CN103619964A - Method for producing carbon fillers having covalently bonded amino groups - Google Patents

Method for producing carbon fillers having covalently bonded amino groups Download PDF

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CN103619964A
CN103619964A CN201280030927.9A CN201280030927A CN103619964A CN 103619964 A CN103619964 A CN 103619964A CN 201280030927 A CN201280030927 A CN 201280030927A CN 103619964 A CN103619964 A CN 103619964A
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carbon
carbonaceous filler
amides
treatment
alkaline
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C·W·维格博斯
M·K·布林克斯
约翰-彼得·梅尔德
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BASF SE
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
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    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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    • B82—NANOTECHNOLOGY
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    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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Abstract

The invention relates to a method for producing carbon fillers having covalently bonded amino groups by reacting a mixture, which contains carbon fillers and alkali and/or alkaline-earth metals and/or amides thereof in liquid water-free ammonia, optionally together with an inert solvent, at temperatures of 35 to 500 DEG C and a pressure of 30 to 250 bar.

Description

Preparation has the method for the carbonaceous filler of covalently bound amino
The present invention relates to a kind of method of preparing the carbonaceous filler with covalently bound amino.
Carbonaceous filler is being used as for a period of time filler, in polymer molding compositions.The example of this carbonaceous filler is that (conduction) is black, graphite, carbon nanotube or Graphene.Can also use activated carbon or carbon fiber.Purposes is not limited to conventional fillers application, and it is contemplated that application, for example, for electronic product and storage medium field, as electric conductor and transistor, electrode materials, storage medium etc.
According to prior art, carbon nanotube (CNT) be interpreted as mainly referring to diameter be approximately 3 to 100nm and length be the cylindrical carbon pipe of diameter several times.This pipe is formed and is had the core of different-shape by one or more layers orderly carbon atom.It is for example also called as " carbon filament " or " hollow carbon fiber " and can obtains (for example bamboo type or onion type) with different forms.
The common structure of these carbon nanotubes is cylindrical structural.Cylindrical structural is divided into single wall list carbon nanotube (SWCNT), double-walled carbon nano-tube (DWCNT) and many walls cylindrical carbon nanotube (MWCNT).Its common preparation method is for example arc discharge method, laser ablation method, chemical vapor deposition method (CVD method) and gas phase catalytic chemistry sedimentation (CCVD method).
Carbon nanotube light weight, has high tensile strength and conduction current.It has been particularly useful as the additive of polymkeric substance at present.
Yet the favourable characteristic of CNT is weakened by a series of shortcoming.CNT has significant caking tendency and in polar solvent or non-polar solvent, has poor solvability.A method Shi Jiang functional group that makes up this defect is the amino outside surface that is applied to CNT for example.
About CNT functionalized, there is a large amount of documents.The preparation that contains amino CNT is known (N.Karousis N.Tagmatrachis for example, D.Tasis, Chem.Rev. also 2010, 100,5366 to 5397 pages).Yet CNT needs to carry out pre-treatment before applying amino conventionally.
Described pre-treatment can be for obtaining for example chemical conversion of carboxyl of functional group.In a step or the other chemical step Zhong Jianggai functional group of multistep, be converted into amino.
Yet pre-treatment can also relate to physics mode, for example Temperature Treatment, Cement Composite Treated by Plasma or supersound process, or by grinding the mechanical treatment of carbon compound.
The pretreated combination of Chemical Pretreatment and physics is passable equally.
Above-mentioned document provides the functionalized good general introduction of carbon nanotube different sorts.Introduce amino and be shown in for example Fig. 2.It is started by acid chloride groups and relates to and reaction of sodium azide.Or described preparation can be undertaken by acid amides.The direct amidation of acyl chlorides is also fine.
CN-A-101774573 has recorded the method that makes carbon nanotube amination, the wherein first pre-treatment by thermal treatment, acid treatment and/or supersound process of carbon nanotube, and then react at the temperature of 340 to 350 ℃ and under 6 to 11MPa pressure with ammoniacal liquor or quadrol.This pre-treatment makes the method very expensive and inconvenient.
