CN107674252A - The preparation method and product of graphene oxide and the manufacture method of tire tread - Google Patents
The preparation method and product of graphene oxide and the manufacture method of tire tread Download PDFInfo
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- CN107674252A CN107674252A CN201710780414.4A CN201710780414A CN107674252A CN 107674252 A CN107674252 A CN 107674252A CN 201710780414 A CN201710780414 A CN 201710780414A CN 107674252 A CN107674252 A CN 107674252A
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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
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
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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
- C08J2307/00—Characterised by the use of natural rubber
-
- 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
- C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
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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
- C08J2421/00—Characterised by the use of unspecified rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Abstract
The invention provides a kind of preparation method of graphene oxide, thus obtained graphene oxide, and a kind of manufacture method of tire tread.The preparation method of graphene oxide includes：Graphite powder, sodium nitrate are well mixed under condition of ice bath with the concentrated sulfuric acid, and add potassium hyperchlorate, potassium permanganate, after stirring, removes ice bath, electromagnetism stirs 20 ~ 24 h；After the min of heating stirring 10 ~ 30, hydrogen peroxide is added；Post processing, obtains graphene oxide.The manufacture method of the tire tread includes：Graphene/carbon nano-tube rubber master batch is prepared using graphene oxide, CNT, rubber master batches and auxiliary agent；Graphene/carbon nano-tube rubber master batch, natural rubber, butadiene rubber, vulcanized rubber powder, ZnO, sulphur, vulcanization accelerator are mixed, mixed refining process, obtain tread mix；By tread mix sulfidization molding, the tire tread is made；It has preferable electric conductivity, and processing characteristics is obviously improved, and reduces the rolling resistance of obtained tire, extends the service life of tire.
Description
Technical field
The invention belongs to tire manufacturing techniques field, and in particular to a kind of preparation method of graphene oxide, by the preparation
Graphene oxide made from method, and a kind of manufacture method of tire tread.
Background technology
Carbon material be on the earth most generally and a kind of most marvellous material, most hard diamond and most soft stone in the world
Ink is all carbon material.In the past 30 years, carbon nanomaterial sets foot in the Disciplinary Frontiers of scientific and technical innovation always, for example, find for 1985
Fullerene and the CNT found in 1991 cause the research boom of carbon nanomaterial.2004, Novoselov hairs
The New Two Dimensional atomic crystal that the monoatomic layer connected by carbon atom with sP2 hydridization is formed is showed：Graphene (GraPhene), its
Basic structural unit is the most stable of hexa-atomic ring-shaped of benzene in organic material, is current optimal two-dimension nano materials, and
Novoselov obtained the Nobel Prize because this finds in 2010.The discovery of graphene, carbon material man is further enriched
Race, form the complete of the fullerene from zero dimension, one-dimensional CNT, the diamond of two-dimentional graphene to three-dimensional and graphite
System, the development for fields such as new material and Condensed Matter Physics provide new growth point.Graphene starts to surmount CNT
Purpose world forward position and focus are advised as enjoying.
With developing rapidly for electronic technology and Information technology, conductive rubber composite material is increasingly by the weight of people
Depending on.And composite conducting rubber is because its is corrosion-resistant, light and can be according to the electrical and mechanical performance for needing to adjust material is used, preferably
It is in the large-scale production the advantages that and famous；Graphene and CNT are all the conductions that combination property is very excellent in carbon system filler
Material, therefore, can be as the filler of composite conducting rubber.However, as nano level particle, all exist in the polymer
The shortcomings of hardly possible is disperseed, easily reunited, this causes its extensive use to have difficulties, and graphene and CNT production cost are high,
Therefore, as filler in use, should composite requirement performance indications planted agent reduce dosage as far as possible.
