CN110066427A - Graphene reclaimed rubber foamed shoe-pad and preparation method thereof - Google Patents
Graphene reclaimed rubber foamed shoe-pad and preparation method thereof Download PDFInfo
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- CN110066427A CN110066427A CN201910435419.2A CN201910435419A CN110066427A CN 110066427 A CN110066427 A CN 110066427A CN 201910435419 A CN201910435419 A CN 201910435419A CN 110066427 A CN110066427 A CN 110066427A
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B17/00—Insoles for insertion, e.g. footbeds or inlays, for attachment to the shoe after the upper has been joined
- A43B17/14—Insoles for insertion, e.g. footbeds or inlays, for attachment to the shoe after the upper has been joined made of sponge, rubber, or plastic materials
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
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- 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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- C08J2307/00—Characterised by the use of natural rubber
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- C08J2317/00—Characterised by the use of reclaimed rubber
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- C08J2407/00—Characterised by the use of natural rubber
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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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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/16—Ethene-propene or ethene-propene-diene copolymers
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- C08J2439/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
- C08J2439/02—Homopolymers or copolymers of vinylamine
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- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
Abstract
The present invention relates to graphene reclaimed rubber foamed shoe-pads, are grouped as by following group: reclaimed rubber, natural rubber, butadiene-styrene rubber, ethylene propylene diene rubber, modified porous Graphene antibiosis master batch, modified kaolin, poly N-ethylene yl acetamide, silicone oil, zinc stearate, stearic acid, paraffin, anti-aging agent, crosslinking agent, foaming agent.The present invention is up to standard in conjunction with existing reclaimed rubber and graphene product acquisition physical property and can enhance the shoe pad product of antibacterial, ventilating performance, the nanoaperture structure of porous three-dimensional network structure can be formed inside insole, antibacterial plant extract is preferably carried on the modified porous graphene of porous network, with sustained-release antibacterial performance, and then has the effect of long acting antibiotic；The gas permeability of shoe pad product is further improved simultaneously, and by the mechanical property of carbon black enhancing shoe pad product.
Description
Technical field
The present invention relates to shoe pad product technical fields, more particularly to a kind of graphene reclaimed rubber foamed shoe-pad and its system
Preparation Method.
Background technique
In general, insole is inserted into the inside of shoes and the component that contacts with foot, the wearing feeling to shoes is not only increased,
It can also absorb and mitigate the impact applied to foot.The enhancing realized with the improvement of people ' s living standards with health environment-friendly, people
Requirement to insole also gradually expands to anti-mould and anti-moth, deodorization and sterilization, health care from soft comfortable, the ventilative, windproof and rain proof of moisture absorption etc.
It is nontoxic etc..Especially after summer and movement, since sweat secretion amount increases severely, microorganism high speed is bred, and largely decomposes sweat
In organic matter and generate stench, if things go on like this even result in a series of foot's diseases such as foot odour, the ringworm of the foot, tinea pedis, directly affect
The physical and mental health of people.
Summary of the invention
It is an object of that present invention to provide a kind of graphene reclaimed rubber foamed shoe-pad and preparation method thereof, in conjunction with it is existing again
It is up to standard and can enhance the shoe pad product of antibacterial, ventilating performance that raw rubber and graphene product obtain physical property.
The technical solution that the present invention uses is:
Graphene reclaimed rubber foamed shoe-pad, is grouped as by the group of following parts by weight: 15-25 parts of reclaimed rubber；Naturally
25-30 parts of rubber；10-15 parts of butadiene-styrene rubber；8-12 parts of ethylene propylene diene rubber；25-30 parts of modified porous Graphene antibiosis master batch；
1.0-1.5 parts of modified kaolin；1.5-1.8 parts of poly N-ethylene yl acetamide；0.8-1.0 parts of silicone oil；Zinc stearate 1.0-1.5
Part；0.5-0.8 parts of stearic acid；1.0-1.5 parts of paraffin；0.5-0.8 parts of anti-aging agent；0.8-1.0 parts of crosslinking agent；Foaming agent 1.5-
1.8 part.
