WO2005035442A1 - フラーレンの分離方法及びフラーレンを有する錯体 - Google Patents
フラーレンの分離方法及びフラーレンを有する錯体 Download PDFInfo
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- WO2005035442A1 WO2005035442A1 PCT/JP2004/011484 JP2004011484W WO2005035442A1 WO 2005035442 A1 WO2005035442 A1 WO 2005035442A1 JP 2004011484 W JP2004011484 W JP 2004011484W WO 2005035442 A1 WO2005035442 A1 WO 2005035442A1
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- fullerene
- complex
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- amine compound
- fullerenes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/152—Fullerenes
- C01B32/156—After-treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/734—Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/84—Manufacture, treatment, or detection of nanostructure
- Y10S977/842—Manufacture, treatment, or detection of nanostructure for carbon nanotubes or fullerenes
- Y10S977/845—Purification or separation of fullerenes or nanotubes
Definitions
- the present invention relates to a method for separating fullerene and a complex of fullerene and aminy conjugate.
- fullerene As a method for producing fullerene, for example, as shown in Japanese Patent Publication No. 6-507879, a method for producing fullerene by burning a carbon compound has been proposed, and at present, aromatic hydrocarbons such as benzene are used. A method for producing fullerene by introducing an oxygen-containing gas into a reactor and causing incomplete combustion under reduced pressure has also been proposed.
- Soot-like substances including fullerenes produced by combustion methods and the like include C60, C70, and higher-order fullerenes having more than 70 carbon atoms (such as C76, C78, C82, C84, C90, C96, C120, A fullerene mixture having at least one or two or more, at least two, and a soot residue (eg, acenaphthylene, fluorene, phenanthrene, pyrene, benzo [b] fluorene, benzo [c] phenanthrene, benzo [a] Polycyclic aromatic hydrocarbons such as anthracene, triphenylene, and / or benzopyrene; carbon having a graphite structure; hydrocarbons having a graphite structure as a skeleton; and carbon-based polymers such as carbon black).
- C60, C70, and higher-order fullerenes having more than 70 carbon atoms such as C76, C78, C82, C84
- a solvent extraction method is also known in which a fullerene-soluble solvent is brought into contact with a soot-like substance to dissolve the fullerene in the solvent, and soot residues insoluble in the solvent are removed to obtain a fullerene mixture.
- a separation method using a column filled with a separation material such as activated carbon is known.
- a method of contacting a host compound such as cyclic phenol sulfide (calixarene having a sulfur atom) with a specific fullerene (guest compound) to form an inclusion compound, and separating it from unencapsulated and fullerene is known (for example, see Japanese Patent No. 2654918 and Japanese Patent Application Laid-Open No. 11-240705).
- the present invention has been made in view of the circumstances, and an object of the present invention is to provide a fullerene separation method for separating a specific fullerene from a fullerene mixture simply and at low cost, and to provide a complex having the fullerene.
- a method for separating fullerenes comprises: a fullerene mixture having any one or more of C60, C70 and a higher fullerene having more than 70 carbon atoms, and an amine compound having two or more nitrogen atoms.
- A is contacted with a specific fullerene in the fullerene mixture to form a complex with the amine compound A, and the complex is separated from a solution in which fullerene that does not form the complex is dissolved.
- the soot-like substance containing a fullerene mixture having at least two of C60, C70, and higher fullerenes having more than 70 carbon atoms may be: (1) a carbonaceous material such as graphite; A method in which an electrode made of a material is used as a raw material to evaporate the raw material by arc discharge between the electrodes (arc discharge method); (2) a method in which a high current is applied to the carbonaceous raw material to evaporate the raw material (resistance heating method); It can be produced by (3) a method of evaporating a carbonaceous material by irradiation with a pulsed laser having a high energy density (laser evaporation method), and (4) a method of incompletely burning organic substances such as benzene (combustion method).
- a carbonaceous material such as graphite
- arc discharge method A method in which an electrode made of a material is used as a raw material to evaporate the raw material by arc discharge between the electrodes
- arc discharge method
- soot-like substances including fullerene produced by these methods include acenaphthylene, fluorene, phenanthrene, pyrene, benzo [b] fluorene, benzo [c] phenanthrene, benzo [a] anthracene, and triphene. It includes polycyclic aromatic hydrocarbons such as diene and benzopyrene, carbon having a graphite structure, hydrocarbons having a skeleton of a graphite structure, and carbon-based polymers such as carbon black.
- the fullerene mixture is a fullerene concentrate obtained by partially removing graphite and carbon black from the soot-like substance.
- a fullerene concentrate consisting of The fullerene concentrate is obtained by concentrating fullerene from a soot-like substance by various methods, and the method of concentration is not particularly limited.For example, a fullerene sublimate obtained from a soot-like substance by a sublimation method, a solvent extraction method, and the like.
