CN109971233A - Graphene with high specific surface aggregation and preparation method thereof, graphene static conductive coating and preparation method thereof - Google Patents

Graphene with high specific surface aggregation and preparation method thereof, graphene static conductive coating and preparation method thereof Download PDF

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CN109971233A
CN109971233A CN201910283113.XA CN201910283113A CN109971233A CN 109971233 A CN109971233 A CN 109971233A CN 201910283113 A CN201910283113 A CN 201910283113A CN 109971233 A CN109971233 A CN 109971233A
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graphene
solvent
specific surface
solution
volatilization
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CN109971233B (en
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杨修宝
郑雅轩
刘天祥
成涛
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SIXTH ELEMENT (CHANGZHOU) Ltd
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SIXTH ELEMENT (CHANGZHOU) Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area
    • 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
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides

Abstract

The present invention provides a kind of graphene with high specific surface aggregation and preparation method thereof, graphene static conductive coating and preparation method thereof.Graphene content is 10wt%-30wt% in the graphene with high specific surface aggregation.The preparation method of the graphene with high specific surface aggregation includes, first disperse graphene in high volatile solvent, the high volatile-type solvent for being dispersed with graphene is mixed with low voc solvent again, it is separated by distillation out high volatile solvent again, graphene with high specific surface aggregation can be obtained, the high-specific surface area aggregation is semi-solid state.Graphene with high specific surface aggregation graphene content provided by the invention is high, is uniformly dispersed, and using more convenient, stability is more preferable, simple agitation can be uniformly dispersed.

Description

Graphene with high specific surface aggregation and preparation method thereof, graphene static conductive coating And preparation method thereof
Technical field
The invention belongs to field of nanometer material technology, it is related to a kind of graphene with high specific surface aggregation and preparation method thereof, system Standby technique and application, this method and technique are suitble to the production of the graphene with high specific surface aggregation of high-content.
Background technique
Graphene has lot of superiority energy as a kind of new material, such as intensity height, good conductivity, high-specific surface area, excellent Good heat conductivity etc.；Thus have in fields such as high-performance nano electronic device, field emmision material, reserves and sensors potential Application value.However, due to the high-specific surface area of graphene there is Van der Waals force in grapheme material between layers, thus It is easy to reunite；In practical applications, grapheme material needs to disperse in the medium, but grapheme material hydrophobic oleophobic, and easily Reunite, to be difficult to be scattered in various media, greatly limits its application.
To solve the graphene dispersion difficult problem in application process, graphene slurry comes into being.Compared to graphene Powder, graphene slurry is easy to use, easy dispersion, and it is i.e. dispersible to be added to composite system simple agitation.Currently, slurry There are mainly two types of preparation methods, first method be by graphene powder by the methods of modification, dispersing agent, grinding be distributed to it is molten Graphene slurry is made in agent；Second method is the method using mechanical stripping, directly in the liquid phase removes graphene and makes At graphene slurry.
But due to the high-specific surface area of graphene, a large amount of solvents is needed to be soaked.With graphene dispersion or removing The raising of degree soaks solvent required for graphene and also becomes more, increases so as to cause the viscosity of system.It is limited to dispersing apparatus Processing upper viscosity limit, the graphene content in graphene slurry is lower, and quality is higher, specific surface area is bigger, the number of plies is lower Graphene, preparation slurry in graphene content it is lower.According to research Acc.Chem.Res.46,14-22 (2013), it is single Layer graphene dispersing solution easily forms gel, concentration threshold 1mg/mL, i.e., 0.1%.In practical application, due to graphene quality It is different, the number of plies is more, and introduce dispersing agent, the means such as modification, the graphene content of graphene slurry generally 1%-10% it Between, particularly with high-specific surface area graphene (specific surface area be greater than 400m2/ g), graphene content is generally less than in slurry 5%.The slurry of this low graphene content, can introduce a large amount of solvents in use, seriously limit its in plastics, without molten The application in the fields such as agent coating, and the environmental protection policy current with China runs in the opposite direction.
The content of background technology part is only the technology that inventor is known, not the existing skill of natural representative this field Art.
Summary of the invention
For the prior art there are one or more of problem, the present invention designs a kind of two step method and prepares high-specific surface area Graphenes aggregations method, prepare the graphenes aggregations of the high-specific surface area of high-content, prepared aggregation is half Solid state, graphene content are 10%-30%.Purpose is to prepare that a kind of use is more convenient, to be easier to dispersion, stability better Graphene with high specific surface aggregation, simple agitation can be uniformly dispersed.Graphene with high specific surface aggregation is applied to stone In black alkene static conductive coating, graphene static conductive coating sheet resistance drops in finely dispersed graphene with high specific surface aggregation It is low, there is excellent electric conductivity.
Based on object above, the present invention provides a kind of graphene with high specific surface aggregation, in the aggregation, graphene Content be 10wt%-30wt%.
Preferably, the aggregation includes graphene, dispersing agent, stabilizer and low volatility solvent.
The content of graphene is very high in graphene with high specific surface aggregation, and the content of solvent is low, occupies little space, and gathers Collective is in semi-solid state, and viscosity is higher, and graphene dispersion is uniform, it is not easy to generate sedimentation and reunite.Solvent in aggregation For low volatility solvent, it is not easy to volatilize, stability is high, convenient for storage and use, by aggregation be applied to coating, plastics, Easily disperse when the fields such as rubber, simple agitation can be uniformly dispersed.The graphene content of aggregation is 10wt%-30wt%, stone Black alkene content is lower, and the content of solvent is more, and the state of aggregation is close to " dough " sample；Graphene content is higher, solvent Content is lower, and graphene surface obtains solvent adsorption more, and the state of aggregation is close to " dry powder " sample.Selection graphene contains Measure in 10wt%-30wt% is because the graphene in aggregation occurs when the content of graphene in aggregation is more than 30wt% Reunite, can not disperse again again, the application aspect in fields such as subsequent coating, plastics, rubber can make degradation.
According to an aspect of the present invention, the specific surface area of the graphene is greater than 400m2/g。
Preferably, the graphene is the graphene powder being prepared by chemical method or physical method.
It is further preferred that the graphene is the graphene powder being prepared by oxidation-reduction method.
According to an aspect of the present invention, the content of the dispersing agent is 10wt%-30wt%.
Preferably, the dispersing agent includes that fatty acid amide, acidic-group copolymer, esters of acrylic acid or esters of acrylic acid are embedding The combination of one or more of section copolymer.
According to an aspect of the present invention, the content of the stabilizer is 0.1wt%-10wt%.
Preferably, the stabilizer includes the N-Methyl pyrrolidone solution of modified polyurea, modified hydrogenated castor oil, swelling The combination of one or more of soil, titanate coupling agent, polyamide wax or polyethylene wax.
According to an aspect of the present invention, the content of the low volatility solvent is 30wt%-80wt%.
According to an aspect of the present invention, the rate of volatilization of the low volatility solvent is no more than butyl acetate volatilization speed The 20% of rate.
Preferably, the low volatility solvent includes propandiol butyl ether, diethylene glycol butyl ether, a contracting propylene glycol fourth Ether, diethylene glycol ethyl ether acetate ester, diethylene glycol monobutyl ether acetate, alcohol ester 12, DBE, butyl, adjacent benzene two The mixed solvent of one or more of formic acid dibutyl ester.
It is further preferred that the low volatility solvent is diethanol butyl ether.
The present invention also provides the preparation methods of graphene with high specific surface aggregation, first disperse graphene in high volatile In solvent, then the high volatile solvent for being dispersed with graphene mixed with low voc solvent, then is separated by distillation out height and waves Hair property solvent, can be obtained graphene with high specific surface aggregation.
According to an aspect of the present invention, the preparation method of the graphene with high specific surface aggregation includes following step It is rapid:
Step 1): graphene, dispersing agent, stabilizer and high rate of volatilization solvent are mixed, and dispersion, grinding obtain first Solution；
Step 2): the first solution is mixed with low volatility solvent, and dispersion obtains the second solution；
Step 3): the second solution of distillation obtains graphene with high specific surface aggregation.
Graphene, dispersing agent, stabilizer and high rate of volatilization solvent are mixed, by dispersing, grinding, by graphene uniform It is dispersed in high rate of volatilization solvent；Low volatility solvent is added, by dispersion, makes high rate of volatilization solvent and low volatilization Rate solvent forms mixed solution, and graphene uniform is enabled to be dispersed in mixed solution；High volatilization is removed by way of distillation again Rate solvent, so that graphene dispersion in low volatility solvent, forms graphene with high specific surface aggregation.Low volatilization speed Rate solvent is substantially non-volatile, increases content of the graphene in aggregation.
According to an aspect of the present invention, in step 1), the graphene, dispersing agent, stabilizer and high rate of volatilization are molten The mass ratio of agent is (0.1-5): (0.1-5): (0.001-1.7): (50-100), preferably (1-3): (1-3): (0.01-1): (80-100)。
Preferably, in step 1), the graphene, dispersing agent, stabilizer and high rate of volatilization solvent mass ratio be 2: 2:0.1:95.9。
According to an aspect of the present invention, the mixing of the graphene, dispersing agent, stabilizer and high rate of volatilization solvent is molten The viscosity of liquid is 90% of milling apparatus processing upper limit viscosity used by grinding.