US7,794,683 have also recorded the preparation of the carbon nanotube of amination, and wherein first hydroxy-acid group is introduced by carrying out acid treatment with sulfuric acid and nitric acid, and then by reacting and be converted into acyl azide with diphenyl phosphoryl azide.Further reaction is hydrolyzed by isocyanate groups the carbon nanotube that forms aminofunctional.A shortcoming of the method is a large amount of reactions steps, and some steps wherein need expensive reagent.
Eur.J.Org.Chem.2008, has recorded the nucleophilic addition(Adn) by lithium amide in THF for 2544 to 2550 pages and has made Single Walled Carbon Nanotube covalency sidewall functionalized.Lithium amide is prepared by n-Butyl Lithium and propylamine in anhydrous THF.This reaction is at room temperature carried out.After reaction, by oxygen, by reaction mixture, this obtains by-NH-CH 2-CH 2-CH 3the carbon nanotube that-structure replaces.
WO2005/090233 has recorded the reductive functionalization of carbon nanotube., carbon nanotube is introduced in liquefied ammonia for this reason, added in addition wherein the lithium as metal.Then add alkylogen or aryl halide, this causes the alkylation of carbon nanotube outside surface; See Fig. 1 and embodiment 1.In cooling by means of acetone/dry ice, react, reaction is heated to room temperature while finishing.Do not record the carbon nanotube of amination.
The invention of above-mentioned record method need to be carried out Chemical Pretreatment and/or physics pre-treatment any to carbon nanotube before functionalized.This pretreated shortcoming is that the structure of carbon compound can pretreatedly destroy.For example, supersound process carbon nanotube can cause destroying, as [0009] section of WO2005/090233 records.The in the situation that of oxidation pre-treatment, the erosion of oxidized dose of the surface of carbon nanotube, this causes lip-deep rejected region.
The object of the present invention is to provide there is the carbonaceous filler of covalently bound amino as the method for carbon nanotube a kind of preparation, wherein can save the pre-treatment to carbonaceous filler, avoid carbonaceous filler as the destruction of carbon nanotube, and functionalized can carrying out with cheap reagent in single step reaction.Even the electroconductibility of destroying carbon nanometer tube, described functionalized also should be preferably only with the electroconductibility of less degree destroying carbon nanometer tube.
This object realizes by a kind of method of preparing the carbonaceous filler with covalently bound amino according to the present invention, described method by making the mixture that contains carbonaceous filler and basic metal and/or alkaline-earth metal and/or its amides (amides) in anhydrous liquid ammonia, optionally transforms and carries out at the temperature of 35 to 500 ℃ and under the pressure of 30 to 250 bar together with a kind of inert solvent.
According to the present invention, have been found that carbonaceous filler to react by the liquefied ammonia with containing basic metal and/or alkaline-earth metal or its amides and there is covalently bound amino through functionalized.
WO2005/090233 only discloses in liquefied ammonia and has reacted and alkylation with alkylogen under the existence of lithium.Eur.J.Org.Chem.2008, has recorded the functionalized of carbon nanotube and n-propyl lithium amide for 2544 to 2550 pages, and wherein propyl group amino is connected to carbon nanotube.Transform and in tetrahydrofuran (THF), at room temperature carry out in addition.
In this application, term " carbonaceous filler " refers to extremely mainly by carbon or the complete particulate solid carbon material being formed as single-element by carbon.The example of this material is carbon nanotube, Graphene, carbon black, graphite, gac or carbon fiber.These materials can be by surface modification, and result is to introduce other chemical element.Yet its characteristic is mainly by the structures shape based on carbon only.Therefore according to the present invention, term " carbonaceous filler " does not mean any specific application, and only refers to structure and the state of matter of particulate state carbon material.For these particulate state carbon materials, can expect and also comprise not only applying filler but also in electronic product and storage medium field (as electric conductor and transistor, electrode materials, storage medium etc.).For example, the black conductive modified for thermoplastic composition of modification conduction.
