CN109705488A - A kind of preparation method of graphene/PVC concentration masterbatch - Google Patents
A kind of preparation method of graphene/PVC concentration masterbatch Download PDFInfo
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Abstract
The present invention relates to technical field of composite materials, to solve the problems, such as that existing graphene/PVC masterbatch preparation cost is high, provide a kind of preparation method of graphene/PVC concentration masterbatch, comprising the following steps: (1) expansible graphite is heated and expanded, obtain graphite worm；(2) oxidation processes are added coupling agent and are modified；(3) plasticizer/PVC mixed liquor is being added, high speed dispersion obtains graphite worm/PVC slurry；(4) continuous circulation dispersion removing, obtains graphene/PVC slurry；(5) masterbatch is concentrated to get graphene/PVC in vacuum spray drying processing.Raw materials requirement of the present invention is at low cost, processing step is simple, low for equipment requirements, strong operability, it is easy to accomplish large-scale industrial production；The concentration masterbatch can add in normal the injection forming process as additive, do not need additional masterbatch prilling, reduce production cost.
Description
Technical field
The present invention relates to technical field of composite materials more particularly to a kind of graphene/PVC concentration masterbatch preparation methods.
Background technique
PVC is the plastics accomplished scale production earliest, and excellent anti-flammability, plasticity and low cost become mainly
One of plastic product.Its disadvantage is also obvious, not UV resistant, easy to oxidize, and mechanical property is common or even relatively low, does not add
Plasticizer is just more crisp, and plasticizer is easy to be lost or be diffused into surface etc..Due to non-conductive and not thermally conductive, it is necessary to pass through addition
Agent enhances these performances.
Graphene has intensity, modulus, thermal conductivity and the conductivity of superelevation, even if being added in high molecular material on a small quantity
The performance of high molecular material, such as thermally conductive, conductive, mechanical strength and modulus etc. can be significantly changed.PVC as plastics
It can be modified by addition graphene enhancing, due to the intensive ultraviolet sink effect and laminated structure of graphene, it is possible to reduce purple
Outside line aging prevents plasticizer from spreading and being lost, can keep the performance of PVC for a long time.
Highly oxidized graphene, i.e. graphene oxide do not have the intrinsic performance of graphene, current so-called graphite
Alkene majority is far below the intrinsic performance of graphene, is difficult from graphene oxide reduction gained, i.e. redox graphene, performance
Graphene intrinsic performance advantage is played to the maximum extent, and graphene oxide is easy accumulation again in reduction as graphite-structure
Cause the loss of graphene characteristic.Graphene oxide is made by the peroxide decomposition of graphite, although the graphite powder of raw material
It is cheap, use more than graphene oxide price made from the acid and oxidant of its 10 times of weight 50 dollars of per kilogram with
On, since largely using acid, the processing of acid waste liquid also occupies high cost, deals with improperly as public hazards.
As the PVC of low price, the Gao Teng of price will be caused by adding high-cost graphene, lose it in the market
Advantage, so the graphene modified as bulk product PVC must be low cost and with existing PVC production forming technology
And environmental protection formulae is compatible.Traditional plastic production technology is to squeeze solid powder and plastic grain using heating spiral rod injection molding machine
Cutting becomes particle after crin, cooling out.In the process, plastics and powder all bear high pressure and shearing force.Single layer first
Graphene is easy to tear since intensity is lower under the action of high shear force, and graphene powder is aggregate, in the mistake of extruding
It is easy to that the superposition again of graphene occurs in journey.So the Graphene powder as plastic applications must be perfect high-strength multilayer,
Surface, which carries out modification, to prevent from being superimposed again.Most of frosting tension is lower, and graphene surface needs modified increase to soak
Property, in order to increase the adhesive force between plastics and graphene, graphene surface needs to possess by increasing the idol of a variety of chemical bonds
It is modified to join agent.
