CN105295098B - A kind of graphene oxide, CNT multi-arm determine the preparation method of configuration heat filling - Google Patents
A kind of graphene oxide, CNT multi-arm determine the preparation method of configuration heat filling Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of the more arm type heat fillings of graphene/carbon nano-tube prepared using mechanical force and chemical method, belong to high-performance powder technical field of material；The present invention is using graphene oxide as kernel, using simple mechanochemistry method, by CNT to hold a fixed-link to form more arm type high heat conduction fillers using the high heat conductance of graphene and CNT to surface of graphene oxide；The increase of high-termal conductivity and specific surface area based on nano-carbon material, the dispersive property and improvement heat-conducting effect of the solution CNT of novel heat-conducting filler energy high degree prepared by the present invention, and also filling-material structure is stable.
Description
Technical field
The present invention relates to the preparation method that a kind of graphene oxide, CNT multi-arm determine configuration heat filling, specifically relate to
And a kind of preparation method of the more arm type heat fillings of graphene/carbon nano-tube prepared using mechanochemistry method, belong to high
Performance dusty material preparing technical field.
Background technology
Metal material is traditional hot good conductor, the substantial amounts of metal material quilt in common industrial products
For making heat conduction and radiating element, also brought while heat conduction demand is met product appearance is simple, weight is larger, intolerant to
The defects of chemical attack.With the progress of science and technology, requirement of the people to Heat Conduction Material has a further raising, light,
Easy processing shaping, shock resistance, resistant to chemical etching, heat-resistant anti-fatigue, excellent electrical insulation capability and chemical stability etc. are all people
New demand to Heat Conduction Material, while integrated package, heat pipe, integrated circuit, copper-clad plate, aero-space electronic equipment, motor communication
Fast development etc. a collection of new industry also improves demand of the people to heat-conductive composite material.
The species of filler, particle diameter, shape, pattern, the quantity of filling, lead with the strong influence such as the interface performance of matrix
No matter the heat conductivility of hot composite, heat filling exist with granular, sheet or threadiness, and heat conductivility all compares high score
Subbase body in itself will height.When the loading very little of heat filling, can not be formed between heat filling really contact and mutually
Effect, this raising to high polymer material heat conductivility are almost nonsensical；Only when in macromolecule matrix, heat filling is filled out
Just there is interaction truly when charge reaches a certain critical value, between heat filling, system could form similar net
The form of shape or chain --- i.e. heat conduction network chain.When the orientation of heat conduction network chain is consistent with direction of heat flow, heat conductivility improves very
It hurry up；When failing to form heat conduction network chain on direction of heat flow, great thermal resistance can be produced, heat conductivility is substantially deteriorated.Therefore, how
Farthest forming heat conduction network chain on direction of heat flow in system turns into the key for improving heat-conducting polymer material heat conductivility
Place.Carbon nanomaterial has extensively been paid close attention to as a major class high heat conduction powder emerging in recent years by scientific research, is utilized it as and is led
Hot doping thing is to form more technical literature.
Carry out mixing the formation that can accelerate heat conduction network chain using carbon material and different shape, the filler of particle diameter, effectively carry
The thermal conductivity of polymer composites is risen, the key for improving thermal conductivity is to form substantial amounts of heat conduction network chain.Patent
CN201410539991.0 gives the preparation method that a kind of liquid phase concentration prepares polyphenylene sulfide/graphene heat-conductive composite material,
Using two-arch tunnel is formed in liquid phase, high-termal conductivity is obtained, patent CN201410221717.9 gives one kind of multiple size oxygen
Change the preparation method of aluminium and graphene compounding as the moulded heat-conductive insulated plastics of heat filling, patent CN201410775161.8 gives
A kind of heat conductive insulating composite of simple compounding graphene/carbon black/CNT heat conduction component is gone out, because heat conduction component contains
Amount（3 ~ 5 parts）Much smaller than insulated type heat filling（60 parts）, in general, in the technical scheme for manufacturing highly heat-conductive material, more
Be to utilize the continuity between filler to form heat conduction site.
Because nano particle has the characteristics such as small-size effect, quantum size effect and skin effect, a large amount of nanometers are caused
Particle is reunited together in process, it is impossible to scattered well so that excellent performance is difficult to show；Bat wool exists
Can be broken cut-out in process, it is difficult to realize the effect of bridge formation；Laminal filter often occurs in the form of multiple-level stack, is adding
It is difficult to be layered during work.It is expected that the simple overlap joint by filler in process realizes hydridization, it is clear that exist not
Certainty.If that realizes heat filling structure determines structure design so by the great service efficiency for improving heat filling and heat conduction
Property.ZL 201210392066.0 proposes a kind of to obtain carbon black/CNT using chemical graft method and determine structure heat filling
Technical method, but the thermal conductivity of carbon black is significantly lower than CNT, while the bulk density of spherical carbon black is relatively low, formation
Thermal resistance is larger, is unfavorable for the implementation of the technical method, the manufacture graphite oxide combined using mechanical force activating with chemical reaction
The multi-arm heat filling that alkene/CNT determines structure combination has not been reported.
The content of the invention
It is an object of the invention to provide the preparation side that a kind of graphene oxide, CNT multi-arm determine configuration heat filling
Method, research is a kind of to determine the more of structure combination using mechanical force activating and manufacture graphene oxide/CNT of chemical reaction combination
Arm heat filling, overcome by processing the problem of unstable hydridization efficiency brought is low.Research is grafted on carbon nanotube chemical
Graphene, the Thermal Arm that is formed by CNT is formed in graphenic surface, and utilization graphene and CNT is highly thermally conductive
Rate forms multi-arm heat filling, and this particle is stable by electron microscopy observation to more arm configurations, filling-material structure.
To achieve these goals, the technical solution adopted by the present invention is as follows：
A kind of graphene oxide, CNT multi-arm determine the preparation method of configuration heat filling, comprise the following steps：
（1）Graphene microchip, CNT mechanical force peel off activation：
Graphene microchip is utilized into constant temperature ball grinding technique, activation is directly peeled off in ball milling peels off liquid phase, will stripping after ball milling
Graphene from oxidation is filtered, and neutrality is washed to using deionized water, obtains oxidation of the surface with carboxyl that constant temperature ball milling is peeled off
Graphene；CNT using mechanical force peel off activation method, using high energy ball milling technology directly with coupling agent ball-milling reaction, instead
After should terminating, the aqueous isopropanol of diimine is added in ball grinder, the Volume fraction of diimine and isopropanol is 2 ~ 10:
100, continue ball milling 1 ~ 4 hour, rotational speed of ball-mill is 1800 revs/min, after ball milling, is washed with deionized water to neutrality, true at 80 DEG C
Sky is dried 12 hours, and grinding forms the Activated Carbon Nanotubes of fracture positioning activation；
（2）The preparation of more arm type heat fillings：
Hydroxyl hydrolysis CNT, and and table are obtained after the Activated Carbon Nanotubes of fracture positioning activation are hydrolyzed
Graphene oxide stripping film of the face with carboxyl room temperature under the effect of diimine class material carries out graft reaction 2 hours, and hydrolysis carbon is received
The mass ratio of mitron, graphene oxide stripping film and diimine class material is 1:1~9:0.06~0.23；
（3）The purifying of more arm type heat fillings：
Powder prepared by graft reaction is flowed back in dimethylbenzene, and filtered, remove the graphene of remaining, CNT,
The impurity such as carbon, obtain the more arm type heat fillings for determining structure design.
