CN109762305A - A kind of graphene master batch and preparation method thereof - Google Patents
A kind of graphene master batch and preparation method thereof Download PDFInfo
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- CN109762305A CN109762305A CN201910061162.9A CN201910061162A CN109762305A CN 109762305 A CN109762305 A CN 109762305A CN 201910061162 A CN201910061162 A CN 201910061162A CN 109762305 A CN109762305 A CN 109762305A
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Abstract
This application involves grapheme material fields, in particular to a kind of graphene master batch and preparation method thereof.A kind of preparation method of graphene master batch, the preparation method of graphene master batch, which is mainly comprised the steps that, is surface-treated fiber carrier using graphene slurry, obtains the fiber carrier i.e. intermediate product of surface coated graphite alkene；Intermediate product is surface-treated using polymer paste, the intermediate product for obtaining surface coated polymer coats material；Cladding material is granulated.Graphene agglomerate preparation method simple process provided by the present application, the cost of raw material is cheap to be easy to get, environmental protection, the not introducing of organic solvent, the equipment for also not needing complex and expensive, industrialized production easy to accomplish.
Description
Technical field
This application involves grapheme material fields, in particular to a kind of graphene master batch and preparation method thereof.
Background technique
Graphene has high conductivity, thermal conductivity, high specific surface area as a kind of novel two-dimentional carbon nanomaterial
With the excellent properties such as Young's modulus.Theoretical research shows that the room temperature thermal conductivity of single-layer graphene is currently known with highest
The material of thermal conductivity.
Polymer nanocomposites are by the way that by made from nanometer additive dispersion in a polymer matrix, research is sent out
It is existing, when using graphene as additive, when additive amount is lower, the performance of polymer can substantially enhance.But due to graphene ratio
Surface area is huge, and there are intrinsic Van der Waals force between graphene sheet layer, graphene sheet layer is very easy to reunite.
Summary of the invention
The embodiment of the present application is designed to provide a kind of graphene master batch and preparation method thereof, is intended to improve existing
Graphene composite material is easy the problem of reuniting.
The application first aspect provides a kind of preparation method of graphene master batch, and the preparation method of graphene master batch is mainly wrapped
Include following steps:
Fiber carrier is surface-treated using graphene slurry, obtain the fiber carrier of surface coated graphite alkene i.e. in
Between product；
Intermediate product is surface-treated using polymer paste, the intermediate product for obtaining surface coated polymer wraps
Cover material；
Cladding material is granulated.
A small amount of graphene can only be added when in the prior art using powder graphene and polymer prills, because of polymer powder
The particle of material is larger, so pre-compounding process is graphene coated in polymer particle surface, but covering amount is limited, polymer particles
Grain surface can only coat a small amount of graphene, therefore when the increase of graphene additive amount, most of graphenes cannot be coated to polymer
Particle surface, therefore will result in reunion when melting.
The application is surface-treated fiber carrier using graphene slurry, and graphene slurry is coated on fiber carrier
Outside, fiber can incite somebody to action a large amount of graphene-supported in fiber surface and not easy to reunite, solution as loading as carrier, graphene
It has determined the above problem.
One layer of polymeric film is coated on the surface of graphene, and fiber carrier, graphene and thin polymer film form " Sanming City
Control structure ", it can fall off in the follow-up process to avoid graphene.In addition, in subsequent graphene master batch preparation process, graphene
It two surfaces of lamella, can be to avoid reunion, it is hereby achieved that preferable dispersion respectively by fiber and polymer wrapped.
Method provided by the present application can use graphene slurry, but be not limited to graphene slurry, can be applicable in a variety of shapes
The graphene of state.In addition, the graphene master batch of the graphene containing high level, the stone of micro-scale can be made in the embodiment of the present application
Black alkene piece surface can come into full contact with polymer, can effectively solve the problems, such as to reunite between graphene sheet layer, make graphene
It is evenly dispersed in master batch, and mutually overlap joint forms comprehensive three-dimensional grapheme network.
It is above-mentioned that fiber carrier is carried out at surface using graphene slurry in some embodiments of the application first aspect
Reason, which specifically includes for fiber carrier to be placed in graphene slurry, to be impregnated or is padded, and is then dried；
Intermediate product is carried out being surface-treated to specifically include using polymer paste intermediate product is placed in polymer paste
In impregnated or padded, then dry.