It discloses and " low cost of graphene nano powder, large-scale production process and its uses in Chinese patent literature
Equipment ", notification number CN105417523A, the invention are had inexpensive, high-purity using the graphene of physical method removing preparation
The advantages of degree and high length-diameter ratio, physical property is more nearly the intrinsic performance of graphene, i.e., high-intensitive, high heat conductance and height electricity
Conductance.
Summary of the invention
The present invention provides a kind of low cost, can be mass-produced to overcome above-mentioned problems of the prior art
Graphene/PVC concentration masterbatch preparation method.
To achieve the goals above, the invention adopts the following technical scheme:
A kind of preparation method of graphene/PVC concentration masterbatch, comprising the following steps:
(1) expansible graphite is heated and is expanded, obtain graphite worm；
(2) surface of graphite worm is subjected to oxidation processes, coupling agent is added and is modified, obtains modified graphite worm；
(3) plasticizer/PVC mixed liquor is added in modified graphite worm, high speed dispersion obtains graphite worm/PVC slurry；
(4) by graphite worm PVC slurry with shear velocity >=10000/s condition continuously recycle dispersion removing, obtain graphene/
PVC slurry；
(5) graphene/PVC slurry is handled through vacuum spray drying and masterbatch is concentrated to get graphene/PVC.
The present invention is using the expansible graphite of high expansioning multiple as raw material, with surface oxidation technology and high shear removing dispersion
Technology is main technical support, and product is that masterbatch is concentrated in graphene/PVC of safety, and production equipment is all industrial equipment.
This technique uses sour intercalation and any expansible graphite for high-temperature expansion graphite worm raw material, high-temperature expansion graphite worm,
Especially high power expansion worm is suitble to the present invention.Hybrid technique carries out in same ribbon heating stirring kettle in each step.This
Invention is suitable for being prepared on a large scale inexpensive graphene/PVC high concentration masterbatch, and expansible graphite powder is made after high-temperature expansion
The graphite worm of high-specific surface area, the inner surface of the graphite worm after the modification of superoxidized modified and coupling agent with PVC solution and
Graphene suspension is made after being blended in high shear removing dispersion in plasticizer, and obtaining graphene mass content after dry is more than 10%
Grain products.The modified graphene in surface and environment-friendly plasticizer are compounded to form the concentration PVC masterbatch of high graphene content by this, should
Masterbatch, which is concentrated, can add in normal the injection forming process as additive, not need additional masterbatch prilling,
Reduce production cost.
Preferably, the expansion multiple of the expansible graphite is greater than 200 times in step (1)；The ratio of the graphite worm
Surface area is greater than 60m2/g；The heating expansion temperature of the expansible graphite is 600~1800 DEG C.
It is more than 350 times that the industrialization product of expansible graphite, which has easily reached expansion multiple, and specific surface area is more than 30 flat
Square rice/gram, the wall thickness of graphite worm honeycomb lacked 90 layers of carbon atom, and more preferably expanded graphite is that expansion multiple is more than
1000 times, specific surface area is more than 60 meters squared per grams, and the wall thickness of graphite worm honeycomb lacked 50 layers of carbon atom.Natural graphite
Be generally less than 10 meters squared per grams with a thickness of micron order its specific surface area, removing to nanoscale graphene needs more energy,
So expansion worm is more preferably raw material.China has tens of enterprises that can produce expansible graphite, such as Yichang new city stone
Ink, tsingtauite sea carbon materials, Qingdao Nan Shu graphite etc..Expansible graphite expands in 600 to 1200 DEG C of high temperature gas flow, such as
Expanded in the high-temperature atmosphere of combustion of natural gas, in order to obtain the worm of high carbon content, can also be expanded in high-temperature electric resistance furnace and
Expansion under microwave nitrogen environment is more preferable, expansion temperature should be higher than 1000 DEG C, more preferably more than 1200 DEG C be more preferably more than
1600 DEG C, and higher, impurity volatilizees during high-temperature process and nitrogen is discharged together, and the carbon content of graphite worm can be with
It obtains preferably being promoted while the nano-pore of generation is also the opening that sovent diffusion immerses, helium and other inertia also can be used
For gas as carrier gas, aerobic air etc. is not suitable as carrier gas because can react into graphite worm in 450 DEG C or more oxygen
For an oxygen and carbon dioxide.Air pressure in high speed exhaust fan attenuating furnace can be used to improve the volatility of impurity.
