CN102807737A - Preparation method of graphene/carbon nano tube disperse system high-polymer based composite material - Google Patents
Preparation method of graphene/carbon nano tube disperse system high-polymer based composite material Download PDFInfo
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Abstract
The invention relates to a preparation method of a graphene/carbon nano tube disperse system high-polymer based composite material. The preparation method comprises the steps of: arranging a carbon nano tube and graphene powder in liquid medium, crushing to form a stable graphene/carbon nano tube disperse system, adding high polymer material in the system, mixing uniformly so as to obtain the graphene/carbon nano tube disperse system high-polymer based composite material. Compared with the prior art, the invention provides the method capable of achieving the stable dispersion of carbon nano tube and graphene easily and efficiently; the graphene/carbon nano tube disperse system high-polymer based composite material with high electric conductivity, high thermal conductivity and high mechanical property is obtained by adopting the obtained graphene/carbon nano tube disperse system in the high-polymer based composite material.
Description
Technical field
The present invention relates to a kind of preparation method of nano material dispersion-s matrix material, especially relate to the preparation method of a kind of Graphene/carbon nanotube dispersion system polymer-based composite.
Background technology
Graphene and carbon nanotube are two kinds of isomers that carbon material has excellent properties and huge applications potentiality.Graphene is the two-dimentional atomic crystal that a kind of normal temperature exists, and constitutes the six-ring dot matrix with sp2 hydridization bonding between its carbon atom.The basic structural unit of carbon nanotube also is the six-ring dot matrix of carbon atom; Can be considered the seamless tubular shaped structure that the lamella of Graphene curls into from structure; The tubular structure that is made up of single-layer graphene is a SWCN, and by the coaxial valve of a plurality of different diameters nested form be called multi-walled carbon nano-tubes.Graphene and carbon nanotube have kept the strong covalent bond of carbon material, big π key characteristic; The quantum effect, small-size effect and the surface interface effect that have nano material simultaneously are also owing to special topology configuration (tubular structure, two-dimension plane structure) has the not available property of big scale carbon material.Graphene and carbon nanotube have Ultrahigh Specific Strength, specific modulus, excessive heat conductance and low-resistivity, and huge specific surface.Above-mentioned characteristic makes two types of materials have broad application prospects in occasions such as the tough structural composite material of height, conduction, heat-conductive composite material, battery and electrode for capacitors, microelectronic device, hydrogen storage material, transmitter, support of the catalyst.
Polymer matrix composites are one of Graphene and carbon nanotube most important applications.Using carbon nanotube, Graphene technology origin in the matrix material is generally: as functive, and the electroconductibility or the thermal conductivity of the high conductivity of using mineral carbon alkene and high electron mobility speed lifting matrix material; The 2nd, strengthen body as structure, the superstrength of using mineral carbon alkene, high-modulus and dimensional properties are to carrying out matrix material enhancing, toughness reinforcing.Obtained lightweight, high structure/function integration polymer matrix composites tough, conduction have high using value and application prospects at national economy key areas such as space flight, aviation, electronics, automobile, Structural Engineerings.
Most of experimental studies results shows that all the highly malleablized effect of Graphene and carbon nanotube all reaches ideal far away in the matrix material but up to now.Carbon nanotube, Graphene lack effectively and disperse, and fail between isolated coacervate to form the active path that load transmission and carrier transport can be provided, and are the mechanical property of its matrix material and the bottleneck place that electroconductibility is unrealized and expects lifting.
Therefore, generally acknowledging in the industry will be at the excellent properties of giving full play to carbon nanotube and Graphene, and its common fundamental requirement is to realize the good distribution of Graphene and carbon nanotube.
Through mechanical such as supersound process, high speed shear the carbon nanotube coacervate is produced broken effect through mechanical force to the carbon nanotube coacervate, make it to become single dispersing material or less coacervate; But the effect of ultra-sonic dispersion also has the limit; Long-time or high-power ultrasonic will the structure of carbon nanotube being damaged, performances such as mechanics, electricity also can thereby descend (Chen Yong etc., the ultrasonic weak point of multi-walled carbon nano-tubes is cut processing; Carbon technique; 2007,26 (5): 20), and simple mechanical such as ultrasonic is difficult to long-term maintenance to the dispersion effect that carbon nanotube produces.
