CN105295098A - Preparation method of graphene oxide/carbon nanotube multi-arm heat conducting filler - Google Patents
Preparation method of graphene oxide/carbon nanotube multi-arm heat conducting filler Download PDFInfo
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Abstract
The invention relates to a mechanical and chemical preparation method of graphene/carbon nanotube multi-arm heat conducting filler, belonging to the technical field of high-performance powdery material preparation. The preparation method comprises the steps of fixedly linking the end of a carbon nanotube to the surface of graphene oxide serving as an inner core by using a simple mechanicl and chemical method, and forming multi-arm filler with high heat conductivity by virtue of the high heat conductivity of graphene and the carbon nanotube. Based on the high heat conductivity of a nanocarbon material the increment of specific surface area, the novel heat conducting filler prepared by using the preparation method can be used for improving the dispersing performance and heat conducting effect of the carbon nanotube to the great extent and is stable in structure.
Description
Technical field
The present invention relates to a kind of graphene oxide, preparation method that carbon nanotube multi-arm determines configuration heat conductive filler, be specifically related to a kind of preparation method of the graphene/carbon nano-tube multi-arm type heat conductive filler utilizing mechanochemistry method to prepare, belong to high-performance powder technical field of material.
Background technology
Metallic substance is the good conductor of traditional heat, metallic substance a large amount of in common Industrial products is used to make heat conduction and radiating element, while meeting heat conduction demand, also bring that product appearance is simple, weight more greatly, the defect of not resistance to chemical attack.Along with the progress of science and technology, people have required further raising to thermally conductive material, light weight, easily machine-shaping, shock resistance, resistance to chemical attack, heat-resistant anti-fatigue, excellent electrical insulation capability and chemical stability etc. are all the new demands of people to thermally conductive material, and the fast development of a collection of new industries such as integrated package, heat pipe, unicircuit, copper-clad plate, aerospace electronics, motor communication simultaneously also improves the demand of people to heat-conductive composite material.
The quantity of the kind of filler, particle diameter, shape, pattern, filling, have impact on the heat conductivility of heat-conductive composite material greatly with the interface performance etc. of matrix, heat conductive filler is no matter with granular, sheet or threadiness exists, and heat conductivility is all than macromolecule matrix height itself.When the loading level of heat conductive filler is very little, can not form real contact and interaction between heat conductive filler, this is almost nonsensical to the raising of macromolecular material heat conductivility; Only have when in macromolecule matrix, when the loading level of heat conductive filler reaches a certain threshold value, just have interaction truly between heat conductive filler, system could form form---the i.e. heat conduction network chain of similar netted or chain.When the orientation of heat conduction network chain is consistent with direction of heat flow, heat conductivility improves very fast; When direction of heat flow being failed form heat conduction network chain, can produce great thermal resistance, heat conductivility is obviously deteriorated.Therefore, in system, on direction of heat flow, how farthest to form heat conduction network chain become the key point improving heat-conducting polymer material heat conductivility.Carbon nanomaterial is extensively paid close attention to by scientific research as a large class high conduction powder emerging in recent years, utilizes it as heat conduction hotchpotch to form more technical literature.
Use carbon material and different shape, the filler of particle diameter carries out mixing the formation accelerating heat conduction network chain, the effective thermal conductivity promoting polymer composites, the key improving thermal conductivity is to define a large amount of heat conduction network chains.Patent CN201410539991.0 gives a kind of liquid phase and concentrates the preparation method preparing polyphenylene sulfide/Graphene heat-conductive composite material, utilize in liquid phase and form two-arch tunnel, obtain high thermal conductivity, patent CN201410221717.9 gives the preparation method of one kind of multiple sized alumina and the composite moulded heat-conductive insulated plastics as heat conductive filler of Graphene, patent CN201410775161.8 gives a kind of heat conductive insulating matrix material of simple composite Graphene/carbon black/carbon nanotube heat conduction component, because heat conduction component concentration (3 ~ 5 parts) is much smaller than insulated type heat conductive filler (60 parts), in general, manufacture in the technical scheme of highly heat-conductive material, more utilize the continuity between filler to form heat conduction site.
There is due to nano particle the characteristics such as small-size effect, quantum size effect and surface effects, cause a large amount of nano particle to reunite in the course of processing together, can not well disperse, make excellent performance be difficult to represent; Bat wool can be broken cut-out in the course of processing, is difficult to the effect realizing building bridge; Laminal filler often occurs with the form of multiple-level stack, is difficult to occur layering in the course of processing.Expect simply to rely on the overlap joint of filler in the course of processing and realize hydridization, obviously there is uncertainty.If realize heat conductive filler structure determine structure design so will improve service efficiency and the thermal conductivity of heat conductive filler greatly.ZL201210392066.0 proposes a kind of technological method determining structure heat conductive filler using chemical graft method to obtain carbon black/carbon nanotube, but the thermal conductivity of carbon black is significantly lower than carbon nanotube, the tap density of spherical carbon black is on the low side simultaneously, the thermal resistance formed is larger, and being unfavorable for the enforcement of this technological method, the manufacture graphene oxide/carbon nanotube utilizing mechanical force activating to be combined with chemical reaction is determined the multi-arm heat conductive filler that structure combines and be have not been reported.
Summary of the invention
The object of this invention is to provide a kind of graphene oxide, preparation method that carbon nanotube multi-arm determines configuration heat conductive filler, study a kind of manufacture graphene oxide/carbon nanotube utilizing mechanical force activating to be combined with chemical reaction and determine the multi-arm heat conductive filler that structure combines, overcome by the problem of the unstable hydridization inefficiency brought of processing.Research carbon nanotube chemical is grafted on Graphene, the Thermal Arm formed by carbon nanotube is formed at graphenic surface, and utilizing the high heat conductance of Graphene and carbon nanotube to form multi-arm heat conductive filler, this particle is by electron microscopy observation to multi-arm structure, and filling-material structure is stablized.