Preferably, in step (2), the process conditions of oxidation processes are as follows: by the hydrogen peroxide of 30~50wt% according to graphite
Worm: hydrogen peroxide weight ratio 1:(0.01~0.1) adding proportion be added in graphite worm, prior to normal-temperature reaction 10~
120min then heats to 80~100 DEG C of 10~60min of reaction.
Graphite worm is mixed with dioxygen water spray in ribbon heating, vacuum stirred tank, after reaction 10~120 minutes, heating
To 80~100 DEG C, continue stirring 10~60 minutes.Stirred tank can using electric heating or heating oil heating, meet 100 DEG C/h with
On heating rate.
Preferably, mixed by spraying using graphite worm in same ribbon heating stirring kettle with coupling agent in step (2),
The coupling agent is the amino silane Hydrolysis alcohol solution of 10~25wt%, such as aminopropyl trimethoxysilane or aminopropyl three
Ethoxysilane Hydrolysis alcohol solution, N-B (aminoethyl)-C- aminopropyl triethoxysilane ethanol solution etc.；The coupling agent
Addition mass ratio with graphite worm is 1:(0.05~0.5)；Modified condition are as follows: prior to reacting at room temperature 10~200min, then
20~300min is reacted after being warming up to 60~82 DEG C.
Preferably, the modified graphite worm and plasticizer/PVC mixed liquor addition mass ratio are 1 in step (3):
(5~30)；The plasticizer/PVC mixed liquor is by PVC with plasticizer, THF and methylene chloride according to weight ratio (10~50):
(10~50): (10~50): 100 are formulated.The plasticizer is epoxidized soybean oil and epoxidized soybean oil and other plasticising
Agent composition.
Preferably, carrying out high speed dispersion using vertical spiral band heating stirring kettle, the vertical spiral band adds in step (3)
Thermal agitation kettle is equipped with liquid spray mechanism；The vertical spiral band heating stirring kettle is described vertical using electric heating or heating oil heating
The heating rate of formula ribbon heating stirring kettle is greater than 100 DEG C/h；It is equipped in the vertical spiral band heating stirring kettle and turns to ribbon, from
On down direction see that the steering ribbon clockwise turns to mixing, rotate to be discharge counterclockwise.Steering ribbon makes stirred
Cheng Gengwei is abundant, mixing direction is adjusted, so that mixing, discharge switch at any time, while being advantageously implemented mixing, discharge program
Serialization improves production efficiency, can be realized graphene/PVC concentration masterbatch continuous production.
Preferably, the temperature of continuous circulation dispersion removing is controlled at 10~35 DEG C in step (4)；The graphene/
The partial size of graphene is less than 30 μm in PVC slurry.
Preferably, carrying out continuous circulation dispersion removing using high speed homogenization device in step (4)；The high speed homogenization
The revolving speed of device is greater than 2500r/min；The high speed homogenization device be high-shear homogenizer, high speed sand mill, high pressure homogenizer or
Colloid mills homogenizer.Preferably colloid mills homogenizer.
Although ultrasonic wave removing has been proved to be effective dispersing method, due to the low not optimal work of production efficiency
Skill, high-shear homogenizer and colloid mills are reasonable effective methods, can be worked under the conditions of higher temperatures and higher pressure, revolving speed
It can be more than 3000 turns, meet requirement and the multistage homogeneous of shear rate, multiple groups stator can be used in every section of link and turn
The combination of son, the distance between stator and rotor are higher apart from smaller shear efficiency at 50 to 200 microns.