The application decentralization agent also is the carbon nanotube dispersion technology (Wan Meixiang etc. that use always; Dispersion agent of a kind of carbon nanotube and preparation method thereof; Chinese patent; ZL 98120629.8), the main effect of dispersion agent is that the sterically hindered or polar effect through promoting agent or functional group stops and disperseed individual reassociating.The bonding force of dispersion agent and carbon nanotube and timeliness are relatively limited; And being carried out functional group's grafting, carbon nanotube can obtain higher bonding strength and more persistent use effectiveness; Surface functional group can play also that (Wang Geng is superfine, electric polyaniline derivative surface modified water decentralized carbon nano-tube and preparation method, Chinese patent with the similar space steric effect of dispersion agent, chemical affinity effect; 200710039182.3); But in the grafting step, need carbon nanotube is handled, also can cause defective, bring degradation.
Carbon nanotube is handled s.t. (Yang Wensheng etc.; A kind of preparation method of water decentralized carbon nano-tube; Chinese patent; 201010174962.0) can realize effective dispersion through short cutting with functional group grafted combined effect such as hydroxyl to carbon nanotube, but the weak point of such treatment process is also very outstanding, and promptly also very remarkable to the damage of carbon nanotube structure and performance.
Similar with carbon nanotube in essence to the dispersion technology means of Graphene.In the dispersion process of Graphene, though tend to follow graphene oxide to be reduced to chemical processes such as Graphene, Graphene is being carried out on the concrete technique means of dispersive, still be similar with the dispersion of carbon nanotube.As, use dispersion agent (Zhang Ping etc., a kind of polymolecularity preparation method of graphene such as water soluble polymer; Chinese patent, 201010274115.1), perhaps the system and the pH value of dispersion medium are carried out preferably (R Nai Sipaer etc.; Individual layer and the stabilising dispersions of multi-layer graphene layer in solution, Chinese patent, 201010274683.1); Perhaps Graphene is carried out surface-functionalized (Marvin's stone etc.; A kind of dispersibility silane-functionalized preparation method of graphene, Chinese patent, 201110242403.3; Marvin's stone etc., a kind of dispersible thanomin functionalization graphene and preparation method thereof, Chinese patent, 201110162046.X).Therefore, the advantage of these dispersing method and defective also still exist in the Graphene system.
Summary of the invention
The object of the invention is exactly for the defective that overcomes above-mentioned prior art existence a kind of simple method that effectively realizes carbon nanotube, Graphene stable dispersion to be provided; Obtaining Graphene/carbon nanotube dispersion system is applied to polymer-based composite, can obtains the Graphene/carbon nanotube dispersion system polymer-based composite of stone tool high conductivity, heat conductance and mechanical property.
The object of the invention can be realized through following technical scheme:
The preparation method of Graphene/carbon nanotube dispersion system polymer-based composite may further comprise the steps:
(1) carbon nanotube and Graphene powder are placed liquid medium; Between carbon nanotube and the Graphene because the difference of topology configuration and surface chemistry similar; Each other as sterically hindered; For " entanglement ", " bundle gathers " that have stoped carbon nanotube reunite with " lamella is superimposed " of Graphene; In type Graphene coacervate is broken for single-root carbon nano-tube, single-layer graphene, perhaps, forms stable Graphene/carbon nanotube dispersion system than Graphene coacervate, the carbon nanotube coacervate of small scale;
(2) with Graphene/carbon nanotube dispersion system as disperse phase, after wherein adding macromolecular material, mixing, prepare Graphene/carbon nanotube dispersion system polymer-based composite.
The mass ratio of carbon nanotube described in the step (1) and Graphene powder is 1: 100～100: 1; Described carbon nanotube is SWCN, multi-walled carbon nano-tubes or their mixing, and described Graphene powder is single-layer graphene, multi-layer graphene or their mixing.