To achieve these goals, the technical solution used in the present invention is as follows:
Graphene oxide, carbon nanotube multi-arm determine a preparation method for configuration heat conductive filler, comprise the steps:
(1) graphene microchip, carbon nanotube mechanical force peel off activation:
Graphene microchip is utilized constant temperature ball grinding technique, peel off in liquid phase at ball milling and directly peel off activation, after ball milling, the Graphene peeling off oxidation is filtered, utilize deionized water to be washed to neutrality, obtain the graphene oxide of the surface band carboxyl that constant temperature ball milling is peeled off; Carbon nanotube adopts mechanical force to peel off activation method, utilize high energy ball milling technology directly and coupling agent ball-milling reaction, after reaction terminates, in ball grinder, add the aqueous isopropanol of diimine, the Volume fraction of diimine and Virahol is 2 ~ 10:100, continue ball milling 1 ~ 4 hour, rotational speed of ball-mill is 1800 revs/min, after ball milling, is washed till neutrality with deionized water, 80 DEG C of vacuum-dryings 12 hours, grinding formed the Activated Carbon Nanotubes of fracture location activation;
(2) preparation of multi-arm type heat conductive filler:
Hydroxyl hydrolysis carbon nanotube is obtained after being hydrolyzed by the Activated Carbon Nanotubes of fracture location activation, and carrying out graft reaction 2 hours with graphene oxide stripping film room temperature under the effect of diimine class material of surface band carboxyl, the mass ratio of hydrolysis carbon nanotube, graphene oxide stripping film and diimine class material is 1:1 ~ 9:0.06 ~ 0.23;
(3) purifying of multi-arm type heat conductive filler:
The powder prepared by graft reaction refluxes in dimethylbenzene, and filters, and removes the impurity such as remaining Graphene, carbon nanotube, carbon, obtains the multi-arm type heat conductive filler determining structure design.
Step (1) described graphene microchip constant temperature ball milling is peeled off by graphene microchip ball milling in tetrafluoroethylene ball grinder, frozen water constant temperature is filled with outside ball grinder, rotational speed of ball-mill is 400 ~ 2000 revs/min, and the reaction times is 12 ~ 24 hours, changes outside frozen water carry out temperature adjusting every 3 hours; Wherein ball milling ball is Ceramic Balls, and the particle diameter of ball milling ball selects 0.5,1,2,5 and 10 millimeter of particle diameter, and ball milling ball configures by a certain percentage, and ball milling sphere volume accounts for 40 ~ 60% of ball grinder volume.
Described ball milling ball is silicon carbide or boron nitride ceramics ball milling ball, and ball milling spherolite footpath is 0.5,1 and 2 millimeter of particle diameter, and its ratio is 1:0.6 ~ 0.8:0.2 ~ 0.05.
It is acid solution that the described ball milling of step (1) peels off liquid phase, and its acid solution is sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, potassium permanganate, one or more the mixture in phosphoric acid; When select sulfuric acid, nitric acid or sulfuric acid, perchloric acid mixture time, its volume ratio is 10:90 ~ 80:20, when select sulfuric acid, potassium permanganate or nitric acid, potassium permanganate mixture time, its mass ratio is 50:50 ~ 80:20.
The caliber of described carbon nanotube is 20 ~ 100nm, and the length-to-diameter ratio of carbon nanotube is 80:1 ~ 200:1.
It is by carbon nanotube ball-milling reaction in tetrafluoroethylene ball grinder that the described mechanical force of step (1) peels off activation method, wherein ball milling peels off the aqueous isopropanol that liquid phase is titanate coupling agent or aluminate coupling agent, the volume ratio of coupling agent and Virahol is 0.003:1 ~ 0.05:1, rotational speed of ball-mill is 800 ~ 3000 revs/min, and the reaction times is 3 ~ 9 hours; Ball milling ball is Ceramic Balls, and the particle diameter of ball milling ball selects 0.5,1,2,5 and 10 millimeter of particle diameter, and ball milling ball configures by a certain percentage, and ball milling sphere volume accounts for 20 ~ 40% of ball grinder volume.
Described titanate coupling agent is sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester, sec.-propyl three (dioctyl phosphoric acid acyloxy) titanic acid ester, sec.-propyl two oleic acid acyloxy (dioctyl phosphoric acid acyloxy) titanic acid ester, Di(dioctylpyrophosphato) ethylene titanate, one in plant acid type monoalkoxy class titanic acid ester, described aluminate coupling agent is two (methyl aceto acetate) aluminic acid diisopropyl ester, the one in two (methyl ethyl diketone) aluminic acid diisopropyl ester; Described ball milling ball is silicon carbide or boron nitride ceramics ball milling ball, and ball milling spherolite footpath is 0.5,1 and 2 millimeter of particle diameter, and its ratio is 1:0.6 ~ 0.8:0.2 ~ 0.05.
Diimine described in step (1) is N-dicyclohexylcarbodiimide (DCC), or the one in N, N'-DIC (DIC) or 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDC).
The described hydrolysis carbon nanotube of step (2) is dissolved in the aqueous solution of ethanol by the grafting carbon nanotube obtained after grafting, the aqueous solution of ethanol is that dehydrated alcohol and deionized water configure according to volume ratio 5:1 ~ 1:5, vibrating dispersion 2 ~ 4 hours in ultrasonic apparatus, obtains hydrolysis carbon nanotube after dry.
Step (2) described diimine is N, N-dicyclohexylcarbodiimide (DCC), or the one in N, N'-DIC (DIC) or 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDC).
The invention has the beneficial effects as follows: by the surface grafting carbon nanotube at graphene oxide, form multi-arm heat conductive filler, the filler of this structure effectively can improve the heat-conducting effect of filler, can promote the formation of heat conduction network chain in matrix, the object realizing thermal conductive network chain formation that can be stable; Meanwhile, improve the dispersing property of carbon nanotube to a certain extent, and there is no the original hollow structure of destroying carbon nanometer tube, expand the application of carbon nanotube in polymer matrix composite.
Accompanying drawing explanation
Fig. 1 multi-arm of the present invention determines the process flow diagram of configuration heat conductive filler preparation method;
The transmission electron microscope picture of the multi-arm heat conductive filler that Fig. 2 embodiment 7 is obtained;
The thermogravimetric analysis figure of the multi-arm heat conductive filler that Fig. 3 embodiment 7 is obtained.
Embodiment
Be described in further details the present invention below by example, these examples are only used for the present invention is described, do not limit the scope of the invention;
Embodiment 1
Graphene microchip is placed in tetrafluoroethylene ball grinder, select 0.5, the silicon carbide ball milling ball of 1 and 2 millimeter of particle diameter, its ratio is 1:0.6:0.2, and it is 40% that ball milling ball accounts for ball grinder volume, adds the vitriol oil of certain volume, ball milling 12 hours under the rotating speed of 400 revs/min, passing into frozen water at ball grinder outer wall during ball milling, every 3 hours with changing primary water, obtaining the graphene oxide of mechanically peel.
