CN106084332A - The preparation method of the pre-dispersed rubber master batch of graphene microchip and process units - Google Patents
The preparation method of the pre-dispersed rubber master batch of graphene microchip and process units Download PDFInfo
- Publication number
- CN106084332A CN106084332A CN201610677684.8A CN201610677684A CN106084332A CN 106084332 A CN106084332 A CN 106084332A CN 201610677684 A CN201610677684 A CN 201610677684A CN 106084332 A CN106084332 A CN 106084332A
- Authority
- CN
- China
- Prior art keywords
- master batch
- graphene microchip
- graphene
- rubber master
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C1/00—Treatment of rubber latex
- C08C1/14—Coagulation
- C08C1/15—Coagulation characterised by the coagulants used
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- 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
- C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2309/06—Copolymers with styrene
-
- 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
- C08J2407/00—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
- C08J2409/06—Copolymers with styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The present invention relates to preparation method and the process units of the pre-dispersed rubber master batch of rubber processing technical field, particularly graphene microchip.It is mixed to prepare mixed material with latex by homogenizer stirring including by graphene microchip dispersion liquid, in above-mentioned mixed material, adds flocculant make mixed material cohesion form slurry；Slurry is dehydrated, is dried prepared rubber master batch.Present invention process is simple, operation safety, it is possible to achieve large-scale continuous production, the preparation technology of more original batch process improves production efficiency；Relative to melt-processed method, in the masterbatch that this method obtains, graphene microchip is capable of high degree of dispersion；And can realize quickly mixing and condensing relative to method before, the drying and dehydrating stage combines the mode that extrusion is dried and dries and shortens drying time, it is to avoid sizing material aging, obtain the pre-dispersed rubber master batch of graphene microchip of excellent performance.
Description
Technical field
The present invention relates to the pre-dispersed rubber master batch of rubber processing technical field, particularly graphene microchip preparation method and
Process units.
Background technology
Graphene, as a kind of new carbon, has the most excellent performance, and it is current the most known thickness
The fully transparent two dimensional crystal material minimum, intensity is the highest, hardness is maximum, heat conductivity at room temperature is up to 5300W/
(m K), resistivity is about 10-6Ω m, for the conductive material that existing resistivity is minimum；Specific surface is about 2600m2/ g, theoretical
Elastic modelling quantity reaches 103GPa, and hot strength reaches 125GPa.Therefore, it is applied to Graphene in composite significantly to carry
The traditional performances such as the intensity of high composite, heat conductivity, electric conductivity, prepare high-performance composite materials.Due to current Graphene
Extensive preparation technology is the most overripened, and the preparation cost causing single-layer graphene is higher, and being applied in industrialization product can significantly
Degree improves product cost, it is impossible to be widely used.Graphene microchip refer to carbon-coating number more than 10 layers, thickness receives in 5～100
Ultra-thin Graphene stratiform accumulation body in the range of meter, maintains the planar carbon hexatomic ring conjugation crystal structure of Graphene, tool
There are the mechanical strength of excellence, conduction, heat conductivility, and good lubrication, high temperature resistant and anticorrosion properties.Relative to common stone
Ink, in the range of the thickness of graphene microchip is in nanoscale, but its radial width can reach several to dozens of micron, tool
Having a shape ratio of super large, and the most domestic possessed ability for mass production, product cost is higher.
But due to Graphene when merely utilizing melting mixing processing method to prepare graphene microchip rubber composite
The Van der Waals force that sheet interlayer is bigger makes it easily reunite in rubber, and dispersibility is poor, does not reaches the preferable performance of material, in order to
Solve this problem, can be had the graphene microchip rubber composite of good dispersion by the preparation of latex co-agglomeration,
Specially utilize most of rubber to have the form of latex, be mixed with graphene microchip dispersion liquid and have under solution state
The graphene microchip of intercalation configuration/latex complex liquid, recycling flocculant wadding avales the stone i.e. obtaining having good dispersion
Ink alkene microplate/rubber composite.All resting on laboratory stage currently for this research on the one hand, utilization is all interval
Method prepares the pre-dispersed rubber master batch of graphene microchip, and latex is long with the incorporation time of Graphene, and drying time is long, and sizing material is long-time high
Temperature environment under the most aging, final products performance is affected.
Summary 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 dispersion rubber master batch, graphite
The defects such as alkene poor dispersion interface interaction is weak, and rubber master batch is the most aging, it is provided that the preparation method of a kind of graphene microchip dispersion rubber master batch
And process units, it is possible to achieve quickly the mix and condense of latex and Graphene, shortening drying time, it is to avoid sizing material old
Change, obtain the pre-dispersed rubber master batch of graphene microchip of excellent performance.
The present invention is to use following technical scheme to realize:
The preparation method of the pre-dispersed rubber master batch of a kind of graphene microchip, passes through high-speed stirring including by graphene microchip dispersion liquid and latex
Mix machine stirring and be mixed to prepare mixed material, in above-mentioned mixed material, add flocculant make mixed material cohesion form slurry；
By slurry by being slightly dried, redrying prepares rubber master batch.
