JP6910602B2 - Manufacturing method of surface-modified nanodiamond and surface-modified nanodiamond - Google Patents
Manufacturing method of surface-modified nanodiamond and surface-modified nanodiamond Download PDFInfo
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Description
本発明は、表面修飾ナノダイヤモンドの製造方法、及び表面修飾ナノダイヤモンドに関する。 The present invention relates to a method for producing surface-modified nanodiamonds and surface-modified nanodiamonds.
ナノダイヤモンドは、比表面積が非常に大きい超微粒子のダイヤモンドであり、高い機械的強度と電気絶縁性、及び優れた熱伝導性を有する。また、消臭効果、抗菌効果、耐薬品性も有する。そのため、研磨材、導電性付与材、絶縁材料、消臭剤、抗菌剤等として使用される。 Nanodiamond is an ultrafine diamond having a very large specific surface area, and has high mechanical strength, electrical insulation, and excellent thermal conductivity. It also has deodorant effect, antibacterial effect, and chemical resistance. Therefore, it is used as an abrasive, a conductivity-imparting material, an insulating material, a deodorant, an antibacterial agent, and the like.
ナノダイヤモンドは、一般的に、爆轟法により合成される。爆轟法で得られるナノダイヤモンドは凝着体を形成している場合が多く、該凝着体を、ビーズミル等の粉砕機を用いた解砕処理に付することで粒子径Ｄ５０（メディアン径）が１０ｎｍ未満のいわゆる一桁ナノダイヤモンドが得られる（特許文献１、２）。 Nanodiamonds are generally synthesized by the detonation method. Nanodiamonds obtained by the detonation method often form adherents, and the adherents are subjected to crushing treatment using a crusher such as a bead mill to have a particle size of D50 (median diameter). So-called single-digit nanodiamonds having a diameter of less than 10 nm can be obtained (Patent Documents 1 and 2).
上記ナノダイヤモンドの特性を活かしながら、放熱材料、光学材料（例えば、高機能フィルム材料）、素材強化材料、熱交換流動媒体、コーティング材（例えば、抗菌コーティング材、消臭コーティング材）、研磨剤、潤滑剤、医療材料等の種々のアプリケーションへ展開するために、ナノダイヤモンドに目的の表面修飾基を導入することが行われている。 While taking advantage of the characteristics of nanodiamond, heat dissipation material, optical material (for example, high-performance film material), material strengthening material, heat exchange flow medium, coating material (for example, antibacterial coating material, deodorant coating material), abrasive, In order to develop into various applications such as lubricants and medical materials, the target surface modifying group is introduced into nanodiamond.
ナノダイヤモンドに表面修飾基を付与する方法としては、ナノダイヤモンド表面を水素化し、次に塩素を導入（塩素化）した後、目的の表面修飾基を有するアルコールと反応（脱塩素化）する方法が知られている（特許文献３）。 As a method of imparting a surface modifying group to nanodiamond, a method of hydrogenating the surface of nanodiamond, then introducing chlorine (chlorination), and then reacting with an alcohol having a desired surface modifying group (dechlorination) is used. It is known (Patent Document 3).
しかし、特許文献３に記載の方法では、ナノダイヤモンド表面に塩素を導入する必要があり、毒ガスである塩素または、腐食性の強い塩酸を扱う必要がある。また、ナノダイヤモンド表面を水素化し、塩素化した後にアルコール等と反応（脱塩素化）させる必要があり、ナノダイヤモンドに表面修飾基を付与するための工程が多い。 However, in the method described in Patent Document 3, it is necessary to introduce chlorine into the surface of nanodiamond, and it is necessary to handle chlorine which is a poisonous gas or hydrochloric acid which is highly corrosive. Further, it is necessary to hydrogenate the surface of nanodiamond, chlorinate it, and then react it with alcohol or the like (dechlorination), and there are many steps for imparting a surface modifying group to nanodiamond.
また、特許文献３に記載の方法で得られる表面修飾ナノダイヤモンドは、ダイヤモンドを水素含有環境内で約７００〜１２００℃という高温で加熱する工程（水素化工程）を含む（［００５７］〜［００５９］）。そのため、ナノダイヤモンド表面に存在している水酸基は、ほとんどが水素化されており、表面修飾基導入後のナノダイヤモンド表面には水酸基はほとんど存在していないと考えられる。 Further, the surface-modified nanodiamond obtained by the method described in Patent Document 3 includes a step (hydrogenation step) of heating the diamond at a high temperature of about 700 to 1200 ° C. in a hydrogen-containing environment ([0057] to [0059] to [0059]. ]). Therefore, it is considered that most of the hydroxyl groups existing on the surface of nanodiamond are hydrogenated, and almost no hydroxyl groups are present on the surface of nanodiamond after the introduction of the surface modifying group.
上記ナノダイヤモンドの特性を付与し、長期にわたって特性を保持するために、ナノダイヤモンドの特性を付与したい母材と反応して強固に結合するための表面修飾基をナノダイヤモンドに付与することが行われている。上記表面修飾基としては、ビニル基やエポキシ基を導入することが特に有用である。 In order to impart the characteristics of the nanodiamond and maintain the characteristics for a long period of time, the nanodiamond is provided with a surface modifying group for reacting with the base material to which the characteristics of the nanodiamond are desired to be firmly bonded. ing. It is particularly useful to introduce a vinyl group or an epoxy group as the surface modifying group.
表面修飾基としてビニル基やエポキシ基を有する場合、このビニル基やエポキシ基と研磨剤、コーティング材等の母材となる他の化合物を反応させることにより、容易にナノダイヤモンドと他の化合物を結合させることができる。さらに、このようなビニル基やエポキシ基を有しつつ、ナノダイヤモンド表面に水酸基を有することにより、水酸基特有の水分散性が良く、水への親和性が良い等の機能をナノダイヤモンドに付与することができる。 When a vinyl group or an epoxy group is provided as a surface modifying group, the nanodiamond and another compound can be easily bonded by reacting the vinyl group or the epoxy group with another compound as a base material such as an abrasive or a coating material. Can be made to. Further, by having a hydroxyl group on the surface of the nanodiamond while having such a vinyl group or an epoxy group, the nanodiamond is imparted with functions such as good water dispersibility peculiar to the hydroxyl group and good affinity for water. be able to.
従って、本発明の目的は、塩素導入を必要とせず、工程が少なく簡便な方法で目的とする表面修飾基を導入することができる表面修飾ナノダイヤモンドの製造方法を提供することにある。また、本発明の目的は、表面に一定の割合の水酸基を残しつつ、表面に特定の割合の表面修飾基を導入した表面修飾ナノダイヤモンドを提供することにある。 Therefore, an object of the present invention is to provide a method for producing surface-modified nanodiamond, which does not require the introduction of chlorine and can introduce the desired surface-modifying group by a simple method with few steps. Another object of the present invention is to provide surface-modified nanodiamonds in which a specific ratio of surface modifying groups is introduced into the surface while leaving a certain ratio of hydroxyl groups on the surface.
本発明者等は上記課題を解決するため鋭意検討した結果、ナノダイヤモンドと両末端ビニル化合物を反応させることで、ナノダイヤモンド表面にビニル基を導入することができ、さらにこのビニル基をエポキシ化することでエポキシ基を導入することができることを見いだした。本発明はこれらの知見に基づいて完成させたものである。 As a result of diligent studies to solve the above problems, the present inventors can introduce a vinyl group on the surface of nanodiamond by reacting the nanodiamond with a vinyl compound at both ends, and further epoxidize the vinyl group. It was found that the epoxy group can be introduced by this. The present invention has been completed based on these findings.
すなわち、本発明は、表面に水酸基を有するナノダイヤモンドと両末端にビニル基を有する化合物を反応させて、末端がビニル基である表面修飾基を有するナノダイヤモンドを得る工程を含む表面修飾ナノダイヤモンドの製造方法を提供する。 That is, the present invention comprises a step of reacting a nanodiamond having a hydroxyl group on the surface with a compound having a vinyl group at both ends to obtain a nanodiamond having a surface modifying group having a vinyl group at the end. Provide a manufacturing method.
また、本発明は、表面に水酸基を有するナノダイヤモンドと両末端にビニル基を有する化合物を反応させて、末端がビニル基である表面修飾基を有するナノダイヤモンドを得る工程、及び前記ビニル基をエポキシ化することにより、末端がエポキシ基である表面修飾基を有するナノダイヤモンドを得る工程を含む表面修飾ナノダイヤモンドの製造方法を提供する。 Further, the present invention is a step of reacting nanodiamond having a hydroxyl group on the surface with a compound having a vinyl group at both ends to obtain nanodiamond having a surface modifying group having a vinyl group at the end, and epoxying the vinyl group. Provided is a method for producing surface-modified nanodiamonds, which comprises a step of obtaining nanodiamonds having a surface-modifying group whose terminal is an epoxy group.
また、本発明は、前記両末端にビニル基を有する化合物を反応させる前に、前記表面に水酸基を有するナノダイヤモンドを熱酸化処理する工程を含む前記の表面修飾ナノダイヤモンドの製造方法を提供する。 The present invention also provides a method for producing the surface-modified nanodiamond, which comprises a step of thermally oxidizing the nanodiamond having a hydroxyl group on the surface before reacting the compound having a vinyl group at both ends.
また、本発明は、前記の表面に水酸基を有するナノダイヤモンドと両末端にビニル基を有する化合物を反応させて、末端がビニル基である表面修飾基を有するナノダイヤモンドを得る工程を、ナノダイヤモンドの解砕及び／又は粉砕処理とともに行う前記の表面修飾ナノダイヤモンドの製造方法を提供する。 Further, in the present invention, the step of reacting the nanodiamond having a hydroxyl group on the surface with a compound having a vinyl group at both ends to obtain a nanodiamond having a surface modifying group having a vinyl group at the end is a step of the nanodiamond. Provided is a method for producing the surface-modified nanodiamond, which is carried out together with crushing and / or crushing treatment.
また、本発明は、前記表面に水酸基を有するナノダイヤモンドとして、爆轟法ナノダイヤモンド又は高温高圧法ナノダイヤモンドを使用する前記の表面修飾ナノダイヤモンドの製造方法を提供する。 The present invention also provides a method for producing the surface-modified nanodiamond, which uses detonation nanodiamonds or high-temperature and high-pressure nanodiamonds as the nanodiamonds having a hydroxyl group on the surface.
また、本発明は、前記両末端にビニル基を有する化合物が、下記式（１）で表される化合物である前記の表面修飾ナノダイヤモンドの製造方法を提供する。
また、本発明は、表面に水酸基、及び末端がビニル基である表面修飾基を有するナノダイヤモンドであり、ナノダイヤモンドに含まれるｓｐ3混成軌道を形成する炭素原子全体（１００％）に対する、前記末端がビニル基である表面修飾基が結合しているナノダイヤモンド炭素原子の比率が０．１〜３０％であり、且つ前記水酸基と結合しているナノダイヤモンド炭素原子の比率が０．１〜３０％である表面修飾ナノダイヤモンドを提供する。 Further, the present invention is a nanodiamond having a hydroxyl group on the surface and a surface modifying group having a vinyl group at the end, and the terminal with respect to the entire carbon atom (100%) forming the sp 3 hybrid orbital contained in the nanodiamond. The ratio of nanodiamond carbon atoms bonded to the surface modifying group, which is a vinyl group, is 0.1 to 30%, and the ratio of nanodiamond carbon atoms bonded to the hydroxyl group is 0.1 to 30%. Provided is a surface-modified nanodiamond.