- a fullerene-containing solid obtained by column-chromatographic separation of a soot-like substance, a mixture thereof, and the like.
- Examples of the solvent used in the method of the first invention include a solvent in which fullerene is soluble, for example, an aromatic hydrocarbon, an aliphatic hydrocarbon, or a chlorinated hydrocarbon. Alternatively, it may be either acyclic or one or more of these solvents may be used in any ratio.
- the aromatic hydrocarbon is a hydrocarbon compound having at least one benzene nucleus in a molecule, for example, benzene, toluene, xylene, ethylbenzene, n-butylpyrubenzene, isopropylbenzene, n-butylbenzene.
- aliphatic hydrocarbon either a cyclic or acyclic aliphatic hydrocarbon can be used.
- cycloaliphatic hydrocarbon include monocyclic aliphatic hydrocarbons such as cyclopentane, cyclohexane, cycloheptane and cyclooctane, and derivatives thereof such as methylcyclopentane, ethylcyclopentane, methylcyclohexane, and ethylcyclohexane.
- Examples of acyclic aliphatic hydrocarbons include n-pentane, n-hexane, n-heptane, n-octane, isooctane, n-nonane, n-decane, n-dodecane, and n-tetradecane.
- chlorinated hydrocarbons include dichloromethane, chlorophonolem, carbon tetrachloride, trichloroethylene, tetrachloroethylene, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, cyclobenzene, dichlorobenzene, or 1_ chloronaphthalene and the like.
- a ketone having 6 or more carbon atoms, an ester having 6 or more carbon atoms, an ether having 6 or more carbon atoms, or carbon disulfide may be used.
- alkylbenzene such as toluene, xylene, methicylene, 1-methylnaphthalene, 1,2,3,5-tetramethylbenzene, or 1,2,4-trimethylbenzene and / or naphthalene of tetralin
- an aromatic hydrocarbon such as a derivative.
- the compound can be used alone or as a mixed solvent of two or more kinds.
- the amine compound may be any compound containing two or more nitrogen atoms and capable of forming a complex with a specific fullerene. Further, the amine compound may be fat-soluble or water-soluble.
- examples of the fat-soluble amine compound include 1,8-diazabicyclo [5.4.0] ndecane 7-ene (l, 8_diazabicyclo [5.4.0] undec-7_ene; hereinafter also referred to as DBU), 5_diazabicyclo [4.3.0] nona_5—ene (l, 5_diazabicyclo [4.3.0] non_5_ene; hereinafter also referred to as DBN), 1,1,3,3-tetramethyldananidin (l, l , 3,3-tetramethylguanidine (hereinafter also referred to as TMG), 2-methinole 2_imidazoline (2_methytri 2-imidazoline; hereinafter also referred to as IDN), 1,2-dimethyl-1- 1,
- Examples of the water-soluble amine compound include 2-aminoviridine and guanidine.
- the amine compound is likely to form a complex preferentially with a higher fullerene having a higher electron accepting property and having more than 70 carbon atoms.
- the addition of the amine compound can be carried out as follows.
- the liquid fat-soluble Aminy conjugate may be added as it is or diluted with a solvent. It is desirable to dissolve the solid fat-soluble aminy conjugate and dissolve it in a solvent that is miscible with the solvent that is capable of dissolving fullerene.
- a water-soluble amine compound is generally difficult to mix with a solvent such as an aromatic hydrocarbon that dissolves fullerene. Therefore, the water-soluble amine compound is preferably dissolved in a polar solvent such as water and brought into contact with a solvent in which fullerene is dissolved in a two-layer system.
- any of the addition methods it is preferable to stir at an appropriate speed.
- the temperature suitable for dropping is from -50 ° C to 100 ° C, and if the temperature is within the range of -20 ° C and 50 ° C, the rate of complex formation is preferably high.
- the amount to be dropped depends on the content of the fullerene to be separated, but it is generally desirable that the amount is 2 to 50 molar equivalents of the fullerene to be separated. After the completion of the dropwise addition, it is important to ripen until the complex is sufficiently formed.
- the formed complex is separated from the fullerene solution, and this complex is generally insoluble in the solvent that dissolves fullerene in many cases. Therefore, it is preferable to use a method such as filtration or decantation for separation.
- a method such as filtration or decantation for separation.
- Fullerene can be recovered from a solution in which fullerene that does not form a complex is dissolved.
- a method of removing the amine compound from the solution by adding an organic acid and precipitating it as a salt, or by mixing with an aqueous acid solution or water and removing the aqueous layer to remove the amine compound. Can be applied. Only the fullerene that does not form a complex is dissolved in the solution from which the amine disulfide is removed, and the fullerene that does not form a complex may be used as a liquid in the next reaction, or a method such as solvent removal, crystallization, or sublimation, or a method thereof. By the combination of the above methods, fullerene may be taken out as a solid.
