WO2013122045A1 - 薄片化黒鉛の製造方法及び薄片化黒鉛 - Google Patents
薄片化黒鉛の製造方法及び薄片化黒鉛 Download PDFInfo
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- WO2013122045A1 WO2013122045A1 PCT/JP2013/053247 JP2013053247W WO2013122045A1 WO 2013122045 A1 WO2013122045 A1 WO 2013122045A1 JP 2013053247 W JP2013053247 W JP 2013053247W WO 2013122045 A1 WO2013122045 A1 WO 2013122045A1
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- C01B32/225—Expansion; Exfoliation
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- the present invention relates to a method for producing exfoliated graphite by exfoliating graphite or primary exfoliated graphite and exfoliated graphite obtained thereby.
- Graphite is a laminated body in which many graphenes are laminated. By exfoliating graphite, exfoliated graphite having fewer graphene layers than graphite can be obtained. The exfoliated graphite is expected to be applied to conductive materials and heat conductive materials.
- Patent Document 1 discloses a method for producing graphene in which a polymer is grafted by co-polymerizing exfoliated graphene and a radical polymerizable monomer.
- the conventional method has a problem that graphene or exfoliated graphite is obtained as a powder and is difficult to handle.
- An object of the present invention is to provide a method for producing exfoliated graphite that can be handled relatively easily by exfoliating graphite without going through a complicated process, and exfoliated graphite obtained thereby.
- the method for producing exfoliated graphite according to the present invention includes a step of preparing a composition containing graphite or primary exfoliated graphite and a polymer, wherein the polymer is fixed to the graphite or primary exfoliated graphite; And pyrolyzing the polymer contained therein to peel off the graphite or primary exfoliated graphite and to remove the polymer by pyrolysis.
- the polymer is thermally decomposed, and the polymer disappears to obtain exfoliated graphite.
- the present invention includes the following first and second inventions that differ in the manner in which the polymer is immobilized with graphite or primary exfoliated graphite.
- the polymer in the step of preparing the composition, in the composition in which the polymer is fixed to graphite or primary exfoliated graphite, the polymer is grafted to the graphite or primary exfoliated graphite.
- exfoliated graphite having a large specific surface area is easily obtained because the polymer in the composition having a structure in which the polymer is grafted to graphite or primary exfoliated graphite is thermally decomposed. Can be provided. This is presumably because, during the thermal decomposition of the polymer, the stress during the thermal decomposition of the polymer acts on the grafting point where the polymer is grafted to graphite or primary exfoliated graphite, and the graphene is peeled off efficiently.
- the exfoliated graphite obtained by the production method of the first invention not only the interlayer distance between graphenes is increased and the specific surface area is increased, but also the central part has a graphite structure, and the edge part is a flake. Because of the structure, the handling is easier than the exfoliated alloy obtained by the conventional manufacturing method.
- the process of preparing the said composition prepares the mixture containing the said graphite or primary exfoliated graphite, and a radically polymerizable monomer. And polymerizing the radical polymerizable monomer contained in the mixture to produce a polymer in which the radical polymerizable monomer is polymerized in the mixture, and grafting the polymer onto the graphite or primary exfoliated graphite. The process of making it into.
- the polymer in the step of preparing the composition, in the presence of the graphite or primary exfoliated graphite, the polymer is 50 ° C. or higher and 400 ° C. or lower.
- the polymer is grafted to the graphite or primary exfoliated graphite by heating to a temperature in the temperature range.
- the composition in the step of preparing the composition, further includes a thermally decomposable foaming agent.
- a thermally decomposable foaming agent in the step of preparing the composition, graphite or primary exfoliated graphite can be more effectively exfoliated. Therefore, the specific surface area of the exfoliated graphite obtained can be further increased.
- the thermally decomposable foaming agent is selected from the group consisting of compounds having structures represented by the following formulas (1) to (4). At least one selected thermal foaming agent.
- the heat contained in the composition Decomposable foaming agent is thermally decomposed.
- the step of generating the polymer and grafting the polymer to the graphite or primary exfoliated graphite is pyrolyzed.
- the step of generating the polymer and grafting the polymer onto the graphite or primary exfoliated graphite Is performed by polymerizing the radical polymerizable monomer contained in the mixture by heating the mixture.
- both the polymerization of the radical polymerizable monomer and the polymerization of the polymer can be performed only by heating the mixture. Therefore, graphite or primary exfoliated graphite can be more easily exfoliated.
- the radical polymerizable monomer is a styrene monomer or glycidyl methacrylate. Since the styrene monomer is inexpensive, the production cost of exfoliated graphite can be reduced.
- a styrene monomer can be suitably used as the radical polymerizable monomer.
- a polymer of glycidyl methacrylate is preferably used as the polymer.
- the exfoliated graphite according to the first invention is exfoliated graphite obtained by the method for producing exfoliated graphite of the first invention.
- the composition in which the polymer is fixed to the graphite or primary exfoliated graphite is graphite or primary exfoliated graphite and the first.
- the method for producing exfoliated graphite according to the second invention includes graphite or primary exfoliated graphite and a first polymer adsorbed on the graphite, and the first polymer is adsorbed on the graphite or primary exfoliated graphite.
- the first polymer disappears by thermal decomposition, and exfoliated graphite can be obtained. Therefore, exfoliated graphite having a large specific surface area can be easily obtained.
- the first polymer is a polymer having adsorptivity to the graphite, and preferably polyvinyl acetate, polybutyral, and polypropylene. At least one polymer selected from the group consisting of glycols.
- the composition in the step of preparing the composition, further includes a thermally decomposable foaming agent.
- the graphite can be more effectively exfoliated. Therefore, the specific surface area of the exfoliated graphite obtained can be further increased.
- the thermally decomposable foaming agent is selected from the group consisting of compounds having structures represented by the following formulas (1) to (4). At least one selected thermal foaming agent.
- the pyrolyzable foaming agent contained in the composition is pyrolyzed in the step of exfoliating the graphite or primary exfoliated graphite.
- the exfoliated graphite obtained by the method for producing exfoliated graphite of the second invention is used as the primary exfoliated graphite, that is, A composition comprising primary exfoliated graphite and a first polymer, wherein the primary exfoliated graphite is adsorbed on the first polymer, is prepared, and the composition is heated again to a temperature equal to or higher than the thermal decomposition temperature of the first polymer. To do. In this case, exfoliated graphite having a larger specific surface area can be obtained.
- the exfoliated graphite thus obtained is used as the primary exfoliated graphite, and the first polymer is adsorbed on the primary exfoliated graphite to prepare a composition,
- the heating step of heating the composition to a temperature equal to or higher than the thermal decomposition temperature of the first polymer to thermally decompose the first polymer to obtain exfoliated graphite is further repeated. Thereby, the specific surface area can be further increased.
- exfoliated graphite having a larger specific surface area can be obtained.
- the step of preparing the composition includes the step of preparing a mixture containing graphite and a radical polymerizable monomer, and the mixture Polymerizing the radically polymerizable monomer contained therein to form a second polymer in which the radically polymerizable monomer is polymerized in the mixture and grafting the second polymer onto the graphite; A third heating step in which the mixture is heated to a temperature equal to or higher than a thermal decomposition temperature of the second polymer to thermally decompose the second polymer, and primary exfoliation obtained in the third heating step. Mixing the graphite and the first polymer to obtain the composition. In this case, exfoliated graphite having a larger specific surface area can be obtained.
- Styrene or glycidyl methacrylate can be preferably used as the radical polymerizable monomer.
- the exfoliated graphite of the second invention is obtained by the exfoliated graphite manufacturing method according to the present invention, and can provide exfoliated graphite having a large specific surface area and easy handling.
- the exfoliated graphite according to the present invention includes graphite or primary exfoliated graphite and a polymer, and the polymer in the composition in which the polymer is fixed to the graphite or primary exfoliated graphite is thermally decomposed to remove the polymer. It was obtained by this.
- exfoliated graphite having a large specific surface area is easily provided because the polymer in the composition having a structure in which the polymer is fixed to graphite or primary exfoliated graphite is thermally decomposed. can do. This is presumably because, during the thermal decomposition of the polymer, the stress during the thermal decomposition of the polymer acts on the portion where the polymer is fixed to graphite or primary exfoliated graphite, and the graphene is efficiently peeled off.
- the exfoliated graphite obtained by the production method of the present invention not only increases the interlayer distance between graphenes and increases the specific surface area, but also has a graphite structure at the center part and the edge part becomes exfoliated. Therefore, it is easier to handle than the exfoliated alloy obtained by the conventional manufacturing method.
- FIG. 1 is a diagram showing a TG / DTA measurement result of azodicarbonamide (ADCA) used in Example 1.
- FIG. 2 is a diagram showing TG / DTA measurement results of expanded graphite as a raw material used in Examples 1 to 5.
- FIG. 3 is a diagram showing a TG / DTA measurement result of exfoliated graphite obtained in Example 1.
- FIG. 4 is a diagram showing a TG / DTA measurement result of exfoliated graphite obtained in Example 2.
- FIG. 5 is a diagram showing a TG / DTA measurement result of exfoliated graphite obtained in Example 3.
- FIG. 6 is a diagram showing a TG / DTA measurement result of exfoliated graphite obtained in Example 4.
- FIG. 1 is a diagram showing a TG / DTA measurement result of azodicarbonamide (ADCA) used in Example 1.