The mode for impregnating or padding can make graphene uniform continuously be coated on fiber carrier surface, and have certain
Adhesive force.Graphene as much as possible can be made to be covered in fiber carrier surface by repeatedly impregnating or padding processing, increased
The content of graphene in final master batch.
One layer of polymeric is wrapped up in intermediate product surface by the way of impregnating or padding, forms intermediate product surface
Thin film, the mode for impregnating or padding are conducive to the comprehensive engagement of graphene and polymer, in one side of master batch preparation process
Face graphene can form mutually overlapped tridimensional network, coated polymer fiber carrier inside another aspect graphene,
Outside, which is formed by " sandwich " structure by polymer overmold, can effectively solve the problems, such as that master batch preparation process graphene is reunited.
In some embodiments of the application first aspect, above-mentioned fiber carrier is placed in graphene slurry impregnates
Perhaps it pads in step in such a way that multiple dipping perhaps repeatedly pads and dipping or carries out after padding every time every time
It is dry then to be impregnated or padded again.
In some embodiments of the application first aspect, graphene slurry is by including graphene, conductive additive, gathering
Close object and solvent composition.
Conductive additive is the combination for including one or more of conductive carbon black, graphite, carbon nanotube, carbon fiber
It is at least one.
Polymer is polyester, polyurethane, aqueous epoxy resins, phenolic aldehyde, polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidine
Appointing in ketone, polymaleic anhydride, poly-quaternary ammonium salt, polyacrylamide, hydrolyzed polyacrylamide or polyacrylic water-base resin
It anticipates one kind.
The solvent of graphene slurry includes the ethanol water that volume fraction is 10%-85%.
The mixed solution of water and ethyl alcohol can increase the dispersibility of graphene in the slurry as the solvent of graphene slurry,
Simultaneously pollution can be reduced to avoid other substances are introduced in graphene master batch.Conductive additive can increase leading for graphene
Electrical property, the use of conductive additive can not only reduce the dosage of graphene, promote effective dispersion of graphene, can also be right
The three-dimensional network that graphene is formed in master batch plays the role of improving reinforcement.Polymer is conducive to graphene in fiber carrier table
Film forming is sprawled in face, while being coated on graphene two sides, reduces the reunion of graphene.
In some embodiments of the application first aspect, the total solid content of graphene and conductive additive is 1%-8%；
The mass ratio of graphene and conductive additive is 1:0.1-1；The quality of graphene and conductive additive quality sum and polymer
Than for 1:0.1-10.
The graphene of 1%-8% and the solid content of conductive additive can be such that graphene in slurry covers in higher efficiency
In fiber carrier surface, continuous graphene sheet layer structure is formed.
In some embodiments of the application first aspect, the solvent of above-mentioned polymer paste is water, and consolidating for polymer contains
Amount is 1%-20%.
Polymer is set continuously to be attached to graphene surface.
In some embodiments of the application first aspect, above-mentioned fiber carrier diameter is less than 30um, preferably fiber carrier
Diameter is less than 5um.
Fiber carrier of the diameter less than 5um has biggish specific surface area, provides infinitely great sky for the attachment of graphene
Between, and fibre diameter is micro/nano level, the graphene and polymer of same scale may be implemented in fiber surface for graphene coated
It is compound.
In some embodiments of the application first aspect, the material of above-mentioned fiber carrier include terylene, polyamide fibre, polypropylene fibre,
Any one in spandex or vinal.
Polymer paste include polyester, polyurethane, epoxy, phenolic aldehyde, polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone,
Any one in polymaleic anhydride, poly-quaternary ammonium salt, polyacrylamide, hydrolyzed polyacrylamide or polyacrylics.
In some embodiments of the application first aspect, above-mentioned be granulated to cladding material further includes that will coat material to carry out before
The surface treatment of surface coated graphite alkene and at least once surface treatment of surface coated polymer at least once；Make fiber carrier
Interval cladding multi-layer graphene and multiple layer polymer.
It can make fiber carrier interval cladding multi-layer graphene and multiple layer polymer according to final demand.
In some embodiments of the application first aspect, the lamella size of above-mentioned graphene is 0.1 μm -25 μm.It can be with
Microcosmic graphene sheet layer structure is formed in fiber carrier surface.