Be 80:1 by length-to-diameter ratio, caliber is that the carbon nanotube of 20nm puts into tetrafluoroethylene ball grinder, select 0.5, the silicon carbide ball milling ball of 1 and 2 millimeter of particle diameter, its ratio is 1:0.8:0.05, it is 20% that ball milling ball accounts for ball grinder volume, add the aqueous isopropanol of sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester of certain volume, wherein the volume ratio of sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester and Virahol is 0.003:1, ball milling 9 hours under the rotating speed of 800 revs/min, after ball milling terminates, N is added again in ball grinder, the aqueous isopropanol of N-dicyclohexylcarbodiimide, wherein N, the volume ratio of N-dicyclohexylcarbodiimide and Virahol is 2:100, with the rotating speed ball milling 1 hour of 1800 revs/min, washing obtains the Activated Carbon Nanotubes of fracture location activation after drying.
The Activated Carbon Nanotubes of fracture location activation is added in flask, 2 hours are hydrolyzed at the coupling agent of the ethanolic soln middle-end position of 5:1 dilution, dry rear and graphene oxide, N, N-dicyclohexylcarbodiimide presses the mass ratio of 1:1:0.06 60 DEG C of reactions 2 hours, by product deionized water, dimethylbenzene suction filtration until neutrality, remove unreacted Graphene, carbon nanotube, obtained multi-arm heat conductive filler, particle diameter is about 1 micron, and effect is better.
Embodiment 2
Graphene microchip is placed in tetrafluoroethylene ball grinder, select 0.5, the boron nitride ball milling ball of 1 and 2 millimeter of particle diameter, its ratio is 1:0.8:0.05, and it is 60% that ball milling ball accounts for ball grinder volume, adds the nitric acid of certain volume, ball milling 24 hours under the rotating speed of 2000 revs/min, passing into frozen water at ball grinder outer wall during ball milling, every 3 hours with changing primary water, obtaining the graphene oxide of mechanically peel.
Be 200:1 by length-to-diameter ratio, caliber is that the carbon nanotube of 10nm puts into tetrafluoroethylene ball grinder, select 0.5, the silicon carbide ball milling ball of 1 and 2 millimeter of particle diameter, its ratio is 1:0.6:0.2, it is 40% that ball milling ball accounts for ball grinder volume, add the aqueous isopropanol of sec.-propyl three (the dioctyl phosphoric acid acyloxy) titanic acid ester of certain volume, wherein the volume ratio of different sec.-propyl three (dioctyl phosphoric acid acyloxy) titanic acid ester and Virahol is 0.05:1, ball milling 3 hours under the rotating speed of 3000 revs/min, after ball milling terminates, N is added again in ball grinder, the aqueous isopropanol of N'-DIC, wherein N, the volume ratio of N'-DIC and Virahol is 10:100, with the rotating speed ball milling 4 hours of 1800 revs/min, washing obtains the Activated Carbon Nanotubes of fracture location activation after drying.
The Activated Carbon Nanotubes of fracture location activation is added in flask, 2 hours are hydrolyzed at the coupling agent of the ethanolic soln middle-end position of 1:5 dilution, dry rear and graphene oxide, N, N'-DIC presses the mass ratio of 1:9:0.23 60 DEG C of reactions 0.5 hour, by product deionized water, dimethylbenzene suction filtration until neutrality, remove unreacted Graphene, carbon nanotube, obtained multi-arm heat conductive filler, particle diameter is about 0.3 micron, and effect is better.
Embodiment 3
Graphene microchip is placed in tetrafluoroethylene ball grinder, select 0.5, the silicon carbide ball milling ball of 1 and 2 millimeter of particle diameter, its ratio is 1:0.7:0.1, and it is 50% that ball milling ball accounts for ball grinder volume, adds the perchloric acid of certain volume, ball milling 16 hours under the rotating speed of 600 revs/min, passing into frozen water at ball grinder outer wall during ball milling, every 3 hours with changing primary water, obtaining the graphene oxide of mechanically peel.
Be 100:1 by length-to-diameter ratio, caliber is that the carbon nanotube of 40nm puts into tetrafluoroethylene ball grinder, select 0.5, the silicon carbide ball milling ball of 1 and 2 millimeter of particle diameter, its ratio is 1:0.6:0.15, it is 30% that ball milling ball accounts for ball grinder volume, add the aqueous isopropanol of sec.-propyl two oleic acid acyloxy (the dioctyl phosphoric acid acyloxy) titanic acid ester of certain volume, wherein the volume ratio of sec.-propyl two oleic acid acyloxy (dioctyl phosphoric acid acyloxy) titanic acid ester and Virahol is 0.01:1, ball milling 4 hours under the rotating speed of 1000 revs/min, after ball milling terminates, the aqueous isopropanol of 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride is added again in ball grinder, wherein the volume ratio of 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride and Virahol is 4:100, with the rotating speed ball milling 2 hours of 1800 revs/min, washing obtains the Activated Carbon Nanotubes of fracture location activation after drying.
The Activated Carbon Nanotubes of fracture location activation is added in flask, 2 hours are hydrolyzed at the coupling agent of the ethanolic soln middle-end position of 3:1 dilution, the mass ratio that afterwards dry and graphene oxide, 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride press 1:3:0.08 reacts 2 hours at 60 DEG C, by product deionized water, dimethylbenzene suction filtration until neutrality, remove unreacted Graphene, carbon nanotube, obtained multi-arm heat conductive filler, particle diameter is about 0.4 micron, and effect is better.
Embodiment 4
Graphene microchip is placed in tetrafluoroethylene ball grinder, select the silicon carbide ball milling ball of 0.5,1 and 2 millimeter of particle diameter, its ratio is 1:0.6:0.15, it is 40% that ball milling ball accounts for ball grinder volume, add the vitriol oil of certain volume and the mixture of nitric acid, wherein the volume ratio of the vitriol oil and nitric acid is 10:90, ball milling 18 hours under the rotating speed of 800 revs/min, passing into frozen water at ball grinder outer wall during ball milling, every 3 hours with changing primary water, obtaining the graphene oxide of mechanically peel.
