CN101384426A - Polymeric materials incorporating carbon nanostructures and methods for making same - Google Patents
Polymeric materials incorporating carbon nanostructures and methods for making same Download PDFInfo
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- CN101384426A CN101384426A CNA2007800051266A CN200780005126A CN101384426A CN 101384426 A CN101384426 A CN 101384426A CN A2007800051266 A CNA2007800051266 A CN A2007800051266A CN 200780005126 A CN200780005126 A CN 200780005126A CN 101384426 A CN101384426 A CN 101384426A
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Abstract
The present invention relates to novel composites that incorporate carbon nanospheres into a polymeric material. The polymeric material can be any polymer or polymerizable material compatible with graphitic materials. The carbon nanospheres are hollow, graphitic nanoparticles. The carbon nanospheres can be manufactured from a carbon precursor using templating catalytic nanoparticles. The unique size, shape, and electrical properties of the carbon nanospheres impart beneficial properties to the composites incorporating these nanomaterials.
Description
Background of invention
I. invention field
The present invention relates generally to combine the polymeric material of carbon nanomaterial.More specifically, the present invention relates to combine the polymeric material of Nano carbon balls.
II. correlation technique
Material with carbon element is used for many fields as high-performance and functional material.Graphite is well-known material with carbon element with critical nature (for example electric conductivity and inertia).In the past decade, researchers have known how to make the graphite-structure with nano-scale.The Nano graphite structure that is subjected to broad research and understanding is a CNT.Recently, researchers have developed other carbon nano-structured method as carbon " nano-onions (nano-onions) ", " nanometer angle (nanohorns) ", " nano-beads (nanobeads) ", " nanofiber " etc. of manufacturing.
In these materials some have been used for preparing compound by nanostructured is attached to polymeric material.Major part in these effort relates to single wall and many walls nanotube is attached in the polymer.It is favourable using CNT to insert in the polymer as packing material, because the intensity of this composite improves, and makes composite materials have electric conductivity.
But, confirmed with CNT be attached in the polymeric material be have challenging.The fiber shape of CNT and their small size make them be difficult to be evenly dispersed in the polymer.For the application that needs electric conductivity, make resistance have a mind to amount that the free burial ground for the destitute reduces required CNT and for major applications, be subjected to the restriction of cost aspect.
Summary of the invention
The present invention relates in polymeric material, combine the novel compound of carbon nanomaterial.Carbon nanomaterial comprises makes polymer composites have the carbon nano-structured of new property.In an embodiment of the invention, being attached to carbon nano-structured in the polymeric material is Nano carbon balls.Nano carbon balls has the graphite wall of the hollow Nano particle of a plurality of qualification circular usually.
Nanosphere can be prepared into various sizes.In one embodiment, external diameter is about 2 nanometer to 500 nanometers, is more preferably 5 nanometer to 250 nanometers, is most preferably 10 nanometer to 150 nanometers.The internal diameter of nanosphere depends on the external diameter and the wall thickness of nanosphere.Internal diameter (being the diameter of hollow parts) is about 0.5 nanometer to 300 nanometer usually, is more preferably 2 nanometer to 200 nanometers, is most preferably 5 nanometer to 100 nanometers.
Randomly, can handle, so that nano material easier dispersion in polymeric material, and/or remove its surperficial functional group (for example acidic group) carbon nanomaterial.In one embodiment, use neutralization bases to remove carboxylic acid and other oxygen-containing functional group.In another embodiment, by after with the oxidant purifying, carrying out the dispersiveness that heat treated improves nano material.
The polymeric material that is used to prepare compound can be any polymer or the polymerizable material compatible with graphite material.The example of polymer comprises polyamine, polyacrylate, polybutadiene, polybutene, polyethylene, polyethylene chlorine (polyethylenechlorinates), ethylene-vinyl alcohol copolymer (ethylene vinylalcohols), fluoropolymer, ionomer, polymethylpentene, polypropylene, polystyrene, polyvinyl chloride, Vingon, condensation polymer, polyamide, polyamide-imides, PAEK, Merlon, polyketone, polyester, polyether-ether-ketone, PEI, polyether sulfone, polyimides, polyphenylene oxide, polyphenylene sulfide, polyphthalamide, poly-phthalimide, polysulfones, polyarylsulfone (PAS), allyl resin, melamine resin, phenolic resins, liquid crystal polymer, polyolefin, silicone, polyurethane, epoxy resin, polyurethane, cellulosic polymer, the combination of these polymer, the copolymer of any polymer in the derivative of these polymer or the above-mentioned polymer.Polymerizable thing material can be polymer or polymerisable material such as monomer, oligomer or other polymerizable resin.
The amount of the Nano carbon balls that mixes with polymeric material is about 0.1 weight % to 70 weight % of compound, is more preferably 0.5 weight % to 50 weight %, is most preferably 1.0 weight % to 30 weight %.Nano carbon balls can add separately, perhaps adds with other graphite material combination, so that compound has conduction property.In order to make compound have conduction property, account for the Nano carbon balls that compound surpasses about 3 weight % preferred the adding, more preferably surpasses about 10 weight %, most preferably surpasses about 15%.
As the method for producing compound of the present invention, can use any known method.For example, the Nano carbon balls of spherolite or pulverous polymeric material and aequum can be done and mix or wet mixing, in heating, in mixing roll mill, mix then, perhaps join in the extruder and extrude, be cut into bead then as the cord-like material.Perhaps, Nano carbon balls can be sneaked in the liquid medium with resin solution or resin dispersion.When using the polymerisable material of thermosetting, can use any known method that is applicable to specific resin that Nano carbon balls is mixed with monomer or oligomer.
Compare with fibrous other nano material (particularly nanotube), nanosphere is because easier being dispersed in polymeric material or the polymerizable material as the shape of sphere more.This makes that nanosphere is easier and disperses as particulate filler rather than fibrous material.Fibrous material more is difficult to disperse than particle usually, needs much higher shearing force to guarantee good dispersion.On the contrary, use lower shearing force that nanosphere is mixed with polymeric material and polymerizable material.Using lower shearing force to mix nanosphere does not make graphite material and graphite material be dispersed in wherein polymeric material degrades so easily.
In order to promote the dispersion of nanosphere in polymeric material, can use any known method and/or the suitable material that uses with graphitic carbon.In addition, as molded be the method for required form, can use any known method, for example extrusion molding, blowing, injection moulding or pressing mold.