The content of the invention
Technical scheme provided by the present invention aims to solve the problem that above-mentioned technical problem present in prior art, and inventor is entering
Go after substantial amounts of further investigation, it is found that it is big, scattered uneven, mechanical single filler composite conducting rubber has amount of filler
The shortcomings of performance is relatively low, and two or more fillers are used in combination and can be achieved to have complementary advantages between filler, effectively improve compound
The combination property of material.In consideration of it, inventor is prepared for a kind of graphene oxide first, then by mechanical blending method by its with
CNT is prepared for graphene/carbon nano-tube rubber master batch together, finally using the graphene/carbon nano-tube rubber master batch as primary raw material,
A kind of brand-new tire tread is manufactured.
Therefore, the first aspect of the present invention provides a kind of preparation method of graphene oxide, comprises the following steps：
First, reactor is assembled in ice-water bath, graphite powder, sodium nitrate and the concentrated sulfuric acid are added into the reactor, stirred
Mix well mixed, and add potassium hyperchlorate under agitation；Then, fraction time adds potassium permanganate, and controlling reaction temperature is not
More than 20 DEG C, after stirring, ice bath is removed, the reactor is transferred on magnetic stirrer, electromagnetism stirs 20~24h；Connect
, be added slowly with stirring deionized water, and heat the reactor, the temperature in the reactor is increased to 95~99
DEG C, after stirring 10~30min, hydrogen peroxide is added to reduce excessive oxidant；After reaction solution is changed into glassy yellow, centrifuge by several times,
To separate graphene oxide suspension, then washed successively with HCl solution and deionized water until separating liquid pH=7；Filtering, will
The filter cake vacuum drying arrived, produces the graphene oxide.
Preferably, in above-mentioned preparation method, the HCl solution is 5%HCl solution.
Preferably, in above-mentioned preparation method, the graphite powder is crystalline graphite powder.
The second aspect of the present invention provides a kind of graphene oxide, and it is as the preparation method described in first aspect present invention
It is made.
The third aspect of the present invention provides a kind of manufacture method of tire tread, comprises the following steps：
S1：Graphite is prepared using the graphene oxide described in second aspect of the present invention, CNT, rubber master batches and auxiliary agent
Alkene/CNT rubber master batch；
S2：By the graphene/carbon nano-tube rubber master batch made from S1, natural rubber, butadiene rubber, vulcanized rubber powder, ZnO,
Sulphur, vulcanization accelerator are admixed together, and mixed refining process is successively carried out in banbury, mill, and tread mix is made；Connect
, the tread mix is put into moulding press sulfidization molding, the tire tread is made.
It is worth supplementary notes, in the manufacture method of above-mentioned tire tread, the rubber master batches are upper sea green tough new
The special rubber master batches of Materials Co., Ltd.
Preferably, in the manufacture method, the CNT is in single-walled carbon nanotube, multi-walled carbon nanotube
It is at least one.
Preferably, in the manufacture method, S1 includes：
By the graphene oxide, the CNT, the rubber master batches, zinc oxide, stearic acid, antioxidant 4010,
Antioxidant RD, accelerant CZ, accelerator TT are added into banbury in the lump, and in 70 DEG C of banburyings 10 minutes, then park 8 hours with
On；Banburying product is conveyed into mill, and adds sulphur, wherein, roller temperature is 40~50 DEG C, and by roll spacing under the roller temperature
2.5mm is gradually amplified to by 1mm, after mill, the graphene/carbon nano-tube rubber master batch is made.Also, on this basis,
Rubber master batches, zinc oxide, stearic acid, antioxidant 4010, antioxidant RD, accelerant CZ, accelerator TT, the mass parts ratio of sulphur are
100：5：2：1：1：1：0.5：1.4.
