CN106084332B - The preparation method and process units of the pre-dispersed rubber master batch of graphene microchip - Google Patents
The preparation method and process units of the pre-dispersed rubber master batch of graphene microchip Download PDFInfo
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Abstract
The present invention relates to the preparation method and process units of the pre-dispersed rubber master batch of rubber processing technical field, particularly graphene microchip.Including graphene microchip dispersion liquid and latex are stirred into obtained mixed material by homogenizer, into above-mentioned mixed material, addition flocculant condenses mixed material to form slurry；Slurry is dehydrated, dries obtained rubber master batch.Present invention process is simple, safe operation, it is possible to achieve large-scale continuous production, the preparation technology of more original batch process improve production efficiency；Graphene microchip can realize high degree of dispersion in the masterbatch obtained relative to melt-processed method, this method；And it can realize quick mixing relative to method before and condense, drying and dehydrating stage combination extrusion is dried and the mode of drying shortens drying time, avoids the aging of sizing material, obtains the pre-dispersed rubber master batch of graphene microchip of excellent performance.
Description
Technical field
The present invention relates to the preparation method of the pre-dispersed rubber master batch of rubber processing technical field, particularly graphene microchip and
Process units.
Background technology
Graphene has very excellent performance, it is current thickness known in the world as a kind of new carbon
The maximum fully transparent two dimensional crystal material of minimum, intensity highest, hardness, thermal conductivity factor at room temperature are up to 5300W/
（m·K）, resistivity is about 10-6Ω m, it is the minimum conductive material of existing resistivity；It is about 2600m than surface2/ g, it is theoretical
Modulus of elasticity reaches 103GPa, and tensile strength reaches 125GPa.Therefore, graphene is applied in composite and can significantly carried
The traditional performances such as the intensity of high composite, thermal conductivity, electric conductivity, prepare high-performance composite materials.Due to current graphene
Extensive preparation technology is not overripened, causes the preparation cost of single-layer graphene higher, applied to can be significantly in industrialization product
Degree improves product cost, can not be widely used.Graphene microchip refers to that carbon-coating number is received more than 10 layers, thickness 5~100
Ultra-thin graphene stratiform accumulation body in the range of rice, maintain the planar carbon hexatomic ring conjugation crystal structure of graphene, tool
There are excellent mechanical strength, conduction, heat conductivility, and good lubrication, high temperature resistant and anticorrosion properties.Relative to common stone
Ink, the thickness of graphene microchip are in the range of nanoscale, but its radial width can reach several and arrive dozens of micron, tool
There is the shape ratio of super large, and the country has possessed ability for mass production at present, product cost is higher.
But due to graphene when merely preparing graphene microchip rubber composite using melting mixing processing method
The larger Van der Waals force of piece interlayer makes it easily reunite in rubber, and dispersiveness is poor, does not reach the preferable performance of material, in order to
Solve this problem, the graphene microchip rubber composite with good dispersion can be prepared by latex co-agglomeration,
Specially there is the form of latex using most of rubber, be mixed with graphene microchip dispersion liquid has under solution state
The graphene microchip of intercalation configuration/latex complex liquid, flocculant wadding is recycled to avale to obtain having the stone of good dispersion
Black alkene microplate/rubber composite.Research currently for this aspect all rests on laboratory stage, and what is utilized is all interval
Method prepares the incorporation time length of the pre-dispersed rubber master batch of graphene microchip, latex and graphene, and drying time length, sizing material is in height for a long time
Easy aging under warm environment, final products performance are affected.
The content of the invention
It is an object of the invention to overcome prior art that batch process can only be used to prepare graphene microchip to disperse rubber master batch, graphite
Alkene poor dispersion interface interaction is weak, the defects of rubber master batch easy aging, there is provided a kind of graphene microchip disperses the preparation method of rubber master batch
And process units, it is possible to achieve the quick of latex and graphene mixes and condensation, drying time shorten, and avoids the old of sizing material
Change, obtain the pre-dispersed rubber master batch of graphene microchip of excellent performance.
The present invention is realized using following technical scheme：
A kind of preparation method of the pre-dispersed rubber master batch of graphene microchip, including graphene microchip dispersion liquid and latex are passed through into height
Fast mixer is stirred obtained mixed material, and flocculant is added into above-mentioned mixed material to be condensed mixed material to form pulpous state
Thing；Rubber master batch is made by slightly dry, redrying in slurry.
