CN105016322A - Preparation method for carbon nanotube antistatic material easy to disperse - Google Patents
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- CN105016322A CN105016322A CN201410181768.3A CN201410181768A CN105016322A CN 105016322 A CN105016322 A CN 105016322A CN 201410181768 A CN201410181768 A CN 201410181768A CN 105016322 A CN105016322 A CN 105016322A
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Abstract
The invention relates to a preparation method for carbon nanotube antistatic material easy to disperse. First, acid-soluble inorganic powder is selected, an iron or cobalt or nickel catalyst is evenly loaded on the surface of the inorganic powder, and the loading capacity of iron or cobalt or nickel is controlled; then, the load catalyst is placed into reducing atmosphere of 300 DEG C-500 DEG C to be activated, then the activated catalyst is conveyed into a reactor containing alkane, olefin, hydrogen and carbon monoxide, and at 500 DEG C-900 DEG C, carbon nanotubes (CNTs) which have oriented growth and are controllable in length-diameter ratio are prepared; finally, by the adoption of acid dissolution carriers, the carbon nanotube antistatic material easy to disperse is obtained, wherein the content of the carbon nanotubes in the carbon nanotube antistatic material is high. When the addition quantity of CNTs in epoxy resin reaches 10<-4> level, a high-transparency and stable-resistance (106-108 omega) film can be obtained, and the film has excellent antistatic performance characteristics and product economy advantages.
Description
Technical field
The present invention relates to a kind of preparation method being easy to the carbon nanotube antistatic material disperseed.The present invention is coated on carrier surface with iron group catalyzer, oriented growth of carbon nanometer tube, again by carrier solubilizes, obtain the pure carbon nanotube anti-static material being easy to disperse, the carbon nanotube prepared has excellent antistatic property and wide prospects for commercial application.
Background technology
Carbon nanotube by graphite atomic monolayer around be coaxially entwined or by mono-layer graphite cylinder along the coaxial pipe overlapping structure layer by layer.Its diameter is generally between one to tens nanometers, and length is then much larger than its diameter.
Carbon nanotube is as monodimension nanometer material, lightweight, and carbon atom is interconnected to hexagonal structure, has many abnormal mechanics, electricity and chemical property.Going deep in recent years along with carbon nanotube and nano materials research, its wide application prospect also constantly shows.Wherein utilize the conduction property of carbon nanotube, the antistatic field of various types of materials can be widely used in.
Carbon atom in carbon nanotube forms large-scale delocalized pi-bond due to P electronics, and conjugative effect is remarkable, and thus carbon nanotube has special electrical properties.The structure of carbon nanotube is identical with the laminated structure of graphite, so have good electric property.Its conductivity of theoretical prediction depends on the helix angle of its caliber and tube wall.When the caliber of CNTs is greater than 6nm, conductivity declines; When caliber is less than 6nm, CNTs can be seen as the One-dimensional Quantum wire with excellent conductive performance.Carbon nanotube is extensive in extraordinary electrical property field application prospect.
The diameter of carbon nanotube can several dust (
) change between several nanometer, the length of CNT (carbon nano-tube) is ten times of its diameter to thousand times simultaneously.After carbon nanotube dispersed is in various types of materials, space conduction advantage can be given full play to, significantly reduce usage quantity, significantly reduce material anti-electrostatic cost, do not affect appearance characteristics and the material mechanical performance of material itself.
CNT (carbon nano-tube) preparation method summarizes:
CNT (carbon nano-tube) from 1991 first synthesis obtain since, because carbon nanotube especially single nanotube has unique performance, your high strength, Chu Qing, electroconductibility, field-electron emission and high-specific surface area and the concern be subject to especially, have potential huge purposes in advanced composite material, flat-panel monitor, fuel cell, lithium cell and super capacitor.Although nanotube part starts to commercially produce, up to now also cannot continuous seepage in enormous quantities.
Preparation method of carbon nano-tube conventional at present mainly contains: arc discharge method, laser ablation method, chemical Vapor deposition process (hydrocarbon gas pyrolysis method), solid-phase pyrolysis, electric glow discharge method, gaseous combustion method and polyreaction synthesis method etc.