Carbon nanotube described in the step (1) and Graphene powder can also pass through functional group's graft modification, obtain can also adding dispersion agent in the dispersion system.
Described functional group comprises hydroxyl, carboxyl or amido.
Described dispersion agent comprises that sodium laurylsulfonate (SDS), polyoxyethylene glycol are to iso-octyl phenyl ether (triton x-100) or cetyl trimethylammonium bromide (CTAB).
Carbon nanotube coacervate, Graphene coacervate are through mechanical disintegration and ultrasonic dispersing in the step (1).
Liquid medium described in the step (1) is selected from one or more in water, acetone, normal hexane, ETHYLE ACETATE, methylene dichloride, chloroform, tetracol phenixin, benzene, toluene or the THF.
The solid-liquid mass ratio of the stable Graphene/carbon nanotube dispersion system that forms in the step (1) is 1: 20～1: 100.
Macromolecular material described in the step (2) is macromolecular material monomer, performed polymer, solution or melt, and the macromolecular material of employing is resin, rubber, elastomerics or its co-mixing system.
Disperse phase described in the step (2) with also mix after macromolecular material mixes through the step of heating, x ray irradiation x, solution blending, melt blending or in-situ polymerization; Can also be to wherein adding solidifying agent; The different solidifying agent of the corresponding employing of different macromolecular materials; This solidifying agent comprise phenolic aldehyde amine, quadrol or 4,4 '-MDA (DDM).
In the matrix material for preparing, the mass percent of Graphene/carbon nanotube dispersion system is 0.1wt%～15wt%.
In the matrix material for preparing, can also add softening agent, inhibitor or mould inhibitor as wild phase, described softening agent comprises Zinic stearas, epoxy soybean oil or DOP (DOP).
Described inhibitor comprises 6-oxyethyl group-2,2,4-trimethylammonium-1,2-dihyaroquinoline (antioxidant A W), N-PBNA (antioxidant D) or N-phenyl-N`-cyclohexyl Ursol D (antioxidant 4010).
Described mould inhibitor comprises 10, the two phenoxazine arsenic (OBPA) of 10 '-oxo, copper 8-quinolinolate or tributyltin chloride.
The reunion of Graphene mainly is because the existence of Van der Waals force produces " lamella is superimposed ".The coacervate origin cause of formation of carbon nanotube is complicated more, between carbon nanotube because " bundle gathers " that the existence of Van der Waals force produces, because the entanglement that the topology configuration of its bent tube form causes also is that the carbon nanotube coacervate is difficult to the dispersive major reason.The present invention is the machine-processed and aggregate structure characteristic to the reunion of Graphene and carbon nanotube then; Proposition is through introduce Graphene and carbon nanotube two mutually simultaneously in liquid phase; After realizing that with means such as machinery such as ultrasonic, high speed shear both aggregate structures are discrete; Can be between carbon nanotube and the Graphene owing to the difference of topology configuration, each other coacervate form sterically hindered, stop carbon nanotube " bundle gathers " and " entanglement " behavior; And the generation of Graphene " lamella is superimposed " behavior, also promptly stoped the reunion again of carbon nanotube and the reunion again of Graphene.Even after the liquid phase drying, the IPN dispersion state between carbon nanotube and the Graphene also can be retained to solid phase.Obtaining Graphene/carbon nanotube dispersion system is applied in the polymer composite; Graphene/carbon nanotube constitutes functive/enhancing volume grid in matrix; Can give full play to the advantages characteristic of nano-carbon material, obtain the G/NT/P matrix material of forming by Graphene (G), carbon nanotube (NT) and macromolecular material matrix (P) with high conduction, high heat conduction and high tough characteristic.