Mixed with latex by Graphene, flocculate formation slurry, and then carry out being dehydrated, be dried, can with continuous prodution,
Production efficiency is greatly improved compared with batch process；In rubber master batch, graphene microchip is capable of high degree of dispersion, combines in final products
Glue content is higher, and can realize quickly mixing and condense of latex and Graphene, drying time relative to method before
Shortening, energy consumption reduces, it is to avoid sizing material aging, obtains the pre-dispersed rubber master batch of graphene microchip of excellent performance.In dry run
Extrusion dehydration is combined with being dried, it is also possible to shorten drying time, reduce energy consumption.Can reduce rapidly during follow-up plasticating
Mooney viscosity, can save drying glue and power consumption of plasticating, and gained sizing material is in addition to mechanical property promotes, and heat reduces, endurance
Performance boost, can apply to the field such as tire and anti-vibration article.
Technique scheme, further, described when preparing mixed liquor the mixing speed of homogenizer be 400～
800rpm, mixing time is 20-40min.
Technique scheme, further, described thick is dried in three stages, and baking temperature interval is followed successively by 120～160
DEG C, 100～150 DEG C, 80～120 DEG C, drying time 5～30min.Stage by stage and the dry side that reduces successively of baking temperature
Formula, it is possible to increase drying efficiency, shortens drying time, reduces energy consumption.
Technique scheme, further, the solid content of described graphene microchip dispersion liquid is 0.1%～40%.
Technique scheme, further, the preparation method of described graphene microchip dispersion liquid is for lead to graphene microchip
Crossing homogenizer to be dispersed in water, mixing speed is 2000-3000rpm, and mixing time is 2-5h.
Technique scheme, further, the solid content of described latex is 30%～60%.
Technique scheme, further, described latex is 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.
Technique scheme, further, described flocculant be the sulphuric 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 for the process units of the pre-dispersed rubber master batch of a kind of graphene microchip, including mixing kettle, Sedimentation tank, is dried
Device；Described mixing kettle has material inlet, mixture outlet；Mixture outlet is connected by pipeline with Sedimentation tank；Flocculant
Storage tank is connected by pipeline with Sedimentation tank, is provided with measuring equipment between described flocculant storage tank and Sedimentation tank；Drying device, described
Drying device includes tablet machine one, tablet machine two, tablet machine three and the crepe machine being linked in sequence successively；Be arranged on Sedimentation tank with
Mechanical arm between drying device；The pH value monitoring device of liquid in detection Sedimentation tank.Graphene dispersing solution is mixing with latex
In still after mix homogeneously, enter Sedimentation tank by pipeline, can be facilitated by measuring equipment and be transported to sink by flocculant accurately
In fall pond, under the effect of flocculant, the mixed material in Sedimentation tank forms slurry, and mechanical arm is collected and carried by slurry
Thick being dried and redrying process is carried out in drying device；This device is capable of the serialization of graphene microchip dispersion rubber master batch
Produce, improve production efficiency, shorten drying time, reduce energy consumption, enhance product performance.It is heavy that pH value monitoring device is used for monitoring
The acid-base value of fall mediocre person's material, makes pH value control in the range of 4～6.The equipment manufacturing cost used in this process units is relatively low, enterprise
Self existing equipment can be utilized to transform, it is possible to alleviate enterprise's production cost, be suitable for promoting.
Technique scheme, further, also include for mixing kettle conveying latex latex cylinder, described latex cylinder with
The material inlet of mixing kettle is connected by pipeline；For preparation and to the Graphene agitator tank of mixing kettle conveying Graphene, institute
State Graphene agitator tank to be connected by pipeline with mixing kettle material inlet.
Technique scheme, further, also includes auxiliary agent filler measuring device, and described auxiliary agent filler measuring device is with mixed
Close still pipeline to connect, be added as needed on the auxiliary agents such as corresponding plasticizer age resistor environment protection oil.
Present invention process is simple, operation safety, it is possible to achieve large-scale continuous production, the preparation work of more original batch process
Skill improves production efficiency；Relative to melt-processed method, in the masterbatch that this method obtains, graphene microchip is capable of height point
Dissipate；And can realize quickly mixing and condensing relative to method before, the drying and dehydrating stage combines extrusion and is dried and dries
Mode shorten drying time, it is to avoid sizing material aging, obtain the pre-dispersed rubber master batch of graphene microchip of excellent performance.Actual
Application can reduce rapidly during plasticating Mooney viscosity, drying glue and power consumption of plasticating can be saved, gained sizing material except
Outside mechanical property promotes, heat reduces, fatigue performance promotes.Can realize on factory's existing equipment and Process ba-sis continuously
Metaplasia is produced, and simplifies the drying glue in application process and plasticating technology, reaches energy-conservation, improves the target of work efficiency, made
Standby sizing material has good physical and mechanical properties and functional.The present invention is prepared for different graphene microchip content and not
With rubber master batch scattered in elastomer substrates, graphene microchip can be dispersed in elastomeric compound, it is to avoid the reunion of self, contains
Measure controlled, and technique is simple, cost is relatively low, be the novel processing step of a kind of worth exploitation.