Arc discharge method: Japanese physicist Sumio Iijimas in 1991 Late Cambrian carbon nanotube from the carbon fiber that arc discharge method is produced.The detailed process of arc discharge method is: Graphite Electrodes is placed in the reaction vessel being full of helium or argon gas, between the two poles of the earth, inspires electric arc, and now temperature can reach about 4000 degree.Under these conditions, graphite can evaporate, and the product of generation has the carbon nanotube of soccerballene (C60), agraphitic carbon and single wall or many walls.By controlling the hydrogen content in catalyzer and container, the fractional yield of several product can be regulated.This method is used to prepare in carbon nanotube technology fairly simple, but the products such as the carbon nanotube generated and C60 are mixed in together, be difficult to obtain the higher carbon nanotube of purity, and what obtain is often all multilayer carbon nanotube, and in practical study people often it is desirable that the carbon nanotube of individual layer.In addition the method reaction consumed energy is too large.Some researchist finds in recent years, if adopt the lithium chloride of melting to prepare anode as carbon nanotube, can effectively reduce the energy consumed in reaction, product purification is also than being easier to.Development in recent years has gone out chemical Vapor deposition process, or is called hydrocarbon gas pyrolysis method, overcomes the defect of arc discharge method to a certain extent.This method is the template allowing hydrocarbon gas pass through to be attached with catalyst particles, and under the condition of 800 ~ 1200 degree, hydrocarbon gas can decompose Formed nanotube.The advantage that this method is outstanding is Residual reactants is gas, and can leave reaction system, obtain the carbon nanotube that purity is higher, simultaneous temperature does not also need very high, saves energy comparatively speaking.But obtained carbon nanotube caliber is irregular, out-of-shape, and must use catalyzer in preparation process.The main direction of studying of current this method wishes to be controlled by the arrangement mode of catalyzer on Control architecture the structure of the carbon nanotube generated, and achieved certain progress.
Laser ablation method: laser ablation method detailed process is the graphite target of placing a metal catalyst/graphite mixing in the middle of a rectangular silica tube, and this Guan Ze is placed in a process furnace.When furnace temperature rises to certain temperature, rare gas element is poured in pipe, and beam of laser is focused in graphite target.Under laser radiation, generate gaseous carbon, these gaseous carbons and catalyst particle by air-flow from high temperature zone to cold zone time, under the effect of catalyzer, grow into CNTs.
Solid-phase pyrolysis: solid-phase pyrolysis is the novel method of the metastable solid of the conventional carbon containing of a kind of use at high temperature pyrolysis carbon nano-tube, and this procedure is more stable, does not need catalyzer, and is growth in situ.But be subject to the restriction of raw material, production can not mass-producing and serialization.
Ion or Laser vaporization: though this method is easy to continuous seepage, the reason due to equipment limits its scale.
Polyreaction synthesis method: polyreaction synthesis method refers generally to the method utilizing template duplicating to increase.The general preparation process of carbon nanotube and organic synthesis similar, its side reaction complexity is various, be difficult to ensure same stove carbon nanotube be arm chair nanotube or zigzag nanotubes.
Catalystic pyrolysis: catalystic pyrolysis is under the effect of the temperature of 600 ~ 1000 DEG C and catalyzer, makes carbonaceous gas raw material (as carbon monoxide, methane, ethene, propylene and benzene etc.) decompose a kind of method preparing carbon nanotube.This method makes carbon compound be cracked into carbon atom at relatively high temperatures, and carbon atom, under Transition metal-catalyzed dose of effect, is attached to catalyst particles and is formed as carbon nanotube on the surface.The catalyst activity component used in catalystic pyrolysis mostly is the 8th group 4 transition metal or its alloy, adds the adjustable activity metal energy states such as Cu, Zn, Mg on a small quantity, changes its chemisorption and the ability of decomposing carbonaceous gas.Catalyst precursor has impact to the activity forming metal simple-substance, and metal oxide, sulfide, carbide and organometallic compound are also previously used.