Preferably, the modified porous Graphene antibiosis master batch is grouped as by the group of following parts by weight: EVA resin powder
20-25 parts；1.0-1.5 parts of surfactant；1.0-1.5 parts of dispersing agent；3-5 parts of antibacterial plant extract；3-6 parts of carbon black；Change
10-15 parts of porous graphene of property.
Preferably, the surfactant be one of polyvinyl alcohol, sodium lignin sulfonate, dodecyl sodium sulfate or
A variety of compositions, the dispersing agent are one of calgon, methanonaphthalene sodium sulfonate or polyethylene pyrrole network alkanone or a variety of
Composition.
Preferably, the antibacterial plant extract is chamomile extracting solution or extract solution from aloe.
Preferably, the foaming agent is azodicarbonamide, and the crosslinking agent is insoluble sulfur.
Preferably, the anti-aging agent is at least one of antioxidant NBC, anti-aging agent RD, antioxidant 4010NA.
Preferably, the method for modifying of the modified kaolin are as follows: first go the weight such as the kaolin addition of 10-15 parts by weight
In ionized water, 30min is stood after being uniformly dispersed, the silane of the polyacrylamide and 0.5-1 parts by weight that add 2-3 parts by weight is even
Join agent, utilized Surface Treatment with Plasma 15-18 seconds after being sufficiently mixed, microwave reactor is recycled to handle 3min-3.5min, gained
Mixture is sent into freeze drier, well-dried rear grind into powder.
The present invention also provides a kind of preparation methods of graphene reclaimed rubber foamed shoe-pad, specifically comprise the following steps:
One, modified porous Graphene antibiosis master batch is prepared；
Two, it is kneaded, is granulated
Step 2.1: the reclaimed rubber, natural rubber, butadiene-styrene rubber, ternary second of the parts by weight are put into mixer
Third rubber and anti-aging agent carry out mixing 10min~15min, and temperature is controlled at 135 DEG C~140 DEG C, obtain rubber internal mixing material；
Step 2.2: pouring out the good rubber internal mixing material of mixing, then upper open mill thins 2 times, slice；
Step 2.3: the rubber internal mixing material after thinning being placed into mixer, the modification for being subsequently added into the parts by weight is more
Hole Graphene antibiosis master batch, poly N-ethylene yl acetamide, silicone oil, modified kaolin, zinc stearate, stearic acid, flow promortor
Mixing 15min~20min is carried out, temperature is controlled at 110 DEG C~115 DEG C；
Step 2.4: be added in mixer again the parts by weight foaming agent and crosslinking agent then mixing 5min~
8min obtains rubber compound；
Step 2.5: the mixing glue poured out after mixing being thinned 2 times on a mill, slice obtains mill glue；
Step 2.6: extruder on mill glue being carried out extruding pelletization, obtains graphene reclaimed rubber master batch；
Three, enter mold forming
Step 3: accurately weighing graphene reclaimed rubber master batch according to multiple proportions, be put into mold, heating pressurization, sulfidization molding.