Therefore according to the present invention, the purposes of functionalized carbonaceous filler is not limited to filler.Comprise in addition all favourable application.Or term " particulate state carbon material " can be for term " carbonaceous filler ".
In the methods of the invention, do not need the carbonaceous filler to using to carry out pre-treatment.Therefore, in one embodiment of the invention, carbonaceous filler does not carry out pre-treatment.More specifically, do not carry out sour pre-treatment, hot pre-treatment, plasma body pre-treatment and/or the ultrasonic pretreatment that prior art is carried out.
In addition, described reaction is not preferably having halogen compounds, and particularly Organohalogen compounds are as carried out under the existence of alkylogen or aryl halide.
After reaction, preferably from mixture, remove ammoniacal liquor, then excessive basic metal and/or alkaline-earth metal or its amides react with alcohol and/or water, and shift out the carbonaceous filler with covalently bound amino from reaction mixture.
Excessive basic metal and/or alkaline-earth metal or its amides preferably with C 1-4reaction of alkanol.
The carbonaceous filler that present method is used is preferably selected from Single Walled Carbon Nanotube or multi-walled carbon nano-tubes, Graphene, carbon black, graphite, gac, carbon fiber and composition thereof.
The carbonaceous filler that the inventive method is used can be selected from any suitable carbonaceous filler.Ignore possible impurity, filler mainly only comprises that carbon is as chemical element.
Carbonaceous filler has greying surface tissue especially.
Single Walled Carbon Nanotube, double-walled carbon nano-tube or the multi-walled carbon nano-tubes (SWCNT, DWCNT, MWCNT) of the example of single wall or multi-walled carbon nano-tubes for for example as above recording.
Suitable carbon nanotube and Graphene are known to the person skilled in the art.For describing suitable carbon nanotube (CNT), can be with reference to DE-A-10243592, particularly [0025] to [0027] section, and WO2008/012233, particularly the 16th page 11 is walked to 41 row, or DE-A-10259498, [0131] to [0135] section.In addition, suitable carbon nanotube is recorded in WO2006/026691, [0069] to [0074] section.Suitable carbon nanotube is recorded in WO2009/000408 in addition, and page 2 28 walks to page 3 11 row.
In the context of the invention, carbon nanotube is interpreted as referring to carbon containing macromole, and wherein carbon (mainly) has graphite-structure and each graphite linings and arranges with the form of pipe.Nanotube and synthetic in the literature known (J.Hu et al.Acc.Chem.Res.32 (1999) for example, 435-445).In the context of the invention, can use in principle the nanotube of any kind.
The diameter of single tubular type graphite linings (carbon tube) is preferably 0.3 to 100nm, and particularly 0.3 to 30nm.Nanotube can be divided into single-walled nanotube (SWCNT) and many walls nanotube (MWCNT) in principle.Therefore,, in MWCNT, there are a plurality of concentric carbon tubes.
In addition, the outer shape of pipe can change; It can inside and outside there is identical shaped diameter, but can also prepare nodositas pipe and the shape structure of wriggling.
Long-width ratio (length of particular graphite pipe and its diameter ratio) is >10 at least, preferably >5.Nanotube length is at least 10nm.In the context of the invention, preferred B component) be MWCNT.More specifically, the long-width ratio of MWCNT is about 500:1 and mean length scope is 1 to 500 μ m.
BET specific surface area is generally 50 to 2000m 2/ g, preferably 130 to 1200m 2/ g.According to HRTEM, the impurity (for example metal oxide) occurring in catalysis preparation is generally 0.1 to 12%, and preferably 0.2 to 10%.
Suitable nanotube can be with " multiwall " title by Hyperion Catalysis Int., Cambridge MA (USA) buys and (also sees EP205556, EP969128, EP270666, US6,844,061), and by BAYER Marerial Science, Nanocyl, Arkema and FutureCarbon buy.