Compared with prior art, the present invention has the following advantages:
(1) because Graphene and characteristic and the difference of carbon nanotube on topology configuration; Play the sterically hindered effect of reuniting each other; Can realize stable dispersion, need not carry out the surface functional group grafting, thereby avoid damage and the degradation of this process carbon nanotube, graphene-structured; Need not introduce dispersion agent yet, thereby avoid the existence of dispersion agent between carbon nanomaterial to influence between its electron transport, carbon nanomaterial and matrix because the existence of dispersion agent influence boundary strength and the whole mechanical property of matrix material and the technological deficiency in material prepn, brought owing to generation bubbles such as dispersion agent gasification etc.;
(2) through in the prepared G/NT/P matrix material of the inventive method, carbon nanotube, Graphene good dispersion in network-like dispersion and the matrix, help matrix material and obtain good electroconductibility, thermal conductivity and mechanical property.
Embodiment
Below in conjunction with specific embodiment the present invention is elaborated.
Embodiment 1
With the multi-walled carbon nano-tubes of diameter 10～30mm, length 1～100 μ m and 1～6 layer; The cloth bag type Graphene of diameter 200～300nm is added in the acetone according to 1: 4 mass ratio; The solid-liquid mass ratio is 1: 49; Pulverize knife up speed decollator with stainless steel and disperse 60min with the VELOCITY SHEAR of 8000r/min, the back is with the ultra-sonic dispersion device ultra-sonic dispersion 30min of frequency 40KHz, power 100W, volume 3L.
Weighing 50g gained mixture is added in the mixture of E51 epoxy resin prepolymer and 20g pnenolic aldehyde amine hardener T31 of 80g, is heated to 50 ℃ and keeps 20min.The volume specific resistance of the G/NT/P matrix material that obtains is 2.3 * 10
3Ω cm, tensile strength is 71.3MPa, flexural strength is 142.4MPa.And to the E51 epoxy resin prepolymer of 80g and the mixture of 20g pnenolic aldehyde amine hardener, the volume specific resistance of the epoxide resin material that makes with same curing system is higher than 1 * 10
10Ω cm, tensile strength is 58.6MPa, flexural strength is 97.5MPa.
Embodiment 2
With the multi-walled carbon nano-tubes of diameter 20～40mm, length 40～400 μ m and 1～10 layer; The Graphene microplate of diameter 400～600nm is added in the absolute ethyl alcohol according to 1: 1 mass ratio; The solid-liquid mass ratio is 1: 99; Pulverize knife up speed decollator with stainless steel and disperse 30min with the VELOCITY SHEAR of 1200r/min, the back is with the ultra-sonic dispersion device ultra-sonic dispersion 45min of frequency 40KHz, power 100W, volume 3L.
Weighing 8000g gained mixture; At 80 ℃ of following vacuum-drying 6h; The gained powder mixes in high-speed mixer with the PC pellet of 7.85kg, the softening agent Zinic stearas of 15g, the inhibitor 2921 of 15g, and the gained mixture carries out mixing granulation on extruding granulator, and stuff and other stuff is on forcing machine; Carry out injection moulding under 310 ℃, obtain the G/NT/P matrix material.The surface resistivity of this matrix material is 1.4 * 10
4Ω cm, tensile strength is 77.5MPa, notched Izod impact strength is 88.4kJ/m
2, the normal temperature thermal conductivity is 1.81W/ (mK).Surface resistivity to same PC raw material, same granulation and the prepared pure PC material of expressing technique is higher than 1 * 10
11Ω cm, tensile strength is 53.1MPa, notched Izod impact strength is 42.7kJ/m
2, the normal temperature thermal conductivity is 0.16W/ (mK).
Embodiment 3
SWCN and thickness 0.8～1.2 μ m (individual layer rate＞80%) with diameter＜2mm, length 5～15 μ m; The Graphene microplate of diameter 0.5～2 μ m is added in the absolute ethyl alcohol according to 4: 1 mass ratio; Above-mentioned mixed powder 1g is joined in the 200g absolute ethyl alcohol; The KH570 that adds 1.5g pulverizes knife up speed decollator with stainless steel and disperses 30min with the VELOCITY SHEAR of 1200r/min, and the back is with the ultra-sonic dispersion device ultra-sonic dispersion 30min of frequency 40KHz, power 100W, volume 3L.Mixing liquid at 80 ℃ of following vacuum-drying 6h, is obtained surface grafting functionalized carbon nano-tube and Graphene powder.