Composite of the present invention is owing to wherein unique shape, chemical property and other character of the Nano carbon balls of combination have useful performance.Especially, have been found that with the CNT or the carbon black of a great deal of and compare that Nano carbon balls can reduce the resistance of many polymer more significantly.For example, when the CNT of the carbon black of the 16 weight % that have an appointment in the polymeric material or 7 weight %, can realize required low resistance, surprisingly, the Nano carbon balls of an offer 3 weight % just can be realized identical required low resistance.
Can more fully understand these and other advantage of the present invention and feature from the following description and the appended claims.
Brief Description Of Drawings
In order further to set forth above-mentioned and other advantage and feature of the present invention, the present invention is more specifically described by the specific embodiment of middle explanation with reference to the following drawings.Should be understood that these accompanying drawings have only described exemplary embodiment of the present invention, therefore should not think that they have limited scope of the present invention.By using the following drawings concrete especially and describe and explain the present invention in detail:
Figure 1A is that this carbon nanomaterial comprises a large amount of nanosphere clusters according to the high-resolution SEM image of the carbon nanomaterial of embodiments of the present invention formation;
Figure 1B is the high-resolution SEM image of the close up view (closer image) of each carbon nano-structured cluster of expression, and has shown a cluster, and this cluster breaks apart, and has exposed to constitute a plurality of carbon nano-structured of cluster;
Fig. 2 is the high-resolution TEM image of the carbon nanomaterial of Figure 1A, shows together carbon nano-structured of a plurality of reunions, and has shown carbon nano-structured many walls and the hollow features that forms cluster;
Fig. 3 is presented at the high-resolution TEM image that its center has the carbon nano-structured feature details (close-up) of catalytic templating nano particle;
Fig. 4 shows the intensity of x x ray diffraction of the carbon nanomaterial of Figure 1A;
Fig. 5 shows the Raman spectrum of the carbon nanomaterial of making according to the present invention, and has shown because the difference of the carbon nanomaterial that heat treated difference causes;
Fig. 6 be according to manufacturing of the present invention through purifying but also not have to pass through the high-resolution TEM image of the middle carbon material of the processing remove functional group;
Fig. 7 is a high-resolution TEM image of having removed the carbon nanomaterial shown in Figure 6 of functional group with alkali treatment;
Fig. 8 is the image of polymer that combines the middle carbon material of purifying shown in Figure 6; With
Fig. 9 is the image that combines the polymer of carbon nanomaterial shown in Figure 7.
The detailed description of illustrative embodiments
I. be used to prepare the component of compound
Composite polymeric materials of the present invention comprises the mixture of polymeric material and carbon nanomaterial.Carbon nanomaterial comprises Nano carbon balls, and Nano carbon balls makes compound have new property, the resistance that for example reduces.Randomly, composite polymeric materials can also comprise other additive, for example filler, or other carbon nanomaterial.For the purposes of the present invention, term " nanosphere " comprises graphite, hollow bead or the ball with rule or irregular contour.
A. polymeric material
Any can be compatible or can all can be used for new compound of the present invention with graphite material compatible polymers material through handling with graphite material.Polymeric material can be polymer or polymerisable material.Polymeric material can be synthesize, the natural polymer or the resin of natural or modification.The suitable polymers material comprises thermosetting and thermoplastic polymer and/or polymerizable thing material.
The polymeric material that is applicable to compound of the present invention comprises following polymer (and/or select to be used to form in the following polymer one or more polymerizable thing material): polyamine, polyacrylate, polybutadiene, polybutene, polyethylene, polyethylene chlorine, ethylene-vinyl alcohol copolymer, fluoropolymer, ionomer, polymethylpentene, polypropylene, polystyrene, polyvinyl chloride, Vingon, condensation polymer, polyamide, polyamide-imides, PAEK, Merlon, polyketone, polyester, polyether-ether-ketone, PEI, polyether sulfone, polyimides, polyphenylene oxide, polyphenylene sulfide, polyphthalamide, poly-phthalimide, polysulfones, the polyarylsulfone (PAS) allyl resin, melamine resin, phenolic resins, liquid crystal polymer, polyolefin, silicone, polyurethane, epoxy resin, polyurethane, cellulosic polymer, the combination of these polymer, the copolymer of any polymer in the derivative of these polymer or the above-mentioned polymer.Polymeric material can be the thermoplastic polymer that mixes with Nano carbon balls subsequently through heating.Perhaps, can use thermosetting polymer.Usually, thermosetting polymer provides as one or more polymerisable monomers or oligomer, mixes with Nano carbon balls then, and polymerization forms compound.
Those skilled in the art know monomer and/or the oligomer that can be used for forming above-mentioned polymer.For example, polyurethane makes by the reaction of NCO and hydroxyl; Polyureas makes by the reaction of isocyanates and amine; Silicone makes by the hydrolysis of silane and/or siloxanes, or the like.The present invention also comprises one or more the copolymer of block that comprises in the above-mentioned polymer.United States Patent (USP) the 6th, 689 has disclosed other polymer and polymerizable material in No. 835.
The example of suitable thermoplasticity polymerizable material comprises acrylonitrile-butadiene-styrene (ABS), acrylonitrile-ethylene/propene-styrene, methyl methacrylate-butadiene-styrene, acrylonitrile-butadiene-methyl methacrylate-styrene, acrylonitrile-n-butyl acrylate-styrene, the polystyrene of modified rubber (impact polystyrene), polyethylene, polypropylene, polystyrene, polymethyl methacrylate, polyvinyl chloride, cellulose-acetic acid esters, polyamide, polyester, polyacrylonitrile, Merlon, polyphenylene oxide, polyketone, polysulfones, polyphenylene sulfide, fluorine resin, silicone, polyimides, polybenzimidazoles, polyamide elastomer, their combination, their derivative, or the like.
The example of suitable thermosetting resin comprises phenol resin, carbamide resin, melamine-formaldehyde, melocol latex, xylene resin, diallyl phthalate resin, epoxy resin, anline resin, furane resins, silicones, polyurethane resin, their combination, their derivative etc.
B. carbon nanomaterial
Comprise carbon nanomaterial in the composite of the present invention, so that compound has required character.The new property of compound is owing to account for all or part of carbon nano-structured causing of carbon nanomaterial at least in part.Carbon nano-structured in the carbon nanomaterial has useful properties, for example Du Te shape, size and/or electrical properties.In one embodiment, carbon nano-structured is Nano carbon balls.
Carbon nanomaterial can comprise the material beyond the Nano carbon balls.For example, carbon nanomaterial can comprise graphite (being graphite flake), amorphous carbon and/or iron nano-particle.The percentage composition of Nano carbon balls can influence the character of compound.In one embodiment, the weight percentage of Nano carbon balls is about 2 weight % to 100 weight % in the carbon nanomaterial.Perhaps, the percentage composition of Nano carbon balls is at least about 10 weight %, more preferably is at least about 15%.