Step（1）The graphene microchip constant temperature ball milling is that ball milling is shelled in polytetrafluoroethylene (PTFE) ball grinder by graphene microchip
From ball grinder outside is filled with frozen water constant temperature, and rotational speed of ball-mill is 400 ~ 2000 revs/min, and the reaction time is 12 ~ 24 hours, every 3
Hour changes outside frozen water and carries out temperature adjusting；Wherein ball milling ball is Ceramic Balls, and the particle diameter of ball milling ball selects 0.5,1,2,5
With 10 millimeters of particle diameters, ball milling ball configures by a certain percentage, and ball milling sphere volume accounts for the 40 ~ 60% of ball milling tank volume.
The ball milling ball is carborundum or boron nitride ceramics ball milling ball, and ball milling spherolite footpath is 0.5,1 and 2 millimeter of particle diameter, its
Ratio is 1:0.6~0.8:0.2~0.05.
Step（1）It is acid solution that the ball milling, which peels off liquid phase, and its acid solution is sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, potassium permanganate,
One or more mixtures in phosphoric acid；When selecting the mixture of sulfuric acid, nitric acid or sulfuric acid, perchloric acid, its volume ratio is
10:90~80:20, when selecting the mixture of sulfuric acid, potassium permanganate or nitric acid, potassium permanganate, its mass ratio is 50:50~80:
20。
The caliber of the CNT is 20 ~ 100nm, and the draw ratio of CNT is 80:1~200:1.
Step（1）The mechanical force peels off activation method as ball milling is anti-in polytetrafluoroethylene (PTFE) ball grinder by CNT
Should, wherein ball milling peels off the aqueous isopropanol that liquid phase is titanate coupling agent or aluminate coupling agent, coupling agent and isopropanol
Volume ratio is 0.003:1~0.05:1, rotational speed of ball-mill is 800 ~ 3000 revs/min, and the reaction time is 3 ~ 9 hours；Ball milling ball is pottery
Porcelain ball, the particle diameter of ball milling ball select 0.5,1,2,5 and 10 millimeter of particle diameter, and ball milling ball configures by a certain percentage, ball milling sphere volume
Account for the 20 ~ 40% of ball milling tank volume.
Described titanate coupling agent is isopropyl three（Dioctylphyrophosphoric acid acyloxy）Titanate esters, (two is pungent for isopropyl three
Base phosphoric acid acyloxy) titanate esters, the oleic acid acyloxy of isopropyl two（Dioctyl phosphoric acid acyloxy）Titanate esters, double (two octyloxies are burnt
It is phosphate-based) ethylene titanate esters, one kind in plant acid type monoalkoxy class titanate esters, described aluminate coupling agent is two
（Ethyl acetoacetate）Aluminic acid diisopropyl ester, two（Acetylacetone,2,4-pentanedione）One kind in aluminic acid diisopropyl ester；The ball milling ball is carbonization
Silicon or boron nitride ceramics ball milling ball, ball milling spherolite footpath are 0.5,1 and 2 millimeter of particle diameter, and its ratio is 1:0.6~0.8:0.2~0.05.
Step（1）Described diimine is N- dicyclohexylcarbodiimides（DCC）, or N, N'- DIC
（DIC）Or 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides（EDC）In one kind.
Step（2）The hydrolysis CNT is that the grafting carbon nanotube that will be obtained after grafting is molten in the aqueous solution of ethanol
Solution, the aqueous solution of ethanol be absolute ethyl alcohol with deionized water according to volume ratio 5:1~1:5 configuration, in Ultrasound Instrument vibrating dispersion 2 ~
4 hours, hydrolysis CNT is obtained after drying.
Step（2）The diimine is N, N- dicyclohexylcarbodiimides（DCC）, or N, N'- DIC
（DIC）Or 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides（EDC）In one kind.
The beneficial effects of the invention are as follows：By the surface grafting CNT in graphene oxide, form multi-arm heat conduction and fill out
Material, the filler of this structure can effectively improve the heat-conducting effect of filler, can promote the formation of heat conduction network chain in matrix, can be stable
Realize thermal conductive network chain formed purpose；Meanwhile the dispersive property of CNT is improved to a certain extent, and do not destroy
The original hollow structure of CNT, expand application of the CNT in polymer matrix composite.
Brief description of the drawings
Fig. 1 multi-arms of the present invention determine the process flow diagram of configuration heat filling preparation method；
The transmission electron microscope picture of multi-arm heat filling made from Fig. 2 embodiments 7；
The thermogravimetric analysis figure of multi-arm heat filling made from Fig. 3 embodiments 7.
Embodiment
The present invention is described in further details below by example, these examples are only used for illustrating the present invention, and unlimited
The scope of the present invention processed；
Embodiment 1
Graphene microchip is placed in polytetrafluoroethylene (PTFE) ball grinder, from the carborundum ball milling of 0.5,1 and 2 millimeter of particle diameter
Ball, its ratio are 1:0.6:0.2, it is 40% that ball milling ball, which accounts for ball milling tank volume, the concentrated sulfuric acid of certain volume is added, at 400 revs/min
Ball milling 12 hours under the rotating speed of clock, frozen water is passed through in ball milling tank wall during ball milling, every 3 hours with changing primary cooling water, is obtained
The graphene oxide of mechanical stripping.