Preferably, in step (5), in carrying out vacuum spray drying processing in vaccum spray drying tower, using infrared ray
It heats, temperature is higher than 100 DEG C in the vaccum spray drying tower, and pressure is lower than 3kPa, and all solvents is made to obtain vaporizing side by side
Out outside tower, solvent vapo(u)r passes through different temperatures condensing recovery different solvents, more environmentally protective.
Preferably, the mass percentage of graphene is greater than in the graphene/PVC concentration masterbatch in step (5)
10%, it is high graphene concentration.
Therefore, the invention has the following beneficial effects:
(1) raw materials requirement of the present invention is at low cost, processing step is simple, low for equipment requirements, and strong operability is easy to
Realize large-scale industrial production；
(2) the resulting graphene/PVC high concentration masterbatch of present invention process production has compatible with PVC production technology, can be improved
The advantages of intensity of PVC, UV resistant, service life, stability, conductivity, thermal conductivity, before wide application
Scape；
(3) the concentration masterbatch can add in normal the injection forming process as additive, not need additional masterbatch
Prilling reduces production cost.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of graphene of the present invention/PVC concentration masterbatch preparation method equipment therefor.
In figure: hopper 1, screw feeder 2, high temperature electrical heating expansion furnace 3, silicon carbide heating rod 4, air pump 5, vertical spiral
Band heating stirring kettle 6, discharge port 7, hot oil inlet 8, hot oil outlet 9, liquid spray mechanism 10 turn to ribbon 11, drive motor
12, dioxygen water storage tank 13, coupling agent storage tank 14, plasticizer/PVC mixing liquid storage tank 15, colloid mills homogenizer 16, mashing pump
17, discharge valve 18, flowmeter 19.
Specific embodiment
Below by specific embodiment, and in conjunction with attached drawing, the technical solutions of the present invention will be further described.
In the present invention, if not refering in particular to, all devices and raw material is commercially available or the industry is common are following
Method in embodiment is unless otherwise instructed conventional method in that art.
As shown in Figure 1, the structural schematic diagram of the preparation method equipment therefor of masterbatch is concentrated for graphene of the present invention/PVC, packet
Include the expansible graphite batch charging mechanism being made of hopper 1 and screw feeder 2, high temperature electrical heating expansion furnace 3, the heating of vertical spiral band
Stirred tank 6, dioxygen water storage tank 13, coupling agent storage tank 14, plasticizer/PVC mixing liquid storage tank 15 and colloid mills homogenizer 16,
Silicon carbide heating rod 4 is equipped in high temperature electrical heating expansion furnace, high temperature electrical heating expansion furnace is connected by air pump 5 with reaction kettle
It connects, be equipped in reaction kettle by drive motor 12, agitating shaft and turn to the rabbling mechanism and heat that ribbon 11 forms around agitating shaft
Oily heating mechanism, the upper end of reaction kettle are equipped with liquid spray mechanism 10, and lower end is equipped with discharge port 7, and reaction kettle outer wall is equipped with collet,
Collet lower end is equipped with hot oil inlet 8, and upper end is equipped with hot oil outlet 9；Oxidant storage tank and coupling agent storage tank are controlled by flowmeter 19
Flow processed, and be connected with liquid spray mechanism；The input end of colloid mills homogenizer passes through mashing pump 17 and reaction kettle
Discharge port is connected, and outlet end is connected with the upper end of reaction kettle, constitutes graphene recirculation gas stripper system, mashing pump and high speed glue
Body, which is ground, is equipped with discharge valve 18 between homogenizer, the rotation direction for turning to ribbon is adjustable, mixing when rotating forward, discharge when reverse.
Homogenizer used in the present invention is the configuration of this field high standard, and Charles Ross and can be referred to by representing design
Son Company(www.mixers.com).The flow of homogenizer is 2000 liters per hour, is made of 3 groups of stators and rotor, fixed
The distance between son and rotor are 150 microns, and less than the partial size of powder, revolving speed is 2950 revs/min.Colloid mills homogenizer is asked
With reference to Shanghai Yi Ken CM2000.