The catalyzer such as iron, cobalt, nickel can be dispersed on pottery, silicon, graphite or glass substrate by one of catalytic decomposition method method, by Catalytic Thermal Decomposition carbide-containing single-wall carbon nanotube synthesizing on substrate, the carbide-containing of use is generally hydro carbons or carbon monoxide.But the resultant velocity of this method slowly, and usually with the stroke of multi-walled carbon nano-tubes, be difficult to be suitable for a large amount of production.
Another kind method is as support of the catalyst using the nano-powder of some inorganicss (as silicon-dioxide, aluminium sesquioxide, magnesium oxide etc.), load, as transition metal (iron, cobalt, nickel, molybdenum etc.) and its formation nano-complex particle of catalyzer, prepares higher-quality Single Walled Carbon Nanotube with this.The most common methods preparing this nano-complex particle is mixed with the nitrate solution of metal by mineral powder, and then through super-dry, calcining, reduction, finally becomes the nano-complex particle of metal and inorganic carrier.This process need consumes long time, and major cause will grow up to suitable particle size at the catalyzer of carrier surface to need the long time, have impact on production efficiency.
The improvement of fixed catalytic agent method is used as these, flowing catalysis method is as ferrocene, penta hydroxy group close iron etc. and be evaporated in reactor by complex catalyst precursor, decompose directly formation metal catalyst particles in the gas phase make carbon source catalyse pyrolysis and form carbon nanotube, as Shenyang Inst. of Metals, Chinese Academy of Sciences with ferrocene as catalyst precursor, synthesized Single Walled Carbon Nanotube.But this method needs relatively high temperature, carbon source pyrolysis rate is too fast, is easy to form thicker carbon nanotube; Granules of catalyst also can collide in the gas flow mutually simultaneously, and the speed of growth is very fast, as long as so can generate the granules of catalyst of suitable dimension in narrow scope, harsher to conditional request, and test is repeatable poor.The research group of Rice Univ USA develops closes the presoma of iron as catalyzer with CO as carbon source, penta hydroxy group, single-wall carbon nanotube synthesizing at high temperature under high pressure, but this method with harmful carbon monoxide as raw material, and carry out under the condition of elegance, a lot of problem will be there is in a large amount of production process.Therefore a kind of method of more satisfactory synthesizing carbon nanotubes in quantity is not up to the present also had.
Summary of the invention
The present invention, in order to overcome the deficiencies in the prior art, provides a kind of preparation method being easy to the carbon nanotube antistatic material disperseed.The catalyzer of this preparation method for carrier, can prepare through reaction the carbon nanotube CNTs that generation is not easily wound around with decomposable asymmetric choice net material; That the carbon nanotube (CNTs) prepared has oriented growth, that length-to-diameter ratio is controlled feature, can obtain the carbon nanotube antistatic material that content of carbon nanotubes is high, be easy to dispersion with acid treatment after dissolving carrier granule.Carbon nanotube efficient anti-static material of the present invention, pass through simple agitation, can obtain dispersed in epoxy coating, in actual application when carbon nanotube addition is 0.02% ~ 0.08% mass percent, the antistatic epoxide resin coatingsurface resistance of formation can reach 10
6Ω ~ 10
8Ω.
To achieve these goals, the present invention adopts following technical scheme:
The preparation method being easy to the carbon nanotube antistatic material disperseed of the present invention: first preparation has the growing carrier of catalysis, select can be acid-soluble inorganic powder, this carrier is the powdery inorganic particulates such as calcium carbonate, rhombspar, calcium oxide, magnesium oxide, at its coated with uniform iron content (or cobalt, nickel) catalyzer, and control the mol ratio of iron (or cobalt, nickel) catalyst content.The reducing atmosphere having the particulate of catalyzer to put into 300 ~ 500 DEG C load afterwards activates.Load there is the catalyst particles of activation to send in the reactor containing alkane, alkene, hydrogen, CO (carbon monoxide converter) gas again, under the condition of 500 ~ 950 DEG C, prepare that tool goes out oriented growth, that length-to-diameter ratio is controlled carbon nanotube (CNTs).Finally surface growth there is is the particulate matter acid treatment of carbon nanotube, dissolve the carrier particles such as calcium carbonate, rhombspar, calcium oxide, magnesium oxide, the carbon nanotube antistatic material that content of carbon nanotubes is high, be easy to dispersion can be obtained.