It is 80 by draw ratio:1, caliber is that 20nm CNT is put into polytetrafluoroethylene (PTFE) ball grinder, from 0.5,1 He
The carborundum ball milling ball of 2 millimeters of particle diameters, its ratio are 1:0.8:0.05, it is 20% that ball milling ball, which accounts for ball milling tank volume, adds certain body
Long-pending isopropyl three（Dioctylphyrophosphoric acid acyloxy）The aqueous isopropanol of titanate esters, wherein isopropyl three（Dioctylphyrophosphoric acid
Acyloxy）Titanate esters and the volume ratio of isopropanol are 0.003:1, ball milling 9 hours under 800 revs/min of rotating speed, ball milling terminates
Afterwards, then into ball grinder N, the wherein aqueous isopropanol of N- dicyclohexylcarbodiimides, N, N- dicyclohexylcarbodiimides are added
Volume ratio with isopropanol is 2:100, with 1800 revs/min of rotating speed ball milling 1 hour, fracture positioning is obtained after washing drying and is lived
The Activated Carbon Nanotubes of change.
The Activated Carbon Nanotubes of fracture positioning activation are added in flask, 5:The idol of the ethanol solution middle-end position of 1 dilution
Join agent to hydrolyze 2 hours, 1 is pressed with graphene oxide, N, N- dicyclohexylcarbodiimides after drying:1:0.06 mass ratio is at 60 DEG C
Reaction 2 hours, product deionized water, dimethylbenzene are filtered up to neutrality, remove unreacted graphene, CNT, is made
Multi-arm heat filling is obtained, particle diameter is about 1 micron, and effect is preferable.
Embodiment 2
Graphene microchip is placed in polytetrafluoroethylene (PTFE) ball grinder, from the boron nitride ball milling of 0.5,1 and 2 millimeter of particle diameter
Ball, its ratio are 1:0.8:0.05, it is 60% that ball milling ball, which accounts for ball milling tank volume, the nitric acid of certain volume is added, at 2000 revs/min
Ball milling 24 hours under the rotating speed of clock, frozen water is passed through in ball milling tank wall during ball milling, every 3 hours with changing primary cooling water, is obtained
The graphene oxide of mechanical stripping.
It is 200 by draw ratio:1, caliber is that 10nm CNT is put into polytetrafluoroethylene (PTFE) ball grinder, from 0.5,1
With the carborundum ball milling ball of 2 millimeters of particle diameters, its ratio is 1:0.6:0.2, it is 40% that ball milling ball, which accounts for ball milling tank volume, is added certain
The aqueous isopropanol of isopropyl three (dioctyl phosphoric acid acyloxy) titanate esters of volume, wherein (the dioctyl phosphoric acid of different isopropyl three
Acyloxy) volume ratio of titanate esters and isopropanol is 0.05:1, ball milling 3 hours under 3000 revs/min of rotating speed, ball milling terminates
Afterwards, then into ball grinder N, the wherein aqueous isopropanol of N'- DICs, N, the Asia of N'- diisopropyls carbon two are added
The volume ratio of amine and isopropanol is 10:100, obtain fracture with 1800 revs/min of rotating speed ball milling 4 hours, after washing drying and determine
The Activated Carbon Nanotubes of position activation.
The Activated Carbon Nanotubes of fracture positioning activation are added in flask, 1:The idol of the ethanol solution middle-end position of 5 dilutions
Join agent to hydrolyze 2 hours, 1 is pressed with graphene oxide, N, N'- DICs after drying:9:0.23 mass ratio is 60
DEG C reaction 0.5 hour, product deionized water, dimethylbenzene are filtered until neutral, remove unreacted graphene, carbon nanometer
Pipe, multi-arm heat filling is made, particle diameter is about 0.3 micron, and effect is preferable.
Embodiment 3
Graphene microchip is placed in polytetrafluoroethylene (PTFE) ball grinder, from the carborundum ball milling of 0.5,1 and 2 millimeter of particle diameter
Ball, its ratio are 1:0.7:0.1, it is 50% that ball milling ball, which accounts for ball milling tank volume, the perchloric acid of certain volume is added, at 600 revs/min
Ball milling 16 hours under the rotating speed of clock, frozen water is passed through in ball milling tank wall during ball milling, every 3 hours with changing primary cooling water, is obtained
The graphene oxide of mechanical stripping.
It is 100 by draw ratio:1, caliber is that 40nm CNT is put into polytetrafluoroethylene (PTFE) ball grinder, from 0.5,1
With the carborundum ball milling ball of 2 millimeters of particle diameters, its ratio is 1:0.6:0.15, it is 30% that ball milling ball, which accounts for ball milling tank volume, is added certain
The oleic acid acyloxy of isopropyl two of volume（Dioctyl phosphoric acid acyloxy）The aqueous isopropanol of titanate esters, the wherein oleic acid of isopropyl two
Acyloxy（Dioctyl phosphoric acid acyloxy）Titanate esters and the volume ratio of isopropanol are 0.01:1, under 1000 revs/min of rotating speed
Ball milling 4 hours, after ball milling terminates, then 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides are added into ball grinder
Aqueous isopropanol, the volume ratio of wherein 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides and isopropanol is 4:
100, with 1800 revs/min of rotating speed ball milling 2 hours, the Activated Carbon Nanotubes of fracture positioning activation are obtained after washing drying.
The Activated Carbon Nanotubes of fracture positioning activation are added in flask, 3:The idol of the ethanol solution middle-end position of 1 dilution
Join agent to hydrolyze 2 hours, 1 is pressed with graphene oxide, 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides after drying:
3:0.08 mass ratio reacts 2 hours at 60 DEG C, product deionized water, dimethylbenzene is filtered until neutral, removing unreacted
Graphene, CNT, multi-arm heat filling is made, particle diameter is about 0.4 micron, and effect is preferable.
Embodiment 4
Graphene microchip is placed in polytetrafluoroethylene (PTFE) ball grinder, from the carborundum ball milling of 0.5,1 and 2 millimeter of particle diameter
Ball, its ratio are 1:0.6:0.15, it is 40% that ball milling ball, which accounts for ball milling tank volume, adds the concentrated sulfuric acid of certain volume and mixing for nitric acid
The volume ratio of compound, the wherein concentrated sulfuric acid and nitric acid is 10:90, in, ball milling 18 hours under 800 revs/min of rotating speed, during ball milling
Ball milling tank wall is passed through frozen water, every 3 hours with changing primary cooling water, obtains the graphene oxide of mechanical stripping.
It is 150 by draw ratio:1, caliber is that 60nm CNT is put into polytetrafluoroethylene (PTFE) ball grinder, from 0.5,1
With the carborundum ball milling ball of 2 millimeters of particle diameters, its ratio is 1:0.65:0.1, it is 40% that ball milling ball, which accounts for ball milling tank volume, is added certain
The aqueous isopropanol of the plant acid type monoalkoxy class titanate esters of volume, wherein plant acid type monoalkoxy class titanate esters and isopropyl
The volume ratio of alcohol is 0.02:1, ball milling 6 hours under 1500 revs/min of rotating speed, after ball milling terminates, then added into ball grinder
The aqueous isopropanol of diimine N- dicyclohexylcarbodiimides, the wherein body of diimine N- dicyclohexylcarbodiimides and isopropanol
Product is than being 6:100, with 1800 revs/min of rotating speed ball milling 3 hours, the activated carbon that fracture positioning activation is obtained after washing drying is received
Mitron.