Embodiment 1
(1) 50 mesh expansible graphites are placed in hopper and electrical heating high-temperature expansion furnace is sent by screw feed, through 1000 DEG C
It is heated at high temperature expansion process, obtains the graphite worm of high-specific surface area, high-carbon content, about 600 times of the expansion multiple of worm, compare table
Area 70m2/ g, graphite worm, which is directly blown into vertical spiral band heating stirring kettle to kettle, by blower expires, and sprays into while stirring
The weight ratio of 30% hydrogen peroxide, worm and hydrogen peroxide is 1:0.1, and the flow of hydrogen peroxide can be controlled with flow pump, persistently be stirred
It mixes 30 minutes, 100 DEG C are warming up within a hour and maintain 50 minutes, lasting stirring is cooled to 50 DEG C or less；
(2) continue to stir worm, spray into 15wt% aminopropyl trimethoxysilane Hydrolysis alcohol solution, worm and coupling agent solution
Weight ratio be 1:0.3, the flow of coupling agent solution can control with flow pump, be stirred to react after sixty minutes, in a hour
80 DEG C are inside warming up to, stirring 60 minutes is continued, it is modified to complete surface；
(3) the PVC/ plasticizer solution of 25 times of graphite worm weight is added, continues to stir, the PVC and plasticizer epoxy of the solution
The weight ratio of soybean oil, THF and methylene chloride is 30:40:30:100, obtains viscous paste；
(4) change and turn to ribbon rotation direction, slurry is discharged, while starting mashing pump and high speed disperser, revolving speed is per minute
It 2950 turns, starts the cycle over removing and is dispersed to average grain diameter less than 30 microns, the test method of partial size is laser particle tester；
(5) it is then turned on discharge valve discharging, is sent into vaccum spray drying tower；The temperature of spray drying tower maintains 110 DEG C, very
Pneumatics power is 2kPa.Solvent vapo(u)r is recycled through cryogenic condensation.It obtains graphene/PVC and masterbatch, the content of graphene about 10% is concentrated.
Embodiment 2
(1) 50 mesh, 600 times of expansible graphites are placed in hopper and electrical heating high-temperature expansion furnace, warp is sent by screw feed
950 DEG C of high-temperature heating expansion process, obtain specific surface area 68m2The graphite worm of/g is being blown into vertical spiral band heating stirring kettle, side
The weight ratio of the hydrogen peroxide of stirring side penetrating 50%, worm and hydrogen peroxide is 1:0.05, and the flow of hydrogen peroxide can use flow pump
Control is persistently stirred 50 minutes, and 95 DEG C are warming up within a hour and is maintained 60 minutes, lasting stirring be cooled to 50 DEG C with
Under；
(2) continue to stir worm, spray into 20% aminopropyl triethoxysilane Hydrolysis alcohol solution, worm and coupling agent solution
Weight ratio is 1:0.35, and the flow of coupling agent solution can be controlled with flow pump, is stirred to react after sixty minutes, within a hour
80 DEG C are warming up to, stirring 60 minutes is continued, it is modified to complete surface；
(3) the PVC plasticizer solution of 5 times of graphite worm weight is added, continues to stir, the PVC of the solution and plasticizer, THF and
The weight ratio of methylene chloride is 30:40:30:100, and plasticizer is epoxidized soybean oil and the one-to-one mixture of DOP, obtains sticky slurry
Material；
(4) change the rotation direction for turning to ribbon, slurry is discharged, while starting mashing pump and colloid mills homogenizer, turn
It 2950 turns per minute of speed, starts the cycle over removing and is dispersed to average grain diameter less than 30 microns, the test method of partial size is laser particle
Tester；
(5) it is then turned on discharge valve discharging, is sent into vaccum spray drying tower；The temperature of spray drying tower maintains 110 DEG C, very
Pneumatics power is 2kPa.Solvent vapo(u)r is recycled through cryogenic condensation.It obtains graphene/PVC and masterbatch is concentrated, the content of graphene is about
12.5%.