また、本発明は、前記末端がビニル基である表面修飾基が、下記式（２）で表される基である前記の表面修飾ナノダイヤモンドを提供する。
また、本発明は、前記末端がビニル基である表面修飾基を有するナノダイヤモンドにおける、ナノダイヤモンドに含まれるｓｐ3混成軌道を形成する炭素原子全体（１００％）に対する、ＣＯＯ構造をもつ官能基と結合している炭素原子の比率が、０．０１〜２０％である前記の表面修飾ナノダイヤモンドを提供する。 Further, the present invention relates to a functional group having a COO structure with respect to the entire carbon atom (100%) forming the sp 3 hybrid orbital contained in the nanodiamond in the nanodiamond having a surface modifying group whose terminal is a vinyl group. Provided are the surface-modified nanodiamonds having a bonded carbon atom ratio of 0.01 to 20%.
また、本発明は、表面に水酸基、及び末端がエポキシ基である表面修飾基を有するナノダイヤモンドであり、ナノダイヤモンドに含まれるｓｐ3混成軌道を形成する炭素原子全体（１００％）に対する、前記末端がエポキシ基である表面修飾基が結合しているナノダイヤモンド炭素原子の比率が０．１〜３０％であり、且つ前記水酸基と結合しているナノダイヤモンド炭素原子の比率が０．１〜３０％である表面修飾ナノダイヤモンドを提供する。 Further, the present invention is a nanodiamond having a hydroxyl group on the surface and a surface modifying group having an epoxy group at the end, and the terminal with respect to the entire carbon atom (100%) forming the sp 3 mixed orbital contained in the nanodiamond. The ratio of nanodiamond carbon atoms bonded to the surface modifying group, which is an epoxy group, is 0.1 to 30%, and the ratio of nanodiamond carbon atoms bonded to the hydroxyl group is 0.1 to 30%. Provided are surface-modified nanodiamonds.
また、本発明は、前記末端がエポキシ基である表面修飾基が、下記式（３）で表される基である前記の表面修飾ナノダイヤモンドを提供する。
また、本発明は、前記末端がエポキシ基である表面修飾基を有するナノダイヤモンドにおける、ナノダイヤモンドに含まれるｓｐ3混成軌道を形成する炭素原子全体（１００％）に対する、ＣＯＯ構造をもつ官能基と結合している炭素原子の比率が、０．０１〜２０％である前記の表面修飾ナノダイヤモンドを提供する。 Further, the present invention relates to a functional group having a COO structure with respect to the entire carbon atom (100%) forming the sp 3 hybrid orbital contained in the nanodiamond in the nanodiamond having a surface modifying group whose terminal is an epoxy group. Provided are the surface-modified nanodiamonds having a bonded carbon atom ratio of 0.01 to 20%.
本発明の表面修飾ナノダイヤモンドの製造方法は、上記構成を有することで、塩素導入を必要とせず、工程が少なく簡便な方法で目的とする表面修飾基（ビニル基、エポキシ基）を導入することができる。また、本発明の表面修飾ナノダイヤモンドは、表面に特定の割合の水酸基、及び表面修飾基（ビニル基、エポキシ基）を有するため、研磨剤、コーティング材等の母材となる他の化合物を反応性の良さを有しつつ、表面の水酸基特有の水分散性が良く、水への親和性が良いという機能を付与することができる。 The method for producing surface-modified nanodiamonds of the present invention does not require the introduction of chlorine by having the above-mentioned structure, and introduces a target surface-modifying group (vinyl group, epoxy group) by a simple method with few steps. Can be done. Further, since the surface-modified nanodiamond of the present invention has a specific ratio of hydroxyl groups and surface-modifying groups (vinyl group, epoxy group) on the surface, it reacts with other compounds serving as a base material such as an abrasive and a coating material. It is possible to impart the function of having good properties, good water dispersibility peculiar to hydroxyl groups on the surface, and good affinity for water.
また、本発明の表面修飾ナノダイヤモンドの製造方法で得られた表面修飾ナノダイヤモンド、及び本発明の表面修飾ナノダイヤモンドは、母材となる他の化合物との高い反応性を有し、様々な化合物と反応させることにより、例えば、放熱材料、光学材料（例えば、高機能フィルム材料）、素材強化材料、熱交換流動媒体、コーティング材（例えば、抗菌コーティング材、消臭コーティング材）、研磨剤、潤滑剤、医療材料等として好適に使用することができる。 Further, the surface-modified nanodiamond obtained by the method for producing the surface-modified nanodiamond of the present invention and the surface-modified nanodiamond of the present invention have high reactivity with other compounds as a base material and various compounds. By reacting with, for example, heat dissipation material, optical material (for example, high-performance film material), material strengthening material, heat exchange flow medium, coating material (for example, antibacterial coating material, deodorant coating material), abrasive, lubrication. It can be suitably used as an agent, a medical material, or the like.
［表面修飾ナノダイヤモンドの製造方法］
本発明の表面修飾ナノダイヤモンドの製造方法は、表面に水酸基を有するナノダイヤモンドと両末端にビニル基を有する化合物を反応させて、末端がビニル基である表面修飾基を有するナノダイヤモンドを得る工程（表面修飾基導入工程）を含む。また、本発明の表面修飾ナノダイヤモンドの製造方法は、表面に水酸基を有するナノダイヤモンドと両末端にビニル基を有する化合物を反応させて、末端がビニル基である表面修飾基を有するナノダイヤモンドを得る工程（表面修飾基導入工程）、及び前記ビニル基をエポキシ化することにより、末端がエポキシ基である表面修飾基を有するナノダイヤモンドを得る工程（エポキシ化工程）を含む。
[Manufacturing method of surface-modified nanodiamond]
The method for producing surface-modified nanodiamonds of the present invention is a step of reacting nanodiamonds having a hydroxyl group on the surface with a compound having vinyl groups at both ends to obtain nanodiamonds having surface-modifying groups having vinyl groups at the ends ( Surface modifying group introduction step) is included. Further, in the method for producing surface-modified nanodiamonds of the present invention, nanodiamonds having a hydroxyl group on the surface and a compound having vinyl groups at both ends are reacted to obtain nanodiamonds having a surface-modifying group having a vinyl group at the ends. A step (a step of introducing a surface modifying group) and a step of obtaining nanodiamonds having a surface modifying group having an epoxy group at the end by epoxidizing the vinyl group (epoxidation step) are included.
（表面修飾基導入工程）
表面修飾基導入工程は、表面に水酸基を有するナノダイヤモンドの水酸基と両末端にビニル基を有する化合物の一方のビニル基を反応させる工程であり、例えば下記式で表される。すなわち、ナノダイヤモンド表面の水酸基と両末端にビニル基を有する化合物の一方のビニル基が反応する。
The surface modifying group introduction step is a step of reacting the hydroxyl group of nanodiamond having a hydroxyl group on the surface with one vinyl group of a compound having a vinyl group at both ends, and is represented by, for example, the following formula. That is, the hydroxyl group on the surface of nanodiamond reacts with one vinyl group of the compound having vinyl groups at both ends.
上記表面に水酸基を有するナノダイヤモンドとしては、例えば、爆轟法ナノダイヤモンド（すなわち、爆轟法によって生成したナノダイヤモンド）や、高温高圧法ナノダイヤモンド（すなわち、高温高圧法によって生成したナノダイヤモンド）を使用することができる。本発明においては、なかでも、一次粒子の粒子径が一桁ナノメートルであり、分散性に優れる点で、爆轟法ナノダイヤモンドを使用することが好ましい。また、表面に水酸基を有するナノダイヤモンドは、反応性に優れ、効率よく表面修飾基を導入できる点から、粉体状であることが好ましい。 Examples of the nanodiamond having a hydroxyl group on the surface include detonation nanodiamonds (that is, nanodiamonds produced by the detonation method) and high-temperature and high-pressure nanodiamonds (that is, nanodiamonds produced by the high-temperature and high-pressure method). Can be used. In the present invention, it is preferable to use detonation nanodiamonds because the particle size of the primary particles is a single digit nanometer and the dispersibility is excellent. Further, nanodiamond having a hydroxyl group on the surface is preferably in the form of powder because it has excellent reactivity and can efficiently introduce a surface modifying group.
前記爆轟法には、空冷式爆轟法と水冷式爆轟法が含まれる。本発明においては、なかでも、空冷式爆轟法が水冷式爆轟法よりも一次粒子が小さいナノダイヤモンドを得ることができるうえで好ましい。また、爆轟は大気雰囲気下で行っても良く、窒素雰囲気、アルゴン雰囲気等の不活性ガス雰囲気下で行っても良い。従って、上記表面修飾工程に付すナノダイヤモンドは、爆轟法ナノダイヤモンド、すなわち爆轟法によって生成したナノダイヤモンドが好ましく、より好ましくは空冷式爆轟法ナノダイヤモンドである。 The detonation method includes an air-cooled detonation method and a water-cooled detonation method. In the present invention, the air-cooled detonation method is particularly preferable because it can obtain nanodiamonds having smaller primary particles than the water-cooled detonation method. Further, the detonation may be carried out in an atmospheric atmosphere, or may be carried out in an inert gas atmosphere such as a nitrogen atmosphere or an argon atmosphere. Therefore, the nanodiamonds subjected to the surface modification step are preferably detonation nanodiamonds, that is, nanodiamonds produced by the detonation method, and more preferably air-cooled detonation nanodiamonds.
上記表面に水酸基を有するナノダイヤモンドの粒子径Ｄ５０（メディアン径）は、例えば５０００ｎｍ以下、好ましくは１００ｎｍ以下、より好ましくは１０ｎｍ以下である。ナノダイヤモンドの粒子径Ｄ５０の下限は、例えば１ｎｍである。 The particle size D50 (median diameter) of nanodiamond having a hydroxyl group on the surface is, for example, 5000 nm or less, preferably 100 nm or less, and more preferably 10 nm or less. The lower limit of the particle size D50 of nanodiamond is, for example, 1 nm.
上記表面に水酸基を有するナノダイヤモンドとしては、市販品を用いることもでき、商品名「ＮａｎｏＡｍａｎｄｏ」（株式会社ナノ炭素研究所社製）、超分散ナノダイヤモンド（株式会社ダイセル製）等を使用することができる。 As the nanodiamond having a hydroxyl group on the surface, a commercially available product can be used, and the trade name "NanoAmando" (manufactured by Nanocarbon Research Institute Co., Ltd.), ultra-dispersed nanodiamond (manufactured by Daicel Co., Ltd.), etc. should be used. Can be done.
