JP2004168570A - Method for manufacturing soluble carbon nanotube - Google Patents
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【０００１】
【発明の属する技術分野】
本発明は、カーボンナノチューブ、特に単層カーボンナノチューブ（以下、ＳＷＣＮＴと表す場合もある。）を、化学修飾により溶媒に可溶性にしたカーボンナノチューブを温和な条件下で製造する方法に関する
【０００２】
【従来の技術】
カーボンナノチューブは製法により、径や長さ、カイラリティ、層数、終端の形態等の違った多様な特性のものが得られる。特に、単層カーボンナノチューブにおいては、製造直後の単層カーボンナノチューブは先端に５員環を含む炭素骨格を有するために閉管状態となっており、またチューブの周りにカーボンナノ粒子やアモルファスカーボン等の炭素不純物が多数付着している。したがって、前記不純物の除去、開口処理、形態の違いとその形態の持つ特徴的な特性の把握、および多様な構造の中から選択した構造のものを特異的に、かつ安定的に量産できる技術の確立が、基本的な問題として重要である。
前記確立の後には、産業界および社会生活において有用性を持ったものとするために、確立された特定の構造形態のカーボンナノチューブの生産に裏付けられた材料の有用性を高める処理技術、すなわち、該カーボンナノチューブに機械的または化学的変形や修飾などにより新しい機能を付与する技術、の確立が必要になる。
そして、前記化学的変形や修飾等による改質処理は溶液中で行えることが、化学反応の容易性の観点から望まれるところであるから、カーボンナノチューブを溶媒に可溶化する技術の確立も重要であり、そのような研究もされている。
【０００３】
【特許文献１】
特開平８−１２３１０号公報（特に、請求の範囲、〔０００３〕〜〔０００６〕、各実施例）
【非特許文献１】
編者 田中 一義「カーボンナノチューブ」ナノデバイスへの挑戦、（株）化学同人、２００１年１月３０日、ｐ．１００−１０３
【０００４】
前記特許文献１には、粗カーボン・ナノチューブを硫酸・硝酸混合溶液などで処理することにより開口、精製、官能基の導入などを緩和な条件で行う方法の発明が記載されている。また、前記非特許文献１には、カーボンナノチューブの末端の開口に最も広く用いられているものとして、酸処理と超音波処理を組み合わせた方法があり、該方法においては、超音波の周波数などの調整により、長さ分布の調整された開口したカーボン・ナノチューブが得られることが記載されている。更に、このようにして得られた開口したカーボン・ナノチューブの開口部へオクタデシルアミンを修飾することにより、ベンゼンなどの有機溶媒に可溶のＳＷＣＮＴが合成されることが記載されている。しかしながら、前記修飾により可溶化したＳＷＣＮＴの合成方法は、カルボン酸の酸塩化物への変換、さらにはアミド化の過程を経るという点で簡易な方法とは言い難い。
【０００５】
【発明が解決しようとする課題】
本発明の課題は、温和な条件下で、かつ高効率の脱水反応を進行させ、非常に高純度の有機溶媒可溶性のＳＷＮＴを合成する方法を提供することである。
前記課題を解決するために、本発明者らは、開口処理したＳＷＣＮＴを簡易に溶媒可溶性に修飾する手段を検討する中で、有機アミン、特に有機溶媒に親和性の基を有するアミン類を、脱水剤の存在下で前記開口処理したＳＷＣＮＴと反応させ修飾処理することにより、より容易に溶媒可溶性にすることが出来ることを見出し、前記課題を解決することが出来た。
【０００６】
【課題を解決するための手段】
本発明は、単層カーボンナノチューブを少なくとも硫酸−硝酸の混合溶液中での超音波処理および硫酸と過酸化水素の混合溶液中での超音波処理をした後、前記処理した単層カーボンナノチューブに有機アミンおよび脱水剤の存在下で前記アミンと反応させ前記アミンで修飾して溶媒に可溶化した単層カーボンナノチューブを製造する方法である。好ましくは、前記有機アミンが一級、二級アルキルアミン、一級芳香族アミンおよび二級芳香族アミンからなる群から選択される少なくとも１種であることを特徴とする前記前記アミンで修飾して溶媒に可溶化した単層カーボンナノチューブを製造する方法であり、より好ましくは、脱水剤がジシクロヘキシルカルボジイミド、Ｎ，Ｎ’−カルボニルジイミダゾール、３，４，５−トリフルオロベンゼンボロニックアシッドおよびビス（ビストリメチルシリルアミノ）スズからなる群から選択される少なくとも１種であることを特徴とする前記各アミンで修飾して溶媒に可溶化した単層カーボンナノチューブを製造する方法である。また、使用するＳＷＣＮＴがアーク放電法で製造された物の場合、硫酸−硝酸の混合溶液中での超音波処理および硫酸と過酸化水素の混合溶液中での超音波処理の前に３５０℃±２０℃の温度、大気下での熱処理および室温における塩酸溶液中での超音波処理をすることを特徴とする前記各アミンで修飾して溶媒に可溶化した単層カーボンナノチューブを製造する方法である。
【０００７】
【本発明の実施の態様】
本発明をより詳細に説明する。
Ａ．従来技術では、ＳＷＣＮＴ上のカルボキシル基とアミン類との脱水プロセスは熱反応ににより実施していたので、収率が低い、純度が低いなどの問題点があった。そこで本発明においては、前記脱水プロセスを有機脱水剤の存在下で実施する方法を開発し、前記不都合を改善したものである。
Ｂ．前記脱水剤としては、ＳＷＣＮＴ上のカルボキシル基とアミン類との脱水プロセス（アミド脱水縮合）に選択的、かつ効率で機能するものであれば充分であるが、ジシクロヘキシルカルボジイミド、Ｎ，Ｎ’−カルボニルジイミダゾール、３，４，５−トリフルオロベンゼンボロニックアシッドおよびビス（ビストリメチルシリルアミノ）スズを好ましいものとして、また、ジシクロヘキシルカルボジイミドを特に好ましいものとして挙げることができる。
Ｃ．前記ＳＷＣＮＴ上のカルボキシル基とアミン類との脱水プロセスは、ジメチルホルムアミド（ＤＭＦ）、テトラヒドロフランなどの溶媒を用いるのが好ましい。
Ｄ．前記ＳＷＣＮＴ上のカルボキシル基とアミン類との脱水プロセスは、１２０℃±１０℃において、少なくとも６０時間行うことにより、ＳＷＣＮＴ上のカルボキシル基がアミド化された。重量基準の７５％の収率で得られた。
Ｅ．ＳＷＣＮＴの開口処理は前記文献に記載の方法を採用することが出来る。
【０００８】
【実施例】
以下、実施例により本発明を具体的に説明するが、この例示により本発明が限定的に解釈されるものではない。
得られた溶媒可溶性のカーボンナノチューブの紫外（ＵＶ）・可視（ＶＬ）・近赤外（ＮＲＩ）吸収スペクトルは、島津製作所製のＵＶ−３１５０型吸収スペクトル測定装置を用いて測定した。また、ＡＦＭイメージはビーコインスツルメント社製のナノスコープＩＩＩ型原子間力顕微鏡およびＳＥＭイメージは日立製作所製のＳ−４３００型走査型電子顕微鏡を用いて測定した。
【０００９】
実施例１
アーク放電法で製造の単層カーボンナノチューブ（Ｃａｒｂｏｌｅｘ社製の単層カーボンナノチューブ、ＡＰ−ＳＷＣＮＴ）１５０ｍｇを１８時間３５０℃で熱処理し、塩酸（１００ｍＬ／３６％）に室温で超音波分散した。硫酸（５ｍＬ／９７％）と硝酸（１８ｍＬ／７０％）の混合溶液、硫酸（４８ｍＬ／９７％）と過酸化水素（１２ｍＬ／３０％）の混合溶液中、室温にて超音波処理した。さらにＳＷＮＴ９．５ｍｇをジメチルホルムアミド（２０ｍＬ）中に分散し、オクタデシルアミン（１ｇ）とジシクロヘキシルカルボジイミド（ＤＣＣ）（０．５ｇ）を加え、１２０℃で６０時間反応し、可溶性単層カーボンナノチューブを合成した。
収率７５％、生成化合物の純度９７％。
【００１０】
実施例２
レーザーアブレーション法で製造の単層カーボンナノチューブ（Ｔｕｂｅ＠Ｒｉｃｅ社製 精製ＳＷＣＮＴ）１００ｍｇを硫酸（１２０ｍＬ／９７％）と硝酸（４０ｍＬ／７０％）の混合溶液中、〜４０℃にて超音波処理した後、硫酸（１２０ｍＬ／９７％）と過酸化水素（３０ｍＬ／３０％）の混合溶液中撹拌した。さらにＳＷＮＴ２９．２ｍｇをジメチルホルムアミド（６０ｍＬ）中に分散し、オクタデシルアミン（１ｇ）とジシクロヘキシルカルボジイミド（０．５ｇ）を混合し、１２０℃で６０時間反応し、可溶性単層カーボンナノチューブを合成した。
【００１１】
実施例３、実施例１、および２で得られた可溶性ＳＷＣＮＴの特性；可視近赤外（ＶＬ−ＮＩＲ）吸収スペクトル。
可溶化した単層カーボンナノチューブをジクロロメタン、トルエン、テトラヒドロフラン（ＴＨＦ）中で超音波処理し、過剰のオクタデシルアミン（ＯＤＡ）とジシクロヘキシルカルボジイミド（ＤＣＣ）を濾別した。可溶化単層カーボンナノチューブをＴＨＦに溶解し、可視近赤外（ＶＬ−ＮＩＲ）吸収スペクトルの測定を行測定を行い、可溶性ＳＷＣＮＴの生成が確認され。その結果を図１に示す。
【００１２】
実施例４、実施例１、および２で得られた可溶性ＳＷＣＮＴのラマンスペクトル
可溶化した単層カーボンナノチューブをジクロロメタン、トルエン、テトラヒドロフラン（ＴＨＦ）中で超音波し、過剰のオクタデシルアミン（ＯＤＡ）とジシクロヘキシルカルボジイミド（ＤＣＣ）を濾別した。可溶性単層カーボンナノチューブの薄膜をメンブランフィルター上に作成し、ラマンスペクトルを測定を行い、可溶性ＳＷＣＮＴの生成が確認された。測定結果を図２に示す。
【００１３】
実施例５、実施例１、および２で得られた可溶性ＳＷＣＮＴの原子間力顕微鏡像
可溶化した単層カーボンナノチューブをジクロロメタン、トルエン、テトラヒドロフラン（ＴＨＦ）中で超音波し、過剰のオクタデシルアミン（ＯＤＡ）とジシクロヘキシルカルボジイミド（ＤＣＣ）を濾別した。ＴＨＦに溶解した可溶性単層カーボンナノチューブをマイカ基盤上に展開し、原子間力顕微鏡でＡＦＭイメージ図の測定を行測定を行い、高純度ＳＷＣＮＴの生成が確認された。結果を図３に示す。
【００１４】
実施例５、実施例１、および２で得られた可溶性ＳＷＣＮＴの走査型電子顕微鏡像
可溶化した単層カーボンナノチューブをジクロロメタン、トルエン、テトラヒドロフラン（ＴＨＦ）中で超音波し、過剰のオクタデシルアミン（ＯＤＡ）とジシクロヘキシルカルボジイミド（ＤＣＣ）を濾別した。ＴＨＦに溶解した可溶性単層カーボンナノチューブをマイカ基盤上に展開し、走査型電子顕微鏡でＳＥＭイメージ図の測定を行い、高純度ＳＷＣＮＴの生成が確認された。その結果を図４に示す。
【００１５】
【発明の効果】
以上述べたように、本発明の、ＳＷＣＮＴ上のカルボキシル基とアミン類との脱水プロセスに、脱水剤を用いるという構成により、ＳＷＣＮＴを溶媒可溶化修飾して得られる化合物の収率および純度が向上するという優れた効果がもたらされる。
【図面の簡単な説明】
【図１】実施例１、２の溶媒可溶化ＳＷＣＮＴの可視近赤外（ＶＬ−ＮＩＲ）吸収スペクトル、（ａ）は実施例１、（ｂ）は実施例２
【図２】実施例１、２の溶媒可溶化ＳＷＣＮＴのラマンスペクトル、（ａ）は実施例１、（ｂ）は実施例２
【図３】実施例１、２の溶媒可溶化ＳＷＣＮＴのＡＦＭイメージ、（ａ）は実施例１、（ｂ）は実施例２
【図４】実施例１、２の溶媒可溶化ＳＷＣＮＴのＳＥＭイメージ、（ａ）は実施例１、（ｂ）は実施例２[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing carbon nanotubes, particularly single-walled carbon nanotubes (hereinafter sometimes referred to as SWCNTs), under mild conditions, by making the carbon nanotubes soluble in a solvent by chemical modification.
[Prior art]
Depending on the manufacturing method, carbon nanotubes having various characteristics such as diameter, length, chirality, number of layers, and terminal form can be obtained. In particular, in the single-walled carbon nanotube, the single-walled carbon nanotube immediately after production is in a closed state because it has a carbon skeleton containing a five-membered ring at the tip, and the carbon nanotubes and amorphous carbon are surrounded around the tube. Many carbon impurities are attached. Therefore, the technique of removing impurities, performing opening treatment, grasping the difference in form and the characteristic characteristics of the form, and a method capable of specifically and stably mass-producing a structure selected from various structures. Establishment is important as a fundamental issue.
After the establishment, in order to have utility in industry and social life, processing technology that enhances the usefulness of the material backed by the production of carbon nanotubes of an established specific structural form, that is, It is necessary to establish a technique for imparting a new function to the carbon nanotube by mechanical or chemical deformation or modification.
Since it is desired from the viewpoint of the easiness of the chemical reaction that the modification treatment by the chemical deformation or modification can be performed in a solution, it is also important to establish a technique for solubilizing the carbon nanotubes in a solvent. , Such research has been done.
[0003]
[Patent Document 1]
JP-A-8-12310 (particularly, claims, [0003] to [0006], each embodiment)
[Non-patent document 1]
Editor: Kazuyoshi Tanaka Challenge to "Carbon Nanotube" Nanodevice, Kagaku Dojin, January 30, 2001, p. 100-103
[0004]
Patent Document 1 describes an invention of a method in which opening, purification, introduction of a functional group, and the like are performed under mild conditions by treating a crude carbon nanotube with a mixed solution of sulfuric acid and nitric acid. In Non-Patent Document 1, there is a method that combines acid treatment and ultrasonic treatment as one of the most widely used methods for opening the ends of carbon nanotubes. It is described that the adjustment results in an open carbon nanotube having an adjusted length distribution. Furthermore, it is described that by modifying octadecylamine on the opening of the open carbon nanotube thus obtained, SWCNT soluble in an organic solvent such as benzene is synthesized. However, the method for synthesizing SWCNT solubilized by the modification is not a simple method in that it involves a process of converting carboxylic acid into acid chloride and further amidation.
[0005]
[Problems to be solved by the invention]
It is an object of the present invention to provide a method for synthesizing an organic solvent-soluble SWNT of very high purity by promoting a highly efficient dehydration reaction under mild conditions.
In order to solve the above-mentioned problems, the present inventors have studied means for easily modifying the SWCNT that has been subjected to the opening treatment to be solvent-soluble, and have found that organic amines, particularly amines having an affinity group for an organic solvent, The present inventors have found that by performing the modification treatment by reacting with the SWCNT subjected to the opening treatment in the presence of a dehydrating agent, the solvent can be more easily made soluble in the solvent, and the above-mentioned problem can be solved.
[0006]
[Means for Solving the Problems]
In the present invention, the single-walled carbon nanotubes are subjected to at least ultrasonic treatment in a mixed solution of sulfuric acid and nitric acid and ultrasonic treatment in a mixed solution of sulfuric acid and hydrogen peroxide. This is a method for producing single-walled carbon nanotubes which are reacted with the amine in the presence of an amine and a dehydrating agent, modified with the amine and solubilized in a solvent. Preferably, the organic amine is at least one selected from the group consisting of primary, secondary alkylamines, primary aromatic amines and secondary aromatic amines, wherein the organic amine is modified with the amine to form a solvent. It is a method for producing solubilized single-walled carbon nanotubes, and more preferably, the dehydrating agent is dicyclohexylcarbodiimide, N, N'-carbonyldiimidazole, 3,4,5-trifluorobenzeneboronic acid and bis (bistrimethylsilyl) A method for producing single-walled carbon nanotubes modified with each of the amines and solubilized in a solvent, wherein the single-walled carbon nanotubes are at least one selected from the group consisting of amino) tin. When the SWCNT used is manufactured by the arc discharge method, the temperature is set at 350 ° C. ± before the ultrasonic treatment in the mixed solution of sulfuric acid and nitric acid and the ultrasonic treatment in the mixed solution of sulfuric acid and hydrogen peroxide. A method for producing single-walled carbon nanotubes modified with each of the amines and solubilized in a solvent, wherein the single-walled carbon nanotubes are modified by a heat treatment at 20 ° C. in the atmosphere and an ultrasonic treatment in a hydrochloric acid solution at room temperature. .
[0007]
[Embodiment of the present invention]
The present invention will be described in more detail.
A. In the prior art, since the dehydration process between the carboxyl group on SWCNT and the amines was performed by a thermal reaction, there were problems such as low yield and low purity. Therefore, in the present invention, a method for performing the dehydration process in the presence of an organic dehydrating agent has been developed, and the above disadvantage has been improved.
B. As the dehydrating agent, it is sufficient that the dehydrating agent selectively and efficiently functions in a dehydration process (amide dehydration condensation) between a carboxyl group on SWCNT and an amine, but dicyclohexylcarbodiimide, N, N'-carbonyl Preferred are diimidazole, 3,4,5-trifluorobenzeneboronic acid and bis (bistrimethylsilylamino) tin, and particularly preferred is dicyclohexylcarbodiimide.
C. It is preferable to use a solvent such as dimethylformamide (DMF) or tetrahydrofuran for the dehydration process of the carboxyl group on SWCNT and amines.
D. The carboxyl group on the SWCNT was amidated by performing the dehydration process of the carboxyl group on the SWCNT and the amines at 120 ° C. ± 10 ° C. for at least 60 hours. It was obtained in a yield of 75% by weight.
E. FIG. For the opening treatment of the SWCNT, the method described in the above-mentioned document can be adopted.
[0008]
【Example】
Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.
The ultraviolet (UV), visible (VL), and near-infrared (NRI) absorption spectra of the obtained solvent-soluble carbon nanotubes were measured using a UV-3150 absorption spectrum measuring device manufactured by Shimadzu Corporation. The AFM image was measured using a Nanoscope type III atomic force microscope manufactured by Becoin Instrument, and the SEM image was measured using an S-4300 type scanning electron microscope manufactured by Hitachi, Ltd.
[0009]
Example 1
150 mg of single-walled carbon nanotubes (Carbonex single-walled carbon nanotubes, AP-SWCNT) manufactured by an arc discharge method was heat-treated at 350 ° C. for 18 hours, and ultrasonically dispersed in hydrochloric acid (100 mL / 36%) at room temperature. Ultrasonic treatment was performed at room temperature in a mixed solution of sulfuric acid (5 mL / 97%) and nitric acid (18 mL / 70%) and a mixed solution of sulfuric acid (48 mL / 97%) and hydrogen peroxide (12 mL / 30%). Further, 9.5 mg of SWNT was dispersed in dimethylformamide (20 mL), octadecylamine (1 g) and dicyclohexylcarbodiimide (DCC) (0.5 g) were added, and the mixture was reacted at 120 ° C. for 60 hours to synthesize a soluble single-walled carbon nanotube. .
Yield 75%, purity of product compound 97%.
[0010]
Example 2
100 mg of single-walled carbon nanotubes (purified SWCNT manufactured by Tube @ Rice) manufactured by a laser ablation method were subjected to ultrasonic treatment at ４０40 ° C. in a mixed solution of sulfuric acid (120 mL / 97%) and nitric acid (40 mL / 70%). Thereafter, the mixture was stirred in a mixed solution of sulfuric acid (120 mL / 97%) and hydrogen peroxide (30 mL / 30%). Further, 29.2 mg of SWNT was dispersed in dimethylformamide (60 mL), octadecylamine (1 g) and dicyclohexylcarbodiimide (0.5 g) were mixed, and reacted at 120 ° C. for 60 hours to synthesize a soluble single-walled carbon nanotube.
[0011]
Properties of the soluble SWCNTs obtained in Examples 3, 1 and 2; Visible and near infrared (VL-NIR) absorption spectra.
The solubilized single-walled carbon nanotubes were sonicated in dichloromethane, toluene, and tetrahydrofuran (THF), and excess octadecylamine (ODA) and dicyclohexylcarbodiimide (DCC) were separated by filtration. The solubilized single-walled carbon nanotubes were dissolved in THF, and visible and near-infrared (VL-NIR) absorption spectra were measured and measured, and the formation of soluble SWCNT was confirmed. The result is shown in FIG.
[0012]
Raman spectra of soluble SWCNTs obtained in Examples 4, 1 and 2 The solubilized single-walled carbon nanotubes were sonicated in dichloromethane, toluene, tetrahydrofuran (THF) and excess octadecylamine (ODA) and dicyclohexyl Carbodiimide (DCC) was filtered off. A thin film of a soluble single-walled carbon nanotube was formed on a membrane filter, and a Raman spectrum was measured. As a result, generation of a soluble SWCNT was confirmed. FIG. 2 shows the measurement results.
[0013]
Atomic force microscopy images of the soluble SWCNTs obtained in Examples 5, 1 and 2 The solubilized single-walled carbon nanotubes were sonicated in dichloromethane, toluene, tetrahydrofuran (THF) and excess octadecylamine (ODA) ) And dicyclohexylcarbodiimide (DCC) were filtered off. The soluble single-walled carbon nanotube dissolved in THF was developed on a mica substrate, and an AFM image diagram was measured with an atomic force microscope, and the measurement was performed. As a result, generation of high-purity SWCNT was confirmed. The results are shown in FIG.
[0014]
Scanning Electron Microscope Images of Soluble SWCNTs Obtained in Examples 5, 1 and 2 The solubilized single-walled carbon nanotubes were sonicated in dichloromethane, toluene, tetrahydrofuran (THF) and excess octadecylamine (ODA). ) And dicyclohexylcarbodiimide (DCC) were filtered off. The soluble single-walled carbon nanotubes dissolved in THF were developed on a mica substrate, and SEM image diagrams were measured with a scanning electron microscope, and the generation of high-purity SWCNT was confirmed. The result is shown in FIG.
[0015]
【The invention's effect】
As described above, by using a dehydrating agent in the dehydration process of the carboxyl group on SWCNT and amines of the present invention, the yield and purity of the compound obtained by solubilizing and modifying SWCNT in a solvent are improved. The effect is excellent.
[Brief description of the drawings]
FIG. 1 is a visible and near infrared (VL-NIR) absorption spectrum of solvent-solubilized SWCNTs of Examples 1 and 2, (a) is Example 1, and (b) is Example 2.
FIG. 2 is a Raman spectrum of solvent-solubilized SWCNTs of Examples 1 and 2, (a) is Example 1, (b) is Example 2
FIG. 3 is an AFM image of solvent-solubilized SWCNTs of Examples 1 and 2, (a) is Example 1, (b) is Example 2.
FIG. 4 is an SEM image of solvent-solubilized SWCNTs of Examples 1 and 2, (a) of Example 1 and (b) of Example 2
Claims (4)
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