Embodiment 3
(1) 50 mesh, 800 times of expansible graphites are placed in hopper and electrical heating high-temperature expansion furnace, warp is sent by screw feed
1800 DEG C of high-temperature heating expansion process, obtain specific surface area 83m2The graphite worm of/g is being blown into vertical spiral band heating stirring kettle, side
The weight ratio of the hydrogen peroxide of stirring side penetrating 50%, worm and hydrogen peroxide is 1:0.07, and the flow of hydrogen peroxide can use flow pump
Control is persistently stirred 50 minutes, and 100 DEG C are warming up within a hour and is maintained 50 minutes, lasting stirring be cooled to 50 DEG C with
Under；
(2) continue to stir worm, spray into 25%N-B (aminoethyl)-C- aminopropyl triethoxysilane ethanol solution, worm and idol
The weight ratio for joining agent solution is 1:0.3, and the flow of coupling agent solution can control with flow pump, be stirred to react after sixty minutes,
80 DEG C are warming up in one hour, continues stirring 60 minutes, it is modified to complete surface；
(3) the PVC plasticizer solution of 30 times of graphite worm weight is added, continues to stir, the PVC and plasticizer epoxy of the solution are big
The weight ratio of soya-bean oil, THF and methylene chloride is 25:50:25:100, obtains viscous paste；
(4) change the rotation direction for turning to ribbon, slurry is discharged, while starting mashing pump and colloid mills homogenizer, turn
It 2950 turns per minute of speed, starts the cycle over removing and is dispersed to average grain diameter less than 30 microns, the test method of partial size is laser particle
Tester；
(5) it is then turned on discharge valve discharging, is sent into vaccum spray drying tower；The temperature of spray drying tower maintains 110 DEG C, very
Pneumatics power is 2kPa.Solvent vapo(u)r is recycled through cryogenic condensation.It obtains graphene/PVC and masterbatch, the content of graphene about 11% is concentrated.
Graphene produced by the present invention/PVC concentration masterbatch application method is as follows:
By graphene made from embodiment 1/PVC concentration masterbatch respectively with additive amount 0wt% (comparative example), 5wt%, 10wt% and
20wt% and PVC/ epoxy soybean oil solution is formulated, and the weight ratio of PVC and epoxidized soybean oil is 10:1.With blender by three
Then person's mixing is molded into the stretching of 2mm thickness, thermal conductivity and conductivity test sample with injection molding machine, by national standard GB/T1040-2006
It is tested with 1410, thermal conductivity uses steady state method, and test result is as shown in table 1:
The test result of the different graphenes of table 1./PVC concentration masterbatch additive amount PVC performance
As can be seen from Table 1, PVC material made from graphene of the present invention/PVC concentration masterbatch is added not add relative to comparative example
The PVC material of graphene/PVC concentration masterbatch is added to have the advantages that higher mechanical strength, conductivity and thermal conductivity, and with adding
The increase of dosage, performance are further improved, and the graphene/PVC concentration for being primarily due to technique production of the invention is female
Graphene in material possesses the characteristics such as high intensity, high length-diameter ratio, highly conductive and high thermal conductivity.
The graphene of embodiment 2 and embodiment 3/PVC concentration masterbatch application method and performance and embodiment 1 are suitable, no
It repeats again.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the present invention in any form, and is not surpassing
There are also other variations and modifications under the premise of technical solution documented by claim out.
Claims (10)
1. a kind of graphene/PVC concentration masterbatch preparation method, which comprises the following steps:
(1) expansible graphite is heated and is expanded, obtain graphite worm；
(2) surface of graphite worm is subjected to oxidation processes, coupling agent is added and is modified, obtains modified graphite worm；
(3) plasticizer/PVC mixed liquor is added in modified graphite worm, high speed dispersion obtains graphite worm/PVC slurry；
(4) by graphite worm PVC slurry with shear velocity >=10000/s condition continuously recycle dispersion removing, obtain graphene/
PVC slurry；
(5) graphene/PVC slurry is handled through vacuum spray drying and masterbatch is concentrated to get graphene/PVC.