Be 150:1 by length-to-diameter ratio, caliber is that the carbon nanotube of 60nm puts into tetrafluoroethylene ball grinder, select 0.5, the silicon carbide ball milling ball of 1 and 2 millimeter of particle diameter, its ratio is 1:0.65:0.1, it is 40% that ball milling ball accounts for ball grinder volume, add the aqueous isopropanol of the plant acid type monoalkoxy class titanic acid ester of certain volume, wherein the volume ratio of plant acid type monoalkoxy class titanic acid ester and Virahol is 0.02:1, ball milling 6 hours under the rotating speed of 1500 revs/min, after ball milling terminates, the aqueous isopropanol of diimine N-dicyclohexylcarbodiimide is added again in ball grinder, wherein the volume ratio of diimine N-dicyclohexylcarbodiimide and Virahol is 6:100, with the rotating speed ball milling 3 hours of 1800 revs/min, washing obtains the Activated Carbon Nanotubes of fracture location activation after drying.
The Activated Carbon Nanotubes of fracture location activation is added in flask, 3 hours are hydrolyzed at the coupling agent of the ethanolic soln middle-end position of 2:1 dilution, the mass ratio that afterwards dry and graphene oxide, diimine N-dicyclohexylcarbodiimide press 1:5:0.01 reacts 2 hours at 60 DEG C, by product deionized water, dimethylbenzene suction filtration until neutrality, remove unreacted Graphene, carbon nanotube, obtained multi-arm heat conductive filler, particle diameter is about 0.5 micron, and effect is better.
Embodiment 5
Graphene microchip is placed in tetrafluoroethylene ball grinder, select the silicon carbide ball milling ball of 0.5,1 and 2 millimeter of particle diameter, its ratio is 1:0.7:0.15, it is 40% that ball milling ball accounts for ball grinder volume, add the vitriol oil of certain volume and the mixture of nitric acid, wherein the volume ratio of the vitriol oil and nitric acid is 80:20, ball milling 20 hours under the rotating speed of 1000 revs/min, passing into frozen water at ball grinder outer wall during ball milling, every 3 hours with changing primary water, obtaining the graphene oxide of mechanically peel.
Be 190:1 by length-to-diameter ratio, caliber is that the carbon nanotube of 80nm puts into tetrafluoroethylene ball grinder, select 0.5, the silicon carbide ball milling ball of 1 and 2 millimeter of particle diameter, its ratio is 1:0.75:0.05, it is 40% that ball milling ball accounts for ball grinder volume, add the aqueous isopropanol of two (methyl aceto acetate) aluminic acid diisopropyl ester of certain volume, wherein the volume ratio of two (methyl aceto acetate) aluminic acid diisopropyl ester and Virahol is 0.04:1, ball milling 6 hours under the rotating speed of 1500 revs/min, after ball milling terminates, the aqueous isopropanol of diimine N-dicyclohexylcarbodiimide is added again in ball grinder, wherein the volume ratio of diimine N-dicyclohexylcarbodiimide and Virahol is 8:100, with the rotating speed ball milling 3 hours of 1800 revs/min, washing obtains the Activated Carbon Nanotubes of fracture location activation after drying.
The Activated Carbon Nanotubes of fracture location activation is added in flask, 2 hours are hydrolyzed at the coupling agent of the ethanolic soln middle-end position of 1:1 dilution, the mass ratio that afterwards dry and graphene oxide, diimine N-dicyclohexylcarbodiimide press 1:6:0.02 reacts 2 hours at 60 DEG C, by product deionized water, dimethylbenzene suction filtration until neutrality, remove unreacted Graphene, carbon nanotube, obtained multi-arm heat conductive filler, particle diameter is about 0.4 micron, and effect is better.
Embodiment 6
Graphene microchip is placed in tetrafluoroethylene ball grinder, select the silicon carbide ball milling ball of 0.5,1 and 2 millimeter of particle diameter, its ratio is 1:0.65:0.15, it is 40% that ball milling ball accounts for ball grinder volume, add the vitriol oil of certain volume and the mixture of nitric acid, wherein the volume ratio of the vitriol oil and nitric acid is 40:60, ball milling 20 hours under the rotating speed of 1400 revs/min, passing into frozen water at ball grinder outer wall during ball milling, every 3 hours with changing primary water, obtaining the graphene oxide of mechanically peel.
Be 190:1 by length-to-diameter ratio, caliber is that the carbon nanotube of 80nm puts into tetrafluoroethylene ball grinder, select 0.5, the silicon carbide ball milling ball of 1 and 2 millimeter of particle diameter, its ratio is 1:0.75:0.05, it is 40% that ball milling ball accounts for ball grinder volume, add the aqueous isopropanol of two (methyl aceto acetate) aluminic acid diisopropyl ester of certain volume, wherein the volume ratio of two (methyl aceto acetate) aluminic acid diisopropyl ester and Virahol is 0.04:1, ball milling 6 hours under the rotating speed of 1500 revs/min, after ball milling terminates, the aqueous isopropanol of diimine N-dicyclohexylcarbodiimide is added again in ball grinder, wherein the volume ratio of diimine N-dicyclohexylcarbodiimide and Virahol is 8:100, with the rotating speed ball milling 3 hours of 1800 revs/min, washing obtains the Activated Carbon Nanotubes of fracture location activation after drying.
The Activated Carbon Nanotubes of fracture location activation is added in flask, 2 hours are hydrolyzed at the coupling agent of the ethanolic soln middle-end position of 1:1 dilution, the mass ratio that afterwards dry and graphene oxide, diimine N-dicyclohexylcarbodiimide press 1:6:0.02 reacts 2 hours at 60 DEG C, by product deionized water, dimethylbenzene suction filtration until neutrality, remove unreacted Graphene, carbon nanotube, obtained multi-arm heat conductive filler, particle diameter is about 0.4 micron, and effect is better.
Embodiment 7
Graphene microchip is placed in tetrafluoroethylene ball grinder, select the silicon carbide ball milling ball of 0.5,1 and 2 millimeter of particle diameter, its ratio is 1:0.65:0.05, it is 40% that ball milling ball accounts for ball grinder volume, add the vitriol oil of certain volume and the mixture of perchloric acid, wherein the volume ratio of the vitriol oil and nitric acid is 10:90, ball milling 12 hours under the rotating speed of 1800 revs/min, passing into frozen water at ball grinder outer wall during ball milling, every 3 hours with changing primary water, obtaining the graphene oxide of mechanically peel.