As another independent characteristic or the feature arranged side by side with carbon nano-structured percetage by weight, this new carbon nanomaterial can not have surface functional group.In one embodiment, determine the functionalized situation of carbon nanomaterial by the acidity of water lotion.In one embodiment, be 1:1 based on the weight ratio of washing lotion and carbon nanomaterial, carbon nanomaterial acid-functionalized makes the about 5.0-8.0 of pH of washing lotion, more preferably from about 6.0-7.5,6.5-7.25 most preferably from about.The carbon nanomaterial of pH in above-mentioned scope can be advantageously with to acid packing material (for example polystyrene butadiene rubber) sensitive polymers mixed with resin.But, the present invention includes the carbon nanomaterial of pH outside described scope, if desired, these carbon nanomaterials can be with acid packing material sensitive polymers resin is used.
1. Nano carbon balls
Nano carbon balls can be rule or erose hollow Nano particle.In one embodiment, Nano carbon balls is roughly spherical in shape.
As mentioned below, in an embodiment of the invention, carbon nano-structuredly make by template nano particle and carbon precursor.In this process, around the template nano particle, form carbon nano-structured.In this embodiment, the size and dimension of nanostructured is mainly determined by the size and dimension of template nano particle.Since carbon nano-structured formation around the template nano particle, the external diameter that therefore carbon nano-structured aperture or internal diameter are equivalent to the template nano particle usually.Carbon nano-structured internal diameter can be in 0.5 nanometer between about 90 nanometers.
Figure 1A and 1B have shown the example of the nanosphere that use catalytic templating nano particle is made, and its detailed description is seen embodiment 1.Fig. 2 and 3 is TEM images of the nano material of Figure 1A and 1B demonstration.The TEM image that shows according to the SEM image shows that in one embodiment nanosphere has shape roughly spherical in shape.
In Figure 1A, the SEM image shows that at least in some embodiments, carbon nanomaterial comprises the Nano carbon balls cluster of sphere or " botryoidalis (grape-like) ".Figure 1B is that thereby partial rupture is opened the feature details of the Nano carbon balls cluster that exposes a plurality of Nano carbon balls.The TEM image of Fig. 2 has also shown the cluster that is formed by a plurality of less nanospheres.The nanosphere cluster that Fig. 2 shows shows that nanostructured is hollow and has shape roughly spherical in shape.
As if Fig. 3 has been that the heart the is residual therein more enlarged image of Nano carbon balls of swage plate nano particle.The Nano carbon balls explanation that Fig. 3 shows is carbon nano-structured to be formed around the catalytic templating nano particle.
The TEM image show many carbon nano-structured in, the external diameter of nanosphere is about 10 nanometer to 60 nanometers, the diameter of hollow parts is about 10 nanometer to 40 nanometers.But, the present invention includes nanostructured with bigger and littler diameter.Usually, carbon nano-structured external diameter is less than about 100 nanometers, to keep the integrality of structure.
Thickness from the internal diameter of the wall of nanostructured to the outside diameter measuring nanosphere of wall.By limiting the degree of following carbon precursor polymeric and/or carbonization, can in preparation process, regulate the thickness of nanostructured.Usually, the thickness of Nano carbon balls is between about 1 nanometer to 20 nanometer.But, if desired, can prepare thicker and thinner wall.The advantage for preparing thicker wall is to obtain better structural intergrity.The advantage for preparing thinner wall is to obtain higher surface area and porosity.
Can also form carbon nano-structured wall by a plurality of graphite linings.In an illustrative embodiments, Nano carbon balls has about 2-100 graphite linings, more preferably about 5-50 graphite linings, the wall of 5-20 graphite linings more preferably from about.Carbon nano-structured graphite feature it is believed that can give the carbon nano-structured beneficial property (for example splendid electric conductivity) that is similar to multi-walled carbon nano-tubes.Nano carbon balls can place of carbon nanotubes, can be used for the spendable any application of CNT, and obtain foreseeable excellent results usually, and/or save cost.
Though SEM image and TEM image show that nanostructured is roughly spherical in shape, the present invention extends to has the nanostructured that is different from spherical shape.In addition, nanostructured can be to be the fragment of ball shaped nano ball at first.Usually, carbon nano-structured shape is determined by the shape of template nano particle at least in part.Therefore, the formation of non-spherical template nano particle may cause aspheric carbon nano-structured.
Except the good electron transitivity, carbon nano-structured also have high porosity and high surface of the present invention.Absorption is conciliate adsorption isotherm and is shown the carbon nano-structured mesopore material that formed.Carbon nano-structured BET specific area can be about 80-400 rice
2/ gram is preferably greater than about 120 meters
2/ gram is about 200 meters usually
2/ gram is apparently higher than common 100 meters of CNT
2/ gram.Even it is carbon nano-structured that method of the present invention obtains mixing with non-structured graphite, the surface area of this graphite mixture (being carbon nanomaterial) is usually also greater than CNT.
2. the method for preparing carbon nanomaterial
Can use in the following steps all or part of to prepare of the present invention carbon nano-structured: (i) to form the precursor mixture that comprises carbon precursor and a plurality of template nano particles; (ii) leave carbon precursor or impel the polymerization around the catalytic templating nano particle of carbon precursor; (iii) make the precursor mixture carbonization, form the intermediate material with carbon element that comprises a plurality of nanostructureds (for example Nano carbon balls), amorphous carbon and catalytic metal; (iv) come the purify intermediates material with carbon element by amorphous carbon and the optional a part of catalytic metal of removing at least a portion; (v) randomly, by purified intermediary material being heat-treated and/or, removing at least a portion in any functional group residual on the purified intermediate carbon material surface with the purified intermediary material of alkali treatment.
(i) form precursor mixture
By selection carbon precursor, and make a large amount of catalytic templating nanoparticulate dispersed in the carbon precursor, form precursor mixture.
The material with carbon element of any kind can be used as carbon precursor of the present invention, as long as this material with carbon element can disperse template particles, and can get final product in carbonization around the template particles when heat treatment.The example of suitable polymerizable carbon precursor comprises resorcinol-formaldehyde gel, resorcinol, phenol resin, melamine-formaldehyde gel, poly furfuryl alcohol, polyacrylonitrile, sucrose, asphalt etc.Other polymerisable benzene, quinone and similar compounds also can be used as the carbon precursor, and are well known by persons skilled in the art.In an illustrative embodiments, but the carbon precursor is the organic compound of hydrothermal solution polymerization.This suitable class organic compound comprises citric acid, acrylic acid, benzoic acid, acrylate, butadiene, styrene, cinnamic acid etc.