Mixed by graphene with latex, flocculating forms slurry, and then be dehydrated, dry, can with continuous production,
Production efficiency greatly improves compared with batch process；Graphene microchip can realize high degree of dispersion in rubber master batch, be combined in final products
Glue content is higher, and can realize that the quick of latex and graphene mixes and condensation relative to method before, drying time
Shorten, energy consumption reduces, and avoids the aging of sizing material, obtains the pre-dispersed rubber master batch of graphene microchip of excellent performance.In drying process
Extrusion dehydration is combined with drying, also can shorten drying time, reduce energy consumption.It can be reduced rapidly during follow-up plasticate
Mooney viscosity, can save drying glue and power consumption of plasticating, and gained sizing material is outer except mechanical property lifting, heat reduction, endurance
Performance boost, it can apply to the fields such as tire and anti-vibration article.
Above-mentioned technical proposal, further, the mixing speed of homogenizer when preparing mixed liquor for 400~
800rpm, mixing time 20-40min.
Above-mentioned technical proposal, further, described slightly to dry in three stages, drying temperature section is followed successively by 120~160
DEG C, 100~150 DEG C, 80~120 DEG C, 5~30min of drying time.Stage by stage and the drying side that reduces successively of drying temperature
Formula, it is possible to increase drying efficiency, shorten drying time, reduce energy consumption.
Above-mentioned technical proposal, further, the solid content of the graphene microchip dispersion liquid is 0.1%~40%.
Above-mentioned technical proposal, further, the preparation method of the graphene microchip dispersion liquid are to lead to graphene microchip
Cross homogenizer to be dispersed in water, mixing speed 2000-3000rpm, mixing time 2-5h.
Above-mentioned technical proposal, further, the solid content of the latex is 30%~60%.
Above-mentioned technical proposal, further, the latex are Heveatex, styrene-butadiene latex, carboxylic styrene butadiene latex, NBR
One or more in breast, carboxylic acrylonitrile butadiene rubber latex, EPDM latex, polychloroprene latex, butyl latex.
Above-mentioned technical proposal, further, the flocculant is the sulfuric acid of mass fraction 0.1%~25%, hydrochloric acid, acetic acid,
One or more in calcium chloride solution, sodium chloride solution, Klorvess Liquid, ethanol.
The present invention also provides a kind of process units of the pre-dispersed rubber master batch of graphene microchip, including mixing kettle, settling tank, drying
Device；The mixing kettle has material inlet, mixture outlet；Mixture outlet is connected with settling tank by pipeline；Flocculant
Storage tank is connected with settling tank by pipeline, and measuring equipment is provided between the flocculant storage tank and settling tank；Drying device, it is described
Drying device includes tablet press machine one, tablet press machine two, tablet press machine three and the crepe machine being linked in sequence successively；Be arranged on settling tank with
Mechanical arm between drying device；Detect the pH value monitoring device of liquid in settling tank.Graphene dispersing solution is mixing with latex
After being well mixed in kettle, settling tank is entered by pipeline, it is heavy conveniently accurately can be transported to flocculant by measuring equipment
Drop in pond, in the presence of flocculant, the mixed material in settling tank forms slurry, and mechanical arm is collected and conveys slurry
Thick drying and redrying processing are carried out into drying device；The present apparatus can realize that graphene microchip disperses the serialization of rubber master batch
Production, production efficiency is improved, shorten drying time, reduced energy consumption, enhance product performance.PH value monitoring device is heavy for monitoring
The acid-base value of mediocre person's material is dropped, makes pH value control in the range of 4~6.The equipment manufacturing cost used in this process units is relatively low, enterprise
It can be transformed using itself existing equipment, enterprise's production cost can be mitigated, be adapted to promote.
Above-mentioned technical proposal, further, in addition to for mixing kettle convey latex latex cylinder, the latex cylinder with
The material inlet of mixing kettle is connected by pipeline；For preparing and being conveyed to mixing kettle the graphene agitator tank of graphene, institute
Graphene agitator tank is stated to be connected by pipeline with mixing kettle material inlet.
Above-mentioned technical proposal, further, in addition to auxiliary agent filler measuring device, the auxiliary agent filler measuring device is with mixing
The connection of kettle pipeline is closed, is added as needed on the auxiliary agents such as corresponding plasticizer age resistor environment protection oil.