Wherein: the preparation of the modified porous Graphene antibiosis master batch specifically comprises the following steps:
Step 1.1: 3-6 parts of carbon black and 0.5-0.8 parts of dispersing agent are added in deionized water, stirring and dissolving is uniform,
Ultrasonic disperse 1.5h~2.0h, obtains carbon black dispersion liquid；
Step 1.2: sequentially added in the carbon black dispersion liquid of step 1.1 1.0-1.5 parts surfactant and 10-15 parts
Modified porous graphene, re-ultrasonic dispersion 10min~20min after stirring obtains graphene-carbon black dispersion aqueous solution；
Step 1.3: 3-5 parts of antibacterial plant extract is added into graphene-carbon black dispersion aqueous solution of step 1.2,
60 DEG C~90 DEG C are warming up to, continues to stir 20min~25min, then ultrasonic disperse 3h~4h, obtains graphene-carbon black-extract
Suspension；
Step 1.4: graphene-carbon black-extract suspension of step 1.3 being set through freezing, vacuum drying treatment, is obtained
Obtain the modified porous Graphene antibiosis powder that area load has antibacterial plant extract and carbon black；
Step 1.5: modified porous Graphene antibiosis powder, 20-25 parts of the EVA of step 1.4 being added in high-speed kneading machine
Resin-oatmeal, 0.5-0.8 parts of dispersing agent is mediated to coated state, and the mixture after kneading is put into double screw extruder
Extruding pelletization obtains modified porous Graphene antibiosis master batch.
Beneficial effects of the present invention:
1, carbon black is first interspersed between porous graphene lamella by the present invention, reduces the model moral of porous graphene piece interlayer
Hua Li reduces reuniting certainly for porous graphene lamella, and carbon black is uniformly distributed in graphene under nm regime, so that two kinds of grains
Son intersects isolation, avoid single filler be added it is internal reunite, improve the dispersion of graphene and carbon black in rubber matrix
Property and interface compatibility, for inside insole formed porous three-dimensional network structure nanoaperture structure create conditions, make simultaneously
Obtaining antibacterial plant extract can preferably be carried on the modified porous graphene of porous network, and enhance insole by carbon black
The mechanical property of product；
2, the nanoporous structure of the modified porous Graphene antibiosis master batch of the present invention has prosperity and connection, antibacterial plant
Extract has excellent absorption and load effect, and therefore, antibacterial plant extract can be extensive and be distributed evenly in modified more
On the pore interior of hole graphene and surface layer, and modified porous graphene specific surface area with higher and surface have it is abundant
Oxygen-containing functional group, can in antibacterial plant extract carboxyl or phenolic hydroxyl group forms chemical hydrogen bond or coordination is strong forms complex compound,
The rate of release of antimicrobial component is adjusted with limitation, and is not related to chemically reacting, so that the antibacterial activity of antibacterial plant extract
Not will receive destruction, good anti-bacterial effect had both met the requirement of effective antibacterial, also meet the requirement of antibacterial duration length, so that
Antibacterial plant extract has sustained-release antibacterial performance, and then has the effect of long acting antibiotic；Meanwhile the prosperity and connection having
Nanoporous structure, further improve the gas permeability of shoe pad product；In addition, the addition of sulfated chitosan can also assign
The good anti-microbial property of insole.
3, the present invention is using with amphiphilic spiral shape non-ionic dispersing agent poly N-ethylene yl acetamide and silicone
The ingredients such as oil and modified kaolin, are dispersed in modified porous Graphene antibiosis master batch in each rubber mass, while assigning this
The excellent thermal stability of invention rubber pange insole, wearability, tensile strength improve permanent compression set performance.
Specific embodiment
Embodiment 1
The present embodiment provides a kind of graphene reclaimed rubber foamed shoe-pads, are grouped as by the group of following parts by weight: regeneration
15 parts of rubber；25 parts of natural rubber；12 parts of butadiene-styrene rubber；12 parts of ethylene propylene diene rubber；Modified porous Graphene antibiosis master batch 25
Part；1.0 parts of modified kaolin；1.8 parts of poly N-ethylene yl acetamide；1.0 parts of silicone oil；1.2 parts of zinc stearate；Stearic acid 0.8
Part；1.2 parts of paraffin；0.5 part of antioxidant NBC；1.0 parts of insoluble sulfur crosslinking agent；1.5 parts of azodicarbonamide.