Be 100:1 by length-to-diameter ratio, caliber is that the carbon nanotube of 40nm puts into tetrafluoroethylene ball grinder, select 0.5, the silicon carbide ball milling ball of 1 and 2 millimeter of particle diameter, its ratio is 1:0.75:0.05, it is 40% that ball milling ball accounts for ball grinder volume, add the aqueous isopropanol of two (methyl ethyl diketone) aluminic acid diisopropyl ester of certain volume, wherein the volume ratio of two (methyl ethyl diketone) aluminic acid diisopropyl ester and Virahol is 0.04:1, ball milling 4 hours under the rotating speed of 2500 revs/min, after ball milling terminates, the aqueous isopropanol of diimine N-dicyclohexylcarbodiimide is added again in ball grinder, wherein the volume ratio of diimine N-dicyclohexylcarbodiimide and Virahol is 4:100, with the rotating speed ball milling 1 hour of 1800 revs/min, washing obtains the Activated Carbon Nanotubes of fracture location activation after drying.
The Activated Carbon Nanotubes of fracture location activation is added in flask, 2 hours are hydrolyzed at the coupling agent of the ethanolic soln middle-end position of 1:3 dilution, the mass ratio that afterwards dry and graphene oxide, diimine N-dicyclohexylcarbodiimide press 1:7:0.04 reacts 2 hours at 60 DEG C, by product deionized water, dimethylbenzene suction filtration until neutrality, remove unreacted Graphene, carbon nanotube, obtained multi-arm heat conductive filler, particle diameter is about 0.8 micron, best results, is shown in Fig. 2, Fig. 3.
Fig. 2 is the transmission electron microscope picture of multi-arm heat conductive filler, can find out from appearance, achieve at graphenic surface grafting carbon nanotube, forms the structure of multi-arm.Fig. 3 is the thermogravimetric analysis figure of multi-arm heat conductive filler, from test result, has faint weightlessness at 200 degree, this is relevant with the fracture active group of non-complete reaction, generally speaking the thermotolerance of powder is better, and main Weight lose appears at 620 DEG C, can meet common polymer processing.
Embodiment 8
Graphene microchip is placed in tetrafluoroethylene ball grinder, select the silicon carbide ball milling ball of 0.5,1 and 2 millimeter of particle diameter, its ratio is 1:0.65:0.05, it is 40% that ball milling ball accounts for ball grinder volume, add the vitriol oil of certain volume and the mixture of perchloric acid, wherein the volume ratio of the vitriol oil and nitric acid is 80:20, ball milling 12 hours under the rotating speed of 1800 revs/min, passing into frozen water at ball grinder outer wall during ball milling, every 3 hours with changing primary water, obtaining the graphene oxide of mechanically peel.
Be 130:1 by length-to-diameter ratio, caliber is that the carbon nanotube of 60nm puts into tetrafluoroethylene ball grinder, select 0.5, the silicon carbide ball milling ball of 1 and 2 millimeter of particle diameter, its ratio is 1:0.75:0.05, it is 40% that ball milling ball accounts for ball grinder volume, add the aqueous isopropanol of the Di(dioctylpyrophosphato) ethylene titanate of certain volume, wherein the volume ratio of Di(dioctylpyrophosphato) ethylene titanate and Virahol is 0.02:1, ball milling 4 hours under the rotating speed of 2500 revs/min, after ball milling terminates, the aqueous isopropanol of diimine N-dicyclohexylcarbodiimide is added again in ball grinder, wherein the volume ratio of diimine N-dicyclohexylcarbodiimide and Virahol is 3:100, with the rotating speed ball milling 1 hour of 1800 revs/min, washing obtains the Activated Carbon Nanotubes of fracture location activation after drying.
The Activated Carbon Nanotubes of fracture location activation is added in flask, 2 hours are hydrolyzed at the coupling agent of the ethanolic soln middle-end position of 1:3 dilution, the mass ratio that afterwards dry and graphene oxide, diimine N-dicyclohexylcarbodiimide press 1:5:0.04 reacts 2 hours at 60 DEG C, by product deionized water, dimethylbenzene suction filtration until neutrality, remove unreacted Graphene, carbon nanotube, obtained multi-arm heat conductive filler, particle diameter is about 0.7 micron, and effect is better.
Embodiment 9
Graphene microchip is placed in tetrafluoroethylene ball grinder, select the silicon carbide ball milling ball of 0.5,1 and 2 millimeter of particle diameter, its ratio is 1:0.6:0.05, it is 40% that ball milling ball accounts for ball grinder volume, add the vitriol oil of certain volume and the mixture of perchloric acid, wherein the volume ratio of the vitriol oil and nitric acid is 50:50, ball milling 12 hours under the rotating speed of 1800 revs/min, passing into frozen water at ball grinder outer wall during ball milling, every 3 hours with changing primary water, obtaining the graphene oxide of mechanically peel.
Be 130:1 by length-to-diameter ratio, caliber is that the carbon nanotube of 60nm puts into tetrafluoroethylene ball grinder, select 0.5, the silicon carbide ball milling ball of 1 and 2 millimeter of particle diameter, its ratio is 1:0.75:0.05, it is 40% that ball milling ball accounts for ball grinder volume, add the aqueous isopropanol of the Di(dioctylpyrophosphato) ethylene titanate of certain volume, wherein the volume ratio of Di(dioctylpyrophosphato) ethylene titanate and Virahol is 0.02:1, ball milling 4 hours under the rotating speed of 2500 revs/min, after ball milling terminates, the aqueous isopropanol of diimine N-dicyclohexylcarbodiimide is added again in ball grinder, wherein the volume ratio of diimine N-dicyclohexylcarbodiimide and Virahol is 3:100, with the rotating speed ball milling 1 hour of 1800 revs/min, washing obtains the Activated Carbon Nanotubes of fracture location activation after drying.
The Activated Carbon Nanotubes of fracture location activation is added in flask, 2 hours are hydrolyzed at the coupling agent of the ethanolic soln middle-end position of 1:3 dilution, the mass ratio that afterwards dry and graphene oxide, diimine N-dicyclohexylcarbodiimide press 1:5:0.04 reacts 2 hours at 60 DEG C, by product deionized water, dimethylbenzene suction filtration until neutrality, remove unreacted Graphene, carbon nanotube, obtained multi-arm heat conductive filler, particle diameter is about 0.6 micron, and effect is better.
Embodiment 10
Graphene microchip is placed in tetrafluoroethylene ball grinder, select 0.5, the silicon carbide ball milling ball of 1 and 2 millimeter of particle diameter, its ratio is 1:0.8:0.15, it is 40% that ball milling ball accounts for ball grinder volume, add the vitriol oil of certain volume and the mixture of potassium permanganate, wherein the mass ratio of the vitriol oil and potassium permanganate is 50:50,, ball milling 16 hours under the rotating speed of 1800 revs/min, passing into frozen water at ball grinder outer wall during ball milling, every 3 hours with changing primary water, obtaining the graphene oxide of mechanically peel.