- FIG. 2 is a diagram showing TG / DTA measurement results of expanded graphite as a raw material
- FIG. 7 is a diagram showing a TG / DTA measurement result of exfoliated graphite obtained in Example 5.
- FIG. 8 is an XRD spectrum of exfoliated graphite obtained in Example 2.
- FIG. 9 is an XRD spectrum of exfoliated graphite obtained in Example 4.
- FIG. 10 is a photograph of the exfoliated graphite used in Examples 1 to 5 taken with a scanning electron microscope (SEM).
- FIG. 11 is a photograph of the exfoliated graphite obtained in Example 1 taken with a scanning electron microscope (SEM).
- FIG. 12 is a photograph of the exfoliated graphite obtained in Example 2 taken with a scanning electron microscope (SEM).
- FIG. 13 is a photograph of the exfoliated graphite obtained in Example 3 taken with a scanning electron microscope (SEM).
- FIG. 14 is a photograph of the exfoliated graphite obtained in Example 4 taken with a scanning electron microscope (SEM).
- FIG. 15 is a photograph of the exfoliated graphite obtained in
- the method for producing exfoliated graphite according to the present invention comprises the steps of preparing a composition comprising graphite or primary exfoliated graphite and a polymer, wherein the polymer is fixed to the graphite or primary exfoliated graphite, and A step of exfoliating graphite or primary exfoliated graphite by thermally decomposing the contained polymer.
- the polymer is thermally decomposed and finally removed. Therefore, the obtained exfoliated graphite does not contain a polymer.
- the composition includes graphite or primary exfoliated graphite and a polymer in which a radical polymerizable monomer is polymerized, and the polymer is grafted to graphite or primary exfoliated graphite.
- a radical polymerizable monomer is polymerized, and the polymer is grafted to graphite or primary exfoliated graphite.
- the above graphite is a laminate of a plurality of graphene layers, and for example, natural graphite, artificial graphite, expanded graphite and the like can be used.
- expanded graphite can be used as the graphite.
- Expanded graphite can be easily peeled off because the interlayer of the graphene layer is larger than that of normal graphite. Therefore, exfoliated graphite can be easily produced by using expanded graphite as the graphite.
- the number of graphene layers is about 100,000 to 1,000,000, and the specific surface area by BET is 20 m 2 / g or less.
- the exfoliated graphite obtained by the first invention means one having a graphene lamination number of 100 or less and a specific surface area by BET of 40 m 2 / g or more and 2500 m 2 / g or less.
- primary exfoliated graphite may be used instead of graphite as a raw material.
- the primary exfoliated graphite widely includes exfoliated graphite obtained by exfoliating graphite by various methods described later in addition to exfoliated graphite obtained by exfoliating graphite by the production method of the first invention. Shall be.
- a composition containing primary exfoliated graphite and a first polymer, in which the first polymer is adsorbed on the primary exfoliated graphite is prepared. Since primary exfoliated graphite is obtained by exfoliating graphite, the specific surface area may be larger than that of graphite.
- First method In the first method, first, a mixture containing graphite or primary exfoliated graphite and a radical polymerizable monomer is prepared. Next, the radical polymerizable monomer contained in the mixture is polymerized to produce a polymer in which the radical polymerizable monomer is polymerized in the mixture, and the polymer is grafted to graphite or primary exfoliated graphite.
- a composition containing graphite or primary exfoliated graphite and a radical polymerizable monomer is prepared.
- the radical polymerizable monomer is not particularly limited as long as it is a monomer having a functional group generally known as radical polymerizable, and a monomer having an appropriate radical polymerizable functional group can be used.
- examples of the radical polymerizable monomer include styrene, methyl ⁇ -ethyl acrylate, methyl ⁇ -benzyl acrylate, methyl ⁇ - [2,2-bis (carbomethoxy) ethyl] acrylate, dibutyl itaconate, and itaconic acid.
- ⁇ -substituted acrylic acid ester consisting of dimethyl, dicyclohexyl itaconate, ⁇ -methylene- ⁇ -valerolactone, ⁇ -methylstyrene, ⁇ -acetoxystyrene, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, hydroxyethyl methacrylate, Vinyl monomers having a glycidyl group or hydroxyl group such as hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl methacrylate; allylamine, diethylaminoethyl (meth) acrylate, dimethyl Vinyl monomers having an amino group such as aminoethyl (meth) acrylate; methacrylic acid, maleic anhydride, maleic acid, itaconic acid, acrylic acid, crotonic acid, 2-acryloyloxyethyl succinate, 2-methacryloyloxy
- the blending ratio of the graphite and the radical polymerizable monomer is not particularly limited, but is preferably 1: 1 to 1: 100 by weight. By making the said mixture ratio into the said range, the said graphite or primary exfoliated graphite can be peeled effectively, and exfoliated graphite can be obtained much more effectively.
- a composition further including a thermally decomposable foaming agent that generates a gas upon thermal decomposition is prepared.
- the graphite or primary exfoliated graphite can be more effectively exfoliated by heating described later.
- the thermal decomposable foaming agent is not particularly limited as long as it is a compound that spontaneously decomposes by heating and generates a gas upon decomposition.
- the thermally decomposable foaming agent include foaming agents such as azocarboxylic acid-based, diazoacetamide-based, azonitrile compound-based, benzenesulfohydrazine-based or nitroso compound-based which generate nitrogen gas during decomposition, carbon monoxide during decomposition, A foaming agent that generates carbon dioxide, methane, aldehyde, or the like can be used.
- the above pyrolyzable foaming agents may be used alone or in combination of a plurality of types of foaming agents.
- thermally decomposable foaming agent azodicarbonamide (ADCA) having a structure represented by the following formula (1), or a foaming agent having a structure represented by the following formulas (2) to (4): Can be used.
- ADCA azodicarbonamide
- foaming agents decompose spontaneously by heating, and generate nitrogen gas during decomposition.
- the thermal decomposition temperature of the thermally decomposable foaming agent is not particularly limited, and may be lower or higher than the temperature at which the radical polymerizable monomer spontaneously starts polymerization.
- the thermal decomposition temperature of ADCA having the structure represented by the above formula (1) is 210 ° C.
- the temperature at which styrene spontaneously starts polymerization is higher than 150 ° C. High temperature.
- the thermal decomposition starting temperatures of the foaming agents having the structures represented by the above formulas (2) to (4) are 88 ° C., 96 ° C., and 110 ° C. in this order, which are from the temperature of 150 ° C. at which styrene spontaneously starts polymerization. Is also a low temperature.
- the mixing ratio of the graphite or primary exfoliated graphite and the thermally decomposable foaming agent is not particularly limited, but the pyrolyzable foaming agent is 100 parts by weight to 300 parts by weight with respect to 100 parts by weight of the graphite or primary exfoliated graphite. It is preferable to blend partly.
- the compounding quantity of the said heat decomposable foaming agent into the said range, the said graphite or primary exfoliated graphite can be peeled off more effectively, and exfoliated graphite can be obtained effectively.
- the method for preparing the composition is not particularly limited, and examples thereof include a method in which the radical polymerizable monomer is used as a dispersion medium and the graphite or primary exfoliated graphite is dispersed in the radical polymerizable monomer.
- the composition further containing the thermally decomposable foaming agent can be prepared by dissolving or dispersing the thermally decomposable foaming agent in the radical polymerizable monomer.
- the radical polymerizable monomer generates free radicals, whereby the radical polymerizable monomer undergoes radical polymerization, thereby generating a polymer in which the radical polymerizable monomer is polymerized.
- the graphite contained in the composition is a laminate of a plurality of graphene layers and thus has radical trapping properties. Therefore, when the radically polymerizable monomer is co-polymerized in the composition containing the graphite or primary exfoliated graphite, the free radicals are adsorbed on the end and surface of the graphene layer of the graphite or primary exfoliated graphite. . Therefore, the polymer having the free radicals or the radical polymerizable monomer generated at the time of polymerization is grafted to the end portion and the surface of the graphene layer of the graphite or primary exfoliated graphite.
- Examples of a method for polymerizing the radical polymerizable monomer contained in the composition include a method in which the composition is heated to a temperature higher than the temperature at which the radical polymerizable monomer spontaneously starts polymerization. By heating the composition to the temperature or higher, free radicals can be generated in the radical polymerizable monomer contained in the composition. Thereby, the polymerization and grafting described above can be carried out.
- both the polymerization of the radical polymerizable monomer and the thermal decomposition of the polymer described later can be performed only by heating the composition. . Accordingly, the graphite or primary exfoliated graphite can be more easily separated.
- the heating method is not particularly limited as long as the composition can be heated to the temperature or higher, and the composition can be heated by an appropriate method and apparatus. Moreover, in the case of the said heating, you may heat without sealing, ie, a normal pressure.
- the temperature may be further maintained for a certain period of time after heating to a temperature equal to or higher than the temperature at which the radical polymerizable monomer spontaneously starts polymerization.
- the time for maintaining the temperature near the above temperature is preferably in the range of 0.5 to 5 hours, although it depends on the kind and amount of the radical polymerizable monomer to be used.
- the step of thermally decomposing the polymer is performed by heating the composition to the thermal decomposition temperature of the polymer.
- the polymer contained in the composition and the polymer or the like grafted on the end portion and surface of the graphene layer of the graphite or primary exfoliated graphite are thermally decomposed.
- the polymer is heated until it is thermally decomposed and removed.
- the thermal decomposition temperature of the polymer means a decomposition end point temperature dependent on TGA measurement. For example, when the polymer is polystyrene, the thermal decomposition temperature of the polymer is about 350 ° C.
