CN1304657C - Preparation of stable carbon nanotube dispersions in liquids - Google Patents

Preparation of stable carbon nanotube dispersions in liquids Download PDF

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Publication number
CN1304657C
CN1304657C CNB028280075A CN02828007A CN1304657C CN 1304657 C CN1304657 C CN 1304657C CN B028280075 A CNB028280075 A CN B028280075A CN 02828007 A CN02828007 A CN 02828007A CN 1304657 C CN1304657 C CN 1304657C
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acid
oil
ester
dispersant
alkyl
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CN1617958A (en
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F·E·洛克沃德
Z·张
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Ashland Inc
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Ashland Inc
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/06—Particles of special shape or size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/02—Carbon; Graphite
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/02—Water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/04—Elements
    • C10M2201/041—Carbon; Graphite; Carbon black
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/108—Polyethers, i.e. containing di- or higher polyoxyalkylene groups etherified

Abstract

The introduction of nanotubes in a liquid provides a means for changing the physical and/or chemical properties of the liquid. Improvements in heat transfer, electrical properties, viscosity, and lubricity can be realized upon dispersion of nanotubes in liquids; however, nanotubes behave like hydrophobic particles and tend to clump together in liquids. Methods of preparing stable dispersions of nanotubes are described and surfactants/dispersants are identified which can disperse carbon nanotubes in aqueous and petroleum liquid medium. The appropriate dispersant is chosen for the carbon nanotube and the water or oil based medium and the dispersant is dissolved into the liquid medium to form a solution. The carbon nanotube is added to the dispersant containing the solution with agitation, ultrasonication, and/or combinations thereof.

Description

The preparation of the stabilising dispersions of CNT in liquid
Background of invention
The application's book requires in the priority of the non-temporary patent application serial number 10/021,761 of the U.S. that is entitled as " preparation of the stabilising dispersions of CNT in liquid " of submission on December 12 calendar year 2001.
Technical field
Use selected dispersant and mixed method, CNT can be scattered in water and the petroleum liquid medium, form stable CNT dispersion, the application's book is described these methods, and has determined these surfactants.
The explanation of prior art
CNT is the material that a kind of novel carbon simple substance forms, and has the character different with other forms of material with carbon element.It has special atomic structure, high draw ratio and unique mechanical performance (intensity and flexibility), makes it can be used as the desirable fortifying fibre of composite and other structural materials.
CNT generally is meant the porous carbon three-dimensional structure of rigidity, and this structure contains carbon nano-fiber, has very big surface area and porosity, low bulk density, the crush strength of a spot of micropore and increase.This method is applicable to the nanotube that contains or do not contain amorphous carbon.
Term " nanotube " is meant that cross section (if any the polygonal fiber on limit) or diameter (as circle) are less than 1 micron slim-lined construction.Structure can be a hollow or solid.Therefore, " nanotube " comprises " nanofiber " and " Baji-tube " (bucky).When these structures are introduced in the structure, because its size and dimension just can provide great surface area.In addition, these fibers can have very high purity and uniformity.
Preferably, the diameter of the used nanotube of the present invention is less than 1 μ m, is more preferably less than about 0.5 μ m, is more preferably less than 0.1 μ m, most preferably less than 0.05 μ m.
Term " internal structure " is meant the internal structure of assembly, comprise the relative orientation of fiber, the diversity of fiber orientation (diversity) and total average orientation, the distance between the fiber, interfibrous gap and the space or the hole of causing at interval, and the fluid course that is connected to form by space and/or hole or size, shape, quantity and the orientation of path.This structure also comprises the relevant feature of size, spacing and orientation with the aggregate particles that forms assembly.Term " relative orientation " is meant an independent fiber or the aggregation orientation (promptly arranging and non-arrangement) with respect to other." diversity " and " total average orientation " of fiber or aggregation orientation is meant the scope (with respect to the arrangement and the orientation of the outer surface of structure) of the interior fiber orientation of structure.
CNT can be used to form the rigid group zoarium, or to make diameter be 3.5 ~ 70nm.The related nanotube of the application, fubril, Baji-tube and carbon must (whisker) is different with commercially available continuous carbon fibre as reinforcing material.And have very greatly, but be not that the CNT of unlimited draw ratio is compared, the draw ratio of continuous carbon fibre (L/D) is at least 10 4, be generally 10 6Or it is bigger.The diameter of continuous carbon fibre is also much larger than the diameter of nanotube, and is general＞1.0 μ m, typically is 5 ~ 7 μ m.Continuous carbon fibre is generally artificial fibre, polyacrylonitrile (PAN) and pitch and makes by pyrolytic organic precursor fiber.Thereby, just may contain hetero atom in their structure.The graphite characteristic of the continuous carbon fibre that as above makes is different, but they can carry out follow-up graphitization processing.The difference of the degree of graphitization of graphite plane, orientation and degree of crystallinity (if existence), heteroatomic may the existence, even the antipode of matrix diameter makes little to the predicting function of nanofiber chemical property about the experience of continuous carbon fibre.
CNT generally is that diameter is the hollow graphite pipe of several to dozens of nanometers.CNT has many kinds of existence forms.The form of nanofiber can be the fiber of separation or the accumulating particulate of nanofiber.The former makes structure have suitable uniformity.The latter makes structure have double-decker, and its total macrostructure is that the accumulating particulate of nanofiber is combined together to form porous mass; Microstructure is that nanofiber twines mutually in single accumulating particulate.For example, a kind of diameter substantially constant of carbon fiber of form, greater than 5 times of diameter, its orderly perimeter is the continuous substantially orderly carbon atomic layer of catalytic growth, multilayer to length approximately, the about 3.5 ~ 70nm of external diameter, the inside center zone is then different fully.Each layer and center and fiber circle pulling shaft almost coaxial.Fiber contains pyrolytic deposition carbon hardly, and the diameter of fiber equals the external diameter of its orderly perimeter.