Accompanying drawing explanation
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 tank；5 Sedimentation tanks；6 measuring equipments；7pH
Value monitoring device；8 tablet machine one；9 tablet machine two；10 tablet machine three；11 crepe machines；12 auxiliary agent filler measuring devices.
Detailed description of the invention
In order to be more clearly understood from the above-mentioned purpose of the present invention, feature and advantage, below in conjunction with embodiment to this
Invention is described further.
Embodiment 1
(1) preparation of graphene microchip dispersion liquid
Take 600L water, 6kg graphene microchip joins in Graphene agitator tank 2, and under room temperature, 2500rpm high-speed stirred is disperseed 5 little
Time, prepare the graphene microchip aqueous dispersions that mass fraction is 1%.
(2) mixing of graphene microchip dispersion liquid/Heveatex and condensation
By pipeline, the graphene microchip aqueous dispersions prepared in Graphene agitator tank 2 is transported in mixing kettle 1, will simultaneously
Latex delivery in latex cylinder 3, in mixing kettle, controls fluid flow, the Heveatex making 1000kg dry rubber content be 60 % with
Time add in homogenizer, mixing speed is 400rpm, and mixing time is 40min, prepares mixed material；Mixed material is defeated
Deliver in Sedimentation tank 5；Flocculant storage tank 4 stores the CaCl that mass fraction is 10%2Solution, CaCl2Solution by metering
Equipment is transported in Sedimentation tank 5, through stirring, the slurry that the latex particle in Sedimentation tank 5 is formed with graphene microchip cohesion.
Detection Sedimentation tank is additionally provided with pH value monitoring device, for monitoring the acid-base value of material in Sedimentation tank, makes pH value control 6.
(3) dehydration of rubber master batch
Mechanical arm collects the slurry in Sedimentation tank, and is fed sequentially into tablet machine 1, pressure by after the washing of above-mentioned slurry dewatering
Slightly being dried in sheet machine 29, tablet machine 3 10, the thick temperature being dried is followed successively by 120 DEG C, 100 DEG C, 80 DEG C, drying time
30min, then carries out redrying by crepe machine 11, prepares rubber master batch.
(4) molding of rubber master batch
According to demand the material through processed is pressed into film.
(5) preparation of vulcanite
The rubber master batch of above-mentioned preparation and commercially available natural rubber are added mill according to the mass ratio of 1:9, by formula add vulcanizing agent,
The auxiliary agent such as age resistor, antioxidant i.e. obtains pre-dispersed elastomeric compound, prepares the vulcanite of graphene-containing microplate after sulfuration, and it is correlated with
Performance is as shown in table 1.
Embodiment 2
(1) preparation of graphene microchip dispersion liquid
Take 600L water, 1Kg dodecylbenzene sodium sulfonate joins in Graphene agitator tank 2, and stir prepared aqueous solution；Again will
30Kg graphene microchip joins in above-mentioned aqueous solution, and under room temperature, 3000rpm high-speed stirred is disperseed 3 hours, prepares mass fraction
It it is the graphene microchip aqueous dispersions of 5 %.
(2) mixing of graphene microchip dispersion liquid/Heveatex and condensation
By pipeline, the graphene microchip aqueous dispersions prepared in Graphene agitator tank 2 is transported in mixing kettle 1, will simultaneously
Latex delivery in latex cylinder 3, in mixing kettle 1, controls fluid flow, the Heveatex making 3000kg dry rubber content be 60 %
Being simultaneously introduced in homogenizer, mixing speed is 800rpm, and mixing time is 20min, prepares mixed material；By mixed material
It is transported in Sedimentation tank 5；Storing the acetic acid solution that mass fraction is 2 % in flocculant storage tank, acetic acid solution is set by metering
Standby 6 are transported in Sedimentation tank, through stirring, the slurry that the latex particle in Sedimentation tank 5 is formed with graphene microchip cohesion.Inspection
Survey in Sedimentation tank and be additionally provided with pH value monitoring device, for monitoring the acid-base value of material in Sedimentation tank, make pH value control 4.
(3) dehydration of rubber master batch
Mechanical arm collects the slurry in Sedimentation tank 5, and be fed sequentially into after above-mentioned slurry dewatering is washed tablet machine 1,
Slightly being dried in tablet machine 29, tablet machine 3 10, the thick temperature being dried is followed successively by 140 DEG C, 120 DEG C, 90 DEG C, drying time
30min, then carries out redrying by crepe machine, prepares rubber master batch.
(4) molding of rubber master batch
According to demand the material through processed is pressed into adhesive tape or pelletize processes.