上記表面に水酸基を有するナノダイヤモンドは、水酸基以外にも、カルボキシル基等のＣＯＯ構造をもつ官能基、メチル基、エチル基、プロピル基、アミノ基等の表面官能基を有していてもよい。また、ナノダイヤモンドは、グラファイト（黒鉛）等の不純物を含有している場合もある。よって、表面に水酸基を有するナノダイヤモンドを熱酸化処理する工程を含むことが好ましい。熱酸化処理する工程を含む場合、表面に水酸基を有するナノダイヤモンドに含まれるグラファイト（黒鉛）等の不純物を除去でき、また、メチル基、エチル基、メチン基等の表面官能基を除去、若しくは水酸基に変換してナノダイヤモンドの表面官能基全体における水酸基の割合を高くすることができる。表面官能基全体における水酸基の割合を高くすることにより、表面修飾基の導入量を高くすることができる。 The nanodiamond having a hydroxyl group on its surface may have a functional group having a COO structure such as a carboxyl group, and a surface functional group such as a methyl group, an ethyl group, a propyl group and an amino group in addition to the hydroxyl group. In addition, nanodiamond may contain impurities such as graphite. Therefore, it is preferable to include a step of thermally oxidizing nanodiamond having a hydroxyl group on the surface. When the step of thermal oxidation treatment is included, impurities such as graphite contained in nanodiamond having a hydroxyl group on the surface can be removed, and surface functional groups such as a methyl group, an ethyl group and a methine group can be removed or a hydroxyl group. Can be converted to increase the proportion of hydroxyl groups in the total surface functional groups of nanodiamonds. By increasing the proportion of hydroxyl groups in the entire surface functional group, the amount of surface modifying group introduced can be increased.
上記熱酸化処理における温度は、例えば温度２００〜６００℃（好ましくは３００〜５００℃）であり、処理時間は、例えば１〜２０時間（好ましくは２〜１０時間）である。熱酸化処理には、例えば、マッフル炉等を用いることができ、空気雰囲気下以外にも窒素雰囲気下で行ってもよい。 The temperature in the thermal oxidation treatment is, for example, 200 to 600 ° C. (preferably 300 to 500 ° C.), and the treatment time is, for example, 1 to 20 hours (preferably 2 to 10 hours). For the thermal oxidation treatment, for example, a muffle furnace or the like can be used, and the thermal oxidation treatment may be performed in a nitrogen atmosphere as well as in an air atmosphere.
上記両末端にビニル基を有する化合物は、例えば、下記式（１）で表される化合物である。
式中のＸは、好ましくは直鎖状の炭素数１〜２０のアルキレン基であり、より好ましくは直鎖状の炭素数２〜１８のアルキレン基、さらに好ましくは直鎖状の炭素数３〜１６のアルキレン基、特に好ましくは直鎖状の炭素数４〜１２のアルキレン基である。 X in the formula is preferably a linear alkylene group having 1 to 20 carbon atoms, more preferably a linear alkylene group having 2 to 18 carbon atoms, and further preferably a linear alkylene group having 3 to 18 carbon atoms. It is an alkylene group of 16, particularly preferably a linear alkylene group having 4 to 12 carbon atoms.
上記両末端にビニル基を有する化合物としては、例えば、１，３−ブタジエン、１，４−ペンタジエン、１，５−ヘキサジエン、１，６−ヘプタジエン、１，７−オクタジエン、１，８−ノナジエン、１，９−デカジエン、１，１０−ウンデカジエン、１，１１−ドデカジエン、１，１２−トリデカジエン、１，１３−テトラデカジエン、１，１４−ペンタデカジエン、１，１５−ヘキサデカジエン、１，１６−ヘプタデカジエン、１，１７−オクタデカジエン、１，１８−ノナデカジエン等が挙げられる。 Examples of the compound having a vinyl group at both ends include 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, and 1,8-nonadiene. 1,9-Decadiene, 1,10-Undecadiene, 1,11-Dodecadiene, 1,12-Tridecadiene, 1,13-Tetradecadiene, 1,14-Pentadecadiene, 1,15-Hexadecadiene, 1, Examples thereof include 16-heptadecadiene, 1,17-octadecadiene, and 1,18-nonadecadiene.
上記反応における両末端にビニル基を有する化合物の使用量は、ナノダイヤモンド１００重量部に対して、例えば２００〜１００００重量部程度、好ましくは３００〜５０００重量部、より好ましくは５００〜２０００重量部である。両末端にビニル基を有する化合物を上記範囲で使用すると、反応性良くナノダイヤモンド表面に両末端にビニル基を有する化合物由来のアルケニル基を導入することができる。また、両末端のビニル基両方が、ナノダイヤモンドと反応することを抑制することができる。 The amount of the compound having vinyl groups at both ends in the above reaction is, for example, about 200 to 10000 parts by weight, preferably 300 to 5000 parts by weight, and more preferably 500 to 2000 parts by weight with respect to 100 parts by weight of nanodiamond. be. When a compound having vinyl groups at both ends is used in the above range, an alkenyl group derived from a compound having vinyl groups at both ends can be introduced into the surface of nanodiamond with good reactivity. In addition, it is possible to suppress the reaction of both vinyl groups at both ends with nanodiamond.
上記反応は、例えば、表面に水酸基を有するナノダイヤモンドと両末端にビニル基を有する化合物を、加熱、撹拌することにより行うことができる。反応は溶媒中にナノダイヤモンドを分散させて行ってもよく、使用する溶媒としては、例えば、トルエン、酢酸エチル、エタノール、メタノール、ヘキサン、クロロホルム、ジクロロメタン、四塩化炭素、キシレン等が挙げられる。 The above reaction can be carried out, for example, by heating and stirring nanodiamond having a hydroxyl group on the surface and a compound having vinyl groups at both ends. The reaction may be carried out by dispersing nanodiamonds in a solvent, and examples of the solvent used include toluene, ethyl acetate, ethanol, methanol, hexane, chloroform, dichloromethane, carbon tetrachloride, xylene and the like.
反応温度は、例えば室温〜２００℃程度（好ましくは５０〜１５０℃）である。反応時間は、例えば１〜５０時間（好ましくは２〜３０時間）である。また、反応はバッチ式、セミバッチ式、連続式等の何れの方法でも行うことができる。また、反応雰囲気は、例えば、空気雰囲気、窒素雰囲気、アルゴン雰囲気等の何れであってもよい。 The reaction temperature is, for example, about room temperature to 200 ° C. (preferably 50 to 150 ° C.). The reaction time is, for example, 1 to 50 hours (preferably 2 to 30 hours). Further, the reaction can be carried out by any method such as batch type, semi-batch type and continuous type. The reaction atmosphere may be, for example, an air atmosphere, a nitrogen atmosphere, an argon atmosphere, or the like.
上記反応は、超音波処理、ビーズミリング等によりナノダイヤモンドの解砕及び／又は粉砕処理とともに行うことが、ナノダイヤモンドの一次粒子表面に存在する水酸基と両末端にビニル基を有する化合物を効率良く反応させることができ、得られる表面修飾ナノダイヤモンドにおいて表面修飾基の導入量を高くすることができる点で好ましい。 The above reaction can be carried out together with the crushing and / or crushing treatment of nanodiamond by sonication, bead milling, etc., to efficiently react the hydroxyl groups present on the surface of the primary particles of nanodiamond with the compounds having vinyl groups at both ends. It is preferable in that the amount of the surface-modifying group introduced into the obtained surface-modified nanodiamond can be increased.
反応終了後、得られた反応生成物は、例えば、濾過、遠心分離、抽出、洗浄、中和等や、これらを組み合わせた手段により精製処理を施してもよい。遠心分離の条件としては、例えば回転数２００〜５００００ｒｐｍ（好ましくは５００〜３００００ｒｐｍ）、例えば遠心力１００〜１０００００ｇ（好ましくは５００〜５００００ｇ）である。洗浄に用いる溶媒としては、例えば、トルエン、酢酸エチル、エタノール、メタノール、ヘキサン、クロロホルム、ジクロロメタン、四塩化炭素、キシレン等が挙げられ、これらの溶媒で複数回洗浄を行ってもよく、洗浄の際に超音波処理を行ってもよい。 After completion of the reaction, the obtained reaction product may be purified by, for example, filtration, centrifugation, extraction, washing, neutralization, or a combination thereof. The conditions for centrifugation are, for example, a rotation speed of 200 to 50,000 rpm (preferably 500 to 30,000 rpm), for example, a centrifugal force of 100 to 100,000 g (preferably 500 to 50,000 g). Examples of the solvent used for washing include toluene, ethyl acetate, ethanol, methanol, hexane, chloroform, dichloromethane, carbon tetrachloride, xylene and the like, and these solvents may be used for washing multiple times. You may perform ultrasonic treatment on the solvent.
また、精製処理後は乾燥処理を施してもよい。乾燥処理を施すことにより、本発明の表面修飾ナノダイヤモンド（末端がビニル基である表面修飾基を有するナノダイヤモンド）の粉体が得られる。乾燥処理の手法としては、例えば、減圧加熱乾燥（減圧下で噴霧乾燥装置を使用して行う噴霧乾燥や、減圧下でエバポレーターを使用して行う蒸発乾固が含まれる）等が挙げられる。 Further, after the purification treatment, a drying treatment may be performed. By performing the drying treatment, the powder of the surface-modified nanodiamond of the present invention (nanodiamond having a surface-modifying group having a vinyl group at the end) can be obtained. Examples of the drying treatment method include vacuum heating drying (including spray drying performed using a spray drying device under reduced pressure and evaporation dryness performed using an evaporator under reduced pressure).
（エポキシ化工程）
上記表面修飾基導入工程にて、末端がビニル基である表面修飾基を有するナノダイヤモンドを得た後、当該ビニル基をエポキシ化することにより、末端がエポキシ基である表面修飾基を有するナノダイヤモンドを得ることができる。当該反応は、例えば、下記式で表される。
In the above-mentioned surface modifying group introduction step, a nanodiamond having a surface modifying group having a vinyl group at the end is obtained, and then the vinyl group is epoxidized to obtain a nanodiamond having a surface modifying group having an epoxy group at the end. Can be obtained. The reaction is represented by, for example, the following formula.
上記エポキシ化としては、一般的なオレフィンのエポキシ化の手法を用いることができ、例えば過酸等の酸化剤を用いてオレフィンをエポキシドに変換する方法が挙げられる。用いられる過酸としては、メタクロロ過安息香酸（ｍＣＰＢＡ）、ジメチルジオキシラン等が挙げられる。過酸等の酸化剤の使用量は、エポキシ化に十分な量であればよく、ナノダイヤモンド１００重量部に対して、例えば５０〜３０００重量部程度、好ましくは１００〜１０００重量部である。 As the epoxidation, a general olefin epoxidation method can be used, and examples thereof include a method of converting an olefin into an epoxide using an oxidizing agent such as peracid. Examples of the peracid used include metachloroperbenzoic acid (mCPBA), dimethyldioxirane and the like. The amount of the oxidizing agent such as peracid used may be a sufficient amount for epoxidation, and is, for example, about 50 to 3000 parts by weight, preferably 100 to 1000 parts by weight, based on 100 parts by weight of nanodiamond.
エポキシ化は、例えばジクロロメタン等の溶媒にナノダイヤモンドを分散させ、過酸等の酸化剤を加えて撹拌することにより行うことができる。エポキシ化の反応温度は、例えば−２０〜５０℃程度（好ましくは−１０〜３０℃）である。エポキシ化の反応時間は、例えば１〜５０時間（好ましくは２〜３０時間）である。また、反応はバッチ式、セミバッチ式、連続式等の何れの方法でも行うことができる。 Epoxidation can be carried out by dispersing nanodiamonds in a solvent such as dichloromethane, adding an oxidizing agent such as peracid, and stirring the mixture. The reaction temperature for epoxidation is, for example, about -20 to 50 ° C. (preferably -10 to 30 ° C.). The reaction time for epoxidation is, for example, 1 to 50 hours (preferably 2 to 30 hours). Further, the reaction can be carried out by any method such as batch type, semi-batch type and continuous type.