The present invention is easy to the preparation method of the carbon nanotube antistatic material disperseed, and specifically comprises the steps:
1), with iron, cobalt or nickel for catalyzer, the powdery inorganic particulate carrier surfaces such as calcium carbonate, rhombspar, calcium oxide, magnesium oxide are evenly coated on; Wherein in iron, cobalt or nickel catalyzator, the coating content span of control of iron, cobalt or nickel and powdery inorganic particulate carrier is 0.01 ~ 1.0mol/kg;
2) reducing atmosphere, the particulate carrier being enclosed with iron, cobalt or nickel catalyzator being put into 300 ~ 500 DEG C activates, obtain the catalyst particles that load has activation, this reducing gas is the mixture of hydrogen and CO (carbon monoxide converter) gas, wherein hydrogen volume per-cent is 10% ~ 90%, and CO (carbon monoxide converter) gas volume percent is 90% ~ 10%.
3) catalyst particles of activation, load is had to send in the reactor containing alkane, alkene, hydrogen and CO (carbon monoxide converter) gas, under the condition of 500 ~ 950 DEG C, that have oriented growth, that length-to-diameter ratio is controlled carbon nanotube (CNTs) is prepared in reaction, obtains the particulate matter that surface growth has carbon nanotube; Wherein the volume hundred of alkane, alkene, hydrogen and CO (carbon monoxide converter) gas than control is: alkane: alkene: hydrogen: carbon monoxide=(10 ~ 20): (20 ~ 40): (30 ~ 40): (0 ~ 40); The average response residence time controls at 1 ~ 200min;
4) particulate matter of carbon nanotube, surface growth is had first to process with the aqueous solution of the hydrochloric acid-hydrofluoric acid containing 5% ~ 20% volume ratio, dissolve and remove the carrier particles such as calcium carbonate, rhombspar, calcium oxide, magnesium oxide, in the aqueous solution of wherein hydrochloric acid-hydrofluoric acid, the volume ratio of hydrochloric acid and hydrofluoric acid is 1:1; Again successively through washing, drying after process, be easy to the carbon nanotube antistatic material disperseed described in can obtaining, this carbon nanotube antistatic material being easy to disperse is the carbon nano-tube material being easy to the efficient anti-static disperseed.
Preferably, described iron, cobalt or nickel catalyzator adopt the form of respective element nitrate.
Preferably, step 3) in, alkane is selected from methane, ethane, propane, butane, and alkene is selected from ethene, propylene.
Further, step 3) in, load had the catalyst particles of activation to send in the reactor containing alkane, alkene and hydrogen and react, the mixed gas of this reaction does not add carbon monoxide.
Present invention also offers a kind of antistatic epoxide resin coating: be dispersed in epoxy resin by the above-mentioned carbon nanotube antistatic material being easy to disperse and form through applying drying.
The carbon nano-tube material being easy to the efficient anti-static disperseed the present invention obtained adds in epoxy coating, pass through simple agitation, can obtain dispersed in epoxy coating, in actual application when carbon nanotube addition is 0.02% ~ 0.08% mass percentage, the antistatic epoxide resin coatingsurface resistance of formation can reach 10
6Ω ~ 10
8Ω.Material of the present invention is a kind of carbon nano-tube material of efficient anti-static being easy to disperse as seen.
The innovation point of preparation method being easy to the carbon nanotube antistatic material disperseed of the present invention is as follows:
(1) catalyzer is with decomposable asymmetric choice net material for carrier, can prepare through reaction the carbon nanotube CNTs that generation is not easily wound around;
(2) the carbon nanotube CNTs that prepared by the present invention directly can add in resin and be disperseed fully;
(3) do not dissolve remove the surface growth that the composite carbon nanometer tube CNTs (i.e. step 3) of carrier obtains and have the particulate matter of carbon nanotube) anti-electrostatic of plastics, rubber item can be directly applied to, also can be applicable in the anti-static coatings such as epoxy resin;
(4) above-mentioned carbon nanotube CNTs in the epoxy addition reach 10
-4during level level, high transparency, resistance stabilization (10 can be obtained
6Ω ~ 10
8film Ω), has excellent antistatic property characteristic and product economy advantage.