(5) preparation of vulcanite
The rubber master batch of above-mentioned preparation and commercially available natural rubber are added mill according to the mass ratio of 1:7, by formula add vulcanizing agent,
The auxiliary agent such as age resistor, antioxidant i.e. obtains pre-dispersed elastomeric compound, prepares the vulcanite of graphene-containing microplate after sulfuration, and it is correlated with
Performance is as shown in table 1.
Embodiment 3
(1) preparation of graphene microchip dispersion liquid
Take 600L water, 2Kg dodecylbenzene sodium sulfonate joins in Graphene agitator tank, and stir prepared aqueous solution；Again will
240Kg graphene microchip joins in above-mentioned aqueous solution, and under room temperature, 3000rpm high-speed stirred is disperseed 5 hours, prepares mass fraction
It it is the graphene microchip aqueous dispersions of 40%.
(2) mixing of graphene microchip dispersion liquid/Heveatex and condensation
By pipeline, the graphene microchip aqueous dispersions prepared in Graphene agitator tank is transported in mixing kettle, simultaneously by glue
Latex delivery in breast tank, to mixing kettle kind, controls fluid flow, and the Heveatex making 1000kg dry rubber content be 60 % is simultaneously
Adding in homogenizer, mixing speed is 600rpm, and mixing time is 40min, prepares mixed material；Mixed material is carried
In Sedimentation tank；Flocculant storage tank stores the CaCl that mass fraction is 1%2Solution, CaCl2Solution defeated by measuring equipment
Deliver in Sedimentation tank, through stirring, the slurry that the latex particle in Sedimentation tank is formed with graphene microchip cohesion.Detection sedimentation
Pond is additionally provided with pH value monitoring device, for monitoring the acid-base value of material in Sedimentation tank, makes pH value control 5.
(3) dehydration of rubber master batch
Mechanical arm collects the slurry in Sedimentation tank 5, and be fed sequentially into after above-mentioned slurry dewatering is washed tablet machine 1,
Slightly being dried in tablet machine 29, tablet machine 3 10, the thick temperature being dried is followed successively by 160 DEG C, 150 DEG C, 120 DEG C, drying time
30min, then carries out redrying by crepe machine, prepares rubber master batch.
(4) molding of rubber master batch
According to demand the material through processed is pressed into blob of viscose.
(5) preparation of vulcanite
The rubber master batch of above-mentioned preparation and commercially available natural rubber are added mill according to the mass ratio of 3:7, by formula add vulcanizing agent,
The auxiliary agent such as age resistor, antioxidant i.e. obtains pre-dispersed elastomeric compound, prepares the vulcanite of graphene-containing microplate after sulfuration, and it is correlated with
Performance is as shown in table 1.
Embodiment 4
(1) preparation of graphene microchip dispersion liquid
Take 600L water, 0.5Kg dodecylbenzene sodium sulfonate joins in Graphene agitator tank, and stir prepared aqueous solution；Again
6kg graphene microchip being joined in above-mentioned aqueous solution, under room temperature, 2000rpm high-speed stirred is disperseed 3 hours, prepares mass fraction
It it is the graphene microchip aqueous dispersions of 1 %.
(2) mixing of graphene microchip dispersion liquid/Heveatex and condensation
By pipeline, the graphene microchip aqueous dispersions prepared in Graphene agitator tank is transported in mixing kettle, simultaneously by glue
Latex delivery in breast tank, to mixing kettle kind, controls fluid flow, and the Heveatex making 1000kg dry rubber content be 60 % is simultaneously
Adding in homogenizer, mixing speed is 600rpm, and mixing time is 40min, prepares mixed material；Mixed material is carried
In Sedimentation tank；Flocculant storage tank stores the CaCl that mass fraction is 1%2Solution, CaCl2Solution pass through measuring equipment
It is transported in Sedimentation tank, through stirring, the slurry that the latex particle in Sedimentation tank is formed with graphene microchip cohesion.Detection is heavy
Fall is additionally provided with pH value monitoring device in pond, for monitoring the acid-base value of material in Sedimentation tank, makes pH value control 5.5.
(3) dehydration of rubber master batch
Mechanical arm collects the slurry in Sedimentation tank, and is fed sequentially into tablet machine one, pressure by after the washing of above-mentioned slurry dewatering
Slightly being dried in sheet machine two, tablet machine three, the thick temperature being dried is followed successively by 140 DEG C, 120 DEG C, 100 DEG C, and drying time amounts to
30min, then carries out redrying by crepe machine, prepares rubber master batch.
(4) molding of rubber master batch
According to demand the material through processed is cut into micelle.
(5) preparation of vulcanite
The rubber master batch of above-mentioned preparation and commercially available natural rubber are added mill according to the mass ratio of 1:9, by formula add vulcanizing agent,
The auxiliary agent such as age resistor, antioxidant i.e. obtains pre-dispersed elastomeric compound, prepares the vulcanite of graphene-containing microplate after sulfuration, and it is correlated with
Performance is as shown in table 1.