反応終了後、得られた反応生成物は、例えば、濾過、遠心分離、抽出、洗浄、中和等や、これらを組み合わせた手段により精製処理を施すことが好ましい。遠心分離の条件、洗浄に用いる溶媒は、両末端にビニル基を有する化合物における反応で述べたとおりである。また、精製処理後は乾燥処理を施してもよい。乾燥処理を施すことにより、本発明の表面修飾ナノダイヤモンド（末端がエポキシ基である表面修飾基を有するナノダイヤモンド）の粉体が得られる。乾燥処理の手法は、上記表面修飾基導入工程で述べたとおりである。 After completion of the reaction, the obtained reaction product is preferably purified by, for example, filtration, centrifugation, extraction, washing, neutralization, or a combination of these. The conditions for centrifugation and the solvent used for washing are as described in the reaction for compounds having vinyl groups at both ends. Further, after the purification treatment, a drying treatment may be performed. By performing the drying treatment, the powder of the surface-modified nanodiamond of the present invention (nanodiamond having a surface-modifying group having an epoxy group at the end) can be obtained. The method of the drying treatment is as described in the above-mentioned surface modifying group introduction step.
［表面修飾ナノダイヤモンド］
（末端がビニル基である表面修飾基を有するナノダイヤモンド）
本発明の表面修飾ナノダイヤモンド（末端がビニル基である表面修飾基を有するナノダイヤモンド）は、表面に水酸基、及び末端がビニル基である表面修飾基を有するナノダイヤモンドであり、ナノダイヤモンドに含まれるｓｐ3混成軌道を形成する炭素原子全体（１００％）に対する、前記末端がビニル基である表面修飾基が結合しているナノダイヤモンド炭素原子の比率が０．１〜３０％であり、且つ前記水酸基と結合しているナノダイヤモンド炭素原子の比率が０．１〜３０％である。本発明の表面修飾ナノダイヤモンドは、例えば上記本発明の表面修飾ナノダイヤモンドの製造方法で得られる。
[Surface-modified nanodiamond]
(Nanodiamond having a surface modifying group whose terminal is a vinyl group)
The surface-modified nanodiamond of the present invention (nanodiamond having a surface-modifying group having a vinyl group at the end) is a nanodiamond having a hydroxyl group on the surface and a surface-modifying group having a vinyl group at the end, and is included in the nanodiamond. The ratio of the nanodiamond carbon atom to which the surface modifying group having a vinyl group at the end is bonded to the total carbon atom (100%) forming the sp 3 mixed orbital is 0.1 to 30%, and the hydroxyl group. The ratio of nanodiamond carbon atoms bonded to is 0.1 to 30%. The surface-modified nanodiamond of the present invention can be obtained, for example, by the above-mentioned method for producing surface-modified nanodiamond of the present invention.
上記末端がビニル基である表面修飾基は、例えば下記式（２）で表される。
式（２）中のＸは、好ましくは直鎖状の炭素数１〜２０のアルキレン基であり、より好ましくは直鎖状の炭素数２〜１８のアルキレン基、さらに好ましくは直鎖状の炭素数３〜１６のアルキレン基、特に好ましくは直鎖状の炭素数４〜１２のアルキレン基である。 X in the formula (2) is preferably a linear alkylene group having 1 to 20 carbon atoms, more preferably a linear alkylene group having 2 to 18 carbon atoms, and further preferably a linear carbon number. It is an alkylene group having a number of 3 to 16, particularly preferably a linear alkylene group having 4 to 12 carbon atoms.
上記式（２）で表される表面修飾基は、例えばアルケニルオキシ基が挙げられる。アルケニルオキシ基としては、例えば炭素数４〜２４のアルケニルオキシ基が挙げられ、具体的には、３−ブテニルオキシ基、４−ペンテニルオキシ基、５−ヘキセニルオキシ基、６−ヘプテニルオキシ基、７−オクテニルオキシ基、８−ノネニルオキシ基、９−デセニルオキシ基、１０−ウンデセニルオキシ基、１１−ドデセニルオキシ基、１２−トリデセニルオキシ基、１３−テトラデセニルオキシ基、１４−ペンタデセニルオキシ基、１５−ヘキサデセニルオキシ基、１６−ヘプタデセニルオキシ基、１７−オクタデセニルオキシ基、１８−ノナデセニルオキシ基等が挙げられる。アルケニルオキシ基としては、７−オクテニルオキシ基、８−ノネニルオキシ基、９−デセニルオキシ基、１０−ウンデセニルオキシ基、１１−ドデセニルオキシ基、１３−テトラデセニルオキシ基が特に好ましい。 Examples of the surface modifying group represented by the above formula (2) include an alkenyloxy group. Examples of the alkenyloxy group include an alkenyloxy group having 4 to 24 carbon atoms, and specifically, a 3-butenyloxy group, a 4-pentenyloxy group, a 5-hexenyloxy group, a 6-heptenyloxy group, and a 7-octane group. Tenyloxy group, 8-nonenyloxy group, 9-decenyloxy group, 10-undecenyloxy group, 11-dodecenyloxy group, 12-tridecenyloxy group, 13-tetradecenyloxy group, 14-pentadecenyl Examples thereof include an oxy group, a 15-hexadecenyloxy group, a 16-heptadecenyloxy group, a 17-octadecenyloxy group, and an 18-nonadesenyloxy group. As the alkenyloxy group, a 7-octenyloxy group, an 8-nonenyloxy group, a 9-decenyloxy group, a 10-undecenyloxy group, an 11-dodecenyloxy group and a 13-tetradecenyloxy group are particularly preferable.
上記末端がビニル基である表面修飾基を有するナノダイヤモンドは、表面修飾基として導入した末端がビニル基である表面修飾基以外に原料のナノダイヤモンド由来の水酸基、ＣＯＯ構造をもつ官能基、水素原子、メチル基、アミノ基等の表面官能基を有していてもよい。ＣＯＯ構造をもつ官能基としては、カルボキシル（ＣＯＯＨ）基、メトキシカルボニル（ＣＯＯＣＨ3）基、エトキシカルボニル（ＣＯＯＣ2Ｈ5）基等が挙げられる。 The nanodiamond having a surface modifying group having a vinyl group at the end is a hydroxyl group derived from the raw material nanodiamond, a functional group having a COO structure, and a hydrogen atom in addition to the surface modifying group having a vinyl group at the end introduced as the surface modifying group. , May have a surface functional group such as a methyl group or an amino group. Examples of the functional group having a COO structure, carboxyl (COOH) group, a methoxycarbonyl (COOCH 3) group, an ethoxycarbonyl (COOC 2 H 5) group and the like.
上記末端がビニル基である表面修飾基を有するナノダイヤモンドにおける、ナノダイヤモンドに含まれるｓｐ3混成軌道を形成する炭素原子全体（１００％）に対する、上記アルケニル基を含む表面修飾基が結合しているナノダイヤモンド炭素原子の比率は０．１〜３０％であり、好ましくは０．５〜２５％、より好ましくは１〜２０％、さらに好ましくは２〜１５％、特に好ましくは２．５〜１０％である。比率が上記範囲であると、ビニル基を適度に有することにより他の化合物との反応性を高くすることができる。 In a nanodiamond having a surface modifying group whose terminal is a vinyl group, the surface modifying group containing the alkenyl group is bonded to the entire carbon atom (100%) forming the sp 3 mixed orbital contained in the nanodiamond. The ratio of nanodiamond carbon atoms is 0.1 to 30%, preferably 0.5 to 25%, more preferably 1 to 20%, even more preferably 2 to 15%, particularly preferably 2.5 to 10%. Is. When the ratio is in the above range, the reactivity with other compounds can be enhanced by having an appropriate vinyl group.
上記末端がビニル基である表面修飾基を有するナノダイヤモンドにおける、ナノダイヤモンドに含まれるｓｐ3混成軌道を形成する炭素原子全体（１００％）に対する、上記水酸基と結合している炭素原子の比率は、例えば０．１〜３０％であり、好ましくは０．５〜２５％、より好ましくは１〜２０％、さらに好ましくは２〜２０％、特に好ましくは２．５〜１５％である。水酸基の比率が上記範囲であると、親水性等の水酸基の機能を適度にナノダイヤモンドに付与することができる。 In nanodiamonds with surface modification group the terminal is a vinyl group, to the total carbon atoms forming the sp 3 hybrid orbital contained nanodiamond (100%), the ratio of carbon atom bonded to the hydroxyl group, For example, it is 0.1 to 30%, preferably 0.5 to 25%, more preferably 1 to 20%, still more preferably 2 to 20%, and particularly preferably 2.5 to 15%. When the ratio of hydroxyl groups is in the above range, the functions of hydroxyl groups such as hydrophilicity can be appropriately imparted to nanodiamonds.
上記末端がビニル基である表面修飾基を有するナノダイヤモンドにおける、ナノダイヤモンドに含まれるｓｐ3混成軌道を形成する炭素原子全体（１００％）に対する、上記ＣＯＯ構造をもつ官能基と結合している炭素原子の比率は、例えば０．０１〜２０％であり、好ましくは０．０５〜１５％、より好ましくは０．１〜１０％、さらに好ましくは０．５〜８％、特に好ましくは１〜６％である。ＣＯＯ構造をもつ官能基の比率が上記範囲であると、親水性等のＣＯＯ構造をもつ官能基の機能を適度にナノダイヤモンドに付与することができる。 In nanodiamond having a surface modifying group whose terminal is a vinyl group, the carbon bonded to the functional group having the COO structure with respect to the entire carbon atom (100%) forming the sp 3 hybrid orbital contained in the nanodiamond. The ratio of atoms is, for example, 0.01 to 20%, preferably 0.05 to 15%, more preferably 0.1 to 10%, still more preferably 0.5 to 8%, and particularly preferably 1 to 6. %. When the ratio of the functional group having a COO structure is within the above range, the function of the functional group having a COO structure such as hydrophilicity can be appropriately imparted to the nanodiamond.
上記末端がビニル基である表面修飾基が結合しているナノダイヤモンド炭素原子、及び水酸基と結合する炭素原子の比率（ナノダイヤモンドに含まれるｓｐ3混成軌道を形成する炭素原子全体（１００％）に対する）は、例えば、固体13Ｃ−ＮＭＲ分析で得られた、表面修飾ナノダイヤモンドのスペクトルより各炭素原子のピーク（ピーク面積）から算出することにより求めることができる。各炭素原子のピークが重なる場合は、波形分離等の手法を用いることにより比率を求めることができる。 The ratio of the nanodiamond carbon atom to which the surface modifying group whose terminal is a vinyl group is bonded and the carbon atom bonded to the hydroxyl group (with respect to the entire carbon atom (100%) forming the sp 3 mixed orbital contained in the nanodiamond). ) Can be obtained, for example, by calculating from the peak (peak area) of each carbon atom from the spectrum of the surface-modified nanodiamond obtained by the solid 13 C-NMR analysis. When the peaks of each carbon atom overlap, the ratio can be obtained by using a method such as waveform separation.