A kind of graphene master batch, the preparation method for the graphene master batch that graphene master batch is provided by the application first aspect
It is made.
Graphene master batch provided by the embodiments of the present application can obtain the addition of high-content graphene, graphene and polymer
Multiple be coated in interval can effectively contact polymer conducive to melting process graphene two sides, form surface coated polymer
Graphene film avoids the reunion again of graphene, to obtain dispersion well.On fiber carrier surface, coated graphite alkene can be with
Make graphene master batch that there is mutually overlapped three-dimensional grapheme network, the performances such as the conductive, thermally conductive of master batch, far infrared and antibacterial are aobvious
It writes.
Detailed description of the invention
Technical solution in ord to more clearly illustrate embodiments of the present application, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only some embodiments of the application, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 shows the schematic diagram of internal structure of the graphene master batch of the application one embodiment offer.
Fig. 2 shows the surface sweeping electron microscopes for the graphene master batch that comparative example 1 provides；
Fig. 3 shows the surface sweeping electron microscope of the graphene master batch of the offer of comparative example 2；
Fig. 4 shows the surface sweeping electron microscope of the graphene master batch of the offer of embodiment 5.
Icon: 101- fiber carrier；The first graphene layer of 102-；103- first polymer layer；The second graphene layer of 104-；
105- the second polymer layer.
Specific embodiment
It, below will be in the embodiment of the present application to keep the purposes, technical schemes and advantages of the embodiment of the present application clearer
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Graphene master batch of the embodiment of the present application and preparation method thereof is specifically described below.
The application provides a kind of preparation method of graphene master batch, and the preparation method of graphene master batch mainly includes following step
It is rapid:
Fiber carrier is surface-treated using graphene slurry, obtain the fiber carrier of surface coated graphite alkene i.e. in
Between product.
Intermediate product is surface-treated using polymer paste, the intermediate product for obtaining surface coated polymer wraps
Cover material.
Cladding material is granulated.
Fiber carrier is surface-treated using graphene slurry, graphene slurry is coated on outside fiber carrier, it is fine
Dimension is used as carrier, and graphene is used as loading, can will be a large amount of graphene-supported in fiber surface, solving can only load on a small quantity
The problem of graphene.
In addition, graphene slurry is compared with for graphene powder, graphene can be made to spread in slurry as far as possible molten
Be conducive to graphene in agent, after surface treatment in fiber surface drawout, and in subsequent melt granulation process, drawout
Coated polymer has largely reduced and has rolled into a ball so as to reduce the curling fold of graphene in master batch on graphene two sides
Poly-, the later period uses the performance that can farthest play graphene.
Further, in some embodiments of the present application, fiber carrier is placed in graphene slurry carry out dipping or
Person is padded, and is then dried.
The mode for impregnating or padding can make graphene uniform continuously be coated on fiber carrier surface, and have certain
Adhesive force.Graphene as much as possible can be made to be covered in fiber carrier surface by repeatedly impregnating or padding processing, increased
The content of graphene in final master batch.
It is understood that the fiber carrier of surface coated graphite alkene can also lead in the other embodiments of the application
Other modes realization is crossed, for example, by using the mode etc. of spraying.
Further, in some embodiments of the present application, graphene slurry be by include graphene, conductive additive,
Polymer and solvent composition.
Conductive additive be include at least one of conductive carbon black, graphite, carbon nanotube and carbon fiber.
Polymer is polyester, polyurethane, aqueous epoxy resins, phenolic aldehyde, polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidine
Any one in ketone, polymaleic anhydride, poly-quaternary ammonium salt, polyacrylamide, hydrolyzed polyacrylamide or polyacrylic；
The solvent of graphene slurry includes the ethanol water that volume fraction is 10%-85%.
Further, the total solid content of graphene and conductive additive is 1%-8%；The matter of graphene and conductive additive
Amount is than being 1:0.1-1；The mass ratio of graphene and conductive additive quality sum and polymer is 1:0.1-10.
