WO2011096342A1 - 選択的に化学修飾されたカーボンナノチューブの製造方法 - Google Patents
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- C01B32/15—Nano-sized carbon materials
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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
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- 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.
- Y10S977/742—Carbon nanotubes, CNTs
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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
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- 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.
- Y10S977/742—Carbon nanotubes, CNTs
- Y10S977/745—Carbon nanotubes, CNTs having a modified surface
Definitions
- the present invention relates to a method for producing selectively chemically modified carbon nanotubes.
- SWNTs Single-walled carbon nanotubes inevitably have a mixture of metallic (m-SWNTs) and semiconducting (s-SWNTs) in the synthesis process.
- m-SWNTs metallic
- s-SWNTs semiconducting
- FET field effect transistor
- Patent Documents and Non-Patent Documents 1 and 2 describe that a carbon nanotube and a cyclic disulfide are chemically reacted under ultraviolet irradiation. However, no knowledge has been suggested regarding the reactivity between carbon nanotubes and linear disulfides and the selective chemical modification based on the electrical properties and diameter of carbon nanotubes. JP 2006-131428 A Chemistry Letters 2006, 35, 742. Diamond & Related Materials 2007, 16, 1091-1094.
- the present invention has been made in view of the circumstances as described above, and the carbon nanotubes of the raw material in which metallic carbon nanotubes and semiconducting carbon nanotubes are mixed are selectively selected based on their electrical characteristics or diameters. It is an object to provide a new method for conversion.
- the present inventor made carbon nanotubes and linear disulfides or linear sulfides exist in an organic solvent, so that the active species produced by photoreaction of carbon nanotubes with linear disulfides or linear sulfides were obtained.
- metallic carbon nanotubes can be selectively modified or the carbon nanotubes can be chemically modified in a diameter-selective manner due to a clear difference in chemical reactivity based on electrical characteristics or diameter, and the present invention has been completed. .
- the method for producing a selectively chemically modified carbon nanotube according to the present invention includes a raw material carbon nanotube in which metallic carbon nanotubes and semiconducting carbon nanotubes are mixed, and the following formula (I ) Or formula (II)
- R 1 and R 2 each independently represents a hydrocarbon group which may have a substituent
- the disulfide or sulfide represented by It is characterized in that the disulfide represented by (I) or the sulfide represented by formula (II) and a carbon nanotube are photoreacted to selectively chemically modify the metallic carbon nanotube.
- the method for producing a selectively chemically modified carbon nanotube of the present invention includes a raw material carbon nanotube in which metallic carbon nanotubes and semiconducting carbon nanotubes are mixed, and the following formula (I) or formula (II):
- R 1 and R 2 each independently represents a hydrocarbon group which may have a substituent
- the disulfide or sulfide represented by It is characterized in that the carbon nanotubes are chemically modified in a diameter selective manner by photoreacting the carbon sulfide with the disulfide represented by (I) or the sulfide represented by the formula (II).
- physical properties are controlled by selectively converting metallic carbon nanotubes or diameter-selectively molecularly converting carbon nanotubes from raw carbon nanotubes in which metallic carbon nanotubes and semiconducting carbon nanotubes are mixed. can do.
- the method of the present invention comprises a raw material carbon nanotube in which metallic carbon nanotubes and semiconducting carbon nanotubes are mixed, and a disulfide represented by the above formula (I) or a sulfide represented by the formula (II) in an organic solvent.
- a disulfide represented by the formula (I) or a sulfide represented by the formula (II) in an organic solvent By allowing it to exist, the disulfide represented by the formula (I) or the sulfide represented by the formula (II) and the carbon nanotube are photoreacted, and the metallic carbon nanotube is selectively chemically modified, or carbon. It is characterized by chemically modifying nanotubes in a diameter selective manner.
- the carbon nanotube used as a raw material in the present invention is not particularly limited, and for example, single-walled carbon nanotubes or multi-walled carbon nanotubes such as double-walled carbon nanotubes can be used.
- the method for producing the carbon nanotube is not particularly limited, and for example, a HiPco method, an arc method, a laser ablation method, a CVD method, or the like can be used.