Preferably, in the manufacture method, S1 includes：
By the graphene oxide, the CNT, the rubber master batches, zinc oxide, stearic acid, antioxidant 4010,
Antioxidant RD, accelerant CZ, accelerator TT, sulphur add be kneaded into two-roll mill in the lump, wherein, roller temperature during mixing is
40~120 DEG C, roll spacing during mixing is 1~10mm；Then, thin logical 3~6 times, adjustment roll spacing bottom sheet, obtains piece to 2~20mm
The graphene/carbon nano-tube rubber master batch of shape.Also, on this basis, rubber master batches, zinc oxide, stearic acid, age resistor
4010th, antioxidant RD, accelerant CZ, accelerator TT, the mass parts ratio of sulphur are 100：5：2：1：1：1：0.5：1.4.
Preferably, in the manufacture method, S1 includes：
By the graphene oxide, the CNT, the rubber master batches, zinc oxide, stearic acid, antioxidant 4010,
Antioxidant RD, accelerant CZ, accelerator TT, sulphur add be kneaded into banbury in the lump, wherein, rotor speed during mixing is
20~200r/min, 40-120 DEG C of initial temperature；It is fully mixed to after being kneaded torque or power stability, is kneaded and completes, dumping, i.e.,
Obtain the graphene/carbon nano-tube rubber master batch of scatter mass structure.Also, on this basis, rubber master batches, zinc oxide, stearic acid, anti-old
Agent 4010, antioxidant RD, accelerant CZ, accelerator TT, the mass parts ratio of sulphur are 100：5：2：1：1：1：0.5：1.4.
Preferably, in the manufacture method, S1 includes：
By the graphene oxide, the CNT, the rubber master batches, zinc oxide, stearic acid, antioxidant 4010,
Antioxidant RD, accelerant CZ, accelerator TT, sulphur add the extrusion molding into screw extruder in the lump, from the institute of shape of the mouth as one speaks extrusion strip
State graphene/carbon nano-tube rubber master batch；Wherein, the temperature of screw speed 20-200r/min, machine barrel and the shape of the mouth as one speaks is 60-120 DEG C.
Also, on this basis, rubber master batches, zinc oxide, stearic acid, antioxidant 4010, antioxidant RD, accelerant CZ, accelerator TT,
The mass parts ratio of sulphur is 100：5：2：1：1：1：0.5：1.4.
In addition, it is noted that the tire tread more than obtained by each optimal technical scheme is annular.
Finally, what deserves to be explained is, compared with prior art, technical scheme provided by the present invention has following technology excellent
Gesture and beneficial effect：
Technical scheme provided by the present invention, graphene oxide/CNT can be made to evenly spread in rubber master batches,
The synergy of graphene oxide and CNT can effectively reduce total dosage of filler, wherein, the electric conductivity of graphene oxide
Can be more superior than CNT, the good dispersion in rubber, filler aggregation can be more broadly reduced in the composite
Distance between body, so that graphene oxide and CNT can also obtain preferable electric conductivity under less dosage；This
Outside, after adding graphene oxide and CNT, the processing characteristics of elastomeric compound, which has, to be obviously improved, the hardness of vulcanizate, resilience
Rate, tensile strength and tearing strength are significantly improved, and also effectively reduce the rolling resistance of obtained tire in addition.
Therefore, the high speed performance of the tire with tire tread of the present invention is better than tire of the prior art；Especially, invent
People also by the addition of graphene oxide, the tire tread of CNT carried out heat transfer coefficient test, described in discovery
Heat transfer coefficient of the tire tread under 60 degrees Celsius and 80 degrees Celsius improves 25%；In road test, its crown surface temperature
Degree and groove bottom temperature significantly reduce, and tire wear performance improves 30%, so as to extend the use longevity of tire
Life.
Embodiment
With reference to embodiment, the present invention is further elaborated, but the present invention is not limited to following embodiment party
Formula.
