WO2015125740A1 - Method of producing flaked graphite, flaked graphite, and flaked graphite-resin composite material - Google Patents
Method of producing flaked graphite, flaked graphite, and flaked graphite-resin composite material Download PDFInfo
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- WO2015125740A1 WO2015125740A1 PCT/JP2015/054162 JP2015054162W WO2015125740A1 WO 2015125740 A1 WO2015125740 A1 WO 2015125740A1 JP 2015054162 W JP2015054162 W JP 2015054162W WO 2015125740 A1 WO2015125740 A1 WO 2015125740A1
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- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
Definitions
- the present invention relates to a method for producing exfoliated graphite using GIC (Graphite interpolation compounds) and to exfoliated graphite obtained by the method for producing exfoliated graphite.
- GIC Graphite interpolation compounds
- the present invention also relates to a exfoliated graphite-resin composite material obtained by mixing the exfoliated graphite and a resin.
- Graphene is excellent in toughness, electrical conductivity, thermal conductivity and heat resistance. Therefore, various methods for producing exfoliated graphite having fewer graphene layers than graphene and the original raw graphite have been proposed.
- GIC Graphite interpolation compounds
- Patent Document 1 discloses an example of such a manufacturing method.
- a method of producing graphene or exfoliated graphite by mechanically dispersing GIC using an alkali metal in a specific solvent is disclosed.
- Non-Patent Document 1 discloses a method in which a metal halide such as iron chloride or aluminum chloride acting as an acceptor for an aromatic compound is dissolved in a solvent such as nitromethane or thionyl chloride and immersed in graphite. ing. According to this method, an acceptor type GIC can be produced by a solvent method.
- Non-Patent Document 1 Although a method for obtaining an acceptor-type GIC by a solvent method has been reported, a method for producing graphene or exfoliated graphite from the acceptor-type GIC is not shown.
- An object of the present invention is to provide a method for producing exfoliated graphite, which makes it possible to efficiently mass-produce exfoliated graphite excellent in dispersibility in a resin.
- Another object of the present invention is to provide exfoliated graphite obtained by the above exfoliated graphite manufacturing method and exfoliated graphite-resin composite material containing the exfoliated graphite.
- the method for producing exfoliated graphite according to the present invention includes a step of inserting a catalyst between graphite layers, and exfoliating the graphite by chemically bonding a reactive compound to the graphite using the catalyst to obtain exfoliated graphite.
- the reactive compound is preferably a Diels-Alder reactive compound.
- the upper reactive compound is preferably a Fridel-Crafts reactive compound.
- the catalyst is a compound that acts as a charge acceptor for an aromatic compound. More preferably, the catalyst is a metal halide.
- the step of inserting a catalyst between the graphite layers may be performed in a solvent.
- the step of inserting a catalyst between the graphite layers may be performed in the presence of a supercritical fluid.
- a gaseous catalyst may be inserted between the graphite layers in the step of inserting the catalyst between the graphite layers.
- the step of exfoliating the graphite may be performed in the presence of a supercritical fluid.
- the reactive compound may be chemically bonded to the graphite by bringing the reactive compound in a gaseous state into contact with the graphite in the step of exfoliating the graphite.
- the catalyst is a compound that acts as a charge acceptor for an aromatic compound, and the catalyst forms a complex with the solvent in the solvent.
- the ligand of the complex is preferably an electron donating compound.
- the ligand of the complex is preferably a compound having an aromatic ring.
- the ligand of the complex is preferably a compound having a lone pair of electrons.
- the solubility parameter of the solvent is 10 or less.
- the exfoliated graphite according to the present invention can be obtained by the above method for producing exfoliated graphite.
- a Diels-Alder reactive compound is preferably chemically bonded.
- the Fridel-Crafts reactive compound is chemically bonded.
- the exfoliated graphite-resin composite material according to the present invention includes exfoliated graphite according to the present invention and a resin.
- exfoliated graphite having excellent dispersibility in a resin can be mass-produced efficiently.
- the exfoliated graphite-resin composite material according to the present invention contains the exfoliated graphite. Therefore, according to the present invention, it is possible to provide a exfoliated graphite-resin composite material that is remarkably excellent in mechanical strength.
- FIG. 1 is a diagram showing XRD spectra of samples obtained in Examples 1 to 5 and Comparative Example 1 and raw graphite.
- FIG. 2 is a schematic diagram of the reaction apparatus used in Example 4.
- FIG. 3 is a diagram showing a schematic diagram of the reaction apparatus used in Example 5.
- the inventors of the present application can easily obtain exfoliated graphite by inserting a catalyst between graphite layers and then chemically bonding a reactive compound to graphite using the catalyst. As a result, the inventors have made the present invention.
- the first step of inserting a catalyst between graphite layers, and exfoliating the graphite by chemically bonding a reactive compound to the graphite using the catalyst, exfoliated graphite is performed.
- a catalyst is inserted between the graphite layers of the raw graphite to obtain expanded graphite.
- expanded graphite refers to a GIC in which a catalyst which is an intercarrant is inserted between graphene layers, or a graphite compound in which the layers are highly opened via the GIC.
- the intercarrant is inserted between the graphene layers, the distance between the graphene layers is increased.
- raw graphite examples include natural graphite, artificial graphite, thermally expandable graphite, and HOPG.
- HOPG Highly Oriented Pyrolytic Graphite
- Thermally expandable graphite refers to graphite having a certain amount of acid intercalated between graphite graphene layers by acid treatment or the like, and having the ability to expand when the acid volatilizes by heat treatment.
- thermally expanded graphite is available from Air Water Co., Ltd., Suzuhiro Chemical Co., Ltd. and the like.
- a fibrous material having a graphene structure, such as carbon fiber can also be used as raw material graphite. That is, the form of raw graphite is not particularly limited.
- exfoliated graphite is a graphene sheet laminate or a single layer graphene sheet.
- Exfoliated graphite can be obtained by exfoliating graphite. That is, exfoliated graphite is a graphene sheet laminate or a single layer graphene sheet that is thinner than the original graphite.
- the number of graphene sheets laminated in exfoliated graphite is 1 or more. From the viewpoint of more effectively increasing the mechanical strength such as the tensile modulus of the resin, the number of graphene sheets stacked is preferably 1000 or less, and more preferably 150 or less.
- Exfoliated graphite has a structure in which thin graphene sheets are laminated. Therefore, the aspect ratio of exfoliated graphite is relatively large.
- the aspect ratio of exfoliated graphite refers to the ratio of the maximum dimension in the laminate surface direction of exfoliated graphite to the thickness of exfoliated graphite.
- the preferable lower limit of the aspect ratio of exfoliated graphite is about 50, and the preferable upper limit is about 5000.
- the catalyst is not particularly limited, but is preferably a compound that acts as a charge acceptor for an aromatic compound.
- a compound that acts as a charge acceptor for an aromatic compound For example, the following (1) metal halide represented by MXn (where M is a metal of group 2 to 7 in the periodic table, X is halogen, and n is an integer of 2 to 5), (2) represented by MAX (3) a complex compound represented by ML or MLX, (4) a charge acceptor comprising an organic compound, or (5) a trivalent phosphorus compound.
- M is a metal of Groups 2 to 7 of the periodic table.
- Such metals include beryllium, boron, magnesium, aluminum, silicon, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, zinc, gallium, strontium, yttrium, zirconium, niobium, molybdenum, and technetium.
- X is halogen, which is fluorine, chlorine, bromine or iodine.
- N is an integer of 2 to 5 depending on the valence of the metal.
- preferred metal halides include copper chloride, iron chloride, zinc chloride or aluminum chloride, wherein X is chlorine.
- the metal chloride is preferable because it is inexpensive and has relatively low toxicity.
- the metal halide represented by MXn may be a metal halide containing a plurality of halogens such as MX 1 X 2 .
- X 1 and X 2 are different halogen elements.
- A is an acid, it is a complex salt of an acid, a halogen and a metal represented by MAX.
- M is a metal element belonging to Groups 2 to 7 of the periodic table.
- A is an acid.
- the acid may be an inorganic acid such as sulfuric acid, nitric acid, phosphoric acid or boric acid, or an organic acid.
- X is the halogen described above.
- Complex compound represented by ML or MLX M is a metal element of Group 2 to Group 7.
- L is a compound that acts as a ligand such as acetylacetone, ethylenediamine, phthalocyanine, ammonia, carbon monoxide, or cyanide.
- X is the halogen described above.
- Charge acceptor comprising an organic compound
- the organic compound acting as the charge acceptor include p-benzoquinone, 2,3,5,6-tetramethyl-p-benzoquinone, 2-methyl-1,4-naphthoquinone,
- CT complex charge transfer complex
- aromatic compound such as tetrafluoro-1,4-benzoquinone, 7,7,8,8-tetracyanoquinodimethane, and 2-cyanopyridine.
- Trivalent phosphorus compound examples include triphenyl phosphite and trialkyl phosphite.
- the method for inserting the catalyst between the graphite layers is not particularly limited.
- a method of inserting a catalyst between graphite layers by a solvent method using a solvent can be mentioned.
- the catalyst may be inserted between the graphite layers, or a gaseous catalyst may be inserted between the graphite layers.
- a complex of a solvent and a compound acting as a charge acceptor for graphite is formed in a solvent.
- a catalyst is inserted between the graphite layers, and the graphite is expanded.
- a solvent that can form a charge transfer complex (CT complex) with a compound that acts as a charge acceptor for the aromatic compound is preferably used.
- CT complex charge transfer complex
- Whether or not to form a CT complex with the compound acting as the charge acceptor can be confirmed by a light absorption spectrum. That is, whether or not a CT complex is formed can be qualitatively determined based on whether or not absorption specific to a CT complex called a CT band appears in a long wavelength region during mixing.
- Examples of the solvent that forms the CT complex with the compound serving as the charge acceptor include solvents composed of aromatic compounds such as benzene, toluene, xylene, and tetralin, and derivatives or mixtures thereof.
- the solvent capable of forming a CT complex with the compound acting as a charge acceptor may be a solvent composed of an aromatic compound such as N-methylpyrrolidone or pyridine.
- a solvent having a lone pair such as methyl ethyl ketone or diethyl ether may be used.
- a solvent having a lone pair such as methyl ethyl ketone or diethyl ether may be used.
- Such a solvent has a low ability to form a CT complex, but can be used in the present invention because it has an electron donating property.
- a mixed solvent of a compound that functions as a charge acceptor with a solvent that forms a CT complex and another solvent that does not have the ability to form a CT complex may be used.
- other solvents having no CT complex forming ability include normal alkanes and cycloalkanes.
- organic halogen-type solvents such as chloroform, methyl chloride, methyl dichloride, ethylene dichloride, a methylene diide dye, and ethylene dibromide, as said other solvent.
- the solubility parameter of the solvent is preferably 10 or less, and more preferably 9.5 or less.
- Solvents having a solubility parameter of 10 or less include benzene, toluene, ethylbenzene, xylene, methyl ethyl ketone, diethyl ketone, benzaldehyde, di-n-butyl phosphate, dibutyl phthalate, etc., as described in various documents. Can do.
- Tetrahydrofurfuran has a low solubility parameter of 9.1, but is not preferred because of the high proportion of hydrogen bonding components in the solubility parameter. This is supported by the fact that the CT band does not appear on the light absorption spectrum even when the compound acting as a charge acceptor is added to THF.
- unsaturated hydrocarbons such as limonene, pinene, ferrandrene, carene, butadiene, norbornene, fluorene, etc., in which a part of alkane or cycloalkane is a double bond can also be used.
- a solution obtained by dissolving the compound serving as the charge acceptor and the compound forming the CT complex in a solvent can be mentioned.
- the compound that forms the CT complex serves as a ligand.
- the solvent is not particularly limited, and an inert solvent may be used, or a solvent that forms a CT complex with a compound that acts as a charge acceptor.
- the compound having the CT complex forming ability may be a compound that itself constitutes a solvent having a CT complex forming ability. Further, it may be an aromatic compound such as naphthalene, biphenyl, anthracene, phenanthrene or pyrene in a solid state.
- inert solvent examples include cycloalkanes, normal alkanes, and halogenated carbon solvents.
- the solvent used in the first step is preferably a solvent having some interaction with the compound acting as the charge acceptor because it must dissolve the compound acting as the charge acceptor. It is preferable that there is no such interaction.
- the solvent is preferably a solvent that does not exert a strong ionic interaction with the compound acting as a charge acceptor.
- the compound serving as the charge acceptor and graphite are mixed in the solvent.
- the compound acting as a charge acceptor forms a complex in the solvent, and the complex is brought into contact with the raw material graphite.
- the raw material graphite may be added simultaneously with the addition of the compound acting as the charge acceptor to the solvent, or the raw material graphite may be charged after the compound acting as the charge acceptor is charged.
- the heating temperature is preferably less than the boiling point of the solvent.
- a higher heating temperature is preferable, and a higher temperature than normal temperature is desirable.
- the compound acting as the charge acceptor in the first step, is inserted between the graphene layers from the complex of the compound acting as the charge acceptor. In this way, expanded graphite is formed in the solvent.
- the interlayer of graphene is not so wide. This point will be described later.
- the expanded graphite obtained in the first step by the solvent method can be separated from the solvent by filtration or centrifugation.
- the expanded graphite may be taken out from the solvent as it is.
- a catalyst in the presence of a supercritical fluid, a catalyst may be inserted between graphite layers to obtain expanded graphite.
- the supercritical fluid is not particularly limited, and supercritical carbon dioxide or supercritical water can be used.
- the expanded catalyst may be obtained by bringing a catalyst in a gaseous state into contact with the raw material graphite and thereby inserting the catalyst between graphite layers.
- the second step is performed after the first step, and the expanded graphite obtained in the first step is brought into contact with the reactive compound. That is, a chemical bond is generated by contacting and reacting raw material graphite in contact with the catalyst, that is, graphite intercalated with a compound acting as a charge acceptor, with a reactive compound. Therefore, the reactive compound larger than the compound acting as the original charge acceptor is inserted between the graphite layers. Thereby, a graphite interlayer is further expanded, graphite peels, and exfoliated graphite can be obtained.
- the peeling treatment can be easily performed by chemically bonding the reactive compound to the graphite.
- the amount of the reactive compound chemically bonded in the second step is preferably 0.5% by weight or more, more preferably 1.0% by weight or more with respect to 100% by weight of the raw material graphite. It is more preferably 0% by weight, and further preferably 5.0% by weight or more.
- the amount of the reactive compound chemically bonded in the second step is preferably 200% by weight or less with respect to 100% by weight of the raw material graphite.
- the reactive compound used in the second step is not particularly limited as long as it is a known reactive organic compound that forms a chemical bond with the graphite raw material, and is a Diels-Alder reactive compound, a Fridel-Crafts reactive compound, or a radical reactive property. Compounds and the like.
- Examples of the Diels-Alder reactive compound include maleic acid derivatives such as maleic anhydride and dimethyl maleate, maleimides such as N-phenylmaleimide, furfural, furfuryl alcohol, furfurylamine, 5-methyl-2-fur Furfural derivatives such as aldehyde, furfuryl mercaptan, 2-furoyl chloride, furan derivatives such as 2-methylfuran, 2-ethylfuran, 2-methoxyfuran, 2-furonitrile, vinyl acetate, p-chlorostyrene, N-vinyl And vinyl-modified solvents such as -2 pyrrolidone or imines such as phenylimidazoline. These compounds may be used alone or in combination of two or more.
- maleimides such as N-phenylmaleimide
- furfural furfuryl alcohol
- furfurylamine furfurylamine
- 5-methyl-2-fur Furfural derivatives such as aldehyde, furfury
- Fridel-Crafts reactive compound any general halide, carboxylic acid halide, acid anhydride and the like can be used.
- 1-chlorododecane, N-chlorooctane, N-octanoyl Alkyl halogens such as chloride, aliphatic acid halides, benzoic acid halides such as benzoyl chloride, and acid anhydrides such as succinic anhydride, phthalic anhydride, and propionic anhydride can be used. These compounds may be used alone or in combination of two or more.
- the radical reactive compound generally includes a compound having a radical reactive functional group, for example, (meth) acryl group, vinyl group, vinyl ether group, glycidyl group, thiol group, halogeno group, carbonyl group, carboxyl group. And a compound having at least one selected from the group consisting of a group, a sulfo group, an amino group, a hydroxy group, an oxime group, a nitrile group, an isocyanate group, a silyl group, and derivatives thereof.
- a radical reactive functional group for example, (meth) acryl group, vinyl group, vinyl ether group, glycidyl group, thiol group, halogeno group, carbonyl group, carboxyl group.
- reaction using these reactive compounds may be performed in a solvent or in the presence of a supercritical fluid. Moreover, you may perform processes, such as a heating, as needed. Further, a reactive compound in a gaseous state may be brought into contact with graphite.
- the Diels-Alder reactive compound is used and a Lewis acidic compound such as a metal halide is used as the compound that acts as the charge acceptor
- the compound that acts as the charge acceptor also acts as a reaction catalyst. Since the reaction proceeds even at room temperature, the productivity is extremely high.
- a surface modification effect can be expected by bonding these reactive compounds to exfoliated graphite.
- the surface modification effect can be selected as necessary, such as hydrophilization, hydrophobization, and addition of an organic reactive functional group.
- chlorinated alkyls can be used as reactive compounds to modify the flake graphite. Since this alkyl-modified exfoliated graphite is excellent in compatibility with the resin, it is advantageous in forming a resin composite described later.
- the graphene layer further expands due to the bonding of the reactive compound at the graphene edge or between the layers, and peeling occurs.
- mechanical peeling treatment such as ultrasonic treatment or mechanical shearing treatment may be performed as necessary. In that case, exfoliated graphite with a higher degree of exfoliation can be obtained. Further, the degree of peeling can be further increased by repeating a series of operations in the first step and the second step described here.
- the method for producing exfoliated graphite of the present invention can be processed using the same solvent in the first step and the second step, and is excellent in productivity because it can be made into a single facility or a continuous facility.
- the expanded graphite may be taken out after the first step, and the exfoliation treatment may be performed using another solvent in the second step.
- the reactive compound since a suitable solvent can be selected for the binding reaction of the reactive compound in the second step, the reactive compound can be widely selected.
- exfoliated graphite is obtained by using, for example, a compound acting as a charge acceptor, a solvent, a reactive organic compound, or the like instead of a dangerous compound such as an alkali metal. Can do. Therefore, it is possible to mass-produce exfoliated graphite more safely.
- the reactive compound of the second step may be added to the expanded graphite solvent dispersion after the first step, and the exfoliated graphite can be produced substantially by a single facility or a continuous facility. In that case, higher mass productivity and lower cost can be realized.
- the manufacturing method of the present invention does not necessarily require high-temperature heating or vacuum treatment. Therefore, in that case, the scale-up can be facilitated, and the mass productivity of exfoliated graphite can be further effectively improved.
- either the first step or the second step may be performed in the presence of the supercritical fluid described above, or both the first step and the second step may be performed in the presence of the supercritical fluid. You may go. However, it is preferable to perform both the first step and the second step in the presence of a supercritical fluid.
- steps such as filtration, washing and drying can be omitted.
- the catalyst and the reactive compound are supplied into the reaction vessel only by the necessary amount accompanying the chemical equilibrium via the supercritical carbon dioxide, the loss of each raw material can be further reduced.
- the raw material graphite is charged into the reaction vessel, whereby the expansion and exfoliation processes can be repeated.
- the first step may be performed using a gaseous catalyst, or the second step may be performed using a gaseous reactive compound. It is preferable to perform the first step using a gaseous catalyst and to perform the second step using a gaseous reactive compound.
- the filtration and washing steps can be omitted.
- the catalyst and the reactive compound are volatilized and only a necessary amount accompanying chemical equilibrium is supplied into the reaction vessel, the loss of each raw material can be further reduced. Further, after the exfoliated graphite is recovered, the raw material graphite is charged into the reaction vessel, whereby the expansion and exfoliation processes can be repeated.
- exfoliated graphite of the present invention is produced according to the above exfoliated graphite production method. Therefore, exfoliated graphite in which the graphene layer is sufficiently expanded or exfoliated graphite which is a single layer graphene sheet is obtained.
- exfoliated graphite is a graphene sheet laminate or a single-layer graphene sheet.
- exfoliated graphite can be obtained by exfoliating graphite. That is, exfoliated graphite is a graphene sheet laminate or a single layer graphene sheet that is thinner than the original graphite.
- the number of graphene sheets laminated in exfoliated graphite is 1 or more. From the viewpoint of more effectively increasing the mechanical strength such as the tensile modulus of the resin, the number of graphene sheets stacked is preferably 1000 or less, and more preferably 150 or less.
- Exfoliated graphite has a structure in which thin graphene sheets are laminated. Therefore, the aspect ratio of exfoliated graphite is relatively large.
- the aspect ratio of exfoliated graphite refers to the ratio of the maximum dimension in the laminate surface direction of exfoliated graphite to the thickness of exfoliated graphite.
- the preferable lower limit of the aspect ratio of exfoliated graphite is about 50, and the preferable upper limit is about 5000.
- exfoliated graphite having a BET specific surface area of 30 m 2 / g or more after drying can be provided. Since such exfoliated graphite has a large BET specific surface area, the mechanical strength and the like of the resin can be sufficiently increased by adding a small amount to the resin.
- the exfoliated graphite according to the present invention preferably has a BET specific surface area after drying of 30 m 2 / g or more, and more preferably 300 m 2 / g or more. Further, the BET specific surface area after drying is preferably 2800 m 2 / g or less, which is the theoretical surface area of graphene.
- the exfoliated graphite in the present invention is a composite in which a reactive compound is bonded to exfoliated graphite. Therefore, the compatibility with the resin is better than that of exfoliated graphite to which no reactive compound is bonded.
- a Fridel-Crafts reactive compound such as chlorinated alkyls is preferably used. When the Fridel-Crafts reactive compound is used, the compatibility of the obtained exfoliated graphite with the resin can be further enhanced.
- the reactive compound is preferably chemically bonded to 100 to 100 parts by weight of exfoliated graphite, and is preferably chemically bonded to 1.0 to 500 parts by weight. More preferably, 3.0 to 100 parts by weight are chemically bonded.
- the reactive compound may form a layer between exfoliated graphite and the composite resin, resulting in phase separation. If the amount is too small, the exfoliated graphite and composite resin are compatibilized. The effect may be reduced.
- the 26.4 degree peak derived from the graphite layer in the XRD spectrum is small or substantially absent. That is, in the exfoliated graphite according to the present invention, the 26.4 degree peak intensity derived from the graphite layer in the XRD spectrum is preferably 30% or less, more preferably 15% or less with respect to the peak intensity of the raw graphite. Is more preferable, and it is further more preferable that it is 5% or less. More preferably, there is substantially no 26.4 degree peak. In that case, the space between the graphenes is sufficiently widened to have a larger specific surface area.
- the exfoliated graphite obtained by the production method of the present invention is hardly oxidized. Therefore, in the present invention, exfoliated graphite having excellent electrical conductivity and thermal conductivity can be obtained. In addition, by combining the exfoliated graphite with a resin, it becomes easy to provide a tough composite material having a high elastic modulus.
- exfoliated graphite obtained in the present invention is excellent in dispersibility in polar solvents such as water.
- surface treatment with a reactive compound is easy. Therefore, it can be suitably used as a filler added to the resin. Thereby, it is possible to easily improve the mechanical strength and elastic modulus of the resin.
- exfoliated graphite-resin composite material The exfoliated graphite-resin composite material is obtained by combining the exfoliated graphite and the resin.
- the obtained composite material can be used for electrochemical materials such as electrical conductivity, thermoelectricity, dielectrics, electromagnetic wave absorption, or sensor materials, and mechanical strength materials such as rigidity, heat resistance, and dimensional stability.
- the resin various known synthetic resins can be used.
- a thermoplastic resin is used as the synthetic resin.
- various molded products can be easily obtained using various molding methods under heating.
- thermoplastic resin examples include polyethylenes such as high-density polyethylene, low-density polyethylene, and linear low-density polyethylene, polyolefins typified by polypropylenes such as homopolypropylene, block polypropylene, and random polypropylene, and cyclics such as norbornene resin.
- Polyvinyl acetates such as polyolefins, polyvinyl acetate and ethylene vinyl acetate, polyvinyl acetate derivatives such as polyvinyl alcohol and polyvinyl butyral, polyesters such as PET, polycarbonate and polylactic acid, polyethylene oxide, polyphenylene ether, Polyether resins such as polyether ether ketone, acrylic resins such as PMMA, sulfone resins such as polysulfone and polyether sulfone, PTFE, PVDF, etc.
- Tsu fluorinated resins polyamide resins such as nylon, polyvinyl chloride, halogenated resins such as vinylidene chloride, polystyrene, polyacrylonitrile or a copolymer resin thereof such and the like.
- Particularly preferred are polyolefins that are inexpensive and easy to mold under heating.
- thermosetting resin may be used as the synthetic resin.
- a resin composite material using a thermosetting resin a molded product having excellent heat resistance and chemical resistance can be obtained because the resin after thermosetting has a three-dimensional bonding structure.
- thermosetting resin examples include phenolic resins, epoxy resins, melamine resins, urea resins, urethane resins, acrylic resins, furan resins, ester resins, imide resins, and the like.
- synthetic resin only 1 type may be used and 2 or more types may be used together.
- the exfoliated graphite is preferably contained in the range of 0.3 to 100 parts by mass, and in the range of 0.5 to 30 parts by mass with respect to 100 parts by mass of the resin composite material. More preferably. This is because if the exfoliated graphite is too small, a sufficient addition effect may not be obtained, and if it is too large, the addition effect may be saturated and other physical properties may be adversely affected.
- exfoliated graphite according to the present invention is a composite in which exfoliated graphite is chemically bonded to a reactive compound. Accordingly, since the interaction with the resin can be designed, the properties of the obtained composite material as an electrochemical and mechanical material are particularly excellent.
- Example 1 Into a flask subjected to nitrogen substitution, 40 g of toluene (manufactured by Wako Pure Chemical Industries, Ltd.), 0.4 g of aluminum chloride (manufactured by Wako Pure Chemical Industries, Ltd.) as a compound acting as a charge acceptor, graphite raw material (manufactured by Toyo Tanso Co., Ltd., trade name “PF powder”) 8 ”) 0.5 g was added and stirred with a stirrer at room temperature for 7 days to obtain expanded graphite.
- PF powder graphite raw material
- Example 2 Exfoliated graphite was obtained in the same manner as in Example 1 except that 1-chlorododecane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the Friedel-Crafts reactive monomer instead of the Diels-Alder reactive monomer.
- Example 3 Exfoliated graphite was obtained in the same manner as in Example 1 except that vinyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the Diels-Alder reactive monomer.
- FIG. 2 is a schematic diagram of the reaction apparatus used in Example 4.
- Reactor 1 has graphite raw material (trade name “PF Powder 8” manufactured by Toyo Tanso Co., Ltd.) 1.0 g, and iron (III) chloride as a compound acting as a charge acceptor in first raw material container 2 (manufactured by Wako Pure Chemical Industries, Ltd.) 1.7 g of maleic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) 1.5 g as Diels-Alder reactive monomer was added to the second raw material container 3.
- graphite raw material trade name “PF Powder 8” manufactured by Toyo Tanso Co., Ltd.
- iron (III) chloride as a compound acting as a charge acceptor
- first raw material container 2 manufactured by Wako Pure Chemical Industries, Ltd.
- maleic anhydride manufactured by Wako Pure Chemical Industries, Ltd.
- Diels-Alder reactive monomer was added to the second raw material container 3.
- the second on-off valve 6 is opened and the temperature of the first reaction area 10 is set.
- the pressure was 60 ° C. and 11 MPa.
- the first on-off valve 4 was closed and allowed to stand for 10 days, whereby iron (III) chloride was brought into contact with the graphite raw material via supercritical carbon dioxide to obtain expanded graphite.
- the second on-off valve 6 is closed, the third on-off valve 7 is opened and the second raw material container 3 and the second carbon dioxide cylinder 8 are connected, the fourth on-off valve 9 is opened and the second on-off valve 9 is opened.
- the temperature and pressure in the reaction area 11 of 2 were 60 ° C. and 11 MPa.
- the third on-off valve 7 was closed and allowed to stand for 2 days, whereby maleic anhydride was brought into contact with the expanded graphite via supercritical carbon dioxide to obtain exfoliated graphite.
- the obtained exfoliated graphite was recovered by closing the fourth on-off valve 9 and opening the reactor 1.
- FIG. 3 is a schematic diagram of the reaction apparatus used in Example 5.
- Graphite raw material (trade name “PF powder 8” manufactured by Toyo Tanso Co., Ltd.) 0.5 g is added to the reactor 1, and iron (III) chloride (made by Wako Pure Chemical Industries) 2 as a charge acceptor compound is added to the first raw material container 2.
- iron (III) chloride made by Wako Pure Chemical Industries
- 0.02 g and 3.5 g of vinyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a Diels-Alder reactive monomer were added to the second raw material container 3, respectively.
- the first and second on-off valves 4 and 6 were opened, and the reactor 1 and the first raw material container 2 were evacuated by the vacuum pump 12. Thereafter, the first on-off valve 4 was closed, and the reactor 1 and the first raw material container 2 were heated at 360 ° C. for 12 hours, whereby iron (III) chloride was brought into contact with the graphite raw material to obtain expanded graphite.
- the second on-off valve 6 is closed, the fourth on-off valve 9 is opened, the reactor 1 is at 80 ° C., and the second raw material container 3 is By heating at 65 ° C. for 6 hours, the vinyl acetate was volatilized and contacted with expanded graphite to obtain exfoliated graphite.
- the exfoliated graphite obtained was recovered by drying the excess vinyl acetate by closing the fourth on-off valve 9 and opening the first and second on-off valves 4 and 6 again to create a vacuum.
- Graft ratio (% by weight) (weight at 150 ° C. ⁇ weight at 500 ° C.) / Weight at 150 ° C. ⁇ 100
- XRD measurement X-ray diffraction measurement was performed using an Rigaku X-ray diffractometer SmartLab. Diffraction was obtained by the 2 ⁇ - ⁇ method with a tube voltage of 40 kV and a tube current of 200 mA. The scan speed was 4 degrees / minute. The sample was placed and pressed so that the dent portion on the powder sample stage was flat, and XRD measurement was performed. According to the production method of the present invention, in the X-ray diffraction measurement, the peak located at 26.4 degrees derived from the layer crystal of the raw material graphite becomes smaller as the peeling, that is, the thinning progresses. This principle was used as a measure of the degree of exfoliation of graphite. The results are shown in FIG. In FIG. 1, A is raw graphite, B is Comparative Example 1, C is Example 1, D is Example 2, E is Example 3, F is Example 4, and G is XRD spectrum of Example 5. It shall be shown.
Abstract
Description
第1工程においては、原料黒鉛の黒鉛層間に触媒を挿入し、膨張化黒鉛を得る。ここでいう膨張化黒鉛とは、グラフェン層間にインターカーラントである触媒が挿入されているGIC、もしくはそのGICを経由して高度に層間が開かれた状態の黒鉛化合物をいうものとする。本発明においては、上記インターカーラントがグラフェン層間に挿入されているため、グラフェン層間の距離が広げられている。 (First step)
In the first step, a catalyst is inserted between the graphite layers of the raw graphite to obtain expanded graphite. The term “expanded graphite” as used herein refers to a GIC in which a catalyst which is an intercarrant is inserted between graphene layers, or a graphite compound in which the layers are highly opened via the GIC. In the present invention, since the intercarrant is inserted between the graphene layers, the distance between the graphene layers is increased.
Mは、周期律表の2族~7族の金属である。このような金属としては、ベリリウム、ホウ素、マグネシウム、アルミニウム、ケイ素、カルシウム、スカンジウム、チタン、バナジウム、クロム、マンガン、鉄、コバルト、ニッケル、亜鉛、ガリウム、ストロンチウム、イットリウム、ジルコニウム、ニオブ、モリブデン、テクネチウム、ルテニウム、ロジウム、パラジウム、銀、カゴミウム、インジウム、錫、アンチモン、ハフニウム、タンタル、タングステン、レニウム、オスニウム、イリジウム、白金、金、水銀、タリウム、鉛、ビスマスなどが挙げられる。
上記Xは、ハロゲンであり、フッ素、塩素、臭素またはヨウ素である。上記nは、金属のもつ原子価に応じた2~5の整数である。 (1) Metal halide represented by MXn:
M is a metal of
X is halogen, which is fluorine, chlorine, bromine or iodine. N is an integer of 2 to 5 depending on the valence of the metal.
Aを酸とした場合、MAXで表される、酸とハロゲンと金属との複合塩である。Mは上述した通り、周期律表の2族~7族の金属元素である。Aは酸である。酸としては、硫酸、硝酸、リン酸またはホウ酸などの無機酸であってもよく、有機酸であってもよい。Xは、上述したハロゲンである。 (2) Complex salt represented by MAX:
When A is an acid, it is a complex salt of an acid, a halogen and a metal represented by MAX. As described above, M is a metal element belonging to
Mは2族~7族の金属元素である。Lは、アセチルアセトン、エチレンジアミン、フタロシアニン、アンモニア、一酸化炭素またはシアンなどの配位子として働く化合物である。Xは、上述したハロゲンである。 (3) Complex compound represented by ML or MLX M is a metal element of
上記電荷アクセプターとして働く有機化合物としては、例えば、p-ベンゾキノン、2,3,5,6-テトラメチル-p-ベンゾキノン、2-メチル-1,4-ナフトキノン、テトラフルオロ-1,4-ベンゾキノン、7,7,8,8-テトラシアノキノジメタン、2-シアノピリジンなどの芳香族化合物と電荷移動錯体(CT錯体)を形成する能力のある有機化合物を用いることができる。 (4) Charge acceptor comprising an organic compound Examples of the organic compound acting as the charge acceptor include p-benzoquinone, 2,3,5,6-tetramethyl-p-benzoquinone, 2-methyl-1,4-naphthoquinone, Use an organic compound capable of forming a charge transfer complex (CT complex) with an aromatic compound such as tetrafluoro-1,4-benzoquinone, 7,7,8,8-tetracyanoquinodimethane, and 2-cyanopyridine. be able to.
3価のリン化合物としては、トリフェニルフォスファイト、トリアルキルフォスファイトなどを挙げることができる。 (5) Trivalent phosphorus compound Examples of the trivalent phosphorus compound include triphenyl phosphite and trialkyl phosphite.
本発明では、第2工程は、第1工程の後に行われ、第1工程で得られた膨張化黒鉛を反応性化合物に接触させる。すなわち、上記触媒と接触した原料黒鉛、すなわち電荷アクセプターとして働く化合物がインターカレーションされた黒鉛を反応性化合物に接触、反応させることで化学結合を生じさせる。従って、黒鉛層間に、もとの電荷アクセプターとして働く化合物よりも大きい、上記反応性化合物が挿入される。これにより、黒鉛層間がさらに広げられ、黒鉛が剥離し、薄片化黒鉛を得ることができる。 (Second step)
In the present invention, the second step is performed after the first step, and the expanded graphite obtained in the first step is brought into contact with the reactive compound. That is, a chemical bond is generated by contacting and reacting raw material graphite in contact with the catalyst, that is, graphite intercalated with a compound acting as a charge acceptor, with a reactive compound. Therefore, the reactive compound larger than the compound acting as the original charge acceptor is inserted between the graphite layers. Thereby, a graphite interlayer is further expanded, graphite peels, and exfoliated graphite can be obtained.
本発明の薄片化黒鉛は、上記薄片化黒鉛の製造方法に従って製造される。従って、グラフェン層間が十分に広げられた薄片化黒鉛又は単層のグラフェンシートである薄片化黒鉛が得られる。
なお、本発明において、薄片化黒鉛とは、グラフェンシートの積層体又は単層のグラフェンシートである。上記のように薄片化黒鉛は、黒鉛を剥離処理することにより得られる。すなわち、薄片化黒鉛は、元の黒鉛よりも薄い、グラフェンシートの積層体又は単層のグラフェンシートである。 (Flaky graphite)
The exfoliated graphite of the present invention is produced according to the above exfoliated graphite production method. Therefore, exfoliated graphite in which the graphene layer is sufficiently expanded or exfoliated graphite which is a single layer graphene sheet is obtained.
In the present invention, exfoliated graphite is a graphene sheet laminate or a single-layer graphene sheet. As described above, exfoliated graphite can be obtained by exfoliating graphite. That is, exfoliated graphite is a graphene sheet laminate or a single layer graphene sheet that is thinner than the original graphite.
上記薄片化黒鉛と、樹脂とを複合化することで、薄片化黒鉛-樹脂複合材料が得られる。得られた複合材料は、導電、熱電、誘電、電磁波吸収又はセンサ材料等の電気化学的素材や、剛性、耐熱性、寸法安定性等の力学的強度素材等に用いることができる。 (Exfoliated graphite-resin composite material)
The exfoliated graphite-resin composite material is obtained by combining the exfoliated graphite and the resin. The obtained composite material can be used for electrochemical materials such as electrical conductivity, thermoelectricity, dielectrics, electromagnetic wave absorption, or sensor materials, and mechanical strength materials such as rigidity, heat resistance, and dimensional stability.
以下、本発明の具体的な実施例及び比較例を挙げることにより、本発明を明らかにする。なお、本発明は以下の実施例に限定されるものではない。 (Examples and Comparative Examples)
Hereinafter, the present invention will be clarified by giving specific examples and comparative examples of the present invention. In addition, this invention is not limited to a following example.
窒素置換を行ったフラスコに、トルエン(和光純薬社製)40g、電荷アクセプターとして働く化合物として塩化アルミニウム(和光純薬社製)0.4g、黒鉛原料(東洋炭素社製、商品名「PFパウダー8」)0.5gを加え、室温にて7日間スターラー撹拌させて膨張化黒鉛を得た。次に、Diels-Alder反応性モノマーとしての無水マレイン酸(和光純薬社製)0.5gをトルエン30gに溶解し、膨張化黒鉛に滴下した。しかる後、内容物を濾過洗浄、真空乾燥することで薄片化黒鉛を得た。 Example 1
Into a flask subjected to nitrogen substitution, 40 g of toluene (manufactured by Wako Pure Chemical Industries, Ltd.), 0.4 g of aluminum chloride (manufactured by Wako Pure Chemical Industries, Ltd.) as a compound acting as a charge acceptor, graphite raw material (manufactured by Toyo Tanso Co., Ltd., trade name “PF powder”) 8 ") 0.5 g was added and stirred with a stirrer at room temperature for 7 days to obtain expanded graphite. Next, 0.5 g of maleic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) as a Diels-Alder reactive monomer was dissolved in 30 g of toluene and added dropwise to expanded graphite. Thereafter, exfoliated graphite was obtained by filtering, washing and vacuum drying the contents.
Diels-Alder反応性モノマーの代わりに、Friedel-Crafts反応性モノマーとして、1-クロロドデカン(東京化成工業社製)を用いたこと以外は、実施例1と同様にして薄片化黒鉛を得た。 (Example 2)
Exfoliated graphite was obtained in the same manner as in Example 1 except that 1-chlorododecane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the Friedel-Crafts reactive monomer instead of the Diels-Alder reactive monomer.
Diels-Alder反応性モノマーとして、酢酸ビニル(東京化成工業社製)を用いたこと以外は実施例1と同様にして薄片化黒鉛を得た。 Example 3
Exfoliated graphite was obtained in the same manner as in Example 1 except that vinyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the Diels-Alder reactive monomer.
図2は、実施例4で用いた反応装置の模式図である。反応器1に黒鉛原料(東洋炭素社製、商品名「PFパウダー8」)1.0g、第1の原料容器2に電荷アクセプターとして働く化合物としての塩化鉄(III)(和光純薬社製)1.7g、第2の原料容器3に、Diels-Alder反応性モノマーとして無水マレイン酸(和光純薬社製)1.5gをそれぞれ投入した。 Example 4
FIG. 2 is a schematic diagram of the reaction apparatus used in Example 4.
図3は、実施例5で用いた反応装置の模式図である。反応器1に黒鉛原料(東洋炭素社製、商品名「PFパウダー8」)0.5g、第1の原料容器2に電荷アクセプター型化合物としての塩化鉄(III)(和光純薬社製)2.0g、第2の原料容器3にDiels-Alder反応性モノマーとしての酢酸ビニル(東京化成工業社製)3.5gをそれぞれ投入した。 (Example 5)
FIG. 3 is a schematic diagram of the reaction apparatus used in Example 5. Graphite raw material (trade name “
Diels-Alder反応性モノマーを加えなかったこと以外は実施例1と同様にして試料を得た。 (Comparative Example 1)
A sample was obtained in the same manner as in Example 1 except that the Diels-Alder reactive monomer was not added.
熱分析測定;
Sii社製、熱分析装置(TG/DTA6300)で、加熱による重量減少でグラフト率を測定した。評価条件は、室温から5℃/分で550℃まで昇温を行い、下記の式にてグラフト率を算出した。結果を下記表1に示す。 (Evaluation)
Thermal analysis measurement;
The graft ratio was measured by weight reduction by heating with a thermal analyzer (TG / DTA6300) manufactured by Sii. As evaluation conditions, the temperature was raised from room temperature to 550 ° C. at 5 ° C./min, and the graft ratio was calculated by the following formula. The results are shown in Table 1 below.
X線回折測定をリガク社製X線回折装置SmartLabを用いて行った。管電圧40kV、管電流200mAとし、2θ-θ法により回折を得た。スキャンスピードは4度/分の速度でスキャンした。紛体用試料台にある凹み部分が平らになるようにサンプルを入れ押し固め、XRD測定を行った。なお、本発明の製造方法によれば、X線回折測定において、原料である黒鉛が有する層結晶由来の26.4度に位置するピークが、剥離すなわち薄片化の進行とともに小さくなっていく。この原理を利用して黒鉛の剥離度の目安とした。結果を図1に示す。なお、図1中において、Aは原料黒鉛、Bは比較例1、Cは実施例1、Dは実施例2、Eは実施例3、Fは実施例4、Gは実施例5のXRDスペクトルを示すものとする。 XRD measurement;
X-ray diffraction measurement was performed using an Rigaku X-ray diffractometer SmartLab. Diffraction was obtained by the 2θ-θ method with a tube voltage of 40 kV and a tube current of 200 mA. The scan speed was 4 degrees / minute. The sample was placed and pressed so that the dent portion on the powder sample stage was flat, and XRD measurement was performed. According to the production method of the present invention, in the X-ray diffraction measurement, the peak located at 26.4 degrees derived from the layer crystal of the raw material graphite becomes smaller as the peeling, that is, the thinning progresses. This principle was used as a measure of the degree of exfoliation of graphite. The results are shown in FIG. In FIG. 1, A is raw graphite, B is Comparative Example 1, C is Example 1, D is Example 2, E is Example 3, F is Example 4, and G is XRD spectrum of Example 5. It shall be shown.
2,3…第1,第2の原料容器
4…第1の開閉弁
5…第1の二酸化炭素ボンベ
6…第2の開閉弁
7…第3の開閉弁
8…第2の二酸化炭素ボンベ
9…第4の開閉弁
10,11…第1,第2の反応エリア
12…真空ポンプ DESCRIPTION OF
Claims (19)
- 黒鉛層間に触媒を挿入する工程と、
前記触媒を用いて、反応性化合物を黒鉛に化学結合させることにより黒鉛に剥離処理を施し、薄片化黒鉛を得る工程とを備える、薄片化黒鉛の製造方法。 Inserting a catalyst between the graphite layers;
A method for producing exfoliated graphite, comprising: a step of chemically exfoliating graphite by chemically bonding a reactive compound to graphite using the catalyst to obtain exfoliated graphite. - 前記反応性化合物が、Diels-Alder反応性化合物である、請求項1に記載の薄片化黒鉛の製造方法。 The method for producing exfoliated graphite according to claim 1, wherein the reactive compound is a Diels-Alder reactive compound.
- 前記反応性化合物が、Fridel-Crafts反応性化合物である、請求項1に記載の薄片化黒鉛の製造方法。 The method for producing exfoliated graphite according to claim 1, wherein the reactive compound is a Fridel-Crafts reactive compound.
- 前記触媒が芳香族化合物に対して電荷アクセプターとして働く化合物である、請求項1~3のいずれか1項に記載の薄片化黒鉛の製造方法。 The method for producing exfoliated graphite according to any one of claims 1 to 3, wherein the catalyst is a compound that acts as a charge acceptor for an aromatic compound.
- 前記触媒が金属ハロゲン化合物である、請求項4に記載の薄片化黒鉛の製造方法。 The method for producing exfoliated graphite according to claim 4, wherein the catalyst is a metal halide.
- 前記黒鉛層間に触媒を挿入する工程が、溶媒中で行われる、請求項1~5のいずれか1項に記載の薄片化黒鉛の製造方法。 The method for producing exfoliated graphite according to any one of claims 1 to 5, wherein the step of inserting a catalyst between the graphite layers is performed in a solvent.
- 前記黒鉛層間に触媒を挿入する工程が、超臨界流体の存在下で行われる、請求項1~5のいずれか1項に記載の薄片化黒鉛の製造方法。 The method for producing exfoliated graphite according to any one of claims 1 to 5, wherein the step of inserting a catalyst between the graphite layers is performed in the presence of a supercritical fluid.
- 前記黒鉛層間に触媒を挿入する工程において、気体状態の触媒を黒鉛層間に挿入する、請求項1~5のいずれか1項に記載の薄片化黒鉛の製造方法。 6. The method for producing exfoliated graphite according to claim 1, wherein in the step of inserting the catalyst between the graphite layers, a gaseous catalyst is inserted between the graphite layers.
- 前記黒鉛に剥離処理を施す工程が、超臨界流体の存在下で行われる、請求項1~8のいずれか1項に記載の薄片化黒鉛の製造方法。 The method for producing exfoliated graphite according to any one of claims 1 to 8, wherein the step of exfoliating the graphite is performed in the presence of a supercritical fluid.
- 前記黒鉛に剥離処理を施す工程において、気体状態の反応性化合物を黒鉛に接触させることにより、反応性化合物を黒鉛に化学結合させる、請求項1~8のいずれか1項に記載の薄片化黒鉛の製造方法。 The exfoliated graphite according to any one of claims 1 to 8, wherein in the step of subjecting the graphite to a peeling treatment, the reactive compound is chemically bonded to the graphite by bringing the reactive compound in a gaseous state into contact with the graphite. Manufacturing method.
- 前記触媒が芳香族化合物に対して電荷アクセプターとして働く化合物であって、前記溶媒中において、前記触媒が前記溶媒と錯体を形成する、請求項6に記載の薄片化黒鉛の製造方法。 The method for producing exfoliated graphite according to claim 6, wherein the catalyst serves as a charge acceptor for an aromatic compound, and the catalyst forms a complex with the solvent in the solvent.
- 前記錯体の配位子が電子供与性化合物である、請求項11に記載の薄片化黒鉛の製造方法。 The method for producing exfoliated graphite according to claim 11, wherein the ligand of the complex is an electron donating compound.
- 前記錯体の配位子が芳香族環を有する化合物である、請求項11又は12に記載の薄片化黒鉛の製造方法。 The method for producing exfoliated graphite according to claim 11 or 12, wherein the ligand of the complex is a compound having an aromatic ring.
- 前記錯体の配位子が孤立電子対を有する化合物である、請求項11~13のいずれか1項に記載の薄片化黒鉛の製造方法。 The method for producing exfoliated graphite according to any one of claims 11 to 13, wherein the ligand of the complex is a compound having a lone pair of electrons.
- 前記溶媒の溶解パラメータが10以下である、請求項6及び11~14のいずれか1項に記載の薄片化黒鉛の製造方法。 The method for producing exfoliated graphite according to any one of claims 6 and 11 to 14, wherein a solubility parameter of the solvent is 10 or less.
- 請求項1~15のいずれか1項に記載の薄片化黒鉛の製造方法により得られた、薄片化黒鉛。 Exfoliated graphite obtained by the method for producing exfoliated graphite according to any one of claims 1 to 15.
- Diels-Alder反応性化合物が化学結合している、請求項16に記載の薄片化黒鉛。 The exfoliated graphite according to claim 16, wherein the Diels-Alder reactive compound is chemically bonded.
- Fridel-Crafts反応性化合物が化学結合している、請求項16に記載の薄片化黒鉛。 The exfoliated graphite according to claim 16, wherein the Fridel-Crafts reactive compound is chemically bonded.
- 請求項16~18のいずれか1項に記載の薄片化黒鉛と、樹脂とを含む、薄片化黒鉛-樹脂複合材料。 A exfoliated graphite-resin composite material comprising exfoliated graphite according to any one of claims 16 to 18 and a resin.
Priority Applications (3)
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JP2015510223A JPWO2015125740A1 (en) | 2014-02-18 | 2015-02-16 | Exfoliated graphite manufacturing method, exfoliated graphite and exfoliated graphite-resin composite material |
CN201580003216.6A CN105829245A (en) | 2014-02-18 | 2015-02-16 | Method of producing flaked graphite, flaked graphite, and flaked graphite-resin composite material |
KR1020167016201A KR20160122693A (en) | 2014-02-18 | 2015-02-16 | Method of producing flaked graphite, flaked graphite, and flaked graphite-resin composite material |
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JP2020527534A (en) * | 2017-07-13 | 2020-09-10 | カーボン アップサイクリング テクノロジーズ インク.Carbon Upcycling Technologies Inc. | Mechachemical process for producing exfoliated nanoparticles |
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CN110746796B (en) * | 2019-11-11 | 2021-01-26 | 长沙天源羲王材料科技有限公司 | Modified graphene and preparation method of slurry containing modified graphene |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5082024A (en) * | 1973-11-13 | 1975-07-03 | ||
JPH0585957A (en) * | 1991-02-22 | 1993-04-06 | Bayer Ag | Process for preparing 2,2-bis(3,4-dimethylphenyl)propane |
JPH08148148A (en) * | 1994-11-24 | 1996-06-07 | Sony Corp | Manufacture of electrode material for nonaqueous electrolyte battery and nonaqueous electrolyte battery using the material thereby obtained |
JP2001502310A (en) * | 1996-10-04 | 2001-02-20 | トーマス・スワン・アンド・カンパニー・リミテツド | Alkylation and acylation reactions |
WO2004048259A1 (en) * | 2002-11-21 | 2004-06-10 | California Institute Of Technology | Carbon-based compositions for reversible hydrogen storage |
JP2011213583A (en) * | 2010-03-15 | 2011-10-27 | Sekisui Chem Co Ltd | Method for producing graphite intercalation compound |
CN102862976A (en) * | 2012-08-25 | 2013-01-09 | 华南理工大学 | Method for preparing functionalized graphene and composite material of functionalized graphene |
US20130137894A1 (en) * | 2011-11-30 | 2013-05-30 | Chang Gung University | Chemically-modified graphene and method for producing the same |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2919856B1 (en) | 2007-08-09 | 2010-03-12 | Centre Nat Rech Scient | GRAPHENE SOLUTIONS |
-
2015
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- 2015-02-16 WO PCT/JP2015/054162 patent/WO2015125740A1/en active Application Filing
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Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5082024A (en) * | 1973-11-13 | 1975-07-03 | ||
JPH0585957A (en) * | 1991-02-22 | 1993-04-06 | Bayer Ag | Process for preparing 2,2-bis(3,4-dimethylphenyl)propane |
JPH08148148A (en) * | 1994-11-24 | 1996-06-07 | Sony Corp | Manufacture of electrode material for nonaqueous electrolyte battery and nonaqueous electrolyte battery using the material thereby obtained |
JP2001502310A (en) * | 1996-10-04 | 2001-02-20 | トーマス・スワン・アンド・カンパニー・リミテツド | Alkylation and acylation reactions |
WO2004048259A1 (en) * | 2002-11-21 | 2004-06-10 | California Institute Of Technology | Carbon-based compositions for reversible hydrogen storage |
JP2011213583A (en) * | 2010-03-15 | 2011-10-27 | Sekisui Chem Co Ltd | Method for producing graphite intercalation compound |
US20130137894A1 (en) * | 2011-11-30 | 2013-05-30 | Chang Gung University | Chemically-modified graphene and method for producing the same |
CN102862976A (en) * | 2012-08-25 | 2013-01-09 | 华南理工大学 | Method for preparing functionalized graphene and composite material of functionalized graphene |
Non-Patent Citations (1)
Title |
---|
E.-K. CHOI ET AL.: "Strain-induced delamination of edge-grafted graphite", CHEM. COMMUN., vol. 48, no. 90, 2012, pages 11109 - 11111, XP055219800, ISSN: 1359-7345 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2020527534A (en) * | 2017-07-13 | 2020-09-10 | カーボン アップサイクリング テクノロジーズ インク.Carbon Upcycling Technologies Inc. | Mechachemical process for producing exfoliated nanoparticles |
JP7372239B2 (en) | 2017-07-13 | 2023-10-31 | カーボン アップサイクリング テクノロジーズ インク. | Mechanochemical process to produce exfoliated nanoparticles |
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KR20160122693A (en) | 2016-10-24 |
JPWO2015125740A1 (en) | 2017-03-30 |
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