2. a kind of graphene according to claim 1/PVC concentration masterbatch preparation method, which is characterized in that step (1)
In, the expansion multiple of the expansible graphite is greater than 200 times；The specific surface area of the graphite worm is greater than 60m2/g；It is described can
The heating expansion temperature of expanded graphite is 600~1800 DEG C.
3. a kind of graphene according to claim 1/PVC concentration masterbatch preparation method, which is characterized in that step (2)
In, the process conditions of oxidation processes are as follows: by the hydrogen peroxide of 25~50wt% according to graphite worm: hydrogen peroxide weight ratio 1:(0.01
~0.1) adding proportion is added in graphite worm, prior to 10~120min of normal-temperature reaction, then heats to 80~100 DEG C instead
Answer 10~60min.
4. a kind of graphene according to claim 1/PVC concentration masterbatch preparation method, which is characterized in that step (2)
In, the coupling agent is the amino silane Hydrolysis alcohol solution of 10~25wt%；The addition matter of the coupling agent and graphite worm
Amount is than being 1:(0.05~0.5)；Modified condition are as follows: anti-after then heating to 60~82 DEG C prior to reacting at room temperature 10~200min
Answer 20~300min.
5. a kind of graphene according to claim 1/PVC concentration masterbatch preparation method, which is characterized in that step (3)
In, the modified graphite worm and plasticizer/PVC mixed liquor addition mass ratio are 1:(5~30)；The plasticizer/PVC is mixed
Conjunction liquid is by PVC with plasticizer, THF and methylene chloride according to weight ratio (10~50): (10~50): (10~50): 100 prepare
It forms.
6. a kind of graphene according to claim 1/PVC concentration masterbatch preparation method, which is characterized in that step (3)
In, high speed dispersion is carried out using vertical spiral band heating stirring kettle, the vertical spiral band heating stirring kettle is equipped with liquid spray mechanism；
The vertical spiral band heating stirring kettle is using electric heating or heating oil heating, heating rate of the vertical spiral with heating stirring kettle
Greater than 100 DEG C/h；It is equipped in the vertical spiral band heating stirring kettle and turns to ribbon, the steering ribbon clockwise turns to mixed
Material, rotates to be discharge counterclockwise.
7. a kind of graphene according to claim 1/PVC concentration masterbatch preparation method, which is characterized in that step (4)
In, the temperature of continuous circulation dispersion removing is controlled at 10~35 DEG C；The partial size of graphene is less than in the graphene/PVC slurry
30μm。
8. a kind of graphene according to claim 1/PVC concentration masterbatch preparation method, which is characterized in that step (4)
In, continuous circulation dispersion removing is carried out using high speed homogenization device；The revolving speed of the high speed homogenization device is greater than 2500r/min；
The high speed homogenization device is high-shear homogenizer, high speed sand mill, high pressure homogenizer or colloid mills homogenizer.
9. a kind of graphene according to claim 1/PVC concentration masterbatch preparation method, which is characterized in that step (5)
In, in progress vacuum spray drying processing in vaccum spray drying tower, using infrared heating, in the vaccum spray drying tower
Temperature is higher than 100 DEG C, and pressure is lower than 3kPa.
10. a kind of graphene according to claim 1/PVC concentration masterbatch preparation method, which is characterized in that step (5)
In, the mass percentage of graphene is greater than 10% in the graphene/PVC concentration masterbatch.
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| CN110423415A (en) * | 2019-07-17 | 2019-11-08 | 鄂尔多斯市紫荆创新研究院 | A kind of preparation method and masterbatch of graphene modified PVC composite material masterbatch |
| CN114479221A (en) * | 2022-03-21 | 2022-05-13 | 南通大学 | Graphene modified rubber composite material for tire tread and mixing method thereof |
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