- exfoliated graphite can be obtained by separating the graphene layers of the graphite or primary exfoliated graphite.
- exfoliated graphite is a graphene laminate after exfoliation obtained by exfoliating the original graphite or primary exfoliated graphite, and the ratio is higher than that of the original graphite or primary exfoliated graphite.
- the heating method is not particularly limited as long as it can be heated to the thermal decomposition temperature of the polymer, and the composition can be heated by an appropriate method and apparatus. Moreover, in the case of the said heating, you may heat without sealing, ie, a normal pressure. Therefore, exfoliated graphite can be produced inexpensively and easily.
- the temperature may be further maintained for a certain time after heating to a temperature equal to or higher than the thermal decomposition temperature of the polymer.
- the time for maintaining the temperature near the above temperature is preferably in the range of 0.5 to 5 hours, although it depends on the kind and amount of the radical polymerizable monomer to be used.
- the heat treatment in the step of producing the polymer and the heat treatment in the step of thermally decomposing the polymer described later are the same.
- the method and apparatus may be used continuously.
- the thermally decomposable foaming agent is contained in the composition when the composition is heated to the thermal decomposition temperature of the thermally decomposable foaming agent. Pyrolysis with On the other hand, the thermally decomposable foaming agent generates gas and foams during thermal decomposition. At this time, when the pyrolyzable foaming agent is thermally decomposed in the vicinity of the graphene layer of the graphite or primary exfoliated graphite, the gas generated by the pyrolysis enters between the graphene layers, and the interval between the graphene layers is widened.
- graphite or primary exfoliated graphite can be more effectively exfoliated by using the radically polymerizable monomer and / or the polymer and the thermally decomposable foaming agent in combination.
- the reason why graphite or primary exfoliated graphite can be more effectively exfoliated by such a method is not clear, the following reasons are conceivable.
- the radical polymerizable monomer when the radical polymerizable monomer generates a free radical, the polymer having the free radical generated during polymerization or the radical polymerizable monomer is an end of the graphene layer of the graphite or primary exfoliated graphite. And graft onto the surface.
- the thermally decomposable foaming agent since the thermally decomposable foaming agent has a property of having high affinity with radicals, it is attracted to free radicals trapped in the graphene layer of the graphite or primary exfoliated graphite in the composition. Therefore, the thermally decomposable foaming agent is easily thermally decomposed in the vicinity of the graphene sheet laminated surface of graphite or primary exfoliated graphite. Therefore, by the thermal decomposition of the thermally decomposable foaming agent, a peeling force can be effectively applied between the graphene layers of the graphite or primary exfoliated graphite.
- the thermal decomposition of the thermally decomposable foaming agent is not necessarily performed in the process of thermally decomposing the polymer.
- the thermal decomposition temperature of the thermally decomposable foaming agent is lower than the temperature at which the radical polymerizable monomer spontaneously starts polymerization, the radical polymerizable monomer is heated by heating in the step of producing the polymer.
- the thermally decomposable foaming agent may be thermally decomposed.
- the thermal decomposition of the thermally decomposable foaming agent may be performed before the polymerization of the radical polymerizable monomer, after the polymerization, or simultaneously with the polymerization.
- the temperature may be maintained for a certain time after heating to a temperature equal to or higher than the thermal decomposition temperature of the thermally decomposable foaming agent.
- the time for maintaining the temperature near the above temperature is preferably in the range of 0.5 to 5 hours, although it depends on the kind and amount of the thermally decomposable foaming agent to be used.
- a polymer radical generated by thermally decomposing a polymer is obtained by heating the polymer obtained in advance to the specific temperature range in the presence of graphite or primary exfoliated graphite. It can be grafted directly to graphite or primary exfoliated graphite.
- an appropriate pyrolytic radical-generating polymer can be used as the polymer that can be used in the second method.
- a polymer of a vinyl group-containing monomer is preferably used.
- examples of such a vinyl group-containing monomer include monomers such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and benzyl acrylate.
- Examples of the polymer formed by polymerizing the vinyl group-containing monomer include (meth) acrylic acid alkyl ester, polypropylene, polyvinyl phenol, polyphenylene sulfide, polyphenylene ether, and the like.
- polymers containing halogen elements such as chlorine such as polyvinyl chloride, chlorinated vinyl chloride resin, ethylene fluoride resin, vinylidene fluoride resin, and vinylidene chloride resin
- halogen elements such as chlorine
- polyvinyl chloride, chlorinated vinyl chloride resin, ethylene fluoride resin, vinylidene fluoride resin, and vinylidene chloride resin can be used.
- Ethylene vinyl acetate copolymer (EVA), polyvinyl acetal, polyvinyl pyrrolidone and copolymers thereof can also be used.
- Polymers obtained by cationic polymerization such as polyisobutylene and polyalkylene ether can also be used.
- Polyurethane, epoxy resin, modified silicone resin, silicone resin, etc. formed by crosslinking oligomers can also be used.
- Polyallylamine may be used, and in that case, an amino group can be grafted to graphite or primary exfoliated graphite.
- Polyvinylphenol or polyphenols may be used, in which case the phenolic OH can be grafted to graphite or primary exfoliated graphite.
- the phosphate group can be grafted.
- condensation polymers such as polyester and polyamide may be used.
- the decomposition product is grafted although the radical concentration obtained at the decomposition temperature is low.
- a homopolymer of glycidyl methacrylate, polystyrene, polyvinyl acetate, polypropylene glycol, polybutyral and the like are preferably used.
- graphite or primary exfoliated graphite can be more effectively exfoliated.
- the blending ratio of the graphite or primary exfoliated graphite and the polymer is not particularly limited, but it is desirable that the weight ratio is 1: 5 to 1:20. By setting the blending ratio within this range, graphite or primary exfoliated graphite can be more effectively exfoliated and exfoliated graphite can be obtained effectively.
- the step of preparing the composition in the step of preparing the composition, it is preferable to further include a thermally decomposable foaming agent in the composition.
- the graphite or primary exfoliated graphite can be more effectively exfoliated by heating that causes thermal decomposition of the polymer described later.
- the thermally decomposable foaming agent that can be used is the same as in the first method. Therefore, it is preferable to use a foaming agent having a structure represented by the above formulas (1) to (4).
- the blending ratio of graphite or primary exfoliated graphite and the pyrolyzable foaming agent is not particularly limited, but the pyrolyzable foaming agent is 100 to 300 per 100 parts by weight of graphite or primary exfoliated graphite. It is preferable to mix
- a specific method for preparing the composition is not limited. For example, a method in which the polymer and graphite or primary exfoliated graphite are put in an appropriate solvent or dispersion medium and heated is mentioned. It is done.
- the polymer is grafted to graphite or primary exfoliated graphite by the above heating.
- the heating temperature is preferably in the range of 50 ° C to 400 ° C. By setting it within this temperature range, the polymer can be effectively grafted onto the graphite. Thereby, graphite or primary exfoliated graphite can be more effectively exfoliated. The reason for this is considered as follows.
- the composition may be heated to a temperature higher than the thermal decomposition temperature of the polymer. More specifically, heating is performed at a temperature equal to or higher than the thermal decomposition temperature of the polymer. In particular, the polymer is further burned off by further heating above the pyrolysis temperature. Thereby, exfoliated graphite containing no polymer can be obtained.
- the thermal decomposition temperature of polystyrene is about 280 ° C. to 400 ° C.
- the thermal decomposition temperature of polyglycidyl methacrylate is about 250 ° C. to 350 ° C.
- the thermal decomposition temperature of polybutyral is about 250 ° C. to 560 ° C. in the atmosphere. It is.
- exfoliated graphite can be obtained by thermal decomposition of the polymer is considered to be due to the above-mentioned reason. That is, it is considered that when the polymer grafted on the graphite is baked, a large stress acts on the graft point, thereby increasing the distance between the graphenes.
- the heating for polymerizing the radical polymerizable monomer and the thermal decomposition of the polymer may be carried out continuously in the same heating step, but in the second method, Alternatively, a heating step for grafting the polymer onto graphite or primary exfoliated graphite and a heating step for pyrolyzing the polymer may be performed continuously.
- the exfoliated graphite is used as the primary exfoliated graphite of the raw material of the first method. By repeating the method once or more, exfoliated graphite having a larger specific surface area can be obtained.
- the obtained exfoliated graphite is used as the primary exfoliated graphite of the raw material in the second method.
- the second method and thermal decomposition of the polymer may be carried out to obtain exfoliated graphite. Even in that case, exfoliated graphite having a larger specific surface area can be obtained.
- the exfoliated graphite is used as a primary exfoliated graphite as a raw material of the second method, and hereinafter the same as the second method. In this way, exfoliated graphite may be obtained.
- the exfoliated graphite is used as the primary exfoliated graphite of the raw material of the first method, and hereinafter the same as the first method.
- the composition may be prepared, and the polymer may be thermally decomposed by heating to obtain exfoliated graphite.
- the exfoliated graphite obtained by the production method of the first invention is further used as primary exfoliated graphite as a raw material, and the exfoliation by the production method of the first invention is repeated one or more times. It is possible to obtain exfoliated graphite having a larger specific surface area.
- the flakes are obtained by pyrolyzing the polymer in the composition having a structure in which the polymer in which the radical polymerizable monomer is polymerized as described above is grafted to graphite or primary exfoliated graphite.
- Graphite has been obtained.