Wherein: the modified porous Graphene antibiosis master batch is grouped as by the group of following parts by weight: EVA resin powder 20
Part；1.2 parts of polyvinyl alcohol surfactant；1.5 parts of calgon dispersing agent；3 parts of chamomile extracting solution；5 parts of carbon black；It is modified
10 parts of porous graphene, the modified porous graphene is to pass through gas phase to the porous graphene using dimethyl silicone polymer
Modified porous graphene made of deposition is modified.Take 25 parts of modified porous Graphene antibiosis master batches as the present embodiment graphene again
Raw rubber foamed shoe-pad prepares raw material.
Embodiment 2
The present embodiment provides a kind of graphene reclaimed rubber foamed shoe-pads, are grouped as by the group of following parts by weight: regeneration
25 parts of rubber；30 parts of natural rubber；10 parts of butadiene-styrene rubber；8 parts of ethylene propylene diene rubber；Modified porous Graphene antibiosis master batch 30
Part；1.2 parts of modified kaolin；1.5 parts of poly N-ethylene yl acetamide；1.0 parts of silicone oil；1.5 parts of zinc stearate；Stearic acid 0.8
Part；1.0 parts of paraffin；0.3 part of antioxidant NBC；0.5 part of antioxidant 4010NA；1.0 parts of insoluble sulfur crosslinking agent；Azo diformazan
1.8 parts of amide.
Wherein: the modified porous Graphene antibiosis master batch is grouped as by the group of following parts by weight: EVA resin powder 25
Part；1.5 parts of lignin sulfonic acid natrium surfactant；1.5 parts of dispersing agent of polyethylene pyrrole network alkanone；5 parts of extract solution from aloe；Carbon black 6
Part；15 parts of modified porous graphene, the modified porous graphene are using dimethyl silicone polymer to the porous graphene
Modified porous graphene made of being modified by vapor deposition.Take 30 parts of modified porous Graphene antibiosis master batches as the present embodiment
Graphene reclaimed rubber foamed shoe-pad prepares raw material.
Embodiment 3
The present embodiment provides a kind of graphene reclaimed rubber foamed shoe-pads, are grouped as by the group of following parts by weight: regeneration
20 parts of rubber；25 parts of natural rubber；15 parts of butadiene-styrene rubber；10 parts of ethylene propylene diene rubber；Modified porous Graphene antibiosis master batch 30
Part；1.5 parts of modified kaolin；1.5 parts of poly N-ethylene yl acetamide；0.8 part of silicone oil；1.0 parts of zinc stearate；Stearic acid 0.5
Part；1.5 parts of paraffin；0.6 part of anti-aging agent RD；0.8 part of insoluble sulfur crosslinking agent；1.6 parts of azodicarbonamide.
Wherein: the modified porous Graphene antibiosis master batch is grouped as by the group of following parts by weight: EVA resin powder 20
Part；1.0 parts of lignin sulfonic acid natrium surfactant；1.0 parts of methanonaphthalene sodium sulfonate dispersing agent；4 parts of chamomile extracting solution；Carbon black
6 parts；15 parts of modified porous graphene, the modified porous graphene are using dimethyl silicone polymer to the porous graphene
Modified porous graphene made of being modified by vapor deposition.Take 30 parts of modified porous Graphene antibiosis master batches as the present embodiment
Graphene reclaimed rubber foamed shoe-pad prepares raw material.
Embodiment 4
The present embodiment provides a kind of graphene reclaimed rubber foamed shoe-pads, are grouped as by the group of following parts by weight: regeneration
25 parts of rubber；25 parts of natural rubber；10 parts of butadiene-styrene rubber；10 parts of ethylene propylene diene rubber；Modified porous Graphene antibiosis master batch 28
Part；1.2 parts of modified kaolin；1.5 parts of poly N-ethylene yl acetamide；1.0 parts of silicone oil；1.2 parts of zinc stearate；Stearic acid 0.6
Part；1.2 parts of paraffin；0.6 part of antioxidant 4010NA；1.0 parts of insoluble sulfur crosslinking agent；1.8 parts of azodicarbonamide.