Preferably, the viscosity of the mixed solution of the graphene, dispersing agent, stabilizer and high rate of volatilization solvent is 500- 5000mpa·s。
It is because increasing for graphene content can make slurry that the high graphene slurry of content can not be prepared in the prior art Viscosity increase, viscosity, which crosses conference, grind milling apparatus can not.Content of the graphene in high rate of volatilization solvent be not high, but It is to make the graphene of same amount in low volatilization speed by adding a small amount of high rate of volatilization solvent of low volatility solvent re-evaporation Content in rate solvent is higher than the content in high rate of volatilization solvent, to obtain the graphenes aggregations of high-content.
According to an aspect of the present invention, the graphene is the Graphene powder being prepared by chemical method or physical method Body.
Preferably, the graphene is the graphene powder being prepared by oxidation-reduction method.
It is further preferred that the specific surface area of the graphene is greater than 400m2/g。
According to an aspect of the present invention, the dispersing agent be fatty acid amide, acidic-group copolymer, esters of acrylic acid or The combination of one or more of acrylate based block copolymer.
As graphene increases in solution, it is easy to reunite, the viscosity of solution system can increase, and the addition of dispersing agent can The viscosity for reducing slurry, increases the dispersibility and mobility of graphene.
According to an aspect of the present invention, the stabilizer is the N-Methyl pyrrolidone solution of modified polyurea, modified hydrogen Change the combination of one or more of castor oil, bentonite, titanate coupling agent, polyamide wax or polyethylene wax.
Preferably, the stabilizer is the combination of polyamide wax and polyethylene wax.
According to an aspect of the present invention, the high rate of volatilization solvent is rate of volatilization not less than butyl acetate volatilization speed The solvent of rate.
Preferably, the high rate of volatilization solvent include butyl acetate, toluene, methanol, ethyl alcohol, isopropanol, ethyl acetate, The mixed solvent of one or more of acetone, butanone, methylene chloride, hexamethylene, carbon tetrachloride or tetrahydrofuran.
It is further preferred that the high rate of volatilization solvent is ethyl alcohol.
According to an aspect of the present invention, in step 1), described be separated into is stirred using dispersion machine.
Preferably, the mixing time of the dispersion machine is 10-30min, preferably 20min.
It is further preferred that the revolving speed of the dispersion machine is 400-1000rpm, preferably 800rpm.
According to an aspect of the present invention, in step 1), the milling apparatus that uses of grinding is horizontal sand mill, vertical Sand mill, basket type sand mill, three-roll grinder or homogenizer.
Preferably, the milling apparatus used that grinds is horizontal sand mill.
According to an aspect of the present invention, in step 1), the method for the grinding is by graphene, dispersing agent, stabilizer Partial size is ground to less than 10 μm with the mixed solution of high rate of volatilization solvent.
According to an aspect of the present invention, in step 2), the quality of first solution and the low volatility solvent Than for 100:(1-100), preferably 100:(1-30).
Preferably, in step 2), the mass ratio of first solution and the low volatility solvent is 100:6.
Graphene content is 10wt%-30wt% in the graphenes aggregations of high-specific surface area, low volatility solvent Depending on additive amount is mainly the content according to graphene in aggregation.When graphene, dispersing agent, stabilizer and high rate of volatilization When the mass ratio of solvent is 2:2:0.1:95.9, content of the graphene in the first solution is 2%, and dispersion effect is best, at this time When the mass ratio of the first solution and low volatility solvent being selected to be 100:6, the graphene of the high-specific surface area finally prepared gathers Graphene content is 20wt% in collective.Graphene content is that the graphenes aggregations of the high-specific surface area of 20wt% are applied to down Effect is best when swimming product, and by taking paint field as an example, the graphene for the high-specific surface area that graphene content is 20wt% is assembled When body is added in static conductive coating, the sheet resistance of coating is substantially reduced.
According to an aspect of the present invention, the rate of volatilization of the low volatility solvent is no more than butyl acetate volatilization speed The 20% of rate.
Preferably, the low volatility solvent includes propandiol butyl ether, diethylene glycol butyl ether, a contracting propylene glycol fourth Ether, diethylene glycol ethyl ether acetate ester, diethylene glycol monobutyl ether acetate, alcohol ester 12, DBE, butyl, adjacent benzene two The mixed solvent of one or more of formic acid dibutyl ester.
It is further preferred that the low volatility solvent is butyl.
According to an aspect of the present invention, in step 2), the dispersion is stirred using dispersion machine.
Preferably, the mixing time of the dispersion machine is 10-30min, preferably 20min.
It is further preferred that the revolving speed of the dispersion machine is 400-1000rpm, preferably 800rpm.
According to an aspect of the present invention, it when the dispersion, is ground after the completion of stirring.Grinding can make point of graphene Dissipate better effect.
Preferably, the time of the grinding is 1h-6h.
According to an aspect of the present invention, in step 3), the equipment of the distillation is the distillation equipment with condensing condition.
Preferably, the condensation temperature is -5 DEG C -5 DEG C, preferably 0 DEG C.
According to an aspect of the present invention, in step 3), the temperature of the distillation is 50-80 DEG C, preferably 55-65 DEG C.
Preferably, the time of the distillation is 1-10h, preferably 6h.
When high rate of volatilization solvent is mixed with low volatility solvent, because the volatility of high rate of volatilization solvent is very strong, It differs greatly with the rate of volatilization of low volatility solvent, by way of distillation, can remove high rate of volatilization solvent.Graphite Alkene is uniformly dispersing after dispersion in the mixed solution of high rate of volatilization solvent and low volatility solvent, when distillation is high When rate of volatilization solvent, as solvent tails off, the viscosity of system constantly increases, and the graphene of high-specific surface area can adsorb low volatilization Rate solvent changes entire solution from liquid condition to semi-solid state, or even is intended to dry powder.Graphene specific surface Product is bigger, and the ability for adsorbing low volatility solvent is stronger.And the content of graphene is higher, the content of low volatility solvent is got over Low, the graphene with high specific surface aggregation prepared more is intended to dry powder.Height is volatilized by way of distillation condensation Rate solvent recovery, is recycled, and meets the needs of industrial environment friendly and pollution-free, large-scale production.High-specific surface area stone The surface of black alkene aggregation coats this dispersing agent and low volatility solvent, and dispersion is also easy in downstream application.
The present invention also provides a kind of graphene static conductive coatings, using the graphene with high specific surface aggregation, packet It includes: acrylic resin soln, auxiliary rheological agents, graphene with high specific surface aggregation, organosilicon silicone grease, levelling agent, butyl acetate And dimethylbenzene.
Preferably, in parts by mass, when the graphene static conductive coating total number is 199.4 parts, acrylic resin is molten Liquid is 120 parts, auxiliary rheological agents are 18 parts, graphene with high specific surface aggregation is (2-6) part, organosilicon silicone grease is 0.4 part, stream Flat agent is 0.2 part, butyl acetate is 30 parts and dimethylbenzene is (24.8-28.8) part.
Preferably, acrylic resin accounts for the 50wt% of acrylic resin soln.
It is further preferred that the solvent in acrylic resin soln is dimethylbenzene or butyl acetate.
Preferably, the auxiliary rheological agents include acetylbutyrylcellulose solution and polyamide wax.
It is further preferred that the mass ratio of the acetylbutyrylcellulose and polyamide wax is 8:1.
Preferably, acetylbutyrylcellulose accounts for the 20wt% of acetylbutyrylcellulose solution.
It is further preferred that the solvent in the acetylbutyrylcellulose solution is butyl acetate.
Compared to the previous graphene slurry using low content, graphene static conductive coating uses graphene with high specific surface The additive amount of grapheme material is greatly lowered in aggregation；And graphene with high specific surface aggregation is semi-solid state, stone Black alkene is well dispersed, it is only necessary to graphene with high specific surface aggregation and other materials be mixed, graphene can be obtained Well dispersed graphene static conductive coating.Since graphene dispersion is uniform, the resistance of graphene static conductive coating is low, electric conductivity It can be excellent.Dimethylbenzene is different according to the difference of graphene additive amount.
Of the invention also provides the preparation method of graphene static conductive coating, prepares the graphene static conductive coating. The preparation method of graphene static conductive coating is, by acrylic resin soln, auxiliary rheological agents, the graphene with high specific surface Aggregation, organosilicon silicone grease, levelling agent, butyl acetate and dimethylbenzene mixing, dispersion stirring obtain graphene static conductive coating.
Preferably, the revolving speed for the dispersion machine that the dispersion stirring uses is 1000-2000rpm, preferably 1500rpm.
It is further preferred that the time of the dispersion stirring is 0.5-1.5h, preferably 1h.
Beneficial effects of the present invention:
The present invention proposes the preparation method of easy " two-step method ", prepares the graphene with high specific surface aggregation of high-content Body, graphene content are high, good using easy, easy dispersion, stability；The stone prepared using graphene with high specific surface aggregation Black alkene static conductive coating is uniformly dispersed, and sheet resistance is low, and electric conductivity is excellent.Superiority of the present invention is carried out by the following It illustrates:
1, " two-step method " preparation method proposed by the present invention is easy, distills the recyclable benefit of high rate of volatilization solvent of separation With, it is environment friendly and pollution-free, it is suitble to large-scale production.
2, graphene content is high in graphene with high specific surface aggregation of the invention, few using solvent, is able to solve existing There is low graphene content slurry in technology application field additive amount is big, the problem more than solvent usage, meet environmental requirement, except answering Outside for paint field, plastics, rubber etc. can also be applied to the field of solvent-susceptible.
3, graphene with high specific surface aggregation of the invention is semi-solid state, and system viscosity is high, and graphene will not sink Drop is reunited, and solvent rate of volatilization is slow, substantially non-volatile under room temperature, and stability is high, convenient for storage.
4, graphene with high specific surface aggregation of the invention can be uniformly dispersed using simple, easily dispersion, simple agitation.