- fullerene is obtained from the fullerene mixture by the method according to the first invention. And fullerenes that do not form a complex can be separated.
- the complex insoluble in the solvent.
- this complex forms a precipitate in the solvent, the complex can be separated from the solution in which fullerene that does not form a complex is dissolved, by a method such as filtration or decantation.
- the complex is dissociated into the specific fullerene and the amine compound A, and the specific Get fullerene.
- this method in order to dissociate the complex into a specific fullerene and an amine compound, it is advisable to add a substance having a stronger interaction with the amine compound than the specific fullerene, and in particular, remove acids such as organic acids and inorganic acids. And good.
- dissociation can be performed by chromatography having a stationary phase that strongly interacts with the amine in the amine compound.
- the dissociation of the complex is performed by bringing the complex into contact with an acid.
- the complex is suspended in a solvent capable of dissolving fullerene.
- an acid for example, an organic acid such as acetic acid, trifluoroacetic acid, or methanesulfonic acid, or an inorganic acid such as sulfuric acid, hydrochloric acid, or phosphoric acid is added, and the amine compound is added.
- the fullerene is dissociated into a solution by converting it into an acid salt.
- a solution of a specific fullerene and a salt of an amine compound and an acid can be obtained.
- This solution may be used as it is for the reaction or the like, or fullerene can be taken out as a solid by a method such as solvent removal, crystallization or sublimation, or a combination of these methods.
- a method for separating fullerenes comprises: An amine compound B having two or more nitrogen atoms is brought into contact with a fullerene mixture having a higher fullerene having more than 70 carbon atoms in a solvent to form a first fullerene formed from the higher fullerene and the amine compound B.
- a fourth step of separating the second complex from the second solution in which the C60 is dissolved is also the same as that of the first invention.
- the first and second complexes formed are generally insoluble in a solvent that dissolves fullerene in many cases. Therefore, it is preferable to use a method such as filtration or decantation for the separation. Further, when the formed complex is soluble in a solvent, fullerene that does not form a complex can be separated from the complex by crystallization or the like.
- the second solution contains an excess amount of an amine compound
- a method for removing the amine compound for example, a method in which an organic acid is added to a solution to form a salt of the aminy conjugate and the organic acid to precipitate the solution, or a method in which the solution is mixed with an aqueous acid solution or water. And removing the amine compound from the aqueous layer.
- C60 In the solution from which the amine compound has been removed, only C60 is dissolved, and this may be used as a liquid in the next reaction, or a method such as solvent removal, crystallization, or sublimation, or a combination of these methods C60 may be taken out as a solid.
- C60, C70, and higher fullerenes having more than 70 carbon atoms can be easily separated at low cost.
- the first and second complexes are insoluble in the solvent.
- the complexes are formed by a method such as filtration or decantation. Dissolves the fullerene and can be separated from the solution.
- the method for separating fullerenes according to a seventh invention is the method according to the fifth or sixth invention, wherein the first complex is dissociated into the higher fullerene and the Aminich compound B to convert the higher fullerenes. obtain.
- a substance having a stronger interaction with the amidi conjugate than the higher order fullerene may be removed.
- acids such as inorganic acids may be removed.
- the dissociation can also be performed by chromatography having a stationary phase that has a strong interaction with the amine in the amine compound.
- the method for separating fullerenes according to an eighth invention is the method according to the seventh invention, wherein the dissociation of the first complex is performed by bringing an acid into contact with the first complex. That is, the first complex is suspended in a solvent capable of dissolving fullerene. Next, while stirring well, an acid, for example, an organic acid such as acetic acid, trifluoroacetic acid, or methanesulfonic acid, or an inorganic acid such as sulfuric acid, hydrochloric acid, or phosphoric acid is added to form a salt between the amine compound and the acid. This dissociates the fullerene to form a solution.
- an acid for example, an organic acid such as acetic acid, trifluoroacetic acid, or methanesulfonic acid, or an inorganic acid such as sulfuric acid, hydrochloric acid, or phosphoric acid is added to form a salt between the amine compound and the acid. This dissociates the fullerene to form a solution.
- a solution of a specific fullerene (higher fullerene) having a strong interaction with the amine compound can be obtained.
- This solution may be used as it is for the reaction or the like, or fullerene may be taken out as a solid by a method such as solvent removal, crystallization or sublimation, or a combination of these methods.
- the method for separating fullerenes according to a ninth invention is directed to the method according to any one of the fifth to eighth inventions, wherein the second complex is dissociated into the C70 and the amine compound C. The C70 is obtained.