Weighing 15g gained powder is added among the initiator B PO of MMA monomer and 0.2g of 99.7g, 85 ℃ of following prepolymerization 60min, and behind the vacuum defoamation 30min, in the injection moulding mould, 45 ℃ of following polymerization 40h.Obtaining with PMMA through in-situ polymerization is the G/NT/P matrix material of matrix.
The surface resistivity of this G/NT/P matrix material is 2.2 * 10
3Ω cm.To with same PMMA monomer, graphitiferous alkene/carbon nano-tube composite powder not is higher than 1 * 10 through the surface resistivity of the PMMA material that obtains with sampling technology
11Ω cm.
Embodiment 4
SWCN and thickness 0.8～1.2 μ m (individual layer rate＞80%) with diameter＜2mm, length 5～15 μ m; The Graphene microplate of diameter 0.5～2 μ m is added in the absolute ethyl alcohol according to 100: 1 mass ratio; Above-mentioned mixed powder 1g is joined in the 200g absolute ethyl alcohol; Pulverize knife up speed decollator with stainless steel and disperse 30min with the VELOCITY SHEAR of 1200r/min, the back is with the ultra-sonic dispersion device ultra-sonic dispersion 30min of frequency 40KHz, power 100W, volume 3L.Mixing liquid at 80 ℃ of following vacuum-drying 6h, is obtained Graphene/carbon nano-tube composite powder.
Weighing 1g gained powder carries out mixingly with 959g paracril (NBR) sizing material, 40g plasticizer DOP, divides three-stage mixing, and melting temperature is 45 ℃, mixing time 20min, intersegmental interval 3h.The gained rubber unvulcanizate is being carried out compression molding, 160 ℃ of temperature, pressure 15MPa, clamp time 8min in steel die on the vulcanizing press; It is 26.8MPa that the gained matrix material records tensile strength.With same NBR and DOP raw material, do not add Graphene/carbon nano-tube composite powder, warp is with the prepared NBR material of sampling technology, and its tensile strength is 18.2MPa.
Embodiment 5
With the multi-walled carbon nano-tubes of diameter 20～40mm, length 40～400 μ m and 1～10 layer; The Graphene microplate of diameter 400～600nm is added in the absolute ethyl alcohol according to 1: 100 mass ratio; The solid-liquid mass ratio is 1: 99; Pulverize knife up speed decollator with stainless steel and disperse 30min with the VELOCITY SHEAR of 1200r/min, the back is with the ultra-sonic dispersion device ultra-sonic dispersion 45min of frequency 40KHz, power 100W, volume 3L.Mixing liquid at 80 ℃ of following vacuum-drying 6h, is obtained Graphene/carbon nanotube mixed powder.
Weighing 15g gained powder adds SE (PVC) powder of 750g, the NBR powder of 200g, the plasticizer DOP of 35g, in high-speed mixer, carries out high-speed stirring 20min; Batch mixing is carried out in mill in the back, and 2 sections of mixing branches, melting temperature are 55 ℃; Mixing time 20min, intersegmental interval 4h.The gained rubber unvulcanizate is being carried out compression molding, 170 ℃ of temperature, pressure 12MPa, clamp time 6min in steel die on the vulcanizing press; It is 8.33MPa that the gained matrix material records tensile strength.With same NBR, PVC and DOP raw material, do not add Graphene/carbon nano-tube composite powder, warp is with the prepared NBR/PVC rubber plastic blend of sampling technology body, and its tensile strength is 6.42MPa.