Be 130:1 by length-to-diameter ratio, caliber is that the carbon nanotube of 40nm puts into tetrafluoroethylene ball grinder, select 0.5, the silicon carbide ball milling ball of 1 and 2 millimeter of particle diameter, its ratio is 1:0.75:0.05, it is 40% that ball milling ball accounts for ball grinder volume, add the aqueous isopropanol of the Di(dioctylpyrophosphato) ethylene titanate of certain volume, wherein the volume ratio of Di(dioctylpyrophosphato) ethylene titanate and Virahol is 0.02:1, ball milling 4 hours under the rotating speed of 2500 revs/min, after ball milling terminates, the aqueous isopropanol of diimine N-dicyclohexylcarbodiimide is added again in ball grinder, wherein the volume ratio of diimine N-dicyclohexylcarbodiimide and Virahol is 3:100, with the rotating speed ball milling 1 hour of 1800 revs/min, washing obtains the Activated Carbon Nanotubes of fracture location activation after drying.
The Activated Carbon Nanotubes of fracture location activation is added in flask, 2 hours are hydrolyzed at the coupling agent of the ethanolic soln middle-end position of 1:3 dilution, the mass ratio that afterwards dry and graphene oxide, diimine N-dicyclohexylcarbodiimide press 1:5:0.04 reacts 2 hours at 60 DEG C, by product deionized water, dimethylbenzene suction filtration until neutrality, remove unreacted Graphene, carbon nanotube, obtained multi-arm heat conductive filler, particle diameter is about 0.7 micron, and effect is better.
Embodiment 11
Graphene microchip is placed in tetrafluoroethylene ball grinder, select 0.5, the silicon carbide ball milling ball of 1 and 2 millimeter of particle diameter, its ratio is 1:0.8:0.15, it is 40% that ball milling ball accounts for ball grinder volume, add the vitriol oil of certain volume and the mixture of potassium permanganate, wherein the mass ratio of the vitriol oil and potassium permanganate is 80:20,, ball milling 16 hours under the rotating speed of 1800 revs/min, passing into frozen water at ball grinder outer wall during ball milling, every 3 hours with changing primary water, obtaining the graphene oxide of mechanically peel.
Be 130:1 by length-to-diameter ratio, caliber is that the carbon nanotube of 40nm puts into tetrafluoroethylene ball grinder, select 0.5, the silicon carbide ball milling ball of 1 and 2 millimeter of particle diameter, its ratio is 1:0.75:0.05, it is 40% that ball milling ball accounts for ball grinder volume, add the aqueous isopropanol of the Di(dioctylpyrophosphato) ethylene titanate of certain volume, wherein the volume ratio of Di(dioctylpyrophosphato) ethylene titanate and Virahol is 0.02:1, ball milling 4 hours under the rotating speed of 2500 revs/min, after ball milling terminates, the aqueous isopropanol of diimine N-dicyclohexylcarbodiimide is added again in ball grinder, wherein the volume ratio of diimine N-dicyclohexylcarbodiimide and Virahol is 3:100, with the rotating speed ball milling 1 hour of 1800 revs/min, washing obtains the Activated Carbon Nanotubes of fracture location activation after drying.
The Activated Carbon Nanotubes of fracture location activation is added in flask, 2 hours are hydrolyzed at the coupling agent of the ethanolic soln middle-end position of 1:3 dilution, the mass ratio that afterwards dry and graphene oxide, diimine N-dicyclohexylcarbodiimide press 1:5:0.04 reacts 2 hours at 60 DEG C, by product deionized water, dimethylbenzene suction filtration until neutrality, remove unreacted Graphene, carbon nanotube, obtained multi-arm heat conductive filler, particle diameter is about 0.6 micron, and effect is better.
Embodiment 12
Graphene microchip is placed in tetrafluoroethylene ball grinder, select 0.5, the silicon carbide ball milling ball of 1 and 2 millimeter of particle diameter, its ratio is 1:0.8:0.15, it is 40% that ball milling ball accounts for ball grinder volume, add the vitriol oil of certain volume and the mixture of potassium permanganate, wherein the mass ratio of the vitriol oil and potassium permanganate is 60:40,, ball milling 16 hours under the rotating speed of 1800 revs/min, passing into frozen water at ball grinder outer wall during ball milling, every 3 hours with changing primary water, obtaining the graphene oxide of mechanically peel.
Be 130:1 by length-to-diameter ratio, caliber is that the carbon nanotube of 40nm puts into tetrafluoroethylene ball grinder, select 0.5, the silicon carbide ball milling ball of 1 and 2 millimeter of particle diameter, its ratio is 1:0.75:0.05, it is 40% that ball milling ball accounts for ball grinder volume, add the aqueous isopropanol of the Di(dioctylpyrophosphato) ethylene titanate of certain volume, wherein the volume ratio of Di(dioctylpyrophosphato) ethylene titanate and Virahol is 0.02:1, ball milling 4 hours under the rotating speed of 2500 revs/min, after ball milling terminates, the aqueous isopropanol of diimine N-dicyclohexylcarbodiimide is added again in ball grinder, wherein the volume ratio of diimine N-dicyclohexylcarbodiimide and Virahol is 3:100, with the rotating speed ball milling 1 hour of 1800 revs/min, washing obtains the Activated Carbon Nanotubes of fracture location activation after drying.
The Activated Carbon Nanotubes of fracture location activation is added in flask, 2 hours are hydrolyzed at the coupling agent of the ethanolic soln middle-end position of 1:3 dilution, the mass ratio that afterwards dry and graphene oxide, diimine N-dicyclohexylcarbodiimide press 1:5:0.04 reacts 2 hours at 60 DEG C, by product deionized water, dimethylbenzene suction filtration until neutrality, remove unreacted Graphene, carbon nanotube, obtained multi-arm heat conductive filler, particle diameter is about 0.65 micron, and effect is better.
Embodiment 13
Graphene microchip is placed in tetrafluoroethylene ball grinder, select the silicon carbide ball milling ball of 0.5,1 and 2 millimeter of particle diameter, its ratio is 1:0.8:0.15, it is 40% that ball milling ball accounts for ball grinder volume, add the nitric acid of certain volume and the mixture of potassium permanganate, wherein the mass ratio of nitric acid and potassium permanganate is 50:50, ball milling 16 hours under the rotating speed of 1800 revs/min, passing into frozen water at ball grinder outer wall during ball milling, every 3 hours with changing primary water, obtaining the graphene oxide of mechanically peel.