First aspect, there is provided a kind of preparation method of graphene oxide, comprise the following steps：
First, reactor is assembled in ice-water bath, graphite powder, sodium nitrate and the concentrated sulfuric acid are added into the reactor, stirred
Mix well mixed, and add potassium hyperchlorate under agitation；Then, fraction time adds potassium permanganate, and controlling reaction temperature is not
More than 20 DEG C, after stirring, ice bath is removed, the reactor is transferred on magnetic stirrer, electromagnetism stirs 20~24h；Connect
, be added slowly with stirring deionized water, and heat the reactor, the temperature in the reactor is increased to 95~99
DEG C, after stirring 10~30min, hydrogen peroxide is added to reduce excessive oxidant；After reaction solution is changed into glassy yellow, centrifuge by several times,
To separate graphene oxide suspension, then washed successively with HCl solution and deionized water until separating liquid pH=7；Filtering, will
The filter cake vacuum drying arrived, produces the graphene oxide.
In a preferred embodiment, the HCl solution is 5%HCl solution.
In a preferred embodiment, the graphite powder is crystalline graphite powder.
Second aspect, there is provided a kind of graphene oxide, it is made as the preparation method described in first aspect.
The third aspect, there is provided a kind of manufacture method of tire tread, comprise the following steps：
S1：Graphite is prepared using graphene oxide according to claim 4, CNT, rubber master batches and auxiliary agent
Alkene/CNT rubber master batch；
S2：By the graphene/carbon nano-tube rubber master batch made from S1, natural rubber, butadiene rubber, vulcanized rubber powder, ZnO,
Sulphur, vulcanization accelerator are admixed together, and mixed refining process is successively carried out in banbury, mill, and tread mix is made；Connect
, the tread mix is put into moulding press sulfidization molding, the tire tread is made.
In a preferred embodiment, the CNT in single-walled carbon nanotube, multi-walled carbon nanotube at least
It is a kind of.
In a preferred embodiment, S1 includes：
By the graphene oxide, the CNT, the rubber master batches, zinc oxide, stearic acid, antioxidant 4010,
Antioxidant RD, accelerant CZ, accelerator TT are added into banbury in the lump, and in 70 DEG C of banburyings 10 minutes, then park 8 hours with
On；Banburying product is conveyed into mill, and adds sulphur, wherein, roller temperature is 40~50 DEG C, and by roll spacing under the roller temperature
2.5mm is gradually amplified to by 1mm, after mill, the graphene/carbon nano-tube rubber master batch is made.
In a preferred embodiment, S1 includes：
By the graphene oxide, the CNT, the rubber master batches, zinc oxide, stearic acid, antioxidant 4010,
Antioxidant RD, accelerant CZ, accelerator TT, sulphur add be kneaded into two-roll mill in the lump, wherein, roller temperature during mixing is
40~120 DEG C, roll spacing during mixing is 1~10mm；Then, thin logical 3~6 times, adjustment roll spacing bottom sheet, obtains piece to 2~20mm
The graphene/carbon nano-tube rubber master batch of shape.
In a preferred embodiment, S1 includes：
By the graphene oxide, the CNT, the rubber master batches, zinc oxide, stearic acid, antioxidant 4010,
Antioxidant RD, accelerant CZ, accelerator TT, sulphur add be kneaded into banbury in the lump, wherein, rotor speed during mixing is
20~200r/min, 40-120 DEG C of initial temperature；After the completion of mixing, dumping, the graphene/carbon nano-tube of scatter mass structure is produced
Rubber master batch.
In a preferred embodiment, S1 includes：
By the graphene oxide, the CNT, the rubber master batches, zinc oxide, stearic acid, antioxidant 4010,
Antioxidant RD, accelerant CZ, accelerator TT, sulphur add the extrusion molding into screw extruder in the lump, from the institute of shape of the mouth as one speaks extrusion strip
State graphene/carbon nano-tube rubber master batch；Wherein, the temperature of screw speed 20-200r/min, machine barrel and the shape of the mouth as one speaks is 60-120 DEG C.