Embodiment 6
The preparation method of Graphene/carbon nanotube dispersion system polymer-based composite may further comprise the steps:
(1) be to place acetone at 1: 100 with SWCN and single-layer graphene by mass ratio; Wherein SWCN, single-layer graphene can also carry out modification through hydroxyl; And disperse to wherein adding dispersion agent sodium laurylsulfonate (SDS); Between carbon nanotube and the Graphene because the difference of topology configuration and surface chemistry similar; As sterically hindered,, be single-root carbon nano-tube, single-layer graphene through mechanical disintegration and ultrasonic dispersing each other with in type Graphene coacervate for " entanglement ", " bundle gathers " that have stoped carbon nanotube reunite with " lamella is superimposed " of Graphene; Perhaps than Graphene coacervate, the carbon nanotube coacervate of small scale, form stable solid-liquid mass ratio and be Graphene/carbon nanotube dispersion system of 1: 20;
(2) with Graphene/carbon nanotube dispersion system as disperse phase; To wherein adding macromolecule resin; Prepare Graphene/carbon nanotube dispersion system polymer-based composite after mixing, wherein the mass percent of Graphene/carbon nanotube dispersion system is 0.1wt%.
Embodiment 7
The preparation method of Graphene/carbon nanotube dispersion system polymer-based composite may further comprise the steps:
(1) be to place normal hexane at 10: 1 with multi-walled carbon nano-tubes and multi-layer graphene by mass ratio; Between carbon nanotube and the Graphene because the difference of topology configuration and surface chemistry similar; Each other as sterically hindered; For " entanglement ", " bundle gathers " that have stoped carbon nanotube reunite with " lamella is superimposed " of Graphene; Is single-root carbon nano-tube, single-layer graphene with in type Graphene coacervate through mechanical disintegration and ultrasonic dispersing, perhaps than Graphene coacervate, the carbon nanotube coacervate of small scale, forms stable solid-liquid mass ratio and be Graphene/carbon nanotube dispersion system of 1: 50;
(2) with Graphene/carbon nanotube dispersion system as disperse phase; To wherein adding resin prepolymer, mix through the step of heating, x ray irradiation x, solution blending, melt blending or in-situ polymerization, can also be to wherein adding curing agent ethylene diamine; In addition can also be to wherein adding softening agent Zinic stearas, inhibitor 6-oxyethyl group-2; 2,4-trimethylammonium-1,2-dihyaroquinoline (antioxidant A W), mould inhibitor 10; Prepare Graphene/carbon nanotube dispersion system polymer-based composite after the two phenoxazine arsenic (OBPA) of 10 '-oxo mix, wherein the mass percent of Graphene/carbon nanotube dispersion system is 5wt%.
Embodiment 8
The preparation method of Graphene/carbon nanotube dispersion system polymer-based composite may further comprise the steps:
(1) by mass ratio the mixed solvent that places methylene dichloride and chloroform to constitute at 100: 1 with multi-walled carbon nano-tubes and multi-layer graphene; And iso-octyl phenyl ether (triton x-100) is disperseed to wherein adding the dispersion agent polyoxyethylene glycol; Between carbon nanotube and the Graphene because the difference of topology configuration and surface chemistry similar; Each other as sterically hindered; For " entanglement ", " bundle gathers " that have stoped carbon nanotube reunite with " lamella is superimposed " of Graphene; Is single-root carbon nano-tube, single-layer graphene with in type Graphene coacervate through mechanical disintegration and ultrasonic dispersing, perhaps than Graphene coacervate, the carbon nanotube coacervate of small scale, forms stable solid-liquid mass ratio and be Graphene/carbon nanotube dispersion system of 1: 100;
(2) with Graphene/carbon nanotube dispersion system as disperse phase; To wherein adding the rubber performed polymer; Step through heating, x ray irradiation x, solution blending, melt blending or in-situ polymerization is mixed; Can also be to wherein adding solidifying agent 4; 4 '-MDA (DDM), in addition can also be to wherein adding plasticizer phthalic acid dioctyl ester (DOP), preparing Graphene/carbon nanotube dispersion system polymer-based composite after inhibitor N-phenyl-N`-cyclohexyl Ursol D (antioxidant 4010) mixes, wherein the mass percent of Graphene/carbon nanotube dispersion system is 15wt%.