And the CNT that is suitable for this method use is defined as the cylindrical carbon fiber, and its diameter substantially constant is about 3.5 ~ 70nm; Length is about more than 5 times of diameter, less than about 5000 times of diameter; The perimeter and the diverse interior zone that contain orderly carbon atom multilayer; Each layer and center are coaxial with fiber circle pulling shaft.Preferably, whole CNT does not almost have the RESEARCH OF PYROCARBON skin.Here " cylindrical " is meant the geometry kenel of broad sense, promptly straight line be parallel to one fixedly straight line parallel move, and transversal be a curve, the surface that its track forms.Circle or ellipse are to be in cylindrical many possible curves two kinds.The inside center zone of nanotube may be a hollow, or contains carbon atom, and the arrangement of these carbon atoms does not have the perimeter carbon atom so orderly.Here used phrase " orderly carbon atom " is meant that the C axle of graphite microcell is vertical substantially with the round sample axle of nanotube.In an example, the length of nanotube is greater than about 20 times of its diameter.In another example, the diameter of nanotube is about 7 ~ 25nm.In another embodiment, the diameter in inside center zone is approximately greater than 2nm.
Be dispersed in nanotube organic or aqueous medium in the time, have a difficult problem, promptly nanotube tends to assemble, and forms aggregation block, and and separated dispersion.
Some commercial Application need a kind of method that can prepare the dispersion of stable selected CNT in liquid medium.
For example, the United States Patent (USP) 5,523,006 of Strumban proposes to have used a kind of surfactant and a kind of oily medium; Yet used particulate is the Cu-Ni-Sn-Zn alloy particle of size greater than 0.01 μ m, and it is stable that suspension can only keep in about 30 days of limited time.And used surfactant does not comprise the dispersant that those often use in lubricated industry.
It is the aqueous medium that contains surfactant that the United States Patent (USP) 5,560,898 of Uchida etc. proposes liquid medium; Yet, since water centrifugation from suspension, the result of no stability of suspension.
Disperse the nanotube of disentanglement in the polar solvent that the United States Patent (USP) 5,853,877 of Shibuta proposes, form the coating composition that contains additive such as dispersant; But the undeclared method that obtains stabilising dispersions.
The United States Patent (USP) 6,099,965 of Tennent etc. uses kneader, makes dispersant disperse instrument to mix in liquid medium with other reactants by high moment of torsion, yet undeclared, does not also propose to keep the stability of this dispersion.
Conventional method does not all provide a kind of following the present invention explanation and claimed can and remain on method in the suspension with the nanotube dispersion.
Summary of the invention
In the present invention, be used in combination physics and chemical treatment, to obtain a kind of method for preparing stable CNT dispersion.
The invention provides the selected CNT of a kind of preparation at liquid medium, as water or arbitrarily group water solution or oil, in the method for stabilising dispersions, this method need be used in combination surfactant and stirring (as the ultrasonic wave effect) or other stirring modes.CNT can be single wall or many walls, and draw ratio is generally 500 ~ 5000; Yet the present invention also can use the nanotube of other structures.The length of the CNT that mixture is contained is 1 μ m or longer, and diameter is 50nm or littler.Raw material also can contain size at above-mentioned extraneous CNT.CNT and the nonessential hydrophilic surface that carries out are handled being dispersed in the aqueous medium, but also can randomly handle.Selected surfactant is solvable in liquid medium maybe can be disperseed.
Term among the present invention " surfactant " is meant the surface tension that can reduce liquid when being dissolved in liquid, maybe can reduce between two kinds of liquid or liquid-solid interfacial tension appoint the combination compound.Normally, but be not uniquely, long-chain molecule is made up of two parts: hydrophilic segment and oleophilic moiety." hydrophilic " and " oleophylic " part is meant the part of distinguishing hydrophilic and oleophylic in the molecule.This is a broad terms, has covered all and has had surface-active material, comprises wetting agent, dispersant, emulsifying agent, washing agent and foaming agent etc.Term among the present invention " dispersant " is meant and adds the surfactant to promote that superfine solid particle (being generally the colloid size) evenly suspends in the medium to.In lubricated industry, term " dispersant " is generally believed it is the oil-soluble or the dispersed compound of long-chain, and it works to disperse " cold residue " (cold sludge) of forming in the engine.These two terms are interchangeable basically in the present invention; Yet in some cases, term " dispersant " more lays particular emphasis on finger employed dispersant in lubricated industry usually, but is not to be confined to this.
Prepare the stable method that contains particle dispersion and comprise physical agitation and chemical treatment combination.Physical mixed comprises high shear mixing, for example adopts super mixer, homogenizer, Micro Fluid machine, Kady grinder, colloid mill etc., and HI high impact mixes, for example grater, ball mill and pebble plain etc. and ultrasonic wave action method.Mixed method has also obtained the help of the sterically hindered effect of electrolytical electrostatic stabilization effect and polymeric surfactant (dispersant).
The use of the surfactant/dispersant of chemical treatment and proposition is very crucial to obtaining nanotube mixed liquor steady in a long-term.Processing comprises selected dispersant is dissolved in the selected liquid medium.Chemical method comprises the processing of two steps: dispersant is dissolved in liquid medium, under mechanical agitation or ultrasonic wave effect selected CNT is joined in the mixture of dispersant liq medium then.The order of these steps can be put upside down, but may can not get satisfied result.Liquid medium can be water or the aqueous solution, petroleum distillate, petroleum oil, artificial oil, vegetable oil arbitrarily.The dispersant that is used for the oil-based liquid medium is the surfactant with low hydrophilic lipophilic balance (HLB＜8), or in lubricated industry the polymeric dispersant of used type.Be preferably nonionic, or the mixture of nonionic and ion-type.The preferred dispersants that is used for water-based liquid medium has high HLB value (HLB＞10), is preferably Nonylphenoxy polyoxyethylene ethanol class surfactant.Certainly, also can use the alcohol radical glycol of other high HLB values.The even pipe dispersion that makes has required viscosity in the matter in liquid.The form of the nanotube dispersion that makes in petroleum liquid medium or aqueous medium has pastel, gel or grease-like.
This dispersion also may contain one or more a large amount of other chemical compounds, is preferably high polymer, is not for the purpose of disperseing, but in order to make its thickening, or other fluid properties that need.