上記末端がビニル基である表面修飾基が結合しているナノダイヤモンド炭素原子は、式（２）で表される表面修飾基の場合、式（２）で表される表面修飾基の左端と結合しているナノダイヤモンド炭素原子となる。この式（２）で表される表面修飾基の左端と結合しているナノダイヤモンド炭素原子と式（２）で表される表面修飾基のビニル基を形成する炭素原子のうち末端の炭素原子の比率は、同一の表面修飾基に由来するため同じとなる。よって、式（２）で表される表面修飾基の右端の炭素原子の比率を求め、末端がビニル基である表面修飾基が結合しているナノダイヤモンド炭素原子の比率としてもよい。 In the case of the surface modifying group represented by the formula (2), the nanodiamond carbon atom to which the surface modifying group whose terminal is a vinyl group is bonded is bonded to the left end of the surface modifying group represented by the formula (2). It becomes a nanodiamond carbon atom. Of the carbon atoms forming the nanodiamond carbon atom bonded to the left end of the surface modifying group represented by the formula (2) and the vinyl group of the surface modifying group represented by the formula (2), the terminal carbon atom The ratios are the same because they are derived from the same surface modifying group. Therefore, the ratio of the carbon atom at the right end of the surface modifying group represented by the formula (2) may be obtained, and the ratio may be the ratio of the nanodiamond carbon atom to which the surface modifying group having a vinyl group at the end is bonded.
末端がビニル基である表面修飾基を有するナノダイヤモンド全重量に占める当該表面修飾基の重量の割合は、例えば０．１〜５０重量％、好ましくは０．５〜４５重量％、より好ましくは５〜４０重量％、さらに好ましくは１０〜３５重量％である。当該表面修飾基の重量の割合が上記範囲であると、ビニル基を適度に有することにより他の化合物との反応性を高くすることができる。 The ratio of the weight of the surface modifying group to the total weight of the nanodiamond having a surface modifying group having a vinyl group at the end is, for example, 0.1 to 50% by weight, preferably 0.5 to 45% by weight, and more preferably 5. ~ 40% by weight, more preferably 10 to 35% by weight. When the weight ratio of the surface modifying group is in the above range, the reactivity with other compounds can be enhanced by having an appropriate vinyl group.
末端がビニル基である表面修飾基を有するナノダイヤモンド全重量に占める表面官能基の重量の割合は、例えば０．０１〜３０重量％、好ましくは０．５〜２５重量％、より好ましくは５〜２５重量％、さらに好ましくは１０〜２５重量％、特に好ましくは１５〜２５重量％である。また、末端がビニル基である表面修飾基を有するナノダイヤモンド全重量に占めるナノダイヤモンドの重量の割合は、例えば７０〜９９．９９重量％、好ましくは７５〜９９．５重量％、より好ましくは７５〜９５重量％、特に好ましくは７５〜９０重量％、最も好ましくは７５〜８５重量％である。なお、表面官能基には、上記末端がビニル基である表面修飾基も含まれる。 The ratio of the weight of the surface functional group to the total weight of the nanodiamond having a surface modifying group having a vinyl group at the end is, for example, 0.01 to 30% by weight, preferably 0.5 to 25% by weight, more preferably 5 to 5%. It is 25% by weight, more preferably 10 to 25% by weight, and particularly preferably 15 to 25% by weight. The ratio of the weight of the nanodiamond to the total weight of the nanodiamond having a surface modifying group having a vinyl group at the end is, for example, 70 to 99.99% by weight, preferably 75 to 99.5% by weight, and more preferably 75. It is ~ 95% by weight, particularly preferably 75 to 90% by weight, and most preferably 75 to 85% by weight. The surface functional group also includes a surface modifying group whose terminal is a vinyl group.
表面修飾ナノダイヤモンドにおける表面修飾基等の重量は、例えば、表面修飾ナノダイヤモンドを熱重量測定に付し、特定温度範囲における減量率から求めることができる。詳細には、表面修飾ナノダイヤモンドを空気雰囲気下での熱重量測定に付すと、２００℃以上、５００℃未満の温度範囲において重量の減少が観測される。これは、表面修飾ナノダイヤモンドにおける表面官能基部分の熱分解による。従って、上記温度範囲における重量減少率が表面修飾ナノダイヤモンド全量における表面官能基部分の占める割合に相当する。また、５００℃以上（例えば、５００〜６００℃）において急激に重量が減少する。これは表面修飾ナノダイヤモンドにおけるナノダイヤモンド部分の熱分解による。従って、上記温度範囲における重量減少率が、表面修飾ナノダイヤモンド全量におけるナノダイヤモンド部分の占める割合に相当する。 The weight of the surface-modifying group or the like in the surface-modified nanodiamond can be obtained, for example, from the weight loss rate in a specific temperature range when the surface-modified nanodiamond is subjected to thermogravimetric analysis. Specifically, when surface-modified nanodiamonds are subjected to thermogravimetric analysis in an air atmosphere, weight loss is observed in the temperature range of 200 ° C. and above and below 500 ° C. This is due to the thermal decomposition of the surface functional group portion of the surface-modified nanodiamond. Therefore, the weight loss rate in the above temperature range corresponds to the proportion of the surface functional group portion in the total amount of surface-modified nanodiamonds. In addition, the weight decreases sharply at 500 ° C. or higher (for example, 500 to 600 ° C.). This is due to the thermal decomposition of the nanodiamond portion of the surface-modified nanodiamond. Therefore, the weight loss rate in the above temperature range corresponds to the proportion of the nanodiamond portion in the total amount of surface-modified nanodiamonds.
（末端がエポキシ基である表面修飾基を有するナノダイヤモンド）
本発明の表面修飾ナノダイヤモンド（末端がエポキシ基である表面修飾基を有するナノダイヤモンド）は、表面に水酸基、及び末端がエポキシ基である表面修飾基を有するナノダイヤモンドであり、ナノダイヤモンドに含まれるｓｐ3混成軌道を形成する炭素原子全体（１００％）に対する、前記末端がエポキシ基である表面修飾基が結合しているナノダイヤモンド炭素原子の比率が０．１〜３０％であり、且つ前記水酸基と結合しているナノダイヤモンド炭素原子の比率が０．１〜３０％である。末端がエポキシ基である表面修飾基を有するナノダイヤモンドは、例えば上記本発明の表面修飾ナノダイヤモンドの製造方法で得られる。
(Nanodiamond having a surface modifying group whose terminal is an epoxy group)
The surface-modified nanodiamond of the present invention (nanodiamond having a surface-modifying group having an epoxy group at the end) is a nanodiamond having a hydroxyl group on the surface and a surface-modifying group having an epoxy group at the end, and is included in the nanodiamond. The ratio of the nanodiamond carbon atom to which the surface modifying group whose terminal is an epoxy group is bonded is 0.1 to 30% of the total carbon atom (100%) forming the sp 3 mixed orbital, and the hydroxyl group. The ratio of nanodiamond carbon atoms bonded to is 0.1 to 30%. Nanodiamonds having a surface-modifying group having an epoxy group at the end can be obtained, for example, by the above-mentioned method for producing surface-modified nanodiamonds of the present invention.
上記末端がエポキシ基である表面修飾基は、例えば下記式（３）で表される表面修飾基である。
式（３）中のＸは、好ましくは直鎖状の炭素数１〜２０のアルキレン基であり、より好ましくは直鎖状の炭素数２〜１８のアルキレン基、さらに好ましくは直鎖状の炭素数３〜１６のアルキレン基、特に好ましくは直鎖状の炭素数４〜１２のアルキレン基である。 X in the formula (3) is preferably a linear alkylene group having 1 to 20 carbon atoms, more preferably a linear alkylene group having 2 to 18 carbon atoms, and further preferably a linear carbon number. It is an alkylene group having a number of 3 to 16, particularly preferably a linear alkylene group having 4 to 12 carbon atoms.
上記末端がエポキシ基である表面修飾基は、表面修飾基として導入したエポキシ基以外に原料のナノダイヤモンド由来の水酸基、カルボキシル基等のＣＯＯ構造をもつ官能基、水素原子、メチル基、アミノ基等の表面官能基を有していてもよい。 The surface modifying group whose terminal is an epoxy group includes a functional group having a COO structure such as a hydroxyl group and a carboxyl group derived from nanodiamond as a raw material, a hydrogen atom, a methyl group, an amino group and the like, in addition to the epoxy group introduced as the surface modifying group. It may have a surface functional group of.
上記末端がエポキシ基である表面修飾基を有するナノダイヤモンドにおける、ナノダイヤモンドに含まれるｓｐ3混成軌道を形成する炭素原子全体（１００％）に対する、上記末端がエポキシ基である表面修飾基が結合しているナノダイヤモンド炭素原子の比率は０．１〜３０％であり、好ましくは０．５〜２５％、より好ましくは１〜２０％、さらに好ましくは２〜１５％、特に好ましくは２．５〜１０％である。比率が上記範囲であると、エポキシ基を適度に有することにより他の化合物との反応性を高くすることができる。 In nanodiamond having a surface modifying group having an epoxy group at the end, the surface modifying group having an epoxy group at the end is bonded to the entire carbon atom (100%) forming the sp 3 hybrid orbital contained in the nanodiamond. The proportion of nanodiamond carbon atoms is 0.1 to 30%, preferably 0.5 to 25%, more preferably 1 to 20%, still more preferably 2 to 15%, and particularly preferably 2.5 to. It is 10%. When the ratio is in the above range, the reactivity with other compounds can be enhanced by having an appropriate epoxy group.
上記末端がエポキシ基である表面修飾基を有するナノダイヤモンドにおける、ナノダイヤモンドに含まれるｓｐ3混成軌道を形成する炭素原子全体（１００％）に対する、上記水酸基と結合している炭素原子の比率は、例えば０．１〜３０％であり、好ましくは０．５〜２５％、より好ましくは１〜２０％、さらに好ましくは２〜２０％、特に好ましくは２．５〜１５％である。比率が上記範囲であると、親水性等の水酸基の機能を適度にナノダイヤモンドに付与することができる。上記末端がエポキシ基である表面修飾基が結合しているナノダイヤモンド炭素原子、及び上記水酸基と結合している炭素原子の比率は、例えば固体13Ｃ−ＮＭＲ分析による上述の方法により算出することができる。 The ratio of carbon atoms bonded to the hydroxyl group to the total carbon atoms (100%) forming the sp 3 hybrid orbital contained in the nanodiamond in the nanodiamond having a surface modifying group whose terminal is an epoxy group is For example, it is 0.1 to 30%, preferably 0.5 to 25%, more preferably 1 to 20%, still more preferably 2 to 20%, and particularly preferably 2.5 to 15%. When the ratio is in the above range, the function of the hydroxyl group such as hydrophilicity can be appropriately imparted to the nanodiamond. The ratio of the nanodiamond carbon atom to which the surface modifying group whose terminal is an epoxy group is bonded and the carbon atom bonded to the hydroxyl group can be calculated by, for example, the above method by solid 13 C-NMR analysis. can.