Wherein: the modified porous Graphene antibiosis master batch is grouped as by the group of following parts by weight: EVA resin powder 22
Part；1.2 parts of dodecyl sodium sulfate surfactant；1.2 parts of calgon dispersing agent；5 parts of extract solution from aloe；3 parts of carbon black；
12 parts of modified porous graphene, the modified porous graphene are to be passed through using dimethyl silicone polymer to the porous graphene
Modified porous graphene made of vapor deposition is modified.Take 28 parts of modified porous Graphene antibiosis master batches as the present embodiment graphite
Alkene reclaimed rubber foamed shoe-pad prepares raw material.
The method of modifying of the modified kaolin of above-described embodiment 1-4 are as follows: first the kaolin of 10-15 parts by weight is added
Etc. in weight deionized water, stand 30min after being uniformly dispersed, add the polyacrylamide and 0.5-1 parts by weight of 2-3 parts by weight
Silane coupling agent, after being sufficiently mixed utilize Surface Treatment with Plasma 15-18 second, recycle microwave reactor processing 3min-
3.5min, gained mixture are sent into freeze drier, well-dried rear grind into powder.
The preparation method of the graphene reclaimed rubber foamed shoe-pad of above-described embodiment 1-4, is all made of following method, specific to wrap
Include following steps:
One, modified porous Graphene antibiosis master batch is prepared
Step 1.1: the carbon black and 0.5-0.8 parts of dispersing agent of the parts by weight being added in deionized water, stirs molten
Uniformly, ultrasonic disperse 1.5h~2.0h obtains carbon black dispersion liquid to solution；
Step 1.2: sequentially adding the surfactant of the parts by weight in the carbon black dispersion liquid of step 1.1 and change
Property porous graphene, re-ultrasonic dispersion 10min~20min after stirring obtain graphene-carbon black dispersion aqueous solution；
Step 1.3: the antibacterial plant of the parts by weight being added into graphene-carbon black dispersion aqueous solution of step 1.2
Extract is warming up to 60 DEG C~90 DEG C, continues to stir 20min~25min, then ultrasonic disperse 3h~4h, obtains graphene-charcoal
Black-extract suspension；
Step 1.4: graphene-carbon black-extract suspension of step 1.3 being set through freezing, vacuum drying treatment, is obtained
Obtain the modified porous Graphene antibiosis powder that area load has antibacterial plant extract and carbon black；
Step 1.5: the modified porous Graphene antibiosis powder of addition step 1.4, the parts by weight in high-speed kneading machine
EVA resin powder, 0.5-0.8 parts of dispersing agent mediates to coated state, and the mixture after kneading put into twin-screw and is squeezed
Extruding pelletization in machine out obtains modified porous Graphene antibiosis master batch.
Two, it is kneaded, is granulated
Step 2.1: the reclaimed rubber, natural rubber, butadiene-styrene rubber, ternary second of the parts by weight are put into mixer
Third rubber and anti-aging agent carry out mixing 10min~15min, and temperature is controlled at 135 DEG C~140 DEG C, obtain rubber internal mixing material；
Step 2.2: pouring out the good rubber internal mixing material of mixing, then upper open mill thins 2 times, slice；
Step 2.3: the rubber internal mixing material after thinning being placed into mixer, the modification for being subsequently added into the parts by weight is more
Hole Graphene antibiosis master batch, poly N-ethylene yl acetamide, silicone oil, modified kaolin, zinc stearate, stearic acid, flow promortor
Mixing 15min~20min is carried out, temperature is controlled at 110 DEG C~115 DEG C；
Step 2.4: be added in mixer again the parts by weight foaming agent and crosslinking agent then mixing 5min~
8min obtains rubber compound；
Step 2.5: the mixing glue poured out after mixing being thinned 2 times on a mill, slice obtains mill glue；
Step 2.6: extruder on mill glue being carried out extruding pelletization, obtains graphene reclaimed rubber master batch；
Three, enter mold forming
Step 3: accurately weighing graphene reclaimed rubber master batch according to multiple proportions, be put into mold, heating pressurization, sulfidization molding.