- R 1 and R 2 are each independently a hydrocarbon group which may have a substituent, for example, a substituent.
- An aromatic hydrocarbon group, a saturated aliphatic hydrocarbon group, or an alicyclic hydrocarbon group which may have for example, C 6 -C 20 , preferably C 6 -C 14 aromatic hydrocarbon group, C 1 -C 40 , preferably C 1 -C 20 saturated aliphatic hydrocarbon group, or C 3 -C 40 ,
- a C 3 -C 20 alicyclic hydrocarbon group and those having a substituent thereon can be used.
- aromatic hydrocarbon group examples include C 6 -C 20 aryl groups such as a phenyl group and a naphthyl group.
- Aromatic hydrocarbon group, a halogen atom as a substituent, hydroxyl group, C 1 -C 40 alkoxy group, C 2 -C 40 alkoxycarbonyl group, C 6 -C 10 aryloxy group, and a C 2 -C 40 acyl group You may have at least 1 sort chosen.
- Saturated aliphatic hydrocarbon groups include, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl Straight chain such as a group, iso-pentyl group, sec-pentyl group, neo-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, etc. Or a branched alkyl group etc. are mentioned.
- You may have at least 1 sort (s) chosen from.
- alicyclic hydrocarbon group examples include cycloalkyl groups such as a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a norbornyl group.
- Alicyclic hydrocarbon groups, a halogen atom as a substituent, hydroxyl group, C 1 -C 6 alkoxy group, C 2 -C 6 alkoxycarbonyl group, C 6 -C 10 aryloxy groups, and C 2 -C 8 acyl group You may have at least 1 sort (s) chosen from.
- the amount of the disulfide represented by the formula (I) or the sulfide represented by the formula (II) is not particularly limited and may be an excessive amount with respect to the carbon nanotube.
- the amount of chemical modification can be adjusted by reducing the amount of disulfide represented by formula (I) or sulfide represented by formula (II) relative to the amount of carbon nanotubes.
- the amount of disulfide represented by formula (I) or sulfide represented by formula (II) can be 0.05 to 1M.
- the amount of chemical modification can also be adjusted by the reaction time.
- organic solvent for the reaction those in which the disulfide represented by the formula (I) is dissolved are preferable.
- organic solvents include, for example, ethers having preferably 4 to 6 carbon atoms such as tetrahydrofuran, 1,4-dioxane and diethyl ether, aromatic hydrocarbons such as benzene, and preferably carbon such as hexane and cyclohexane.
- the hydrocarbons of several 5 to 10 can be used singly or in combination of two or more. Of these, tetrahydrofuran is preferred.
- metallic carbon nanotubes can be selectively converted into molecules.
- carbon nanotubes can be molecularly converted in a diameter selective manner.
- the photoreaction of the raw material carbon nanotube with the disulfide represented by the formula (I) or the sulfide represented by the formula (II) is represented by the disulfide represented by the formula (I) or the formula (II) in an organic solvent.
- the sulfide can be dissolved and the carbon nanotubes can be dispersed and appropriately irradiated with ultrasonic waves.
- a carbon nanotube thin film can be produced on a substrate such as quartz and immersed in an organic solvent containing a disulfide represented by formula (I) or a sulfide represented by formula (II).
- the reaction atmosphere is preferably an oxygen atmosphere such as the air.
- the reaction can easily proceed even at room temperature.
- the reaction temperature is not particularly limited as long as it is not higher than the boiling point of the disulfide represented by the formula (I) or the sulfide represented by the formula (II).
- the reaction can be carried out at -50 to 200 ° C.
- the reaction time is not particularly limited, but if the reaction time is too long, the reaction of semiconducting carbon nanotubes may progress in addition to metallic carbon nanotubes.
- the light wavelength necessary for advancing the photoreaction is 200 to 2000 nm, preferably 300 to 800 nm.
- the photoreaction of the metallic carbon nanotubes contained in the raw material carbon nanotubes with the disulfide represented by the formula (I) or the sulfide represented by the formula (II) is, for example, visible without requiring ultraviolet light irradiation. It can proceed even in the range of 400 nm to 800 nm of light.
- the light source device for photoreaction for example, a halogen lamp, a mercury lamp, a fluorescent lamp or the like can be used.
- the amount of light is sufficient for the reaction to proceed even with a stand-type fluorescent lamp or room lamp.
- a photoreaction of the raw material carbon nanotubes with the disulfide represented by the formula (I) or the sulfide represented by the formula (II) proceeds under the above-described conditions, whereby the formula (I ) Or disulfide represented by the formula (II), and metallic carbon nanotubes selected from metallic and semiconducting materials contained in the raw material carbon nanotubes are selectively chemically modified. Can do. Alternatively, carbon nanotubes can be chemically modified in a diameter selective manner.
- “selectively” chemical modification is attributed to disappearance of characteristic absorption based on metallic carbon nanotubes or metallic carbon nanotubes, for example, as shown in Examples described later. It can be confirmed as a clear difference when compared with that of semiconducting carbon nanotubes due to a decrease in Raman spectrum and an increase in peak intensity of the D band attributed to sp3 bonds.
- the degree of selective reaction can be clearly grasped by the following evaluation, for example. First, it is possible to relatively obtain information on the progress of the entire chemical reaction from the D band. It is also possible to quantify selective chemical reaction information from the peak intensity change or area change of RBM metallic SWNTs and semiconductor SWNTs. Moreover, the extent to which the reaction has progressed selectively by the decrease in the peak intensity of RBM can be evaluated as the spectrum shape.
- diameter selective means that carbon nanotubes with a small diameter react preferentially.
- SWNTs are reacted with a disulfide represented by formula (I) or a sulfide represented by formula (II) using toluene as an organic solvent, metallic SWNTs having a small diameter, semiconductor SWNTs having a small diameter are used. The reaction proceeds in the order of thick metallic SWNTs and thick semiconductor SWNTs.
- the method of the present invention controls the physical properties by selectively converting metallic carbon nanotubes or diameter-selectively molecularly converting carbon nanotubes from raw carbon nanotubes in which metallic carbon nanotubes and semiconducting carbon nanotubes are mixed. Therefore, application in various fields such as improved characteristics as FET materials can be expected.
- the progress of the selective chemical reaction based on the electrical properties or diameters of the mixtures containing metallic SWNTs and semiconducting SWNTs is represented by the absorption characteristics of the absorption spectrum and the RBM and D-band of the Raman spectrum. The rate of increase was evaluated.
- the absorption spectrum (ultraviolet-visible-near infrared absorption spectrum) was measured using a spectrophotometer (UV-3150, manufactured by Shimadzu Corporation).
- the Raman spectrum was measured at a laser excitation wavelength of 514.5 nm and 632.8 nm using a Raman spectrometer (LabRAM® HR-800, HORIBA, Ltd.) for a film prepared by processing carbon nanotubes by suction filtration.
- the light source for photoreaction was irradiated with light from a light source (wavelength of 300 nm or more) mainly using a white fluorescent lamp (Sunline FL15SW-6, manufactured by Hitachi Lighting Co., Ltd.).
- a white fluorescent lamp (Sunline FL15SW-6, manufactured by Hitachi Lighting Co., Ltd.).
- ⁇ Example 1> Place 0.1 mg of single-walled carbon nanotubes (SWNTs, HiPco method) in a Pyrex (registered trademark) reaction vessel, add 10 ml of tetrahydrofuran (THF) containing 0.05 M diphenyl disulfide, and irradiate with ultrasonic waves in the atmosphere. I went for 2 hours. Moreover, the light from the white fluorescent lamp of a light source was irradiated.
- THF tetrahydrofuran
- Example 2 Place 0.1 mg of single-walled carbon nanotubes (SWNTs, HiPco method) in a Pyrex (registered trademark) reaction vessel, add 10 ml of tetrahydrofuran (THF) containing 0.05 M diphenyl disulfide, and irradiate with ultrasonic waves in the atmosphere. 9 hours or 12 hours. Moreover, the light from the white fluorescent lamp of a light source was irradiated.
- SWNTs single-walled carbon nanotubes
- THF tetrahydrofuran
- Example 4 In Example 1, the organic solvent was changed to various types, and the reaction was performed under the same conditions as in Example 1 except that.
- the organic solvent THF, hexane, dioxane, diethyl ether, benzene and the like were used.
- Example 5 Place 0.1 mg of single-walled carbon nanotubes (SWNTs, HiPco method) in a Pyrex (registered trademark) reaction vessel, add 10 ml of tetrahydrofuran (THF) containing 0.05 M diphenyl disulfide, and irradiate with ultrasonic waves in the atmosphere. I went for 2 hours.
- SWNTs single-walled carbon nanotubes
- THF tetrahydrofuran
- Example 7 In Example 1, the disulfide was changed to various types, and the reaction was performed under the same conditions as in Example 1 except that.
- disulfide in addition to diphenyl disulfide, a methyl group, a methoxy group, a chlorine atom, a dodecyl group, an amino group, or a nitro group as a substituent R as shown in the left of FIG. n-Butyl disulfide, di-tert-butyl disulfide, and dicyclohexyl disulfide were used.
- Fig. 9 shows the results of measuring the absorption Raman spectrum after 3 days.
- disappearance of characteristic absorption based on metallic SWNTs was confirmed in various disulfides.
- the solution was filtered with a PEFE membrane filter and subjected to Raman spectrum measurement, the reduction of the Raman spectrum attributed to metallic SWNTs in various disulfides and the peak intensity of the D band attributed to sp3 bonds. The increase was confirmed, and the knowledge that selective chemical reaction to metallic SWNTs was progressing was obtained.
- Example 8 Comparative Example 3> The reactivity of linear disulfide of formula (I) and cyclic disulfide was compared.
- SWNTs was placed in a Pyrex (registered trademark) reaction vessel, and an organic solvent containing diphenyl disulfide was further added to attempt a photoreaction.
- FIG. 10 shows ultraviolet to visible light irradiation with an organic solvent THF in an oxygen atmosphere (light wavelength 254 nm ⁇ ).
- FIG. 10 shows ultraviolet to visible light irradiation with an organic solvent THF in an oxygen atmosphere (light wavelength 254 nm ⁇ ).
- FIG. 11 shows visible light irradiation with an organic solvent THF in an oxygen atmosphere (light wavelength 500 nm ⁇ ).
- FIG. 12 shows the results of ultraviolet to visible light irradiation (light wavelength 254 nm ⁇ ) with an organic solvent acetonitrile in an oxygen atmosphere.
- selective chemical reactions to metallic SWNTs proceeded, and in acetonitrile (the reaction hardly proceeded compared to the THF oxygen system), the reaction proceeded also in a diameter selective manner.
- Dithiane is thought to proceed mainly due to the addition of thiyl radicals generated by photoreaction to SWNTs, but in the case of diphenyl disulfide, photoexcited semiconductor SWNTs and disulfide undergo an electron transfer reaction to generate radical ion species.
- Persulfoxide is generated from the superoxide anion radical and disulfide cation radical generated by the reaction of oxygen and SWNTs anion radical, and this persulfoxide intermediate is thought to selectively react with metallic SWNTs and SWNTs with a specific diameter. It is done.
- Photoreaction was performed using toluene as the organic solvent.
- the reaction was carried out by adding 50 ml of 0.05M diphenyl disulfide / toluene solution to 1.5 mg of SWNTs, and using a halogen lamp (> 300 nm) as a light source and irradiating with light in an oxygen atmosphere.
- a halogen lamp > 300 nm
- the reaction proceeded in a diameter selective manner rather than a metal selective manner.
- the chemical reactivity can be switched from a metal selective reaction to a diameter selective reaction by selecting an organic solvent.
- the reaction proceeded in the order of metallic SWNTs having a small diameter, semiconductor SWNTs having a small diameter, metallic SWNTs having a large diameter, and semiconductor SWNTs having a large diameter, and RBM changes were as shown in Tables 1 and 2.
- Diphenyl sulfide was used for light irradiation with an organic solvent THF (light wavelength: 400 nm ⁇ ) under an oxygen atmosphere.
- THF organic solvent
- FIG. 15 a decrease in the Raman spectrum attributed to metallic SWNTs and an increase in the peak intensity of the D band attributed to sp3 binding were confirmed. The knowledge that a chemical reaction is progressing was obtained.
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Abstract
Description
<実施例1>
パイレックス(登録商標)製の反応容器に0.1mgの単層カーボンナノチューブ(SWNTs、HiPco法)を入れ、さらに0.05Mのジフェニルジスルフィドを含むテトラヒドロフラン(THF)を10ml加え、大気中にて超音波照射を2時間行った。また、光源の白色蛍光ランプからの光を照射した。
<実施例2>
パイレックス(登録商標)製の反応容器に0.1mgの単層カーボンナノチューブ(SWNTs、HiPco法)を入れ、さらに0.05Mのジフェニルジスルフィドを含むテトラヒドロフラン(THF)を10ml加え、大気中にて超音波照射を9時間または12時間行った。また、光源の白色蛍光ランプからの光を照射した。
<実施例3>
スプレー法にて単層カーボンナノチューブ(SWNTs、HiPco法)薄膜を石英基盤上に作製し、これをジフェニルジスルフィドを含むテトラヒドロフラン(THF)10mlに浸漬した。また、光源の白色蛍光ランプからの光を照射した。
<実施例4>
実施例1において、有機溶媒を各種のものに変更し、それ以外は実施例1と同様の条件にて反応を行った。有機溶媒としては、THF、ヘキサン、ジオキサン、ジエチルエーテル、ベンゼン等を用いた。
<比較例1>
スプレー法にて単層カーボンナノチューブ(SWNTs、HiPco法)薄膜を石英基盤上に作製し、これをジフェニルジスルフィドを含むテトラヒドロフラン(THF)10mlに浸漬し、暗所にて放置した。
<比較例2>
パイレックス(登録商標)製の反応容器に0.1mgの単層カーボンナノチューブ(SWNTs、HiPco法)を入れ、さらに0.05Mのジフェニルジスルフィドおよび安定化剤として知られている2,6-ジ-tert-ブチル-4-メチルフェノールを含むテトラヒドロフラン(THF)を10ml加え、大気中にて超音波照射を2時間行った。また、光源の白色蛍光ランプからの光を照射した。
<実施例5>
パイレックス(登録商標)製の反応容器に0.1mgの単層カーボンナノチューブ(SWNTs、HiPco法)を入れ、さらに0.05Mのジフェニルジスルフィドを含むテトラヒドロフラン(THF)を10ml加え、大気中にて超音波照射を2時間行った。
<実施例6>
パイレックス(登録商標)製の反応容器に0.1mgの単層カーボンナノチューブ(SWNTs、HiPco法)を入れ、さらに0.05Mのジフェニルジスルフィドを含むテトラヒドロフラン(THF)を10ml加え、大気中にて超音波照射を2時間行った。また、光源の白色蛍光ランプからの光を照射した。
<実施例7>
実施例1において、ジスルフィドを各種のものに変更し、それ以外は実施例1と同様の条件にて反応を行った。ジスルフィドとしては、ジフェニルジスルフィドの他、そのフェニル基に図10左に示すように置換基Rとしてメチル基、メトキシ基、塩素原子、ドデシル基、アミノ基、またはニトロ基を導入したもの、およびジ-n-ブチルジスルフィド、ジ-tert-ブチルジスルフィド、ジシクロヘキシルジスルフィドを用いた。
<実施例8、比較例3>
式(I)の直鎖ジスルフィドと、環状ジスルフィドの反応性について比較した。実施例8では実施例1と同様にパイレックス(登録商標)製の反応容器にSWNTsを入れ、さらにジフェニルジスルフィドを含む有機溶媒を加えて光反応を試みた。図10は酸素雰囲気下、有機溶媒THFでの紫外~可視領域の光照射(光波長254nm<)、図11は酸素雰囲気下、有機溶媒THFでの可視領域の光照射(光波長500nm<)、図12は酸素雰囲気下、有機溶媒アセトニトリルでの紫外~可視領域の光照射(光波長254nm<)の結果を示す。いずれも金属性SWNTsへの選択的な化学反応が進行し、アセトニトリル(THF酸素系に比べほとんど反応が進行しない)では直径選択的にも反応が進行した。
<実施例9>
有機溶媒としてトルエンを用いて光反応を行った。SWNTs 1.5mgに対し0.05Mのジフェニルジスルフィド/トルエン溶液50mlを加え、光源としてハロゲンランプ(>300nm)を用い、酸素雰囲気下で光照射し反応を行った。その結果を図14に示す。
d=223.5/(ωRBM-12.5)
Claims (8)
- 置換基を有していてもよい炭化水素基は、置換基を有していてもよい芳香族炭化水素基、飽和脂肪族炭化水素基、または脂環式炭化水素基であることを特徴とする請求項1に記載の選択的に化学修飾されたカーボンナノチューブの製造方法。
- 置換基を有していてもよい炭化水素基は、置換基としてハロゲン原子、水酸基、C1-C40アルコキシ基、C2-C40アルコキシカルボニル基、C6-C10アリールオキシ基、およびC2-C40アシル基から選ばれる少なくとも1種を有していてもよいC6-C20芳香族炭化水素基、または、置換基としてハロゲン原子、水酸基、C1-C6アルコキシ基、C2-C6アルコキシカルボニル基、C6-C10アリールオキシ基、およびC2-C8アシル基から選ばれる少なくとも1種を有していてもよいC1-C40飽和脂肪族炭化水素基もしくはC3-C40脂環式炭化水素基であることを特徴とする請求項2に記載の選択的に化学修飾されたカーボンナノチューブの製造方法。
- 有機溶媒としてテトラヒドロフラン、1,4-ジオキサン、ジエチルエーテル、ベンゼン、ヘキサン、またはシクロヘキサンを用いることを特徴とする請求項1から3のいずれかに記載の選択的に化学修飾されたカーボンナノチューブの製造方法。
- 置換基を有していてもよい炭化水素基は、置換基を有していてもよい芳香族炭化水素基、飽和脂肪族炭化水素基、または脂環式炭化水素基であることを特徴とする請求項5に記載の選択的に化学修飾されたカーボンナノチューブの製造方法。
の選択的に化学修飾されたカーボンナノチューブの製造方法。 - 置換基を有していてもよい炭化水素基は、置換基としてハロゲン原子、水酸基、C1-C40アルコキシ基、C2-C40アルコキシカルボニル基、C6-C10アリールオキシ基、およびC2-C40アシル基から選ばれる少なくとも1種を有していてもよいC6-C20芳香族炭化水素基、または、置換基としてハロゲン原子、水酸基、C1-C6アルコキシ基、C2-C6アルコキシカルボニル基、C6-C10アリールオキシ基、およびC2-C8アシル基から選ばれる少なくとも1種を有していてもよいC1-C40飽和脂肪族炭化水素基もしくはC3-C40脂環式炭化水素基であることを特徴とする請求項6に記載の選択的に化学修飾されたカーボンナノチューブの製造方法。
- 有機溶媒としてトルエンまたはキシレンを用いることを特徴とする請求項5から7のいずれかに記載の選択的に化学修飾されたカーボンナノチューブの製造方法。
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US13/577,011 US8940937B2 (en) | 2010-02-04 | 2011-01-28 | Method for producing selectively functionalized carbon nanotubes |
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WO2018180901A1 (ja) * | 2017-03-30 | 2018-10-04 | 日本ゼオン株式会社 | 繊維状炭素ナノ構造体分散液及びその製造方法、並びに繊維状炭素ナノ構造体 |
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EP2532622A1 (en) | 2012-12-12 |
KR20120113767A (ko) | 2012-10-15 |
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