- an acid such as an organic acid or an inorganic acid, especially when a substance having a stronger interaction with the amine compound than C70 is added.
- the angle can also be separated by chromatography having a stationary phase that strongly interacts with the amine in the amine compound.
- the dissociation of the second complex is performed by bringing an acid into contact with the second complex. That is, the second complex is suspended in a solvent in which fullerene can be dissolved. Next, while stirring well, an acid, for example, an organic acid such as acetic acid, trifluoroacetic acid, or methanesulfonic acid, or an inorganic acid such as sulfuric acid, hydrochloric acid, or phosphoric acid is added to form a salt between the amine compound and the acid. This dissociates the fullerene to form a solution.
- an acid for example, an organic acid such as acetic acid, trifluoroacetic acid, or methanesulfonic acid, or an inorganic acid such as sulfuric acid, hydrochloric acid, or phosphoric acid is added to form a salt between the amine compound and the acid. This dissociates the fullerene to form a solution.
- the method for separating fullerenes according to the eleventh invention is characterized in that the aminy conjugate A in the method according to the fourth aspect of the first to fourth inventions is different from the method for separating fullerenes according to the twelfth invention in 5
- the amine compounds B and C in the method according to Force 4 of the tenth invention have a partial structure in which the two nitrogen atoms are bonded via one atom.
- the amine compound that is, the amine compounds A, B and C
- compounds having the same or different chemical composition can be used.
- two nitrogen atoms are bonded through an atom such as carbon or nitrogen.
- tetrakis (dimethylamino) ethylene or 1-alkyl-1,2,3-triazoline and the like are used.
- the amine compound can form a complex with the fullerene preferentially.
- the method for separating fullerenes according to a thirteenth invention is the method according to the eleventh or twelfth invention, wherein the amine compound having a partial structure in which the two nitrogen atoms are bonded is represented by the following formula (1). It has the represented amidine structure. As a result, the amidine structure can form a complex with the fullerene preferentially.
- examples of the amine compound having an amidine structure include TMG, IDN, DBU, DBN, 1,2-dimethinolane 1,4,5,6-tetrahydropyrimidine, 1_methyl_2_imidazoline , 2-alkylamidine, 2-aminopyridine, guanidine and the like.
- a method for separating fullerenes according to a fourteenth invention is the method according to the thirteenth invention, wherein the aminy conjugate having the amidine structure has a cyclic amidine structure represented by formula (2): [0022] [Formula 2]
- the aminy conjugate having a cyclic amidine structure IDN, DBU, DBN, 1,2-dimethyl_1,4,5,6-tetrahydropyrimidine, 1-methyl
- 2-imidazoline and 2-aminoviridine are formed, as shown in the formula (3), the DBU is 1 or 2 distributed relative to fullerene. It becomes a complex having mixed positions (in the formula (3), C60, C70 and higher fullerenes are collectively referred to as Fullerene).
- the amine-conjugated compound having a cyclic amidine structure is 1,8-diazabicyclo [5.4.0] ndeca 7 —One and 1, 5-diazabicyclo [4.3.0] noner is any one of 5-ene
- a complex according to a sixteenth invention for achieving the above object includes fullerene and an amine compound having an amidine structure.
- examples of the amine compound having an amidine structure include linear TMG, 2_alkylamidine, guanidine and the like, and monocyclic IDN, 1,2_dimethyl-1,4,5,6-tetrahydropyrimidine. , 1_methyl_2_imidazoline, 2-aminopyridine, etc., and polycyclic DBU or DBN.
- the complex according to a seventeenth aspect is the complex according to the sixteenth aspect, wherein the fullerene has 70 or more carbon atoms.
- the fullerene has 70 or more carbon atoms.
- C 70, C76, C78, C82, C84, C86, C88, C90, C92, C94, C96 and the like, and their derivatives are also included.
- the complex according to the eighteenth invention is the complex according to the sixteenth or seventeenth invention, wherein the amine compound is 1,8-diazabicyclo [5.4.0] ndecane 7-ene and 1,5 —Zazabicyclo [4.3.0] Nona 1
- the complex according to the sixteenth to eighteenth aspects contains a fullerene and an amine compound having an amidine structure, it can be used as an intermediate for isolating a specific fullerene.
- FIG. 1 is an explanatory diagram of a fullerene manufacturing apparatus to which a fullerene separation method according to one embodiment of the present invention is applied.
- a fullerene production apparatus 10 to which the fullerene separation method according to one embodiment of the present invention is applied is a fullerene mixture having C60, C70 and a higher fullerene having more than 70 carbon atoms. From C60, C70, and higher fullerenes.
- a method of separating fullerenes using the fullerene manufacturing apparatus 10 will be described in detail.