Compared with prior art, the present invention has following beneficial effect:
1, to have preparation technology simple for the carbon nanotube antistatic material preparation method being easy to disperse of the present invention, support of the catalyst adopts the carrier particles such as calcium carbonate, rhombspar, calcium oxide, magnesium oxide, Surface coating iron group catalyzer, after overactivation, carbon nanotube is synthesized under carbon-containing atmosphere condition, again by carrier solubilizes, tool can be obtained and go out carbon nanotube antistatic material.Also under without the condition of CO, there is oriented growth, length-to-diameter ratio is controlled carbon nanotube (CNTs) also can be prepared in addition in carbon-containing atmosphere of the present invention.
2, the present invention is by controlling catalyst cupport preparation condition, temperature of reaction, growth time, effectively can control the oriented growth of carbon nanotube (CNTs), length-to-diameter ratio and efficiency of carbon conversion, and processing condition are easy to control, and raw material is easy to get.
In the carbon nano-tube material of the efficient anti-static that what 3, preparation method of the present invention obtained be easy to disperses, carbon nanotube mass percentage composition reaches more than 95%.
4, the carbon nanotube efficient anti-static material prepared of the present invention, by simple stirring, can obtain dispersed in epoxy coating, in actual application when carbon nanotube addition is 0.02% ~ 0.08% mass percent, the antistatic epoxide resin coatingsurface resistance of formation can reach 10
6Ω ~ 10
8Ω, has excellent antistatic property characteristic and product economy advantage.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.Should be understood that following examples only for illustration of the present invention but not for limiting protection scope of the present invention.
Embodiment 1
By the solution of 200ml containing 0.01mol iron nitrate, under the condition of pH=9 ~ 11, be evenly coated on the 1000g calcium carbonate microparticle surface that particle diameter is 15 ~ 100um.The reducing atmosphere that the particulate being enclosed with iron catalyst puts into 300 DEG C activates, and gaseous fraction is the mixture of hydrogen and CO (carbon monoxide converter) gas, and hydrogen volume per-cent is 10%, and carbon monoxide volume basis ratio is 90%.Load being had the catalyst particles of activation to send into percent by volume ratio is alkane: alkene: hydrogen: in carbon monoxide=10:20:30:40 reactor, (alkane adopts methane, alkene adopts propylene), 950 DEG C, under residence time 200min reaction conditions, that there is oriented growth, that length-to-diameter ratio is controlled carbon nanotube (CNTs) (length-to-diameter ratio is 200 ~ 300) can be prepared.
Surface growth there is hydrochloric acid-hydrofluoric acid 1:1 (volume ratio) solution-treated of the particulate matter of carbon nanotube containing 5% (volume ratio), dissolve calcium carbonate carrier particles, through washing, drying, can obtain the carbon nano-tube material being easy to the efficient anti-static disperseed, in this material, carbon nanotube mass percentage composition reaches more than 95%.
The carbon nanotube efficient anti-static material this process obtained adds in epoxy resin (epoxy resin used is E51 epoxy resin), can be in the epoxy dispersed by simple agitation, when carbon nanotube addition is 0.02% mass percentage, the antistatic epoxide resin coatingsurface resistance of formation can reach 10
8Ω.
Embodiment 2
By the solution of 1000ml containing 1.00mol iron nitrate, under the condition of pH=9 ~ 11, be evenly coated on the 1000g magnesium oxide particle surface that particle diameter is 15 ~ 100um.The reducing atmosphere that the particulate being enclosed with iron catalyst puts into 500 DEG C activates, and gaseous fraction is the mixture of hydrogen and CO (carbon monoxide converter) gas, and hydrogen volume per-cent is 90%, and carbon monoxide volume basis ratio is 10%.Load being had the catalyst particles of activation to send into percent by volume ratio is alkane: alkene: hydrogen: in carbon monoxide=20:40:40:0 reactor, (alkane adopts butane, alkene adopts ethene), 500 DEG C, under residence time 1min reaction conditions, (length-to-diameter ratio is 400 ~ 500 can to prepare that have oriented growth, that length-to-diameter ratio is controlled carbon nanotube (CNTs).