- the exfoliated graphite obtained by the method for producing exfoliated graphite of the first invention may be used as a raw material, and the exfoliation method of graphite other than the exfoliated graphite of the first invention may be further performed.
- exfoliated graphite of 1st invention may implement the manufacturing method of exfoliated graphite of 1st invention by using the primary exfoliated graphite obtained by the exfoliation method of other graphite as a raw material. Even in that case, exfoliated graphite having a larger specific surface area can be obtained.
- a method for exfoliating graphite by electrochemical treatment or an adsorption-pyrolysis method can be used.
- the adsorption-pyrolysis method is a method in which graphite or primary exfoliated graphite is adsorbed with a polymer having a property of adsorbing to graphite such as polyvinyl acetate, and then the polymer is thermally decomposed by heating. .
- stress at the time of thermal decomposition is applied to the adsorption point of the polymer with respect to graphene, the distance between the graphene layers of graphite can be increased as in the case of the manufacturing method of the first invention.
- the exfoliated graphite of the first invention includes graphite or primary exfoliated graphite and a polymer, and thermally decomposes the polymer in the composition in which the polymer is fixed to the graphite or primary exfoliated graphite, thereby removing the polymer. It is obtained by this.
- the exfoliated graphite of the first invention does not substantially contain the polymer used for peeling.
- the exfoliated graphite obtained by the production method of the first invention has a feature that it is relatively difficult to scatter compared to exfoliated graphite obtained by a conventionally known production method.
- exfoliated graphite having a specific surface area of 40 m 2 / g or more can be obtained. Furthermore, exfoliated graphite having a specific surface area of 100 m 2 / g or more can be obtained. Furthermore, exfoliated graphite having a specific surface area of 180 m 2 / g or more can be obtained.
- the exfoliated graphite obtained by the first invention has a large specific surface area, the exfoliated graphite of the first invention is excellent in physical characteristics such as elastic modulus and electrical characteristics such as conductivity. Therefore, for example, by dispersing the exfoliated graphite of the first invention in a resin, a resin composite material having excellent rigidity and combustion resistance can be obtained.
- exfoliated graphite obtained by the first invention can be further exfoliated by a conventionally known exfoliation method to obtain exfoliated graphite having a larger specific surface area. Since the exfoliated graphite obtained by the first invention is thinner than normal graphite and has a larger specific surface area, the exfoliated graphite can be more efficiently used by using the exfoliated graphite in a conventional peeling method. Graphite can be peeled off.
- the composition which contains graphite or primary exfoliated graphite and a 1st polymer as a raw material, and the 1st polymer is adsorbed by graphite or primary exfoliated graphite is prepared.
- the above graphite is a laminate of a plurality of graphene layers, and for example, natural graphite, artificial graphite, expanded graphite and the like can be used.
- expanded graphite can be used as the graphite.
- Expanded graphite can be easily peeled off because the interlayer of the graphene layer is larger than that of normal graphite. Therefore, exfoliated graphite can be easily produced by using expanded graphite as the graphite.
- the number of graphene layers is about 100,000 to 1,000,000, and the specific surface area by BET is 20 m 2 / g or less.
- the exfoliated graphite obtained by the second invention means that the number of graphene layers is 100 or less and the specific surface area by BET is 40 m 2 / g or more and 2000 m 2 / g or less.
- primary exfoliated graphite may be used instead of graphite as a raw material.
- the primary exfoliated graphite widely includes exfoliated graphite obtained by exfoliating graphite by various methods described later in addition to exfoliated graphite obtained by exfoliating graphite by the production method of the second invention. Shall be.
- a composition containing primary exfoliated graphite and a first polymer, in which the first polymer is adsorbed on the primary exfoliated graphite is prepared. Since primary exfoliated graphite is obtained by exfoliating graphite, the specific surface area may be larger than that of graphite.
- First polymer As the first polymer, various polymers that are adsorbed on graphite by sonication in a solvent suitable for dispersion of the polymer and the graphite can be used. Examples of such a polymer include thermally decomposable polymers such as polyvinyl acetate, polybutyral, and polypropylene glycol.
- the blending ratio of the graphite and the first polymer is not particularly limited, but it is desirable that the weight ratio is 1: 1 to 1: 100. By setting the blending ratio within this range, the exfoliation of graphite can be promoted more effectively.
- thermolytic foaming agent In the step of preparing the composition, preferably, a composition further containing a thermally decomposable foaming agent that generates a gas upon thermal decomposition is prepared.
- the composition further contains a thermally decomposable foaming agent when the composition is heated to the thermal decomposition temperature of the thermally decomposable foaming agent, the thermally decomposable foaming agent is thermally decomposed in the composition.
- the thermally decomposable foaming agent generates gas and foams during thermal decomposition.
- the pyrolyzable foaming agent when the pyrolyzable foaming agent is thermally decomposed in the vicinity of the graphene layer of the graphite or primary exfoliated graphite, the gas generated by the pyrolysis enters between the graphene layers, and the interval between the graphene layers is widened. Thereby, a peeling force is generated between the graphene layers, so that the graphite or primary exfoliated graphite can be further peeled. Therefore, the specific surface area of the exfoliated graphite obtained can be further increased by using the above pyrolyzable foaming agent.
- the thermal decomposable foaming agent is not particularly limited as long as it is a compound that spontaneously decomposes by heating and generates a gas upon decomposition.
- the thermally decomposable foaming agent include foaming agents such as azocarboxylic acid-based, diazoacetamide-based, azonitrile compound-based, benzenesulfohydrazine-based or nitroso compound-based which generate nitrogen gas during decomposition, carbon monoxide during decomposition, A foaming agent that generates carbon dioxide, methane, aldehyde, or the like can be used.
- the above pyrolyzable foaming agents may be used alone or in combination of a plurality of types of foaming agents.
- the thermally decomposable foaming agent includes azodicarbonamide (ADCA) having a structure represented by the formula (1) in the first invention and structures represented by the formulas (2) to (4).
- the foaming agent which has can be used. These foaming agents decompose spontaneously by heating, and generate nitrogen gas during decomposition.
- the thermal decomposition temperature of the thermally decomposable foaming agent is not particularly limited, and may be lower or higher than a temperature at which a radical polymerizable monomer, which is an optional component described later, spontaneously starts polymerization.
- the thermal decomposition temperature of ADCA having the structure represented by the above formula (1) is 210 ° C., and when the radical polymerizable monomer is styrene, the temperature at which styrene spontaneously starts polymerization is higher than 150 ° C. High temperature.
- the thermal decomposition starting temperatures of the foaming agents having the structures represented by the above formulas (2) to (4) are 88 ° C., 96 ° C., and 110 ° C. in this order, which are from the temperature of 150 ° C. at which styrene spontaneously starts polymerization. Is also a low temperature.
- the blending ratio of the graphite or primary exfoliated graphite and the thermally decomposable foaming agent is not particularly limited, but the pyrolyzable foaming agent is 100 parts by weight to 300 parts by weight with respect to 100 parts by weight of the graphite or primary exfoliated graphite. It is preferable to blend partly.
- the compounding quantity of the said heat decomposable foaming agent into the said range, the said graphite or primary exfoliated graphite can be peeled effectively and exfoliated graphite can be obtained effectively.
- the method for preparing the composition is not particularly limited.
- a method of dissolving or dispersing the above graphite and the first polymer in an appropriate solvent can be mentioned.
- a solvent tetrahydrofuran, methyl ethyl ketone, toluene, ethyl acetate or the like can be used.
- a thermally decomposable foaming agent may be further added and dispersed or dissolved in the solvent.
- a composition in which the first polymer is adsorbed on graphite or primary exfoliated graphite in a solvent is prepared as the above composition.
- the method for adsorbing the first polymer on graphite or primary exfoliated graphite is not particularly limited.
- a method of mixing graphite or primary exfoliated graphite with the first polymer in the above-described solvent can be used.
- ultrasonic treatment is performed in order for the first polymer to be effectively adsorbed by graphite or primary exfoliated graphite.
- the ultrasonic processing method is not particularly limited. For example, a method of irradiating an ultrasonic wave having an oscillation frequency of about 100 W and an oscillation frequency of about 28 kHz using an appropriate ultrasonic processing apparatus can be used.
- the sonication time is not particularly limited as long as it is longer than the time required for the first polymer to be adsorbed on graphite.
- it is preferably maintained for 30 minutes, 60 minutes, more preferably about 120 minutes.
- the adsorption of the first polymer is considered to be due to the interaction between the surface energy of graphite and the first polymer.
- the said composition is heated to the temperature more than the thermal decomposition of a 1st polymer after the process which prepared the said composition.
- exfoliated graphite having a specific surface area of 40 m 2 / g or more can be obtained. This is due to the fact that the first polymer adsorbed on the graphene of graphite is thermally decomposed and peeled off due to the stress when it disappears.
- exfoliated graphite having a specific surface area of 100 m 2 / g or more can be obtained.
- the heating temperature in the heating step may be equal to or higher than the thermal decomposition temperature of the first polymer, and the heating time may be a time that can sufficiently thermally decompose the first polymer, and is 30 minutes to 300 minutes. It should be about. Within this heating time range, the first polymer can be sufficiently pyrolyzed to obtain exfoliated graphite according to the second invention. In the second invention, the first polymer is removed by thermal decomposition.