- the fullerene production apparatus 10 has a fullerene tank 11 for storing a fullerene mixture.
- a fullerene mixture a soot-like substance obtained by a combustion method or the like is used as a solvent, for example.
- TMB 1,2,4-trimethylbenzene
- the soot used may be manufactured by any of an arc discharge method, a resistance heating method, and a laser-evaporation method, which are not limited to the combustion method.
- the soot-like substance produced by the combustion method contains 10 to 30% by weight of fullerene.
- the power combustion method is preferably used.
- the fullerene mixture as described above, a fullerene concentrate obtained by removing part or all of graphite, carbon black, and the like from a soot-like substance can be used.
- the fullerene production apparatus 10 has a solvent tank 12 for storing a solvent for dissolving fullerene, for example, TMB.
- Examples of the solvent used in the fullerene production apparatus 10 include, in addition to TMB, a solvent in which fullerene is soluble, for example, an aromatic hydrocarbon, an aliphatic hydrocarbon, or a chlorinated hydrocarbon. These solvents may be any of formulas or acyclic ones, and these solvents may be used alone or in any combination of two or more. As mentioned above, these solvents have a boiling point of 100-300 ° C, especially 120 250, at room temperature and liquid from an industrial point of view. C is better.
- the fullerene production apparatus 10 is an example of an amine compound that easily forms a complex with a specific fullerene (particularly, higher fullerene).
- 1,8-Diazabicyclo [5.4.0] Tank 13,8-diazabicyclo [5.4.0] undec-7_ene; liquid; hereinafter also referred to as DBU).
- Any amine compound that contains two or more nitrogen atoms in addition to DBU and can form a complex with a specific fullerene may be used.
- those having a cyclic amidine structure represented by the above formula (1) or a cyclic amidine structure represented by the above formula (2) may be used.
- nona-5-ene (1,5-diazabicyclo [4.3.0] non-5-ene), 1,1,3,3-tetramethynoreguanidine (1,1,3,3- tetramethylguanidine), 2-methinolay 2-imidazoline (
- 2-methyt 2-imidazoline 1,2_dimethyl-1,4,5,6-tetrahydropyrimidine, 1-methylone-2-imidazoline, 2_alkylamidine, guanidine, tetrakis (dimethylamino) ethylene, or 1 —Alkyl-1,2,3-triazoline and the like can also be used.
- the fullerene production apparatus 10 has a first mixing tank 14 for mixing the fullerene mixture and DBU in the TMB to form a first complex of higher fullerene in the fullerene mixture and DBU. ing.
- the first mixing tank 14 includes a temperature control device (not shown) capable of adjusting the temperature in the first mixing tank 14 to ⁇ 50 to 100 ° C., and a stirring blade that efficiently mixes the fullerene mixture and the DBU. Are provided.
- the pressure in the first mixing tank 14 may be carried out at normal pressure, which is not particularly limited.
- the DBU is gradually dropped from the amine brewing mixture tank 13 and supplied.
- Suitable temperature for dropping is, for example, _50 ° C to 100 ° C. In particular, when the temperature is in the range of ⁇ 20 ° C. to 50 ° C., the rate of complex formation is high, which is preferable.
- the amount dropped depends on the content of the fullerene to be separated. Generally, it is desirable that the amount is 2 to 50 molar equivalents of the fullerene to be separated. After completion of the dropwise addition, it is preferable to stir until a complex is sufficiently formed.
- first mixing tank 14 mainly higher order fullerenes in the fullerene mixture and DBU form a first complex represented by the formula (4).
- the generated first complex becomes a precipitate in TMB
- a method such as filtration or decantation can be used for separating the first complex.
- C60, C70, and uncomplexed DBU are dissolved in TMB.
- C60 and C70 also form a complex with a small amount of force SDBU to form a precipitate.
- the fullerene production device 10 includes a separation device for separating the first complex and a solution (first solution) in which C60 and C70 are dissolved, for example, a first continuous pressurized filter 15.
- a separation device for separating the first complex and a solution (first solution) in which C60 and C70 are dissolved, for example, a first continuous pressurized filter 15.
- a decompression type filtration device or a centrifugal separator may be used in addition to the pressure filtration device (the same applies to the separation device described below).
- the fullerene production apparatus 10 has a first dissociation tank 16 for dissociating the first complex separated by the first continuous pressurized filter 15 into higher fullerenes and amine compounds.
- the first dissociation tank 16 is provided with a stirring blade capable of efficiently mixing the first complex and trifluoroacetic acid, and a temperature controller (not shown).
- the fullerene production apparatus 10 has an acid tank 17 for storing acids, for example, trifluoroacetic acid which is an organic acid.