Embodiment 1
Tire tread is prepared according to step in detail below：
(1) first, reactor is assembled in ice-water bath, crystalline graphite powder, sodium nitrate and the concentrated sulfuric acid are added described anti-
Device is answered, is uniformly mixed, and adds potassium hyperchlorate under agitation；Then, fraction time adds potassium permanganate, and controls reaction
Temperature is no more than 20 DEG C, after stirring, removes ice bath, the reactor is transferred on magnetic stirrer, and electromagnetism stirs 20~
24h；Then, deionized water is added slowly with stirring, and heats the reactor, is increased to the temperature in the reactor
95~99 DEG C, after stirring 10~30min, hydrogen peroxide is added to reduce excessive oxidant；After reaction solution is changed into glassy yellow, by several times
Centrifugation, to separate graphene oxide suspension, then is washed until separating liquid pH=7 with 5%HCl solution and deionized water successively；
Filtering, obtained filter cake is dried in vacuo, produces the graphene oxide.
(2) by graphene oxide, single-walled carbon nanotube, rubber master batches, zinc oxide, stearic acid, antioxidant 4010, antioxidant
RD, accelerant CZ, accelerator TT are added into banbury in the lump, and in 70 DEG C of banburyings 10 minutes, then park more than 8 hours；Will
Banburying product is conveyed into mill, and adds sulphur, wherein, roller temperature be 40~50 DEG C, and under the roller temperature by roll spacing by 1mm
Gradually it is amplified to 2.5mm, after mill, the graphene/single-walled carbon nanotube rubber master batch is made；Wherein, rubber master batches, oxidation
Zinc, stearic acid, antioxidant 4010, antioxidant RD, accelerant CZ, accelerator TT, the mass parts ratio of sulphur are 100：5：2：1：1：
1：0.5：1.4.
(3) by the obtained graphene/carbon nano-tube rubber master batch, natural rubber, butadiene rubber, vulcanized rubber powder, ZnO,
Sulphur, vulcanization accelerator are admixed together, and mixed refining process is successively carried out in banbury, mill, and tread mix is made；Connect
, the tread mix is put into moulding press sulfidization molding, the tire tread is made；Wherein, graphene/carbon nano-tube is female
Glue, natural rubber, butadiene rubber, vulcanized rubber powder, ZnO, sulphur, the mass parts ratio of vulcanization accelerator are 12：80：20：50：1.5：
2：1.5.
Embodiment 2
Tire tread is prepared according to step in detail below：
(1) specific steps are the same as embodiment 1.
(2) by graphene oxide, single-walled carbon nanotube, rubber master batches, zinc oxide, stearic acid, antioxidant 4010, antioxidant
RD, accelerant CZ, accelerator TT, sulphur add be kneaded into two-roll mill in the lump, wherein, roller temperature during mixing for 40~
120 DEG C, roll spacing during mixing is 1~10mm；Then, thin logical 3~6 times, adjustment roll spacing bottom sheet, obtains sheet to 2~20mm
The graphene/carbon nano-tube rubber master batch；Wherein, rubber master batches, zinc oxide, stearic acid, antioxidant 4010, antioxidant RD, promotion
Agent CZ, accelerator TT, the mass parts ratio of sulphur are 100：5：2：1：1：1：0.5：1.4.
(3) by the obtained graphene/carbon nano-tube rubber master batch, natural rubber, butadiene rubber, vulcanized rubber powder, ZnO,
Sulphur, vulcanization accelerator are admixed together, and mixed refining process is successively carried out in banbury, mill, and tread mix is made；Connect
, the tread mix is put into moulding press sulfidization molding, the tire tread is made；Wherein, graphene/carbon nano-tube is female
Glue, natural rubber, butadiene rubber, vulcanized rubber powder, ZnO, sulphur, the mass parts ratio of vulcanization accelerator are 10：80：20：50：1.5：
2：1.5.
Embodiment 3
Tire tread is prepared according to step in detail below：
(1) specific steps are the same as embodiment 1.
(2) by graphene oxide, multi-walled carbon nanotube, rubber master batches, zinc oxide, stearic acid, antioxidant 4010, antioxidant
RD, accelerant CZ, accelerator TT, sulphur add be kneaded into banbury in the lump, wherein, rotor speed during mixing for 20~
200r/min, 40-120 DEG C of initial temperature；After the completion of mixing, dumping, the graphene/carbon nano-tube for producing scatter mass structure is female
Glue；Wherein, rubber master batches, zinc oxide, stearic acid, antioxidant 4010, antioxidant RD, accelerant CZ, accelerator TT, the matter of sulphur
Amount part is compared for 100：5：2：1：1：1：0.5：1.4.
(3) by the obtained graphene/carbon nano-tube rubber master batch, natural rubber, butadiene rubber, vulcanized rubber powder, ZnO,
Sulphur, vulcanization accelerator are admixed together, and mixed refining process is successively carried out in banbury, mill, and tread mix is made；Connect
, the tread mix is put into moulding press sulfidization molding, the tire tread is made；Wherein, graphene/carbon nano-tube is female
Glue, natural rubber, butadiene rubber, vulcanized rubber powder, ZnO, sulphur, the mass parts ratio of vulcanization accelerator are 10：80：20：50：1.5：
2：1.6.
Embodiment 4
Tire tread is prepared according to step in detail below：
(1) specific steps are the same as embodiment 1.
(2) by the graphene oxide, the CNT, the rubber master batches, zinc oxide, stearic acid, age resistor
4010th, antioxidant RD, accelerant CZ, accelerator TT, sulphur add the extrusion molding into screw extruder in the lump, and strip is extruded from the shape of the mouth as one speaks
The graphene/carbon nano-tube rubber master batch；Wherein, the temperature of screw speed 20-200r/min, machine barrel and the shape of the mouth as one speaks is 60-120
℃；Wherein, rubber master batches, zinc oxide, stearic acid, antioxidant 4010, antioxidant RD, accelerant CZ, accelerator TT, the matter of sulphur
Amount part is compared for 100：5：2：1：1：1：0.5：1.4.
(3) by the obtained graphene/carbon nano-tube rubber master batch, natural rubber, butadiene rubber, vulcanized rubber powder, ZnO,
Sulphur, vulcanization accelerator are admixed together, and mixed refining process is successively carried out in banbury, mill, and tread mix is made；Connect
, the tread mix is put into moulding press sulfidization molding, the tire tread is made；Wherein, graphene/carbon nano-tube is female
Glue, natural rubber, butadiene rubber, vulcanized rubber powder, ZnO, sulphur, the mass parts ratio of vulcanization accelerator are 15：80：20：50：1.5：
2：1.6.
In addition, inventor according to the performance of tire tread made from the step in above example 1~4 also to being surveyed
Examination, it is as a result as shown in table 1 below：
The testing performance index result of the tire tread of table 1
The specific embodiment of the present invention is described in detail above, but it is intended only as example, it is of the invention and unlimited
It is formed on particular embodiments described above.To those skilled in the art, it is any to the equivalent modifications that carry out of the present invention and
Substitute also all among scope of the invention.Therefore, the impartial conversion made without departing from the spirit and scope of the invention and
Modification, all should be contained within the scope of the invention.
Claims (10)
1. a kind of preparation method of graphene oxide, it is characterised in that comprise the following steps：
First, reactor is assembled in ice-water bath, graphite powder, sodium nitrate and the concentrated sulfuric acid are added into the reactor, stirring is mixed
Close uniformly, and add potassium hyperchlorate under agitation；Then, fraction time adds potassium permanganate, and controlling reaction temperature is no more than
20 DEG C, after stirring, ice bath is removed, the reactor is transferred on magnetic stirrer, electromagnetism stirs 20 ~ 24 h；Then,
Deionized water is added slowly with stirring, and heats the reactor, the temperature in the reactor is increased to 95 ~ 99 DEG C,
After stirring 10 ~ 30 min, hydrogen peroxide is added to reduce excessive oxidant；After reaction solution is changed into glassy yellow, centrifuge by several times, to divide
From graphene oxide suspension, then washed successively with HCl solution and deionized water until separating liquid pH=7；Filtering, by what is obtained
Filter cake is dried in vacuo, and produces the graphene oxide.