By sample made from embodiment 1-4 and physical property measurement is carried out, test result is shown in Table 1.
Table 1: sample physical property measurement result is made in embodiment 1-4
| Physical property | Tensile strength MPa | Rebound value % | Air permenbility | Escherichia coli % | Golden yellow staphylococcus % |
| Implement 1 | 21.6 | 48 | 563 | 99.2 | 98.8 |
| Implement 2 | 23.5 | 52 | 592 | 99.8 | 99.8 |
| Implement 3 | 22.3 | 45 | 585 | 99.1 | 99.5 |
| Implement 4 | 19.7 | 47 | 581 | 99.4 | 99.5 |
| Method | GB/T528 | GB/T 10652 | GB/T23763 | GB/T23763 |
Wherein: for permeability test using the Air permenbility of air permeability tester test each sample, test gas is nitrogen, test
Time is 24 hours, and test pressure is 0.2MPa, and Air permenbility shows that more greatly gas permeability is better.
The basic principles and main features and advantages of the present invention of the invention have been shown and described above, the industry
For technical staff it should be appreciated that the present invention is not limited to the above embodiments, what is described in the above embodiment and the description is only say
Bright the principle of the present invention, under the premise of not departing from the inventive spirit of the present invention and range, the present invention also has various change and changes
Into these changes and improvements all fall within the protetion scope of the claimed invention, and the claimed scope of the invention is by appended right
Claim and its equivalent thereof.
Claims (10)
1. graphene reclaimed rubber foamed shoe-pad, which is characterized in that the foamed shoe-pad is grouped as by the group of following parts by weight: again
15-25 parts of raw rubber；25-30 parts of natural rubber；10-15 parts of butadiene-styrene rubber；8-12 parts of ethylene propylene diene rubber；Modified porous graphite
25-30 parts of alkene antibacterial matrices；1.0-1.5 parts of modified kaolin；1.5-1.8 parts of poly N-ethylene yl acetamide；Silicone oil 0.8-1.0
Part；1.0-1.5 parts of zinc stearate；0.5-0.8 parts of stearic acid；1.0-1.5 parts of paraffin；0.5-0.8 parts of anti-aging agent；Crosslinking agent 0.8-
1.0 part；1.5-1.8 parts of foaming agent.
2. graphene reclaimed rubber foamed shoe-pad according to claim 1, which is characterized in that the modified porous graphene
Antibacterial matrices are grouped as by the group of following parts by weight: 20-25 parts of EVA resin powder；1.0-1.5 parts of surfactant；Dispersing agent
1.0-1.5 part；3-5 parts of antibacterial plant extract；3-6 parts of carbon black；Modified porous graphene 10-15 parts.
3. graphene reclaimed rubber foamed shoe-pad according to claim 2, which is characterized in that the surfactant is poly-
One of vinyl alcohol, sodium lignin sulfonate, dodecyl sodium sulfate or a variety of compositions, the dispersing agent be calgon,
One of methanonaphthalene sodium sulfonate or polyethylene pyrrole network alkanone or a variety of compositions.
4. graphene reclaimed rubber foamed shoe-pad according to claim 2, which is characterized in that the antibacterial plant extract
For chamomile extracting solution or extract solution from aloe.
5. graphene reclaimed rubber foamed shoe-pad according to claim 1, which is characterized in that the foaming agent is azo two
Formamide.
6. graphene reclaimed rubber foamed shoe-pad according to claim 1, which is characterized in that the crosslinking agent is insoluble
Sulphur.
7. graphene reclaimed rubber foamed shoe-pad according to claim 1, which is characterized in that the anti-aging agent is anti-aging agent
At least one of NBC, anti-aging agent RD, antioxidant 4010NA.