Claims (10)
1. the preparation method of Graphene/carbon nanotube dispersion system polymer-based composite is characterized in that this method may further comprise the steps:
(1) carbon nanotube and Graphene powder are placed liquid medium; Established carbon nanotube coacervate, Graphene coacervate are broken for single-root carbon nano-tube, single-layer graphene; Perhaps, form stable Graphene/carbon nanotube dispersion system than Graphene coacervate, the carbon nanotube coacervate of small scale;
(2) with Graphene/carbon nanotube dispersion system as disperse phase, after wherein adding macromolecular material, mixing, prepare Graphene/carbon nanotube dispersion system polymer-based composite.
2. the preparation method of Graphene according to claim 1/carbon nanotube dispersion system polymer-based composite is characterized in that the mass ratio of carbon nanotube described in the step (1) and Graphene powder is 1: 100～100: 1; Described carbon nanotube is SWCN, multi-walled carbon nano-tubes or their mixing, and described Graphene powder is single-layer graphene, multi-layer graphene or their mixing.
3. the preparation method of Graphene according to claim 1/carbon nanotube dispersion system polymer-based composite; It is characterized in that; Carbon nanotube described in the step (1) and Graphene powder can also pass through functional group's graft modification, obtain can also adding dispersion agent in the dispersion system.
4. the preparation method of Graphene according to claim 3/carbon nanotube dispersion system polymer-based composite; It is characterized in that; Described functional group comprises hydroxyl, carboxyl or amido, and described dispersion agent comprises that sodium laurylsulfonate (SDS), polyoxyethylene glycol are to iso-octyl phenyl ether (triton x-100) or cetyl trimethylammonium bromide (CTAB).
5. the preparation method of Graphene according to claim 1/carbon nanotube dispersion system polymer-based composite; It is characterized in that; Carbon nanotube coacervate, Graphene coacervate are through mechanical disintegration and ultrasonic dispersing in the step (1), and the solid-liquid mass ratio of the stable Graphene/carbon nanotube dispersion system of formation is 1: 20～1: 100.
6. the preparation method of Graphene according to claim 1/carbon nanotube dispersion system polymer-based composite; It is characterized in that the liquid medium described in the step (1) is selected from one or more in water, acetone, normal hexane, ETHYLE ACETATE, methylene dichloride, chloroform, tetracol phenixin, benzene, toluene or the THF.
7. the preparation method of Graphene according to claim 1/carbon nanotube dispersion system polymer-based composite; It is characterized in that; Macromolecular material described in the step (2) is macromolecular material monomer, performed polymer, solution or melt, and the macromolecular material of employing is resin, rubber, elastomerics or its co-mixing system.
8. the preparation method of Graphene according to claim 1/carbon nanotube dispersion system polymer-based composite; It is characterized in that; Disperse phase described in the step (2) with also mix after macromolecular material mixes through the step of heating, x ray irradiation x, solution blending, melt blending or in-situ polymerization; Can also be to wherein adding solidifying agent; Different macromolecular material is corresponding adopt different solidifying agent, this solidifying agent comprise phenolic aldehyde amine, quadrol or 4,4 '-MDA (DDM).
9. the preparation method of Graphene according to claim 1/carbon nanotube dispersion system polymer-based composite is characterized in that, in the matrix material for preparing, the mass percent of Graphene/carbon nanotube dispersion system is 0.1wt%～15wt%.
10. the preparation method of Graphene according to claim 1/carbon nanotube dispersion system polymer-based composite; It is characterized in that; In the matrix material for preparing; Can also add softening agent, inhibitor or mould inhibitor as wild phase, described softening agent comprises Zinic stearas, epoxy soybean oil or DOP (DOP); Described inhibitor comprises 6-oxyethyl group-2,2,4-trimethylammonium-1,2-dihyaroquinoline (antioxidant A W), N-PBNA (antioxidant D) or N-phenyl-N`-cyclohexyl Ursol D (antioxidant 4010); Described mould inhibitor comprises 10, the two phenoxazine arsenic (OBPA) of 10 '-oxo, copper 8-quinolinolate or tributyltin chloride.
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