5, in graphene static conductive coating, graphene with high specific surface aggregation is well dispersed, does not reunite, graphite Alkene static conductive coating sheet resistance is low, and electric conductivity is strong, and electric conductivity is not less than the graphite using common low graphene content slurry Alkene static conductive coating.
Detailed description of the invention
Attached drawing is used to provide further understanding of the present invention, and constitutes part of specification, with reality of the invention It applies example to be used to explain the present invention together, not be construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the pictorial diagram of the graphene with high specific surface aggregation of 30wt% graphene content；
Fig. 2 is the pictorial diagram of the graphene with high specific surface aggregation of 20wt% graphene content；
Fig. 3 is the pictorial diagram of the graphene with high specific surface aggregation of 10wt% graphene content；
Fig. 4 is the SEM photograph of graphene with high specific surface aggregation；
Fig. 5 is SEM photograph after graphene with high specific surface aggregation disperses in static conductive coating；
Fig. 6 is after the graphene with high specific surface aggregation of 35.7wt% graphene content disperses in static conductive coating SEM photograph；
Fig. 7 is SEM photograph after graphene powder disperses in static conductive coating.
Specific embodiment
Hereinafter, certain exemplary embodiments are simply just described.As one skilled in the art will recognize that Like that, without departing from the spirit or scope of the present invention, described embodiment can be modified by various different modes. Therefore, attached drawing and description are considered essentially illustrative rather than restrictive.
Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings, it should be understood that preferred reality described herein Apply example only for the purpose of illustrating and explaining the present invention and is not intended to limit the present invention.
As the first of the invention, embodiment there is provided a kind of graphene with high specific surface aggregation, aggregation packets Include graphene, dispersing agent, stabilizer and low volatility solvent.Wherein, the content of graphene is 10wt%-30wt%, such as: 10wt%, 11wt%, 12wt%, 15wt%, 18wt%, 20wt%, 22wt%, 25wt%, 28wt%, 29wt%, 30wt%, Deng.The content of dispersing agent be 10wt%-30wt%, such as: 10wt%, 11wt%, 12wt%, 15wt%, 18wt%, 20wt%, 22wt%, 25wt%, 28wt%, 29wt%, 30wt%, etc..The content of stabilizer is 0.1wt%-10wt%, example Such as: 0.1wt%, 0.2wt%, 0.3wt%, 0.5wt%, 0.8wt%, 1.0wt%, 2wt%, 3wt%, 5wt%, 8wt%, 9wt%, 9.2wt%, 9.5wt%, 9.8wt%, 9.9wt%, etc..The content of low volatility solvent is 30wt%-80wt%, Such as: 30wt%, 31wt%, 32wt%, 34wt%, 36wt%, 38wt%, 40wt%, 42wt%, 45wt%, 48wt%, 50wt%, 52wt%, 55wt%, 58wt%, 60wt%, 62wt%, 65wt%, 68wt%, 70wt%, 72wt%, 75wt%, 78wt%, 79wt%, 80wt%, etc..The specific surface area of graphene is greater than 400m2/ g is prepared by chemical method or physical method Made of graphene powder, preferably oxidation-reduction method.Dispersing agent includes fatty acid amide, acidic-group copolymer, esters of acrylic acid Or the combination of one or more of acrylate based block copolymer.Stabilizer includes the N- methylpyrrole of modified polyurea One or both of alkanone solution, modified hydrogenated castor oil, bentonite, titanate coupling agent, polyamide wax or polyethylene wax Above combination, the combination of preferred polyamide wax and polyethylene wax.The rate of volatilization of low volatility solvent is not more than acetic acid fourth The 20% of ester rate of volatilization, including propandiol butyl ether, diethylene glycol butyl ether, a contracting propandiol butyl ether, diethylene glycol ether One of acetate, diethylene glycol monobutyl ether acetate, alcohol ester 12, DBE, butyl, butyl phthalate Or two or more mixed solvents, preferred butyl.
The content of graphene is very high in graphene with high specific surface aggregation, and the content of solvent is low, occupies little space, and gathers Collective is in semi-solid state, and viscosity is higher, and graphene dispersion is uniform, it is not easy to and it generates sedimentation and reunites, the solvent in aggregation For low volatility solvent, it is not easy to volatilize, stability is high, convenient for storage and use, by aggregation be applied to coating, plastics, Easily disperse when the fields such as rubber, simple agitation can be uniformly dispersed.As shown in figure 4, stone in graphene with high specific surface aggregation Black alkene is uniformly dispersed, and does not generate reunion.The graphene content of aggregation is 10wt%-30wt%, and graphene content is lower, molten The content of agent is more.As shown in figure 3, the state of 10wt% graphene with high specific surface aggregation is close to " dough " sample；Graphite Alkene content is higher, and the content of solvent is lower.As shown in Fig. 2, the state of 20wt% graphene with high specific surface aggregation is " demifacet Half dry powder of group " sample；With the raising of graphene content, as shown in Figure 1, graphene surface obtains solvent adsorption more, 30wt% The state of graphene with high specific surface aggregation is close to " dry powder " sample.Select the content of graphene is in 10wt%-30wt% Because the graphene in aggregation is reunited when the content of graphene in aggregation is more than 30wt%, can not disperse again again, Application aspect in fields such as subsequent coating, plastics, rubber can make degradation.As shown in figure 5, aggregation of the invention exists Graphene dispersion is uniform after dispersing in static conductive coating, does not reunite.And as shown in fig. 6, the graphene of 35.7wt% content is super There is a large amount of reunite in the content for having crossed 30wt% after dispersing in static conductive coating；As shown in fig. 7, graphene powder is distributed to It after solvent, is added directly into static conductive coating, also will appear a large amount of graphenes in static conductive coating and reunite.
The preparation method of graphene with high specific surface aggregation be first disperse graphene in high rate of volatilization solvent, then The high rate of volatilization solvent for being dispersed with graphene is mixed with low volatility solvent, then is separated by distillation out high rate of volatilization Graphene with high specific surface aggregation can be obtained in solvent.Specific step is as follows:
Step 1): graphene, dispersing agent, stabilizer and high rate of volatilization solvent are mixed, and dispersion, grinding obtain first Solution；
Step 2): the first solution is mixed with low volatility solvent, and dispersion obtains the second solution；
Step 3): the second solution of distillation obtains graphene with high specific surface aggregation.
Graphene, dispersing agent, stabilizer and high rate of volatilization solvent are mixed, by dispersing, grinding, by graphene uniform It is dispersed in high rate of volatilization solvent；Low volatility solvent is added, by dispersion, makes high rate of volatilization solvent and low volatilization Rate solvent forms mixed solution, and graphene uniform is enabled to be dispersed in mixed solution；High volatilization is removed by way of distillation again Rate solvent, so that graphene dispersion in low volatility solvent, forms graphene with high specific surface aggregation.Low volatilization speed The amount of rate solvent is fewer than high rate of volatilization solvent, increases content of the graphene in aggregation.
In step 1), graphene, dispersing agent, stabilizer and high rate of volatilization solvent mass ratio be (0.1-5): (0.1- 5): (0.001-1.7): (50-100), such as: 0.1:0.1:0.001:50,1:1:0.01:80,1:1:0.01:97.99,2:2: 0.1:95.9,3:3:1:100,5:5:1.7:100, etc..As preferred embodiment, graphene, dispersing agent, stabilizer and height The mass ratio of rate of volatilization solvent is (1-3): (1-3): (0.01-1): (80-100), such as 1:1:0.01:80,1:1:0.01: 97.99,2:2:0.1:95.9,3:3:1:100, etc..As optimal embodiment, graphene, dispersing agent, stabilizer and height are waved The mass ratio for sending out rate solvent is 2:2:0.1:95.9.Graphene, dispersing agent, the mixing of stabilizer and high rate of volatilization solvent are molten The viscosity of liquid is 90% of milling apparatus processing upper limit viscosity used by grinding.Graphene, dispersing agent, stabilizer and high volatilization The viscosity of the mixed solution of rate solvent be 500-5000mpas, such as: 500mpas, 510mpas, 520mpas, 530mpa·s、540mpa·s、550mpa·s、600mpa·s、700mpa·s、800mpa·s、900mpa·s、 1000mpa·s、1200mpa·s、1400mpa·s、1500mpa·s、1800mpa·s、2000mpa·s、2200mpa·s、 2500mpa·s、2800mpa·s、3000mpa·s、3200mpa·s、3500mpa·s、3800mpa·s、4000mpa·s、 4200mpa·s、4500mpa·s、4800mpa·s、4900mpa·s、4950mpa·s、4960mpa·s、4970mpa·s、 4980mpas, 4990mpas, 5000mpas, etc..The high graphene slurry of content can not be prepared in the prior art is Because increasing for graphene content can be such that the viscosity of slurry increases, viscosity, which crosses conference, grind milling apparatus can not.Graphene exists Content in high rate of volatilization solvent is not high, but molten by adding a small amount of high rate of volatilization of low volatility solvent re-evaporation Agent keeps the graphene of same amount higher than the content in high rate of volatilization solvent in the content in low volatility solvent, thus The graphenes aggregations of high-content are obtained.The specific surface area of graphene is greater than 400m2/ g is by chemical method or physics legal system Graphene powder, preferably oxidation-reduction method made of standby.Dispersing agent includes fatty acid amide, acidic-group copolymer, acrylate The combination of one or more of class or acrylate based block copolymer.Stabilizer includes the N- methyl pyrrole of modified polyurea One of pyrrolidone solution, modified hydrogenated castor oil, bentonite, titanate coupling agent, polyamide wax or polyethylene wax or two Kind or more combination, the combination of preferred polyamide wax and polyethylene wax.The rate of volatilization of high rate of volatilization solvent is not less than acetic acid The rate of volatilization of butyl ester, comprising: butyl acetate, toluene, methanol, ethyl alcohol, isopropanol, ethyl acetate, acetone, butanone, dichloromethane The mixed solvent of one or more of alkane, hexamethylene, carbon tetrachloride or tetrahydrofuran, preferred alcohol.Dispersion, which uses, to divide Scattered machine is stirred, and time of stirring is 10-30min, such as: 10min, 12min, 14min, 15min, 18min, 20min, 22min, 24min, 25min, 26min, 28min, 29min, 30min, etc..The time of stirring preferred 20min.The revolving speed of dispersion machine For 400-1000rpm, such as: 400rpm, 410rpm, 420rpm, 430rpm, 440rpm, 450rpm, 500rpm, 550rpm, 600rpm、650rpm、700rpm、750rpm、800rpm、850rpm、900rpm、950rpm、960rpm、970rpm、980rpm、 990rpm, 1000rpm, etc..The preferred 800rpm of the revolving speed of dispersion machine.Grinding uses horizontal sand mill, vertical grinding machine, basket sand The milling apparatus such as grinding machine, three-roll grinder or homogenizer, preferably horizontal sand mill.Graphene, dispersion machine, stabilizer and height are waved The mixed solution of hair rate solvent is ground to partial size less than 10 μm, obtains the first solution.