The mixed solution of water and ethyl alcohol can increase the dispersibility of graphene in the slurry as the solvent of graphene slurry,
Be conducive to graphene sprawling in fiber carrier or even graphene master batch, while it can be introduced to avoid in graphene master batch
His substance reduces pollution.Conductive additive can increase the electric conductivity of graphene, and the use of conductive additive can not only drop
The dosage of low graphene promotes effective dispersion of graphene, can also play to the three-dimensional network that graphene is formed in master batch
Improve the effect of reinforcement.Polymer in graphene slurry is conducive to graphene and forms a film in fiber carrier surface spreading, and graphite
Two surfaces of alkene can further decrease the reunion between graphene sheet layer prior to coating a small amount of polymer in slurry.1%-8%
Graphene and conductive additive solid content, graphene in slurry can be made to be covered in fiber carrier surface in higher efficiency,
Form continuous graphene sheet layer structure.
It is understood that in the other embodiments of the application, the solution in graphene slurry may be other, example
Such as acetone, water.
It should be noted that the solvent of graphene slurry is the ethanol water that volume fraction is 10%-85%.With graphite
The solvent of alkene slurry is compared for water, largely increases the dispersibility of graphene in the slurry.Further, graphene is starched
The solvent of material is the ethanol water that volume fraction is 30%-75%.In some embodiments of the present application, above-mentioned fiber carrier
Diameter is less than 30um, and further preferably, fibre diameter is less than 5um.
Fiber carrier of the diameter less than 5um has biggish specific surface area, provides infinitely great sky for the attachment of graphene
Between, and fibre diameter is micro/nano level, the graphene and polymer of same scale may be implemented in fiber surface for graphene coated
It is compound.
In some embodiments of the present application, the material of fiber carrier includes terylene, polyamide fibre, polypropylene fibre, spandex or poly- second
Any one in enol fiber.
Further, fiber carrier can be short fibre, fibre bundle, woven, braiding, knitting or non-woven fabric, wherein using
Fabric, which carries out graphene and the dual or multiple cladding of polymer, can significantly improve production efficiency, same graphene master batch preparation
It is to crush the support fabric of coated graphite alkene and polymer, is melted in screw extruder after then sufficiently drying powder
Melt extruding pelletization.
Further, in some embodiments of the present application, using the fiber carrier with odd-shaped cross section, such as Y type, ten
Font, triangle etc. can further increase the specific surface area of fiber；While increasing the load capacity of graphene, irregular table
Face can increase the impetus of graphene, increase adhesive force, avoid falling off.
In some embodiments of the present application, the lamella size of above-mentioned graphene is 0.1 μm -25 μm.
The lamella size of graphene, which is 0.1 μm -25 μm, can form microcosmic graphene sheet layer structure in fiber carrier surface.
Intermediate product is obtained after the coated graphite alkene of fiber carrier surface, then intermediate product is carried out using polymer paste
Surface treatment, the intermediate product for obtaining surface coated polymer coat material.
One layer of polymeric film is coated on the surface of graphene, and fiber carrier, graphene and thin polymer film form " Sanming City
Control structure ", graphene uniform can be made continuously to be supported on fiber carrier surface, polymer uniformly continuous is supported on graphene
Surface prepared to realize two surfaces efficiently contact with polymer comprehensively of graphene in subsequent graphene master batch
Cheng Zhong, two surfaces of graphene sheet layer, can be to avoid reunions, so as to obtain respectively by polymer fiber and polymer wrapped
It obtains and preferably disperses.
In some embodiments of the present application, intermediate product is placed in polymer paste and is impregnated or is padded, so
After be dried to obtain cladding material.
One layer of polymeric is wrapped up in intermediate product surface by the way of impregnating or padding, forms intermediate product surface
Thin film, the mode for impregnating or padding are conducive to increase the combination of graphene and polymer, and it is three-dimensional to form that mutually overlapped
Porous network structure.
It should be noted that in intermediate product surface, package one layer of polymeric can also in the other embodiments of the application
To use other means, such as sprays, wraps up in and the other modes such as set.
In some embodiments of the present application, the solvent of polymer paste is water, and the solid content of polymer is 1%-20%.
Solvent of the water as polymer paste, more environmentally friendly, cost is relatively low, in addition, will not be in final graphene master batch
Middle introducing other impurities.
The solid content of the polymer of 1%-20% can enable polymer to be continuously attached to graphene surface.
In some embodiments of the present application, polymer includes polyester, polyurethane, epoxy, phenolic aldehyde, polyvinyl alcohol, poly- second
Alkene pyrrolidone, polymaleic anhydride, poly-quaternary ammonium salt, polyethylene glycol, polyacrylamide, hydrolyzed polyacrylamide or polyacrylic acid
Any one in resinoid.