The catalytic templating nano particle that is dispersed in the carbon precursor can several different modes provide.The template nano particle can form (being original position) in the carbon precursor, perhaps form in independent reactant mixture, mixes with the carbon precursor then.In some cases, the formation of particle can partly be carried out in independent reaction, mixes in the carbon precursor and/or heats (for example, when the precursor polymeric step begins) time and finish when template particles then.Also can use the dispersant of the granuloplastic one or more aspects of control to form the template nano particle, perhaps make the template nano particle by slaine.
In one embodiment, the template nano particle is formed by slaine in the carbon precursor.In this embodiment, form the template nano particle by selecting one or more catalyst metal salts that can mix with the carbon precursor.Slaine mixes with the carbon precursor, lets alone or make its original position formation nano particle then.
In another embodiment, use dispersant to form template particles (original position or ex situ), with the formation of control particle.In this embodiment, select the dispersant of catalyst atoms He one or more types of one or more types.Described dispersant is selected, had the formation of the nanocatalyst particle of required stability, size and/or homogeneity with promotion.Dispersant in the scope of the invention comprises various little organic molecules, polymer and oligomer.This dispersant can or be dispersed in suitable solvent or the catalyst atoms in the carrier with dissolving and interact and combine, these interactions and combination can be finished by various mechanism, comprise ionic bond, covalent bond, Van der Waals force interaction/combination, lone pair electrons combination or hydrogen bond.
Make catalyst atoms (for example ground state metal or metallic salt form) and dispersant (for example, carboxylic acid or its salt form) reaction or combination form catalyst complex.Catalyst complex is generally by earlier being dissolved in catalyst atoms and dispersant in the suitable solvent, catalyst atoms being combined with dispersant molecule form.Various components can any order or combining form make up or mix.In addition, a part of component can be before adding other component first premix, perhaps all combinations mix simultaneously.
In an embodiment of the invention, mix by the component that will be used for template particles and let alone or made it in about 1 hour to about 14 days and form nano particle.This mixing is carried out under about 0 ℃ to 200 ℃ temperature usually.In one embodiment, this temperature is no more than 100 ℃.Also can use reagent to cause particle to form.For example, in some cases, cause particle or midbody particle to form by advertising the solution of hydrogen by catalyst complex.
The polymerization and/or the carbonization of template nano particle energy catalyzed carbon precursor of the present invention.The concentration of catalytic templating nano particle in the carbon precursor will be selected usually, so that the carbon nano-structured number maximization that forms.Can be according to the amount of the type adjustment catalytic templating particle of the carbon precursor that uses.In an illustrative embodiments, the mol ratio of carbon precursor and catalyst atoms is about 0.1:1 to about 100:1, is more preferably 1:1 to 30:1.The appropriate catalyst examples of material comprises iron, cobalt, nickel etc.
(ii) make precursor mixture generation polymerization
Usually make precursor mixture solidify adequate time, it is carbon nano-structured to form a plurality of intermediates like this around the template nano particle.Because the template nano particle is a catalytic activity, the polymerization near the carbon precursor on template particles surface can preferentially be accelerated and/or cause to the template nano particle.
Forming the intermediate required time of nanostructured depends on the type of the carbon precursor of the pH value of the type of temperature, catalyst material and concentration, solution and use.In polymerization process, intermediate is carbon nano-structured can be the aggregation (association) of organic structure or nanostructured independently, and the aggregation of these nanostructureds is in carbonization and/or remove in the process of amorphous carbon and divide.
Add ammonia and regulate the pH value, can accelerate the speed of polymerization and increase crosslinked amount takes place between the precursor molecule, thereby also can be used for promoting polymerisation.
But for the carbon precursor of hydrothermal solution polymerization, polymerisation is carried out under higher temperature usually.One preferred embodiment in, with the carbon precursor be heated to about 0 ℃ to about 200 ℃ temperature, more preferably be heated to about 25 ℃ to about 120 ℃ temperature.
The example of the appropraite condition of resorcinol-formaldehyde gel (for example contain the iron particle, the pH value of solution value is 1-14) polymerization reaction take place is that solution temperature is 0 ℃ to 90 ℃, and be less than 1 hour to about 72 hours hardening time.Those skilled in the art determine to solidify the required condition of other carbon precursor easily under identical or different parameter.
In one embodiment, not allowing polymerisation last till reacts completely.Before the complete soln polymerization, stop solidification process and help to form a plurality of intermediate nanostructureds, will obtain independently nanostructured, rather than whole group's char-forming material.But the present invention includes following embodiment: it is carbon nano-structured that the carbon precursor forms a plurality of intermediates, and these intermediates are carbon nano-structured to interconnect or the part connection.In this embodiment, in carbonization and/or remove in the process of amorphous carbon and form independently nanostructured.
Forming intermediate by the dispersion of template nano particle, carbon nano-structured to cause forming a plurality of intermediates with unique shape and size carbon nano-structured.At last, the character of nanostructured depends on the shape and size that intermediate is carbon nano-structured at least in part.Have unique shape and size because intermediate is carbon nano-structured, so final nanostructured has favorable properties, for example high surface and high porosity etc.
(iii) carbonization precursor mixture
Make the precursor mixture carbonization by heating, form the intermediate material with carbon element comprise a plurality of carbon nano-structured, amorphous carbon and catalyst metals.Can make this mixture carbonization to about 2500 ℃ temperature by precursor mixture being heated to about 500 ℃.In this heating process, intermediate nanostructured (or the carbon around the template nano particle) is perhaps otherwise left in the volatilization of the atom of oxygen and nitrogen and so on, and carbon atom rearranges or be coalescent, forms the carbon back structure.
Carburising step produces the graphite based nanometer structure usually.Carbon atom in the graphite based nanometer structure is with sp
2The form of hydridization carbon atom is arranged in the structuring lamella.Graphite linings can provide uniqueness and favorable properties, for example electric conductivity and structural strength and/or rigidity.
(iv) purify intermediates material with carbon element
Come the purify intermediates material with carbon element by removing the non-graphite amorphous carbon of at least a portion.This purification step has improved carbon nano-structured weight percentage in the intermediate material with carbon element.
This amorphous carbon is removed by carbon is carried out oxidation usually.The oxidant that is used to remove amorphous carbon is selected, so that the key oxidation in the non-graphite amorphous carbon, but this oxidant is not strong to the activity of the π key in the graphitic carbon nano structure.Can be by in one or more continuous purification steps, applying oxidant or mixture is removed amorphous carbon.The reagent that is used to remove amorphous carbon comprises oxidizing acid and oxidant, and their mixture.The example that is applicable to the mixture of removing amorphous carbon comprises sulfuric acid, KMnO
4, H
2O
2, 5M or the above HNO of 5M
3And chloroazotic acid.