- acids for example, trifluoroacetic acid which is an organic acid.
- Trifluoroacetic acid was supplied from the acid tank 17.
- the first complex and trifluoroacetic acid are mixed. Since trifluoroacetic acid interacts more strongly with DBU than higher fullerenes, the first complex dissociates into higher fullerene dissolved in TMB and salts of DBU and trifluoroacetic acid, and the resulting salt is Settles.
- the fullerene manufacturing apparatus 10 includes a solution of a higher fullerene, a DBU and a trifluorobenzene. It has a separation device for separating salts with acetic acid, for example, a second continuous pressurized filter 18. Further, the fullerene production apparatus 10 has a first conical ribbon stirring and drying machine 19. The solution of the higher fullerene separated by the second continuous pressurized filter 18 is supplied to the first conical ribbon stirring and drying machine 19, and the TMB is set to a temperature higher than the boiling point of the TMB, for example, 130 ° C. and a pressure of 0.3 kPa. Until was completely removed, for example, for 25 hours to obtain a higher fullerene solid.
- the removed TMB was supplied to the solvent tank 12 for reuse.
- the first conical ribbon stirring / drying machine 19 was used.However, a tray type vacuum drying machine or a conical dryer can also be used. The same applies to a stirring dryer.
- a method for removing the amine compound a method of adding an organic acid to the solution to precipitate the amine compound as a salt with the acid, or a method of mixing the solution with an aqueous acid solution or water to remove the amine compound from the aqueous layer Methods (hereinafter, the same applies to separation of C60 and C70).
- the solution from which the aminy conjugate has been removed may be used as it is in the next reaction, or in addition to solvent removal, the higher fullerene may be solidified by a method such as crystallization or sublimation, or a combination of these methods. (The same applies to C60 and C70 below)
- the fullerene production apparatus 10 is a second mixing tank for forming a second complex by reacting the DBU with C70 in the TMB in which C60 and C70 are dissolved by the first continuous pressurized filter 15.
- the second mixing tank 20 includes a temperature controller (not shown) capable of adjusting the temperature in the second mixing tank 20 to ⁇ 50 to 100 ° C., and a stirring blade for efficiently mixing C60 and C70 with DBU.
- the pressure in the second mixing tank 20 may be carried out at normal pressure, which is not particularly limited.
- the DB U is gradually dropped and supplied.
- the temperature of the second mixing tank 20 and the dropping rate of the amine compound may be set in the same manner as when the first complex is formed in the first mixing tank 14.
- the formed second complex becomes a precipitate in TMB
- a method such as filtration or decantation can be used for separating the second complex.
- C60 and DBU not forming a complex are dissolved in TMB.
- C60 also forms a complex with DBU although the amount is small, and precipitates.
- the fullerene production device 10 includes a separation device that separates the second complex and a solution in which C60 is dissolved (second solution), for example, a third continuous pressure filter 21.
- the fullerene production device 10 has a second dissociation tank 22 for dissociating the second complex separated by the third continuous pressurized filter 21 into C70 and an amine compound.
- the second dissociation tank 22 is provided with a stirring blade capable of efficiently mixing the second complex and trifluoroacetic acid supplied from the acid tank 17, and a temperature control device (not shown).
- the second complex separated by the third continuous pressurized filter 21 and the TMB are supplied from the solvent tank 12, and the second complex is suspended in the TMB.
- Trifluoroacetic acid was supplied from the tank 17.
- the second complex and trifluoroacetic acid are mixed. Since trifluoroacetic acid interacts more strongly with DBU than C70, the second complex dissociates into C70 dissolved in TMB and salts with DBU and trifluoroacetic acid, and the resulting salt precipitates. I do.
- the fullerene production device 10 includes a separation device for separating a salt of the C70 solution from the DBU and trifluoroacetic acid, for example, a fourth continuous pressure filter 23. Further, the fullerene manufacturing apparatus 10 has a second conical ribbon stirring and drying machine 24. The solution of C70 separated by the fourth continuous pressurized filter 23 is supplied to the second conical ribbon stirring / drying machine 24, and the TMB is completely heated to a temperature not lower than the boiling point of TMB, for example, 130 ° C. and a pressure of 0.3 kPa. Removed to Drying, for example, for 25 hours to obtain a C70 solid. The removed TMB was supplied to the solvent tank 12 for reuse.
- a separation device for separating a salt of the C70 solution from the DBU and trifluoroacetic acid for example, a fourth continuous pressure filter 23.
- the fullerene manufacturing apparatus 10 has a second conical ribbon stirring and drying machine 24.
- the fullerene production apparatus 10 includes a third conical ribbon stirring and drying machine 25.