Be 130:1 by length-to-diameter ratio, caliber is that the carbon nanotube of 40nm puts into tetrafluoroethylene ball grinder, select 0.5, the silicon carbide ball milling ball of 1 and 2 millimeter of particle diameter, its ratio is 1:0.75:0.05, it is 40% that ball milling ball accounts for ball grinder volume, add the aqueous isopropanol of the Di(dioctylpyrophosphato) ethylene titanate of certain volume, wherein the volume ratio of Di(dioctylpyrophosphato) ethylene titanate and Virahol is 0.02:1, ball milling 4 hours under the rotating speed of 2500 revs/min, after ball milling terminates, the aqueous isopropanol of diimine N-dicyclohexylcarbodiimide is added again in ball grinder, wherein the volume ratio of diimine N-dicyclohexylcarbodiimide and Virahol is 3:100, with the rotating speed ball milling 1 hour of 1800 revs/min, washing obtains the Activated Carbon Nanotubes of fracture location activation after drying.
The Activated Carbon Nanotubes of fracture location activation is added in flask, 2 hours are hydrolyzed at the coupling agent of the ethanolic soln middle-end position of 1:3 dilution, the mass ratio that afterwards dry and graphene oxide, diimine N-dicyclohexylcarbodiimide press 1:5:0.04 reacts 2 hours at 60 DEG C, by product deionized water, dimethylbenzene suction filtration until neutrality, remove unreacted Graphene, carbon nanotube, obtained multi-arm heat conductive filler, particle diameter is about 0.7 micron, and effect is better.
Embodiment 14
Graphene microchip is placed in tetrafluoroethylene ball grinder, select the silicon carbide ball milling ball of 0.5,1 and 2 millimeter of particle diameter, its ratio is 1:0.8:0.15, it is 40% that ball milling ball accounts for ball grinder volume, add the nitric acid of certain volume and the mixture of potassium permanganate, wherein the mass ratio of nitric acid and potassium permanganate is 80:20, ball milling 16 hours under the rotating speed of 1800 revs/min, passing into frozen water at ball grinder outer wall during ball milling, every 3 hours with changing primary water, obtaining the graphene oxide of mechanically peel.
Be 130:1 by length-to-diameter ratio, caliber is that the carbon nanotube of 40nm puts into tetrafluoroethylene ball grinder, select 0.5, the silicon carbide ball milling ball of 1 and 2 millimeter of particle diameter, its ratio is 1:0.75:0.05, it is 40% that ball milling ball accounts for ball grinder volume, add the aqueous isopropanol of the Di(dioctylpyrophosphato) ethylene titanate of certain volume, wherein the volume ratio of Di(dioctylpyrophosphato) ethylene titanate and Virahol is 0.02:1, ball milling 4 hours under the rotating speed of 2500 revs/min, after ball milling terminates, the aqueous isopropanol of diimine N-dicyclohexylcarbodiimide is added again in ball grinder, wherein the volume ratio of diimine N-dicyclohexylcarbodiimide and Virahol is 3:100, with the rotating speed ball milling 1 hour of 1800 revs/min, washing obtains the Activated Carbon Nanotubes of fracture location activation after drying.
The Activated Carbon Nanotubes of fracture location activation is added in flask, 2 hours are hydrolyzed at the coupling agent of the ethanolic soln middle-end position of 1:3 dilution, the mass ratio that afterwards dry and graphene oxide, diimine N-dicyclohexylcarbodiimide press 1:5:0.04 reacts 2 hours at 60 DEG C, by product deionized water, dimethylbenzene suction filtration until neutrality, remove unreacted Graphene, carbon nanotube, obtained multi-arm heat conductive filler, particle diameter is about 0.5 micron, and effect is better.
Embodiment 15
Graphene microchip is placed in tetrafluoroethylene ball grinder, select the silicon carbide ball milling ball of 0.5,1 and 2 millimeter of particle diameter, its ratio is 1:0.8:0.15, it is 40% that ball milling ball accounts for ball grinder volume, add the nitric acid of certain volume and the mixture of potassium permanganate, wherein the mass ratio of nitric acid and potassium permanganate is 70:30, ball milling 16 hours under the rotating speed of 1800 revs/min, passing into frozen water at ball grinder outer wall during ball milling, every 3 hours with changing primary water, obtaining the graphene oxide of mechanically peel.
Be 130:1 by length-to-diameter ratio, caliber is that the carbon nanotube of 40nm puts into tetrafluoroethylene ball grinder, select 0.5, the silicon carbide ball milling ball of 1 and 2 millimeter of particle diameter, its ratio is 1:0.75:0.05, it is 40% that ball milling ball accounts for ball grinder volume, add the aqueous isopropanol of the Di(dioctylpyrophosphato) ethylene titanate of certain volume, wherein the volume ratio of Di(dioctylpyrophosphato) ethylene titanate and Virahol is 0.02:1, ball milling 4 hours under the rotating speed of 2500 revs/min, after ball milling terminates, the aqueous isopropanol of diimine N-dicyclohexylcarbodiimide is added again in ball grinder, wherein the volume ratio of diimine N-dicyclohexylcarbodiimide and Virahol is 3:100, with the rotating speed ball milling 1 hour of 1800 revs/min, washing obtains the Activated Carbon Nanotubes of fracture location activation after drying.
The Activated Carbon Nanotubes of fracture location activation is added in flask, 2 hours are hydrolyzed at the coupling agent of the ethanolic soln middle-end position of 1:3 dilution, the mass ratio that afterwards dry and graphene oxide, diimine N-dicyclohexylcarbodiimide press 1:5:0.04 reacts 2 hours at 60 DEG C, by product deionized water, dimethylbenzene suction filtration until neutrality, remove unreacted Graphene, carbon nanotube, obtained multi-arm heat conductive filler, particle diameter is about 0.7 micron, and effect is better.
Can be known by above-described embodiment, the present invention is a large amount of carbon nanotube of grafting outside graphene oxide successfully, define a kind of multi-arm type filler of new functionalization, compare untreated former powder, nanoparticle agglomeration weakens, dispersion effect obviously improves, and effectively can promote the formation of heat conduction network chain.