Randomly, can remove or remove a part of catalytic metal substantially.Whether remove degree that catalytic metal and catalytic metal remove and will depend on the required application of carbon nanomaterial.In some embodiments of the present invention, having the metal of iron and so on is favourable for some electrical properties and/or magnetic property are provided.Perhaps, need remove catalytic metal and the target application of material be caused adverse effect to prevent catalytic metal.Remove the catalytic templating particle and also can improve porosity, and/or reduce its density.
Usually, use acid or alkali (for example nitric acid, hydrogen fluoride or NaOH) to remove the template nano particle.The method of removing template nano particle or amorphous carbon depends on the type of template nano particle in the compound or catalyst atoms.Usually by being refluxed, composite nanostructure removed catalyst atoms or particle (for example, iron particle or atom) in about 3-6 hour in the 5.0M salpeter solution.
Can use any removal method to remove template nano particle and/or amorphous carbon, as long as this is removed process and can not destroy carbon nano-structured fully.In some cases, it is useful removing some carbonaceous materials at least in part from the intermediate nanostructured in purge process.
In this purge process, oxidant and acid tend to introduce hydrogen ion and oxide group on the surface of carbonaceous material, such as but not limited to carboxylate radical, carbonyl and/or ether.It is believed that functional group can be in carbon nano-structured, with the surface of carbon nano-structured graphite that mixes and/or residual non-graphite amorphous carbon on.
(v) remove the functional group of intermediate carbon material surface
Randomly, can use heat treatment step and/or neutralization bases to remove functional group on the intermediate carbon material surface.Remove surface functional group and/or in and the step of surface functional group usually remove and/or in and functional group can improve carbon nanomaterial dispersed in polymeric material and/or improve in the situation of composite character and carry out.
Can use heat treatment step to remove functional group on the intermediate carbon material surface.Heat treatment step can advantageously carry out under the temperature of selecting, and the concrete functional group that need remove is depended in the selection of temperature.Usually, heat treated temperature is high more, and the type of the functional group that can remove is many more.Heat treatment step after the purifying can be about more than 100 ℃, more preferably from about more than 200 ℃, most preferably from about carry out under the temperature more than 500 ℃.
Randomly, the heat treatment after the purifying can be carried out under the temperature of the carbonization that is enough to carry out amorphous carbon.Surprisingly, behind purifying the intermediate material with carbon element being heated to carburizing temperature can advantageously make considerable residual amorphous carbon be converted into graphite.Have been found that by remove considerable amorphous carbon in purification step, make the material carbonization of purifying then, remaining carbon can more easily be converted into graphite.
The graphite that forms in this second carburising step can join carbon nano-structured, carbon nano-structured secondary structure (for example botryoidalis aggregate of nanosphere), and perhaps this graphite can be and the carbon nano-structured free graphite that mixes.Make remaining amorphous carbon be converted into the graphite purity that graphite can obviously improve carbon nanomaterial.Compare with the effort of attempting the purity of realization par in single carburising step, use two step carbonization methods of the present invention can more effectively produce the high purity carbon nano material.
In another embodiment, perhaps except extra heat treatment step, can use nertralizer to remove some functional groups in the intermediate material with carbon element, such as but not limited to the hydrogen ion group.In this embodiment, intermediary material is mixed with the solution that comprises one or more nertralizers.Suitable alkali comprises hydroxide, comprises NaOH and potassium hydroxide, ammonia, lithium acetate, sodium acetate, potassium acetate, NaHCO
3, KHCO
3, Na
2CO
3, K
2CO
3Deng, and the combination of these alkali.The reaction of alkali and hydrogen ion group can form the accessory substance that can remove by washing.
In one embodiment, by being immersed in, the intermediate material with carbon element removes functional group in the cleaning solution.Can in cleaning solution, add alkali extraly, reach required more neutral pH value up to pH.In one embodiment, the cleaning solution pH that neutralizes is about 5.0-8.0, perhaps is about 6.0-7.5.
That the step of removing functional group from carbon nanomaterial can be used for removing is carbon nano-structured, the functional group of the component of the intermediate material with carbon element of amorphous carbon (graphite or non-graphite) or any other purifying.In one embodiment, remove carbon nano-structured or form the functional group of other graphite material of the part of carbon nanomaterial.If except from nano material, removing the functional group, also need to remove some impurity of de-iron and so on, then high temperature heat treatment step also is favourable.
Nanosphere can use other suitable technique manufacturing.United States Patent (USP) sequence the 11/539th in the applicant's common unexamined, No. 120 (on October 5th, 2006 submitted to, be entitled as " by the carbon nano ring (Carbon Nanorings Manufactured From Templating Nanoparticles) of template nano particle manufacturing " and U. S. application sequence the 11/539th, No. 042 (on October 5th, 2006 submitted to, be entitled as " carbon nano-structured (the Carbon Nanostructures Manufactured From CatalyticTemplating Nanoparticles) that make by the catalytic templating nano particle " and Han etc. " the simple solid phase of hollow plumbago nano particle synthetic and they in application (the Simple Solid-Phase Synthesis ofHollow Graphitic Nanoparticles and their Application to Direct Methanol Fuel CellElectrodes) ＂ (Adv.Mater.2003; No. 15.22; November 17) in the direct methanol fuel cell electrode, disclosed the method for preparing nano material of the present invention that is applicable to, its full content is by with reference to being incorporated into this.
C. additive
The additive that can add filler or dispersant and so in polymeric material is so that compound has required character, and/or Nano carbon balls is dispersed in the polymeric material.Any packing material can be used for the present invention.Appropriate filler comprises carbon black, silica, diatomite, rubble English, talcum, clay, mica, calcium silicates, magnesium silicate, glass dust, calcium carbonate, barium sulfate, zinc carbonate, titanium oxide, aluminium oxide, glass fibre, other carbon fiber and organic fiber.Other suitable additive comprises softening agent, plasticizer, molding auxiliary agent, lubricant, age resister and ultraviolet absorber.
II. preparation combines the method for the compound of Nano carbon balls
By a certain amount of Nano carbon balls and polymeric material and optional one or more additives such as filler or dispersant are formed composite of the present invention.The amount of the Nano carbon balls that mixes with polymeric material accounts for 0.1 weight % to 70 weight % of compound, more preferably accounts for 0.5 weight % to 50 weight %, most preferably accounts for 1.0 weight % to 30 weight %.