In step 2), the mass ratio of the first solution and low volatility solvent is 100:(1-100), such as: 100:1, 100:2、100:3、100:4、100:5、100:6、100:8、100:10、100:12、100:15、100:18、100:20、100: 25、100:30、100:40、100:50、100:60、100:70、100:80、100:90、100:95、100:96、100:97、100: 98,100:99,100:100, etc..As preferred embodiment, the mass ratio of the first solution and low volatility solvent is 100:(1-30), such as: 100:1,100:2,100:3,100:4,100:5,100:6,100:8,100:10,100:12,100: 15,100:18,100:20,100:22,100:25,100:26,100:27,100:28,100:29,100:30, etc..As best Embodiment, the mass ratio of the first solution and low volatility solvent is 100:6.In the graphenes aggregations of high-specific surface area Graphene content is 10wt%-30wt%, and the additive amount of low volatility solvent is mainly according to graphene in aggregation Depending on content.When content of the graphene in the first solution is 2%, dispersion effect is best, and the first solution is selected to wave with low at this time When the mass ratio for sending out rate solvent is 100:6, graphene content is in the graphenes aggregations of the high-specific surface area finally prepared 20wt%.Graphene content is that effect is best when the graphenes aggregations of the high-specific surface area of 20wt% are applied to downstream product, By taking paint field as an example, the graphenes aggregations for the high-specific surface area that graphene content is 20wt% are added to static conductive coating When middle, the sheet resistance of coating is substantially reduced.The rate of volatilization of low volatility solvent is no more than butyl acetate rate of volatilization 20%, including propandiol butyl ether, diethylene glycol butyl ether, a contracting propandiol butyl ether, diethylene glycol ethyl ether acetate ester, a contracting second One or more of glycol monobutyl ether acetate, alcohol ester 12, DBE, butyl, butyl phthalate mix Bonding solvent, preferably butyl.Dispersion is stirred using dispersion machine, and the time of stirring is 10-30min, such as: 10min、12min、14min、15min、18min、20min、22min、24min、25min、26min、28min、29min、 30min, etc..The time of stirring preferred 20min.The revolving speed of dispersion machine is 400-1000rpm, such as: 400rpm, 410rpm, 420rpm、430rpm、440rpm、450rpm、500rpm、550rpm、600rpm、650rpm、700rpm、750rpm、800rpm、 850rpm, 900rpm, 950rpm, 960rpm, 970rpm, 980rpm, 990rpm, 1000rpm, etc..The revolving speed of dispersion machine is preferred 800rpm.When dispersion, ground after the completion of stirring, time of grinding is 1-6h, such as: 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, etc..Grinding can make the dispersion effect of graphene more preferably.
In step 3), the equipment of distillation has condensing unit, and condensation temperature is -5 DEG C -5 DEG C, such as: -5 DEG C, -4 DEG C, -3 DEG C, -2 DEG C, -1 DEG C, 0 DEG C, 1 DEG C, 2 DEG C, 3 DEG C, 4 DEG C, 5 DEG C, etc..Preferably 0 DEG C of condensation temperature.The temperature of distillation is 50-80 DEG C, Such as: 50 DEG C, 51 DEG C, 52 DEG C, 55 DEG C, 56 DEG C, 57 DEG C, 58 DEG C, 59 DEG C, 60 DEG C, 62 DEG C, 64 DEG C, 65 DEG C, 67 DEG C, 68 DEG C, 70 DEG C, 72 DEG C, 74 DEG C, 76 DEG C, 78 DEG C, 79 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, etc..Preferred 55-65 DEG C of vapo(u)rizing temperature, such as: 55 DEG C, 56 DEG C, 57 DEG C, 58 DEG C, 59 DEG C, 60 DEG C, 61 DEG C, 62 DEG C, 63 DEG C, 64 DEG C, 65 DEG C, etc..The time of distillation is 1-10h, such as: 1h, 1.5h, 2h, 3h, 4h, 5h, 5.5h, 6h, 6.5h, 7h, 8h, 9h, 9.5h, 10h, etc..The time of distillation preferred 6h.Height volatilization When rate solvent is mixed with low volatility solvent, by way of distillation, high rate of volatilization solvent can remove, graphene exists It is uniformly dispersing after dispersion in the mixed solution of high rate of volatilization solvent and low volatility solvent, when the high volatilization of distillation When rate solvent, as solvent tails off, the viscosity of system constantly increases, and the graphene of high-specific surface area can adsorb low volatility Solvent changes entire solution from liquid condition to semi-solid state, or even is intended to dry powder.Graphene specific surface area is got over Greatly, the ability for adsorbing low volatility solvent is stronger.And the content of graphene is higher, the content of low volatility solvent is lower, The graphene with high specific surface aggregation prepared more is intended to dry powder.By high rate of volatilization by way of distillation condensation Solvent recovery is recycled, and meets the needs of industrial environment friendly and pollution-free, large-scale production.Graphene with high specific surface The surface of aggregation coats this dispersing agent and low volatility solvent, and dispersion is also easy in downstream application.
As second of embodiment of the invention, a kind of graphene static conductive coating is illustrated, comprising: acrylic resin Solution, auxiliary rheological agents, the graphene with high specific surface aggregation of the first of the invention embodiment, organosilicon silicone grease, levelling agent, Butyl acetate and dimethylbenzene.In parts by mass, graphene static conductive coating total number is 199.4 parts, and acrylic resin soln is 120 parts, auxiliary rheological agents be 18 parts, graphene with high specific surface aggregation is (2-6) part, organosilicon silicone grease is 0.4 part, levelling agent For 0.2 part, butyl acetate be 30 parts and dimethylbenzene is (24.8-28.8) part；Wherein, acrylic resin accounts for acrylic resin soln 50wt%, the solvent in acrylic resin soln is dimethylbenzene or butyl acetate.Auxiliary rheological agents include acetylbutyrylcellulose The mass ratio of solution and polyamide wax, acetylbutyrylcellulose solution and polyamide wax is 8:1.Acetylbutyrylcellulose accounts for acetic acid The 20wt% of cellulose butyrate solution.Solvent in acetylbutyrylcellulose solution is butyl acetate.Compared to previous using low The graphene slurry of content, graphene static conductive coating use graphene with high specific surface aggregation, make adding for grapheme material Dosage is greatly lowered；And graphene with high specific surface aggregation is semi-solid state, graphene dispersion is good, it is only necessary to will be high Specific surface area graphenes aggregations and other materials are mixed, and the good graphene static conductive of graphene dispersion can be obtained and apply Material, since graphene dispersion is uniform, the resistance of graphene static conductive coating is low, and electric conductivity is excellent.
The preparation method of graphene static conductive coating include by acrylic resin soln, auxiliary rheological agents, the present invention the first Graphene with high specific surface aggregation, organosilicon silicone grease, levelling agent, butyl acetate and the dimethylbenzene mixing of embodiment, dispersion Stirring, obtains graphene static conductive coating.Dispersion stirring time be 0.5-1.5h, such as: 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.5h, etc..As preferred embodiment, the time for dispersing stirring is 1h.The revolving speed of the dispersion machine used for 1000-2000rpm, such as: 1000rpm, 1100rpm, 1200rpm, 1300rpm, 1400rpm, 1500rpm, 1600rpm, 1700rpm, 1800rpm, 1900rpm, 2000rpm, etc..As preferred embodiment party Formula, the revolving speed of the dispersion machine used is 1500rpm.
Superiority of the invention is further described below with reference to embodiment and comparative example:
Embodiment 1A:
Present embodiment illustrates a kind of preparation processes of graphene with high specific surface aggregation.
Step 1): the following raw material is provided:
Graphene (specific surface area 463m2/g) 2kg
Acrylate based block copolymer 2kg
Bentonite 0.1kg
Dehydrated alcohol 95.9kg
Step 2): the first solution of preparation:
Graphene, acrylate based block copolymer, bentonite and dehydrated alcohol are mixed, mixed solution is placed in dispersion 20min, dispersing speed 800rpm are stirred in machine；It reuses horizontal sand mill to be ground, is ground to partial size less than 10 μm, Obtain the first solution.