Claims (10)
1. graphene oxide, carbon nanotube multi-arm determine a preparation method for configuration heat conductive filler, it is characterized in that: comprise the steps:
(1) graphene microchip, carbon nanotube mechanical force peel off activation:
Graphene microchip is utilized constant temperature ball grinding technique, peel off in liquid phase at ball milling and directly peel off activation, after ball milling, the Graphene peeling off oxidation is filtered, utilize deionized water to be washed to neutrality, obtain the graphene oxide of the surface band carboxyl that constant temperature ball milling is peeled off; Carbon nanotube adopts mechanical force to peel off activation method, utilize high energy ball milling technology directly and coupling agent ball-milling reaction, after reaction terminates, in ball grinder, add the aqueous isopropanol of diimine, the Volume fraction of diimine and Virahol is 2 ~ 10:100, continue ball milling 1 ~ 4 hour, rotational speed of ball-mill is 1800 revs/min, after ball milling, is washed till neutrality with deionized water, 80 DEG C of vacuum-dryings 12 hours, grinding formed the Activated Carbon Nanotubes of fracture location activation;
(2) preparation of multi-arm type heat conductive filler:
Hydroxyl hydrolysis carbon nanotube is obtained after being hydrolyzed by the Activated Carbon Nanotubes of fracture location activation, and carrying out graft reaction 2 hours with graphene oxide stripping film room temperature under the effect of diimine class material of surface band carboxyl, the mass ratio of hydrolysis carbon nanotube, graphene oxide stripping film and diimine class material is 1:1 ~ 9:0.06 ~ 0.23;
(3) purifying of multi-arm type heat conductive filler:
The powder prepared by graft reaction refluxes in dimethylbenzene, and filters, and removes the impurity such as remaining Graphene, carbon nanotube, carbon, obtains the multi-arm type heat conductive filler determining structure design.
2. a kind of graphene oxide, carbon nanotube multi-arm determine the preparation method of configuration heat conductive filler according to claim 1, it is characterized in that: step (1) described graphene microchip constant temperature ball milling is peeled off by graphene microchip ball milling in tetrafluoroethylene ball grinder, frozen water constant temperature is filled with outside ball grinder, rotational speed of ball-mill is 400 ~ 2000 revs/min, reaction times is 12 ~ 24 hours, changes outside frozen water carry out temperature adjusting every 3 hours; Wherein ball milling ball is Ceramic Balls, and the particle diameter of ball milling ball selects 0.5,1,2,5 and 10 millimeter of particle diameter, and ball milling ball configures by a certain percentage, and ball milling sphere volume accounts for 40 ~ 60% of ball grinder volume.
3. a kind of graphene oxide, carbon nanotube multi-arm determine the preparation method of configuration heat conductive filler according to claim 1, it is characterized in that: it is acid solution that the described ball milling of step (1) peels off liquid phase, its acid solution is sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, potassium permanganate, one or more the mixture in phosphoric acid; When select sulfuric acid, nitric acid or sulfuric acid, perchloric acid mixture time, its volume ratio is 10:90 ~ 80:20, when select sulfuric acid, potassium permanganate or nitric acid, potassium permanganate mixture time, its mass ratio is 50:50 ~ 80:20.
4. a kind of graphene oxide, carbon nanotube multi-arm determine the preparation method of configuration heat conductive filler according to claim 2, it is characterized in that: described ball milling ball is silicon carbide or boron nitride ceramics ball milling ball, ball milling spherolite footpath is 0.5,1 and 2 millimeter of particle diameter, and its ratio is 1:0.6 ~ 0.8:0.2 ~ 0.05.
5. a kind of graphene oxide, carbon nanotube multi-arm determine the preparation method of configuration heat conductive filler according to claim 1, and it is characterized in that: the caliber of described carbon nanotube is 20 ~ 100nm, the length-to-diameter ratio of carbon nanotube is 80:1 ~ 200:1.
6. a kind of graphene oxide, carbon nanotube multi-arm determine the preparation method of configuration heat conductive filler according to claim 1, it is characterized in that: it is by carbon nanotube ball-milling reaction in tetrafluoroethylene ball grinder that the described mechanical force of step (1) peels off activation method, wherein ball milling peels off the aqueous isopropanol that liquid phase is titanate coupling agent or aluminate coupling agent, the volume ratio of coupling agent and Virahol is 0.003:1 ~ 0.05:1, rotational speed of ball-mill is 800 ~ 3000 revs/min, and the reaction times is 3 ~ 9 hours; Ball milling ball is Ceramic Balls, and the particle diameter of ball milling ball selects 0.5,1,2,5 and 10 millimeter of particle diameter, and ball milling ball configures by a certain percentage, and ball milling sphere volume accounts for 20 ~ 40% of ball grinder volume.
7. a kind of graphene oxide according to claim 6, carbon nanotube multi-arm determines the preparation method of configuration heat conductive filler, it is characterized in that: described titanate coupling agent is sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester, sec.-propyl three (dioctyl phosphoric acid acyloxy) titanic acid ester, sec.-propyl two oleic acid acyloxy (dioctyl phosphoric acid acyloxy) titanic acid ester, Di(dioctylpyrophosphato) ethylene titanate, one in plant acid type monoalkoxy class titanic acid ester, described aluminate coupling agent is two (methyl aceto acetate) aluminic acid diisopropyl ester, one in two (methyl ethyl diketone) aluminic acid diisopropyl ester, described ball milling ball is silicon carbide or boron nitride ceramics ball milling ball, and ball milling spherolite footpath is 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, carbon nanotube multi-arm determine the preparation method of configuration heat conductive filler according to claim 1, it is characterized in that: the diimine described in step (1) is N-dicyclohexylcarbodiimide (DCC), or the one in N, N'-DIC (DIC) or 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDC).
9. a kind of graphene oxide, carbon nanotube multi-arm determine the preparation method of configuration heat conductive filler according to claim 1, it is characterized in that: the described hydrolysis carbon nanotube of step (2) is dissolved in the aqueous solution of ethanol by the grafting carbon nanotube obtained after grafting, the aqueous solution of ethanol is that dehydrated alcohol and deionized water configure according to volume ratio 5:1 ~ 1:5, vibrating dispersion 2 ~ 4 hours in ultrasonic apparatus, obtains hydrolysis carbon nanotube after dry.
10. a kind of graphene oxide, carbon nanotube multi-arm determine the preparation method of configuration heat conductive filler according to claim 1, it is characterized in that: step (2) described diimine is N, N-dicyclohexylcarbodiimide (DCC), or the one in N, N'-DIC (DIC) or 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDC).
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