- the thermally decomposable foaming agent may be thermally decomposed at a temperature lower or higher than the thermal decomposition temperature by the polymer in the heating process. That is, when the thermal decomposition temperature of the thermal decomposable foaming agent is lower than the thermal decomposition temperature of the first polymer, the thermal decomposable foaming agent is thermally decomposed at a temperature lower than the thermal decomposition temperature of the polymer. When the thermal decomposition temperature of the thermal decomposable foaming agent is higher than the thermal decomposition temperature of the polymer, the thermal decomposable foaming agent may be thermally decomposed by heating to a temperature higher than the heating temperature in the heating step. In any case, exfoliated graphite having a larger specific surface area can be obtained by foaming due to thermal decomposition of the thermally decomposable foaming agent.
- exfoliated graphite obtained by the heating step as described above may be used as primary exfoliated graphite as a raw material.
- the step of preparing a composition containing primary exfoliated graphite and the first polymer and having the first polymer adsorbed on the primary exfoliated graphite and the heating step are performed again.
- exfoliated graphite having a larger specific surface area can be obtained.
- the exfoliated graphite thus obtained may be used as the primary exfoliated graphite of the raw material, and the adsorption and heating steps may be further repeated. In that case, exfoliated graphite having a larger specific surface area may be obtained.
- primary exfoliated graphite obtained by the heating step may be used for further exfoliation treatment.
- Examples of such a method include a method further comprising the following steps.
- a second polymer in which the radical polymerizable monomer is polymerized in the mixture is generated, and the second polymer is converted into the exfoliated graphite.
- the step of grafting By polymerizing the radical polymerizable monomer contained in the mixture, a second polymer in which the radical polymerizable monomer is polymerized in the mixture is generated, and the second polymer is converted into the exfoliated graphite. The step of grafting.
- a second heating step in which the mixture is heated to a temperature above which the second polymer is thermally decomposed to thermally decompose the second polymer to obtain exfoliated graphite.
- the radical polymerizable monomer is not particularly limited as long as it is a monomer having a functional group generally known as radical polymerizable, and a monomer having an appropriate radical polymerizable functional group similar to the first invention can be used. .
- the blending ratio of the exfoliated graphite and the radical polymerizable monomer is not particularly limited, but is preferably 1: 1 to 1: 100 by weight. By making the said mixture ratio into the said range, the said exfoliated graphite can be peeled further and exfoliated graphite with a still larger specific surface area can be obtained.
- the step of preparing the mixture is not particularly limited, and the obtained exfoliated graphite and the radical polymerizable monomer may be mixed.
- a method in which the radical polymerizable monomer is used as a dispersion medium and the exfoliated graphite is dispersed in the radical polymerizable monomer can be used.
- the composition further containing the thermally decomposable foaming agent can be prepared by dissolving or dispersing the thermally decomposable foaming agent in the radical polymerizable monomer.
- a third heating step for polymerizing the radical polymerizable monomer to generate a second polymer in which the radical polymerizable monomer is polymerized in the composition is performed.
- the heating temperature may be any temperature at which the radical polymerizable monomer is spontaneously polymerized. Therefore, what is necessary is just to select heating temperature according to the kind of radically polymerizable monomer to be used.
- the temperature in the case of styrene, the temperature may be 110 ° C. to 150 ° C., and in the case of glycidyl methacrylate, the temperature may be 320 ° C. to 350 ° C.
- the heating time is not particularly limited as long as the radical polymerizable monomer is sufficiently polymerized and grafted onto exfoliated graphite. The heating time is usually about 30 minutes to 300 minutes.
- the radical polymerizable monomer generates free radicals, whereby the radical polymerizable monomer undergoes radical polymerization, thereby generating a second polymer in which the radical polymerizable monomer is polymerized.
- the exfoliated graphite has a radical trapping property because it is a laminate of a plurality of graphene layers. Therefore, when the radical polymerizable monomer is co-polymerized in the composition containing the exfoliated graphite, the free radicals are adsorbed on the end portion and the surface of the graphene layer. Accordingly, the second polymer or the radical polymerizable monomer having the free radical generated during the polymerization is grafted to the end portion and the surface of the graphene layer of the exfoliated graphite.
- Examples of a method for polymerizing the radical polymerizable monomer contained in the composition include a method in which the composition is heated to a temperature higher than the temperature at which the radical polymerizable monomer spontaneously starts polymerization. By heating the composition to the temperature or higher, free radicals can be generated in the radical polymerizable monomer contained in the composition. Thereby, the polymerization and grafting described above can be carried out.
- both the polymerization of the radical polymerizable monomer and the thermal decomposition of the second polymer described later are performed only by heating the composition. be able to.
- the heating method is not particularly limited as long as the composition can be heated to the temperature or higher, and the composition can be heated by an appropriate method and apparatus. Moreover, in the case of the said heating, you may heat without sealing, ie, a normal pressure.
- the temperature may be further maintained for a certain time after heating to a temperature equal to or higher than a temperature at which the radical polymerizable monomer spontaneously starts polymerization.
- the time for maintaining the temperature near the above temperature is preferably in the range of 0.5 to 2 hours, although it depends on the kind and amount of the radical polymerizable monomer to be used.
- the thermal decomposition temperature of the second polymer refers to a decomposition end point temperature dependent on TGA measurement.
- the thermal decomposition temperature of the second polymer is about 350 ° C.
- the temperature may be 380 ° C. or higher.
- the heating time it is sufficient that the second polymer is heated by thermal decomposition and at least most of the second polymer disappears, and may be about 30 to 300 minutes.
- the heating method in the second heating step is not particularly limited as long as it can be heated to the thermal decomposition temperature of the second polymer, and the composition can be heated by an appropriate method and apparatus. Moreover, in the case of the said heating, you may heat without sealing, ie, a normal pressure. Therefore, exfoliated graphite can be produced inexpensively and easily.
- the temperature may be further maintained for a certain time after heating to a temperature equal to or higher than the thermal decomposition temperature of the second polymer.
- the time for maintaining the temperature near the above temperature is preferably in the range of 0.5 to 2 hours, although it depends on the kind and amount of the radical polymerizable monomer to be used.
- the heat treatment in the step of generating the second polymer and the second polymer to be described later are heated. You may perform continuously the heat processing in the process to decompose
- the exfoliated graphite can be more effectively exfoliated by using the radical polymerizable monomer and / or the second polymer in combination with the thermally decomposable foaming agent.
- the reason why exfoliated graphite can be more effectively exfoliated by such a method is not clear, the following reasons are conceivable.
- the radical polymerizable monomer generates a free radical
- the second polymer or the radical polymerizable monomer having the free radical generated at the time of polymerization is an end portion of the exfoliated graphite graphene layer. And graft onto the surface. Therefore, the free radical is trapped in the graphene layer.
- the thermally decomposable foaming agent since the thermally decomposable foaming agent has a property of having high affinity with radicals, it is attracted to free radicals trapped in the graphene layer of the exfoliated graphite in the composition. Therefore, the thermally decomposable foaming agent is easily thermally decomposed in the vicinity of the graphene laminated surface. Therefore, a peeling force can be effectively applied between the graphene layers of the graphite by the thermal decomposition of the thermally decomposable foaming agent.
- the thermal decomposition of the thermally decomposable foaming agent is not necessarily performed in the step of thermally decomposing the second polymer.
- the thermal decomposition temperature of the thermally decomposable foaming agent is lower than the temperature at which the radical polymerizable monomer spontaneously starts polymerization
- the radical polymerization is performed by heating in the step of generating the second polymer.
- the thermally decomposable foaming agent may be thermally decomposed.
- the thermal decomposition of the thermally decomposable foaming agent may be performed before the polymerization of the radical polymerizable monomer, after the polymerization, or simultaneously with the polymerization.
- the temperature may be maintained for a certain time after heating to a temperature equal to or higher than the thermal decomposition temperature of the thermally decomposable foaming agent.
- the time for maintaining the temperature near the above temperature is preferably in the range of 0.5 to 2 hours, although it depends on the kind and amount of the thermally decomposable foaming agent to be used.
- primary exfoliated graphite obtained by another method may be used in the step of preparing the composition as the raw material described above. That is, the step of preparing the composition includes the steps of preparing a mixture containing graphite and a radical polymerizable monomer, and polymerizing the radical polymerizable monomer contained in the mixture, whereby the radical is incorporated into the mixture.
- a mixture is prepared in the same manner as in the method of further exfoliating exfoliated graphite, and polymerization of the radical polymerizable monomer and grafting of the second polymer may be performed. . Further, if the mixture is subsequently heated to a temperature equal to or higher than the thermal decomposition temperature of the second polymer, and the third heating step for thermally decomposing the second polymer is performed in the same manner as the second heating step described above. Good. Even in this case, exfoliated graphite having a large specific surface area can be obtained.
- the reason why thinning can be achieved by thermal decomposition of the second polymer is considered to be due to the above-described reason. That is, it is considered that when the second polymer grafted on graphite or exfoliated graphite is baked, a large stress acts on the graft point, thereby increasing the distance between the graphenes.
- the primary exfoliated graphite is used as a raw material as described above, a composition in which the primary exfoliated graphite is adsorbed on the first polymer is prepared, and then the Exfoliated graphite having a larger specific surface area can be obtained by carrying out the step of heating above the thermal decomposition temperature of one polymer.
- the exfoliated graphite of the second invention comprises graphite or primary exfoliated graphite and a polymer, wherein the polymer in the composition in which the polymer is fixed to the graphite or primary exfoliated graphite is thermally decomposed to remove the polymer. Is obtained.
- the exfoliated graphite of the second invention does not substantially contain the polymer used for peeling.
- exfoliated graphite obtained by the production method of the second invention has a feature that it is relatively difficult to scatter compared to exfoliated graphite obtained by a conventionally known production method. Therefore, exfoliated graphite obtained by the production method of the second invention is easier to handle than exfoliated graphite obtained by the conventional production method.
- exfoliated graphite having the same characteristics as the exfoliated graphite obtained by the conventional production method can be obtained.
- exfoliated graphite having a specific surface area of 40 m 2 / g or more can be obtained. Furthermore, exfoliated graphite having a specific surface area of 100 m 2 / g or more can be obtained. Furthermore, exfoliated graphite having a specific surface area of 180 m 2 / g or more can be obtained.
- the exfoliated graphite of the second invention Since the specific surface area of exfoliated graphite obtained by the second invention is large, the exfoliated graphite of the second invention is excellent in physical properties such as elastic modulus and electrical properties such as conductivity. Therefore, for example, by dispersing the exfoliated graphite of the present invention in a resin, a resin composite material having excellent rigidity and combustion resistance can be obtained.
- exfoliated graphite obtained by the second invention can be further exfoliated by a conventionally known exfoliation method to obtain exfoliated graphite having a larger specific surface area.
- the exfoliated graphite obtained by the second invention is thinner than normal graphite and has a larger specific surface area. Therefore, the exfoliated graphite can be more efficiently used by using the exfoliated graphite in a conventional peeling method. Graphite can be peeled off.
- the mixture was subjected to ultrasonic treatment at 100 W and an oscillation frequency of 28 kHz for 120 minutes using an ultrasonic treatment apparatus (manufactured by Honda Electronics Co., Ltd.). Thereby, the composition in which the expanded graphite was dispersed in the vinyl acetate polymer was obtained.
- the composition was dried at 80 ° C. for 2 hours and further heated to a temperature of 110 ° C. to completely dry the THF solution. The temperature was further maintained at 230 ° C. for 2 hours. Thereby, the ADCA was thermally decomposed and foamed in the composition.
- the composition was further heated to a temperature of 500 ° C. and maintained for 2 hours. Thereby, the vinyl acetate polymer in the composition was pyrolyzed to obtain exfoliated graphite from which the graphite was peeled off.
- glycidyl methacrylate polymer
- the composition was dried at 80 ° C. for 2 hours and further heated to a temperature of 150 ° C. to completely dry the THF solution.
- the composition was maintained at a temperature of 450 ° C. for 2 hours. Thereby, the glycidyl methacrylate polymer in the composition was thermally decomposed to obtain exfoliated graphite from which the graphite was peeled off.
- a raw material composition was prepared by mixing with 270 g of tetrahydrofuran, and then the raw material composition was irradiated with ultrasonic waves at 100 W and an oscillation frequency of 28 kHz for 2 hours using an ultrasonic treatment apparatus (manufactured by Hyundai Electronics Co., Ltd.). By this ultrasonic treatment, polybutyral was adsorbed on expanded graphite, thus preparing a composition in which polybutyral was adsorbed on expanded graphite.
- the composition is molded by a solution casting method, maintained at a drying temperature of 80 ° C. for 1 hour, and then maintained at a temperature of 110 ° C. for 1 hour, thereby forming a 100 ⁇ m-thick casting sheet. Obtained.
- the raw material composition was prepared by mixing with 200 g of tetrahydrofuran.
- the raw material composition was irradiated with ultrasonic waves at 100 W and an oscillation frequency of 28 kHz for 2 hours using an ultrasonic treatment apparatus (manufactured by Honda Electronics Co., Ltd.).
- an ultrasonic treatment apparatus manufactured by Honda Electronics Co., Ltd.
- polypropylene glycol was adsorbed on the expanded graphite.
- a composition in which polypropylene glycol was adsorbed on expanded graphite was prepared.
- the composition is formed by a solution casting method, maintained at a drying temperature of 80 ° C. for 2 hours, then maintained at a temperature of 110 ° C. for 1 hour, and further maintained at a temperature of 150 ° C. for 1 hour. And maintained at a temperature of 230 ° C. for 2 hours.
- the ADCA was thermally decomposed and foamed in the composition.
- the heating process maintained at the temperature of 400 degreeC for 24 hours was implemented. Thereby, the polypropylene glycol was pyrolyzed to obtain exfoliated graphite.
- ADCA having a structure represented by the above formula (1) as a thermally decomposable foaming agent (Yewa Kasei) 1,200 mg of a product name “AC # R-3K” (thermal decomposition temperature 210
- the composition was heated to a temperature of 120 ° C. and maintained for 1 hour, and further maintained at a temperature of 150 ° C. for 1 hour. Thereby, the styrene monomer in the composition was polymerized.
- the composition was further heated to a temperature of 230 ° C. and maintained at a temperature of 230 ° C. for 1 hour. Thereby, the ADCA was thermally decomposed and foamed in the composition.
- the composition was further heated to a temperature of 450 ° C. and maintained at a temperature of 450 ° C. for 2 hours. Thereby, the polymer in which the styrene monomer in the composition was polymerized was pyrolyzed to obtain exfoliated graphite from which the graphite was peeled off.
- Example 1 The exfoliated graphite (made by Toyo Tanso Co., Ltd., trade name “PF Powder 8”) used in Example 1 was used as a comparative graphite.
- TG / DTA measurement (a) Measurement with respect to thermally decomposable foaming agent
- ADCA used as the thermally decomposable foaming agent in Example 1 was subjected to a rate of 10 ° C / min from 30 ° C to 1000 ° C under an air atmosphere.
- a combustion test was conducted by heating at FIG. 1 shows the TG / DTA measurement results when this combustion test was performed.
- Example 3 XRD measurement The XRD spectrum of the exfoliated graphite obtained in Example 2 is shown by a solid line in FIG.
- the broken line in FIG. 8 is an XRD spectrum of the original expanded graphite (PF-8) used as a raw material.
- the XRD spectrum of the exfoliated graphite obtained in Example 4 is shown by a solid line in FIG.
- the broken line in FIG. 9 is an XRD spectrum of the original expanded graphite (PF-8) used as a raw material.
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Abstract
Description
本発明では、前記ポリマーが熱分解されると共に、該ポリマーが消失して、薄片化黒鉛が得られる。
(原料組成物を用意する工程)
第1の発明に係る薄片化黒鉛の製造方法では、黒鉛または一次薄片化黒鉛と、ラジカル重合性モノマーが重合しているポリマーとを含み、ポリマーが黒鉛または一次薄片化黒鉛にグラフト化している組成物をまず用意する。この組成物を用意する工程としては、以下の第1の方法及び第2の方法を用いることができる。
第1の方法では、まず、黒鉛または一次薄片化黒鉛と、ラジカル重合性モノマーとを含む混合物を用意する。次に、混合物に含まれているラジカル重合性モノマーを重合することにより、混合物中に上記ラジカル重合性モノマーが重合しているポリマーを生成させるとともに、該ポリマーを黒鉛または一次薄片化黒鉛にグラフト化させる。
第2の方法では、黒鉛または一次薄片化黒鉛と、ラジカル重合性モノマーが重合しているポリマーとを含み、ポリマーが黒鉛または一次薄片化黒鉛にグラフト化している組成物を用意する工程において、ポリマーを黒鉛の存在下で、300℃以上かつ500℃以下の温度範囲の温度に加熱することにより、ポリマーを黒鉛にグラフト化させる。すなわち、第1の方法では、黒鉛または一次薄片化黒の存在下でラジカル重合性モノマーを重合してポリマーを生成するとともにポリマーの黒鉛または一次薄片化黒鉛へのグラフト化が図られていたが、これに対して、第2の方法では、予め得られたポリマーを黒鉛または一次薄片化黒鉛の存在下で上記特定の温度範囲に加熱することにより、ポリマーを熱分解することにより生成したポリマーラジカルを直接黒鉛または一次薄片化黒鉛にグラフトさせることができる。
上記第1の方法及び第2の方法のいずれにおいても、上記のようにして組成物を用意したのち、組成物中に含まれるポリマーを熱分解する。それによって、黒鉛または一次薄片化黒鉛が剥離され、薄片化黒鉛を得ることができる。この場合のポリマーの熱分解を果たすために、上記組成物をポリマーの熱分解温度以上に加熱すればよい。より具体的には、ポリマーの熱分解温度以上に加熱する。特に、熱分解温度以上にさらに加熱し、該ポリマーを焼き切って除去する。それによって、ポリマーを含有していない、薄片化黒鉛を得ることができる。例えば、ポリスチレンの熱分解温度を280℃~400℃程度であり、ポリグリシジルメタクリレートの熱分解温度は250℃~350℃程度であり、ポリブチラールの熱分解温度は大気中で250℃~560℃程度である。
なお、第1の発明においては、上記のようにラジカル重合性モノマーが重合しているポリマーが黒鉛または一次薄片化黒鉛にグラフト化している構造を有する組成物中のポリマーを熱分解することにより薄片化黒鉛を得ている。第1の発明では、さらに、他の方法により黒鉛を薄片化する工程を施してもよい。例えば、第1の発明の薄片化黒鉛の製造方法で得られた薄片化黒鉛を原料として用い、第1の発明の薄片化黒鉛以外の黒鉛の薄片化方法をさらに実施してもよい。あるいは、他の黒鉛の薄片化方法で得られた一次薄片化黒鉛を原料として第1の発明の薄片化黒鉛の製造方法を実施してもよい。その場合においても、より一層比表面積の大きい薄片化黒鉛を得ることができる。このような他の黒鉛の薄片化方法としては、例えば、電気化学的処理による黒鉛の薄片化方法、あるいは吸着-熱分解法を用いることができる。吸着-熱分解法とは、黒鉛もしくは一次薄片化黒鉛を、ポリ酢酸ビニルのように黒鉛のグラファイトに吸着する性質を有するポリマーを吸着させ、しかる後、加熱により上記ポリマーを熱分解する方法である。この場合には、ポリマーのグラフェンに対する吸着点に熱分解の際の応力が加わるため、第1の発明の製造方法の場合と同様に、黒鉛のグラフェン層間の距離を広げることができる。
第1の発明の薄片化黒鉛は、黒鉛もしくは一次薄片化黒鉛とポリマーとを含み、ポリマーが黒鉛もしくは一次薄片化黒鉛に固定されている組成物中のポリマーを熱分解し、該ポリマーを除去することにより得られるものである。第1の発明の薄片化黒鉛には、剥離に用いたポリマーが実質的に含まれていない。第1の発明の製造方法により得られた薄片化黒鉛は、従来知られた製造方法により得られる薄片化黒鉛と比べて、比較的飛散し難いという特徴を有する。
次に、第2の発明の詳細について説明する。
第2の発明の製造方法では、原料として、黒鉛もしくは一次薄片化黒鉛と、第1のポリマーとを含み、第1のポリマーが黒鉛もしくは一次薄片化黒鉛に吸着されている組成物を用意する。
上記第1のポリマーとしては、該ポリマーと該黒鉛が分散に適した溶媒中で超音波処理することで黒鉛に吸着する様々なポリマーを用いることができる。このようなポリマーとしては、ポリ酢酸ビニル、ポリブチラール、ポリプロピレングリコールなどの熱分解性ポリマーを挙げることができる。
上記組成物を用意する工程では、好ましくは、熱分解する際にガスを発生する熱分解性発泡剤をさらに含む組成物を用意する。上記組成物が熱分解性発泡剤をさらに含む場合には、上記組成物を上記熱分解性発泡剤の熱分解温度まで加熱すると、上記熱分解性発泡剤が上記組成物中で熱分解する。一方、上記熱分解性発泡剤は、熱分解時にはガスを発生して発泡する。このとき、上記黒鉛または一次薄片化黒鉛のグラフェン層間付近で上記熱分解性発泡剤が熱分解すると、上記グラフェン層間に上記熱分解により発生した上記ガスが入り込み、上記グラフェン層の間隔が広げられる。それによって、上記グラフェン層間に剥離力が生じるため、上記黒鉛または一次薄片化黒鉛をさらに剥離することができる。従って、上記熱分解性発泡剤を用いることによって、得られる薄片化黒鉛の比表面積をより一層大きくすることができる。
上記組成物を用意する方法は特に限定されない。例えば、上記黒鉛と、第1のポリマーとを適宜の溶媒に溶解もしくは分散させる方法を挙げることができる。このような溶媒としては、テトラヒドロフラン、メチルエチルケトン、トルエン、酢酸エチルなどを用いることができる。
第2の発明の製造方法では、上記組成物を用意した工程の後に、上記組成物を第1のポリマーの熱分解以上の温度に加熱する。それによって、驚くべきことに比表面積が40m2/g以上の薄片化黒鉛を得ることができる。これは、黒鉛のグラフェンに吸着していた第1のポリマーが熱分解し、消失する際の応力により、黒鉛が剥離されていることによる。第2の発明によれば、比表面積が100m2/g以上の薄片化黒鉛を得ることができる。
第2の発明の薄片化黒鉛の製造方法では、上記のようにして加熱工程により得られた薄片化黒鉛を、原料としての一次薄片化黒鉛として用いてもよい。この場合には、一次薄片化黒鉛と第1のポリマーとを含み、一次薄片化黒鉛に第1のポリマーが吸着されている組成物を用意する工程及び上記加熱工程を再度実施する。その場合には、より一層比表面積の大きい薄片化黒鉛を得ることができる。さらに、このようにして得られた薄片化黒鉛を原料の一次薄片化黒鉛として用い、吸着及び加熱工程をさらに繰り返してもよい。その場合には、比表面積のさらに大きな薄片化黒鉛を得ることができる場合がある。
第2の発明に係る薄片化黒鉛の製造方法では、加熱工程により得られた一次薄片化黒鉛を用い、さらに他の薄片化処理を施してもよい。このような方法としては、例えば以下の各工程をさらに備える方法が挙げられる。
第2の発明の薄片化黒鉛の製造方法では、前述した原料としての組成物を用意する工程において、他の方法で得られた一次薄片化黒鉛を用いてもよい。すなわち、上記組成物を用意する工程が、黒鉛と、ラジカル重合性モノマーとを含む混合物を用意する工程と、上記混合物に含まれる上記ラジカル重合性モノマーを重合することにより、上記混合物中に上記ラジカル重合性モノマーが重合している第2のポリマーを生成させるとともに、上記第2のポリマーを上記黒鉛にグラフト化させる工程と、上記混合物を上記第2のポリマーの熱分解温度以上の温度に加熱して、上記第2のポリマーを熱分解する第3の加熱工程と、上記第3の加熱工程で得られた一次薄片化黒鉛と上記第1のポリマーとを混合して上記組成物を得る工程とを有していてもよい。
第2の発明の薄片化黒鉛は、黒鉛もしくは一次薄片化黒鉛とポリマーとを含み、ポリマーが黒鉛もしくは一次薄片化黒鉛に固定されている組成物中のポリマーを熱分解し、ポリマーを除去することにより得られるものである。第2の発明の薄片化黒鉛には、剥離に用いたポリマーが実質的に含まれていない。
膨張化黒鉛(東洋炭素社製、商品名「PFパウダー8」、BET比表面積=22m2/g)1000mgと、熱分解性発泡剤として上記式(1)に示される構造を有するADCA(永和化成社製、商品名「AC#R-3K」、熱分解温度210℃)2gと、ラジカル重合性モノマーとして酢酸ビニルポリマー(SN-04T、デンカ社製)10gとテトラヒドロフラン20gを混合し、混合物とした。次に、上記混合物に対し、超音波処理装置(本多電子社製)を用いて、100W、発振周波数28kHzで120分間超音波処理した。それによって、上記膨張化黒鉛が上記酢酸ビニルポリマー中に分散している組成物を得た。
膨張化黒鉛(東洋炭素社製、商品名「PFパウダー8」、BET比表面積=22m2/g)1000mgと、ラジカル重合性ポリマーとしてグリシジルメタクリレートポリマー(日本油脂社製、品番:G2050M、数平均分子量=20万)10gとテトラヒドロフラン90gを混合し、混合物とした。次に、上記混合物に対し、超音波処理装置(本多電子社製)を用いて、100W、発振周波数28kHzで5時間超音波処理した。それによって、上記膨張化黒鉛が上記グリシジルメタクリレートポリマー中に分散している組成物を得た。
膨張化黒鉛(東洋炭素社製、商品名「PFパウダー8」、BET比表面積=22m2/g)3000mgと、ポリブチラール(積水化学社製、品番:BL-1、30gとを、溶剤としてのテトラヒドロフラン270gと混合し、原料組成物を用意した。次に、原料組成物に、超音波処理装置(本多電子社製)を用いて、100W、発振周波数28kHzで2時間超音波を照射した。この超音波処理により、ポリブチラールを膨張化黒鉛に吸着させた。このようにして、ポリブチラールが膨張化黒鉛に吸着されている組成物を用意した。
膨張化黒鉛(東洋炭素社製、商品名「PFパウダー8」、BET比表面積=22m2/g)10gと、ポリプロピレングリコール(PPG、三洋化成社製、品番:サンニックスGP-3000、数平均分子量=3000)200gと熱分解性発泡剤として上記式(1)に示される構造を有するADCA(永和化成社製、商品名「AC#R-3K」、熱分解温度210℃)20gとを、溶剤としてのテトラヒドロフラン200gと混合し、原料組成物を用意した。次に、原料組成物に、超音波処理装置(本多電子社製)を用いて、100W、発振周波数28kHzで2時間超音波を照射した。この超音波処理により、ポリプロピレングリコールを膨張化黒鉛に吸着させた。このようにして、ポリプロピレングリコールが膨張化黒鉛に吸着されている組成物を用意した。
膨張化黒鉛(東洋炭素社製、商品名「PFパウダー8」、BET比表面積=22m2/g)600mgと、熱分解性発泡剤として上記式(1)に示される構造を有するADCA(永和化成社製、商品名「AC#R-3K」、熱分解温度210℃)1200mgと、ラジカル重合性モノマーとしてスチレンモノマー(和光純薬工業社製)20gとを混合し、混合物とした。次に、上記混合物に対し、超音波処理装置(本多電子社製)を用いて、100W、発振周波数28kHzで120分間超音波処理した。それによって、上記膨張化黒鉛が上記スチレンモノマー中に分散している組成物を得た。
実施例1で使用した剥離前の膨張化黒鉛(東洋炭素社製、商品名「PFパウダー8」)を、比較例の黒鉛とした。
1)TG/DTA測定
(a)熱分解性発泡剤に対する測定
また、実施例1において熱分解性発泡剤として使用したADCAに対し、空気雰囲気下で30℃から1000℃まで10℃/分の速度で加熱する燃焼試験を行った。この燃焼試験を行った際のTG/DTA測定結果を図1に示す。
実施例1で用いた原料としての膨張化黒鉛(東洋炭素社製、商品名「PFパウダー8」)に対し、空気雰囲気下で30℃から1000℃まで10℃/分の速度で加熱する燃焼試験を行った。この燃焼試験を行った際のTG/DTA測定結果を図2に示す。
実施例1~5により得られた薄片化黒鉛に対し、空気雰囲気下で30℃から1000℃まで10℃/分の速度で加熱する燃焼試験を行った。この燃焼試験を行った際のTG/DTA測定結果を図3~7に示す。
また、図3~7から、得られた薄片化黒鉛では、樹脂が焼き切って消失していることがわかる。
実施例1~5により得られた上記薄片化黒鉛及び比較例の黒鉛を、島津製作所社製比表面積測定装置ASAP-2000で窒素ガスを用い、BET比表面積を剥離性の指標として測定した。結果を下記の表1に示す。
実施例2により得られた薄片化黒鉛のXRDスペクトルを図8に実線で示す。なお、図8の破線は、原料として用いた元の膨張化黒鉛(PF-8)のXRDスペクトルである。実施例4により得られた薄片化黒鉛のXRDスペクトルを図9に実線で示す。なお、図9の破線は、原料として用いた元の膨張化黒鉛(PF-8)のXRDスペクトルである。
実施例1~5により得られた上記薄片化黒鉛を、走査型電子顕微鏡(SEM)により1000倍に拡大して撮影し、それによって得られた写真を観察した。実施例1~5により得られた上記薄片化黒鉛の上記SEM写真を図10~15に示す。
Claims (21)
- 黒鉛もしくは一次薄片化黒鉛とポリマーとを含み、前記ポリマーが前記黒鉛もしくは一次薄片化黒鉛に固定されている組成物を用意する工程と、
前記組成物中に含まれる前記ポリマーを熱分解することにより、前記黒鉛または一次薄片化黒鉛を剥離すると共に、前記ポリマーの熱分解により該ポリマーを除去する工程とを備える、薄片化黒鉛の製造方法。 - 前記組成物を用意する工程において、前記ポリマーが前記黒鉛もしくは一次薄片化黒鉛に固定されている組成物は、前記ポリマーが前記黒鉛または一次薄片化黒鉛にグラフト化している、請求項1に記載の薄片化黒鉛の製造方法。
- 前記組成物を用意する工程が、
前記黒鉛または一次薄片化黒鉛と、ラジカル重合性モノマーとを含む混合物を用意する工程と、
前記混合物に含まれる前記ラジカル重合性モノマーを重合することによって、前記混合物中に前記ラジカル重合性モノマーが重合しているポリマーを生成すると共に、前記ポリマーを前記黒鉛または一次薄片化黒鉛にグラフト化させる工程とを含む、請求項1または2に記載の薄片化黒鉛の製造方法。 - 前記混合物を用意する工程において、前記混合物が熱分解性発泡剤をさらに含む、請求項3に記載の薄片化黒鉛の製造方法。
- 前記ポリマーを生成すると共に、前記ポリマーを前記黒鉛または一次薄片化黒鉛にグラフト化させる工程において、前記混合物に含まれる前記熱分解性発泡剤を熱分解する、請求項4に記載の薄片化黒鉛の製造方法。
- 前記ポリマーを生成すると共に、前記ポリマーを前記黒鉛または一次薄片化黒鉛にグラフト化させる工程が、前記混合物を加熱することによって前記混合物に含まれる前記ラジカル重合性モノマーを重合することにより行われる、請求項3~5のいずれか1項に記載の薄片化黒鉛の製造方法。
- 前記組成物を用意する工程において、前記ポリマーを前記黒鉛または一次薄片化黒鉛の存在下で、50℃以上かつ400℃以下の温度範囲の温度に加熱することにより前記ポリマーを前記黒鉛にグラフト化させる、請求項2に記載の薄片化黒鉛の製造方法。
- 前記組成物を用意する工程において、前記組成物が熱分解性発泡剤をさらに含む、請求項2に記載の薄片化黒鉛の製造方法。
- 前記ポリマーを熱分解することにより、前記黒鉛または一次薄片化黒鉛を剥離する工程において、前記組成物に含まれる前記熱分解性発泡剤を熱分解する、請求項8に記載の薄片化黒鉛の製造方法。
- 前記混合物を用意する工程において、前記ポリマーが前記黒鉛もしくは一次薄片化黒鉛に固定されている組成物が、黒鉛もしくは一次薄片化黒鉛と第1のポリマーとを含み、前記第1のポリマーが前記黒鉛もしくは一次薄片化黒鉛に吸着されている組成物を用意し、
前記黒鉛または一次薄片化黒鉛を剥離する工程において、前記組成物を前記第1のポリマーの熱分解温度以上の温度に加熱し、前記第1のポリマーを熱分解し、薄片化黒鉛を得る加熱工程を行う、請求項1に記載の薄片化黒鉛の製造方法。 - 前記第1のポリマーが、ポリ酢酸ビニル、ポリブチラール及びポリプロピレングリコールからなる群から選択された少なくとも1種のポリマーである、請求項10に記載の薄片化黒鉛の製造方法。
- 前記混合物を用意する工程において、前記混合物が熱分解性発泡剤をさらに含む、請求項11に記載の薄片化黒鉛の製造方法。
- 請求項10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を前記一次薄片化黒鉛として用いる、請求項11または12に記載の薄片化黒鉛の製造方法。
- 請求項13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を前記一次薄片化黒鉛として用い、前記第1のポリマーを該一次薄片化黒鉛に吸着させて組成物を用意する工程と、
用意された前記組成物を前記第1のポリマーの熱分解温度以上の温度に加熱し、前記第1のポリマーを熱分解し、薄片化黒鉛を得る加熱工程をさらに繰り返す、請求項13に記載の薄片化黒鉛の製造方法。 - 前記加熱工程後に、得られた薄片化黒鉛と、ラジカル重合性モノマーとを含む混合物を用意する工程と、
前記混合物に含まれる前記ラジカル重合性モノマーを重合することにより、前記混合物中に前記ラジカル重合性モノマーが重合している第2のポリマーを生成させるとともに、前記第2のポリマーを前記薄片化黒鉛にグラフト化させる工程と、
前記混合物を前記第2のポリマーが熱分解する温度以上に加熱して前記第2のポリマーを熱分解し、薄片化黒鉛をさらに薄片化する第2の加熱工程をさらに備える、請求項10~14のいずれか1項に記載の薄片化黒鉛の製造方法。 - 前記組成物を用意する工程が、
黒鉛と、ラジカル重合性モノマーとを含む混合物を用意する工程と、
前記混合物に含まれる前記ラジカル重合性モノマーを重合することにより、前記混合物中に前記ラジカル重合性モノマーが重合している第2のポリマーを生成させるとともに、前記第2のポリマーを前記黒鉛にグラフト化させる工程と、
前記混合物を前記第2のポリマーの熱分解温度以上の温度に加熱して、前記第2のポリマーを熱分解する第3の加熱工程と、
前記第3の加熱工程で得られた一次薄片化黒鉛と前記第1のポリマーとを混合して前記組成物を得る工程とを有する、請求項10~14のいずれか1項に記載の薄片化黒鉛の製造方法。 - 前記黒鉛または一次薄片化黒鉛を剥離する工程において、前記混合物に含まれる前記熱分解性発泡剤を熱分解する、請求項4または12に記載の薄片化黒鉛の製造方法。
- 前記ラジカル重合性モノマーがスチレンまたはグリシジルメタクリレートである、請求項8または9に記載の薄片化黒鉛の製造方法。
- 請求項1~10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。
- 黒鉛もしくは一次薄片化黒鉛とポリマーとを含み、前記ポリマーが前記黒鉛もしくは一次薄片化黒鉛に固定されている組成物中のポリマーを熱分解し、ポリマーを除去することにより得られた薄片化黒鉛。
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JP2017536317A (ja) * | 2014-12-11 | 2017-12-07 | エルジー・ケム・リミテッド | 高速均質化前処理および高圧均質化を利用したグラフェンの製造方法 |
EP3228590A4 (en) * | 2014-12-02 | 2018-07-25 | Sekisui Chemical Co., Ltd. | Thermally-conductive sheet and method for producing same |
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US11508498B2 (en) | 2019-11-26 | 2022-11-22 | Trimtabs Ltd | Cables and methods thereof |
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- 2013-02-12 CN CN201380007913.XA patent/CN104093665B/zh active Active
- 2013-02-12 EP EP13749946.3A patent/EP2816010B1/en active Active
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EP2816010A1 (en) | 2014-12-24 |
JP5407008B1 (ja) | 2014-02-05 |
EP2816010A4 (en) | 2015-12-09 |
EP2816010B1 (en) | 2021-06-30 |
JPWO2013122045A1 (ja) | 2015-05-11 |
US20140377161A1 (en) | 2014-12-25 |
CN104093665B (zh) | 2016-06-22 |
CN104093665A (zh) | 2014-10-08 |
TWI593809B (zh) | 2017-08-01 |
KR20140128944A (ko) | 2014-11-06 |
TW201335387A (zh) | 2013-09-01 |
KR101860979B1 (ko) | 2018-05-24 |
US10167198B2 (en) | 2019-01-01 |
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