The Activated Carbon Nanotubes of fracture positioning activation are added in flask, 2:The idol of the ethanol solution middle-end position of 1 dilution
Join agent to hydrolyze 3 hours, 1 is pressed with graphene oxide, diimine N- dicyclohexylcarbodiimides after drying:5:0.01 mass ratio exists
60 DEG C are reacted 2 hours, and product deionized water, dimethylbenzene are filtered until neutrality, removes unreacted graphene, carbon nanometer
Pipe, multi-arm heat filling is made, particle diameter is about 0.5 micron, and effect is preferable.
Embodiment 5
Graphene microchip is placed in polytetrafluoroethylene (PTFE) ball grinder, from the carborundum ball milling of 0.5,1 and 2 millimeter of particle diameter
Ball, its ratio are 1:0.7:0.15, it is 40% that ball milling ball, which accounts for ball milling tank volume, adds the concentrated sulfuric acid of certain volume and mixing for nitric acid
The volume ratio of compound, the wherein concentrated sulfuric acid and nitric acid is 80:20, in, ball milling 20 hours under 1000 revs/min of rotating speed, during ball milling
Frozen water is passed through in ball milling tank wall, every 3 hours with changing primary cooling water, obtains the graphene oxide of mechanical stripping.
It is 190 by draw ratio:1, caliber is that 80nm CNT is put into polytetrafluoroethylene (PTFE) ball grinder, from 0.5,1
With the carborundum ball milling ball of 2 millimeters of particle diameters, its ratio is 1:0.75:0.05, it is 40% that ball milling ball, which accounts for ball milling tank volume, adds one
Determine the two of volume（Ethyl acetoacetate）The aqueous isopropanol of aluminic acid diisopropyl ester, wherein two（Ethyl acetoacetate）Aluminic acid two is different
The volume ratio of propyl ester and isopropanol is 0.04:1, ball milling 6 hours under 1500 revs/min of rotating speed, after ball milling terminates, then to ball
In grinding jar add diimine N- dicyclohexylcarbodiimides aqueous isopropanol, wherein diimine N- dicyclohexylcarbodiimides and
The volume ratio of isopropanol is 8:100, with 1800 revs/min of rotating speed ball milling 3 hours, fracture positioning activation is obtained after washing drying
Activated Carbon Nanotubes.
The Activated Carbon Nanotubes of fracture positioning activation are added in flask, 1:The idol of the ethanol solution middle-end position of 1 dilution
Join agent to hydrolyze 2 hours, 1 is pressed with graphene oxide, diimine N- dicyclohexylcarbodiimides after drying:6:0.02 mass ratio exists
60 DEG C are reacted 2 hours, and product deionized water, dimethylbenzene are filtered until neutrality, removes unreacted graphene, carbon nanometer
Pipe, multi-arm heat filling is made, particle diameter is about 0.4 micron, and effect is preferable.
Embodiment 6
Graphene microchip is placed in polytetrafluoroethylene (PTFE) ball grinder, from the carborundum ball milling of 0.5,1 and 2 millimeter of particle diameter
Ball, its ratio are 1:0.65:0.15, it is 40% that ball milling ball, which accounts for ball milling tank volume, adds the concentrated sulfuric acid of certain volume and mixing for nitric acid
The volume ratio of compound, the wherein concentrated sulfuric acid and nitric acid is 40:60, in, ball milling 20 hours under 1400 revs/min of rotating speed, during ball milling
Frozen water is passed through in ball milling tank wall, every 3 hours with changing primary cooling water, obtains the graphene oxide of mechanical stripping.
It is 190 by draw ratio:1, caliber is that 80nm CNT is put into polytetrafluoroethylene (PTFE) ball grinder, from 0.5,1
With the carborundum ball milling ball of 2 millimeters of particle diameters, its ratio is 1:0.75:0.05, it is 40% that ball milling ball, which accounts for ball milling tank volume, adds one
Determine the two of volume（Ethyl acetoacetate）The aqueous isopropanol of aluminic acid diisopropyl ester, wherein two（Ethyl acetoacetate）Aluminic acid two is different
The volume ratio of propyl ester and isopropanol is 0.04:1, ball milling 6 hours under 1500 revs/min of rotating speed, after ball milling terminates, then to ball
In grinding jar add diimine N- dicyclohexylcarbodiimides aqueous isopropanol, wherein diimine N- dicyclohexylcarbodiimides and
The volume ratio of isopropanol is 8:100, with 1800 revs/min of rotating speed ball milling 3 hours, fracture positioning activation is obtained after washing drying
Activated Carbon Nanotubes.
The Activated Carbon Nanotubes of fracture positioning activation are added in flask, 1:The idol of the ethanol solution middle-end position of 1 dilution
Join agent to hydrolyze 2 hours, 1 is pressed with graphene oxide, diimine N- dicyclohexylcarbodiimides after drying:6:0.02 mass ratio exists
60 DEG C are reacted 2 hours, and product deionized water, dimethylbenzene are filtered until neutrality, removes unreacted graphene, carbon nanometer
Pipe, multi-arm heat filling is made, particle diameter is about 0.4 micron, and effect is preferable.
Embodiment 7
Graphene microchip is placed in polytetrafluoroethylene (PTFE) ball grinder, from the carborundum ball milling of 0.5,1 and 2 millimeter of particle diameter
Ball, its ratio are 1:0.65:0.05, ball milling ball accounts for ball milling tank volume as 40%, adds the concentrated sulfuric acid and perchloric acid of certain volume
The volume ratio of mixture, the wherein concentrated sulfuric acid and nitric acid is 10:90, in ball milling 12 hours, ball milling under 1800 revs/min of rotating speed
When in ball milling tank wall be passed through frozen water, every 3 hours with changing primary cooling water, obtain the graphene oxide of mechanical stripping.
It is 100 by draw ratio:1, caliber is that 40nm CNT is put into polytetrafluoroethylene (PTFE) ball grinder, from 0.5,1
With the carborundum ball milling ball of 2 millimeters of particle diameters, its ratio is 1:0.75:0.05, it is 40% that ball milling ball, which accounts for ball milling tank volume, adds one
Determine the two of volume（Acetylacetone,2,4-pentanedione）The aqueous isopropanol of aluminic acid diisopropyl ester, wherein two（Acetylacetone,2,4-pentanedione）Aluminic acid diisopropyl ester and different
The volume ratio of propyl alcohol is 0.04:1, ball milling 4 hours under 2500 revs/min of rotating speed, after ball milling terminates, then add into ball grinder
Enter the aqueous isopropanol of diimine N- dicyclohexylcarbodiimides, wherein diimine N- dicyclohexylcarbodiimides and isopropanol
Volume ratio is 4:100, with 1800 revs/min of rotating speed ball milling 1 hour, the activated carbon of fracture positioning activation is obtained after washing drying
Nanotube.