Present invention process is simple, safe operation, it is possible to achieve large-scale continuous production, the preparation work of more original batch process
Skill improves production efficiency；Graphene microchip can realize height point in the masterbatch obtained relative to melt-processed method, this method
Dissipate；And it can realize quick mixing relative to method before and condense, drying and dehydrating stage combination extrusion is dried and drying
Mode shorten drying time, avoid the aging of sizing material, obtain the pre-dispersed rubber master batch of graphene microchip of excellent performance.It is actual
Mooney viscosity can be reduced rapidly during plasticating in, drying glue can be saved and power consumption of plasticating, gained sizing material except
Mechanical property lifting is outer, and heat reduces, fatigue performance lifting.It can be realized on factory's existing equipment and Process ba- sis continuous
Metaplasia is produced, and simplifies the drying glue in application process and plasticating technology, is reached energy-conservation, is improved the target of operating efficiency, made
Standby sizing material has good physical and mechanical properties and feature.The present invention is prepared for different graphene microchip contents and not
With the rubber master batch disperseed in elastomer substrates, graphene microchip can be dispersed in elastomeric compound, avoids the reunion of itself, contains
Measure controllable, and technique is simple, cost is relatively low, is a kind of novel processing step of worth exploitation.
Brief description of the drawings
Fig. 1 is the process units structural representation of the present invention.
Wherein, 1 mixing kettle；2 graphene agitator tanks；3 latex cylinders；4 flocculant storage tanks；5 settling tanks；6 measuring equipments；7pH
It is worth monitoring device；8 tablet press machines one；9 tablet press machines two；10 tablet press machines three；11 crepe machines；12 auxiliary agent filler measuring devices.
Embodiment
In order to which the above objects, features and advantages of the present invention is more clearly understood, with reference to embodiment to this
Invention is described further.
Embodiment 1
（1）The preparation of graphene microchip dispersion liquid
600L water, 6kg graphene microchips is taken to be added in graphene agitator tank 2,2500rpm high-speed stirreds are disperseed under normal temperature
5 hours, prepare the graphene microchip aqueous dispersions that mass fraction is 1%.
（2）The mixing and condensation of graphene microchip dispersion liquid/Heveatex
The graphene microchip aqueous dispersions prepared in graphene agitator tank 2 are transported in mixing kettle 1 by pipeline, together
When by the latex delivery in latex cylinder 3 into mixing kettle, control fluid flow, make 1000kg dry rubber contents be 60 % natural gum
Breast is added in homogenizer simultaneously, mixing speed 400rpm, mixing time 40min, and mixed material is made；By mixture
Material is transported in settling tank 5；The CaCl that mass fraction is 10% is stored in flocculant storage tank 42Solution, CaCl2Solution passes through
Measuring equipment is transported in settling tank 5, and by stirring, the latex particle in settling tank 5 condenses the slurry to be formed with graphene microchip
Shape thing.PH value monitoring device is additionally provided with detection settling tank, for monitoring the acid-base value of material in settling tank, pH value control is existed
6。
（3）The dehydration of rubber master batch
Mechanical arm collects the slurry in settling tank, and is fed sequentially into tablet press machine one after above-mentioned slurry draining is washed
8th, slightly dried in tablet press machine 29, tablet press machine 3 10, slightly dry temperature is followed successively by 120 DEG C, 100 DEG C, 80 DEG C, when drying
Between 30min, then pass through crepe machine 11 carry out redrying, be made rubber master batch.
（4）The shaping of rubber master batch
The material Jing Guo dewater treatment is pressed into film according to demand.
（5）Vulcanize the preparation of rubber
By the rubber master batch of above-mentioned preparation and commercially available natural rubber according to 1:9 mass ratio adds mill, and sulphur is added by formula
The auxiliary agents such as agent, age resistor, antioxidant produce pre-dispersed elastomeric compound, and the vulcanization rubber of graphene-containing microplate is made after vulcanization,
Its correlated performance is as shown in table 1.
Embodiment 2
（1）The preparation of graphene microchip dispersion liquid
600L water, 1Kg neopelexes is taken to be added in graphene agitator tank 2, stir the obtained aqueous solution；
30Kg graphene microchips are added in the above-mentioned aqueous solution again, 3000rpm high-speed stirreds are scattered 3 hours under normal temperature, prepare quality
Fraction is 5 % graphene microchip aqueous dispersions.