上記末端がエポキシ基である表面修飾基を有するナノダイヤモンドにおける、ナノダイヤモンドに含まれるｓｐ3混成軌道を形成する炭素原子全体（１００％）に対する、上記ＣＯＯ構造をもつ官能基と結合している炭素原子の比率は、例えば０．０１〜２０％であり、好ましくは０．０５〜１５％、より好ましくは０．１〜１０％、さらに好ましくは０．５〜８％、特に好ましくは１〜６％である。ＣＯＯ構造をもつ官能基の比率が上記範囲であると、親水性等のＣＯＯ構造をもつ官能基の機能を適度にナノダイヤモンドに付与することができる。 In nanodiamond having a surface modifying group whose terminal is an epoxy group, the carbon bonded to the functional group having the COO structure with respect to the entire carbon atom (100%) forming the sp 3 hybrid orbital contained in the nanodiamond. The ratio of atoms is, for example, 0.01 to 20%, preferably 0.05 to 15%, more preferably 0.1 to 10%, still more preferably 0.5 to 8%, and particularly preferably 1 to 6. %. When the ratio of the functional group having a COO structure is within the above range, the function of the functional group having a COO structure such as hydrophilicity can be appropriately imparted to the nanodiamond.
末端がエポキシ基である表面修飾基を有するナノダイヤモンド全重量に占める末端がエポキシ基である表面修飾基の重量の割合は、例えば０．１〜５０重量％、好ましくは０．５〜４５重量％、より好ましくは５〜４０重量％、さらに好ましくは１０〜３５重量％である。末端エポキシ基の割合が上記範囲であると、エポキシ基を適度に有することにより他の化合物との反応性を高くすることができる。 The ratio of the weight of the surface modifying group having an epoxy group to the total weight of the nanodiamond having a surface modifying group having an epoxy group at the end is, for example, 0.1 to 50% by weight, preferably 0.5 to 45% by weight. , More preferably 5 to 40% by weight, still more preferably 10 to 35% by weight. When the ratio of the terminal epoxy group is in the above range, the reactivity with other compounds can be enhanced by having an appropriate epoxy group.
末端がエポキシ基である表面修飾基を有するナノダイヤモンド全重量に占める表面官能基の重量の割合は、例えば０．０１〜３０重量％、好ましくは０．５〜２５重量％、より好ましくは５〜２５重量％、さらに好ましくは１０〜２５重量％、特に好ましくは１５〜２５重量％である。また、末端がエポキシ基である表面修飾基を有するナノダイヤモンド全重量に占めるナノダイヤモンドの重量の割合は、例えば７０〜９９．９９重量％、好ましくは７５〜９９．５重量％、より好ましくは７５〜９５重量％、特に好ましくは７５〜９０重量％、最も好ましくは７５〜８５重量％である。なお、表面官能基には、上記末端がエポキシ基である表面修飾基も含まれる。 The ratio of the weight of the surface functional group to the total weight of the nanodiamond having a surface modifying group having an epoxy group at the end is, for example, 0.01 to 30% by weight, preferably 0.5 to 25% by weight, more preferably 5 to 5%. It is 25% by weight, more preferably 10 to 25% by weight, and particularly preferably 15 to 25% by weight. The ratio of the weight of the nanodiamond to the total weight of the nanodiamond having a surface modifying group having an epoxy group at the end is, for example, 70 to 99.99% by weight, preferably 75 to 99.5% by weight, and more preferably 75. It is ~ 95% by weight, particularly preferably 75 to 90% by weight, and most preferably 75 to 85% by weight. The surface functional group also includes a surface modifying group whose terminal is an epoxy group.
以下、実施例により本発明をより具体的に説明するが、本発明はこれらの実施例により限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
調製例１
（熱酸化処理されたナノダイヤモンドの作製）
ナノダイヤモンド（商品名「ＮａｎｏＡｍａｎｄｏ」、爆轟法ナノダイヤモンド、水酸基割合１６．９％、平均粒径：５ｎｍ、株式会社ナノ炭素研究所社製）をマッフル炉（品番：ＥＰＴＲ−２６Ｋ、株式会社いすゞ社製）を用い、空気雰囲気下において温度４２５℃、昇温温度３℃／ｍｉｎ、保持時間５時間で加熱（熱酸化処理）し、加熱後に自然冷却することにより、熱酸化処理された表面に水酸基を有するナノダイヤモンドを得た。
Preparation Example 1
(Making nanodiamonds that have been thermally oxidized)
Nanodiamond (trade name "NanoAmando", roaring nanodiamond, hydroxyl group ratio 16.9%, average particle size: 5 nm, manufactured by Nanocarbon Research Institute Co., Ltd.) in a muffle furnace (product number: EPTR-26K, Isuzu Co., Ltd.) The surface was heat-oxidized by heating (thermal oxidation treatment) at a temperature of 425 ° C, a temperature rise temperature of 3 ° C / min, and a holding time of 5 hours in an air atmosphere, and then naturally cooling after heating. Nanodiamonds having a hydroxyl group were obtained.
実施例１
（末端がビニル基である表面修飾基を有するナノダイヤモンドの製造）
二ツ口フラスコに調製例１で得られたナノダイヤモンド１５０ｍｇと１，７−オクタジエン（東京化成工業社製）１０ｍＬを加え、冷却器を取り付けた。続いて系内にアルゴンガスを流し、オイルバス（品番：ＯＨＢ−ＧＢＩ、東京理化器械株式会社製）で１２０℃に昇温、撹拌しながら２４時間加熱することで、７−オクテニルオキシ基を導入する反応を行った。その後、トルエン（和光純薬工業社製、和光１級）、酢酸エチル（和光純薬工業社製、試薬特級）、エタノール（和光純薬工業社製、試薬特級）の順で洗浄し、乾燥させることにより、表面修飾ナノダイヤモンド（灰色固体）を得た。なお、上記洗浄は、各溶媒中で３０分間超音波処理をし、溶媒に合わせて、遠心機（品番：Ｃｅｎｔｒｉｆｕｇｅ ５８０４、ＥＰＰＥＮＤＯＲＦ社製）を用いて、遠心力３０００〜１３０００ｇ、回転数５０００〜１００００ｒｐｍで５〜１０分間遠心分離を行い、ナノダイヤモンドと洗浄溶媒を分離する工程を繰り返すことで行った。
Example 1
(Manufacture of nanodiamond having a surface modifying group having a vinyl group at the end)
150 mg of nanodiamond obtained in Preparation Example 1 and 10 mL of 1,7-octadien (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a two-necked flask, and a cooler was attached. Subsequently, argon gas is passed through the system, the temperature is raised to 120 ° C. in an oil bath (product number: OWB-GBI, manufactured by Tokyo Rika Kikai Co., Ltd.), and the mixture is heated for 24 hours with stirring to form a 7-octenyloxy group. The reaction to introduce was carried out. After that, toluene (manufactured by Wako Pure Chemical Industries, Ltd., Wako 1st grade), ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent), and ethanol (manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent) are washed and dried in this order. As a result, surface-modified nanodiamonds (gray solid) were obtained. The above-mentioned washing is performed by ultrasonic treatment in each solvent for 30 minutes, and according to the solvent, using a centrifuge (product number: Centrifuge 5804, manufactured by EPPENDORF), a centrifugal force of 3000 to 13000 g and a rotation speed of 5000 to 10000 rpm. The process was carried out by centrifuging for 5 to 10 minutes and repeating the steps of separating the nanodiamond and the washing solvent.
実施例２
（末端がビニル基である表面修飾基を有するナノダイヤモンドの製造）
湿式微粉砕機・分散機（ビーズミル）（バッチ式ミル、製品名「ラボスターミニ ＨＦＭ０２」、アシザワ・ファインテック株式会社製）を用い、調製例１で得られたナノダイヤモンド１ｇと１，７−オクタジエン（東京化成工業社製）１００ｍＬ、ジルコニアビーズ（直径０．５ｍｍ）をビーズ充填率が７５％となるようにミルに加え、回転速度１５ｍ／ｓで処理して混合されたスラリーを作製し、ジルコニアビーズと分離することでダイヤモンドナノ粒子／１，７−オクタジエン分散液を得た。得られた分散液を二ツ口フラスコに移し、冷却器を取り付け、系内にアルゴンガスを流し、オイルバス（品番：ＯＨＢ−ＧＢＩ、東京理化器械株式会社社製）で１２０℃に昇温、撹拌しながら１８時間加熱することで、７−オクテニルオキシ基を導入する反応を行った。その後、実施例１と同様にして、トルエン（和光純薬工業社製、和光１級）、酢酸エチル（和光純薬工業社製、試薬特級）、エタノール（和光純薬工業社製、試薬特級）の順で洗浄し、乾燥させることにより、表面修飾ナノダイヤモンド（灰色固体）を得た。
Example 2
(Manufacture of nanodiamond having a surface modifying group having a vinyl group at the end)
Using a wet pulverizer / disperser (bead mill) (batch type mill, product name "Labstar Mini HFM02", manufactured by Ashizawa Finetech Co., Ltd.), 1 g of nanodiamonds obtained in Preparation Example 1 and 1,7- Octadien (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 100 mL, zirconia beads (diameter 0.5 mm) were added to a mill so that the bead filling rate was 75%, and treated at a rotation speed of 15 m / s to prepare a mixed slurry. By separating from zirconia beads, diamond nanoparticles / 1,7-octadien dispersion was obtained. Transfer the obtained dispersion to a two-necked flask, install a cooler, let argon gas flow through the system, and heat it to 120 ° C in an oil bath (product number: OWB-GBI, manufactured by Tokyo Rika Kikai Co., Ltd.). A reaction for introducing a 7-octenyloxy group was carried out by heating for 18 hours with stirring. After that, in the same manner as in Example 1, toluene (manufactured by Wako Pure Chemical Industries, Ltd., Wako 1st grade), ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent), ethanol (manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent). Surface-modified nanodiamonds (gray solids) were obtained by washing and drying in this order.
実施例３
（末端がビニル基である表面修飾基を有するナノダイヤモンドの製造）
実施例１における１，７−オクタジエンを１，９−デカジエン（東京化成工業社製）に変え、反応（加熱）温度を１６５℃、反応時間を３６時間とすることで、９−デセニルオキシ基を導入する反応を行った。その後、実施例１と同様にして洗浄、乾燥させることにより表面修飾ナノダイヤモンド（灰色固体）を得た。
Example 3
(Manufacture of nanodiamond having a surface modifying group having a vinyl group at the end)
The 9-decenyloxy group was introduced by changing 1,7-octadien in Example 1 to 1,9-decadien (manufactured by Tokyo Kasei Kogyo Co., Ltd.), setting the reaction (heating) temperature to 165 ° C., and setting the reaction time to 36 hours. The reaction was carried out. Then, the surface-modified nanodiamond (gray solid) was obtained by washing and drying in the same manner as in Example 1.
実施例４
（末端がビニル基である表面修飾基を有するナノダイヤモンドの製造）
実施例１における１，７−オクタジエンを１，１０−ウンデカジエン（東京化成工業社製）に変え、反応（加熱）温度を１８７℃、反応時間を３６時間とすることで、１０−ウンデセニルオキシ基を導入する反応を行った。その後、実施例１と同様にして洗浄、乾燥させることにより表面修飾ナノダイヤモンド（灰色固体）を得た。
Example 4
(Manufacture of nanodiamond having a surface modifying group having a vinyl group at the end)
By changing 1,7-octadien in Example 1 to 1,10-undecadien (manufactured by Tokyo Chemical Industry Co., Ltd.), setting the reaction (heating) temperature to 187 ° C., and setting the reaction time to 36 hours, 10-undecenyloxy The reaction to introduce the group was carried out. Then, the surface-modified nanodiamond (gray solid) was obtained by washing and drying in the same manner as in Example 1.