The Activated Carbon Nanotubes of fracture positioning activation are added in flask, 1:The idol of the ethanol solution middle-end position of 3 dilutions
Join agent to hydrolyze 2 hours, 1 is pressed with graphene oxide, diimine N- dicyclohexylcarbodiimides after drying:7:0.04 mass ratio exists
60 DEG C are reacted 2 hours, and product deionized water, dimethylbenzene are filtered until neutrality, removes unreacted graphene, carbon nanometer
Pipe, multi-arm heat filling is made, particle diameter is about 0.8 micron, best results, sees Fig. 2, Fig. 3.
Fig. 2 is the transmission electron microscope picture of multi-arm heat filling, it can be seen that from the appearance, realizes and is connect in graphenic surface
Branch CNT, form the structure of multi-arm.Fig. 3 is the thermogravimetric analysis figure of multi-arm heat filling, in terms of test result, at 200 degree
There is faint weightlessness, this is relevant with the fracture active group not reacted completely, and generally speaking the heat resistance of powder is preferable, main
Want weightless process to appear in 620 DEG C, common Polymer Processing can be met.
Embodiment 8
Graphene microchip is placed in polytetrafluoroethylene (PTFE) ball grinder, from the carborundum ball milling of 0.5,1 and 2 millimeter of particle diameter
Ball, its ratio are 1:0.65:0.05, ball milling ball accounts for ball milling tank volume as 40%, adds the concentrated sulfuric acid and perchloric acid of certain volume
The volume ratio of mixture, the wherein concentrated sulfuric acid and nitric acid is 80:20, in ball milling 12 hours, ball milling under 1800 revs/min of rotating speed
When in ball milling tank wall be passed through frozen water, every 3 hours with changing primary cooling water, obtain the graphene oxide of mechanical stripping.
It is 130 by draw ratio:1, caliber is that 60nm CNT is put into polytetrafluoroethylene (PTFE) ball grinder, from 0.5,1
With the carborundum ball milling ball of 2 millimeters of particle diameters, its ratio is 1:0.75:0.05, it is 40% that ball milling ball, which accounts for ball milling tank volume, adds one
The aqueous isopropanol of the Di(dioctylpyrophosphato) ethylene titanate of volume is determined, wherein double (two octyloxy pyrophosphates
Base) volume ratio of ethylene titanate esters and isopropanol is 0.02:1, ball milling 4 hours under 2500 revs/min of rotating speed, ball milling terminates
Afterwards, then into ball grinder the aqueous isopropanol of diimine N- dicyclohexylcarbodiimides, wherein diimine N- dicyclohexyls are added
The volume ratio of carbodiimide and isopropanol is 3:100, with 1800 revs/min of rotating speed ball milling 1 hour, broken after washing drying
The Activated Carbon Nanotubes of mouth positioning activation.
The Activated Carbon Nanotubes of fracture positioning activation are added in flask, 1:The idol of the ethanol solution middle-end position of 3 dilutions
Join agent to hydrolyze 2 hours, 1 is pressed with graphene oxide, diimine N- dicyclohexylcarbodiimides after drying:5:0.04 mass ratio exists
60 DEG C are reacted 2 hours, and product deionized water, dimethylbenzene are filtered until neutrality, removes unreacted graphene, carbon nanometer
Pipe, multi-arm heat filling is made, particle diameter is about 0.7 micron, and effect is preferable.
Embodiment 9
Graphene microchip is placed in polytetrafluoroethylene (PTFE) ball grinder, from the carborundum ball milling of 0.5,1 and 2 millimeter of particle diameter
Ball, its ratio are 1:0.6:0.05, ball milling ball accounts for ball milling tank volume as 40%, adds the concentrated sulfuric acid and perchloric acid of certain volume
The volume ratio of mixture, the wherein concentrated sulfuric acid and nitric acid is 50:50, in ball milling 12 hours, ball milling under 1800 revs/min of rotating speed
When in ball milling tank wall be passed through frozen water, every 3 hours with changing primary cooling water, obtain the graphene oxide of mechanical stripping.
It is 130 by draw ratio:1, caliber is that 60nm CNT is put into polytetrafluoroethylene (PTFE) ball grinder, from 0.5,1
With the carborundum ball milling ball of 2 millimeters of particle diameters, its ratio is 1:0.75:0.05, it is 40% that ball milling ball, which accounts for ball milling tank volume, adds one
The aqueous isopropanol of the Di(dioctylpyrophosphato) ethylene titanate of volume is determined, wherein double (two octyloxy pyrophosphates
Base) volume ratio of ethylene titanate esters and isopropanol is 0.02:1, ball milling 4 hours under 2500 revs/min of rotating speed, ball milling terminates
Afterwards, then into ball grinder the aqueous isopropanol of diimine N- dicyclohexylcarbodiimides, wherein diimine N- dicyclohexyls are added
The volume ratio of carbodiimide and isopropanol is 3:100, with 1800 revs/min of rotating speed ball milling 1 hour, broken after washing drying
The Activated Carbon Nanotubes of mouth positioning activation.
The Activated Carbon Nanotubes of fracture positioning activation are added in flask, 1:The idol of the ethanol solution middle-end position of 3 dilutions
Join agent to hydrolyze 2 hours, 1 is pressed with graphene oxide, diimine N- dicyclohexylcarbodiimides after drying:5:0.04 mass ratio exists
60 DEG C are reacted 2 hours, and product deionized water, dimethylbenzene are filtered until neutrality, removes unreacted graphene, carbon nanometer
Pipe, multi-arm heat filling is made, particle diameter is about 0.6 micron, and effect is preferable.
Embodiment 10
Graphene microchip is placed in polytetrafluoroethylene (PTFE) ball grinder, from the carborundum ball milling of 0.5,1 and 2 millimeter of particle diameter
Ball, its ratio are 1:0.8:0.15, it is 40% that ball milling ball, which accounts for ball milling tank volume, adds the concentrated sulfuric acid and potassium permanganate of certain volume
Mixture, wherein the mass ratio of the concentrated sulfuric acid and potassium permanganate be 50:50, ball milling 16 is small under 1800 revs/min of rotating speed
When, frozen water is passed through in ball milling tank wall during ball milling, every 3 hours with changing primary cooling water, obtains the graphite oxide of mechanical stripping
Alkene.