（2）The mixing and condensation of graphene microchip dispersion liquid/Heveatex
The graphene microchip aqueous dispersions prepared in graphene agitator tank 2 are transported in mixing kettle 1 by pipeline, together
When by the latex delivery in latex cylinder 3 into mixing kettle 1, control fluid flow, make 3000kg dry rubber contents be 60 % it is natural
Latex is added in homogenizer simultaneously, mixing speed 800rpm, mixing time 20min, and mixed material is made；Will mixing
Material is transported in settling tank 5；The acetic acid solution that mass fraction is 2 % is stored in flocculant storage tank, acetic acid solution passes through meter
Amount equipment 6 is transported in settling tank, and by stirring, the latex particle in settling tank 5 condenses the pulpous state to be formed with graphene microchip
Thing.PH value monitoring device is additionally provided with detection settling tank, for monitoring the acid-base value of material in settling tank, makes pH value control 4.
（3）The dehydration of rubber master batch
Mechanical arm collects the slurry in settling tank 5, and is fed sequentially into tablet press machine after above-mentioned slurry draining is washed
One 8, slightly dried in tablet press machine 29, tablet press machine 3 10, slightly dry temperature is followed successively by 140 DEG C, 120 DEG C, 90 DEG C, dries
Time 30min, redrying is then carried out by crepe machine, rubber master batch is made.
（4）The shaping of rubber master batch
The material Jing Guo dewater treatment is pressed into adhesive tape according to demand or granulation is handled.
（5）Vulcanize the preparation of rubber
By the rubber master batch of above-mentioned preparation and commercially available natural rubber according to 1:7 mass ratio adds mill, and sulphur is added by formula
The auxiliary agents such as agent, age resistor, antioxidant produce pre-dispersed elastomeric compound, and the vulcanization rubber of graphene-containing microplate is made after vulcanization,
Its correlated performance is as shown in table 1.
Embodiment 3
（1）The preparation of graphene microchip dispersion liquid
600L water, 2Kg neopelexes is taken to be added in graphene agitator tank, stir the obtained aqueous solution；
240Kg graphene microchips are added in the above-mentioned aqueous solution again, 3000rpm high-speed stirreds are scattered 5 hours under normal temperature, prepare quality
Fraction is 40% graphene microchip aqueous dispersions.
（2）The mixing and condensation of graphene microchip dispersion liquid/Heveatex
The graphene microchip aqueous dispersions prepared in graphene agitator tank are transported in mixing kettle by pipeline, simultaneously
By the latex delivery in latex cylinder to mixing kettle kind, fluid flow is controlled, makes the Heveatex that 1000kg dry rubber contents are 60 %
Add simultaneously in homogenizer, mixing speed 600rpm, mixing time 40min, mixed material is made；By mixed material
It is transported in settling tank；The CaCl that mass fraction is 1% is stored in flocculant storage tank2Solution, CaCl2Solution is set by metering
Standby to be transported in settling tank, by stirring, the latex particle in settling tank condenses the slurry to be formed with graphene microchip.Detection
PH value monitoring device is additionally provided with settling tank, for monitoring the acid-base value of material in settling tank, makes pH value control 5.
（3）The dehydration of rubber master batch
Mechanical arm collects the slurry in settling tank 5, and is fed sequentially into tablet press machine after above-mentioned slurry draining is washed
One 8, slightly dried in tablet press machine 29, tablet press machine 3 10, slightly dry temperature is followed successively by 160 DEG C, 150 DEG C, 120 DEG C, dries
Time 30min, redrying is then carried out by crepe machine, rubber master batch is made.
（4）The shaping of rubber master batch
The material Jing Guo dewater treatment is pressed into blob of viscose according to demand.
（5）Vulcanize the preparation of rubber
By the rubber master batch of above-mentioned preparation and commercially available natural rubber according to 3:7 mass ratio adds mill, and sulphur is added by formula
The auxiliary agents such as agent, age resistor, antioxidant produce pre-dispersed elastomeric compound, and the vulcanization rubber of graphene-containing microplate is made after vulcanization,
Its correlated performance is as shown in table 1.
Embodiment 4
（1）The preparation of graphene microchip dispersion liquid
Take 600L water, 0.5Kg neopelexes to be added in graphene agitator tank, stir obtained water-soluble
Liquid；6kg graphene microchips are added in the above-mentioned aqueous solution again, 2000rpm high-speed stirreds are scattered 3 hours under normal temperature, prepare matter
Measure the graphene microchip aqueous dispersions that fraction is 1 %.