Cladding material is granulated.By pelletizing after cladding material progress melt blending, dispersion, extrusion, solidification.
Method graphene master batch preparation process provided by the present application is simple, and the cost of raw material is cheap to be easy to get, and environmental protection does not have
The introducing of solvent, the equipment for also not needing complex and expensive, industrialized production easy to accomplish.
Method provided by the present application is applicable in the graphene of variform, is not limited to graphene slurry, in addition, the application is implemented
Example can be in obtained graphene master batch of the graphene containing high level, and the graphene film surface of micro-scale can be filled with polymer
Tap touching, can effectively solve the problems, such as to reunite between graphene sheet layer, keep graphene evenly dispersed in master batch, and phase interconnection
It connects to form comprehensive three-dimensional grapheme network.
In some embodiments of the present application, above-mentioned be granulated to cladding material further includes that will coat material to carry out at least once before
The surface treatment of surface coated graphite alkene and at least once surface treatment of surface coated polymer；Coat fiber carrier interval
Multi-layer graphene and multiple layer polymer.
In other words, multi-layer graphene, multiple layer polymer can be coated in fiber carrier surface according to demand；With one layer of graphite
The mode of alkene, one layer of polymeric, another layer graphene, one layer of polymeric again.
The application provides a kind of graphene master batch, the preparation side that graphene master batch passes through graphene master batch provided by the present application
Method is made.
Fig. 1 shows the schematic diagram of internal structure of the graphene master batch of the application one embodiment offer, please refers to Fig. 1.
Graphene master batch include by except interior fiber carrier 101, the first graphene layer 102, first polymer layer 103,
Second graphene layer 104 and the second polymer layer 105.
Fiber carrier 101 and 102 boundary of the first graphene layer have that part is mutually interspersed, first polymer layer 103 and the
Two graphene layers, 104 boundary has part mutually interspersed.
It should be noted that one layer of graphene also can be set outside fiber carrier 101 in the other embodiments of the application
One layer of polymeric.The present embodiment is not limited thereof.
Graphene master batch provided by the embodiments of the present application can fall off to avoid graphene in the follow-up process, be conducive to melt
Graphite During The Process alkene two sides can effectively contact polymer, form the graphene film of surface coated polymer, avoid graphene again
Secondary reunion, to obtain dispersion well.Graphene master batch has mutually overlapped a three-dimensional grapheme network, the conduction of master batch,
The performances such as thermally conductive, far infrared and antibacterial are significant.
The feature of the application and performance are described in further detail with reference to embodiments.
Embodiment 1
A kind of graphene master batch is present embodiments provided, is mainly made by following steps:
Take the polyester fiber carrier of diameter 30um；Fiber carrier is placed in graphene slurry and is impregnated, is then dried
Obtain intermediate product；Graphene slurry is made of graphene, carbon nanotube and solvent, and graphene and carbon nanotube consolidates in slurry
Content is 1%, and the mass ratio of graphene and carbon nanotube is 5:2；The lamella size of graphene be 9 μm, graphene slurry it is molten
Agent is the ethanol water that volume fraction is 10%.
Intermediate product is placed in polymer paste and is impregnated and then be dried to obtain cladding material；Polymer is aqueous poly-
Ester；The solvent of polymer paste is water, and the solid content of polymer is 1%.
It repeats the above steps 3 times, obtains the coating of surface interval cladding multi-layer graphene and polymer.
Cladding material is granulated using double screw extruder.
Embodiment 2
A kind of graphene master batch is present embodiments provided, is mainly made by following steps:
Take the vinal carrier of diameter 20um；Fiber carrier is placed in graphene slurry and is padded, then
It is dried to obtain intermediate product；Graphene slurry is made of graphene, graphite, polyvinyl alcohol and solvent, graphene and stone in slurry
The solid content of ink is 3%, and the mass ratio of graphene and graphite is 8:2, and the lamella size of graphene is 7 μm, graphene slurry
Solvent is the ethanol water that volume fraction is 85%.
Intermediate product is placed in polymer paste and is padded, cladding material is then dried to obtain；Polymer is aqueous poly-
Vinyl alcohol；The solvent of polymer paste is water, and the solid content of polymer is 3%.