An object of the present invention is, a kind of dispersant and physical agitation of being used in combination is provided, the method for the stabilising dispersions of preparation CNT in liquid medium.
Another object of the present invention is to use draw ratio to be generally single wall or the multi-walled carbon nano-tubes of 500-5000.
Another object of the present invention is that the CNT of use has randomly carried out the surface hydrophilic processing to the surface, so that it is distributed in the aqueous medium easily.
Another object of the present invention is that the dispersant of use can be dissolved in the selected liquid medium.
Another object of the present invention is that the preparation method of employing is: earlier dispersant is dissolved in the liquid medium, under vigorous stirring or ultrasonic wave effect CNT is joined in the mixture then.
Another object of the present invention is, stir or the ultrasonic wave effect under, CNT is joined in the liquid, add surfactant then.
Another object of the present invention is to adopt petroleum distillate or synthetic petroleum lubricating oil as liquid medium.
Another object of the present invention is that the liquid medium of used type in the lubricated industry of use, or the surfactant of low HLB (＜8), or surfactant mixtures are preferably nonionic, or the mixture of nonionic and ionic surfactant.More generally, dispersant can be a used ashless polymeric dispersant in the lubricated industry.
Another object of the present invention is to use dispersant-washing agent (DI) additive package product of selling as surfactant/dispersant in lubricated industry.
Another object of the present invention is that the liquid medium of use is made up of water or any group water solution.
Another object of the present invention is, uses the dispersant of high HLB value (＞10), is preferably nonyl benzene nitrogen base polyoxyethylene ethanol class surfactant.
Another object of the present invention is to use the nanotube homogeneous dispersion with required viscosity in the petroleum liquid medium.
Another object of the present invention is, makes the nanotube homogeneous dispersion in petroleum liquid medium or aqueous medium, and its form is gel or pastel.
Another object of the present invention is, CNT is dispersed in makes the nanotube homogeneous dispersion in petroleum liquid medium or the aqueous medium, and its form is a grease-like.
Another object of the present invention is, makes all even stable CNT dispersion in the oil-based fluid medium, contains " other " compound of the non-dispersive of dissolving in this medium.
Another object of the present invention is, makes all even stable dispersion in the liquid water medium with " other " compound form of the non-dispersive that contains CNT and dissolving.
Above-mentioned and other purposes of the present invention, with and advantage will in description subsequently, illustrate or show.
The explanation of preferred implementation
The invention provides and a kind of CNT is distributed to method in the liquid medium.
As mentioned above, nanotube can be single wall or many walls, and generally its nanometer grade diameter is 1-500nm.Diameter more typically is about 10-30nm.The length of pipe can be sub-micron or micron order, is generally 500nm to 500 μ m.More typical length is 1 μ m-100 μ m.The draw ratio of nanotube is hundreds of to thousands of, is generally 500-5000.Can use the CNT, fiber, particulate or its combination that obtain by production.In the present invention, use directly the carbon nano-particles of the industrial products of producing by industrial process, comprise that CNT, carbon fiber, carbon particulate or its combination are as matrix.Use the charcoal treatment method to chemical surface treatment,, obtain a preferred embodiment of the present invention to obtain certain hydrophilic nano particle product.In addition, adopt certain chemical reagent, as hydrogen sulfide, vapour deposition, and/or, can both obtain certain hydrophily with strong acid or alkali treatment.
In preferred embodiment, use be the carbon nanotube product that Carbolex provided of University of Kentucky, this product contains the amorphous carbon particle, and thinks the hydrophily that has improved it through charcoal treatment.The Carbolex CNT comprises single-walled nanotube, many walls nanotube and their compound.In addition, compound can contain a spot of material with carbon element of being made up of irregular spherical particle of part and/or short carbon nanometer tube.
Oil basis fluid body medium
The petroleum liquid medium can be petroleum distillate or synthetic petroleum lubricating oil, grease, gel or oil-soluble polymers composition arbitrarily.More typically be mineral base oil or the synthetic base oil that uses in the lubricating oil industry, as I class (solvent refining mineral oil), II class (hydrocracking mineral oil), III class (the height hydrocrackates is also referred to as artificial oil or semi-synthetic oil sometimes), IV class (poly alpha olefin) and V class (ester class, cycloalkanes etc.).A preferred class comprises poly alpha olefin, synthetic ester and poly-alkyl diol.
Synthetic lubricant fluid comprises hydrocarbon ils and halo hydrocarbon ils, as polyolefin and copolyalkenamer (as polybutene, polypropylene, third rare-isobutylene copolymers, chlorinated polybutylenes, poly-(1-octene), poly-(1-decene) etc., and their mixture), alkylbenzene (as detergent alkylate, myristyl benzene, dinonyl benzene, two-(2-ethylhexyl) benzene etc.); Polyphenylene (as biphenyl, terphenyl, alkylation polyphenyl etc.), alkylated biphenyls ether and alkylated biphenyls thioether and their derivative, analog and homologue etc.
Terminal hydroxyl is through the alkylene oxide polymer and the copolymer of modifications such as esterification or etherificate, and derivative has been formed another kind of known artificial oil.
Another kind of suitable artificial oil comprises the ester that is formed by dicarboxylic acids (as phthalic acid, succinic acid, dialkyl succinylsuccinate and alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, decanedioic acid, fumaric acid, adipic acid, alkenyl malonic acid etc.) and various alcohol (as butanols, hexanol, dodecanol, 2-Ethylhexyl Alcohol, ethylene glycol, monoalkyl ethers of diethylene glycol, propylene glycol etc.).The object lesson of these esters has diester that dibutyl adipate, decanedioic acid two (2-ethyl oneself) ester, fumaric acid dihexyl, di-n-octyl sebacate, diisooctyl azelate, two different decayl esters of azelaic acid, dioctyl phthalate, didecyl phthalate, DI(2ETHYLHEXYL)SEBACATE (dicicosyl sebacate), linoleic acid dimer and 2-Ethylhexyl Alcohol form, reacted the mixed ester that obtains etc. by 1 mole of decanedioic acid and 2 moles of tetraethylene glycols and 2 moles of 2 ethyl hexanoic acids.
Ester as artificial oil comprises that also those are by C 5-C 12Monocarboxylic acid and polyalcohol or polyol ethers are as neopentyl glycol, trimethylolpropane, pentaerythrite, dipentaerythritol, tripentaerythritol etc., the ester that makes.Other artificial oil comprises liquid ester (as tricresyl phosphate, trioctyl phosphate, decylphosphonic acid diethylester etc.) that phosphorous acid forms, PolyTHF etc.
Preferred poly alpha olefin (PAO) comprises the SHF liquid of Mobil Chemical company and ETHYLFLO or the ALBERMARLE of EthylCorporation.PAO also comprises Ethyl company, and the ethyl stream series (Ethyl-flow serie) of " Albermarle company " has ethyl stream 162,164,166,168 and 174, and viscosity is about 2-460 li and executes (cSt).
The Mobil SHF-42 of Mobil Chemical company, Emery 3004 and 3006 and QuantumChemical company additional poly alpha olefin base oil is provided.For example, the viscosity of 212  of Emery 3004 poly alpha olefins (100 ℃) is 3.86cSt, and the viscosity of 104  (40 ℃) is 16.75cSt.Viscosity index (VI) is 125, and pour point is-98 , and flash-point is 432 , and ignition point is 478 .In addition, Emery 3006 poly alpha olefins+viscosity of 212  is 5.88cSt, the viscosity of+104  is 31.22cSt.Viscosity index (VI) is 135, and pour point is-87 , and flashing point is 464 , and ignition point is 514 .
The poly alpha olefin of satisfaction in addition is that Uniroyal Inc. sells, the Synton PAO-40 board poly alpha olefin of 40cSt.The Oronite board poly alpha olefin that equally also can use Chevron Chemical company to produce.
Here also can use Gulf Oil Chemicals company, a subsidiary of Chevron company, GulfSynfluid 4cSt PAO, it is similar with Emery3004 on aspect a lot.The Mobil SHF-41 PAO of Mobil Chemical company is also similar with Emery3004 on aspect a lot.
Preferably, the viscosity of poly alpha olefin in the time of 100 ℃ is about 2-40cSt, and special preferred viscosities is 4-10cSt.
Best artificial oil ester additive is polyol ester and diester, two fatty esters as alkyl carboxylic acid, as azelaic acid two (the 2-ethyl is own) ester, diisodecyl adipate (DIDA) and adipic acid double tridecyl ester, can buy with Emery 2960 trades mark from Emery Chemicals, United States Patent (USP) 4 at Waynick, 859,352 are illustrated it.Other suitable polyol esters are produced by Mobil Oil.Be preferably the Mobil polyol ester P-43 and the P-045 that contain two kinds of alcohol especially, and Hatco Corp.2939.
Diester class and other artificial oils are used to replace the mineral oil in the fluid lubricant.Diester has fabulous utmost point low temperature flow and good anti-oxidant decomposability.
Diester oil can comprise two fatty esters of dicarboxylic acids, or diester oil can comprise dialkyl group two fatty esters of alkyl dicarboxylic carboxylic acid, as azelaic acid two (2-ethyl oneself) ester, two different decayl esters of azelaic acid, azelaic acid double tridecyl ester, diisodecyl adipate (DIDA), adipic acid double tridecyl ester.For example, azelaic acid two (the 2-ethyl is own) ester can be buied with Emery 2958 trades mark from EmeryChemicals.
Also can use polyol ester, as the Emery2935 in the Emery series of Henkel company, 2936 and 2939, Hatco 2352,2962,2925,2938,2939,2970,3178 and the 4322 polyol esters (United States Patent (USP) 5 of Ohtani etc. with Hatco company, 344,579 are illustrated it) and the Mobil ester P 24 of Mobil Chemical company.Can use the Mobil ester that makes as by dicarboxylic acids, dihydroxylic alcohols and monoacid or monohydric alcohol reaction, as the Emery 2936 syntholube base oils of Quantum Chemical company and the Mobil P 24 of Mobilchemical company.Polyol ester has good oxidation and hydrolytic stability.Used herein to polyol ester preferably have approximately-100 ℃ or be low to moderate-40 ℃ pour point, viscosity is about 2-460cSt in the time of 100 ℃.
III class oil generally is meant the hydrogenated oil and fat that is used as base oil composition unique among the present invention, and the electric motor oil with respect to other synthetic base oils of traditional nothing or mineral base oil has more performance.
Hydrogenated oil and fat is meant under specific condition mineral oil is carried out hydrogenation or hydrocracking, the mineral oil base oil that obtains to remove wherein unwanted chemical composition and impurity, and it has the composition and the character of artificial oil.General hydrogenated oil and fat is defined as III class petroleum based oil, and its sulfur content has been carried out highly hydrogenated processing and isomerization dewaxing (isodewax) less than 0.03, and saturation degree (saturate) is more than or equal to 90, and viscosity index (VI) is more than or equal to 120; When it used with artificial oil or mineral oil, consumption was up to 90 volume %, was preferably 5.0-50 volume %, more preferably was 20-40 volume %.
Hydrogenated oil and fat is used as base oil composition unique among the present invention, and the electric motor oil with respect to other synthetic base oils of traditional nothing or mineral base oil has more performance.When hydrogenated oil and fat and another traditional artificial oil, as contain the oil of poly alpha olefin or ester, or when using with mineral oil, stereometer with base oil composition, the content of hydrogenated oil and fat is up to 95 volume %, preferably be about 10-80 volume %, be more preferably 20-60 volume %, preferably be about 10-30 volume %.
The base oil of can the partial concentration thing among the present invention or adding this concentrate adds I or II class mineral base oil.This mineral oil basis oil is preferably that Marathon Ashland Petroleum produces be called have SABOLTUNIVERSAL viscosity be 325SUS under 100  solvent refining neutral oil ASHLAND 325 Neutral and be called and have the ASHLAND100 Neutral that SABOLT UNIVERSAL viscosity is the solvent refining neutral oil of 100SUS under 100 .
Other acceptable petroleum base liquid components comprise that viscosity is about the white mineral oil of 20-400cSt, paraffin oil and MVI naphthenic oil.Preferred white mineral oil comprises the white mineral oil that Witco company, Arco Chemical company, PSI and Penreco provide.Preferred paraffin oil comprises the solvent processing neutral oil that solvent neutral oil that Exxon Chemical company provides, HVI neutral oil that Shell Chemical company provides and Arco Chemical company provide.Preferred L VI naphthenic oil comprises solvent extraction bay light yellow oil (coastal pale oil) that Exxon Chemical company provides, MVI extraction/acid treatment oil that Shell Chemical company provides and HydroCal board and the Calsol board naphthenic oil of Calumet, the United States Patent (USP) 5 of Oldiges, 348,668 are illustrated it.
At last, also available in the present invention vegetable oil is as liquid medium.
Aqueous medium
Selected aqueous medium is a water, or contains pure and mild its derivative, as dihydroxylic alcohols, or any group water solution of water miscible inorganic salts or organic compound.
Surfactant/dispersant
The dispersant that uses in the lubricated industry
The dispersant that uses in the lubricated industry generally is used to be dispersed in " the cold residue " that produces in gasoline and the Diesel engine, and it can be " ashless dispersant " or contain metallic atom.Because finding these dispersants is a kind of fabulous ash dispersers, so they also can use in the present invention, and cigarette ash is a kind of amorphous carbon particle that produces in engine crankcase, and combines dust and grease.
Normally used ashless dispersant contains alkyl and hydrophilic polar functional group of an oleophylic in the auto industry.Polar functional group can be carboxylate, ester, amino, acylamino-, imino group, acylimino, hydroxyl, ether, epoxy radicals, phosphorous-containigroups groups, ester carboxyl, acid anhydrides or itrile group.Lipophilic group can be oligomer or high polymer, generally contains 70-200 carbon atom, to guarantee its oil-soluble.Handle hydrocarbon polymer with all ingredients, comprise at first with maleic anhydride or phosphoric sulfide or phosphorus chloride to introduce polar functional group, or heat treatment method, polyolefin such as polyisobutene are handled; And then with processing such as reagent such as polyamine, amine, oxirane and the product that makes.
The general ashless dispersant that uses comprises that N-replaces polyisobutenyl succimide and polyisobutenyl succinate, alkyl methacrylate-vinylpyrrolidone copolymer, alkyl methacrylate-methacrylic acid dialkyl amido ethyl ester (dialkylaminoethyl methacrylate) copolymer, alkyl methacrylate-polyethylene glycol methacrylate-styrene polymer copolymer and poly-stearmide in the petroleum industry.Most important oil-based dispersants preferably includes the dispersant from alkyl succinimide, succinate, amount of polymers amine, mannich base (Mannichbase) and phosphoric acid derivatives among the present invention.Some concrete examples comprise polyisobutenyl succimide-polyethylene polyamines, polyisobutenyl succinate, polyisobutenyl acrinyl-polyethylene polyamines, dihydroxypropyl phosphate.Dispersant also can with used other additive combinations in the lubricated industry together, form a kind of " dispersant-washing agent (DI) " additive package product, as Lubrizol TM9802A, whole DI product can be used as the dispersant of nanotube suspended substance.
For example, Wickliffe, the technology brochure of the Lubrizol company of OH (material safety data slurry, MATERIAL SAFETY DATA SHEET No.1922959-1232446-3384064) is illustrated LUBRIZOL 9802A, and its content is in conjunction with being referred to this.Wherein, LUBRIZOL 9802A is as the electric motor oil additive, thinks that it contains zinc dithiophosphate and/or alkyl zinc dithiophosphate as active component.
Wickliffe, the technology brochure of the Lubrizol company of OH (material safety data slurry, MATERIALSAFETY DATA SHEET No.1272553-1192556-3310026) is illustrated LUBRIZOL 4999, and its content is in conjunction with being referred to this.Wherein, LUBRIZOL 9802A is as the electric motor oil additive, and the alkyl zinc dithiophosphate that contains 5-9.9% is as active component.
The technology brochure of the Chevron Chemical LLC of company " material safety data slurry, MATERIALSAFETY DATA SHEET No.006703 " is illustrated OLOA 9061, and its content is in conjunction with being referred to this.OLOA 9061 is the alkyl zinc dithiophosphate compound.
The technology brochure of Rhodia company " material safety data slurry, MATERIAL SAFETY DATA SHEET " is illustrated IGEPAL CO-630, and its content is in conjunction with being referred to this.IGEPAL CO-630 is a Nonylphenoxy polyoxyethylene ethanol, branched chain compound.
The dispersant of other types
Perhaps, the present invention also can use the surfactant or the surfactant mixture of low HLB value (be generally less than or equal 8), is preferably the mixture of nonionic or nonionic and ion-type.
The dispersant that is used for water base CNT dispersion should have higher H LB value (be generally less than or equal 10), preferably uses Nonylphenoxy polyoxyethylene ethanol class surfactant.
In water and oil-based media, selected dispersant should be able to dissolve or be dispersed in the liquid medium.
The consumption of dispersant is 0.001-30%, is preferably 0.5-20%, is 1.0-8.0% more preferably, is preferably 2-6%.The consumption of CNT is 0.0001-50 weight %.In the practical application, be generally 0.01-2%, be most preferably 0.05-0.5%.The remainder of prescription is selected oil or aqueous medium.
Think that dispersant is by working on the surface that is adsorbed on CNT among the present invention.Dispersant contains a hydrophilic segment and a hydrophobic part, and it is surrounded carbon granule, thereby isolates and the dispersed carbon particle.Selection has the dispersant of specific HLB value to determining dispersing characteristic, and is very important as dispersion rate and dispersion degree of stability in time.
Other compound additives
This dispersion also may contain one or more a large amount of other compounds, is preferably high polymer, is not for the purpose of disperseing, but in order to make its thickening, or other fluid properties that need.
The viscosity improver that uses in the lubricated industry also can be used for oily medium of the present invention, comprises olefin copolymer (OCP), polymethacrylates (PMA), hydrogenated styrene-diene (STD) and styrene-polyester (STPE) polymer.Olefin copolymer is the rubber-like material that is made by vanadium base Ziegler-Nata catalyst by the ethene and third lean mixture.Styrene-diene polymer is made by anionic polymerisation by styrene and butadiene or isoprene.Polymethacrylates is made by radical polymerization by alkyl methacrylate.The preparation method of styrene-polyesters copolymer is: at first make styrene and maleic anhydride copolymerization, use this intermediate product of mixed alcohol esterification then.
Other compounds that can be used for aqueous medium of the present invention or oily medium comprise: acrylate copolymer, as polyacrylic acid and Sodium Polyacrylate, the poly(ethylene oxide) of amount of polymers is as the Polyox of Union Carbon WSR, cellulosic cpd, as carboxymethyl cellulose, polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), xanthans and guar gum, Polysaccharides, the alkanolamide class, the polyamide amine salt is as the Disparlon AQ series of King Industries, through hydrophobic modified oxirane polyurethane (as the Acrysol series of Rohmax), silicate and filler, as mica, silica, cellulose, wood powder, clay (comprising organic clay) and nanoclay, and resinous polymer are as polyvinyl butyral resin, polyurethane resin, acrylic resin and epoxy resin.
Also spendable compound of the present invention such as plasticizer; comprise phthalic acid ester; adipate ester; sebacate has more specifically: three (acetate stearic acid) glyceride; epoxidized soybean oil; epoxy linseed oil; N-n-butylbenzene sulfonamide; aliphatic urethane; poly-two acid esters; triethylene glycol caprate/caprylate; chain alkyl ether; the monomer of dialkyl group glutarate and polymer; and epoxy plasticizer; polyester adipate; the acid of hydrogenation dimer; distillation dimer acid (distilled dimer acid); three polyglycerol fatty acids of polymerization (polymerized fatty acidtrimer); the hydrolytic collagen ethyl ester; isostearic acid and sorbitan oleate (sorbian oleate) and cocoyl hydrolysis of keratin; the PPG-12/PEG-65 lanolin oil; the adipic acid dialkyl; alkyl aryl phosphate; the alkyl diaryl phosphate; modified phosphate triaryl ester; triaryl phosphate; butyl benzyl phthalate; octyl benzyl pathalate; phthalic acid alkyl benzyl ester; dibutoxy ethoxyethyl group adipate ester; the 2-ethylhexyl diphenyl phosphate; dibutoxy ethoxyethyl group formyl; diisopropyl adipate; diisopropyl sebacate; Isodecyl oleate; the neopentyl glycol dicaprate; neopentyl glycol dicaprylate (diotanoate); neopentanoic acid dissident ester; ethoxyquin lanolin; the polyoxyethylene cholesterol; propoxylation (2 moles) lanolin (lanolin) alcohol; propoxylation lanolin (lanoline) alcohol; the acetylation polyoxyethylene deriv and the dimethyl polysiloxane of lanolin.Alternative above-mentioned plasticizer and/or comprise glycerine, polyethylene glycol, dibutyl phthalate and 2 with other plasticizer that above-mentioned plasticizer uses, 2,4-trimethyl-1,3-pentanediol mono isobutyrate and diisononyl phthalate, these compounds can both be dissolved in the solvent carrier.
Physical agitation
The physical mixed method comprises high shear mixing, for example adopts super mixer, homogenizer, Micro Fluid machine, Kady grinder, colloid mill etc., and HI high impact mixes, for example grater, ball mill and pebble plain etc., and ultrasonic method.
Ultrasonic method is best physical method among the present invention, and this is because it is less than above-mentioned additive method to the destruction of carbon nano tube structure.Can carry out ultrasonic vibration with bath type (bath-type) or end type (tip-type) supersonic generator.End type supersonic generator generally is used for high energy output.Requirement with in high instrumental intensity carried out ultrasonic vibration maximum 30 minutes, be generally 10-20 minute, make dispersion have uniformity preferably.
Used ultrasonic disruption instrument is to be positioned at Pittsburgh among the present invention, the 550 type ultrasonic disruption instrument that the FisherScientific company of Pennsylvania produces.The instruction manual of publishing in November, 1996 that is numbered FS-IM-2 has illustrated the using method of 550 type ultrasonic disruption instrument, and its content is in conjunction with being referred to this.Generator power supply is converted into the electric energy of 20kHz with the alternating current of common 50/60Hz, is imported into then in the converter, and electric energy is converted into mechanical vibrational energy.The core of converter is a lead zirconate titanate crystal (piezoelectric), and when applying the voltage of alternation, it will expand and shrink.Converter longitudinally vibrates, and this motion is delivered to the luffing rod end that is immersed in the liquid solution.Atomic little bubble moment formation and implosion, the result of this cavitation makes powerful shock wave pass through whole sample from this end face radiation.Luffing bar and probe can amplify the extensional vibration of converter, and multiplication factor (or gain) is big more, just makes cavitation strong more, and destruction is big more.The termination of probe is big more, and treatable volume is also big more, but intensity diminishes.Regulate converter, it is vibrated with fixed frequency 20kHz.All luffing bars (horn) and probe all are the resonance bodies, also can be adjusted to the frequency of 20kHz and vibrate.Certainly, according to the present invention, also can use other model and similar ultrasonic wave mixing arrangement.
Can adopt the known dry type or the wet lapping method of any appropriate, mixture of raw material is clayed into power.A kind of Ginding process wherein is with mixture of raw material grind into powder in liquid mixture of the present invention, to obtain concentrate, under the help of above-mentioned dispersant, powder-product further is dispersed in the liquid medium then.Yet, grind or pulverize the average aspect ratio that has reduced CNT.
This method that makes the stable suspension of CNT in solution is made up of two key steps.At first,, dispersant is dissolved in the liquid medium, forms solution for CNT and the suitable dispersant of medium selection; Then, under strong agitation, ball milling or ultrasonic vibration solution, CNT is joined in the solution that contains dispersant.
Will the present invention is further described and explanation in following embodiment.
Embodiment
Embodiment 1
Composition Explanation Weight %
CNT dispersant liq ultrasonic wave Without surface treatment, draw ratio is 2000, diameter is 25nm, and length is 50 μ m Lubrizol TMThe 9802A poly alpha olefin, 6cSt Fisher Scientific 550 type ultrasonic disruption instrument, 15 minutes 0.1 4.8 95.1
Embodiment 2
Composition Explanation Weight %
CNT dispersant liq ultrasonic wave Without surface treatment, draw ratio is 2000, diameter is 25nm, and length is 50 μ m Lubrizol TM4999 poly alpha olefins, 6cSt Fisher Scientific 550 type ultrasonic disruption instrument, 15 minutes 0.1 4.8 95.1
Embodiment 3
Composition Explanation Weight %
CNT dispersant liq ultrasonic wave Without surface treatment, draw ratio is 2000, diameter is 25nm, length is 50 μ m OLOA, 9061 poly alpha olefins, 6cSt Fisher Scientific 550 type ultrasonic disruption instrument, 15 minutes 0.1 4.8 95.1
Embodiment 4
Composition Explanation Weight %
CNT dispersant liq ultrasonic wave Through surface treatment Igepal TMCO-630 water Fisher Scientific 550 type ultrasonic disruption instrument, 15 minutes 0.1 5.0 94.9
Dispersion among the embodiment 1-4 is all very even, and stable dispersity can keep 1 year at least, the sign of any separation or gathering do not occur.
Be expected at as can using the dispersant that substitutes in the example of embodiment 1-4, and have identical effect.For example, in embodiment 1, the zinc dithiophosphate of the highest 4.8 weight % can substitute LUBRIZOL 9802A, and this is because it is the main active of this product.In embodiment 2, the alkyl zinc dithiophosphate of the highest 4.8 weight % can substitute LUBRIZOL 4999 products, and pre-in respect of identical effect, and this is because alkyl zinc dithiophosphate is LUBRIZOL 4999 product activity compositions.In embodiment 3, a kind of alkyl zinc dithiophosphate compound of the highest 4.8 weight % can substitute OLOA 9061, and this is because alkyl zinc dithiophosphate is OLOA 9061 product activity compositions.At last, in embodiment 4, a kind of Nonylphenoxy polyoxyethylene ethanol branched chain compound of the highest 5.0 weight % can substitute IGEPAL CO-630 product, and this is because Nonylphenoxy polyoxyethylene ethanol branched chain compound is the main active of IGEPAL CO-630 product.In addition, the percetage by weight of CNT can be up to 10 weight % in the prescription, preferably is up to 1 weight %, is preferably 0.1-1 weight %, and this is determined by the preferred viscosities of final product and chemistry and physical property.Therefore, the percetage by weight of liquid medium can reduce, and the percetage by weight of dispersant can increase and is up to 20 weight %, more preferably is 0.1-10 weight %, is preferably 3-6 weight %.As long as keep required HBL value with obtain having gel, the compound of grease or wax shape denseness, the amount of nanotube, dispersant and liquid medium also can change.
To the discussion of concrete composition, method or example, just for the invention in this specification is described.For a those skilled in the art, on the basis of this specification explanation, the change of these compositions, method or example all is to understand easily, and therefore also they are included as a part of the present invention.The list of references that is proposed in this specification is in order to make patent that these are cited or document to comprise any patent or other lists of references that these documents are quoted clearly with reference to being incorporated into this, just look like this specification illustrate fully like that.Above-mentioned detailed description mainly is in order clearly to understand, and be not interpreted as unnecessary restriction thus, because those skilled in the art has read this specification, can feel to revise is obviously, and these are modified under the condition of the scope that does not deviate from spirit of the present invention and appended claims and make.Therefore the present invention is not subjected to above-mentioned concrete illustrational restriction, but the content that the present invention will cover is in the spirit and scope of appended claims.

Claims (25)

1. method for preparing the stabilising dispersions of carbon nano-particles in liquid may further comprise the steps:
With 0.001-30.0% comprise 8 or the dispersant of the surfactant of littler low hydrophilic lipophilic balance (HLB) be dissolved in a large amount of liquid mediums, to form the dispersant liq medium, this liquid medium is selected from mineral oil, hydrogenated oil and fat, vegetable oil, artificial oil and their combination;
Under churned mechanically condition, be that the carbon nanomaterial of 500-5000 joins in the described dispersant liq medium with the draw ratio of 0.01-10.0 weight %;
Form the symmetric suspension of colloid size solids.
2. method for preparing the stabilising dispersions of carbon nano-particles in liquid may further comprise the steps:
With 0.001-30.0% comprise 8 or the dispersant of the surfactant of littler low hydrophilic lipophilic balance (HLB) be dissolved in a large amount of liquid mediums, to form the dispersant liq medium, this liquid medium is selected from mineral oil, hydrogenated oil and fat, vegetable oil, artificial oil and their combination;
Under the condition of ultrasonic vibration, be that the carbon nanomaterial of 500-5000 joins in the described dispersant liq medium with the draw ratio of 0.01-10.0 weight %;
Form the symmetric suspension of colloid size solids.
3. the method for claim 1 is characterized in that described dispersant is ashless polymeric dispersant.
4. method as claimed in claim 3 is characterized in that described ashless polymeric dispersant contains the alkyl of oleophylic and hydrophilic polar functional group.
5. method as claimed in claim 4 is characterized in that described hydrophilic polar functional group is selected from carboxylate, ester, amino, acylamino-, imino group, acylimino, hydroxyl, ether, epoxy radicals, phosphorous-containigroups groups, ester carboxyl, acid anhydrides, itrile group or their combination.
6. method as claimed in claim 4 is characterized in that described oleophylic alkyl contains 70-200 carbon atom.
7. the method for claim 1, it comprises and adds electrolytical step.
8. the method for claim 1, it is characterized in that described mechanical agitation comprises the step of using high-shear mixer to mix described carbon nano-particles, high-shear mixer is selected from super mixer, homogenizer, Micro Fluid machine, Kady grinder, colloid mill etc., HI high impact mixes, grater, ball mill and pebble plain or their combination.
9. the method for claim 1, it comprises the step of adding viscosity improver.
10. method as claimed in claim 9 is characterized in that described viscosity improver is selected from olefin copolymer, polymethacrylates, hydrogenated styrene-diene and styrene-polyesters copolymer or their combination.
11. method as claimed in claim 9, it comprises thickener, and this thickener is selected from polyacrylic acid and Sodium Polyacrylate, amount of polymers poly(ethylene oxide), carboxymethyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone and their combination.
12. the method for claim 1, it comprises the step of adding plasticizer.
13. method as claimed in claim 12; it is characterized in that described plasticizer is selected from phthalic acid ester; adipate ester; sebacate; three (acetate stearic acid) glyceride; epoxidized soybean oil; epoxy linseed oil; N-n-butylbenzene sulfonamide; aliphatic urethane; polyester glutarate; triethylene glycol caprate/caprylate; chain alkyl ether; the monomer of dialkyl group glutarate and polymer; polyester adipate; the acid of hydrogenation dimer; the acid of distillation dimer; three polyglycerol fatty acids of polymerization; the hydrolytic collagen ethyl ester; isostearic acid and sorbitan oleate and cocoyl hydrolysis of keratin; lanolin oil; the adipic acid dialkyl; alkyl aryl phosphate; the alkyl diaryl phosphate; modified phosphate triaryl ester; triaryl phosphate; butyl benzyl phthalate; octyl benzyl pathalate; phthalic acid alkyl benzyl ester; dibutoxy ethoxyethyl group adipate ester; the 2-ethylhexyl diphenyl phosphate; dibutoxy ethoxyethyl group formic acid esters; diisopropyl adipate; diisopropyl sebacate; Isodecyl oleate; the neopentyl glycol dicaprate; the neopentyl glycol dicaprylate; neopentanoic acid dissident ester; ethoxyquin lanolin; the polyoxyethylene cholesterol; propoxylation (2 moles) lanolin alcohol; the propoxylation lanolin alcohol; the acetylation polyoxyethylene deriv of lanolin; dimethyl polysiloxane; glycerine; polyethylene glycol; dibutyl phthalate; 2; 2; 4-trimethyl-1, the 3-pentanediol mono isobutyrate; diisononyl phthalate or their combination.
14. the method for claim 1 is characterized in that described dispersant is selected from zinc dithiophosphate, alkyl zinc dithiophosphate or their combination.
15. the method for claim 1 is characterized in that described dispersant comprises the surfactant of the even suspension of adding the superfine colloid size solids of promotion in the described liquid medium to.
16. the method for claim 1 is characterized in that described dispersant comprises oil-soluble or dispersed long-chain compound.
17. the method for claim 1 is characterized in that described mineral oil comprises solvent refining neutral oil, white mineral oil, paraffin oil and MVI naphthenic oil or their combination.
18. the method for claim 1 is characterized in that described mineral oil also comprises hydrocracking mineral oil.
19. the method for claim 1 is characterized in that described hydrogenated oil and fat comprises height hydrocracking mineral oil.
20. the method for claim 1, it is characterized in that described artificial oil is selected from poly alpha olefin, ester, cycloalkanes, poly-alkyl diol, hydrocarbon ils, the halo hydrocarbon ils, as polyolefin and copolyalkenamer, polybutene, polypropylene, third rare-isobutylene copolymers, chlorinated polybutylenes, poly-(1-octene), poly-(1-decene), alkylbenzene, detergent alkylate, myristyl benzene, dinonyl benzene, two-(2-ethylhexyl) benzene, polyphenylene, biphenyl, terphenyl, the alkylation polyphenylene, alkylated biphenyls ether, the alkylated biphenyls thioether, terminal hydroxyl is through alkylene oxide polymer and the copolymer and their derivative of esterification modification, dicarboxylic acids, phthalic acid, succinic acid, dialkyl succinylsuccinate and alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, decanedioic acid, fumaric acid, adipic acid, the alkenyl malonic acid, butanols, hexanol, dodecanol, 2-Ethylhexyl Alcohol, ethylene glycol, monoalkyl ethers of diethylene glycol, the ester of propylene glycol, dibutyl adipate, decanedioic acid two (the 2-ethyl is own) ester, the fumaric acid dihexyl, di-n-octyl sebacate, diisooctyl azelate, two different decayl esters of azelaic acid, dioctyl phthalate, didecyl phthalate, DI(2ETHYLHEXYL)SEBACATE, the diester that linoleic acid dimer and 2-Ethylhexyl Alcohol form, polyol ethers, neopentyl glycol, trimethylolpropane, pentaerythrite, dipentaerythritol, tripentaerythritol, polyol ester, diester, two fatty esters of alkyl carboxylic acid, as azelaic acid two (the 2-ethyl is own) ester, diisodecyl adipate (DIDA), adipic acid double tridecyl ester, two fatty esters of dicarboxylic acids, dialkyl group two fatty esters of alkyl dicarboxylic carboxylic acid are as azelaic acid two (the 2-ethyl is own) ester, two different decayl esters of azelaic acid, azelaic acid double tridecyl ester, diisodecyl adipate (DIDA), adipic acid double tridecyl ester.
21. the method for claim 1 is characterized in that described artificial oil is selected from the various artificial oils that viscosity is about 2-460cSt.
22. the method for claim 1 is characterized in that described carbon nano-particles is selected from amorphous carbon particulate nanotube, carbon fiber, short nanotube and their combination.
23. the method for claim 1 is characterized in that with the charcoal treatment method described carbon nano-particles being carried out chemical surface treatment.
24. the method for claim 1 also, it also comprises the amount that changes described carbon nano-particles, described dispersant and described liquid medium, and keeping the HLB value is 8 or littler, the step of the compound of preparation gel, grease or wax shape denseness.
25. the method for claim 1 is characterized in that described dispersant is selected from nonionic surface active agent, ionic surfactant and their mixture.
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