（2）The mixing and condensation of graphene microchip dispersion liquid/Heveatex
The graphene microchip aqueous dispersions prepared in graphene agitator tank are transported in mixing kettle by pipeline, simultaneously
By the latex delivery in latex cylinder to mixing kettle kind, fluid flow is controlled, makes the Heveatex that 1000kg dry rubber contents are 60 %
Add simultaneously in homogenizer, mixing speed 600rpm, mixing time 40min, mixed material is made；By mixed material
It is transported in settling tank；The CaCl that mass fraction is 1% is stored in flocculant storage tank2Solution, CaCl2Solution passes through metering
Equipment is transported in settling tank, and by stirring, the latex particle in settling tank condenses the slurry to be formed with graphene microchip.Inspection
Survey in settling tank and be additionally provided with pH value monitoring device, for monitoring the acid-base value of material in settling tank, make pH value control 5.5.
（3）The dehydration of rubber master batch
Mechanical arm collects the slurry in settling tank, and is fed sequentially into tablet press machine after above-mentioned slurry draining is washed
First, slightly dried in tablet press machine two, tablet press machine three, slightly dry temperature is followed successively by 140 DEG C, 120 DEG C, 100 DEG C, drying time
30min altogether, redrying is then carried out by crepe machine, rubber master batch is made.
（4）The shaping of rubber master batch
The material Jing Guo dewater treatment is cut into micelle according to demand.
（5）Vulcanize the preparation of rubber
By the rubber master batch of above-mentioned preparation and commercially available natural rubber according to 1:9 mass ratio adds mill, and sulphur is added by formula
The auxiliary agents such as agent, age resistor, antioxidant produce pre-dispersed elastomeric compound, and the vulcanization rubber of graphene-containing microplate is made after vulcanization,
Its correlated performance is as shown in table 1.
Embodiment 5
（1）The preparation of graphene microchip dispersion liquid
Take 600L water, 0.5kg dialkyl succinylsuccinate ester sodium sulfonates to be added in graphene agitator tank, stir obtained water-soluble
Liquid；48Kg graphene microchips are added in the above-mentioned aqueous solution, 3000rpm high-speed stirreds are scattered 2 hours under normal temperature, prepare quality
Fraction is 8% graphene microchip aqueous dispersions.
（2）The mixing and condensation of graphene microchip dispersion liquid/styrene-butadiene latex
The graphene microchip aqueous dispersions prepared in graphene agitator tank are transported in mixing kettle by pipeline, simultaneously
By the latex delivery in latex cylinder to mixing kettle kind, fluid flow is controlled, makes the butadiene-styrene rubber breast that 400kg dry rubber contents are 40 %
Add simultaneously in homogenizer, mixing speed 800rpm, mixing time 20min, mixed material is made；By mixed material
It is transported in settling tank；The NaCl solution that mass fraction is 25 % is stored in flocculant storage tank, NaCl solution passes through metering
Equipment is transported in settling tank, and by stirring, the latex particle in settling tank condenses the slurry to be formed with graphene microchip.Inspection
Survey in settling tank and be additionally provided with pH value monitoring device, for monitoring the acid-base value of material in settling tank, make pH value control 5.
（3）The dehydration of rubber master batch
Mechanical arm collects the slurry in settling tank, and is fed sequentially into tablet press machine after above-mentioned slurry draining is washed
First, slightly dried in tablet press machine two, tablet press machine three, slightly dry temperature is followed successively by 150 DEG C, 130 DEG C, 100 DEG C, drying time
25min altogether, redrying is then carried out by crepe machine, rubber master batch is made.
（4）The shaping of rubber master batch
The material Jing Guo dewater treatment is pressed into film according to demand.
（5）Vulcanize the preparation of rubber
By the rubber master batch of above-mentioned preparation and commercially available butadiene-styrene rubber 1502 according to 1:7 mass ratio adds mill, adds by formula
Enter the auxiliary agents such as vulcanizing agent, age resistor, antioxidant and produce pre-dispersed elastomeric compound, the vulcanization rubber of graphene-containing microplate is made after vulcanization
Glue, its correlated performance are as shown in table 1.
Embodiment 6
（1）The preparation of graphene microchip dispersion liquid
Take 600L water, 0.5Kg aliphatic acid polyethenoxy fat to be added in graphene agitator tank, stir obtained water-soluble
Liquid；64Kg graphene microchips are added in the above-mentioned aqueous solution, 2500rpm high-speed stirreds are scattered 5 hours under normal temperature, prepare quality
Fraction is 14% graphene microchip aqueous dispersions.