Embodiment 5
(1) preparation of graphene microchip dispersion liquid
Take 600L water, 0.5kg dialkyl succinylsuccinate ester sodium sulfonate joins in Graphene agitator tank, and stir prepared aqueous solution；
48Kg graphene microchip being joined in above-mentioned aqueous solution, under room temperature, 3000rpm high-speed stirred is disperseed 2 hours, and preparation quality is divided
Number is the graphene microchip aqueous dispersions of 8%.
(2) mixing of graphene microchip dispersion liquid/styrene-butadiene latex and condensation
By pipeline, the graphene microchip aqueous dispersions prepared in Graphene agitator tank is transported in mixing kettle, simultaneously by glue
Latex delivery in breast tank, to mixing kettle kind, controls fluid flow, and the butadiene-styrene rubber breast making 400kg dry rubber content be 40 % is simultaneously
Adding in homogenizer, mixing speed is 800rpm, and mixing time is 20min, prepares mixed material；Mixed material is carried
In Sedimentation tank；Flocculant storage tank stores the NaCl solution that mass fraction is 25 %, NaCl solution pass through measuring equipment
It is transported in Sedimentation tank, through stirring, the slurry that the latex particle in Sedimentation tank is formed with graphene microchip cohesion.Detection is heavy
Fall is additionally provided with pH value monitoring device in pond, for monitoring the acid-base value of material in Sedimentation tank, makes pH value control 5.
(3) dehydration of rubber master batch
Mechanical arm collects the slurry in Sedimentation tank, and is fed sequentially into tablet machine one, pressure by after the washing of above-mentioned slurry dewatering
Slightly being dried in sheet machine two, tablet machine three, the thick temperature being dried is followed successively by 150 DEG C, 130 DEG C, 100 DEG C, and drying time amounts to
25min, then carries out redrying by crepe machine, prepares rubber master batch.
(4) molding of rubber master batch
According to demand the material through processed is pressed into film.
(5) preparation of vulcanite
The rubber master batch of above-mentioned preparation is added mill with commercially available butadiene-styrene rubber 1502 according to the mass ratio of 1:7, adds sulfur by formula
The auxiliary agents such as agent, age resistor, antioxidant i.e. obtain pre-dispersed elastomeric compound, prepare the vulcanite of graphene-containing microplate after sulfuration,
Its correlated performance is as shown in table 1.
Embodiment 6
(1) preparation of graphene microchip dispersion liquid
Take 600L water, 0.5Kg aliphatic acid polyethenoxy fat joins in Graphene agitator tank, and stir prepared aqueous solution；Will
64Kg graphene microchip joins in above-mentioned aqueous solution, and under room temperature, 2500rpm high-speed stirred is disperseed 5 hours, prepares mass fraction
It it is the graphene microchip aqueous dispersions of 14%.
(2) mixing of graphene microchip dispersion liquid/styrene-butadiene latex and condensation
By pipeline, the graphene microchip aqueous dispersions prepared in Graphene agitator tank is transported in mixing kettle, simultaneously by glue
Latex delivery in breast tank, to mixing kettle kind, controls fluid flow, and the butadiene-styrene rubber making 1000kg dry rubber content be 40 % breast is same
Time add in homogenizer, mixing speed is 800rpm, and mixing time is 20min, prepares mixed material；Mixed material is defeated
Deliver in Sedimentation tank；Flocculant storage tank is stored the NaCl solution that mass fraction is 25 %, being set by metering of NaCl solution
For being transported in Sedimentation tank, through stirring, the slurry that the latex particle in Sedimentation tank is formed with graphene microchip cohesion；Detection
Sedimentation tank is additionally provided with pH value monitoring device, for monitoring the acid-base value of material in Sedimentation tank, makes pH value control 6.
(3) dehydration of rubber master batch
Mechanical arm collects the slurry in Sedimentation tank, and is fed sequentially into tablet machine one, pressure by after the washing of above-mentioned slurry dewatering
Slightly being dried in sheet machine two, tablet machine three, the thick temperature being dried is followed successively by 150 DEG C, 120 DEG C, 90 DEG C, and drying time amounts to
20min, then carries out redrying by crepe machine, prepares rubber master batch.
(4) molding of rubber master batch
According to demand the material through processed is pressed into adhesive tape.
(5) preparation of vulcanite
The rubber master batch of above-mentioned preparation and commercially available butadiene-styrene rubber are added mill according to the mass ratio of 5:1, by formula add vulcanizing agent,
The auxiliary agent such as age resistor, antioxidant i.e. obtains pre-dispersed elastomeric compound, prepares the vulcanite of graphene-containing microplate after sulfuration, and it is correlated with
Performance is as shown in table 1.
Embodiment 7
(1) preparation of graphene microchip dispersion liquid
Take 600L water, 0.5Kg dodecylbenzene sodium sulfonate joins in Graphene agitator tank, and stir prepared aqueous solution；Will
30Kg graphene microchip joins in above-mentioned aqueous solution, and under room temperature, 1800rpm high-speed stirred is disperseed 2.5 hours, and preparation quality is divided
Number is the graphene microchip aqueous dispersions of 5%.