Surface growth there is hydrochloric acid-hydrofluoric acid 1:1 (volume ratio) solution-treated of the particulate matter of carbon nanotube containing 20% (volume ratio), dissolved oxygen magnesium carrier particulate, through washing, drying, can obtain the carbon nano-tube material being easy to the efficient anti-static disperseed, in this material, carbon nanotube mass percentage composition reaches more than 95%.
The carbon nanotube efficient anti-static material this process obtained adds in epoxy resin, can be dispersed in epoxy resin (epoxy resin used is E51 epoxy resin) by simple agitation, when carbon nanotube addition is 0.08% mass percentage, the antistatic epoxide resin coatingsurface resistance of formation can reach 10
6Ω.
Embodiment 3
By the solution of 500ml containing 0.12mol Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, under the condition of pH=9 ~ 11, be evenly coated on the 1000g calcium oxide microparticle surfaces that particle diameter is 15 ~ 100um.The reducing atmosphere that the particulate being enclosed with cobalt catalyst puts into 420 DEG C activates, and gaseous fraction is the mixture of hydrogen and CO (carbon monoxide converter) gas, and hydrogen volume per-cent is 30%, and carbon monoxide volume basis ratio is 70%.Load being had the catalyst particles of activation to send into percent by volume ratio is alkane: alkene: hydrogen: in carbon monoxide=10:30:30:30 reactor, (alkane adopts ethane, alkene adopts ethene), 805 DEG C, under residence time 30min reaction conditions, that there is oriented growth, that length-to-diameter ratio is controlled carbon nanotube (CNTs) (length-to-diameter ratio is 300 ~ 400) can be prepared.
Surface growth there is hydrochloric acid-hydrofluoric acid 1:1 (volume ratio) solution-treated of the particulate matter of carbon nanotube containing 10% (volume ratio), dissolved oxygen calcium carrier particles, through washing, drying, can obtain the carbon nano-tube material being easy to the efficient anti-static disperseed, in this material, carbon nanotube mass percentage composition reaches more than 95%.
The carbon nanotube efficient anti-static material this process obtained adds in epoxy resin, can be dispersed in epoxy resin (epoxy resin used is E51 epoxy resin) by simple agitation, when carbon nanotube addition is 0.04% mass percentage, the antistatic epoxide resin coatingsurface resistance of formation can reach 8 × 10
7Ω.
Embodiment 4
By the solution of 800ml containing 0.36mol nickelous nitrate, under the condition of pH=9 ~ 11, be evenly coated on the 1000g dolomite microparticles surface that particle diameter is 15 ~ 100um.The reducing atmosphere that the particulate being enclosed with nickel catalyzator puts into 390 DEG C activates, and gaseous fraction is the mixture of hydrogen and CO (carbon monoxide converter) gas, and hydrogen volume per-cent is 45%, and carbon monoxide volume basis ratio is 55%.Load being had the catalyst particles of activation to send into percent by volume ratio is alkane: alkene: hydrogen: in carbon monoxide=15:23:37:25 reactor, (alkane adopts propane, alkene adopts propylene), 910 DEG C, under residence time 100min reaction conditions, that there is oriented growth, that length-to-diameter ratio is controlled carbon nanotube (CNTs) (length-to-diameter ratio is 500 ~ 1000) can be prepared.
Surface growth there is hydrochloric acid-hydrofluoric acid 1:1 (volume ratio) solution-treated of the particulate matter of carbon nanotube containing 12% (volume ratio), dissolve rhombspar carrier particles, through washing, drying, can obtain the carbon nano-tube material being easy to the efficient anti-static disperseed, in this material, carbon nanotube mass percentage composition reaches more than 95%.
The carbon nanotube efficient anti-static material this process obtained adds in epoxy resin, can be dispersed in epoxy resin (epoxy resin used is E51 epoxy resin) by simple agitation, when carbon nanotube addition is 0.05% mass percentage, the antistatic epoxide resin coatingsurface resistance of formation can reach 2 × 10
7Ω.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not for limiting the present invention.Any person skilled in the art scholar all without prejudice under spirit of the present invention and category, can modify above-described embodiment or changes.Therefore, such as have in art usually know the knowledgeable do not depart from complete under disclosed spirit and technological thought all equivalence modify or change, must be contained by claim of the present invention.