（2）The mixing and condensation of graphene microchip dispersion liquid/styrene-butadiene latex
The graphene microchip aqueous dispersions prepared in graphene agitator tank are transported in mixing kettle by pipeline, simultaneously
By the latex delivery in latex cylinder to mixing kettle kind, fluid flow is controlled, makes the butadiene-styrene rubber that 1000kg dry rubber contents are 40 %
Breast is added in homogenizer simultaneously, mixing speed 800rpm, mixing time 20min, and mixed material is made；By mixture
Material is transported in settling tank；The NaCl solution that mass fraction is 25 % is stored in flocculant storage tank, NaCl solution passes through meter
Amount equipment is transported in settling tank, and by stirring, the latex particle in settling tank condenses the slurry to be formed with graphene microchip；
PH value monitoring device is additionally provided with detection settling tank, for monitoring the acid-base value of material in settling tank, makes pH value control 6.
（3）The dehydration of rubber master batch
Mechanical arm collects the slurry in settling tank, and is fed sequentially into tablet press machine after above-mentioned slurry draining is washed
First, slightly dried in tablet press machine two, tablet press machine three, slightly dry temperature is followed successively by 150 DEG C, 120 DEG C, 90 DEG C, drying time
20min altogether, redrying is then carried out by crepe machine, rubber master batch is made.
（4）The shaping of rubber master batch
The material Jing Guo dewater treatment is pressed into adhesive tape according to demand.
（5）Vulcanize the preparation of rubber
By the rubber master batch of above-mentioned preparation and commercially available butadiene-styrene rubber according to 5:1 mass ratio adds mill, and sulphur is added by formula
The auxiliary agents such as agent, age resistor, antioxidant produce pre-dispersed elastomeric compound, and the vulcanization rubber of graphene-containing microplate is made after vulcanization,
Its correlated performance is as shown in table 1.
Embodiment 7
（1）The preparation of graphene microchip dispersion liquid
Take 600L water, 0.5Kg neopelexes to be added in graphene agitator tank, stir obtained water-soluble
Liquid；30Kg graphene microchips are added in the above-mentioned aqueous solution, 1800rpm high-speed stirreds are scattered 2.5 hours under normal temperature, prepare matter
Measure the graphene microchip aqueous dispersions that fraction is 5%.
（2）The mixing and condensation of graphene microchip dispersion liquid/styrene-butadiene latex
The graphene microchip aqueous dispersions prepared in graphene agitator tank are transported in mixing kettle by pipeline；By glue
Latex delivery in newborn tank controls fluid flow, makes the butadiene-styrene rubber breast that 1000kg dry rubber contents are 40 % same to mixing kettle kind
When add in homogenizer, while auxiliary agent, filler are added in mixing kettle by auxiliary agent filler measuring device, by above-mentioned thing
Expect high-speed stirred, mixing speed 800rpm, mixing time 20min, mixed material is made；Mixed material is transported to sedimentation
Chi Zhong；The NaCl solution that mass fraction is 25 % is stored in flocculant storage tank, NaCl solution is transported to by measuring equipment
In settling tank, by stirring, the latex particle in settling tank condenses the slurry to be formed with graphene microchip.Detect in settling tank
PH value monitoring device is additionally provided with, for monitoring the acid-base value of material in settling tank, makes pH value control 4.
（3）The dehydration of rubber master batch
Mechanical arm collects the slurry in settling tank, and is fed sequentially into tablet press machine after above-mentioned slurry draining is washed
First, slightly dried in tablet press machine two, tablet press machine three, slightly dry temperature is followed successively by 150 DEG C, 120 DEG C, 90 DEG C, drying time
30min altogether, redrying is then carried out by crepe machine, rubber master batch is made.
（4）The shaping of rubber master batch
The material Jing Guo dewater treatment is pressed into blob of viscose according to demand.
（5）Vulcanize the preparation of rubber
The rubber master batch of above-mentioned preparation is added into mill, the auxiliary agents such as filler, vulcanizing agent, age resistor, antioxidant are added by formula
Pre-dispersed elastomeric compound is produced, the vulcanization rubber of graphene-containing microplate is made after vulcanization, its correlated performance is as shown in table 1.
Comparative example 1
By natural gum standard rubber, double-roll type mill is plasticated 2 minutes again after preliminary drying 20 minutes in 50 DEG C of baking ovens, by formula
Various auxiliary agents are added, natural glue sulfurating glue is obtained after vulcanization, its correlated performance is as shown in table 1.
Comparative example 2
By the natural gum standard rubber of 100 mass parts, double-roll type mill plasticates 2 again after preliminary drying 20 minutes in 50 DEG C of baking ovens
Minute, various auxiliary agents and the graphene microchip powder of 1 mass parts are added by formula, melt-processed method graphite is obtained after vulcanization
Alkene microplate/natural glue sulfurating glue, its correlated performance are as shown in table 1.