Step 3): the second solution of preparation:
It chooses butyl to mix as low volatility solvent with the first solution, the first solution and diethylene glycol fourth The mass ratio of ether is 100:2.6, then the mixed solution of butyl and the first solution is placed in dispersion machine and is stirred 20min, dispersing speed 800rpm obtain the second solution.
Step 4): using the distillation equipment for having condensing unit, the second solution is distilled.Vapo(u)rizing temperature is set in 55-65 DEG C, condensing unit temperature is set in 0 DEG C, recycles dehydrated alcohol, distills 6h.High-specific surface area stone is obtained after terminating distillation Black alkene aggregation, the content of graphene is 29.9% in aggregation.
Embodiment 1B:
Present embodiment illustrates graphene with high specific surface aggregations made from the method using embodiment 1A to prepare graphite The method of alkene static conductive coating.
Step 1): following components is mixed:
Acrylic resin soln 120g
Acetylbutyrylcellulose solution 16g
Polyamide wax 2g
Graphene with high specific surface aggregation 2g
Organosilicon silicone grease 0.4g
Levelling agent 0.2g
Butyl acetate 30g
Dimethylbenzene 28.8g
Wherein, acrylic resin accounts for 50wt% in acrylic resin soln, and the solvent in acrylic resin soln is diformazan Benzene.Acetylbutyrylcellulose accounts for the 20wt% of acetylbutyrylcellulose solution, and solvent is butyl acetate.
Step 2): the mixed solution that step 1) is obtained, which is placed in dispersion machine, stirs 1h, dispersing speed 1500rpm, Obtain static conductive coating.
Mode coating and plastic base surface using aerial spraying use the face electricity of megger test static conductive coating Resistance, the resistance value of sheet resistance are 107Ω。
Embodiment 2A:
Present embodiment illustrates a kind of preparation processes of graphene with high specific surface aggregation.
Step 1): the following raw material is provided:
Graphene (specific surface area 490m2/g) 2kg
Acrylate based block copolymer 2kg
Bentonite 0.1kg
Dehydrated alcohol 95.9kg
Step 2): the first solution of preparation:
Graphene, acrylate based block copolymer, bentonite and dehydrated alcohol are mixed, mixed solution is placed in dispersion 20min, dispersing speed 800rpm are stirred in machine；It reuses horizontal sand mill to be ground, is ground to partial size less than 10 μm, Obtain the first solution.
Step 3): the second solution of preparation:
It chooses butyl to mix as low volatility solvent with the first solution, the first solution and diethylene glycol fourth The mass ratio of ether is 100:3, then the mixed solution of butyl and the first solution is placed in dispersion machine and stirs 20min, Dispersing speed is 800rpm, obtains the second solution.
Step 4): using the distillation equipment for having condensing unit, the second solution is distilled, vapo(u)rizing temperature is set in 55-65 DEG C, condensing unit temperature is set in 0 DEG C, recycles dehydrated alcohol, distills 6h.High-specific surface area stone is obtained after terminating distillation Black alkene aggregation, the content of graphene is 28.2% in aggregation.
Embodiment 2B:
Present embodiment illustrates graphene with high specific surface aggregations made from the method using embodiment 2A to prepare graphite The method of alkene static conductive coating.
Step 1): following components is mixed:
Acrylic resin soln 120g
Acetylbutyrylcellulose solution 16g
Polyamide wax 2g
Graphene with high specific surface aggregation 2.1g
Organosilicon silicone grease 0.4g
Levelling agent 0.2g
Butyl acetate 30g
Dimethylbenzene 28.7g
Wherein, acrylic resin accounts for 50wt% in acrylic resin soln, and the solvent in acrylic resin soln is diformazan Benzene.Acetylbutyrylcellulose accounts for the 20wt% of acetylbutyrylcellulose solution, and solvent is butyl acetate.
Step 2): obtain mixed solution is placed in dispersion machine of step 1) is stirred into 1h, dispersing speed is 1500rpm obtains static conductive coating.
Mode coating and plastic base surface using aerial spraying use the face electricity of megger test static conductive coating Resistance, the resistance value of sheet resistance are 107Ω。
Embodiment 3A:
Present embodiment illustrates a kind of preparation processes of graphene with high specific surface aggregation.
Step 1): the following raw material is provided:
Graphene (specific surface area 550m2/g) 2kg
Fatty acid amide 2kg
Bentonite 0.1kg
Dehydrated alcohol 95.9kg
Step 2): the first solution of preparation:
Graphene, fatty acid amide, bentonite and dehydrated alcohol are mixed, mixed solution is placed in dispersion machine and is stirred 20min, dispersing speed 800rpm；It reuses horizontal sand mill to be ground, is ground to partial size less than 10 μm, obtains first Solution.
Step 3): the second solution of preparation:
It chooses butyl to mix as low volatility solvent with the first solution, the first solution and diethylene glycol fourth The mass ratio of ether is 100:4, then the mixed solution of butyl and the first solution is placed in dispersion machine and stirs 20min, Dispersing speed is 800rpm, obtains the second solution.
Step 4): using the distillation equipment for having condensing unit, the second solution is distilled, vapo(u)rizing temperature is set in 55-65 DEG C, condensing unit temperature is set in 0 DEG C, recycles dehydrated alcohol, distills 6h.High-specific surface area stone is obtained after terminating distillation Black alkene aggregation, the content of graphene is 24.7% in aggregation.
Embodiment 3B:
Present embodiment illustrates graphene with high specific surface aggregations made from the method using embodiment 3A to prepare graphite The method of alkene static conductive coating.
Step 1): following components is mixed:
Acrylic resin soln 120g
Acetylbutyrylcellulose solution 16g
Polyamide wax 2g
Graphene with high specific surface aggregation 2.4g
Organosilicon silicone grease 0.4g
Levelling agent 0.2g
Butyl acetate 30g
Dimethylbenzene 28.4g
Wherein, acrylic resin accounts for 50wt% in acrylic resin soln, and the solvent in acrylic resin soln is diformazan Benzene.Acetylbutyrylcellulose accounts for the 20wt% of acetylbutyrylcellulose solution, and solvent is butyl acetate.
Step 2): the mixed solution that step 1) is obtained, which is placed in dispersion machine, stirs 1h, dispersing speed 1500rpm, Obtain static conductive coating.
Mode coating and plastic base surface using aerial spraying use the face electricity of megger test static conductive coating Resistance, the resistance value of sheet resistance are 107Ω。
Embodiment 4A:
Present embodiment illustrates a kind of preparation processes of graphene with high specific surface aggregation.
Step 1): the following raw material is provided:
Graphene (specific surface area 605m2/g) 2kg
Esters of acrylic acid block copolymer dispersant solution 5kg
Bentonite 0.1kg
Dehydrated alcohol 92.9kg
In esters of acrylic acid block copolymer dispersant solution include acrylate based block copolymer and butyl acetate, Middle acrylate based block copolymer accounts for the 40wt% of dispersant solution.
Step 2): the first solution of preparation:
Graphene, esters of acrylic acid block copolymer dispersant solution, bentonite and dehydrated alcohol are mixed, will be mixed molten Liquid, which is placed in dispersion machine, stirs 20min, dispersing speed 800rpm；It reuses horizontal sand mill to be ground, is ground to grain Diameter obtains the first solution less than 10 μm.
Step 3): the second solution of preparation:
It chooses butyl to mix as low volatility solvent with the first solution, the first solution and diethylene glycol fourth The mass ratio of ether is 100:4.5, then the mixed solution of butyl and the first solution is placed in dispersion machine and is stirred 20min, dispersing speed 800rpm obtain the second solution.
Step 4): using the distillation equipment for having condensing unit, the second solution is distilled, vapo(u)rizing temperature is set in 55-65 DEG C, condensing unit temperature is set in 0 DEG C, recycles dehydrated alcohol and butyl acetate, distills 6h.Height is obtained after terminating distillation Specific surface area graphenes aggregations, the content of graphene is 23.3% in aggregation.The dispersing agent of 40wt% in dispersant solution Except be solvent butyl acetate, solvent distillation when can be distilled off together.
Embodiment 4B:
Present embodiment illustrates graphene with high specific surface aggregations made from the method using embodiment 4A to prepare graphite The method of alkene static conductive coating.
Step 1): following components is mixed:
Acrylic resin soln 120g
Acetylbutyrylcellulose solution 16g
Polyamide wax 2g
Graphene with high specific surface aggregation 2.6g
Organosilicon silicone grease 0.4g
Levelling agent 0.2g
Butyl acetate 30g
Dimethylbenzene 28.2g
Wherein, acrylic resin accounts for 50wt% in acrylic resin soln, and the solvent in acrylic resin soln is diformazan Benzene.Acetylbutyrylcellulose accounts for the 20wt% of acetylbutyrylcellulose solution, and solvent is butyl acetate.
Step 2): the mixed solution that step 1) is obtained, which is placed in dispersion machine, stirs 1h, dispersing speed 1500rpm, Obtain static conductive coating.
Mode coating and plastic base surface using aerial spraying use the face electricity of megger test static conductive coating Resistance, the resistance value of sheet resistance are 106Ω。
Embodiment 5A:
Present embodiment illustrates a kind of preparation processes of graphene with high specific surface aggregation.
Step 1): the following raw material is provided:
Graphene (specific surface area 645m2/g) 2kg
Acrylate based block copolymer 2kg
Bentonite 0.1kg
Dehydrated alcohol 95.9kg
Step 2): the first solution of preparation:
Graphene, acrylate based block copolymer, bentonite and dehydrated alcohol are mixed, mixed solution is placed in dispersion 20min, dispersing speed 800rpm are stirred in machine；It reuses horizontal sand mill to be ground, is ground to partial size less than 10 μm, Obtain the first solution.