実施例５
（末端がビニル基である表面修飾基を有するナノダイヤモンドの製造）
実施例１における１，７−オクタジエンを１，１１−ドデカジエン（東京化成工業社製）に変え、反応（加熱）温度を２０７℃、反応時間を３６時間とすることで、１１−ドデセニルオキシ基を導入する反応を行った。その後、実施例１と同様にして洗浄、乾燥させることにより表面修飾ナノダイヤモンド（灰色固体）を得た。
Example 5
(Manufacture of nanodiamond having a surface modifying group having a vinyl group at the end)
The 11-dodecenyloxy group was introduced by changing 1,7-octadien in Example 1 to 1,11-dodecadien (manufactured by Tokyo Kasei Kogyo Co., Ltd.), setting the reaction (heating) temperature to 207 ° C., and setting the reaction time to 36 hours. The reaction was carried out. Then, the surface-modified nanodiamond (gray solid) was obtained by washing and drying in the same manner as in Example 1.
実施例６
（末端がビニル基である表面修飾基を有するナノダイヤモンドの製造）
実施例１における１，７−オクタジエンを１，１３−テトラデカジエン（東京化成工業社製）に変え、反応（加熱）温度を２５０℃、反応時間を３６時間とすることで、１３−テトラデセニルオキシ基を導入する反応を行った。その後、実施例１と同様にして洗浄、乾燥させることにより表面修飾ナノダイヤモンド（灰色固体）を得た。
Example 6
(Manufacture of nanodiamond having a surface modifying group having a vinyl group at the end)
By changing 1,7-octadene in Example 1 to 1,13-tetradecadiene (manufactured by Tokyo Chemical Industry Co., Ltd.), setting the reaction (heating) temperature to 250 ° C. and setting the reaction time to 36 hours, 13-tetrade A reaction for introducing a senyloxy group was carried out. Then, the surface-modified nanodiamond (gray solid) was obtained by washing and drying in the same manner as in Example 1.
実施例７
（末端がビニル基である表面修飾基を有するナノダイヤモンドの製造）
実施例２における加熱時間を１８時間から２４時間に変更したこと以外は、実施例２と同様にして表面修飾ナノダイヤモンド（灰色固体）を得た。
Example 7
(Manufacture of nanodiamond having a surface modifying group having a vinyl group at the end)
Surface-modified nanodiamonds (gray solids) were obtained in the same manner as in Example 2 except that the heating time in Example 2 was changed from 18 hours to 24 hours.
実施例８
（末端がビニル基である表面修飾基を有するナノダイヤモンドの製造）
実施例２における加熱時間を１８時間から３６時間に変更したこと以外は、実施例２と同様にして表面修飾ナノダイヤモンド（灰色固体）を得た。
Example 8
(Manufacture of nanodiamond having a surface modifying group having a vinyl group at the end)
Surface-modified nanodiamonds (gray solids) were obtained in the same manner as in Example 2 except that the heating time in Example 2 was changed from 18 hours to 36 hours.
（ＦＴ−ＩＲ分析）
調製例１で得られたナノダイヤモンド、実施例１〜６で得られた表面修飾ナノダイヤモンドについて、下記の分析装置及び分析方法にて、ＦＴ−ＩＲ分析を行った。
(FT-IR analysis)
The nanodiamonds obtained in Preparation Example 1 and the surface-modified nanodiamonds obtained in Examples 1 to 6 were subjected to FT-IR analysis by the following analyzer and analysis method.
調製例１で得られたナノダイヤモンド、実施例１及び２で得られた表面修飾ナノダイヤモンドのＦＴ−ＩＲスペクトルを図１に示す。実施例１及び２では、２８００−２９００ｃｍ-1に調製例１ではほとんど見られないメチレン鎖由来のＣＨ2伸縮振動のピーク、及び３０８０ｃｍ-1付近にＣＨ2＝ＣＨ−基のＣ−Ｈ伸縮振動のピークが観測された。このことから実施例１及び２では、７−オクテニルオキシ基が導入され、末端ビニル基を有するナノダイヤモンドが得られたことを確認できた。また、実施例１と実施例２を比較すると、実施例２のＣ−Ｈ伸縮振動のピークが相対的に大きくなっていることからビーズミルを用いることにより、修飾量が増加したことが示唆された。 The FT-IR spectra of the nanodiamonds obtained in Preparation Example 1 and the surface-modified nanodiamonds obtained in Examples 1 and 2 are shown in FIG. In Examples 1 and 2, CH stretching vibration of CH 2 = CH- group peaks, and 3080cm around -1 CH 2 stretching vibration derived from the methylene chain hardly seen in Preparation Example 1 to 2800-2900Cm -1 Peak was observed. From this, it was confirmed that in Examples 1 and 2, a 7-octenyloxy group was introduced and nanodiamonds having a terminal vinyl group were obtained. Further, when Example 1 and Example 2 were compared, the peak of the CH expansion and contraction vibration of Example 2 was relatively large, suggesting that the amount of modification was increased by using the bead mill. ..
調製例１で得られたナノダイヤモンド、実施例３〜６で得られた表面修飾ナノダイヤモンドのＦＴ−ＩＲスペクトルを図２に示す。実施例３〜６では、２８００−２９００ｃｍ-1に調製例１ではほとんど見られないメチレン鎖由来のＣＨ2伸縮振動のピーク、及び３０８０ｃｍ-1付近にＣＨ2＝ＣＨ−基のＣ−Ｈ伸縮振動のピークが観測された。このことから実施例３〜６では、それぞれ末端ビニル基を有するナノダイヤモンドが得られたことを確認できた。 The FT-IR spectra of the nanodiamonds obtained in Preparation Example 1 and the surface-modified nanodiamonds obtained in Examples 3 to 6 are shown in FIG. In Examples 3-6, the peak of the CH 2 stretching vibration derived from the methylene chain hardly seen in Preparation Example 1 to 2800-2900Cm -1, and CH stretching vibrations of CH 2 = CH- group near 3080cm -1 Peak was observed. From this, it was confirmed that nanodiamonds having terminal vinyl groups were obtained in Examples 3 to 6, respectively.
分析装置 … 品番：ＦＴ／ＩＲ−６１００、日本分光株式会社製
分析方法 … 試料１ｍｇと臭化カリウム（ＩＲ吸収測定用、和光純薬工業株式会社製）１００ｍｇと乳鉢を用いて粉砕混合し、この試料２６．５ｍｇを４０ＭＰａの圧力で３〜５分間加圧成型してＫＢｒペレットを作製して分析（ＫＢｒ法）
Analytical device: Product number: FT / IR-6100, manufactured by JASCO Corporation Analytical method: 1 mg of sample, 100 mg of potassium bromide (for IR absorption measurement, manufactured by Wako Pure Chemical Industries, Ltd.) and 100 mg of potassium bromide are crushed and mixed using a dairy pot. 26.5 mg of sample was pressure-molded at a pressure of 40 MPa for 3 to 5 minutes to prepare KBr pellets for analysis (KBr method).
（熱重量分析）
調製例１で得られたナノダイヤモンド、実施例１〜８で得られた表面修飾ナノダイヤモンドについて、下記の分析装置及び分析条件にて、熱重量減少を測定した。
(Thermogravimetric analysis)
The thermogravimetric reduction of the nanodiamonds obtained in Preparation Example 1 and the surface-modified nanodiamonds obtained in Examples 1 to 8 was measured with the following analyzer and analytical conditions.
調製例１で得られたナノダイヤモンド、実施例１及び２で得られた表面修飾ナノダイヤモンドのＴＧＡ曲線を図３に示す。実施例１及び実施例２では、２００〜４８０℃にかけて主に７−オクテニルオキシ基の熱分解による調製例１には見られない重量減少が確認された。このことから、実施例１及び実施例２では、７−オクテニルオキシ基が導入されたことが確認できた。また、実施例２は実施例１に比べて４８０℃までの重量減少が大きいことから、ビーズミルを用いることで７−オクテニルオキシ基の導入量が大きく増加していることが分かる。なお、調製例１における４８０℃以降の重量減少は、ダイヤモンドの熱分解によるものと考えられる。実施例２において、重量減少より求めた修飾された７−オクテニルオキシ基の重量は、ナノダイヤモンド粒子１ｇに対して、０．３４６ｇ（ナノダイヤモンド粒子１００重量％に対して、３４．６重量％）であった。また、実施例７及び８において、重量減少より求めた修飾された７−オクテニルオキシ基の重量は、ナノダイヤモンド粒子１ｇに対して、０．４４ｇ（ナノダイヤモンド粒子１００重量％に対して、４４．０重量％）であった。 The TGA curves of the nanodiamonds obtained in Preparation Example 1 and the surface-modified nanodiamonds obtained in Examples 1 and 2 are shown in FIG. In Examples 1 and 2, a weight loss not seen in Preparation Example 1 was confirmed mainly by thermal decomposition of the 7-octenyloxy group from 200 to 480 ° C. From this, it was confirmed that the 7-octenyloxy group was introduced in Examples 1 and 2. Further, since the weight loss of Example 2 up to 480 ° C. is larger than that of Example 1, it can be seen that the amount of 7-octenyloxy group introduced is greatly increased by using the bead mill. The weight loss after 480 ° C. in Preparation Example 1 is considered to be due to thermal decomposition of diamond. In Example 2, the weight of the modified 7-octenyloxy group determined from the weight reduction was 0.346 g with respect to 1 g of the nanodiamond particles (34.6% by weight with respect to 100% by weight of the nanodiamond particles). )Met. Further, in Examples 7 and 8, the weight of the modified 7-octenyloxy group determined from the weight reduction was 0.44 g with respect to 1 g of the nanodiamond particles (44 with respect to 100% by weight of the nanodiamond particles). It was 0.0% by weight).
調製例１で得られたナノダイヤモンド、実施例３〜６で得られた表面修飾ナノダイヤモンドのＴＧＡ曲線を図４に示す。実施例３〜６では、２００〜４８０℃にかけて、主にアルケニレンオキシ基の熱分解による調製例１には見られない重量減少が確認された。このことから、実施例３〜６ではそれぞれアルケニレンオキシ基が導入されたことが確認できた。 The TGA curves of the nanodiamonds obtained in Preparation Example 1 and the surface-modified nanodiamonds obtained in Examples 3 to 6 are shown in FIG. In Examples 3 to 6, a weight loss not seen in Preparation Example 1 was confirmed mainly by thermal decomposition of the alkenylene oxy group from 200 to 480 ° C. From this, it was confirmed that the alkenyleneoxy group was introduced in each of Examples 3 to 6.
分析装置 … 品番：ＴＧＡ／ＤＳＣ １、メトラー・トレド社製
分析条件 … 試料１ｍｇ、空気雰囲気下、昇温速度５℃／ｍｉｎ、測定範囲２００−６００℃、基準物質：アルミナ
Analyzer: Part number: TGA / DSC 1, Analytical conditions manufactured by METTLER TOLEDO: Sample 1 mg, under air atmosphere, temperature rise rate 5 ° C / min, measurement range 200-600 ° C, reference material: alumina
実施例９
（末端がエポキシ基である表面修飾基を有するナノダイヤモンドの製造）
実施例１で得られた表面修飾ナノダイヤモンドにジクロロメタン（和光純薬工業株式会社製）を加え、ジクロロメタンスラリーとした。氷浴下、ジクロロメタンスラリー３．０ｍＬにメタクロロ過安息香酸（３０％含水液、東京化成工業株式会社製）１２６０ｍｇ（５．１１ｍｍｏｌ）を加え、室温に昇温し８時間撹拌し、その後、氷浴下、さらにメタクロロ過安息香酸（３０％含水液）６３０ｍｇ（２．５６ｍｍｏｌ）を加え、室温に昇温し８時間撹拌することにより末端ビニル基のエポキシ化反応を行った。この反応液に亜硫酸水素ナトリウム（和光純薬工業株式会社製）の飽和水溶液を加え反応を停止させ、この反応混合物を遠心機（品番：Ｃｅｎｔｒｉｆｕｇｅ ５８０４、ＥＰＰＥＮＤＯＲＦ社製）を用いて、遠心力２００００ｇ、回転数１２７００ｒｐｍで１０分間遠心分離を行い、上澄み液を除去することで沈殿物を得た。この沈殿物に同様の遠心分離操作を、水、アセトンを用いて順に行い、回収した沈殿物を真空ポンプ（品番：ＧＣＤ−０５０ＸＡ、アルバック機工株式会社社製）を用いて減圧加熱乾燥を６０℃で１時間、その後１２０℃で１時間行い、灰色固体を得た。
Example 9
(Manufacture of nanodiamonds having surface modifying groups whose ends are epoxy groups)
Dichloromethane (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the surface-modified nanodiamond obtained in Example 1 to prepare a dichloromethane slurry. Under an ice bath, 1260 mg (5.11 mmol) of meta-chloroperbenzoic acid (30% hydrous solution, manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 3.0 mL of a dichloromethane slurry, the temperature was raised to room temperature, and the mixture was stirred for 8 hours, and then the ice bath. Below, 630 mg (2.56 mmol) of meta-chloroperbenzoic acid (30% hydrous solution) was further added, the temperature was raised to room temperature, and the mixture was stirred for 8 hours to carry out an epoxidation reaction of the terminal vinyl group. A saturated aqueous solution of sodium hydrogen sulfite (manufactured by Wako Pure Chemical Industries, Ltd.) was added to this reaction solution to stop the reaction, and the reaction mixture was subjected to a centrifugal force of 20000 g using a centrifuge (product number: Centrifuge 5804, manufactured by Eppendorf). Centrifugation was carried out at a rotation speed of 12700 rpm for 10 minutes, and the supernatant was removed to obtain a precipitate. The same centrifugation operation is performed on this precipitate in order using water and acetone, and the recovered precipitate is dried under reduced pressure at 60 ° C. using a vacuum pump (product number: GCD-050XA, manufactured by ULVAC Kiko Co., Ltd.). After 1 hour at 120 ° C. for 1 hour, a gray solid was obtained.
実施例９で得られた灰色固体、及び実施例１で得られた表面修飾ナノダイヤモンドについて、下記の分析装置及び分析方法にてＦＴ−ＩＲ分析を行った。図５で示す原料である末端がビニル基である表面修飾基を有するナノダイヤモンド（実施例１で得られたナノダイヤモンド）ではビニル基由来のピーク（９０８ｃｍ-1、９９１ｃｍ-1）が観測されているが、図６で示す実施例９のエポキシ化後ではビニル基由来のピーク（９０８ｃｍ-1、９９１ｃｍ-1）が減少し、生成したエポキシ基由来のピーク（８３８ｃｍ-1）が見られた。このことから末端がエポキシ基である表面修飾基を有するナノダイヤモンドが得られたことを確認した。 The gray solid obtained in Example 9 and the surface-modified nanodiamond obtained in Example 1 were subjected to FT-IR analysis by the following analyzer and analysis method. In the nanodiamond (nanodiamond obtained in Example 1) having a surface modifying group whose terminal is a vinyl group, which is the raw material shown in FIG. 5, peaks derived from the vinyl group (908 cm -1 , 991 cm -1 ) were observed. However, after the epoxidation of Example 9 shown in FIG. 6, the peaks derived from the vinyl group (908 cm -1 , 991 cm -1 ) decreased, and the peaks derived from the produced epoxy group (838 cm -1 ) were observed. From this, it was confirmed that a nanodiamond having a surface modifying group having an epoxy group at the end was obtained.
分析装置 … 品番：ＦＴ−７２０、株式会社堀場製作所製
分析方法 … 試料と臭化カリウム（ＩＲ吸収測定用、和光純薬工業株式会社製）とを乳鉢を用いて粉砕混合し、加圧成型してＫＢｒペレットを作製して分析（ＫＢｒ法）
Analytical device: Product number: FT-720, manufactured by Horiba Seisakusho Co., Ltd. Analytical method: Sample and potassium bromide (for IR absorption measurement, manufactured by Wako Pure Chemical Industries, Ltd.) are crushed and mixed using a dairy pot and pressure molded. KBr pellets are prepared and analyzed (KBr method)
（定量分析：固体13Ｃ−ＮＭＲ分析）
実施例１で得られた末端がビニル基である表面修飾基を有するナノダイヤモンドについて、下記の分析装置及び分析条件にて、固体13Ｃ−ＮＭＲを測定し、得られた結果から末端がビニル基である表面修飾基を有するナノダイヤモンドにおける炭素原子の比率を求めた。13Ｃ−ＮＭＲスペクトルを図７に示す。３０ｐｐｍ付近に７−オクテニルオキシ基由来のＣＨ2炭素原子、３５ｐｐｍ付近にナノダイヤモンド由来のｓｐ3炭素原子、５０〜５５ｐｐｍにナノダイヤモンド由来のＣＨ炭素原子、６０〜９０ｐｐｍにナノダイヤモンド由来のＣＯＨ炭素原子、１１５ｐｐｍおよび１３９ｐｐｍに７−オクテニルオキシ基由来のＣ＝Ｃ炭素原子、１１０〜１４０ｐｐｍに７−オクテニルオキシ基以外のナノダイヤモンド由来のＣ＝Ｃ炭素原子、１８１ｐｐｍ付近にナノダイヤモンド由来のＣＯＯ炭素原子のピークが観測された。また、１５ｐｐｍ付近にはナノダイヤモンド由来のＣＨ3炭素原子の微小ピークが観測された。
(Quantitative analysis: Solid 13 C-NMR analysis)
With respect to the nanodiamond having a surface modifying group whose terminal is a vinyl group obtained in Example 1, solid 13 C-NMR was measured under the following analyzer and analytical conditions, and from the obtained result, the terminal was a vinyl group. The ratio of carbon atoms in nanodiamond having a surface modifying group was determined. 13 The C-NMR spectrum is shown in FIG. CH 2 carbon atom derived from 7- octenyloxy group around 30ppm, sp 3 carbon atom derived from nanodiamond around 35ppm, CH carbon atom derived from nanodiamond at 50-55ppm, COH carbon derived from nanodiamond at 60-90ppm C = C carbon atom derived from 7-octenyloxy group at 115 ppm and 139 ppm, C = C carbon atom derived from nanodiamond other than 7-octenyloxy group at 110-140 ppm, COO derived from nanodiamond near 181 ppm A peak of carbon atoms was observed. In addition, a minute peak of CH 3 carbon atom derived from nanodiamond was observed around 15 ppm.
得られた13Ｃ−ＮＭＲスペクトルにおける各炭素原子のピークを波形分離することにピーク面積比を算出し、ピーク面積比から各炭素原子の比率を求めた。各炭素原子についてのピーク面積比とナノダイヤモンド由来のｓｐ3炭素原子を１００［％］としたときの各炭素原子の比率［％］を表１に示す。 The peak area ratio was calculated by waveform-separating the peaks of each carbon atom in the obtained 13 C-NMR spectrum, and the ratio of each carbon atom was obtained from the peak area ratio. Table 1 shows the peak area ratio for each carbon atom and the ratio [%] of each carbon atom when the sp 3 carbon atom derived from nanodiamond is 100 [%].
なお、表１における７−オクテニルオキシ基炭素原子は、７−オクテニルオキシ基由来のＣ＝Ｃ炭素原子のうち、ナノダイヤモンドから最も離れている末端の炭素原子という意味である。このナノダイヤモンドから最も離れている末端の炭素原子の比率は、アルケニルオキシ基が結合しているナノダイヤモンド炭素原子の比率と同じである。よって、表１の７−オクテニルオキシ基炭素原子の比率は、アルケニルオキシ基を含む表面修飾基が結合しているナノダイヤモンド炭素原子の比率となる。なお、表１のＣＯＯとはＣＯＯ構造をもつ官能基を意味する。 The 7-octenyloxy group carbon atom in Table 1 means the terminal carbon atom farthest from the nanodiamond among the C = C carbon atoms derived from the 7-octenyloxy group. The ratio of the terminal carbon atom farthest from the nanodiamond is the same as the ratio of the nanodiamond carbon atom to which the alkenyloxy group is bonded. Therefore, the ratio of the 7-octenyloxy group carbon atom in Table 1 is the ratio of the nanodiamond carbon atom to which the surface modifying group containing the alkenyloxy group is bonded. The COO in Table 1 means a functional group having a COO structure.
分析装置 … 品番：ＡＶＡＮＣＥ ４００、Ｂｒｕｋｅｒ社製
測定法 … ＤＤ／ＭＡＳ（Dipolar Decoupling）法
測定核周波数 … 100.6248425 MHz（13C 核）
スペクトル幅 … 40 kHz
パルス幅 … 4.2 sec（９０°パルス）
パルス繰り返し時間 … ACQTM: 0.0256625 sec，PD: 20 sec
観測ポイント … 1024 データポイント: 8192
基準物質 … ヘキサメチルベンゼンのメチル基（外部基準：17.35 ppm）
温度 … 室温（約２２℃）
試料回転数 … 11 kHz
Analyzer: Part number:
Spectral width… 40 kHz
Pulse width: 4.2 sec (90 ° pulse)
Pulse repetition time ... ACQTM: 0.0256625 sec, PD: 20 sec
Observation points… 1024 Data points: 8192
Reference substance: Methyl group of hexamethylbenzene (external standard: 17.35 ppm)
Temperature: Room temperature (about 22 ° C)
Sample rotation speed… 11 kHz
表１より、本発明の表面修飾ナノダイヤモンドでは、末端がビニル基である表面修飾基を有しつつ、ナノダイヤモンド表面に一定量以上の水酸基が存在していることが分かった。 From Table 1, it was found that the surface-modified nanodiamond of the present invention has a surface-modifying group whose terminal is a vinyl group, and at the same time, a certain amount or more of hydroxyl groups are present on the surface of the nanodiamond.
Claims (6)
［式中のＸは、単結合、又は直鎖若しくは分岐鎖状の炭素数１〜２０のアルキレン基を表す］ The method for producing surface-modified nanodiamond according to any one of claims 1 to 5, wherein the compound having vinyl groups at both ends is a compound represented by the following formula (1).
[X in the formula represents a single bond or a linear or branched alkylene group having 1 to 20 carbon atoms]
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