Comparative example 3
The butadiene-styrene rubber 1502 of 100 mass parts is plasticated 2 minutes in double-roll type mill, by formula add various auxiliary agents and
The graphene microchip powder of 1 mass parts, melt-processed method graphene microchip/butadiene-styrene rubber vulcanizate is obtained after vulcanization, it is related
Performance is as shown in table 1.
Comparative example 4
Homogenizer rotating speed is set to 400rpm, is separately added into Heveatex and matter that 100kg dry rubber contents are 60 %
The acetic acid solution that fraction is 2 % is measured, extruder will be passed sequentially through after the slurry draining washing of formation after mixing 30 min
Dehydration, three times drying machine are dried, and drying temperature is followed successively by 140 DEG C, 120 DEG C and 90 DEG C three times, are discharged, are obtained after drying 30 minutes
Natural gum is solidified to emulsion.
The mechanical property of embodiment 1-7 and comparative example 1-4 obtained vulcanization rubber, test index and method are as follows：
Hardness：GB/T531.1-2008；
Tensile strength： GB/T528-2009；
Elongation at break： GB/T528-2009；
100% stress at definite elongation： GB/T528-2009；
Tearing strength：GB/T529-2008；
Heat resistance：GB/T1699-1982；
Test result is as shown in table 1.
The mechanical strength for the vulcanization rubber that 1 different sizing materials of table obtain and dynamic mechanical contrast
As can be seen from Table 1, the vulcanization rubber ratio prepared through rubber master batch method is not added with the vulcanization rubber of graphene microchip
And the mechanical property of vulcanization rubber prepared by melt-blending process will be excellent, and 60 DEG C of fissipation factors also have it is a certain degree of
Reduce, the loss for caused by reducing the rolling resistance of tire has preferable effect.
Embodiment described above is only that the preferred embodiment of the present invention is described, not to the scope of the present invention
It is defined, on the premise of design spirit of the present invention is not departed from, those of ordinary skill in the art are to technical scheme
The various modifications made and improvement, all should fall into present invention determine that protection domain in.
Claims (9)
1. a kind of preparation method of the pre-dispersed rubber master batch of graphene microchip, it is characterised in that comprise the following steps：
Graphene microchip is added in graphene agitator tank, is uniformly dispersed, graphene microchip dispersion liquid is made；Latex is stored
It is standby in latex cylinder；
The graphene microchip dispersion liquid in graphene agitator tank is transported in mixing kettle by pipeline, while by latex cylinder
Latex delivery stirs 20~40min with 400~800rpm rotating speed into mixing kettle, by homogenizer and mixed liquor is made,
Mixed liquor is transported in settling tank；
The flocculant stored in flocculant storage tank is transported in settling tank by measuring equipment, by stirring, in settling tank
Latex particle condenses the slurry to be formed with graphene microchip, the pH value 4- expected by pH value monitoring device control settlement mediocre person
6；
Mechanical arm collects the slurry in settling tank, and is fed sequentially into drying device after above-mentioned slurry draining is washed
Row is thick to be dried, and then carries out redrying by crepe machine, rubber master batch is made.
2. the preparation method of the pre-dispersed rubber master batch of graphene microchip according to claim 1, it is characterised in that：It is described thick dry
In three stages, drying temperature section is followed successively by 120~160 DEG C, 100~150 DEG C, 80~120 DEG C, 5~30min of drying time.
3. the preparation method of the pre-dispersed rubber master batch of graphene microchip according to claim 1 or 2, it is characterised in that：The stone
The solid content of black alkene microplate dispersion liquid is 0.1%~40%.
4. the preparation method of the pre-dispersed rubber master batch of graphene microchip according to claim 3, it is characterised in that：The graphene
Graphene microchip is is dispersed in water by the preparation method of microplate dispersion liquid by homogenizer, mixing speed 2000-
3000rpm, mixing time 2-5h.
5. the preparation method of the pre-dispersed rubber master batch of graphene microchip according to claim 1 or 2, it is characterised in that：The glue
Breast be solid content be 30%~60% Heveatex, styrene-butadiene latex, carboxylic styrene butadiene latex, NBR latex, carboxylic acrylonitrile butadiene rubber latex,
One or more in EPDM latex, polychloroprene latex, butyl latex.
6. the preparation method of the pre-dispersed rubber master batch of graphene microchip according to claim 1 or 2, it is characterised in that：The wadding
Solidifying agent is the sulfuric acid of mass fraction 0.1%~25%, hydrochloric acid, acetic acid, calcium chloride solution, sodium chloride solution, Klorvess Liquid, second
One or more in alcohol.