In the present invention, do not need carbon nanotube to carry out pre-treatment or surface modification.
Suitable Graphene is recorded in for example Macromolecules2010,43,6515 to 6530 pages.
Or use that (conduction) is black, graphite or its mixture.Suitable carbon black and graphite are well known by persons skilled in the art.
Carbon black particularly conduct electricity black or electric lead black, acetylene carbon for example.The conduction used is black can be the carbon black of any conventional classification, and suitable example is the Ketjenblack300 commercially available prod purchased from Akzo.
For conductive modified, can also use conduction black.The result that class graphite linings is embedded in decolorizing carbon is carbon black conduction electron (F.Camona, ANN, Chim.Fr.13,395 (1998)).Electric current conducts in the aggregate being comprised of carbon black pellet, and if the distance between aggregate is enough little, also can between aggregate, conduct.For realizing electroconductibility with minimum dosage, preferably use the carbon black (G.Wehner, Advances in palstic technology, APT2005,11 pages of Katowice2005) with anisotropic structure.For this class carbon black, primary particle is coalescent to form anisotropic structure, thereby the separation that obtains the required carbon black pellet of electroconductibility even can realize (C.Van Bellingen in the compound of relatively low load, N.Probst, E.griver, Advances in Plastics Technology, APT2005, Paper13, Katowice2005).
Applicable types of carbon black for example has at least 60ml/100g, preferably surpasses the oil-absorption(number) (measuring according to ASTM D2414-01) of 90ml/100g.The BET surface-area that is applicable to product is greater than 50m 2g and be preferably greater than 60m 2g (measuring according to ASTM D3037-89).Multiple functional group can be present in carbon blacksurface.Graphitized carbon black can be prepared by several different methods (G.Wehner, Advances in Plastics Technology, APT2005, Paper11, Katowice2005).
In addition, graphite can be used as filler.Graphite is interpreted as referring to the polymorphic form of carbon, for example, be recorded in A.F.Hollewnann, E.Wiberg, " Lehrbuch der anorganischen Chemie " [Inorganic Chemistry], 91-100 version, pph.701-702.The plane carbon-coating that graphite is arranged in another layer of top by one deck forms.Graphite can be pulverized by grinding.Particle size range is 0.01 μ m to 1mm, and preferable range is 1 to 250 μ m.
Carbon black and graphite are recorded in for example Donnet, J.B.et al., Carbon Black Science and Technology, second edition, Marcel Dekker, Inc.New York1993.Can also use the conduction based on high-sequential carbon black black.The latter is recorded in for example DE-A-10243592, and particularly [0028], to [0030], is recorded in EP-A-2049597, particularly the 17th page 1 is walked to 23 row, is recorded in DE-A-10259498, particularly [0136] to [0140] section, and be recorded in EP-A-1999201, particularly page 3 10 walks to 17 row.
Particle diameter depends on that concrete carbon material and preferable range are 1nm to 1mm, more preferably 2nm to 250 μ m.The preferred diameter range of carbon fiber is 1 to 20 μ m, more preferably 5 to 10 μ m.Fiber can also be the form of fibrous bundle.
Described reaction is carried out under the existence of basic metal and/or alkaline-earth metal or its amides.Alkaline-earth metal is preferably Ca or Mg.Basic metal is preferably selected from Li, Na, K and composition thereof.Particularly preferably use Li or Na, particularly Na.
Except alkali and alkaline earth metal ions, can also use corresponding amides, it is independently being prepared in reactions steps.Wherein suitable is lithium amide, sodium amide, amination potassium, amination calcium and magnesium amides, is preferably lithium amide, sodium amide and amination calcium, is particularly preferably lithium amide and sodium amide, and is very particularly preferably sodium amide.