Step 3): the second solution of preparation:
It chooses butyl to mix as low volatility solvent with the first solution, the first solution and diethylene glycol fourth The mass ratio of ether is 100:5, then the mixed solution of butyl and the first solution is placed in dispersion machine and stirs 20min, Dispersing speed is 800rpm, obtains the second solution.
Step 4): using the distillation equipment for having condensing unit, the second solution is distilled, vapo(u)rizing temperature is set in 55-65 DEG C, condensing unit temperature is set in 0 DEG C, recycles dehydrated alcohol, distills 6h.High-specific surface area stone is obtained after terminating distillation Black alkene aggregation, the content of graphene is 22.0% in aggregation.
Embodiment 5B:
Present embodiment illustrates graphene with high specific surface aggregations made from the method using embodiment 5A to prepare graphite The method of alkene static conductive coating.
Step 1): following components is mixed:
Acrylic resin soln 120g
Acetylbutyrylcellulose solution 16g
Polyamide wax 2g
Graphene with high specific surface aggregation 2.7g
Organosilicon silicone grease 0.4g
Levelling agent 0.2g
Butyl acetate 30g
Dimethylbenzene 28.1g
Wherein, acrylic resin accounts for 50wt% in acrylic resin soln, and the solvent in acrylic resin soln is diformazan Benzene.Acetylbutyrylcellulose accounts for the 20wt% of acetylbutyrylcellulose solution, and solvent is butyl acetate.
Step 2): the mixed solution that step 1) is obtained, which is placed in dispersion machine, stirs 1h, dispersing speed 1500rpm, Obtain static conductive coating.
Mode coating and plastic base surface using aerial spraying use the face electricity of megger test static conductive coating Resistance, the resistance value of sheet resistance are 106Ω。
Embodiment 6A:
Present embodiment illustrates a kind of preparation processes of graphene with high specific surface aggregation.
Step 1): the following raw material is provided:
Graphene (specific surface area 550m2/g) 2kg
Esters of acrylic acid block copolymer dispersant solution 5kg
Bentonite 0.1kg
Butyl acetate 92.9kg
In esters of acrylic acid block copolymer dispersant solution include acrylate based block copolymer and butyl acetate, Middle acrylate based block copolymer accounts for the 40wt% of dispersant solution.
Step 2): the first solution of preparation:
Graphene, esters of acrylic acid block copolymer dispersant solution, bentonite and butyl acetate are mixed, will be mixed molten Liquid, which is placed in dispersion machine, stirs 20min, dispersing speed 800rpm；It reuses horizontal sand mill to be ground, is ground to grain Diameter obtains the first solution less than 10 μm.
Step 3): the second solution of preparation:
It chooses butyl to mix as low volatility solvent with the first solution, the first solution and diethylene glycol fourth The mass ratio of ether is 100:6, then the mixed solution of butyl and the first solution is placed in dispersion machine and stirs 20min, Dispersing speed is 800rpm, obtains the second solution.
Step 4): using the distillation equipment for having condensing unit, the second solution is distilled, vapo(u)rizing temperature is set in 55-65 DEG C, condensing unit temperature is set in 0 DEG C, and recovery of acetic acid butyl ester distills 5.5h.High-specific surface area is obtained after terminating distillation Graphenes aggregations, the content of graphene is 19.8% in aggregation.It except the dispersing agent of 40wt% is molten in dispersant solution Agent butyl acetate, solvent can be distilled off together in distillation.
Embodiment 6B:
Present embodiment illustrates graphene with high specific surface aggregations made from the method using embodiment 6A to prepare graphite The method of alkene static conductive coating.
Step 1): following components is mixed:
Acrylic resin soln 120g
Acetylbutyrylcellulose solution 16g
Polyamide wax 2g
Graphene with high specific surface aggregation 3.0g
Organosilicon silicone grease 0.4g
Levelling agent 0.2g
Butyl acetate 30g
Dimethylbenzene 27.8g
Wherein, acrylic resin accounts for 50wt% in acrylic resin soln, and the solvent in acrylic resin soln is diformazan Benzene.Acetylbutyrylcellulose accounts for the 20wt% of acetylbutyrylcellulose solution, and solvent is butyl acetate.
Step 2): the mixed solution that step 1) is obtained, which is placed in dispersion machine, stirs 1h, dispersing speed 1500rpm, Obtain static conductive coating.
Mode coating and plastic base surface using aerial spraying use the face electricity of megger test static conductive coating Resistance, the resistance value of sheet resistance are 107Ω。
Embodiment 7A:
Present embodiment illustrates kind of a preparation processes for graphene with high specific surface aggregation.
Step 1): the following raw material is provided:
Graphene (specific surface area 550m2/g) 2kg
Esters of acrylic acid block copolymer dispersant solution 5kg
Bentonite 0.1kg
Dimethylbenzene 92.9kg
In esters of acrylic acid block copolymer dispersant solution include acrylate based block copolymer and butyl acetate, Middle acrylate based block copolymer accounts for the 40wt% of dispersant solution.
Step 2): the first solution of preparation:
Graphene, esters of acrylic acid block copolymer dispersant solution, bentonite and dimethylbenzene are mixed, by mixed solution It is placed in dispersion machine and stirs 20min, dispersing speed 800rpm；It reuses horizontal sand mill to be ground, is ground to partial size Less than 10 μm, the first solution is obtained.
Step 3): the second solution of preparation:
It chooses butyl to mix as low volatility solvent with the first solution, the first solution and diethylene glycol fourth The mass ratio of ether is 100:10, then the mixed solution of butyl and the first solution is placed in dispersion machine and stirs 20min, Dispersing speed is 800rpm, obtains the second solution.
Step 4): using the distillation equipment for having condensing unit, the second solution is distilled, vapo(u)rizing temperature is set in 55-65 DEG C, condensing unit temperature is set in 0 DEG C, recycles dimethylbenzene and butyl acetate, distills 6h.High ratio is obtained after terminating distillation Surface area graphenes aggregations, the content of graphene is 14.2% in aggregation.In dispersant solution the dispersing agent of 40wt% it It is outside solvent butyl acetate, solvent can be distilled off together in distillation.
Embodiment 7B:
Present embodiment illustrates graphene with high specific surface aggregations made from the method using embodiment 7A to prepare graphite The method of alkene static conductive coating.
Step 1): following components is mixed:
Acrylic resin soln 120g
Acetylbutyrylcellulose solution 16g
Polyamide wax 2g
Graphene with high specific surface aggregation 4.2g
Organosilicon silicone grease 0.4g
Levelling agent 0.2g
Butyl acetate 30g
Dimethylbenzene 26.6g
Wherein, acrylic resin accounts for 50wt% in acrylic resin soln, and the solvent in acrylic resin soln is diformazan Benzene.Acetylbutyrylcellulose accounts for the 20wt% of acetylbutyrylcellulose solution, and solvent is butyl acetate.
Step 2): the mixed solution that step 1) is obtained, which is placed in dispersion machine, stirs 1h, dispersing speed 1500rpm, Obtain static conductive coating.
Mode coating and plastic base surface using aerial spraying use the face electricity of megger test static conductive coating Resistance, the resistance value of sheet resistance are 107Ω。
Embodiment 8A:
Present embodiment illustrates a kind of preparation processes of graphene with high specific surface aggregation
Step 1): the following raw material is provided:
Graphene (specific surface area 550m2/g) 2kg
Esters of acrylic acid block copolymer dispersant solution 5kg
Bentonite 0.1kg
Ethyl acetate 92.9kg
In esters of acrylic acid block copolymer dispersant solution include acrylate based block copolymer and butyl acetate, Middle acrylate based block copolymer accounts for the 40wt% of dispersant solution.
Step 2): the first solution of preparation:
Graphene, esters of acrylic acid block copolymer dispersant solution, bentonite and ethyl acetate are mixed, will be mixed molten Liquid, which is placed in dispersion machine, stirs 20min, dispersing speed 800rpm；It reuses horizontal sand mill to be ground, is ground to grain Diameter obtains the first solution less than 10 μm.
Step 3): the second solution of preparation:
It chooses butyl to mix as low volatility solvent with the first solution, the first solution and diethylene glycol fourth The mass ratio of ether is 100:15, then the mixed solution of butyl and the first solution is placed in dispersion machine and stirs 20min, Dispersing speed is 800rpm, obtains the second solution.
Step 4): using the distillation equipment for having condensing unit, the second solution is distilled, vapo(u)rizing temperature is set in 55-65 DEG C, condensing unit temperature is set in 0 DEG C, and recovery of acetic acid ethyl ester and butyl acetate distill 6h.Height is obtained after terminating distillation Specific surface area graphenes aggregations, the content of graphene is 10.5% in aggregation.The dispersing agent of 40wt% in dispersant solution Except be solvent butyl acetate, solvent distillation when can be distilled off together.
Embodiment 8B:
Present embodiment illustrates graphene with high specific surface aggregations made from the method using embodiment 8A to prepare graphite The method of alkene static conductive coating.
Step 1): following components is mixed:
Acrylic resin soln 120g
Acetylbutyrylcellulose solution 16g
Polyamide wax 2g
Graphene with high specific surface aggregation 5.7g
Organosilicon silicone grease 0.4g
Levelling agent 0.2g
Butyl acetate 30g
Dimethylbenzene 25.1g
Wherein, acrylic resin accounts for 50wt% in acrylic resin soln, and the solvent in acrylic resin soln is diformazan Benzene.Acetylbutyrylcellulose accounts for the 20wt% of acetylbutyrylcellulose solution, and solvent is butyl acetate.