Claims (8)
1. be easy to a preparation method for the carbon nanotube antistatic material disperseed, comprise the steps:
1), with iron, cobalt or nickel for catalyzer, calcium carbonate, rhombspar, calcium oxide, magnesium oxide powdery inorganic particles carrier surface is evenly coated on;
2) reducing atmosphere, the particulate carrier being enclosed with iron, cobalt or nickel catalyzator being put into 300 ~ 500 DEG C activates, obtain the catalyst particles that load has activation, this reducing gas is the mixture of hydrogen and CO (carbon monoxide converter) gas, wherein hydrogen volume per-cent is 10% ~ 90%, and CO (carbon monoxide converter) gas volume percent is 90% ~ 10%.
3) catalyst particles of activation, load is had to send in the reactor containing alkane, alkene, hydrogen and CO (carbon monoxide converter) gas, under the condition of 500 ~ 950 DEG C, the average response residence time controls at 1 ~ 200min, that reaction preparation has oriented growth, that length-to-diameter ratio is controlled carbon nanotube, obtains the particulate matter that surface growth has carbon nanotube;
4), by surface growth there is the particulate matter of carbon nanotube first to process with the aqueous solution of the hydrochloric acid-hydrofluoric acid containing 5% ~ 20% volume ratio, dissolve carrier particles such as removing calcium carbonate, rhombspar, calcium oxide, magnesium oxide; Again successively through washing, drying after process, described in can obtaining, be easy to the carbon nanotube antistatic material disperseed.
2. be easy to the preparation method of the carbon nanotube antistatic material disperseed as claimed in claim 1, it is characterized in that, step 1) in, in iron, cobalt or nickel catalyzator, the coating content span of control of iron, cobalt or nickel and powdery inorganic particulate carrier is 0.01 ~ 1.0mol/kg.
3. be easy to the preparation method of the carbon nanotube antistatic material disperseed as claimed in claim 1, it is characterized in that, step 3) in, the volume hundred of alkane, alkene, hydrogen and CO (carbon monoxide converter) gas than control is: alkane: alkene: hydrogen: carbon monoxide=(10 ~ 20): (20 ~ 40): (30 ~ 40): (0 ~ 40).
4. be easy to the preparation method of the carbon nanotube antistatic material disperseed as claimed in claim 1, it is characterized in that, step 3) in, alkane is selected from methane, ethane, propane and butane, and alkene is selected from ethene and propylene.
5. be easy to the preparation method of the carbon nanotube antistatic material disperseed as claimed in claim 3, it is characterized in that, step 3) in, load had the catalyst particles of activation to send in the reactor containing alkane, alkene, hydrogen and CO (carbon monoxide converter) gas to react, in the mixed gas of this reaction, carbon monoxide is 0.
6. be easy to the preparation method of the carbon nanotube antistatic material disperseed as claimed in claim 1, it is characterized in that, step 4) in, in the aqueous solution of hydrochloric acid-hydrofluoric acid, the volume ratio of hydrochloric acid and hydrofluoric acid is 1:1.
7. the preparation method being easy to the carbon nanotube antistatic material disperseed as described in as arbitrary in claim 1-6, it is characterized in that, the carbon nanotube antistatic material being easy to the to disperse interpolation obtained is scattered in epoxy resin by stirring in the epoxy, antistatic epoxide resin coating is obtained after applying drying, and when the carbon nanotube anti-electrostatic material addition being easy to disperse is 0.02% ~ 0.08% mass percentage, the antistatic epoxide resin coatingsurface resistance of formation can reach 10
6Ω ~ 10
8Ω.
8. an antistatic epoxide resin coating, forms through applying drying for the carbon nanotube antistatic material being easy to disperse arbitrary for claim 1-7 described preparation method being easy to the carbon nanotube antistatic material disperseed obtained is dispersed in epoxy resin.
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