It is 130 by draw ratio:1, caliber is that 40nm CNT is put into polytetrafluoroethylene (PTFE) ball grinder, from 0.5,1
With the carborundum ball milling ball of 2 millimeters of particle diameters, its ratio is 1:0.75:0.05, it is 40% that ball milling ball, which accounts for ball milling tank volume, adds one
The aqueous isopropanol of the Di(dioctylpyrophosphato) ethylene titanate of volume is determined, wherein double (two octyloxy pyrophosphates
Base) volume ratio of ethylene titanate esters and isopropanol is 0.02:1, ball milling 4 hours under 2500 revs/min of rotating speed, ball milling terminates
Afterwards, then into ball grinder the aqueous isopropanol of diimine N- dicyclohexylcarbodiimides, wherein diimine N- dicyclohexyls are added
The volume ratio of carbodiimide and isopropanol is 3:100, with 1800 revs/min of rotating speed ball milling 1 hour, broken after washing drying
The Activated Carbon Nanotubes of mouth positioning activation.
The Activated Carbon Nanotubes of fracture positioning activation are added in flask, 1:The idol of the ethanol solution middle-end position of 3 dilutions
Join agent to hydrolyze 2 hours, 1 is pressed with graphene oxide, diimine N- dicyclohexylcarbodiimides after drying:5:0.04 mass ratio exists
60 DEG C are reacted 2 hours, and product deionized water, dimethylbenzene are filtered until neutrality, removes unreacted graphene, carbon nanometer
Pipe, multi-arm heat filling is made, particle diameter is about 0.7 micron, and effect is preferable.
Embodiment 11
Graphene microchip is placed in polytetrafluoroethylene (PTFE) ball grinder, from the carborundum ball milling of 0.5,1 and 2 millimeter of particle diameter
Ball, its ratio are 1:0.8:0.15, it is 40% that ball milling ball, which accounts for ball milling tank volume, adds the concentrated sulfuric acid and potassium permanganate of certain volume
Mixture, wherein the mass ratio of the concentrated sulfuric acid and potassium permanganate be 80:20, ball milling 16 is small under 1800 revs/min of rotating speed
When, frozen water is passed through in ball milling tank wall during ball milling, every 3 hours with changing primary cooling water, obtains the graphite oxide of mechanical stripping
Alkene.
It is 130 by draw ratio:1, caliber is that 40nm CNT is put into polytetrafluoroethylene (PTFE) ball grinder, from 0.5,1
With the carborundum ball milling ball of 2 millimeters of particle diameters, its ratio is 1:0.75:0.05, it is 40% that ball milling ball, which accounts for ball milling tank volume, adds one
The aqueous isopropanol of the Di(dioctylpyrophosphato) ethylene titanate of volume is determined, wherein double (two octyloxy pyrophosphates
Base) volume ratio of ethylene titanate esters and isopropanol is 0.02:1, ball milling 4 hours under 2500 revs/min of rotating speed, ball milling terminates
Afterwards, then into ball grinder the aqueous isopropanol of diimine N- dicyclohexylcarbodiimides, wherein diimine N- dicyclohexyls are added
The volume ratio of carbodiimide and isopropanol is 3:100, with 1800 revs/min of rotating speed ball milling 1 hour, broken after washing drying
The Activated Carbon Nanotubes of mouth positioning activation.
The Activated Carbon Nanotubes of fracture positioning activation are added in flask, 1:The idol of the ethanol solution middle-end position of 3 dilutions
Join agent to hydrolyze 2 hours, 1 is pressed with graphene oxide, diimine N- dicyclohexylcarbodiimides after drying:5:0.04 mass ratio exists
60 DEG C are reacted 2 hours, and product deionized water, dimethylbenzene are filtered until neutrality, removes unreacted graphene, carbon nanometer
Pipe, multi-arm heat filling is made, particle diameter is about 0.6 micron, and effect is preferable.
Embodiment 12
Graphene microchip is placed in polytetrafluoroethylene (PTFE) ball grinder, from the carborundum ball milling of 0.5,1 and 2 millimeter of particle diameter
Ball, its ratio are 1:0.8:0.15, it is 40% that ball milling ball, which accounts for ball milling tank volume, adds the concentrated sulfuric acid and potassium permanganate of certain volume
Mixture, wherein the mass ratio of the concentrated sulfuric acid and potassium permanganate be 60:40, ball milling 16 is small under 1800 revs/min of rotating speed
When, frozen water is passed through in ball milling tank wall during ball milling, every 3 hours with changing primary cooling water, obtains the graphite oxide of mechanical stripping
Alkene.
It is 130 by draw ratio:1, caliber is that 40nm CNT is put into polytetrafluoroethylene (PTFE) ball grinder, from 0.5,1
With the carborundum ball milling ball of 2 millimeters of particle diameters, its ratio is 1:0.75:0.05, it is 40% that ball milling ball, which accounts for ball milling tank volume, adds one
The aqueous isopropanol of the Di(dioctylpyrophosphato) ethylene titanate of volume is determined, wherein double (two octyloxy pyrophosphates
Base) volume ratio of ethylene titanate esters and isopropanol is 0.02:1, ball milling 4 hours under 2500 revs/min of rotating speed, ball milling terminates
Afterwards, then into ball grinder the aqueous isopropanol of diimine N- dicyclohexylcarbodiimides, wherein diimine N- dicyclohexyls are added
The volume ratio of carbodiimide and isopropanol is 3:100, with 1800 revs/min of rotating speed ball milling 1 hour, broken after washing drying
The Activated Carbon Nanotubes of mouth positioning activation.
The Activated Carbon Nanotubes of fracture positioning activation are added in flask, 1:The idol of the ethanol solution middle-end position of 3 dilutions
Join agent to hydrolyze 2 hours, 1 is pressed with graphene oxide, diimine N- dicyclohexylcarbodiimides after drying:5:0.04 mass ratio exists
60 DEG C are reacted 2 hours, and product deionized water, dimethylbenzene are filtered until neutrality, removes unreacted graphene, carbon nanometer
Pipe, multi-arm heat filling is made, particle diameter is about 0.65 micron, and effect is preferable.
Embodiment 13
Graphene microchip is placed in polytetrafluoroethylene (PTFE) ball grinder, from the carborundum ball milling of 0.5,1 and 2 millimeter of particle diameter
Ball, its ratio are 1:0.8:0.15, ball milling ball accounts for ball milling tank volume as 40%, adds the nitric acid and potassium permanganate of certain volume
The mass ratio of mixture, wherein nitric acid and potassium permanganate is 50:50, in ball milling 16 hours, ball under 1800 revs/min of rotating speed
Frozen water is passed through in ball milling tank wall during mill, every 3 hours with changing primary cooling water, obtains the graphene oxide of mechanical stripping.