7. a kind of process units of the pre-dispersed rubber master batch of graphene microchip, it is characterised in that including mixing kettle, settling tank, dry dress
Put；The mixing kettle has material inlet, mixture outlet；Mixture outlet is connected with settling tank by pipeline；Flocculant stores up
Tank is connected with settling tank by pipeline, and measuring equipment is provided between the flocculant storage tank and settling tank；Drying device, it is described dry
Dry device includes tablet press machine one, tablet press machine two, tablet press machine three and the crepe machine being linked in sequence successively；Settling tank is arranged on doing
Mechanical arm between dry device；Detect the pH value monitoring device of liquid acid-base value in settling tank.
8. the process units of the pre-dispersed rubber master batch of graphene microchip according to claim 7, it is characterised in that also include being used for
To the latex cylinder of mixing kettle conveying latex, the material inlet of the latex cylinder and mixing kettle is connected by pipeline；For preparing simultaneously
And the graphene agitator tank of graphene is conveyed to mixing kettle, the material inlet of the graphene agitator tank and mixing kettle passes through pipeline
Connection.
9. the process units of the pre-dispersed rubber master batch of graphene microchip according to claim 8, it is characterised in that also including auxiliary agent
Filler measuring device, the auxiliary agent filler measuring device are connected with mixing kettle by pipeline.
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| CN108410041B (en) * | 2018-01-31 | 2019-12-13 | 中国科学院长春应用化学研究所 | Preparation method of white carbon black wet masterbatch |
| CN108329535B (en) * | 2018-03-21 | 2020-09-04 | 多凌新材料科技股份有限公司 | High-dispersion graphene-rubber master batch and preparation method thereof |
| CN108641133B (en) * | 2018-05-15 | 2020-04-24 | 浙江奋飞橡塑制品有限公司 | Anti-firing conveyer belt |
| CN109233027A (en) * | 2018-08-08 | 2019-01-18 | 青岛领军节能与新材料研究院 | A kind of preparation method of the tread rubber of automobile tires based on graphene |
| CN109306094B (en) * | 2018-10-18 | 2021-01-05 | 中轻联（大连）包装研究院有限公司 | Preparation method of graphene rubber master batch |
| CN109627530B (en) * | 2018-11-26 | 2021-03-23 | 国宏中晶集团有限公司 | Graphene-containing wear-resistant composite material and preparation method thereof |
| CN111363208A (en) * | 2018-12-26 | 2020-07-03 | 唐山建华实业集团有限公司 | Preparation method of graphene natural rubber composite material |
| CN110240736B (en) * | 2019-06-27 | 2022-06-07 | 海南中橡科技有限公司 | Multiphase parallel flow solidification method for natural latex |
| CN111346587A (en) * | 2020-03-09 | 2020-06-30 | 青岛华高墨烯科技股份有限公司 | Preparation device for graphene conductive silica gel |
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| CN101864098B (en) * | 2010-06-03 | 2012-01-04 | 四川大学 | Preparation method of polymer/graphene composite material through in situ reduction |
| CN102786726B (en) * | 2012-07-24 | 2014-07-16 | 南京理工大学 | High performance XNBR vulcanized rubber containing graphene oxide and its preparation method |
| CN103224656A (en) * | 2013-04-24 | 2013-07-31 | 北京化工大学 | Oxidized grapheme/carbon black rubber nanocomposite and preparation method thereof |
| EP2960205A1 (en) * | 2014-06-23 | 2015-12-30 | Solvay SA | Stable aqueous graphene suspension and its use in producing graphene polymer nanocomposites |
| CN104072832B (en) * | 2014-06-27 | 2016-03-16 | 青岛大学 | A kind of oil-filled oxygenation functionalized graphene emulsion beta-rubber and preparation method thereof altogether |
| CN104693546B (en) * | 2015-02-15 | 2017-01-04 | 北京化工大学 | A kind of preparation method of High-performance graphite oxide alkene/solution polymerized butadiene styrene rubber composite |
| CN105482201A (en) * | 2016-01-04 | 2016-04-13 | 青岛双星轮胎工业有限公司 | High-performance tire containing oxidized graphene |
| CN205974343U (en) * | 2016-08-16 | 2017-02-22 | 青岛蓝湾烯碳材料科技有限责任公司 | Apparatus for producing of rubber master batch that looses is presorted to graphite alkene microplate |
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