In the form adding polymeric material that Nano carbon balls can be pure substantially.Perhaps, the component of Nano carbon balls as carbon nanomaterial can be joined in the polymeric material.In one embodiment, the content of Nano carbon balls in carbon nanomaterial is at least about 2 weight %, more preferably is at least about 10 weight %, most preferably is at least about 15 weight %.
When mixing with polymeric material of the present invention, because the spherical form of nanosphere, Nano carbon balls can provide unique benefit.Compare with fibrous CNT, Nano carbon balls has more as coating of particles.In some embodiments of the present invention, granular shape makes compound have some character of similar granular filler than fibrous compound.
Can add a certain amount of Nano carbon balls in polymeric material, this addition should be able to provide required character.The amount of the Nano carbon balls that for example, adds in polymeric material should be able to be given electric conductivity and/or be reduced surface resistivity.Surprisingly, produce the descend amount of needed Nano carbon balls of required sheet resistance and be significantly less than identical resistance the descend required CNT or the amount of carbon black of realizing.It is believed that carbon nanomaterial is to obtain this improved reason, this is that the more uniform network structure of particle provides better osmotic effect because compare with CNT.Lower sheet resistance is tangible especially for polished surface.In one embodiment, be about 0.5 weight % to 7 weight % in the Nano carbon balls load capacity, when being more preferably 1 weight % to 5 weight %, the surface resistivity of polymer composites of the present invention is about 1 * 10
4To 1 * 10
6(Ω/sq).
Except electric conductivity, Nano carbon balls can be used as fire retardant and is attached in the polymeric material.
As the method for producing compound of the present invention, can use any known method.In an embodiment of the invention, can polymer and carbon nanomaterial be mixed make compound by making the polymeric material fusing.Perhaps, can when existing, Nano carbon balls prepare (being polymerization) polymeric material.
For example, the Nano carbon balls of spherolite or pulverous polymeric material and aequum can be done and mix or wet mixing, mixes in mixing roll mill in heating then.Perhaps, the compound that mixes can be joined in the extruder,, be cut into bead then so that compound is extruded as the cord-like material.
Perhaps, Nano carbon balls can be sneaked in the liquid medium with resin solution or resin dispersion.Can also be by wet master batch method (Wet Master Batch method) mixed complex.When using thermosetting resin, can use any known method that is applicable to specific polymerizable material that Nano carbon balls is mixed with monomer or oligomer.
In order to improve the dispersion effect of nanosphere in polymeric material, can use any known method and/or the suitable material that uses with graphitic carbon.In addition, as molded be the method for required form, can use any known method, for example extrusion molding, blowing, injection moulding or pressing mold.
Can compound of the present invention be prepared into froth pulp by adding blowing agent, thereby obtain having the foamed resin of electric conductivity and/or blackness.Although can use any above-mentioned different polymeric materials to prepare this class A foam A product, preferred use thermoplastic resin such as polyethylene, polypropylene, polyvinyl chloride, polystyrene, polybutadiene, polyurethane, vinyl-vinyl acetate copolymer etc. and thermoplastic polymeric material.As blowing agent, can use various resin expanded dose, organic solvent and gas, for example butane.
Can use the method for the conductive foam that any known method contains as production the present invention.For example, when using thermoplastic resin, make this resin fusing, mix with the Nano carbon balls of aequum by extruder then.Then, in the gas injection of polymer material with butane and so on.Perhaps, can use CBA to replace gas.
The compound that the present invention is contained also can be used as paint, so that other substrate surface has electric conductivity and/or blackness.Suitable substrates comprises various resins, elastomer, rubber, timber, inorganic material etc.In addition, can be with further molding of these materials or shaping.
The desired thickness of the film of this compounds coating that the present invention is contained is greater than 0.1 micron.
III. embodiment
Following examples provide the universal method of preparation according to containing of an embodiment of the invention of carbon nano-structured carbon nanomaterial.
(a) preparation ferrous solution (0.1M)
Use 84 gram iron powders, 289 gram citric acids and 15 premium on currency to prepare the ferrous solution of 0.1M.To mix 3 days in the mixture of this iron content airtight bottle on shake table, once a day or twice short interruption,, continue then to mix with the vapor space of air purge bottle.
(b) preparation precursor mixture
916.6 gram resorcinols and 1350 gram formaldehyde (37%, in water) are put into round-bottomed flask.Stir this solution, dissolve fully up to resorcinol.The ferrous solution that under agitation slowly adds 15 liters of steps (a) drips 1025 milliliters of ammonium hydroxide (28-30% is in water) then under vigorous stirring, the pH of gained suspension is 10.26.This slurry solidified 10 hours 80-90 ℃ (water-bath).By solid collected by filtration carbon precursor mixture, dried overnight in baking oven.
(c) carbonization
The precursor mixture of polymerization is placed in the crucible of adding a cover, and transfers in the heating furnace.Use following temperature progress to flow down and carry out carburising step at the nitrogen of abundance: room temperature → with 20 ℃/minute speed be elevated to 1160 ℃ → 1160 ℃ keep 5 hours → get back to room temperature.This carburising step produces the intermediate material with carbon element with carbon nano-structured, amorphous carbon and iron.
(d) purifying is to remove amorphous carbon and iron
The purifying of the carbon product (being the intermediate material with carbon element) of process carbonization carries out as follows: the product of process carbonization is at 5M HNO
3In reflux about 12 hours → be the KMnO of 1:0.01:0.003 with deionization (DI) water washing → with mol ratio
4+ H
2SO
4+ H
2The mixture of O handle (keeping about 12 hours) → spend at about 90 ℃ deionised water → with 4M HCl handle (keeping about 12 hours) at about 90 ℃ → spend deionised water → collection product, and in about 100 ℃ baking oven drying 2 days.
(e) heat treatment is to reduce surface functional group
After purification process, carbon product is heat-treated, farthest to reduce surface functional group, increase content of graphite.The temperature progress that is used for this processing is as follows: begin from room temperature to heat with 4 ℃/minute speed → 100 ℃ → 100 ℃ keep 2 hours → with 15 ℃/minute speed be heated to 250 ℃ → 250 ℃ keep 2 hours → with 15 ℃/minute speed be heated to 1000 ℃ → 1000 ℃ keep 2 hours → get back to room temperature.This heat treatment process produces the carbon nanomaterial of mainly being made up of Nano carbon balls.
The carbon nanomaterial of making by SEM and tem analysis embodiment 1 then.Figure 1A and 1B have shown carbon nano-structured SEM image, and this image has shown that a plurality of Nano carbon balls reunions form botryoidal cluster together.The TEM image of Fig. 2 and Fig. 3 has shown the botryoidalis cluster that is formed by a plurality of less hollow plumbago nanostructureds or Nano carbon balls.
Use the carbon nano-structured content of graphite of X-ray diffraction test implementation example 1.Fig. 4 shows the X ray diffracting spectrum of the carbon nanomaterial of embodiment 1.At about 26 ° broad peak is because the shortrange order of Nano graphite structure causes.This diffraction image with typical graphite flake forms contrast, and the latter often has extremely narrow peak.Show also that at about 26 ° broad peak this material is a graphite, because amorphous carbon often has diffraction maximum at 20 °.
Use Raman spectrum to determine in the process of heat treatment step (e) content of graphite of the carbon nanomaterial under the different temperatures.Extract the carbon nanomaterial of sample A when heat treatment temperature is 1000 ℃, sample B extracts when being heat-treated to 600 ℃, and sample C is the sample (being that sample C is the purified intermediate material with carbon element of step (d)) of not heat-treating.The results are shown among Fig. 5 of Raman spectrum.The collection of illustrative plates of Fig. 5 has two tangible peaks, and one at 1354 centimetres
-1The place, another is at 1581 centimetres
-1The place.Show that as this collection of illustrative plates heat treated sample A of process and B are at 1354 centimetres
-1The place has bigger peak.These peaks show that amorphous carbon is graphite, therefore do not burnout (promptly having less mass loss).As a comparison, sample C is at 1354 centimetres
-1The peak at place shows tangible mass loss, and this shows it is non-graphite amorphous carbon.Therefore, except removing functional group, heat treatment step can increase the content of graphite of any residual carbon effectively.Surprisingly, this conversion can take place under lower temperature, for example between 500 ℃ to 1400 ℃.
Use extra heat treatment step, the content of graphite of the carbon nanomaterial of making according to the present invention is higher, and the result makes carbon nanomaterial have superior electric conductivity and purity.Except improving graphite concentration, heat treatment also shows other impurity that can obviously reduce iron and so on.
The part of the purified material with carbon element that obtains in the step (d) with embodiment (1) is mixed with the deionized water of q.s, and Dropwise 5 M NaOH is adjusted to about 7.0 with the pH with solution then.By filtering the carbon nanomaterial of collecting gained, with the deionized water washing of q.s, to remove the Na+ ion.Collect final product, drying is two days in about 100 ℃ baking oven.
Embodiment 3: Comparative Examples
In order to compare, collect the purified material with carbon element that obtains in the step (d) of a part of embodiment 1, do not carry out the heat treatment step described in the step (e) of embodiment 1, do not carry out embodiment 2 described neutralization bases treatment steps yet.
Obtain the carbon nano-structured TEM image of embodiment 2 and embodiment 3, to determine whether recurring structure changes in the process of neutralization procedure.Fig. 7 is the TEM image of the material with carbon element (i.e. neutralization after material with carbon element) of embodiment 2, and Fig. 6 is the TEM image of the material with carbon element (i.e. material with carbon element before the neutralization) of embodiment 3, and both compare, and shows that neutralization procedure does not have an adverse effect to carbon nano-structured.
Can be attached in the polymer by the nano material that will not contain acid, and with comprise identical basically but have the polymer phase ratio of the nano material of acid functional group, the beneficial property of the anacidity carbon nanomaterial of embodiment 2 is described.In order to test this situation, embodiment 2 and 3 carbon nanomaterial are respectively separately and mixed with polymers.Fig. 8 has shown the polymer with the carbon nanomaterial that comprises acid functional group.This polymer demonstrates tangible bubble and irregularly shaped in its surface.As a comparison, the polymer of carbon nanomaterial through neutralization that comprises embodiment 2 presents even curface.
The present invention can implement with other concrete form under the situation that does not depart from its spirit or principal character.Described embodiment can be considered to just be used for explanation in every respect and not be construed as limiting.Therefore, scope of the present invention is defined by the description of appended claims rather than front.Implication and all changes within the equivalency range at claims are included within its scope.
Claims (26)
1. composite, it comprises:
The polymeric material that comprises polymer or polymerizable material; With
A plurality of Nano carbon balls that are dispersed in the described polymeric material,
Wherein said Nano carbon balls account for composite at least about 0.1 weight %.
2. composite as claimed in claim 1 is characterized in that, described Nano carbon balls comprises hollow, many walls particle, and its external diameter is less than about 1 micron.
3. composite as claimed in claim 1 is characterized in that, described Nano carbon balls account for composite at least about 0.5 weight %.
4. composite as claimed in claim 1 is characterized in that, described Nano carbon balls account for composite at least about 1 weight %.
5. composite as claimed in claim 1 is characterized in that, also comprises Nano carbon balls carbon nanomaterial in addition, accounts at least about 2 weight % in the total amount of wherein said Nano carbon balls carbon nanomaterial in compound.
6. composite as claimed in claim 5 is characterized in that, described Nano carbon balls accounts in the total amount of the contained carbon nanomaterial of compound at least about 3 weight %.
7. composite as claimed in claim 5 is characterized in that, described Nano carbon balls accounts in the total amount of the contained carbon nanomaterial of compound at least about 15 weight %.
8. composite as claimed in claim 1, it is characterized in that described polymeric material comprises the polymer that is selected from down group: polyamine, polyacrylate, polybutadiene, polybutene, polyethylene, polyethylene chlorine, ethylene-vinyl alcohol copolymer, fluoropolymer, ionomer, polymethylpentene, polypropylene, polystyrene, polyvinyl chloride, Vingon, condensation polymer, polyamide, polyamide-imides, PAEK, Merlon, polyketone, polyether-ether-ketone, PEI, polyether sulfone, polyimides, polyphenylene oxide, polyphenylene sulfide, polyphthalamide, poly-phthalimide, polysulfones, the polyarylsulfone (PAS) allyl resin, melamine resin, phenolic resins, liquid crystal polymer, polyolefin, polyester, silicone, polyurethane, epoxy resin, cellulosic polymer and their combination.
9. composite as claimed in claim 1, it is characterized in that described polymeric material comprises the thermoplastic, polymeric materials that is selected from down group: acrylonitrile-butadiene-styrene (ABS), acrylonitrile-ethylene/propene-styrene, methyl methacrylate-butadiene-styrene, acrylonitrile-butadiene-methyl methacrylate-styrene, acrylonitrile-n-butyl acrylate-styrene, the polystyrene of modified rubber, polyethylene, polypropylene, polystyrene, polymethyl methacrylate, polyvinyl chloride, cellulose-acetate resins, polyamide, polyester, polyacrylonitrile, Merlon, polyphenylene oxide, polyketone, polysulfones, polyphenylene sulfide, fluorine resin, silicone, polyimides, polybenzimidazoles, polyamide elastomer and their combination.