Alkali metal amino compound and alkaline-earth metal amides can, by liquefied ammonia, optionally transform metal and prepare under catalyzer exists.Sodium amide synthesizes (Ullmanns Encylopedia of Technical Chemistry, the 5th edition, A2,151 to 161 pages) industrial by making gaseous ammonia pass through molten sodium.
Ammonia is used with anhydrous liquid ammonia form." anhydrous " is interpreted as referring to that water-content is less than 1000ppm.
Described conversion can be carried out in anhydrous liquid ammonia.Or can also use under reaction conditions is the solvent of inertia or thinner.
Under reaction conditions for the useful solvent of inertia comprises that ether is if tetrahydrofuran (THF), diox, methyl tertiary butyl ether and aliphatic hydrocrbon, clicyclic hydrocarbon, aromatic hydrocarbon are as the mixture of hexane, hexanaphthene and toluene, dimethyl formamide or these solvents.
The consumption of mentioned solvent is 0 to 20000 % by weight, 0 to 2000 % by weight particularly, the carbon compound meter based on using.
Carbonaceous filler can be introduced in reactor and be suspended in mentioned solvent.After amination, it can suspend or is dissolved in the solvent removing after ammonia and obtains.Using the result of solvent is only to occur very small amount of dust.This makes to carry out safety operation.
The weight ratio of carbonaceous filler and ammonia is preferably 1:200, more preferably 1:20 to 1:90.
The mol ratio of alkali and alkaline earth metal ions or alkali metal amino compound and alkaline-earth metal amides and ammonia is preferably 1:1000, more preferably 1:50 to 1:400.
Carbon compound, at 35 to 500 ℃, preferably 50 to 250 ℃, more preferably carries out amination at the temperature of 80 to 180 ℃.
The pressure that the total pressure of using exists with liquid form for ammonia.Pressure is 30 to 250MPa(bar), particularly 70 to 150MPa(cling to).
Conversion can be carried out in can bearing any suitable reactor of described pressure and described temperature.In the process transforming, preferably in reactor, mix or stir described reaction mixture.
Described reaction mixture preferably under described reaction conditions in reactor vigorous stirring.Stirring velocity is 50 to 1000rpm, and particularly 250 to 350rpm.Before use, reactor is preferably used rare gas element, preferred nitrogen or argon purge.
Conversion of the present invention is preferably carried out 2 to 24 hours, more preferably 4 to 8 hours, preferably intermittently carries out or carries out continuously.
For aftertreatment, described reaction mixture preferably reduces pressure and is cooled to 20 to 40 ℃.In decompression process, ammonia can evaporate and by cooling recovery.Can also in distillation tower, remove ammonia.
The unconverted basic metal existing in output in reaction or alkaline-earth metal or corresponding amides are preferably converted into the compound can non-hazardous mode removing.The example that is used for the suitable compound of this conversion is alcohol or water, is preferably straight chain alkanol or the branching alkanol with 1 to 4 carbon atom, and more preferably methyl alcohol or ethanol, most preferably be methyl alcohol.The alkoxide forming as reaction product can remove with corresponding alcohol excess carbon compound from amination together with any solvent.This preferably for example removes carbon compound and carries out by absorbing on glass suction filter at suction filter.The aperture of suction filter is preferably 10 to 16 μ m.Carbonaceous filler can be with alcohol washing until filtrate be no longer alkalescence.
If need dry carbon compound, it can be dried to constant weight, for example drying under reduced pressure at 50 to 100 ℃.
The present invention describes in detail by following examples.
Embodiment
The carbonaceous filler of the amination obtaining after preparation by XPS analysis to determine nitrogen content.
For studying the method for the XPS of CNT degree of functionalization, describe hereinafter:
The conventional charge neutrality method of functionalized use for example, is determined by having the XPS of the alpha-emitting standard laboratory spectrometer of monochromatic aluminium K (Phi5600LS, PhiVersaProbe or Kratos Axis Nova).Elementary composition by full spectrum (overview spectrum) (1350eV, to-5eV, walks wide 0.5eV, logical can 112-160eV) quantitatively.For quantitatively, use the relative sensitivity factor (RSF) that particular instrument is determined, and carry out sherry background deduction (Shirley background subtraction).