8. graphene reclaimed rubber foamed shoe-pad according to claim 1, which is characterized in that the modified kaolin changes
Property method are as follows: first the kaolin of 10-15 parts by weight is added etc. in weight deionized water, stands 30min after being uniformly dispersed, then plus
Enter the polyacrylamide of 2-3 parts by weight and the silane coupling agent of 0.5-1 parts by weight, Surface Treatment with Plasma is utilized after being sufficiently mixed
15-18 seconds, microwave reactor is recycled to handle 3min-3.5min, gained mixture is sent into freeze drier, after well-dried
Grind into powder.
9. a kind of preparation method of such as described in any item graphene reclaimed rubber foamed shoe-pads of claim 1-8, feature exist
In specifically comprising the following steps:
One, modified porous Graphene antibiosis master batch is prepared；
Two, it is kneaded, is granulated
Step 2.1: reclaimed rubber, natural rubber, butadiene-styrene rubber, the ethylene-propylene-diene monomer of the parts by weight are put into mixer
Glue and anti-aging agent carry out mixing 10min~15min, and temperature is controlled at 135 DEG C~140 DEG C, obtain rubber internal mixing material；
Step 2.2: pouring out the good rubber internal mixing material of mixing, then upper open mill thins 2 times, slice；
Step 2.3: the rubber internal mixing material after thinning being placed into mixer, is subsequently added into the modified porous stone of the parts by weight
Black alkene antibacterial matrices, poly N-ethylene yl acetamide, silicone oil, modified kaolin, zinc stearate, stearic acid, flow promortor carry out
It is kneaded 15min~20min, temperature is controlled at 110 DEG C~115 DEG C；
Step 2.4: the foaming agent and crosslinking agent then mixing 5min~8min of the parts by weight is added in mixer again, obtains
Rubber compound；
Step 2.5: the mixing glue poured out after mixing being thinned 2 times on a mill, slice obtains mill glue；
Step 2.6: extruder on mill glue being carried out extruding pelletization, obtains graphene reclaimed rubber master batch；
Three, enter mold forming
Step 3: accurately weighing graphene reclaimed rubber master batch according to multiple proportions, be put into mold, heating pressurization, sulfidization molding.
10. the preparation method of graphene reclaimed rubber foamed shoe-pad according to claim 9, which is characterized in that described to change
The preparation of property porous graphene antibacterial matrices specifically comprises the following steps:
Step 1.1: 3-6 parts of carbon black and 0.5-0.8 parts of dispersing agent being added in deionized water, stirring and dissolving is uniform, ultrasound
Disperse 1.5h~2.0h, obtains carbon black dispersion liquid；
Step 1.2: the surfactant that 1.0-1.5 parts are sequentially added in the carbon black dispersion liquid of step 1.1 and 10-15 parts change
Property porous graphene, re-ultrasonic dispersion 10min~20min after stirring obtain graphene-carbon black dispersion aqueous solution；
Step 1.3: 3-5 parts of antibacterial plant extract, heating being added into graphene-carbon black dispersion aqueous solution of step 1.2
To 60 DEG C~90 DEG C, continue to stir 20min~25min, then ultrasonic disperse 3h~4h, obtains graphene-carbon black-extract and suspend
Liquid；
Step 1.4: graphene-carbon black-extract suspension of step 1.3 being set through freezing, vacuum drying treatment, table is obtained
Face loads the modified porous Graphene antibiosis powder for having antibacterial plant extract and carbon black；
Step 1.5: the modified porous Graphene antibiosis powder of addition step 1.4,20-25 parts of EVA resin in high-speed kneading machine
Powder, 0.5-0.8 parts of dispersing agent is mediated to coated state, and the mixture after kneading is put into double screw extruder and is squeezed out
It is granulated, obtains modified porous Graphene antibiosis master batch.
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