- the solution of C60 separated in the third continuous pressurized filter 21 is heated to a temperature equal to or higher than the boiling point of TMB, for example, 130 ° C. and a pressure of 0.3 kPa, and TMB is completely cooled. It was dried, for example, for 25 hours until it was removed to obtain a C60 solid. The removed TMB was supplied to the solvent tank 12 for reuse.
- fullerene purity can be determined by combining any of four or two or more of the conventional methods for separating fullerenes, such as chromatography, crystallization, sublimation, and inclusion (complex formation). It is effective as a method for increasing the purity of fullerenes.
- Fullerene mixture (C60: 64 Weight 0/0, Rei_70: 23 wt%, higher fullerenes:. 13 having a composition by weight 0/0 or less, the same) of 0. 56 g, was dissolved in TMB19 4g,. The solution was cooled down to 0 ° C. Here, 0.56 g of the fullerene mixture contains 36 g of C60 power, 0.13 g of C70 power, and 0.07 g of higher fullerene. Further, DBUO. 20 g was gradually added over 1 minute. After stirring the solution for 1.5 hours, a sedimentable precipitate, the first complex, was formed.
- This solution was filtered to obtain a first complex and a first solution.
- the first complex was suspended in TMBOOg, 0.55 g of trifluoroacetic acid was added and heated to 40 ° C. This was stirred for 2 hours to obtain a higher fullerene and a precipitate of salts of DBU and trifluoroacetic acid, and this precipitate was separated by filtration.
- the obtained filtrate was washed with 10.0 g of demineralized water (ion-exchanged water) until the washing liquid became neutral, for example, three times.
- TMB solution contains 60% by weight of higher order fullerenes, and the recovery rate from higher order fullerenes in the fullerene mixture is 3% by weight. there were. Further, TMB can be removed from the TMB solution of higher fullerene to obtain solid higher fullerene.
- the obtained first solution was kept at 0 ° C., and DBU.40 g was gradually added over 1 minute. After stirring the solution for 1 hour, a sedimentable precipitate, ie, a second complex, formed. This solution was filtered to obtain a second complex and a second solution.
- the second complex was suspended in TMBOOOg, and 0.55 g of trifluoroacetic acid was added thereto, and the mixture was heated to 40 ° C. This was stirred for 2 hours to obtain C70 and a precipitate of a salt of DBU and trifluoroacetic acid, and this precipitate was separated by filtration. The resulting filtrate was washed with 10. Og of demineralized water until the washing became neutral, for example, three times.
- TMB solution C70 is included 64 weight 0/0, 4 weight recovery rate of C70 fullerene mixture 0 /. Met. Further, TMB can be removed from the TMB solution of C70 to obtain solid C70.
- the second solution was washed with 10. Og of demineralized water until the washing solution became neutral, for example, three times.
- the TMB solution was analyzed by high performance chromatography, and 0.27 g of fullerene containing C60 as a main component was obtained.
- the obtained TMB solution contained 99% by weight of C60, and the recovery of C60 power in the fullerene mixture was 74% by weight. Further, TMB can be removed from a C60 TMB solution to obtain solid C60.
- 0.34 g of the fullerene mixture was dissolved in 19.7 g of TMB, and the solution was cooled to 0 ° C.
- 0.34 g of fullerene compound contains 22 g of C60 power, 0.08 g of C70 power, and 0.04 g of higher fullerene.
- 0.28 g of DBN was added for 1 minute to gradually add the calories.
- a sedimentable complex formed, which was filtered off.
- the filtrate was washed with 20.0 g of demineralized water until the washings became neutral, for example, three times.
- the TMB solution was analyzed by high-speed chromatography. As a result, 0.18 g of fullerene mainly composed of C60 was obtained.
- TMB solution contained 96% by weight of C60, and the recovery from C60 in the fullerene mixture was 82% by weight. Further, TMB can be removed from a C60 TMB solution to obtain solid C60.
- Example 3 Separation of C60 from fullerene mixture using IDN
- TMB solution 0.34 g of the fullerene mixture was dissolved in 19.7 g of TMB, and the solution was cooled to 0 ° C. Further, 30 g of IDNO. was gradually added over 1 minute. After stirring the solution for 3 hours, a sedimentable complex was formed, which was filtered off. The filtrate was washed with 20. Og of demineralized water, for example, three times until the washings became neutral. After washing, the TMB solution was analyzed by high-performance chromatography to obtain 0.13 g of fullerene mainly composed of C60. This is obtained TMB solution, C60 69 contains by weight 0/0, the recovery rate from C60 fullerene mixture was 60 weight 0/0. Further, the TMB solution strength of C60 can be removed to obtain solid C60.
- the present invention is not limited to the above-described Examples and Experimental Examples, and can be modified without departing from the scope of the present invention.