It is functionalized that by detailed spectrum, (useful range is from peak-peak ± 5-10eV, energy resolution 0.1eV, logical energy 20-30eV) for example, by the correlation data with known (Beamson G.Briggs D.High Resolution XPS of Organic Polymer:the Scienta ESCA300Database (1992)) comparison carbon and heteroatomic peak-peak, determine.
For quantitatively, the carbon line shape of reactant is measured (detailed spectrum, sherry background deduction) under identical measuring condition on identical spectrometer with the carbon line shape of product.
The peak-peak of carbon is calibrated to 284.5eV(aromatics carbon) and functionalized variation by the linear measure spectrum that corresponds to product at the linear of reactant and each reference peak is determined.
Embodiment 1
MWCNT amination in liquefied ammonia under sodium exists
In stirred autoclave (reaction volume 3.5l, has disc agitator), transform.Reactor argon purge.Introduce 30g's
Figure BDA0000444267780000081
c150P MWCNT(is wetting with 140ml tetrahydrofuran (THF)) and 8g sodium.After off-response still, by 1200ml(720g) ammonia is metered into liquid form.Under the agitator speed of 300rpm, reactor is heated to 120 ℃.Determine that pressure is 84 bar.After 3 hours, reactor is cooled to 40 ℃.Pump into 0.5l methyl alcohol to transform any residual sodium and sodium amide.Reactor is reduced pressure gradually and remain at 40 ℃ and exit 1 hour.Again pump into 0.5l methyl alcohol, by the emptying reactor of vertical pipeline (riser line).
Reaction output filters by glass suction filter (10-16 μ m) and by 1 liter of methanol wash.CNT is transferred to after 1l Erlenmeyer flask, itself and 1 liter of methyl alcohol are stirred 15 minutes and again carry out suction strainer.This operation in triplicate.Subsequently, at 70 ℃, under reduced pressure CNT is dried to constant weight.
By the detailed spectrum of the nitrogen of XPS analysis, amine is shown and is positioned at 400.6eV.Nitrogen analysis is 0.6at%(3 the mean value of measuring).
Embodiment 2
Graphene amination in liquefied ammonia under sodium exists
Be similar to embodiment 1,100mg Graphene (Vor-X) is suspended in to 10ml tetrahydrofuran (THF) and in 300ml reactor at 120ml(72g) under 120 ℃ and 300rpm, stir 5 hours under the existence of ammonia and 800mg sodium.Determine that stagnation pressure is 100 bar.
Reactor is cooled to 40 ℃.The Graphene of amination washes out and uses 0.5 μ m teflon membrane to carry out suction strainer from reactor with methyl alcohol.Then Graphene is suspended in 100ml methyl alcohol, stirs 30 minutes and again carries out suction strainer.
At 70 ℃, under reduced pressure Graphene is dried to before constant weight, this operation is repeated once again.
By the detailed spectrum of the nitrogen of XPS analysis, illustrated that amine is positioned at 400.7eV and imines is positioned at 398.9eV.The nitrogen analysis of this amine is that the nitrogen analysis of 0.6at% and imines is the mean value that 0.9at%(respectively does for oneself and measures for 5 times).
It is not definitely necessary injecting nitrogen.
Embodiment 3
MWCNT amination in liquefied ammonia under sodium amide exists
Be similar to embodiment 2, by 2500mg's
Figure BDA0000444267780000091
c150P MWCNT transforms under the existence of 10ml tetrahydrofuran (THF), 250mg sodium amide and 120ml liquefied ammonia.After the aftertreatment described in embodiment 2 and being dried, carry out XPS analysis.
By the detailed spectrum of the nitrogen of XPS analysis, illustrated that amine is positioned at 400.4eV and imines is positioned at 398.9eV.The nitrogen analysis of this amine is that the nitrogen analysis of 1.1at% and imines is the mean value that 0.9at%(respectively does for oneself and measures for 5 times).