It repeats the above steps 2 times, obtains the coating of surface interval cladding multi-layer graphene and polymer.
Cladding material is granulated using double screw extruder.
Embodiment 3
A kind of graphene master batch is present embodiments provided, is mainly made by following steps:
Take the polypropylene fiber carrier of diameter 10um；Fiber carrier is placed in graphene slurry and is padded, is then dried to obtain
Intermediate product；Graphene slurry is made of graphene, conductive carbon black, carbon nanotube, polyacrylic acid and solvent；Graphite in slurry
The solid content of alkene, conductive carbon black and carbon nanotube is 3.5%, and the mass ratio of graphene, conductive carbon black and carbon nanotube is 6:3:
1, the solid content of polyacrylic acid is 2% in slurry；The lamella size of graphene is 5 μm, and the solvent of graphene slurry is volume point
The ethanol water that number is 30%.
Intermediate product is placed in polymer paste and is padded, cladding material is then dried to obtain；Polymer is aqueous poly-
Acrylic acid, the solvent of polymer paste are water, and the solid content of polymer is 1%.
It repeats the above steps 3 times, obtains the coating of surface interval cladding multi-layer graphene and polymer.It is squeezed using twin-screw
Machine is granulated cladding material out.
Embodiment 4
A kind of graphene master batch is present embodiments provided, is mainly made by following steps:
Take the polyester fiber carrier of diameter 5um；
Fiber carrier is placed in graphene slurry and is impregnated or is padded, intermediate product is then dried to obtain；Graphite
Alkene slurry is made of graphene, conductive carbon black, waterborne polyester and solvent, and the solid content of graphene and conductive carbon black is in slurry
2.5%, the mass ratio of graphene and conductive carbon black is 9:1, and the solid content of waterborne polyester is 2% in slurry, the lamella of graphene
Having a size of 7 μm, the solvent of graphene slurry is the ethanol water that volume fraction is 15%.
Intermediate product is placed in polymer paste and is impregnated or is padded, cladding material is then dried to obtain；Polymer
For waterborne polyester；The solvent of polymer paste is water, and the solid content of polymer is 1%.
It repeats the above steps 4 times, obtains the coating of surface interval cladding multi-layer graphene and polymer.
Cladding material is granulated using double screw extruder.
Embodiment 5
A kind of graphene master batch is present embodiments provided, is mainly made by following steps:
Take the polyester fiber carrier of diameter 14um；Fiber carrier is placed in graphene slurry and is padded, is then dried
Obtain intermediate product；Graphene slurry is made of graphene, aqueous polyurethane and solvent, and the solid content of graphene is in slurry
3%, the lamella size of graphene is 7 μm, and the solid content of aqueous polyurethane is 1.5%, and the solvent of graphene slurry is volume point
The ethanol water that number is 50%.
Intermediate product is placed in polymer paste and is impregnated or is padded, cladding material is then dried to obtain；Polymer
For aqueous polyurethane；The solvent of polymer paste is water, and the solid content of polymer is 1.5%.
It repeats the above steps 2 times, obtains the coating of surface interval cladding multi-layer graphene and polymer.
Cladding material is granulated using double screw extruder.
Comparative example 1
PET particle and graphene powder is used to be mixed with graphene mass fraction as 1% master batch.
Comparative example 2
It is mixed using PET powder with graphene powder, prepares the master batch that graphene mass fraction is 5%.
Test example 1
Sheet resistance test is carried out to the graphene master batch that embodiment 1- embodiment 5 provides, the results are shown in Table 1.
The performance test results for the graphene master batch that 1 embodiment 1-5 of table is provided
| Group | Sheet resistance (Ω) |
| Embodiment 1 | 107 |
| Embodiment 2 | 105 |
| Embodiment 3 | 104 |
| Embodiment 4 | 103 |
| Embodiment 5 | 104 |
As it can be seen from table 1 the electric conductivity that embodiment 1- embodiment 5 provides is preferable, the sheet resistance of embodiment 4 is low,
The graphene master batch provided better than embodiment 1- embodiment 3 and embodiment 5.
