof |
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| CN101665594A (en) * | 2008-09-05 | 2010-03-10 | 江苏省派登鞋业有限公司 | Sole material for high temperature resistant labor protection shoes |
| CN101735495A (en) * | 2009-12-21 | 2010-06-16 | 泰亚鞋业股份有限公司 | Formula of sole of high oil resistant rubber sneakers and manufacturing method of soles |
| CN102898699A (en) * | 2012-09-29 | 2013-01-30 | 广东智达行新材料有限公司 | Conducting rubber for sole and preparation method thereof |
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Application publication date: 20181221 |