Embodiment 4
Be similar to embodiment 1,10g Nanocyl7000MWCNT is at 140ml tetrahydrofuran (THF), 5g sodium and 1200ml(720g) transform under the existence of ammonia.Aftertreatment is carried out as described in Example 1 with dry.
By the detailed spectrum of the nitrogen of XPS analysis, amine is shown and is positioned at 400.7eV.Nitrogen analysis is 1.1at%(3 the mean value of measuring).
Embodiment 5
Be similar to embodiment 1,30g Arkema C100MWCNT is at 140ml tetrahydrofuran (THF), 15g sodium and 1200ml(720g) transform under the existence of ammonia.Aftertreatment is carried out as described in Example 1 with dry.
By the detailed spectrum of the nitrogen of XPS analysis, amine is shown and is positioned at 400.5eV.Nitrogen analysis is 1.0at%(5 the mean value of measuring).
Embodiment 6
Be similar to embodiment 2, by 500mg acetylene carbon (ABCR-50% compression, median size: 0.042 μ m, density: 0.100g/cm 3, surface-area: 80m 2/ g) at 10ml tetrahydrofuran (THF), 500mg sodium and 120ml(72g) liquefied ammonia exist under and inject 30 bar nitrogen after transform.Aftertreatment is carried out as described in Example 2 with dry.
By the detailed spectrum of the nitrogen of XPS analysis, amine is shown and is positioned at 399.7eV.Nitrogen analysis is 1.1at%(5 the mean value of measuring).
Embodiment 7
Be similar to embodiment 2,500mg SWCNT(for example obtained by Nanocyl) at 10ml tetrahydrofuran (THF), 500mg sodium and 120ml(72g) liquefied ammonia exist under and inject 30 bar nitrogen after transform.Aftertreatment is carried out as described in Example 2 with dry.
By the detailed spectrum of the nitrogen of XPS analysis, amine is shown and is positioned at 399.7eV.Nitrogen analysis is 0.9at%(5 the mean value of measuring).

Claims (10)

1. a method of preparing the carbonaceous filler with covalently bound amino, described method by making the mixture that contains carbonaceous filler and basic metal and/or alkaline-earth metal and/or its amides in anhydrous liquid ammonia, optionally transforms and carries out at the temperature of 35 to 500 ℃ and under the pressure of 30 to 250 bar together with a kind of inert solvent.
2. the process of claim 1 wherein after described conversion, from mixture, remove ammonia, excessive basic metal and/or alkaline-earth metal or its amides are reacted with alcohol and/or water, and from reaction mixture, shift out the carbonaceous filler with covalently bound amino.
3. the method for claim 2, wherein excessive basic metal and/or alkaline-earth metal or its amides and C 1-4reaction of alkanol.
4. the method for any one in claims 1 to 3, wherein carbonaceous filler is selected from Single Walled Carbon Nanotube or multi-walled carbon nano-tubes, Graphene, carbon black, graphite, gac, carbon fiber and composition thereof.
5. the method for any one in claim 1 to 4, wherein said reaction is carried out under the alkali-metal existence that is selected from Li, Na, K and composition thereof.
6. the method for any one in claim 1 to 5, wherein said conversion is carried out at the temperature of 50 to 250 ℃.
7. the method for any one in claim 1 to 6, wherein said conversion is carried out under the pressure of 30 to 250 bar.
8. the method for any one in claim 1 to 7, wherein said conversion is not having halogen compounds, especially Organohalogen compounds to carry out under as alkylogen or aryl halide.
9. the method for any one in claim 1 to 8, the carbonaceous filler that wherein used is not pretreated.
10. the method for claim 9, the carbonaceous filler that wherein used is not by sour pre-treatment, hot pre-treatment, plasma body pre-treatment and/or ultrasonic pretreatment.
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