Step 2): the mixed solution that step 1) is obtained, which is placed in dispersion machine, stirs 1h, dispersing speed 1500rpm, Obtain static conductive coating.
Mode coating and plastic base surface using aerial spraying use the face electricity of megger test static conductive coating Resistance, the resistance value of sheet resistance are 107Ω。
Comparative example 9A:
This comparison is illustrated a kind of preparation process of graphene with high specific surface aggregation.
Step 1): the following raw material is provided:
Graphene (specific surface area 550m2/g) 2kg
Esters of acrylic acid block copolymer dispersant solution 5kg
Bentonite 0.1kg
Dehydrated alcohol 92.9kg
In esters of acrylic acid block copolymer dispersant solution include acrylate based block copolymer and butyl acetate, Middle acrylate based block copolymer accounts for the 40wt% of dispersant solution.
Step 2): the first solution of preparation:
Graphene, esters of acrylic acid block copolymer dispersant solution, bentonite and dehydrated alcohol are mixed, will be mixed molten Liquid, which is placed in dispersion machine, stirs 20min, dispersing speed 800rpm；It reuses horizontal sand mill to be ground, is ground to grain Diameter obtains the first solution less than 10 μm.
Step 3): the second solution of preparation:
It chooses butyl to mix as low volatility solvent with the first solution, the first solution and diethylene glycol fourth The mass ratio of ether is 100:2, then the mixed solution of butyl and the first solution is placed in dispersion machine and stirs 20min, Dispersing speed is 800rpm, obtains the second solution.
Step 4): using the distillation equipment for having condensing unit, the second solution is distilled, vapo(u)rizing temperature is set in 55-65 DEG C, condensing unit temperature is set in 0 DEG C, recycles dehydrated alcohol and butyl acetate, distills 6h.Height is obtained after terminating distillation Specific surface area graphenes aggregations, the content of graphene is 32.8% in aggregation.The dispersing agent of 40wt% in dispersant solution Except be solvent butyl acetate, solvent distillation when can be distilled off together.
Comparative example 9B:
This comparison is illustrated graphene with high specific surface aggregation made from the method using comparative example 9A and prepares graphite The method of alkene static conductive coating.
Step 1): following components is mixed:
Acrylic resin soln 120g
Acetylbutyrylcellulose solution 16g
Polyamide wax 2g
Graphene with high specific surface aggregation 1.8g
Organosilicon silicone grease 0.4g
Levelling agent 0.2g
Butyl acetate 30g
Dimethylbenzene 29.0g
Wherein, acrylic resin accounts for 50wt% in acrylic resin soln, and the solvent in acrylic resin soln is diformazan Benzene.Acetylbutyrylcellulose accounts for the 20wt% of acetylbutyrylcellulose solution, and solvent is butyl acetate.
Step 2): the mixed solution that step 1) is obtained, which is placed in dispersion machine, stirs 1h, dispersing speed 1500rpm, Obtain static conductive coating.
Mode coating and plastic base surface using aerial spraying use the face electricity of megger test static conductive coating Resistance, the resistance value of sheet resistance are 1011Ω。
Comparative example 10A:
This comparison is illustrated a kind of preparation process of graphene with high specific surface aggregation.
Step 1): the following raw material is provided:
Graphene (specific surface area 550m2/g) 2kg
Acrylate based block copolymer 2kg
Bentonite 0.1kg
Dehydrated alcohol 95.9kg
Step 2): the first solution of preparation:
Graphene, acrylate based block copolymer, bentonite and dehydrated alcohol are mixed, mixed solution is placed in dispersion 20min, dispersing speed 800rpm are stirred in machine；It reuses horizontal sand mill to be ground, is ground to partial size less than 10 μm, Obtain the first solution.
Step 3): the second solution of preparation:
It chooses butyl to mix as low volatility solvent with the first solution, the first solution and diethylene glycol fourth The mass ratio of ether is 100:1.5, then the mixed solution of butyl and the first solution is placed in dispersion machine and is stirred 20min, dispersing speed 800rpm obtain the second solution.
Step 4): using the distillation equipment for having condensing unit, the second solution is distilled, vapo(u)rizing temperature is set in 55-65 DEG C, condensing unit temperature is set in 0 DEG C, recycles dehydrated alcohol, distills 6h.High-specific surface area stone is obtained after terminating distillation Black alkene aggregation, the content of graphene is 35.7% in aggregation.
Comparative example 10B:
This comparison is illustrated graphene with high specific surface aggregation made from the method using comparative example 10A and prepares graphite The method of alkene static conductive coating.
Step 1): following components is mixed:
Acrylic resin soln 120g
Acetylbutyrylcellulose solution 16g
Polyamide wax 2g
Graphene with high specific surface aggregation 1.7g
Organosilicon silicone grease 0.4g
Levelling agent 0.2g
Butyl acetate 30g
Dimethylbenzene 29.1g
Wherein, acrylic resin accounts for 50wt% in acrylic resin soln, and the solvent in acrylic resin soln is diformazan Benzene.Acetylbutyrylcellulose accounts for the 20wt% of acetylbutyrylcellulose solution, and solvent is butyl acetate.
Step 2): the mixed solution that step 1) is obtained, which is placed in dispersion machine, stirs 1h, dispersing speed 1500rpm, Obtain static conductive coating.
Mode coating and plastic base surface using aerial spraying use the face electricity of megger test static conductive coating The resistance value of resistance, sheet resistance is greater than 1012Ω。
Comparative example 11A:
This comparison is illustrated a kind of preparation process of common graphite alkene slurry:
Step 1): the following raw material is provided:
Graphene (specific surface area 550m2/g) 2kg
Esters of acrylic acid block copolymer dispersant solution 5kg
Bentonite 0.1kg
Dehydrated alcohol 92.9kg
In esters of acrylic acid block copolymer dispersant solution include acrylate based block copolymer and butyl acetate, Middle acrylate based block copolymer accounts for the 40wt% of dispersant solution.
Step 2): graphene slurry is prepared:
Graphene, esters of acrylic acid block copolymer dispersant solution, bentonite and dehydrated alcohol are mixed, will be mixed molten Liquid, which is placed in dispersion machine, stirs 20min, dispersing speed 800rpm；It reuses horizontal sand mill to be ground, is ground to grain Diameter obtains common graphite alkene slurry less than 10 μm, and the content of graphene is 2% in graphene slurry.
Comparative example 11B:
This comparison is illustrated graphene slurry preparation graphene static conductive coating made from the method using comparative example 11A Method.
Step 1): following components is mixed:
Acrylic resin soln 120g
Acetylbutyrylcellulose solution 16g
Polyamide wax 2g
Graphene slurry 30g
Organosilicon silicone grease 0.4g
Levelling agent 0.2g
Butyl acetate 30g
Dimethylbenzene 0.8g
Wherein, acrylic resin accounts for 50wt% in acrylic resin soln, and the solvent in acrylic resin soln is diformazan Benzene.Acetylbutyrylcellulose accounts for the 20wt% of acetylbutyrylcellulose solution, and solvent is butyl acetate.
Step 2): the mixed solution that step 1) is obtained, which is placed in dispersion machine, stirs 1h, dispersing speed 1500rpm, Obtain static conductive coating.
Mode coating and plastic base surface using aerial spraying use the face electricity of megger test static conductive coating The resistance value of resistance, sheet resistance is greater than 107Ω。
Comparative example 12A:
This comparison is illustrated a kind of preparation process of graphene powder dispersed paste.
Step 1): the following raw material is provided:
Graphene (specific surface area 550m2/g) 2kg
Esters of acrylic acid block copolymer dispersant solution 5kg
Bentonite 0.1kg
Dimethylbenzene 92.9kg
In esters of acrylic acid block copolymer dispersant solution include acrylate based block copolymer and butyl acetate, Middle acrylate based block copolymer accounts for the 40wt% of dispersant solution.
Step 2): graphene powder dispersed paste is prepared:
Graphene, esters of acrylic acid block copolymer dispersant solution, bentonite and dimethylbenzene are mixed, by mixed solution It is placed in dispersion machine and stirs 20min, dispersing speed 800rpm；It is standing and soaking 2h again, obtains graphene powder dispersed paste, The content of graphene is 2% in graphene powder dispersed paste.
Comparative example 12B:
This comparison is illustrated the preparation graphene of graphene powder dispersed paste made from the method using comparative example 12A and leads The method of electrostatic coatings.
Step 1): following components is mixed:
Acrylic resin soln 120g
Acetylbutyrylcellulose solution 16g
Polyamide wax 2g
Graphene powder dispersed paste 30g
Organosilicon silicone grease 0.4g
Levelling agent 0.2g
Butyl acetate 30g
Dimethylbenzene 0.8g
Wherein, acrylic resin accounts for 50wt% in acrylic resin soln, and the solvent in acrylic resin soln is diformazan Benzene.Acetylbutyrylcellulose accounts for the 20wt% of acetylbutyrylcellulose solution, and solvent is butyl acetate.
Step 2): the mixed solution that step 1) is obtained, which is placed in dispersion machine, stirs 1h, dispersing speed 1500rpm, Obtain static conductive coating.
Mode coating and plastic base surface using aerial spraying use the face electricity of megger test static conductive coating The resistance value of resistance, sheet resistance is greater than 1012Ω。
It is compared by test result of the below table to embodiment 1B-8B and comparative example 9B-12B:
Used it can be seen from embodiment 1B-8B and comparative example 11B method of the invention prepare graphene content for The graphene with high specific surface aggregation of 10%-30% and use prior art preparation graphene content for 2% graphene starch Expect that the surface resistance for the graphene static conductive coating prepared is low, electric conductivity is excellent, and graphene dispersion effect is good.It can also be with by Fig. 5 Find out, the graphenes aggregations of high-specific surface area of the invention are uniformly dispersed in static conductive coating, and no graphene is reunited.
Graphene with high specific surface of the graphene content greater than 30% gathers it can be seen from comparative example 9B and comparative example 10B In the graphene static conductive coating that collective prepares, graphene dispersion is uneven, and graphene static conductive coating surface resistance is big, electric conductivity It can be poor.As shown in fig. 6, the graphenes aggregations of the high-specific surface area of 35.7wt% graphene content produce in static conductive coating Raw a large amount of reunions, dispersion effect are bad.
Comparative example 11B uses the graphene content of prior art preparation to need more solvents for 2% graphene slurry, Graphene static conductive coating is prepared using the graphene powder of same amount, the additive amount of graphene with high specific surface aggregation is only / 10th of graphene slurry can make graphene static conductive coating reach identical electric conductivity.
Graphene powder dispersed paste is only stirred slurry it can be seen from comparative example 12B, does not grind slurry It grinds, the graphene partial size in slurry is larger, disperses graphene in graphene static conductive coating bad, surface resistance is more than 1012Ω, electric conductivity is poor, by Fig. 7 it can also be seen that graphene powder dispersed paste has a large amount of graphite in static conductive coating Alkene is reunited.
Finally, it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not intended to restrict the invention, Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features. All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in of the invention Within protection scope.

Claims (10)

1. a kind of graphene with high specific surface aggregation, which is characterized in that the content of graphene is 10wt%- in the aggregation 30wt%；
Preferably, the aggregation includes graphene, dispersing agent, stabilizer and low volatility solvent.
2. graphene with high specific surface aggregation according to claim 1, which is characterized in that the specific surface of the graphene Product is greater than 400m2/g；
Preferably, the graphene is the graphene powder being prepared by chemical method or physical method；It is further preferred that institute Stating graphene is the graphene powder being prepared by oxidation-reduction method；
Preferably, the content of the dispersing agent is 10wt%-30wt%；
Preferably, the dispersing agent includes that fatty acid amide, acidic-group copolymer, esters of acrylic acid or esters of acrylic acid block are total The combination of one or more of polymers；
Preferably, the content of the stabilizer is 0.1wt%-10wt%；
Preferably, the stabilizer include the N-Methyl pyrrolidone solution of modified polyurea, modified hydrogenated castor oil, bentonite, A combination of one or more in titanate coupling agent, polyamide wax or polyethylene wax；It is further preferred that the stabilizer For the combination of polyamide wax and polyethylene wax；
Preferably, the content of the low volatility solvent is 30wt%-80wt%；
Preferably, the rate of volatilization of the low volatility solvent is not more than the 20% of butyl acetate rate of volatilization；Preferably, institute Stating low volatility solvent includes propandiol butyl ether, diethylene glycol butyl ether, a contracting propandiol butyl ether, diethylene glycol ether vinegar One of acid esters, diethylene glycol monobutyl ether acetate, alcohol ester 12, DBE, butyl, dibutyl phthalate Or two or more mixed solvent；It is further preferred that the low volatility solvent is butyl.
3. a kind of preparation method of graphene with high specific surface aggregation according to claim 1 or 2, which is characterized in that It first disperses graphene in high rate of volatilization solvent, then the high rate of volatilization solvent and low volatility that graphene will be dispersed with Solvent mixing, then it is separated by distillation out high rate of volatilization solvent, graphene with high specific surface aggregation can be obtained.
4. the preparation method of graphene with high specific surface aggregation according to claim 3, which is characterized in that including following Step:
Step 1): graphene, dispersing agent, stabilizer and high rate of volatilization solvent are mixed, and dispersion, grinding obtain the first solution；
Step 2): the first solution is mixed with low volatility solvent, and dispersion obtains the second solution；
Step 3): the second solution of distillation obtains graphene with high specific surface aggregation.
5. the preparation method of graphene with high specific surface aggregation according to claim 4, which is characterized in that step 1) In, the graphene, dispersing agent, stabilizer and high rate of volatilization solvent mass ratio be (0.1-5): (0.1-5): (0.001- 1.7): (50-100), preferably (1-3): (1-3): (0.01-1): (80-100), further preferably 2:2:0.1:95.9；
Preferably, the viscosity of the mixed solution of the graphene, dispersing agent, stabilizer and high rate of volatilization solvent is adopted by grinding Milling apparatus processes the 90% of upper limit viscosity；
Preferably, the viscosity of the mixed solution of the graphene, dispersing agent, stabilizer and high rate of volatilization solvent is 500- 5000mpa·s；
Preferably, the graphene is the graphene powder being prepared by chemical method or physical method；It is further preferred that institute Stating graphene is the graphene powder being prepared by oxidation-reduction method；
Preferably, the specific surface area of the graphene is greater than 400m2/g；
Preferably, the dispersing agent is fatty acid amide, acidic-group copolymer, esters of acrylic acid or esters of acrylic acid block copolymerization The combination of one or more of object；
Preferably, the stabilizer is N-Methyl pyrrolidone solution, modified hydrogenated castor oil, the bentonite, titanium of modified polyurea The combination of one or more of acid esters coupling agent, polyamide wax or polyethylene wax；It is further preferred that the stabilizer For the combination of polyamide wax and polyethylene wax；
Preferably, the high rate of volatilization solvent is the solvent that rate of volatilization is not less than butyl acetate rate of volatilization；Preferably, institute Stating high rate of volatilization solvent includes butyl acetate, toluene, methanol, ethyl alcohol, isopropanol, ethyl acetate, acetone, butanone, dichloromethane The mixed solvent of one or more of alkane, hexamethylene, carbon tetrachloride or tetrahydrofuran；It is further preferred that the height Rate of volatilization solvent is ethyl alcohol；
Preferably, described be separated into is stirred using dispersion machine；Preferably, the mixing time of the dispersion machine is 10- 30min, preferably 20min；Preferably, the revolving speed of the dispersion machine is 400-1000rpm, preferably 800rpm；
The milling apparatus used that grinds is horizontal sand mill, vertical grinding machine, basket type sand mill, three-roll grinder or homogeneous Machine；It is further preferred that the milling apparatus used that grinds is horizontal sand mill；
Preferably, the method for the grinding is to grind the mixed solution of graphene, dispersing agent, stabilizer and high rate of volatilization solvent Partial size is milled to less than 10 μm.
6. the preparation method of graphene with high specific surface aggregation according to claim 4, which is characterized in that step 2) In, the mass ratio of first solution and the low volatility solvent is 100:(1-100), preferably 100:(1-30), into one Walk preferred 100:6；
Preferably, the rate of volatilization of the low volatility solvent is not more than the 20% of butyl acetate rate of volatilization；Preferably, institute Stating low volatility solvent includes propandiol butyl ether, diethylene glycol butyl ether, a contracting propandiol butyl ether, diethylene glycol ether vinegar One of acid esters, diethylene glycol monobutyl ether acetate, alcohol ester 12, DBE, butyl, dibutyl phthalate Or two or more mixed solvent；It is further preferred that the low volatility solvent is butyl；
Preferably, described be separated into is stirred using dispersion machine；Preferably, the mixing time of the dispersion machine is 10- 30min, preferably 20min；Preferably, the revolving speed of the dispersion machine is 400-1000rpm, preferably 800rpm；
Preferably, it when the dispersion, is ground after the completion of stirring；Preferably, the time of the grinding is 1h-6h.
7. the preparation method of graphene with high specific surface aggregation according to claim 4, which is characterized in that step 3) In, the equipment of the distillation is the distillation equipment with condensing condition；It is further preferred that the condensation temperature is -5 DEG C -5 DEG C, preferably 0 DEG C；
Preferably, the temperature of the distillation is 50-80 DEG C, preferably 55-65 DEG C；
Preferably, the time of the distillation is 1-10h, preferably 6h.
8. a kind of graphene static conductive coating characterized by comprising acrylic resin soln, auxiliary rheological agents, claim 1 Or graphene with high specific surface aggregation, organosilicon silicone grease described in 2, levelling agent, butyl acetate and dimethylbenzene；
Preferably, in parts by mass, the graphene static conductive coating total number is 199.4 parts, acrylic resin soln 120 Part, auxiliary rheological agents are 18 parts, graphene with high specific surface aggregation is (2-6) part, organosilicon silicone grease is 0.4 part, levelling agent is 0.2 part, butyl acetate be 30 parts and dimethylbenzene be (24.8-28.8) part；
Preferably, acrylic resin accounts for the 50wt% of acrylic resin soln；
Preferably, the solvent in acrylic resin soln is dimethylbenzene or butyl acetate；
Preferably, the auxiliary rheological agents include acetylbutyrylcellulose solution and polyamide wax；
Preferably, the mass ratio of the acetylbutyrylcellulose solution and polyamide wax is 8:1；
Preferably, acetylbutyrylcellulose accounts for the 20wt% of acetylbutyrylcellulose solution；
Preferably, the solvent in the acetylbutyrylcellulose solution is butyl acetate.
9. the preparation method of graphene static conductive coating according to claim 8, which is characterized in that each component is mixed, Dispersion stirring, obtains graphene static conductive coating.
10. the preparation method of graphene static conductive coating according to claim 9, which is characterized in that the dispersion stirring The revolving speed of the dispersion machine used is 1000-2000rpm, preferably 1500rpm；
Preferably, the time of the dispersion stirring is 0.5-1.5h, preferably 1h.
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