Test example 2
The picture of the graphene master batch of comparative example 1-2 and the offer of embodiment 5 is provided using surface sweeping Electronic Speculum.Fig. 2 shows
The surface sweeping electron microscope for the graphene master batch that comparative example 1 provides；Fig. 3 shows the surface sweeping electricity of the graphene master batch of the offer of comparative example 2
Mirror figure；Fig. 4 shows the surface sweeping electron microscope of the graphene master batch of the offer of embodiment 5.
The graphene that can be seen that comparative example 1-2 from Fig. 2-Fig. 3 is reunited obvious；The graphene that embodiment 5 provides is female
The graphene uniform dispersion of grain, and graphene is the state that drawout is presented.
Illustrate graphene master batch provided by the embodiments of the present application while having graphene content big and graphene dispersion
Good advantage.
The foregoing is merely preferred embodiment of the present application, are not intended to limit this application, for the skill of this field
For art personnel, various changes and changes are possible in this application.Within the spirit and principles of this application, made any to repair
Change, equivalent replacement, improvement etc., should be included within the scope of protection of this application.
Claims (10)
1. a kind of preparation method of graphene master batch, which is characterized in that the preparation method of the graphene master batch mainly include with
Lower step:
Fiber carrier is surface-treated using graphene slurry, obtains the i.e. intermediate production of fiber carrier of surface coated graphite alkene
Object；
The intermediate product is surface-treated using polymer paste, the intermediate product for obtaining surface coated polymer wraps
Cover material；
The cladding is expected to be granulated.
2. the preparation method of graphene master batch according to claim 1, which is characterized in that described to use graphene slurry pair
Fiber carrier carries out being surface-treated to specifically include for fiber carrier to be placed in graphene slurry being impregnated or being padded, and then does
It is dry；
It is described using polymer paste to the intermediate product carry out surface treatment specifically include the intermediate product is placed in it is poly-
It closes and is impregnated or padded in object slurry, then dry.
3. the preparation method of graphene master batch according to claim 2, which is characterized in that
The fiber carrier is placed in the graphene slurry impregnated perhaps pad in step using multiple dipping or
The mode repeatedly padded, and dipping or each pad are dried later and then are impregnated or padded again every time.
4. the preparation method of graphene master batch according to claim 1, which is characterized in that
The graphene slurry includes graphene, conductive additive, polymer and solvent；
The conductive additive includes at least one of conductive carbon black, graphite, carbon nanotube and carbon fiber；
The polymer is polyester, polyurethane, aqueous epoxy resins, phenolic aldehyde, polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidine
Appointing in ketone, polymaleic anhydride, poly-quaternary ammonium salt, polyacrylamide, hydrolyzed polyacrylamide and polyacrylic water-base resin
It anticipates one kind；
The solvent of the graphene slurry includes the ethanol water that volume fraction is 10%-85%.
5. the preparation method of graphene master batch according to claim 4, which is characterized in that
The total solid content of the graphene and the conductive additive is 1%-8%；The graphene and the conductive additive
Mass ratio be 1:0.1-1；The quality of the graphene and the conductive additive and be 1:0.1- with the mass ratio of polymer
10。
6. the preparation method of graphene master batch according to claim 1, which is characterized in that
The solvent of the polymer paste is water, and the solid content of polymer is 1%-20%.
7. the preparation method of graphene master batch according to claim 1, which is characterized in that
The fibre diameter is less than 30um；
Preferably, the fiber carrier diameter is less than 5um.
8. the preparation method of graphene master batch according to claim 1, which is characterized in that
The material of the fiber carrier includes any one in terylene, polyamide fibre, polypropylene fibre, spandex and vinal；Institute
Stating polymer paste includes polyester, polyurethane, aqueous epoxy resins, phenolic aldehyde, polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidine
Any one in ketone, polymaleic anhydride, poly-quaternary ammonium salt, polyacrylamide, hydrolyzed polyacrylamide and polyacrylic.
9. the preparation method of graphene master batch according to claim 1, which is characterized in that
It further include carrying out cladding material at the surface of surface coated graphite alkene at least once before being granulated to cladding material
The surface treatment of reason and at least once surface coated polymer；Keep the fiber carrier interval cladding multi-layer graphene and multilayer poly-
Close object.
10. a kind of graphene master batch, which is characterized in that the graphene master batch passes through the described in any item stones of claim 1-9
The preparation method of black alkene master batch is made.
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| CN109762305B (en) | 2021-09-10 |
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