(2) mixing of graphene microchip dispersion liquid/styrene-butadiene latex and condensation
By pipeline, the graphene microchip aqueous dispersions prepared in Graphene agitator tank is transported in mixing kettle；By latex cylinder
In latex delivery to mixing kettle kind, control fluid flow, the butadiene-styrene rubber breast making 1000kg dry rubber content be 40 % adds simultaneously
Enter in homogenizer, auxiliary agent, filler are joined in mixing kettle by auxiliary agent filler measuring device simultaneously, above-mentioned material is high
Speed stirring, mixing speed is 800rpm, and mixing time is 20min, prepares mixed material；Mixed material is transported to Sedimentation tank
In；Flocculant storage tank stores the NaCl solution that mass fraction is 25 %, NaCl solution be transported to sink by measuring equipment
In fall pond, through stirring, the slurry that the latex particle in Sedimentation tank is formed with graphene microchip cohesion.In detection Sedimentation tank also
It is provided with pH value monitoring device, for monitoring the acid-base value of material in Sedimentation tank, makes pH value control 4.
(3) dehydration of rubber master batch
Mechanical arm collects the slurry in Sedimentation tank, and is fed sequentially into tablet machine one, pressure by after the washing of above-mentioned slurry dewatering
Slightly being dried in sheet machine two, tablet machine three, the thick temperature being dried is followed successively by 150 DEG C, 120 DEG C, 90 DEG C, and drying time amounts to
30min, then carries out redrying by crepe machine, prepares rubber master batch.
(4) molding of rubber master batch
According to demand the material through processed is pressed into blob of viscose.
(5) preparation of vulcanite
The rubber master batch of above-mentioned preparation is added mill, adds the auxiliary agents such as filler, vulcanizing agent, age resistor, antioxidant by formula and get final product
Pre-dispersed elastomeric compound, prepares the vulcanite of graphene-containing microplate after sulfuration, and its correlated performance is as shown in table 1.
Comparative example 1
By natural gum standard rubber in 50 DEG C of baking ovens after preliminary drying 20 minutes again double-roll type mill plasticate 2 minutes, add by formula
Various auxiliary agents, obtain natural glue sulfurating glue after sulfuration, and its correlated performance is as shown in table 1.
Comparative example 2
By the natural gum standard rubber of 100 mass parts in 50 DEG C of baking ovens after preliminary drying 20 minutes again double-roll type mill plasticate 2 minutes,
Add various auxiliary agents and the graphene microchip powder of 1 mass parts by formula, after sulfuration, obtain melt-processed method Graphene micro-
Tablet per day right glue vulcanizate, its correlated performance is 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, adds various auxiliary agents and 1 matter by formula
The graphene microchip powder of amount part, obtains melt-processed method graphene microchip/butadiene-styrene rubber vulcanizate, its correlated performance after sulfuration
As shown in table 1.
Comparative example 4
Homogenizer rotating speed is set to 400rpm, is separately added into Heveatex that 100kg dry rubber content is 60 % and quality is divided
Number is the acetic acid solution of 2 %, pass sequentially through after the slurry dewatering of formation being washed after mix and blend 30 min extruder dehydration,
No. three times drying machine is dried, and three times baking temperature is followed successively by 140 DEG C, 120 DEG C and 90 DEG C, discharging after being dried 30 minutes, obtains breast
Liquid solidification natural gum.
The mechanical property of the vulcanite prepared of embodiment 1-7 and comparative example 1-4, test index and method are as follows:
Hardness: GB/T531.1-2008；
Hot strength: GB/T528-2009；
Elongation at break: GB/T528-2009；
100% stress at definite elongation: GB/T528-2009；
Tearing strength: GB/T529-2008；
Thermostability: GB/T1699-1982；
Test result is as shown in table 1.
The mechanical strength of the vulcanite that the different sizing material of table 1 obtains and dynamic mechanical contrast
As can be seen from Table 1, the vulcanite prepared through rubber master batch method than be not added with graphene microchip vulcanite and
The mechanical property of vulcanite prepared by melt-blending process will be excellent, and 60 DEG C of fissipation factors also have a certain degree of fall
Low, the loss caused for reducing the resistance to rolling of tire has preferable effect.
Embodiment described above is only to be described, the preferred embodiment of the present invention not to the scope of the present invention
Being defined, on the premise of designing spirit without departing from the present invention, those of ordinary skill in the art are to technical scheme
The various deformation made and improvement, all should fall in the protection domain that present invention determine that.
Claims (10)
1. the preparation method of the pre-dispersed rubber master batch of graphene microchip, it is characterised in that include by graphene microchip dispersion liquid with
Latex is mixed to prepare mixed material by homogenizer stirring, adds flocculant and make mixed material coagulate in above-mentioned mixed material
Combinate form pulp thing；By slurry by being slightly dried, redrying prepares rubber master batch.