2. preparation method according to claim 1, it is characterised in that the HCl solution is 5%HCl solution.
3. preparation method according to claim 1, it is characterised in that the graphite powder is crystalline graphite powder.
4. a kind of graphene oxide, it is characterised in that it is as according to the preparation method system any one of claim 1 ~ 3
.
5. a kind of manufacture method of tire tread, it is characterised in that comprise the following steps：
S1：Graphene/carbon is prepared using graphene oxide according to claim 4, CNT, rubber master batches and auxiliary agent
Nanotube rubber master batch；
S2：By the graphene/carbon nano-tube rubber master batch made from S1, natural rubber, butadiene rubber, vulcanized rubber powder, ZnO, sulphur,
Vulcanization accelerator is admixed together, and mixed refining process is successively carried out in banbury, mill, and tread mix is made；Then, by institute
Tread mix input moulding press sulfidization molding is stated, the tire tread is made.
6. manufacture method according to claim 5, it is characterised in that the CNT is selected from single-walled carbon nanotube, more
At least one of wall carbon nano tube.
7. manufacture method according to claim 5, it is characterised in that S1 includes：
By the graphene oxide, the CNT, the rubber master batches, zinc oxide, stearic acid, antioxidant 4010, antioxygen
Agent RD, accelerant CZ, accelerator TT are added into banbury in the lump, and in 70 DEG C of banburyings 10 minutes, then park more than 8 hours；
Banburying product is conveyed into mill, and adds sulphur, wherein, roller temperature be 40 ~ 50 DEG C, and under the roller temperature by roll spacing by 1
Mm is gradually amplified to 2.5 mm, and after mill, the graphene/carbon nano-tube rubber master batch is made.
8. manufacture method according to claim 5, it is characterised in that S1 includes：
By the graphene oxide, the CNT, the rubber master batches, zinc oxide, stearic acid, antioxidant 4010, antioxygen
Agent RD, accelerant CZ, accelerator TT, sulphur add be kneaded into two-roll mill in the lump, wherein, roller temperature during mixing for 40 ~
120 DEG C, roll spacing during mixing is 1 ~ 10mm；Then, thin logical 3 ~ 6 times, adjustment roll spacing bottom sheet, obtains the institute of sheet to 2 ~ 20mm
State graphene/carbon nano-tube rubber master batch.
9. manufacture method according to claim 5, it is characterised in that S1 includes：
By the graphene oxide, the CNT, the rubber master batches, zinc oxide, stearic acid, antioxidant 4010, antioxygen
Agent RD, accelerant CZ, accelerator TT, sulphur add be kneaded into banbury in the lump, wherein, rotor speed during mixing for 20 ~
200r/min, 40-120 DEG C of initial temperature；After the completion of mixing, dumping, the graphene/carbon nano-tube for producing scatter mass structure is female
Glue.
10. manufacture method according to claim 5, it is characterised in that S1 includes：
By the graphene oxide, the CNT, the rubber master batches, zinc oxide, stearic acid, antioxidant 4010, antioxygen
Agent RD, accelerant CZ, accelerator TT, sulphur add the extrusion molding into screw extruder in the lump, from the stone of shape of the mouth as one speaks extrusion strip
Black alkene/CNT rubber master batch；Wherein, the temperature of screw speed 20-200r/min, machine barrel and the shape of the mouth as one speaks is 60-120 DEG C.
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