- some of the aforementioned Examples and Experimental Examples or are included in the scope of the present invention also when they are combined to form the fullerene separation method and the fullerene-containing complex of the present invention.
- the specific fullerene and the two or more fullerenes in the fullerene mixture having at least two of C60, C70, and higher fullerenes having more than 70 carbon atoms are included.
- separating the fullerene that does not form a complex with a specific fullerene from the fullerene mixture is performed. Can be. This makes it possible to separate specific fullerenes easily and at low cost, and to provide less expensive fullerenes to the market.
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EP04771471.2A EP1683760B1 (en) | 2003-10-08 | 2004-08-10 | Method of fullerene separation and complex containing fullerene |
US10/574,805 US7648691B2 (en) | 2003-10-08 | 2004-08-10 | Method of fullerene separation and complex containing fullerene |
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JP2003349911A JP4316344B2 (ja) | 2003-10-08 | 2003-10-08 | フラーレンの分離方法 |
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US (1) | US7648691B2 (ja) |
EP (1) | EP1683760B1 (ja) |
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WO2019211854A1 (en) | 2018-05-03 | 2019-11-07 | Collplant Holdings Ltd. | Dermal fillers and applications thereof |
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JP4647377B2 (ja) * | 2005-04-19 | 2011-03-09 | フロンティアカーボン株式会社 | フラーレンの分離方法 |
US7505720B2 (en) * | 2005-12-28 | 2009-03-17 | Konica Minolta Business Technologies, Inc. | Developing roller and developing method thereof |
US8691166B2 (en) * | 2008-01-08 | 2014-04-08 | Carbonxt Group Limited | System and method for activating carbonaceous material |
US8617492B2 (en) * | 2008-01-08 | 2013-12-31 | Carbonxt Group Limited | System and method for making low volatile carboneaceous matter with supercritical CO2 |
US8628707B2 (en) | 2008-01-08 | 2014-01-14 | Carbonxt Group Limited | System and method for making carbon foam anodes |
US20090172998A1 (en) * | 2008-01-08 | 2009-07-09 | Carbonxt Group Limited | System and method for refining carbonaceous material |
KR20200010806A (ko) | 2018-07-23 | 2020-01-31 | 삼성전자주식회사 | 연마 슬러리 및 그 제조 방법과 반도체 소자의 제조 방법 |
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JPH07237911A (ja) * | 1994-01-09 | 1995-09-12 | Res Dev Corp Of Japan | フラーレンの精製方法 |
JP2002234717A (ja) * | 2001-02-05 | 2002-08-23 | Tokyo Kasei Kogyo Kk | ホモオキサカリックスアレーンによるc70の分離法 |
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US7494638B1 (en) | 1990-08-30 | 2009-02-24 | Mitsubishi Corporation | Form of carbon |
US5273729A (en) | 1991-05-24 | 1993-12-28 | Massachusetts Institute Of Technology | Combustion method for producing fullerenes |
US5904852A (en) * | 1997-04-16 | 1999-05-18 | University Of South Carolina | Process for purifying fullerenes |
JPH11240705A (ja) | 1998-02-27 | 1999-09-07 | Cosmo Sogo Kenkyusho Kk | フラーレン用分離剤及びそれを用いるフラーレンの精製方法 |
ATE295345T1 (de) * | 1998-03-10 | 2005-05-15 | Fujisawa Pharmaceutical Co | Fullerenverbindungen |
WO2002079142A1 (en) * | 2001-03-30 | 2002-10-10 | Council Of Scientific And Industrial Research | A process for the production of amides from amines |
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- 2004-08-10 US US10/574,805 patent/US7648691B2/en active Active
- 2004-08-10 EP EP04771471.2A patent/EP1683760B1/en active Active
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JPH07237911A (ja) * | 1994-01-09 | 1995-09-12 | Res Dev Corp Of Japan | フラーレンの精製方法 |
JP2002234717A (ja) * | 2001-02-05 | 2002-08-23 | Tokyo Kasei Kogyo Kk | ホモオキサカリックスアレーンによるc70の分離法 |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019211854A1 (en) | 2018-05-03 | 2019-11-07 | Collplant Holdings Ltd. | Dermal fillers and applications thereof |
US11801329B2 (en) | 2018-05-03 | 2023-10-31 | Collplant Ltd. | Dermal fillers and applications thereof |
Also Published As
Publication number | Publication date |
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EP1683760A1 (en) | 2006-07-26 |
EP1683760B1 (en) | 2016-04-27 |
US20070134150A1 (en) | 2007-06-14 |
US7648691B2 (en) | 2010-01-19 |
EP1683760A4 (en) | 2011-03-09 |
JP4316344B2 (ja) | 2009-08-19 |
JP2005112675A (ja) | 2005-04-28 |
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