The preparation method of the pre-dispersed rubber master batch of graphene microchip the most according to claim 1, it is characterised in that: described preparation mixes
When closing liquid, the mixing speed of homogenizer is 400～800rpm, and mixing time is 20～40min.
The preparation method of the pre-dispersed rubber master batch of graphene microchip the most according to claim 1, it is characterised in that: described thick dry
In three stages, baking temperature interval is followed successively by 120～160 DEG C, 100～150 DEG C, 80～120 DEG C, drying time 5～30min.
4. according to the preparation method of the pre-dispersed rubber master batch of graphene microchip described in any one of claim 1-3, it is characterised in that: institute
The solid content stating graphene microchip dispersion liquid is 0.1%～40%.
The preparation method of the pre-dispersed rubber master batch of graphene microchip the most according to claim 4, it is characterised in that: described Graphene
The preparation method of microplate dispersion liquid is for be dispersed in water graphene microchip by homogenizer, and mixing speed is 2000-
3000rpm, mixing time is 2-5h.
6. according to the preparation method of the pre-dispersed rubber master batch of graphene microchip described in any one of claim 1-3, it is characterised in that: institute
State latex be solid content be 30%～60% Heveatex, styrene-butadiene latex, carboxylic styrene butadiene latex, NBR latex, carboxyl butyronitrile glue
One or more in breast, EPDM latex, polychloroprene latex, butyl latex.
7. according to the preparation method of the pre-dispersed rubber master batch of graphene microchip described in any one of claim 1-3, it is characterised in that: institute
State flocculant be the sulphuric acid of mass fraction 0.1%～25%, hydrochloric acid, acetic acid, calcium chloride solution, sodium chloride solution, Klorvess Liquid,
One or more in ethanol.
8. the process units of the pre-dispersed rubber master batch of graphene microchip, it is characterised in that include mixing kettle, Sedimentation tank, be dried dress
Put；Described mixing kettle has material inlet, mixture outlet；Mixture outlet is connected by pipeline with Sedimentation tank；Flocculant stores up
Tank is connected by pipeline with Sedimentation tank, is provided with measuring equipment between described flocculant storage tank and Sedimentation tank；Drying device, described dry
Dry device includes tablet machine one, tablet machine two, tablet machine three and the crepe machine being linked in sequence successively；It is arranged on Sedimentation tank with dry
Mechanical arm between dry device；The pH value monitoring device of liquid acid basicity in detection Sedimentation tank.
The process units of the pre-dispersed rubber master batch of graphene microchip the most according to claim 8, it is characterised in that also include for
To the latex cylinder of mixing kettle conveying latex, described latex cylinder is connected by pipeline with the material inlet of mixing kettle；For preparation also
And to the Graphene agitator tank of mixing kettle conveying Graphene, described Graphene agitator tank passes through pipeline with the material inlet of mixing kettle
Connect.
The process units of the pre-dispersed rubber master batch of graphene microchip the most according to claim 9, it is characterised in that also include helping
Agent filler measuring device, described auxiliary agent filler measuring device is connected by pipeline with mixing kettle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610677684.8A CN106084332B (en) | 2016-08-16 | 2016-08-16 | The preparation method and process units of the pre-dispersed rubber master batch of graphene microchip |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610677684.8A CN106084332B (en) | 2016-08-16 | 2016-08-16 | The preparation method and process units of the pre-dispersed rubber master batch of graphene microchip |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106084332A true CN106084332A (en) | 2016-11-09 |
| CN106084332B CN106084332B (en) | 2018-01-30 |
Family
ID=58069341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610677684.8A Expired - Fee Related CN106084332B (en) | 2016-08-16 | 2016-08-16 | The preparation method and process units of the pre-dispersed rubber master batch of graphene microchip |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106084332B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108329535A (en) * | 2018-03-21 | 2018-07-27 | 多凌新材料科技股份有限公司 | High dispersive graphene-rubber master batch and preparation method thereof |
| CN108410041A (en) * | 2018-01-31 | 2018-08-17 | 中国科学院长春应用化学研究所 | A kind of preparation method of white carbon wet masterbatch |
| CN108641133A (en) * | 2018-05-15 | 2018-10-12 | 浙江奋飞橡塑制品有限公司 | Graphene modified rubber and its preparation method and application |
| 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 |
| CN109306094A (en) * | 2018-10-18 | 2019-02-05 | 中轻联（大连）包装研究院有限公司 | The preparation method of graphene rubber master batches |
| CN109627530A (en) * | 2018-11-26 | 2019-04-16 | 国宏中晶集团有限公司 | A kind of wearing composite material and preparation method thereof containing graphene |
| CN110240736A (en) * | 2019-06-27 | 2019-09-17 | 海南中橡科技有限公司 | A kind of Heveatex multiphase cocurrent clotting method |
| 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 |
| 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 |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864098A (en) * | 2010-06-03 | 2010-10-20 | 四川大学 | Preparation method of polymer/graphene composite material through in situ reduction |