It is 130 by draw ratio:1, caliber is that 40nm CNT is put into polytetrafluoroethylene (PTFE) ball grinder, from 0.5,1
With the carborundum ball milling ball of 2 millimeters of particle diameters, its ratio is 1:0.75:0.05, it is 40% that ball milling ball, which accounts for ball milling tank volume, adds one
The aqueous isopropanol of the Di(dioctylpyrophosphato) ethylene titanate of volume is determined, wherein double (two octyloxy pyrophosphates
Base) volume ratio of ethylene titanate esters and isopropanol is 0.02:1, ball milling 4 hours under 2500 revs/min of rotating speed, ball milling terminates
Afterwards, then into ball grinder the aqueous isopropanol of diimine N- dicyclohexylcarbodiimides, wherein diimine N- dicyclohexyls are added
The volume ratio of carbodiimide and isopropanol is 3:100, with 1800 revs/min of rotating speed ball milling 1 hour, broken after washing drying
The Activated Carbon Nanotubes of mouth positioning activation.
The Activated Carbon Nanotubes of fracture positioning activation are added in flask, 1:The idol of the ethanol solution middle-end position of 3 dilutions
Join agent to hydrolyze 2 hours, 1 is pressed with graphene oxide, diimine N- dicyclohexylcarbodiimides after drying:5:0.04 mass ratio exists
60 DEG C are reacted 2 hours, and product deionized water, dimethylbenzene are filtered until neutrality, removes unreacted graphene, carbon nanometer
Pipe, multi-arm heat filling is made, particle diameter is about 0.7 micron, and effect is preferable.
Embodiment 14
Graphene microchip is placed in polytetrafluoroethylene (PTFE) ball grinder, from the carborundum ball milling of 0.5,1 and 2 millimeter of particle diameter
Ball, its ratio are 1:0.8:0.15, ball milling ball accounts for ball milling tank volume as 40%, adds the nitric acid and potassium permanganate of certain volume
The mass ratio of mixture, wherein nitric acid and potassium permanganate is 80:20, in ball milling 16 hours, ball under 1800 revs/min of rotating speed
Frozen water is passed through in ball milling tank wall during mill, every 3 hours with changing primary cooling water, obtains the graphene oxide of mechanical stripping.
It is 130 by draw ratio:1, caliber is that 40nm CNT is put into polytetrafluoroethylene (PTFE) ball grinder, from 0.5,1
With the carborundum ball milling ball of 2 millimeters of particle diameters, its ratio is 1:0.75:0.05, it is 40% that ball milling ball, which accounts for ball milling tank volume, adds one
The aqueous isopropanol of the Di(dioctylpyrophosphato) ethylene titanate of volume is determined, wherein double (two octyloxy pyrophosphates
Base) volume ratio of ethylene titanate esters and isopropanol is 0.02:1, ball milling 4 hours under 2500 revs/min of rotating speed, ball milling terminates
Afterwards, then into ball grinder the aqueous isopropanol of diimine N- dicyclohexylcarbodiimides, wherein diimine N- dicyclohexyls are added
The volume ratio of carbodiimide and isopropanol is 3:100, with 1800 revs/min of rotating speed ball milling 1 hour, broken after washing drying
The Activated Carbon Nanotubes of mouth positioning activation.
The Activated Carbon Nanotubes of fracture positioning activation are added in flask, 1:The idol of the ethanol solution middle-end position of 3 dilutions
Join agent to hydrolyze 2 hours, 1 is pressed with graphene oxide, diimine N- dicyclohexylcarbodiimides after drying:5:0.04 mass ratio exists
60 DEG C are reacted 2 hours, and product deionized water, dimethylbenzene are filtered until neutrality, removes unreacted graphene, carbon nanometer
Pipe, multi-arm heat filling is made, particle diameter is about 0.5 micron, and effect is preferable.
Embodiment 15
Graphene microchip is placed in polytetrafluoroethylene (PTFE) ball grinder, from the carborundum ball milling of 0.5,1 and 2 millimeter of particle diameter
Ball, its ratio are 1:0.8:0.15, ball milling ball accounts for ball milling tank volume as 40%, adds the nitric acid and potassium permanganate of certain volume
The mass ratio of mixture, wherein nitric acid and potassium permanganate is 70:30, in ball milling 16 hours, ball under 1800 revs/min of rotating speed
Frozen water is passed through in ball milling tank wall during mill, every 3 hours with changing primary cooling water, obtains the graphene oxide of mechanical stripping.
It is 130 by draw ratio:1, caliber is that 40nm CNT is put into polytetrafluoroethylene (PTFE) ball grinder, from 0.5,1
With the carborundum ball milling ball of 2 millimeters of particle diameters, its ratio is 1:0.75:0.05, it is 40% that ball milling ball, which accounts for ball milling tank volume, adds one
The aqueous isopropanol of the Di(dioctylpyrophosphato) ethylene titanate of volume is determined, wherein double (two octyloxy pyrophosphates
Base) volume ratio of ethylene titanate esters and isopropanol is 0.02:1, ball milling 4 hours under 2500 revs/min of rotating speed, ball milling terminates
Afterwards, then into ball grinder the aqueous isopropanol of diimine N- dicyclohexylcarbodiimides, wherein diimine N- dicyclohexyls are added
The volume ratio of carbodiimide and isopropanol is 3:100, with 1800 revs/min of rotating speed ball milling 1 hour, broken after washing drying
The Activated Carbon Nanotubes of mouth positioning activation.
The Activated Carbon Nanotubes of fracture positioning activation are added in flask, 1:The idol of the ethanol solution middle-end position of 3 dilutions
Join agent to hydrolyze 2 hours, 1 is pressed with graphene oxide, diimine N- dicyclohexylcarbodiimides after drying:5:0.04 mass ratio exists
60 DEG C are reacted 2 hours, and product deionized water, dimethylbenzene are filtered until neutrality, removes unreacted graphene, carbon nanometer
Pipe, multi-arm heat filling is made, particle diameter is about 0.7 micron, and effect is preferable.
By above-described embodiment it is recognised that the present invention has successfully been grafted substantial amounts of carbon nanometer on the outside of graphene oxide
Pipe, a kind of more arm type fillers of new functionalization are formd, compared to untreated former powder, nano-particle agglomeration weakens,
Dispersion effect is obviously improved, and can effectively facilitate the formation of heat conduction network chain.
Claims (10)
1. a kind of graphene oxide, CNT multi-arm determine the preparation method of configuration heat filling, it is characterised in that：Including as follows
Step：
（1）Graphene microchip, CNT mechanical force peel off activation：
Graphene microchip is utilized into constant temperature ball grinding technique, activation is directly peeled off in ball milling peels off liquid phase, oxygen will be peeled off after ball milling
The graphene filtering of change, neutrality is washed to using deionized water, obtains graphite oxide of the surface with carboxyl that constant temperature ball milling is peeled off
Alkene；CNT peels off activation method using mechanical force, is directly tied using high energy ball milling technology with coupling agent ball-milling reaction, reaction
The Volume fraction of Shu Hou, the aqueous isopropanol of addition diimine in ball grinder, diimine and isopropanol is 2 ~ 10:100, after
Continuous ball milling 1 ~ 4 hour, rotational speed of ball-mill is 1800 revs/min, after ball milling, is washed with deionized water to neutrality, in 80 DEG C of vacuum drying
12 hours, grinding formed the Activated Carbon Nanotubes of fracture positioning activation；
（2）The preparation of more arm type heat fillings：
Obtain hydroxyl hydrolysis CNT after the Activated Carbon Nanotubes of fracture positioning activation are hydrolyzed, and with surface band
The graphene oxide stripping film of carboxyl room temperature under the effect of diimine class material carries out graft reaction 2 hours, hydrolysis CNT,
The mass ratio of graphene oxide stripping film and diimine class material is 1:1~9:0.06~0.23；
（3）The purifying of more arm type heat fillings：
Powder prepared by graft reaction is flowed back in dimethylbenzene, and filtered, the graphene, CNT, carbon for removing remaining are miscellaneous
Matter, obtain the more arm type heat fillings for determining structure design.
2. a kind of graphene oxide, CNT multi-arm determine the preparation method of configuration heat filling according to claim 1, its
It is characterised by：Step（1）The graphene microchip constant temperature ball milling be by graphene microchip in polytetrafluoroethylene (PTFE) ball grinder ball milling
Peel off, frozen water constant temperature is filled with the outside of ball grinder, rotational speed of ball-mill is 400 ~ 2000 revs/min, and the reaction time is 12 ~ 24 hours, often
Outside frozen water was changed every 3 hours and carries out temperature adjusting；Wherein ball milling ball is Ceramic Balls, and the particle diameter of ball milling ball selects 0.5,1,2,
5 and 10 millimeters of particle diameters, ball milling ball configure by a certain percentage, and ball milling sphere volume accounts for the 40 ~ 60% of ball milling tank volume.
3. a kind of graphene oxide, CNT multi-arm determine the preparation method of configuration heat filling according to claim 1, its
It is characterised by：Step（1）It is acid solution that the ball milling, which peels off liquid phase, and its acid solution is sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, in phosphoric acid
One or more mixtures；When selecting the mixture of sulfuric acid, nitric acid or sulfuric acid, perchloric acid, its volume ratio is 10:90~80:
20。
4. a kind of graphene oxide, CNT multi-arm determine the preparation method of configuration heat filling according to claim 2, its
It is characterised by：The ball milling ball is carborundum or boron nitride ceramics ball milling ball, and ball milling spherolite footpath is 0.5,1 and 2 millimeter of particle diameter, its
Ratio is 1:0.6~0.8:0.2~0.05.
5. a kind of graphene oxide, CNT multi-arm determine the preparation method of configuration heat filling according to claim 1, its
It is characterised by：The caliber of the CNT is 20 ~ 100nm, and the draw ratio of CNT is 80:1~200:1.
6. a kind of graphene oxide, CNT multi-arm determine the preparation method of configuration heat filling according to claim 1, its
It is characterised by：Step（1）The mechanical force peels off activation method as ball milling is anti-in polytetrafluoroethylene (PTFE) ball grinder by CNT
Should, wherein ball milling peels off the aqueous isopropanol that liquid phase is titanate coupling agent or aluminate coupling agent, coupling agent and isopropanol
Volume ratio is 0.003:1~0.05:1, rotational speed of ball-mill is 800 ~ 3000 revs/min, and the reaction time is 3 ~ 9 hours；Ball milling ball is pottery
Porcelain ball, the particle diameter of ball milling ball select 0.5,1,2,5 and 10 millimeter of particle diameter, and ball milling ball configures by a certain percentage, ball milling sphere volume
Account for the 20 ~ 40% of ball milling tank volume.
7. a kind of graphene oxide, CNT multi-arm determine the preparation method of configuration heat filling according to claim 6, its
It is characterised by：Described titanate coupling agent is isopropyl three（Dioctylphyrophosphoric acid acyloxy）Titanate esters, (two is pungent for isopropyl three
Base phosphoric acid acyloxy) titanate esters, the oleic acid acyloxy of isopropyl two（Dioctyl phosphoric acid acyloxy）Titanate esters, double (two octyloxies are burnt
It is phosphate-based) ethylene titanate esters, one kind in plant acid type monoalkoxy class titanate esters, described aluminate coupling agent is two
（Ethyl acetoacetate）Aluminic acid diisopropyl ester, two（Acetylacetone,2,4-pentanedione）One kind in aluminic acid diisopropyl ester；The ball milling ball is carbonization
Silicon or boron nitride ceramics ball milling ball, ball milling spherolite footpath are 0.5,1 and 2 millimeter of particle diameter, and its ratio is 1:0.6~0.8:0.2~0.05.
8. a kind of graphene oxide, CNT multi-arm determine the preparation method of configuration heat filling according to claim 1, its
It is characterised by：Step（1）Described diimine is N, N'- dicyclohexylcarbodiimides（DCC）, or N, N'- diisopropyl carbon two
Imines（DIC）Or 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides（EDC）In one kind.
9. a kind of graphene oxide, CNT multi-arm determine the preparation method of configuration heat filling according to claim 1, its
It is characterised by：Step（2）The hydrolysis CNT is the aqueous solution of the Activated Carbon Nanotubes in ethanol that fracture is positioned to activation
Middle dissolving, the aqueous solution of ethanol be absolute ethyl alcohol with deionized water according to volume ratio 5:1~1:5 configurations, the vibration point in Ultrasound Instrument
Dissipate 2 ~ 4 hours, hydrolysis CNT is obtained after drying.
10. a kind of graphene oxide, CNT multi-arm determine the preparation method of configuration heat filling according to claim 1,
It is characterized in that：Step（2）The diimine class material is N, N'- dicyclohexylcarbodiimides（DCC）, or N, N'- diisopropyl
Base carbodiimide（DIC）Or 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides（EDC）In one kind.
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