10. composite as claimed in claim 1, it is characterized in that described polymeric material comprises the thermoset copolymer material that is selected from down group: phenol resin, carbamide resin, melamine-formaldehyde resin, melocol latex, xylene resin, diallyl phthalate resin, epoxy resin, anline resin, furane resins, polyurethane and their combination.
11. a composite, the carbon nanomaterial that it comprises polymer or polymerizable material and mixes with it, wherein said composite are according to the method preparation that may further comprise the steps:
Formation comprises the precursor mixture of carbon precursor and a plurality of template nano particles, and described template nano particle comprises catalytic metal;
Make described precursor mixture carbonization, form the intermediate material with carbon element comprise a plurality of carbon nano-structured, amorphous carbon and optional residual catalytic metal;
Come the purify intermediates material with carbon element by the residual catalytic metal of a part of removing at least a portion amorphous carbon and choose wantonly, generate carbon nanomaterial; With
Described carbon nanomaterial is mixed with thermoplastic polymer that is in liquid state or mecystasis or polymerizable material, leave or impel thermoplastic polymer or polymerizable material to solidify, generate composite.
12. composite as claimed in claim 11 is characterized in that, the method for described manufacturing carbon nanomaterial also comprises the functional group of removing purified intermediate material with carbon element by following steps:
(i) purified intermediate material with carbon element is heated to above about 100 ℃ temperature; And/or
(ii) use the purified intermediate material with carbon element of alkali treatment.
13. composite as claimed in claim 11 is characterized in that, the described method for preparing carbon nanomaterial comprises purified intermediate material with carbon element is heated to above about 200 ℃ temperature.
14. composite as claimed in claim 11 is characterized in that, the described method for preparing carbon nanomaterial comprises purified intermediate material with carbon element is heated to above about 500 ℃ temperature.
15. composite as claimed in claim 11 is characterized in that, the described method for preparing carbon nanomaterial comprises purified intermediate carbon is heated to above about 1000 ℃ temperature.
16. composite as claimed in claim 11 is characterized in that, the described method for preparing carbon nanomaterial comprises with NaOH and/or the purified intermediate material with carbon element of potassium hydroxide treatment.
17. composite as claimed in claim 11, it is characterized in that described composite comprises the polymer that is selected from down group: acrylonitrile-butadiene-styrene (ABS), acrylonitrile-ethylene/propene-styrene, methyl methacrylate-butadiene-styrene, acrylonitrile-butadiene-methyl methacrylate-styrene, acrylonitrile-n-butyl acrylate-styrene, the polystyrene of modified rubber, polyethylene, polypropylene, polystyrene, polymethyl methacrylate, polyvinyl chloride, cellulose-acetate resins, polyamide, polyester, polyacrylonitrile, Merlon, polyphenylene oxide, polyketone, polysulfones, polyphenylene sulfide, fluorine resin, silicone, polyimides, polybenzimidazoles, polyamide elastomer and their combination.
18. a method for preparing composite, it comprises:
The thermoplastic polymer or the polymerizable material that are in liquid state or mecystasis are provided;
About 1 weight % is sneaked in thermoplastic polymer or the polymerizable material to the graphite material of about 50 weight %, and described graphite material comprises the Nano carbon balls greater than 3 weight %; With
Leave or impel thermoplastic polymer or polymerizable material to solidify, generate composite.
19. method as claimed in claim 18, it is characterized in that, described composite is formed by thermoplastic polymer, before this method also is included in and mixes with graphite material or when mixing, described thermoplastic polymer is heated to the fusing point of this thermoplastic polymer or the temperature more than the glass transition temperature, reach liquid state or mecystasis, cool off this thermoplastic polymer then, to generate composite.
20. method as claimed in claim 19, it is characterized in that described thermoplastic polymer is selected from down group: acrylonitrile-butadiene-styrene (ABS), acrylonitrile-ethylene/propene-styrene, methyl methacrylate-butadiene-styrene, acrylonitrile-butadiene-methyl methacrylate-styrene, acrylonitrile-n-butyl acrylate-styrene, the polystyrene of modified rubber, polyethylene, polypropylene, polystyrene, polymethyl methacrylate, polyvinyl chloride, cellulose-acetate resins, polyamide, polyester, polyacrylonitrile, Merlon, polyphenylene oxide, polyketone, polysulfones, polyphenylene sulfide, fluorine resin, silicone, polyimides, polybenzimidazoles, polyamide elastomer and their combination.
21. method as claimed in claim 18 is characterized in that, described composite forms by being in the polymerizable material that liquid state or mecystasis, polymerization subsequently form polymeric material at first.
22. method as claimed in claim 21, it is characterized in that described polymerizable material comprises and is applicable to and forms monomer or the oligomer be selected from down the polymeric material of organizing: polyacrylate, polybutadiene, polybutene, polyethylene, polyethylene chlorine, ethylene-vinyl alcohol copolymer, fluoropolymer, ionomer, polymethylpentene, polypropylene, polystyrene, polyvinyl chloride, Vingon, condensation polymer, polyamide, polyamide-imides, PAEK, Merlon, polyketone, polyether-ether-ketone, PEI, polyether sulfone, polyimides, polyphenylene oxide, polyphenylene sulfide, polyphthalamide, poly-phthalimide, polysulfones, the polyarylsulfone (PAS) allyl resin, melamine resin, urea formaldehyde, liquid crystal polymer, polyolefin, polyester, silicone, polyurethane, epoxy resin, cellulosic polymer and their combination.
23. method as claimed in claim 18 is characterized in that, described Nano carbon balls prepares according to following steps:
(i) by in the presence of a plurality of template nano particles, making carbon precursor generation polymerization form one or more intermediate Nano carbon balls;
(ii) make the carbonization of intermediate Nano carbon balls, form a plurality of composite nanostructures; With
(iii) randomly from composite nanostructure, remove the template nano particle, obtain Nano carbon balls.
24. method as claimed in claim 23 is characterized in that, described template nano particle comprises at least a in iron, nickel or the cobalt.
25. method as claimed in claim 23 is characterized in that, carbonization is carried out under about 500 ℃-2500 ℃ temperature.
26. method as claimed in claim 23 is characterized in that, removes template nano particle in the composite nanostructure by carry out etching with acid, alkali or bronsted lowry acids and bases bronsted lowry.
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|---|---|---|---|
| US35162006A | 2006-02-09 | 2006-02-09 | |
| US11/351,620 | 2006-02-09 | ||
| US11/614,006 | 2006-12-20 |
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| CN102515150A (en) * | 2011-12-08 | 2012-06-27 | 同济大学 | Method for preparing multilayer graphene-carbon material |
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