| CN102786726A (en) * | 2012-07-24 | 2012-11-21 | 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 |
| CN104072832A (en) * | 2014-06-27 | 2014-10-01 | 青岛大学 | Oil-filled and graphene oxide emulsion-filled co-coagulated rubber and preparation method thereof |
| CN104693546A (en) * | 2015-02-15 | 2015-06-10 | 北京化工大学 | Preparation method of high-performance graphene oxide/solution polymerized styrene-butadiene rubber composite material |
| EP2960205A1 (en) * | 2014-06-23 | 2015-12-30 | Solvay SA | Stable aqueous graphene suspension and its use in producing graphene polymer nanocomposites |
| 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 |
-
2016
- 2016-08-16 CN CN201610677684.8A patent/CN106084332B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864098A (en) * | 2010-06-03 | 2010-10-20 | 四川大学 | Preparation method of polymer/graphene composite material through in situ reduction |
| CN102786726A (en) * | 2012-07-24 | 2012-11-21 | 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 |
| CN104072832A (en) * | 2014-06-27 | 2014-10-01 | 青岛大学 | Oil-filled and graphene oxide emulsion-filled co-coagulated rubber and preparation method thereof |
| CN104693546A (en) * | 2015-02-15 | 2015-06-10 | 北京化工大学 | Preparation method of high-performance graphene oxide/solution polymerized styrene-butadiene rubber composite material |
| 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 |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108410041A (en) * | 2018-01-31 | 2018-08-17 | 中国科学院长春应用化学研究所 | A kind of preparation method of white carbon wet masterbatch |
| CN108329535A (en) * | 2018-03-21 | 2018-07-27 | 多凌新材料科技股份有限公司 | High dispersive graphene-rubber master batch and preparation method thereof |
| 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 |
| CN108641133A (en) * | 2018-05-15 | 2018-10-12 | 浙江奋飞橡塑制品有限公司 | Graphene modified rubber and its preparation method and application |
| 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 |
| CN109306094A (en) * | 2018-10-18 | 2019-02-05 | 中轻联（大连）包装研究院有限公司 | The preparation method of graphene rubber master batches |
| CN109627530A (en) * | 2018-11-26 | 2019-04-16 | 国宏中晶集团有限公司 | A kind of wearing composite material and preparation method thereof containing graphene |
| 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 |
| CN110240736A (en) * | 2019-06-27 | 2019-09-17 | 海南中橡科技有限公司 | A kind of Heveatex multiphase cocurrent clotting method |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106084332B (en) | 2018-01-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106084332A (en) | The preparation method of the pre-dispersed rubber master batch of graphene microchip and process units | |
| CN107325343B (en) | A kind of graphene/rubber composite material preparation method | |
| CN102604175B (en) | Method for preparing graphene oxide/white carbon black/rubber nanocomposite | |
| CN107457933A (en) | A kind of filler/rubber composite preparation method | |
| CN102786726B (en) | High performance XNBR vulcanized rubber containing graphene oxide and its preparation method | |
| CN103408801B (en) | Modified calcium carbonate for wear-resistant rubber shoe soles and preparation method thereof | |
| CN105459284A (en) | Liquid phase continuous mixing process of high dispersion carbon nanotube masterbatch and rubber product thereof | |
| CN106366418B (en) | The method of nano-graphite load graphene nanobelt modified poly ethylene film | |
| CN107501656B (en) | A kind of preparation method of the wear-resisting nitrile rubber of conduction | |
| CN102153792A (en) | Preparation method of wet process mixed natural rubber material | |
| CN103627040A (en) | Method for preparing pretreated white carbon black/natural rubber composite material | |
| CN102153794A (en) | Method for preparing polymer/clay nano-composite | |
| CN106589496A (en) | Functional rubber/modified graphene oxide composite material and preparation method thereof | |
| CN105419009A (en) | Method for preparing high-filling composite masterbatch through semi-open type superheated steam spray-drying method | |
| CN106279804A (en) | The preparation method of graphene microchip/white carbon black compounded rubber | |
| CN104710661A (en) | carboxy terminated nitrile rubber/graphene nanocomposite and preparation method thereof | |
| CN110734587B (en) | Method for preparing nitrile rubber from modified carbon black | |
| CN107312208A (en) | A kind of white carbon/rubber composite preparation method | |
| CN109705527A (en) | Graphene dispersion cream, preparation method and application method | |
| CN102964648B (en) | Insulation shielding material for mining rubber jacketed cable and preparation method of insulation shielding material | |
| CN110734590B (en) | Method for preparing emulsion polymerized styrene-butadiene rubber from ionic liquid and chitosan modified carbon black | |
| CN104033607B (en) | A kind of crystalline flake graphite compound seal plate and manufacture method | |
| CN107266733B (en) | A kind of carbon carbon/rubber composite material preparation method | |
| CN105690587B (en) | It is a kind of to be first atomized the rubber wet method mixing method remixed | |
| CN104877199A (en) | Method for preparing rubber masterbatch by calcium carbonate dispersed by lignin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180130 Termination date: 20180816 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |