JP2019194146A - Method for producing carbon material composite - Google Patents
Method for producing carbon material composite Download PDFInfo
- Publication number
- JP2019194146A JP2019194146A JP2019082887A JP2019082887A JP2019194146A JP 2019194146 A JP2019194146 A JP 2019194146A JP 2019082887 A JP2019082887 A JP 2019082887A JP 2019082887 A JP2019082887 A JP 2019082887A JP 2019194146 A JP2019194146 A JP 2019194146A
- Authority
- JP
- Japan
- Prior art keywords
- graphite oxide
- carbon material
- material composite
- graphite
- nonionic surfactant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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Abstract
Description
本発明は、炭素材料複合体の製造方法に関する。より詳しくは、触媒、電池やキャパシタの電極活物質、熱電変換材料、導電性材料、発光材料、潤滑油用添加剤、高分子（樹脂）用添加剤、透過膜材料、抗菌材料、撥水材料、吸着材料等として好適に用いることができる炭素材料複合体の製造方法に関する。 The present invention relates to a method for producing a carbon material composite. More specifically, catalysts, battery and capacitor electrode active materials, thermoelectric conversion materials, conductive materials, light emitting materials, lubricant additives, polymer (resin) additives, permeable membrane materials, antibacterial materials, water repellent materials The present invention relates to a method for producing a carbon material composite that can be suitably used as an adsorbing material.
炭素材料は、硬度等の特性に優れ、半導体、電池、自動車、情報通信、産業機器等の分野で種々用いられている。
炭素材料の１種である酸化黒鉛は、ｓｐ２結合で結合した炭素原子が平面的に並んだ層状構造をもつ黒鉛を酸化し、酸素含有官能基を付与したものであり、その特異な構造や物性のために数多くの研究がなされている。酸化黒鉛は、触媒、電池やキャパシタの電極活物質、熱電変換材料、導電性材料、発光材料、潤滑油用添加剤、高分子用添加剤、透過膜材料、抗菌材料、撥水材料、吸着材料等の種々の用途に用いることが期待されている。
Carbon materials are excellent in properties such as hardness, and are used in various fields such as semiconductors, batteries, automobiles, information communication, and industrial equipment.
Graphite oxide, which is a kind of carbon material, is obtained by oxidizing graphite having a layered structure in which carbon atoms bonded by sp 2 bonds are arranged in a plane and imparting an oxygen-containing functional group. Numerous studies have been conducted for physical properties. Graphite oxide is a catalyst, electrode active materials for batteries and capacitors, thermoelectric conversion materials, conductive materials, luminescent materials, additives for lubricants, additives for polymers, permeable membrane materials, antibacterial materials, water repellent materials, adsorbent materials It is expected to be used for various applications such as.
酸化黒鉛の製造方法としては、黒鉛を酸溶媒中で強力な酸化剤と作用させることで酸化黒鉛を合成する方法が一般的であり、酸化剤として硫酸と過マンガン酸カリウムを用いるＨｕｍｍｅｒｓ法が知られている（非特許文献１参照）。またその他の方法として、硝酸と塩素酸カリウムを用いるＢｒｏｄｉｅ法、酸化剤として硫酸、硝酸と塩素酸カリウムを用いるＳｔａｕｄｅｎｍａｉｅｒ法等が知られている。 As a method for producing graphite oxide, a method of synthesizing graphite oxide by generally reacting graphite with a strong oxidizing agent in an acid solvent is known, and a Hummers method using sulfuric acid and potassium permanganate as an oxidizing agent is known. (See Non-Patent Document 1). As other methods, a Brodie method using nitric acid and potassium chlorate, a Staudenmaier method using sulfuric acid, nitric acid and potassium chlorate as oxidizing agents, and the like are known.
例えば、酸化黒鉛誘導体の製造方法として、黒鉛を酸化する工程と、酸化黒鉛誘導体を得る工程との間に、酸化工程で得られる酸化黒鉛を含む反応液に、水に対する溶解度が０．０１％以上であって、かつ、水と任意には混和しない溶媒を添加した後、酸化黒鉛含有組成物を分離することが開示されている（特許文献１参照）。
ところで、精製済みの酸化グラフェン（酸化黒鉛）とカチオン性脂質とから得られる複合体が凝集してなる凝集物が開示されている（特許文献２参照）。また、酸化黒鉛がよく分散した酸化黒鉛分散体を得るために、精製・乾燥済みの酸化黒鉛粉末を脱イオン水に分散させた分散体に低分子量のポリエチレングリコールを添加し、超音波処理を行ったことが開示されている（非特許文献２参照）。
For example, as a method for producing a graphite oxide derivative, the solubility in water is 0.01% or more in a reaction solution containing graphite oxide obtained in the oxidation step between the step of oxidizing graphite and the step of obtaining graphite oxide derivative. In addition, it is disclosed that a graphite oxide-containing composition is separated after adding a solvent that is arbitrarily immiscible with water (see Patent Document 1).
By the way, an aggregate formed by aggregating a complex obtained from purified graphene oxide (graphite oxide) and a cationic lipid is disclosed (see Patent Document 2). In addition, in order to obtain a graphite oxide dispersion in which graphite oxide is well dispersed, low molecular weight polyethylene glycol is added to the dispersion in which purified and dried graphite oxide powder is dispersed in deionized water, and sonication is performed. (See Non-Patent Document 2).
上記のとおり、炭素材料の１種である酸化黒鉛の製造方法として種々の方法が知られているが、酸化工程で酸化黒鉛を得た後、酸化黒鉛を反応溶液中から精製することが一般的であり、通常は遠心分離を繰り返して行ったり、反応液をろ過したりする。前者の場合、工程が煩雑になるとともに廃液の量が多くなるといった課題があり、後者の場合、フィルターが目詰まりしやすいという課題があった。いずれの場合も、精製に手間がかかるため、高コスト化し、酸化黒鉛を製造する場合に効率的な生産の面から改善の余地があった。特に特許文献２では精製済みの酸化黒鉛にカチオン性脂質を作用させ複合体を得ることが想定されており、複合体を作製するためには精製が必要であり、工業的に実施する場合高コストとなる。これに対して、特許文献１に記載の方法は、水層・有機層の液／液分離により酸化黒鉛の分離を効率的に行うことが可能となり、高品質な酸化黒鉛を簡便に得ることができるものである。一方、酸化黒鉛を工業的に製造するうえで、酸化黒鉛の分離工程、特にろ過工程を更に効率的に行い、高品質な酸化黒鉛をより簡便に製造することが強く望まれていた。 As described above, various methods are known as a method for producing graphite oxide, which is one type of carbon material, but it is common to purify graphite oxide from a reaction solution after obtaining graphite oxide in the oxidation step. Usually, centrifugation is repeated or the reaction solution is filtered. In the former case, there is a problem that the process becomes complicated and the amount of waste liquid increases, and in the latter case, there is a problem that the filter is easily clogged. In either case, since refining takes time, the cost is increased, and there is room for improvement in terms of efficient production when producing graphite oxide. In particular, in Patent Document 2, it is assumed that a complex is obtained by allowing a cationic lipid to act on purified graphite oxide, and purification is necessary to produce the complex. It becomes. On the other hand, the method described in Patent Document 1 can efficiently separate graphite oxide by liquid / liquid separation of an aqueous layer and an organic layer, and can easily obtain high-quality graphite oxide. It can be done. On the other hand, when industrially producing graphite oxide, it has been strongly desired to more efficiently carry out a graphite oxide separation process, particularly a filtration process, and to produce high-quality graphite oxide more easily.
本発明は、上記現状に鑑みてなされたものでもあり、高品質な酸化黒鉛を簡便に製造することができる方法を提供することを目的とする。 This invention is also made | formed in view of the said present condition, and it aims at providing the method which can manufacture a high quality graphite oxide simply.
本発明者らは、高品質な酸化黒鉛をより簡便に製造することができる方法について種々検討し、酸化工程で得られる酸化黒鉛が分散してなる水系分散液からの酸化黒鉛の精製の際に、水系分散液と非イオン性界面活性剤とを混合し、その後、非イオン性界面活性剤及び酸化黒鉛を含んで構成される炭素材料複合体を精製すると、水系分散液中に酸が残留していても非イオン性界面活性剤の作用によって炭素材料複合体が凝集し、分散性の低い大きな凝集体となるため、水系分散液をろ過してもフィルターの目詰まりが起こりにくい等、精製に要する時間が非常に短くなるとともに、酸を充分に除去することができ、炭素材料複合体を極めて効率的に精製できることを見出した。この理由は、本発明者らの最新の知見によると以下の通りであると考えられる。先ず、酸が残留していても非イオン性界面活性剤の作用によって炭素材料複合体が凝集する作用について、酸化黒鉛は、水中で酸基が電離する弱酸であるが、硫酸等の強酸存在下では酸基が電離せず中性になる。ここで、酸化工程で得られる酸化黒鉛が分散してなる水系分散液と、非イオン性界面活性剤とを混合すると、酸化黒鉛と非イオン性界面活性剤とが疎水的相互作用し、非イオン性界面活性剤及び酸化黒鉛を含んで構成される炭素材料複合体として凝集させることができる。また、凝集力の弱い非イオン性界面活性剤による炭素材料複合体の凝集はあまり強固ではないので、凝集塊中に水が入って硫酸を洗い除くことができる。更に、当該凝集はあまり強固ではないので、剥離工程を経ることで容易に凝集を解き、再度分散媒に分散させることも可能である。本発明者らは、このような精製方法により、高品質な炭素材料複合体を低コストかつ簡便に製造することが可能となり、この方法を特に炭素材料複合体の工業的製造に適用した場合に当該効果が顕著なものとなることを見出し、上記課題をみごとに解決することができることに想到し、本発明に到達したものである。 The inventors of the present invention have studied various methods for more easily producing high-quality graphite oxide, and in purifying graphite oxide from an aqueous dispersion obtained by dispersing graphite oxide obtained in the oxidation step. Then, when the aqueous dispersion and the nonionic surfactant are mixed, and then the carbon material composite comprising the nonionic surfactant and graphite oxide is purified, the acid remains in the aqueous dispersion. However, the carbon material composite aggregates due to the action of the nonionic surfactant, resulting in a large aggregate with low dispersibility. Therefore, even if the aqueous dispersion is filtered, the filter is not easily clogged. It has been found that the time required is very short, the acid can be sufficiently removed, and the carbon material composite can be purified very efficiently. The reason is considered as follows according to the latest knowledge of the present inventors. First, regarding the effect that the carbon material composite aggregates due to the action of the nonionic surfactant even if the acid remains, graphite oxide is a weak acid in which acid groups are ionized in water, but in the presence of a strong acid such as sulfuric acid. Then, acid groups become neutral without ionization. Here, when an aqueous dispersion obtained by dispersing graphite oxide obtained in the oxidation step and a nonionic surfactant are mixed, the graphite oxide and the nonionic surfactant interact with each other in a hydrophobic manner. It can be made to agglomerate as a carbon material composite comprising a surfactant and graphite oxide. In addition, since the aggregation of the carbon material composite by the nonionic surfactant having a weak cohesive force is not so strong, water can enter the aggregate and the sulfuric acid can be washed away. Furthermore, since the aggregation is not so strong, it is possible to easily release the aggregation through a peeling step and disperse it again in the dispersion medium. The present inventors have made it possible to produce a high-quality carbon material composite at low cost and simply by such a purification method, and particularly when this method is applied to industrial production of a carbon material composite. The present inventors have found that the effect is remarkable and have conceived that the above problem can be solved brilliantly, and have reached the present invention.
すなわち本発明は、非イオン性界面活性剤及び酸化黒鉛を含んで構成される炭素材料複合体を製造する方法であって、該製造方法は、黒鉛を酸化する工程、及び、該酸化工程で得られた酸化黒鉛が分散してなる水系分散液と非イオン性界面活性剤とを混合した後、炭素材料複合体を精製する工程を含むことを特徴とする炭素材料複合体の製造方法である。 That is, the present invention is a method for producing a carbon material composite comprising a nonionic surfactant and graphite oxide, and the production method comprises the steps of oxidizing graphite and the oxidation step. A method for producing a carbon material composite comprising a step of purifying a carbon material composite after mixing an aqueous dispersion obtained by dispersing the obtained graphite oxide and a nonionic surfactant.
本発明はまた、酸化黒鉛を製造する方法であって、該製造方法は、黒鉛を酸化する工程、及び、該酸化工程で得られた酸化黒鉛が分散してなる水系分散液と非イオン性界面活性剤とを混合した後、酸化黒鉛を精製する工程を含むことを特徴とする酸化黒鉛の製造方法でもある。 The present invention is also a method for producing graphite oxide, which comprises a step of oxidizing graphite, and an aqueous dispersion formed by dispersing graphite oxide obtained in the oxidation step and a nonionic interface. It is also a method for producing graphite oxide, comprising a step of purifying graphite oxide after mixing with an activator.
なお、本発明の炭素材料複合体の製造方法又は本発明の酸化黒鉛の製造方法の好ましい一実施形態では、上記精製工程は、ろ過、デカンテーション、遠心分離、及び、分液抽出からなる群より選択される少なくとも１種の方法により炭素材料複合体又は酸化黒鉛を精製する工程である。 In one preferred embodiment of the method for producing a carbon material composite of the present invention or the method for producing graphite oxide of the present invention, the purification step is performed from the group consisting of filtration, decantation, centrifugation, and liquid separation extraction. It is a step of purifying the carbon material composite or graphite oxide by at least one selected method.
本発明の炭素材料複合体の製造方法により、高品質な炭素材料複合体を低コストで簡便に得ることができる。また得られた炭素材料複合体は、分散媒に非常によく分散できる。 By the method for producing a carbon material composite of the present invention, a high-quality carbon material composite can be easily obtained at low cost. Further, the obtained carbon material composite can be very well dispersed in the dispersion medium.
以下に本発明を詳述する。
なお、以下において段落に分けて記載される個々の本発明の好ましい特徴を２つ以上組み合わせた形態も、本発明の好ましい形態である。
The present invention is described in detail below.
In addition, the form which combined two or more each preferable characteristic of this invention described separately in a paragraph below is also a preferable form of this invention.
＜炭素材料複合体の製造方法＞
本発明の炭素材料複合体の製造方法における、上記酸化工程以降の各工程の順序については特に限定されないが、必要に応じて後述する酸化反応停止（クエンチ）工程を行った後、上記混合工程、上記精製工程をこの順で行う。また、上記混合工程前に更に酸化黒鉛の精製工程を適宜行ってもよく、例えば、必要に応じて酸化反応停止工程を行った後、酸化黒鉛の精製工程、上記混合工程、上記精製工程（炭素材料複合体の精製工程）をこの順で行ってもよい。
<Method for producing carbon material composite>
In the method for producing a carbon material composite of the present invention, the order of each step after the oxidation step is not particularly limited, but after performing an oxidation reaction stop (quenching) step, which will be described later, if necessary, the mixing step, The above purification steps are performed in this order. Further, a graphite oxide purification step may be appropriately performed before the mixing step. For example, after performing an oxidation reaction stopping step as necessary, the graphite oxide purification step, the mixing step, the purification step (carbon The purification step of the material composite may be performed in this order.
本発明の炭素材料複合体の製造方法により得られる炭素材料複合体は、非イオン性界面活性剤及び酸化黒鉛を含んで構成される。
上記酸化黒鉛は、グラフェン、黒鉛（グラファイト）等の黒鉛質の炭素材料を酸化することにより酸素が結合したもの（該炭素材料に酸素が結合したもの）であり、該酸素は黒鉛質の炭素材料に対しカルボキシル基、カルボニル基、水酸基、エポキシ基等の置換基として存在している。
上記酸化黒鉛は、グラフェンの炭素に酸素が結合した酸化グラフェンであることが好ましい。
なお、一般的にグラフェンとは、ｓｐ２結合で結合した炭素原子が平面的に並んだ１層からなるシートをいい、グラフェンシートが多数積層されたものはグラファイトといわれるが、本発明における酸化グラフェンには、炭素原子１層のみからなるシートだけではなく、２層〜１００層程度積層した構造を有するものも含まれる。該酸化グラフェンは、炭素原子１層のみからなるシートであるか、又は、２層〜２０層程度積層した構造を有するものであることが好ましい。
上記酸化黒鉛は、更に、硫黄含有基、窒素含有基等の官能基を有していてもよいが、全構成元素に対する炭素、水素、及び、酸素の構成元素としての含有率が９７モル％以上であることが好ましく、９９モル％以上であることがより好ましく、酸化黒鉛が炭素、水素、及び、酸素のみを構成元素とするものであることが更に好ましい。
The carbon material composite obtained by the method for producing a carbon material composite of the present invention includes a nonionic surfactant and graphite oxide.
The graphite oxide is oxygen bonded by oxidizing a graphitic carbon material such as graphene, graphite (graphite) (oxygen bonded to the carbon material), and the oxygen is a graphite carbon material. On the other hand, it exists as a substituent such as a carboxyl group, a carbonyl group, a hydroxyl group or an epoxy group.
The graphite oxide is preferably graphene oxide in which oxygen is bonded to carbon of graphene.
In general, graphene refers to a sheet composed of one layer in which carbon atoms bonded by sp 2 bonds are arranged in a plane, and a stack of graphene sheets is referred to as graphite. In the present invention, graphene oxide Includes not only a sheet composed of only one carbon atom layer but also a sheet having a structure in which about 2 to 100 layers are laminated. The graphene oxide is preferably a sheet composed of only one carbon atom layer, or has a structure in which about 2 to 20 layers are laminated.
The graphite oxide may further have a functional group such as a sulfur-containing group and a nitrogen-containing group, but the content of carbon, hydrogen, and oxygen as constituent elements with respect to all constituent elements is 97 mol% or more. It is preferable that it is 99 mol% or more, and it is still more preferable that the graphite oxide contains only carbon, hydrogen, and oxygen as constituent elements.
以下では、先ず、本発明の炭素材料複合体の製造方法における精製工程に関し、酸化工程で得られる酸化黒鉛が分散してなる水系分散液と非イオン性界面活性剤との混合、並びに、炭素材料複合体の精製について順に説明する。次いで、精製工程で精製された炭素材料複合体に含まれる酸化黒鉛の層間を剥離する工程、精製工程前の黒鉛を酸化する工程について説明する。 In the following, first, regarding the purification step in the method for producing a carbon material composite of the present invention, a mixture of an aqueous dispersion obtained by dispersing graphite oxide obtained in the oxidation step and a nonionic surfactant, and a carbon material The purification of the complex will be described in order. Next, a process for peeling the graphite oxide layers contained in the carbon material composite purified in the purification process and a process for oxidizing the graphite before the purification process will be described.
（精製工程）
〔水系分散液と非イオン性界面活性剤との混合〕
本発明では、酸化工程で得られる酸化黒鉛が分散してなる水系分散液と非イオン性界面活性剤とを混合する。
混合方法は、特に限定されず、公知の方法で適宜行うことが可能であるが、例えば、撹拌や超音波処理を行ったり、公知の分散機を用いたりして固形分を均一に分散させることが好ましい。
なお、水系分散液と非イオン性界面活性剤とを混合する際には、例えば、水系分散液に非イオン性界面活性剤を添加してもよく、非イオン性界面活性剤に水系分散液を添加してもよく、反応容器に対して水系分散液と非イオン性界面活性剤とを同時に添加してもよい。
(Purification process)
[Mixing of aqueous dispersion and nonionic surfactant]
In the present invention, an aqueous dispersion obtained by dispersing graphite oxide obtained in the oxidation step and a nonionic surfactant are mixed.
The mixing method is not particularly limited and can be appropriately performed by a known method. For example, the solid content is uniformly dispersed by performing stirring or ultrasonic treatment or using a known disperser. Is preferred.
When mixing the aqueous dispersion and the nonionic surfactant, for example, a nonionic surfactant may be added to the aqueous dispersion, and the aqueous dispersion may be added to the nonionic surfactant. An aqueous dispersion and a nonionic surfactant may be added simultaneously to the reaction vessel.
本明細書中、非イオン性界面活性剤は、一般的に界面活性剤と称される疎水性基と親水性基とを有する化合物のうち、酸化工程で得られる酸化黒鉛が分散してなる水系分散液中で実質的にイオンに電離しないものである。
酸化黒鉛は、このような非イオン性界面活性剤と疎水的相互作用し、炭素材料複合体として凝集する。これにより、ろ過等の精製工程を効率的に行うことができ、炭素材料複合体の製造を低コスト化できる。
In the present specification, the nonionic surfactant is an aqueous system in which graphite oxide obtained in the oxidation step is dispersed among compounds having a hydrophobic group and a hydrophilic group generally called a surfactant. In the dispersion, it is not substantially ionized into ions.
Graphite oxide interacts with such nonionic surfactants in a hydrophobic manner and aggregates as a carbon material composite. Thereby, purification processes, such as filtration, can be performed efficiently, and manufacture of a carbon material composite can be reduced.
上記非イオン性界面活性剤の疎水性基としては、例えば脂肪族炭化水素基、芳香族炭化水素基等の炭化水素基が好ましいものとして挙げられる。炭化水素基の炭素数は、３以上であることがより好ましく、６以上であることが更に好ましく、９以上であることが特に好ましい。炭化水素基の炭素数は、例えば２４以下であることが好ましい。また、非イオン性界面活性剤の親水性基としては、例えばアルキレンオキシド基、エーテル基、エステル基、アミド基、水酸基等が好ましいものとして挙げられる。アルキレンオキシド基は、エチレンオキシド基であることがより好ましい。
上記非イオン性界面活性剤としては、例えば、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルケニルエーテル、ポリオキシエチレンアルキルフェニルエーテル、高級脂肪酸アルカノールアミド又はそのエチレンオキサイド付加物、ショ糖脂肪酸エステル、アルキルグリコキシド、脂肪酸グリセリンモノエステル、アルコールエトキシレート、ソルビタンエステル類、ポリオキシエチレンソルビタンエステル類、又は、これらの誘導体等が好ましいものとして挙げられ、これらの１種又は２種以上を用いることができる。例えば、非イオン性界面活性剤は、アルコールエトキシレートがもつ（ポリ）エチレングリコール鎖の末端に水酸基（−ＯＨ）を有するもの（例えば、ソフタノール５０、ソフタノール１２０〔株式会社日本触媒製〕）、ポリオキシエチレンソルビタンエステル類（例えば、ニューコール８５〔日本乳化剤株式会社製〕）であることが特に好ましい。
Preferred examples of the hydrophobic group of the nonionic surfactant include hydrocarbon groups such as aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The number of carbon atoms of the hydrocarbon group is more preferably 3 or more, still more preferably 6 or more, and particularly preferably 9 or more. The number of carbon atoms of the hydrocarbon group is preferably 24 or less, for example. Moreover, as a hydrophilic group of a nonionic surfactant, an alkylene oxide group, an ether group, an ester group, an amide group, a hydroxyl group etc. are mentioned as a preferable thing, for example. The alkylene oxide group is more preferably an ethylene oxide group.
Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, polyoxyethylene alkyl phenyl ether, higher fatty acid alkanolamide or ethylene oxide adduct thereof, sucrose fatty acid ester, alkyl glycoxide , Fatty acid glycerin monoester, alcohol ethoxylate, sorbitan esters, polyoxyethylene sorbitan esters, or derivatives thereof are preferable, and one or more of these can be used. For example, nonionic surfactants include those having a hydroxyl group (—OH) at the end of the (poly) ethylene glycol chain of the alcohol ethoxylate (for example, Softanol 50, Softanol 120 [manufactured by Nippon Shokubai Co., Ltd.]), poly Particularly preferred are oxyethylene sorbitan esters (for example, New Coal 85 [manufactured by Nippon Emulsifier Co., Ltd.])
上記精製工程において水系分散液と混合する非イオン性界面活性剤の量は適宜設定すればよいが、酸化黒鉛が分散してなる水系分散液中の酸化黒鉛１００質量％に対して１０〜１０００質量％であることが好ましい。非イオン性界面活性剤の量は、より好ましくは、酸化黒鉛を含む水系分散液中の酸化黒鉛１００質量％に対して２０〜７００質量％であり、更に好ましくは３０〜６００質量％であり、特に好ましくは４０〜５００質量％である。 The amount of the nonionic surfactant to be mixed with the aqueous dispersion in the purification step may be appropriately set, but is 10 to 1000 mass with respect to 100 mass% of graphite oxide in the aqueous dispersion in which graphite oxide is dispersed. % Is preferred. The amount of the nonionic surfactant is more preferably 20 to 700% by mass, further preferably 30 to 600% by mass, with respect to 100% by mass of graphite oxide in the aqueous dispersion containing graphite oxide. Especially preferably, it is 40-500 mass%.
上記水系分散液は、酸化工程直後の反応組成物であってもよく、その後の濃縮工程で反応組成物から硫酸を除去したり、酸化反応停止（クエンチ）工程で反応組成物に水及び／又は過酸化水素水を添加したりした液であってもよいが、例えば酸化反応停止工程で反応組成物に水及び／又は過酸化水素水を添加した液であることが好ましい。
なお、水系分散液は、分散媒として水を含有していれば良く、その他に水と混和する有機分散媒を更に含有していてもよいが、炭素材料複合体の凝集し易さの観点から、有機分散媒を含有しないことが好ましい。
The aqueous dispersion may be a reaction composition immediately after the oxidation step. In the subsequent concentration step, sulfuric acid is removed from the reaction composition, or water and / or water is added to the reaction composition in the oxidation reaction stop (quenching) step. Although it may be a liquid to which hydrogen peroxide water is added, for example, a liquid in which water and / or hydrogen peroxide water is added to the reaction composition in the oxidation reaction stopping step is preferable.
The aqueous dispersion only needs to contain water as a dispersion medium, and may further contain an organic dispersion medium that is miscible with water, but from the viewpoint of easy aggregation of the carbon material composite. It is preferable that no organic dispersion medium is contained.
本発明の炭素材料複合体の製造方法において、上記水系分散液（非イオン性界面活性剤との混合前の水系分散液）は、水系分散液１００質量％に対して水濃度が２０質量％以上であることが好ましい。
上記水濃度は、２５質量％以上であることがより好ましく、３０質量％以上であることが更に好ましく、３５質量％以上であることが特に好ましい。
このような水濃度の範囲内とすることで、酸化工程等で用いた硫酸存在下であっても、非イオン性界面活性剤が酸化黒鉛と相互作用して凝集するという意外な作用がより充分に発現し、本発明の効果がより顕著なものになる。
また上記水濃度は、例えば、９９質量％以下であることが好ましく、９５質量％以下であることがより好ましい。
In the method for producing a carbon material composite of the present invention, the water-based dispersion (water-based dispersion before mixing with a nonionic surfactant) has a water concentration of 20% by weight or more with respect to 100% by weight of the water-based dispersion. It is preferable that
The water concentration is more preferably 25% by mass or more, further preferably 30% by mass or more, and particularly preferably 35% by mass or more.
By setting it within such a water concentration range, even in the presence of sulfuric acid used in the oxidation step, etc., the unexpected effect that the nonionic surfactant interacts and aggregates with graphite oxide is more sufficient. The effect of the present invention becomes more remarkable.
The water concentration is, for example, preferably 99% by mass or less, and more preferably 95% by mass or less.
本発明の炭素材料複合体の製造方法において、非イオン性界面活性剤と混合される上記水系分散液は、水系分散液１００質量％に対して硫酸イオンを１質量％以上含有することが好ましい。
上記硫酸イオンの含有量は、３質量％以上であることがより好ましく、５質量％以上であることが更に好ましい。また、該硫酸イオンの含有量は、９０質量％以下であることが好ましく、７０質量％以下であることがより好ましい。
上記硫酸イオンの含有量は、硫酸由来の硫酸イオンと、硫酸塩由来の硫酸イオンとの合計含有量である。
更に、上記水系分散液は、ｐＨが２以下であることが好ましく、１．５以下であることがより好ましい。ｐＨは、その下限値は特に限定されないが、通常−１以上である。
本発明では、酸化工程等で用いた硫酸等の強酸存在下で、非イオン性界面活性剤が酸化黒鉛と相互作用して凝集するという意外な作用が発現し、本発明の効果を発揮できる。
In the method for producing a carbon material composite of the present invention, the aqueous dispersion mixed with a nonionic surfactant preferably contains 1% by mass or more of sulfate ions with respect to 100% by mass of the aqueous dispersion.
The content of the sulfate ion is more preferably 3% by mass or more, and further preferably 5% by mass or more. Moreover, the content of the sulfate ion is preferably 90% by mass or less, and more preferably 70% by mass or less.
The content of the sulfate ion is the total content of sulfate ion derived from sulfuric acid and sulfate ion derived from sulfate.
Furthermore, the aqueous dispersion preferably has a pH of 2 or less, and more preferably 1.5 or less. The lower limit of pH is not particularly limited, but is usually −1 or more.
In the present invention, in the presence of a strong acid such as sulfuric acid used in the oxidation step or the like, an unexpected action that the nonionic surfactant interacts and aggregates with graphite oxide is exhibited, and the effects of the present invention can be exhibited.
〔炭素材料複合体の精製工程〕
酸化工程で得られた酸化黒鉛が分散してなる水系分散液と非イオン性界面活性剤とを混合した後、炭素材料複合体を精製する工程が行われる。なお、精製工程は特に限定されず、従来公知の方法を適宜用いることができるが、例えばろ過、デカンテーション、遠心分離、及び、分液抽出からなる群より選択される少なくとも１種の方法より精製する工程であることが好ましい。
これらの方法を用いることで、水系分散液中の硫酸を効率的かつ充分に除去することができ、炭素材料複合体を短時間で精製することができる。その結果、炭素材料複合体の精製の際に、炭素材料複合体に含まれる酸化黒鉛が有する反応性の酸素含有官能基が還元及び／又は不活化されてしまうことを充分に防止でき、高品質な炭素材料複合体を得ることができる。なお、本明細書中、精製工程とは、水系分散液から固形不純物（例えば、過マンガン酸塩等の酸化剤等）及び／又は酸化反応時の溶媒（硫酸等の強酸等）を除く工程を言う。
これらの方法の中でも、より好ましくはろ過、分液抽出であり、更に好ましくはろ過である。上記精製工程によれば、非イオン性界面活性剤の作用により水系分散液中で炭素材料複合体粒子の凝集が促進され、炭素材料複合体粒子が大きな凝集体となり、その結果、水系分散液をろ過してもフィルターの目詰まりが起こりにくく、ろ過に要する時間が非常に短い。また、凝集力の弱い非イオン性界面活性剤による炭素材料複合体の凝集はあまり強固ではないので、凝集塊中に水が入って硫酸を充分に洗い除くことができる。このため、炭素材料複合体を精製する方法としてろ過を用いることで、高品質な炭素材料複合体を非常に簡便に得ることができる。
[Carbon material composite purification process]
After mixing the aqueous dispersion obtained by dispersing graphite oxide obtained in the oxidation step and the nonionic surfactant, a step of purifying the carbon material composite is performed. The purification step is not particularly limited, and a conventionally known method can be appropriately used. For example, the purification step is performed by at least one method selected from the group consisting of filtration, decantation, centrifugation, and liquid separation extraction. It is preferable that it is a process to perform.
By using these methods, sulfuric acid in the aqueous dispersion can be efficiently and sufficiently removed, and the carbon material composite can be purified in a short time. As a result, it is possible to sufficiently prevent the reactive oxygen-containing functional group of the graphite oxide contained in the carbon material composite from being reduced and / or inactivated during the purification of the carbon material composite. Carbon material composite can be obtained. In the present specification, the purification step refers to a step of removing solid impurities (for example, an oxidizing agent such as permanganate) and / or a solvent during oxidation reaction (such as a strong acid such as sulfuric acid) from the aqueous dispersion. To tell.
Among these methods, filtration and separation extraction are more preferable, and filtration is more preferable. According to the above purification step, aggregation of the carbon material composite particles is promoted in the aqueous dispersion by the action of the nonionic surfactant, and the carbon material composite particles become large aggregates. As a result, the aqueous dispersion Even if it is filtered, clogging of the filter hardly occurs and the time required for filtration is very short. In addition, since the aggregation of the carbon material composite by the nonionic surfactant having a weak cohesive force is not so strong, water can enter the aggregate and the sulfuric acid can be sufficiently washed away. For this reason, a high quality carbon material composite can be obtained very simply by using filtration as a method for purifying the carbon material composite.
本発明の炭素材料複合体の製造方法において、炭素材料複合体をより簡便に得る観点からは、上記精製工程は、上述したうちの２種以下の方法により行われることが好ましく、１種の方法により行われることがより好ましい。また、上記方法を繰り返すことなく１工程で完了することが本発明の製造方法における好ましい形態の１つである。
またより充分に炭素材料複合体を精製する観点からは、上記方法は繰り返すことが好ましい。中でも、ろ過、デカンテーション、遠心分離、及び、分液抽出からなる群より選択される少なくとも１種の方法を繰り返して行うことが本発明の製造方法における好ましい形態の１つである。
上記精製工程は、空気中で行ってもよく、窒素、ヘリウム、アルゴン等の不活性ガス雰囲気中で行ってもよい。また、加圧条件下、常圧条件下、減圧条件下のいずれで行ってもよい。
In the method for producing a carbon material composite according to the present invention, from the viewpoint of more easily obtaining the carbon material composite, the purification step is preferably performed by two or less of the methods described above. It is more preferable that this is performed. Moreover, it is one of the preferable forms in the manufacturing method of this invention to complete in one process, without repeating the said method.
Moreover, it is preferable to repeat the said method from a viewpoint of refine | purifying a carbon material composite body more fully. Among these, it is one of the preferable modes in the production method of the present invention to repeatedly perform at least one method selected from the group consisting of filtration, decantation, centrifugation, and liquid separation extraction.
The purification step may be performed in air or in an inert gas atmosphere such as nitrogen, helium, or argon. Moreover, you may carry out on any of pressurization conditions, normal-pressure conditions, and pressure reduction conditions.
本発明の製造方法は、例えば、ろ過、デカンテーション、遠心分離、及び、分液抽出からなる群より選択される少なくとも１種の方法により炭素材料複合体を精製した後、水洗等のその他の精製工程を含んでいてもよい。なお、上記精製工程の後、水洗を繰り返して行う場合、水洗の回数は、硫酸をより充分に除去し、後述する剥離工程において酸化黒鉛の層をより好適に剥離する観点からは、例えば１回以上であることが好ましく、２回以上であることがより好ましい。また、本発明の製造方法により得られる炭素材料複合体から非イオン性界面活性剤を除き過ぎない観点からは、水洗の回数は、例えば１０回以下であることが好ましく、７回以下であることがより好ましい。なお、非イオン性界面活性剤を除き過ぎない観点から、水の代わりに水と非イオン性界面活性剤の混合液で洗浄してもよい。さらに最終的に得られる炭素材料複合体中の酸化黒鉛と非イオン性界面活性剤との比率を任意に調整することもこの洗浄液を調製することで可能となる。 The production method of the present invention includes, for example, purifying the carbon material composite by at least one method selected from the group consisting of filtration, decantation, centrifugation, and liquid separation extraction, and then other purification such as washing with water. A process may be included. In addition, when performing washing with water repeatedly after the purification step, the number of times of washing is, for example, once from the viewpoint of more sufficiently removing sulfuric acid and more suitably peeling the graphite oxide layer in the peeling step described later. It is preferable that it is more than 2 times, and it is more preferable that it is 2 times or more. Further, from the viewpoint of not excessively removing the nonionic surfactant from the carbon material composite obtained by the production method of the present invention, the number of water washings is preferably 10 times or less, for example, 7 times or less. Is more preferable. In addition, from the viewpoint of not excluding the nonionic surfactant, it may be washed with a mixed solution of water and a nonionic surfactant instead of water. Further, it is possible to arbitrarily adjust the ratio of graphite oxide and nonionic surfactant in the finally obtained carbon material composite by preparing this cleaning liquid.
（剥離工程）
また本発明の製造方法は、更に、上記精製工程で精製された炭素材料複合体に含まれる酸化黒鉛の層間を剥離する工程を含むことが好ましい。剥離工程は、上述したように酸化黒鉛の層間を剥離する工程であり、超音波処理やホモジナイザー処理等によって行うことができ、通常、剥離工程によりその層間が剥離された酸化黒鉛を含む炭素材料複合体は、分散媒に分散する。剥離工程は、精製工程で精製された非イオン性界面活性剤及び酸化黒鉛を含んで構成される炭素材料複合体と分散媒とを混合したうえで行うことができる。分散媒は、水を含有する水系分散媒、有機分散媒のいずれであってもよく、エチレンカーボネート、プロピレンカーボネート等の炭酸エステル類、Ｎ−メチル−１−ピロリドン等のラクタム類、ジメチルホルムアミド、ジメチルアセトアミド等のアミド類、テトラヒドロフラン、ジエチルエーテル等のエーテル類、γ−ブチロラクトン等のラクトン類、メタノール、エタノール、プロパノール、ジアセトンアルコール等のアルコール類、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類、酢酸メチル、酢酸エチル、酢酸ブチル等のエステル類、水等が好ましく、これらの１種又は２種以上の混合分散媒を使用できる。中でも、炭酸エステル類、ラクタム類、アミド類、エーテル類、ラクトン類、アルコール類、水がより好ましく、プロピレンカーボネート、Ｎ−メチル−１−ピロリドン、ジメチルホルムアミド、ジメチルアセトアミド、テトラヒドロフラン、γ−ブチロラクトン、ジアセトンアルコール、水が更に好ましく、γ−ブチロラクトン、ジアセトンアルコール、水が特に好ましい。換言すれば、水系分散媒が好ましい。
上記精製工程により硫酸を充分に除去できることと、非イオン性界面活性剤の酸化黒鉛への作用が強すぎず適度なものであることから、剥離工程において酸化黒鉛の層を非常に好適に剥離し、その結果、炭素材料複合体を分散媒に分散させることができる。
(Peeling process)
Moreover, it is preferable that the manufacturing method of this invention further includes the process of peeling the interlayer of the graphite oxide contained in the carbon material composite refine | purified at the said refinement | purification process. The peeling step is a step of peeling the graphite oxide layer as described above, and can be performed by ultrasonic treatment, homogenizer treatment, etc., and is usually a carbon material composite containing graphite oxide from which the layer has been peeled by the peeling step. The body is dispersed in a dispersion medium. The peeling step can be performed after mixing the carbon material composite including the nonionic surfactant and graphite oxide purified in the purification step and the dispersion medium. The dispersion medium may be either an aqueous dispersion medium containing water or an organic dispersion medium. Carbonates such as ethylene carbonate and propylene carbonate, lactams such as N-methyl-1-pyrrolidone, dimethylformamide, dimethyl Amides such as acetamide, ethers such as tetrahydrofuran and diethyl ether, lactones such as γ-butyrolactone, alcohols such as methanol, ethanol, propanol and diacetone alcohol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, acetic acid Esters such as methyl, ethyl acetate, and butyl acetate, water, and the like are preferred, and one or more of these mixed dispersion media can be used. Of these, carbonates, lactams, amides, ethers, lactones, alcohols, and water are more preferable, and propylene carbonate, N-methyl-1-pyrrolidone, dimethylformamide, dimethylacetamide, tetrahydrofuran, γ-butyrolactone, di Acetone alcohol and water are more preferable, and γ-butyrolactone, diacetone alcohol and water are particularly preferable. In other words, an aqueous dispersion medium is preferable.
Since the sulfuric acid can be sufficiently removed by the above purification process and the action of the nonionic surfactant on the graphite oxide is not too strong and appropriate, the graphite oxide layer is peeled off very suitably in the peeling process. As a result, the carbon material composite can be dispersed in the dispersion medium.
また上記分散媒としては、液状高分子化合物もまた好ましい。該液状高分子化合物としては、ポリエチレングリコール、ポリプロピレングリコール、シリコーンオイル等が挙げられ、これらの１種又は２種以上を使用できる。 Further, as the dispersion medium, a liquid polymer compound is also preferable. Examples of the liquid polymer compound include polyethylene glycol, polypropylene glycol, and silicone oil, and one or more of these can be used.
更に、上記分散媒としては、樹脂前駆体（モノマー）もまた好ましい。樹脂前駆体としては、親水性（水系）樹脂前駆体であっても親油性（有機系）樹脂前駆体であってもよく、従来公知の熱可塑性樹脂の前駆体、熱硬化性樹脂の前駆体、光硬化性樹脂の前駆体等を適宜使用できる。 Further, as the dispersion medium, a resin precursor (monomer) is also preferable. The resin precursor may be a hydrophilic (aqueous) resin precursor or an oleophilic (organic) resin precursor, and a conventionally known thermoplastic resin precursor or thermosetting resin precursor. A precursor of a photocurable resin or the like can be used as appropriate.
上記熱可塑性樹脂としては、例えば、ポリエチレン、ポリプロピレン、エチレン−オレフィン共重合体（エチレン−プロピレン共重合体等）、ポリメチルペンテン等のオレフィン系樹脂；ポリ（メタ）アクリレート樹脂、ポリ（メタ）アクリル酸樹脂、ポリ（メタ）アクリロニトリル樹脂等の（メタ）アクリル系樹脂；ポリスチレン、ＡＳ樹脂（アクリロニトリル−スチレン樹脂）、ＡＢＳ樹脂（アクリロニトリル−ブタジエン−スチレン樹脂）、ＡＣＳ樹脂（塩素化ポリエチレン−アクリロニトリル−スチレン樹脂）、ＡＥＳ樹脂（アクリロニトリル−エチレン−スチレン樹脂）等のスチレン系樹脂；ポリ塩化ビニル、ポリ塩化ビニリデン、ポリフッ化ビニリデン等のハロゲン化ビニル樹脂；脂肪族ポリアミド、芳香族ポリアミド等のアミド樹脂；ポリ酢酸ビニル、エチレン−酢酸ビニル共重合体等の酢酸ビニル樹脂；ポリビニルアルコール樹脂、ポリビニルアセタール樹脂、ポリビニルエーテル樹脂、ポリビニルケトン樹脂等のその他のビニル樹脂；ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステル樹脂；ＰＰＥ樹脂（ポリフェニレンエーテル樹脂）、変性ＰＰＥ樹脂、ポリフェニレンオキシド、ポリフェニレンスルフィド等のフェニレン基含有樹脂；ポリテトラフルオロエチレン等のフッ素樹脂；ポリエーテルエーテルケトン、ポリエーテルケトン、ポリエーテルスルホン、ポリエーテルニトリル等のポリエーテル樹脂；ポリカーボネート；シリコーン樹脂；ポリスルホン樹脂；液晶ポリマー；これら樹脂を得るために用いられるモノマーを適宜組み合わせて得られる共重合体等が挙げられる。 Examples of the thermoplastic resin include olefin-based resins such as polyethylene, polypropylene, ethylene-olefin copolymers (ethylene-propylene copolymer, etc.), polymethylpentene; poly (meth) acrylate resins, poly (meth) acrylic. (Meth) acrylic resins such as acid resins and poly (meth) acrylonitrile resins; polystyrene, AS resin (acrylonitrile-styrene resin), ABS resin (acrylonitrile-butadiene-styrene resin), ACS resin (chlorinated polyethylene-acrylonitrile-styrene) Resin), AES resin (acrylonitrile-ethylene-styrene resin) and other styrene resins; polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride and other halogenated resins; aliphatic polyamide, aromatic polyamide and other Resin; Vinyl acetate resin such as polyvinyl acetate and ethylene-vinyl acetate copolymer; Other vinyl resins such as polyvinyl alcohol resin, polyvinyl acetal resin, polyvinyl ether resin, polyvinyl ketone resin; polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate Polyester resins such as phthalates; PPE resins (polyphenylene ether resins), modified PPE resins, phenylene group-containing resins such as polyphenylene oxide and polyphenylene sulfide; Fluorine resins such as polytetrafluoroethylene; polyether ether ketone, polyether ketone, polyether Polyether resins such as sulfones and polyether nitriles; polycarbonates; silicone resins; polysulfone resins; liquid crystal polymers; to obtain these resins Copolymers based on a proper combination of monomers used and the like.
上記熱硬化性樹脂としては、例えばエポキシ樹脂、フェノール樹脂、シアン酸エステル樹脂、メラミン樹脂、ポリイミド樹脂、ビスマレイミド樹脂、ユリア樹脂、アルキド樹脂、シリコーン樹脂、ビニルエステル樹脂、ベンゾオキサジン樹脂、ウレタン樹脂等が挙げられる。 Examples of the thermosetting resin include epoxy resin, phenol resin, cyanate ester resin, melamine resin, polyimide resin, bismaleimide resin, urea resin, alkyd resin, silicone resin, vinyl ester resin, benzoxazine resin, urethane resin, etc. Is mentioned.
上記光硬化性樹脂としては、例えばウレタン（メタ）アクリル系樹脂、エポキシ（メタ）アクリル系樹脂等の光硬化性（メタ）アクリル系樹脂；ポリビニルアセテート樹脂等のポリビニルカーボネート樹脂等が挙げられる。 Examples of the photocurable resin include photocurable (meth) acrylic resins such as urethane (meth) acrylic resins and epoxy (meth) acrylic resins; and polyvinyl carbonate resins such as polyvinyl acetate resins.
上記樹脂前駆体としては、上述した樹脂（例えば、熱可塑性樹脂、熱硬化性樹脂、光硬化性樹脂）を得るために用いられるモノマーを使用でき、中でも、エチレン性不飽和二重結合を有するモノマー（ビニルモノマー）、エポキシ化合物（エポキシモノマー）が好ましい。
上記エチレン性不飽和二重結合を有するモノマーとしては、単官能であってもよく、多官能であってもよく、例えば（メタ）アクリル酸エステル、（メタ）アクリル酸、（メタ）アクリロニトリル等の（メタ）アクリル系モノマー：スチレン、ジビニルベンゼン等のスチレン系モノマー、酢酸ビニル、塩化ビニル、ビニルエーテル、ブタジエン等のその他のビニルモノマー等が挙げられ、これらの１種又は２種以上を使用できる。
また上記エポキシ化合物としては、例えば脂環式エポキシ化合物、芳香族エポキシ化合物、水添エポキシ化合物等が挙げられ、これらの１種又は２種以上を使用できる。
As said resin precursor, the monomer used in order to obtain resin mentioned above (for example, a thermoplastic resin, a thermosetting resin, a photocurable resin) can be used, Especially, the monomer which has an ethylenically unsaturated double bond (Vinyl monomer) and an epoxy compound (epoxy monomer) are preferable.
The monomer having an ethylenically unsaturated double bond may be monofunctional or polyfunctional, such as (meth) acrylic acid ester, (meth) acrylic acid, (meth) acrylonitrile, etc. (Meth) acrylic monomers: styrene monomers such as styrene and divinylbenzene, and other vinyl monomers such as vinyl acetate, vinyl chloride, vinyl ether, and butadiene, and one or more of these can be used.
Moreover, as said epoxy compound, an alicyclic epoxy compound, an aromatic epoxy compound, a hydrogenated epoxy compound etc. are mentioned, for example, These 1 type (s) or 2 or more types can be used.
また上記分散媒は、水、有機分散媒、液状高分子化合物、及び、樹脂前駆体からなる群より選択される少なくとも２種を組み合わせた混合分散媒であってもよい。
例えば、水系分散媒又は有機分散媒に、上述した液状高分子化合物や、樹脂前駆体が溶解又は分散しているものであってもよい。
The dispersion medium may be a mixed dispersion medium in which at least two selected from the group consisting of water, an organic dispersion medium, a liquid polymer compound, and a resin precursor are combined.
For example, the above-described liquid polymer compound or resin precursor may be dissolved or dispersed in an aqueous dispersion medium or an organic dispersion medium.
また上記分散媒は、樹脂を含むものであってもよく、例えば、上記分散媒が水及び／又は有機分散媒を含んでいて、該水及び／又は有機分散媒に、上述した樹脂が溶解又は分散しているものであってもよい。樹脂としては、上述した熱可塑性樹脂、熱硬化性樹脂、光硬化性樹脂が挙げられ、これらの１種又は２種以上を使用できる。例えば、水に水溶性樹脂が溶解しているものや、水にエマルション粒子が分散しているもの、有機分散媒にビニル樹脂等のポリマーが溶解しているものを分散媒として好適に使用できる。
なお、有機分散媒として、上述した剥離工程における好ましい有機分散媒を用いることが好ましい。
The dispersion medium may contain a resin. For example, the dispersion medium contains water and / or an organic dispersion medium, and the resin described above is dissolved or dissolved in the water and / or the organic dispersion medium. It may be dispersed. Examples of the resin include the thermoplastic resins, thermosetting resins, and photocurable resins described above, and one or more of these can be used. For example, a material in which a water-soluble resin is dissolved in water, a material in which emulsion particles are dispersed in water, or a material in which a polymer such as a vinyl resin is dissolved in an organic dispersion medium can be suitably used as the dispersion medium.
In addition, it is preferable to use the preferable organic dispersion medium in the peeling process mentioned above as an organic dispersion medium.
以上を纏めると、上記分散媒は、水、有機分散媒、液状高分子化合物、樹脂、及び、樹脂前駆体からなる群より選択される１種であってもよく、少なくとも２種を適宜組み合わせた混合分散媒であってもよい。 In summary, the dispersion medium may be one selected from the group consisting of water, an organic dispersion medium, a liquid polymer compound, a resin, and a resin precursor, and at least two types are appropriately combined. A mixed dispersion medium may be used.
なお、上述したように、上記分散媒のうち、樹脂及び／又は樹脂前駆体を含む樹脂分散媒としては、例えば、エポキシ化合物（エポキシモノマー）、エポキシ樹脂、エチレン性不飽和二重結合を有するモノマー（ビニルモノマー）、ビニル樹脂、これらモノマーを２種以上組み合わせて得られる共重合体、これらの２種以上の混合分散媒が好ましいものとして挙げられる。また、該樹脂分散媒が、更に、有機分散媒及び／又は水を含むものであっても構わない。 In addition, as mentioned above, as a resin dispersion medium containing a resin and / or a resin precursor among the above dispersion media, for example, an epoxy compound (epoxy monomer), an epoxy resin, and a monomer having an ethylenically unsaturated double bond (Vinyl monomer), vinyl resin, a copolymer obtained by combining two or more of these monomers, and a mixed dispersion medium of two or more of these are preferred. The resin dispersion medium may further contain an organic dispersion medium and / or water.
なお、上記剥離工程における分散媒中の硫酸含有量は、例えば、分散媒１００質量％に対して０．１質量％以下であることが好ましい。 In addition, it is preferable that the sulfuric acid content in the dispersion medium in the said peeling process is 0.1 mass% or less with respect to 100 mass% of dispersion media, for example.
上記剥離工程は、例えば空気中、又は、窒素、ヘリウム、アルゴン等の不活性ガス雰囲気中で行うことができる。また、上記剥離工程は、その温度条件は特に限定されないが、例えば１０〜５０℃の範囲内で行うことが好ましい。また、上記剥離工程は、その圧力条件は特に限定されず、加圧条件下、常圧条件下、減圧条件下のいずれで行ってもよいが、例えば常圧条件下で行うことが好ましい。
上記剥離工程の時間は、炭素材料複合体分散液の総量、剥離装置のサイズにより適宜調整すればよいが、例えば、１分〜１２０時間とすることができる。また、１〜１００分とすることが好ましく、２〜８０分とすることがより好ましい。
The said peeling process can be performed, for example in air or inert gas atmosphere, such as nitrogen, helium, and argon. Moreover, although the temperature conditions are not specifically limited for the said peeling process, For example, it is preferable to carry out within the range of 10-50 degreeC. In addition, the pressure condition of the peeling step is not particularly limited, and may be performed under any of a pressurized condition, a normal pressure condition, and a reduced pressure condition. For example, it is preferably performed under normal pressure conditions.
Although the time of the said peeling process should just be suitably adjusted with the total amount of carbon material complex dispersion liquid and the size of a peeling apparatus, it can be made into 1 minute-120 hours, for example. Moreover, it is preferable to set it as 1 to 100 minutes, and it is more preferable to set it as 2 to 80 minutes.
（黒鉛を酸化する工程）
上記黒鉛を酸化する工程は、黒鉛が酸化されることになる限り、その方法は特に制限されず、上述したＨｕｍｍｅｒｓ法、Ｂｒｏｄｉｅ法、Ｓｔａｕｄｅｎｍａｉｅｒ法等のいずれの方法における黒鉛の酸化方法を用いてもよく、Ｈｕｍｍｅｒｓ法における酸化方法を採用した、黒鉛と硫酸とを含む混合液に過マンガン酸塩を添加する工程であってもよい。
(Process of oxidizing graphite)
The step of oxidizing the graphite is not particularly limited as long as the graphite is oxidized, and any method such as the above-described Hummers method, Brodie method, or Staudenmaier method may be used. It may be a step of adding permanganate to a mixed solution containing graphite and sulfuric acid, which employs an oxidation method in the Hummers method.
上述した黒鉛を酸化する方法では、上記酸化工程は、通常、酸を用いて黒鉛を酸化する。
本発明の製造方法は、精製工程に供される水系分散液中に酸が残留するが、該酸が残留していても、非イオン性界面活性剤が酸化黒鉛と相互作用して凝集し、酸等の不純物を容易に除くことが可能になるという意外な作用が発現する。その結果、高品質な炭素材料複合体を簡便に製造することができる。
In the above-described method for oxidizing graphite, the oxidation step usually oxidizes graphite using an acid.
In the production method of the present invention, acid remains in the aqueous dispersion used in the purification step, but even if the acid remains, the nonionic surfactant interacts with graphite oxide and aggregates, An unexpected effect that impurities such as acids can be easily removed is exhibited. As a result, a high-quality carbon material composite can be easily produced.
中でも、上記酸化工程が、黒鉛と硫酸とを含む混合液に過マンガン酸塩を添加する工程であることは、本発明の好適な実施形態の１つである。
また上記酸化工程において、硫酸の使用量は、黒鉛に対する硫酸の質量比（硫酸／黒鉛）が２５〜６０となる量であることが好ましい。該質量比が２５以上であることにより、酸化反応中に反応組成物（混合液）の高粘度化を充分に防止して酸化黒鉛を効率的に製造することができる。また、該質量比が６０以下であることにより、廃液量を充分に少なくすることができる。
Especially, it is one of the suitable embodiment of this invention that the said oxidation process is a process of adding permanganate to the liquid mixture containing graphite and a sulfuric acid.
Moreover, in the said oxidation process, it is preferable that the usage-amount of a sulfuric acid is a quantity from which the mass ratio (sulfuric acid / graphite) of sulfuric acid with respect to graphite will be 25-60. When the mass ratio is 25 or more, graphite oxide can be efficiently produced by sufficiently preventing the viscosity of the reaction composition (mixed solution) during the oxidation reaction. Further, when the mass ratio is 60 or less, the amount of waste liquid can be sufficiently reduced.
上記酸化工程に用いる黒鉛は、平均粒子径が３μｍ以上、８０μｍ以下であることが好ましい。このような平均粒子径のものを用いることで、酸化反応をより効率的に進めることができる。黒鉛の平均粒子径は、より好ましくは３．２μｍ以上、７０μｍ以下である。
上記平均粒子径は、レーザー回折・散乱式粒度分布測定装置により測定した体積基準の平均粒子径を採用することが好ましい。
The graphite used in the oxidation step preferably has an average particle size of 3 μm or more and 80 μm or less. By using a material having such an average particle size, the oxidation reaction can be advanced more efficiently. The average particle diameter of graphite is more preferably 3.2 μm or more and 70 μm or less.
The average particle diameter is preferably a volume-based average particle diameter measured by a laser diffraction / scattering particle size distribution analyzer.
上記酸化工程に用いる黒鉛の形状は特に制限されず、微粉状、粉状、粒状、顆粒状、鱗片状、多面体状、ロッド状、曲面含有状等が挙げられる。なお、平均粒子径が上述のような範囲の粒子は、例えば、粒子を粉砕機等により粉砕する方法や、粒子をふるい等にかけて粒子径を選別する方法、これら方法の組み合わせのほか、粒子を製造する段階で調製条件を最適化し、所望の粒子径の粒子を得る方法等により製造することが可能である。 The shape of the graphite used for the oxidation step is not particularly limited, and examples thereof include fine powder, powder, granule, granule, scale, polyhedron, rod, and curved surface-containing shape. In addition, the particles having the average particle diameter in the above range are produced by, for example, a method of pulverizing the particles with a pulverizer, a method of selecting the particle diameter by sieving the particles, a combination of these methods, or the like. It is possible to manufacture by optimizing the preparation conditions at the stage of obtaining and obtaining particles having a desired particle diameter.
上記黒鉛と硫酸とを含む混合液中における黒鉛の含有量は、混合液１００質量％に対して０．５質量％以上であることが好ましく、１質量％以上であることがより好ましく、１．５質量％以上であることが更に好ましく、２質量％以上であることが特に好ましい。該黒鉛の含有量は、１０質量％以下であることが好ましく、８質量％以下であることがより好ましく、７質量％以下であることが更に好ましく、６質量％以下であることが特に好ましい。
本発明の製造方法における酸化工程に用いる黒鉛は、１種のみであってもよく、上記平均粒子径、形状等のいずれかにおいて異なる２種以上のものを用いてもよい。
The graphite content in the mixed solution containing graphite and sulfuric acid is preferably 0.5% by mass or more, more preferably 1% by mass or more, with respect to 100% by mass of the mixed solution. The content is more preferably 5% by mass or more, and particularly preferably 2% by mass or more. The graphite content is preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 7% by mass or less, and particularly preferably 6% by mass or less.
Only one type of graphite may be used in the oxidation step in the production method of the present invention, or two or more types different in any of the average particle diameter, shape, and the like may be used.
上記酸化工程が黒鉛と硫酸とを含む混合液に過マンガン酸塩を添加する工程である場合、上記酸化工程で添加する過マンガン酸塩としては、過マンガン酸ナトリウム、過マンガン酸カリウム、過マンガン酸アンモニウム、過マンガン酸銀、過マンガン酸亜鉛、過マンガン酸マグネシウム、過マンガン酸カルシウム、過マンガン酸バリウム等が挙げられ、これらの１種又は２種以上を使用できるが、中でも過マンガン酸ナトリウム、過マンガン酸カリウムが好ましく、過マンガン酸カリウムがより好ましい。 When the oxidation step is a step of adding permanganate to a mixed solution containing graphite and sulfuric acid, the permanganate added in the oxidation step includes sodium permanganate, potassium permanganate, permanganate. Ammonium acid, silver permanganate, zinc permanganate, magnesium permanganate, calcium permanganate, barium permanganate, and the like can be used, and one or more of these can be used, among which sodium permanganate , Potassium permanganate is preferred, and potassium permanganate is more preferred.
上記酸化工程が黒鉛と硫酸とを含む混合液に過マンガン酸塩を添加する工程である場合、上記酸化工程における上記過マンガン酸塩の全添加量は、上記混合液中の黒鉛量１００質量％に対し、５０〜５００質量％であることが好ましい。これにより、酸化黒鉛を安全かつ効率的に製造することができる。なお、酸化剤の全添加量を変化させることで、酸化黒鉛に導入される酸素原子の量を調節することができる。 When the oxidation step is a step of adding permanganate to a mixed solution containing graphite and sulfuric acid, the total amount of the permanganate added in the oxidation step is 100% by mass of graphite in the mixed solution. It is preferable that it is 50-500 mass% with respect to. Thereby, graphite oxide can be manufactured safely and efficiently. In addition, the amount of oxygen atoms introduced into the graphite oxide can be adjusted by changing the total amount of the oxidizing agent added.
上記酸化工程が黒鉛と硫酸とを含む混合液に過マンガン酸塩を添加する工程である場合、上記酸化工程では、過マンガン酸塩を一括で添加してもよく、複数回に分けて添加してもよく、また連続的に添加しても良いが、複数回に分けて添加するか連続的に添加することが好ましい。これにより、酸化反応が急激に進行することを抑えて反応の制御をよりしやすくすることができる。
上記過マンガン酸塩を複数回に分けて添加する場合、１回当たりの添加量は、それぞれ同じであってもよく、異なっていてもよい。
When the oxidation step is a step of adding permanganate to a mixed solution containing graphite and sulfuric acid, in the oxidation step, the permanganate may be added all at once or added in multiple times. Alternatively, it may be added continuously, but it is preferable to add in multiple portions or add continuously. Thereby, it is possible to control the reaction more easily by suppressing the rapid progress of the oxidation reaction.
When the permanganate is added in a plurality of times, the amount added per time may be the same or different.
上記酸化工程が黒鉛と硫酸とを含む混合液に過マンガン酸塩を添加する工程である場合、上記酸化工程では、上記混合液の温度を１０〜５０℃の範囲内に維持しながら過マンガン酸塩を添加することが好ましい。このような温度範囲に維持することで、酸化反応を制御しながら充分に進行させることができる。
また上記酸化工程が黒鉛と硫酸とを含む混合液に過マンガン酸塩を添加する工程である場合、上記酸化工程は、上記混合液の温度変化を３０℃以下に維持しながら過マンガン酸塩を添加する工程であることが好ましい。これにより、より安定的に酸化工程を行うことができる。
When the oxidation step is a step of adding permanganate to a mixed solution containing graphite and sulfuric acid, in the oxidation step, permanganic acid while maintaining the temperature of the mixed solution within a range of 10 to 50 ° C. It is preferred to add a salt. By maintaining in such a temperature range, it is possible to sufficiently proceed while controlling the oxidation reaction.
Further, when the oxidation step is a step of adding permanganate to a mixed solution containing graphite and sulfuric acid, the oxidation step is carried out while maintaining the temperature change of the mixed solution at 30 ° C. or less. The step of adding is preferable. Thereby, an oxidation process can be performed more stably.
上記酸化工程が黒鉛と硫酸とを含む混合液に過マンガン酸塩を添加する工程である場合、上記酸化工程では、安定的に酸化工程を行う観点から、過マンガン酸塩を１０分〜１０時間の間にわたって添加することが好ましい。 In the case where the oxidation step is a step of adding permanganate to a mixed solution containing graphite and sulfuric acid, in the oxidation step, the permanganate is added for 10 minutes to 10 hours from the viewpoint of performing the oxidation step stably. It is preferable to add over the period.
上記酸化工程は、公知の撹拌機等を用いて撹拌しながら行うことが好ましい。
上記酸化工程は、例えば空気中、又は、窒素、ヘリウム、アルゴン等の不活性ガス雰囲気中で行うことができる。また、上記酸化工程は、その圧力条件は特に限定されず、加圧条件下、常圧条件下、減圧条件下のいずれであってもよいが、例えば常圧条件下で行うことが好ましい。
上記酸化工程は、連続的に行ってもよいし、断続的に行ってもよい。
The oxidation step is preferably performed while stirring using a known stirrer or the like.
The oxidation step can be performed, for example, in air or in an inert gas atmosphere such as nitrogen, helium, or argon. In addition, the pressure condition of the oxidation step is not particularly limited, and may be any of a pressurized condition, a normal pressure condition, and a reduced pressure condition. For example, it is preferably performed under a normal pressure condition.
The oxidation step may be performed continuously or intermittently.
上記混合液は、黒鉛、硫酸、及び、必要に応じてその他の成分を混合して得ることができる。上記混合は、公知の方法で適宜行うことが可能であるが、例えば、超音波処理を行ったり、公知の分散機を用いたりして黒鉛を均一に分散させることが好ましい。 The liquid mixture can be obtained by mixing graphite, sulfuric acid, and other components as required. The mixing can be appropriately performed by a known method. For example, it is preferable to uniformly disperse graphite by performing ultrasonic treatment or using a known disperser.
本発明の炭素材料複合体の製造方法は、上述した黒鉛を酸化する工程と、上記精製工程との間に、熟成工程、酸化反応停止工程、濃縮工程等のその他の工程を含んでいてもよい。上述したように、例えば、酸化反応停止工程で反応組成物に水及び／又は過酸化水素水を添加した液を精製工程で水系分散液として用いることが好ましい。 The method for producing a carbon material composite of the present invention may include other steps such as an aging step, an oxidation reaction stop step, and a concentration step between the step of oxidizing graphite and the purification step. . As described above, for example, a liquid obtained by adding water and / or hydrogen peroxide solution to the reaction composition in the oxidation reaction stopping step is preferably used as the aqueous dispersion in the purification step.
上記熟成工程において、酸化工程で得られた反応組成物を熟成させる温度及び時間は適宜選択すればよいが、反応組成物を０〜９０℃の温度に維持することが好ましい。
また熟成させる時間は、０．１〜２４時間であることが好ましい。
In the aging step, the temperature and time for aging the reaction composition obtained in the oxidation step may be appropriately selected, but it is preferable to maintain the reaction composition at a temperature of 0 to 90 ° C.
The aging time is preferably 0.1 to 24 hours.
上記酸化反応停止工程は、空気中で行ってもよく、窒素、ヘリウム、アルゴン等の不活性ガス雰囲気中で行ってもよい。また真空中で行ってもよい。
上記酸化反応停止工程は、例えば、反応組成物の温度を５〜１５℃に設定し、反応組成物に水を添加し、次いで還元剤として過酸化水素水を添加したり、過酸化水素水のみを添加したりして行うことができる。また、反応組成物を、５〜２５℃に設定した、水又は過酸化水素水に添加して行ってもよい。
上記酸化反応停止工程の時間は、例えば０．０１〜５時間とすることができる。
The oxidation reaction stopping step may be performed in air or in an inert gas atmosphere such as nitrogen, helium, or argon. Moreover, you may carry out in a vacuum.
In the oxidation reaction stopping step, for example, the temperature of the reaction composition is set to 5 to 15 ° C., water is added to the reaction composition, and then hydrogen peroxide solution is added as a reducing agent, or only hydrogen peroxide solution is added. Can be added. Moreover, you may carry out by adding the reaction composition to water set to 5-25 degreeC or water or hydrogen peroxide solution.
The time for the oxidation reaction stopping step can be, for example, 0.01 to 5 hours.
上記濃縮工程により反応組成物から酸や水を適度に除去することで、酸や水の量を好適な範囲内に調節することができる。この工程は、遠心分離、水等を加え再分散、ろ過、減圧濃縮等の方法を使用して行うことができる。また、これらの工程は繰り返してもよいが、繰り返すことなく１工程で完了することが好ましい。 By appropriately removing acid and water from the reaction composition by the concentration step, the amount of acid and water can be adjusted within a suitable range. This step can be performed using a method such as centrifugation, re-dispersion with addition of water, filtration, concentration under reduced pressure, or the like. Moreover, although these processes may be repeated, it is preferable to complete by one process, without repeating.
本発明の製造方法は、上記精製工程の後、該精製工程で精製される炭素材料複合体に含まれる酸化黒鉛と、酸化黒鉛の酸素含有官能基と反応する化合物とを反応させて酸化黒鉛誘導体を得る工程を含んでいてもよい。
上記酸化黒鉛の酸素含有官能基と反応する化合物は、例えば、アルコール、シラン化合物、脂肪酸（塩）、脂肪酸エステル、イソシアネート化合物、及び、アミンからなる群より選択される少なくとも１種を含むことが好ましい。なお、シラン化合物は、酸化黒鉛の酸素含有官能基との反応性を良好なものとする観点から、珪素原子と直接結合したシロキシ基及び／又はアルコキシ基を有することが好ましい。
In the production method of the present invention, after the purification step, the graphite oxide derivative contained in the carbon material composite purified in the purification step is reacted with a compound that reacts with the oxygen-containing functional group of the graphite oxide. The process of obtaining may be included.
The compound that reacts with the oxygen-containing functional group of the graphite oxide preferably contains at least one selected from the group consisting of alcohol, silane compound, fatty acid (salt), fatty acid ester, isocyanate compound, and amine, for example. . The silane compound preferably has a siloxy group and / or an alkoxy group directly bonded to a silicon atom from the viewpoint of improving the reactivity with the oxygen-containing functional group of graphite oxide.
＜炭素材料複合体＞
本発明は、少なくとも非イオン性界面活性剤及び酸化黒鉛を含んで構成される炭素材料複合体である。本発明の炭素材料複合体は、分散媒中で好適に分散することができる。本発明の炭素材料複合体の好ましい形態は、非イオン性界面活性剤及び酸化黒鉛を含んで構成される炭素材料複合体であって、該酸化黒鉛は、酸素原子数に対する炭素原子数の比（Ｃ／Ｏ）が５．５以下である炭素材料複合体である。この炭素材料複合体は、分散媒中でより充分に分散することができる。
該比は、５以下であることが好ましく、４以下であることがより好ましい。また、１以上であることが好ましい。
酸素原子数に対する炭素原子数の比は、ＸＰＳ測定で得られるＯ１ｓ領域の全ピーク面積とＣ１ｓ領域の全ピーク面積との比率により確認することができる。
本発明の炭素材料複合体は、本発明の炭素材料複合体の製造方法により得ることができる。
<Carbon material composite>
The present invention is a carbon material composite comprising at least a nonionic surfactant and graphite oxide. The carbon material composite of the present invention can be suitably dispersed in a dispersion medium. A preferred form of the carbon material composite of the present invention is a carbon material composite comprising a nonionic surfactant and graphite oxide, wherein the graphite oxide has a ratio of the number of carbon atoms to the number of oxygen atoms ( C / O) is a carbon material composite having 5.5 or less. This carbon material composite can be more fully dispersed in the dispersion medium.
The ratio is preferably 5 or less, and more preferably 4 or less. Moreover, it is preferable that it is 1 or more.
The ratio of the number of carbon atoms to the number of oxygen atoms can be confirmed by the ratio of the total peak area of the O1s region and the total peak area of the C1s region obtained by XPS measurement.
The carbon material composite of the present invention can be obtained by the method for producing a carbon material composite of the present invention.
＜分散体＞
本発明は、本発明の炭素材料複合体が分散媒中に分散してなる分散体でもある。
分散媒は、水系分散媒、有機分散媒のいずれであってもよく、剥離工程において上述した水、有機分散媒を好適に使用でき、例えば、プロピレンカーボネート、Ｎ−メチル−１−ピロリドン、ジメチルホルムアミド、ジメチルアセトアミド、テトラヒドロフラン、γ−ブチロラクトン、ジアセトンアルコール、水等が好ましく、γ−ブチロラクトン、ジアセトンアルコール、水であることがより好ましい。なお、これら分散媒の１種又は２種以上の混合分散媒を使用できる。
<Dispersion>
The present invention is also a dispersion formed by dispersing the carbon material composite of the present invention in a dispersion medium.
The dispersion medium may be either an aqueous dispersion medium or an organic dispersion medium, and the water and the organic dispersion medium described above in the peeling step can be suitably used. For example, propylene carbonate, N-methyl-1-pyrrolidone, dimethylformamide Dimethylacetamide, tetrahydrofuran, γ-butyrolactone, diacetone alcohol, water and the like are preferable, and γ-butyrolactone, diacetone alcohol and water are more preferable. In addition, 1 type, or 2 or more types of these dispersion media can be used.
また上記分散媒として、水、有機分散媒の他、上述した液状高分子化合物、樹脂、又は、樹脂前駆体を好適に使用できる。液状高分子化合物、樹脂、樹脂前駆体としては剥離工程の説明で示したものを用いることができ、その好ましいものは、それぞれ、剥離工程の説明で上述したものと同様である。
液状高分子化合物としては、例えば、ポリエチレングリコール、ポリプロピレングリコールが好適なものとして挙げられる。
樹脂としては、例えば、（メタ）アクリル樹脂等のビニル樹脂、エポキシ樹脂が好適なものとして挙げられる。
樹脂前駆体としては、例えば、（メタ）アクリルモノマー等のビニルモノマー、エポキシモノマーが好適なものとして挙げられる。
上記分散媒は、水、有機分散媒、液状高分子化合物、樹脂、及び、樹脂前駆体からなる群より選択される少なくとも２種を適宜組み合わせた混合分散媒であってもよい。好ましい組み合わせは、剥離工程において上述した通りである。
なお、上記有機分散媒としては、上述した剥離工程における好ましい有機分散媒を用いることが好ましい。
本発明の分散体中の本発明の炭素材料複合体の含有割合は、適宜調整することができる。
In addition to water and organic dispersion media, the above-described liquid polymer compound, resin, or resin precursor can be suitably used as the dispersion medium. As the liquid polymer compound, resin, and resin precursor, those described in the description of the peeling step can be used, and preferable ones are the same as those described above in the description of the peeling step.
As the liquid polymer compound, for example, polyethylene glycol and polypropylene glycol are preferable.
Suitable examples of the resin include vinyl resins such as (meth) acrylic resins and epoxy resins.
Suitable resin precursors include, for example, vinyl monomers such as (meth) acrylic monomers and epoxy monomers.
The dispersion medium may be a mixed dispersion medium in which at least two selected from the group consisting of water, an organic dispersion medium, a liquid polymer compound, a resin, and a resin precursor are appropriately combined. A preferred combination is as described above in the peeling step.
In addition, as said organic dispersion medium, it is preferable to use the preferable organic dispersion medium in the peeling process mentioned above.
The content ratio of the carbon material composite of the present invention in the dispersion of the present invention can be appropriately adjusted.
上述したように、本発明の分散体は、本発明の炭素材料複合体が樹脂及び／又は樹脂前駆体中に分散してなるもの（樹脂分散体）であってもよい。なお、樹脂分散体は、更に、分散媒として水、有機分散媒、及び、液状高分子化合物からなる群より選択される少なくとも１種を含むものであっても構わない。 As described above, the dispersion of the present invention may be a dispersion (resin dispersion) in which the carbon material composite of the present invention is dispersed in a resin and / or a resin precursor. The resin dispersion may further include at least one selected from the group consisting of water, an organic dispersion medium, and a liquid polymer compound as a dispersion medium.
上記樹脂分散体の形態は、液体状又はゲル状の組成物であってもよく、固形状のもの（例えば、成形体）であってもよい。
上記樹脂分散体は、例えば、本発明の炭素材料複合体を水系分散媒又は有機分散媒中に分散してなる分散体、又は、本発明の炭素材料複合体そのもの（粉体）と、上述した樹脂（熱可塑性樹脂、熱硬化性樹脂、又は、光硬化性樹脂）とを混錬（好ましくは、樹脂を溶融させたうえで混錬）する工程を経て得ることができる。
また上記成形体は、例えば、本発明の樹脂分散体であって、液体状又はゲル状の組成物であるものを用いて得ることができ、例えば、該組成物を塗布・成膜したり、成形したり、該組成物中の樹脂前駆体等を重合・硬化したりして得ることができる。
本発明の樹脂分散体としては、例えば、液体状又はゲル状の組成物；膜（フィルム）、シート、繊維、ペレット、粒子等の固形状のもの等が挙げられる。
上記膜としては、塗膜、自立膜等が挙げられる。
The form of the resin dispersion may be a liquid or gel composition, or may be a solid (for example, a molded product).
The resin dispersion is, for example, a dispersion obtained by dispersing the carbon material composite of the present invention in an aqueous dispersion medium or an organic dispersion medium, or the carbon material composite itself (powder) of the present invention. It can be obtained through a step of kneading (preferably kneading after melting the resin) resin (thermoplastic resin, thermosetting resin, or photocurable resin).
The molded body can be obtained using, for example, the resin dispersion of the present invention, which is a liquid or gel composition. For example, the composition can be applied and formed into a film, It can be obtained by molding or polymerizing and curing a resin precursor or the like in the composition.
Examples of the resin dispersion of the present invention include liquid or gel compositions; solid materials such as films (films), sheets, fibers, pellets, and particles.
Examples of the film include a coating film and a self-supporting film.
＜酸化黒鉛の製造方法＞
本発明は、酸化黒鉛を製造する方法であって、該製造方法は、黒鉛を酸化する工程、及び、該酸化工程で得られた酸化黒鉛が分散してなる水系分散液と非イオン性界面活性剤とを混合した後、酸化黒鉛を精製する工程を含む酸化黒鉛の製造方法でもある。
本発明の酸化黒鉛の製造方法の好ましい一実施形態では、上記精製工程は、ろ過、デカンテーション、遠心分離、及び、分液抽出からなる群より選択される少なくとも１種の方法により炭素材料複合体を精製する工程である。
本発明の酸化黒鉛の製造方法は、上述した本発明の炭素材料複合体の製造方法と同様の方法により行うことができるが、例えば、上述した特定の精製工程を繰り返し行ったり、該精製工程の後、水洗を繰り返し行ったりすることで、炭素材料複合体から不純物とともに非イオン性界面活性剤を除くことで酸化黒鉛を得ることができる。なお、非イオン性界面活性剤を除く観点からは、非イオン性界面活性剤を含まない水による洗浄（上記水洗）が好ましい。本発明の酸化黒鉛の製造方法は、高品質な酸化黒鉛を簡便に得ることができるものである。
例えば、上記酸化黒鉛を精製する工程は、非イオン性界面活性剤が実質的に残存しないように界面活性剤を除く工程と言い換えることができる。
非イオン性界面活性剤が実質的に残存しないとは、例えば非イオン性界面活性剤の質量割合が１０００ｐｐｍ以下であることをいう。
<Method for producing graphite oxide>
The present invention is a method for producing graphite oxide, which comprises a step of oxidizing graphite, an aqueous dispersion obtained by dispersing graphite oxide obtained in the oxidation step, and a nonionic surfactant It is also a method for producing graphite oxide including a step of purifying graphite oxide after mixing with an agent.
In a preferred embodiment of the method for producing graphite oxide of the present invention, the purification step is a carbon material composite by at least one method selected from the group consisting of filtration, decantation, centrifugation, and liquid separation extraction. Is a step of purifying
The method for producing graphite oxide of the present invention can be carried out by the same method as the method for producing the carbon material composite of the present invention described above. For example, the specific purification step described above can be repeated, Thereafter, by repeatedly washing with water, graphite oxide can be obtained by removing the nonionic surfactant together with the impurities from the carbon material composite. In addition, from the viewpoint of excluding the nonionic surfactant, washing with water not containing the nonionic surfactant (the above washing with water) is preferable. The method for producing graphite oxide of the present invention can easily obtain high-quality graphite oxide.
For example, the step of purifying the graphite oxide can be rephrased as a step of removing the surfactant so that the nonionic surfactant does not substantially remain.
The phrase “nonionic surfactant substantially does not remain” means, for example, that the mass ratio of the nonionic surfactant is 1000 ppm or less.
本発明の炭素材料複合体の製造方法で得られる炭素材料複合体、本発明の炭素材料複合体、本発明の分散体、本発明の酸化黒鉛の製造方法で得られる酸化黒鉛のいずれも、触媒、電池やキャパシタの電極活物質、熱電変換材料、導電性材料、発光材料、潤滑用添加剤、高分子用添加剤、透過膜材料、抗菌材料、撥水材料、吸着材料等として好適に用いることができる。
本発明の製造方法で得られる炭素材料複合体や酸化黒鉛は水系分散媒中で好適に分散することから、上記の中でも、水や湿気が存在し得る用途に特に好適に用いることができる。
なお、上記電池としては、例えば、リチウムイオン二次電池、固体高分子型燃料電池、金属−空気電池等が挙げられる。
上記熱電変換材料が用いられる熱電変換装置としては、例えば、地熱・温泉熱発電機、太陽熱発電機、工場や自動車等の廃熱発電機、体温発電機等の発電機や、該発電機を電源の少なくとも一つとして用いた各種電気製品、電動機、人工衛星等が挙げられる。
Any of the carbon material composite obtained by the carbon material composite production method of the present invention, the carbon material composite of the present invention, the dispersion of the present invention, and the graphite oxide obtained by the graphite oxide production method of the present invention is a catalyst. Suitable for use as electrode active materials for batteries and capacitors, thermoelectric conversion materials, conductive materials, luminescent materials, additives for lubrication, additives for polymers, permeable membrane materials, antibacterial materials, water repellent materials, adsorbent materials, etc. Can do.
Since the carbon material composite and graphite oxide obtained by the production method of the present invention are suitably dispersed in an aqueous dispersion medium, among them, the carbon material composite and graphite oxide can be particularly suitably used for applications where water and moisture can exist.
In addition, as said battery, a lithium ion secondary battery, a polymer electrolyte fuel cell, a metal-air battery etc. are mentioned, for example.
Examples of the thermoelectric conversion device in which the thermoelectric conversion material is used include, for example, a geothermal / hot spring thermal power generator, a solar heat power generator, a waste heat power generator such as a factory or an automobile, a power generator such as a body temperature power generator, Examples include various electric products, electric motors, artificial satellites, and the like used as one.
以下に実施例を掲げて本発明を更に詳細に説明するが、本発明はこれらの実施例のみに限定されるものではない。なお、特に断りのない限り、「部」は「質量部」を、「％」は「質量％」を意味するものとする。 The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by mass” and “%” means “% by mass”.
＜酸化黒鉛含有水系分散液の合成＞
（合成例）
酸化黒鉛を以下の工程で合成した。反応容器にあらかじめ黒鉛（伊藤黒鉛株式会社製Ｚ−２５）１５ｇ、硫酸（和光純薬工業株式会社製）６４０ｇを入れ、３０℃に調整しながら過マンガン酸カリウム（和光純薬工業株式会社製）４５ｇを入れた。投入後、３０分、３５℃に昇温し２時間反応させた。反応後反応液を水１０７０ｍｌ、３０％過酸化水素水（和光純薬工業株式会社製）４２ｍｌを加え反応停止させ、酸化黒鉛含有水系分散液（水総質量１８１２ｇ、原料黒鉛換算濃度０．８３％、水濃度６１％、硫酸イオン濃度３６％）を得た。得られた酸化黒鉛含有水系分散液中の酸化黒鉛のＣ／Ｏは１．８であった。
<Synthesis of graphite oxide-containing aqueous dispersion>
(Synthesis example)
Graphite oxide was synthesized by the following steps. In a reaction vessel, 15 g of graphite (Z-25 manufactured by Ito Graphite Co., Ltd.) and 640 g of sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.) are put in advance, and potassium permanganate (manufactured by Wako Pure Chemical Industries, Ltd.) is adjusted to 30 ° C. 45 g was added. After the addition, the temperature was raised to 35 ° C. for 30 minutes and reacted for 2 hours. After the reaction, 1070 ml of water and 42 ml of 30% hydrogen peroxide water (manufactured by Wako Pure Chemical Industries, Ltd.) were added to stop the reaction, and a graphite oxide-containing aqueous dispersion (total water mass 1812 g, raw material graphite equivalent concentration 0.83%) Water concentration 61%, sulfate ion concentration 36%). C / O of graphite oxide in the obtained graphite oxide-containing aqueous dispersion was 1.8.
＜精製効率の評価＞
（実施例１）
上記合成例で得られた酸化黒鉛含有水系分散液（１００ｇ）に、原料黒鉛に対し０．７５質量当量のソフタノール１２０（株式会社日本触媒製）を投入し凝集させた。撹拌の後、ろ過したところ、ろ過性は非常に良好（１０分以内にろ過が完了）であった。またろ過ウェットケーキに水を投入した後ろ過を行い水洗したところ、良好なろ過性を維持（１０分以内にろ過が完了）していた。水洗は２回行い、２回とも良好なろ過性を維持していた。
<Evaluation of purification efficiency>
Example 1
Into the graphite oxide-containing aqueous dispersion (100 g) obtained in the above synthesis example, 0.75 mass equivalent of SOFTANOL 120 (manufactured by Nippon Shokubai Co., Ltd.) was added and aggregated with respect to the raw graphite. When it was filtered after stirring, the filterability was very good (filtration was completed within 10 minutes). In addition, when water was added to the filtration wet cake, filtration and washing were carried out, and good filterability was maintained (filtration was completed within 10 minutes). Washing with water was performed twice, and good filterability was maintained both times.
（実施例２）
非イオン性界面活性剤として原料黒鉛に対し０．７５質量当量のソフタノール１２０（株式会社日本触媒製）の代わりに同当量のソフタノール５０（株式会社日本触媒製）を用いた以外は実施例１に記載の方法と同様にろ過性を確認したところ、ろ過性は良好であった。
(Example 2)
Example 1 except that 0.75 mass equivalent of SOFTANOL 120 (manufactured by Nippon Shokubai Co., Ltd.) was used as a nonionic surfactant instead of 0.75 mass equivalent of SOFTANOL 120 (manufactured by Nippon Shokubai Co., Ltd.) When the filterability was confirmed in the same manner as described, the filterability was good.
（実施例３）
非イオン性界面活性剤として原料黒鉛に対し０．７５質量当量のソフタノール１２０（株式会社日本触媒製）の代わりに同当量のニューコール８５（日本乳化剤株式会社製）を用いた以外は実施例１に記載の方法と同様にろ過性を確認したところ、ろ過性は良好であった。
(Example 3)
Example 1 except that 0.75 mass equivalent of SOFTANOL 120 (manufactured by Nippon Shokubai Co., Ltd.) was used as a nonionic surfactant instead of 0.75 mass equivalent of raw material graphite, the same equivalent of New Coal 85 (manufactured by Nippon Emulsion Co., Ltd.) When the filterability was confirmed in the same manner as described in 1., the filterability was good.
（比較例１）
凝集剤を用いないものとして、非イオン性界面活性剤（ソフタノール１２０）を添加しなかった以外は実施例１に記載の方法と同様にろ過性を確認したところ、ろ過性は非常に悪く、ろ紙が詰まり、ろ過不可能であった。
(Comparative Example 1)
When the filterability was confirmed in the same manner as in the method described in Example 1 except that the non-ionic surfactant (Softanol 120) was not added as a non-flocculating agent, the filterability was very poor. Was clogged and could not be filtered.
（比較例２）
非イオン性界面活性剤の代わりに陰イオン性界面活性剤を使用したものとして、原料黒鉛に対し０．７５質量当量のソフタノール１２０（株式会社日本触媒製）の代わりに同当量の直鎖ドデシルベンゼンスルホン酸ナトリウム（和光純薬工業株式会社製）を用いた以外は実施例１に記載の方法と同様にろ過性を確認したところ、ろ過性は非常に悪く、ろ紙が詰まり、ろ過不可能であった。
(Comparative Example 2)
Assuming that an anionic surfactant is used instead of a nonionic surfactant, 0.75 mass equivalent of SOFTANOL 120 (manufactured by Nippon Shokubai Co., Ltd.) is used instead of 0.75 mass equivalent of raw material graphite. Except for using sodium sulfonate (manufactured by Wako Pure Chemical Industries, Ltd.), the filterability was confirmed in the same manner as in the method described in Example 1. The filterability was very poor and the filter paper was clogged and could not be filtered. It was.
＜酸化黒鉛複合体の分散＞
（実施例４）
実施例１で得られた酸化黒鉛複合体含有ウェットケーキ（原料黒鉛１ｇ相当分）に水１００ｇを加え、撹拌した後、３０分超音波を印加し、酸化黒鉛複合体の水分散体を作製した。水分散体を２４時間静置したところ、相分離は起きず均一な外観を維持しており、非常に良好な分散性を示していた。
<Dispersion of graphite oxide composite>
Example 4
100 g of water was added to the graphite oxide composite-containing wet cake obtained in Example 1 (equivalent to 1 g of raw material graphite) and stirred, and then ultrasonic waves were applied for 30 minutes to prepare an aqueous dispersion of the graphite oxide composite. . When the aqueous dispersion was allowed to stand for 24 hours, phase separation did not occur and a uniform appearance was maintained, indicating very good dispersibility.
（実施例５）
使用した酸化黒鉛複合体含有ウェットケーキが実施例２で得られたものであること以外は実施例４に記載の方法と同様にして酸化黒鉛複合体の水分散体を作製した後２４時間静置したところ、水分散体は均一な外観を維持しており、非常に良好な分散性を示していた。
(Example 5)
A graphite oxide composite aqueous dispersion was prepared in the same manner as in Example 4 except that the used graphite oxide composite-containing wet cake was obtained in Example 2, and then allowed to stand for 24 hours. As a result, the aqueous dispersion maintained a uniform appearance and exhibited very good dispersibility.
（実施例６）
使用した酸化黒鉛複合体含有ウェットケーキが実施例３で得られたものであること以外は実施例４に記載の方法と同様にして酸化黒鉛複合体の水分散体を作製した後２４時間静置したところ、水分散体は均一な外観を維持しており、非常に良好な分散性を示していた。
(Example 6)
A graphite oxide composite aqueous dispersion was prepared in the same manner as described in Example 4 except that the used graphite oxide composite-containing wet cake was obtained in Example 3, and then allowed to stand for 24 hours. As a result, the aqueous dispersion maintained a uniform appearance and exhibited very good dispersibility.
（実施例７）
使用した分散媒がγ−ブチロラクトンであること以外は実施例４に記載の方法と同様にして酸化黒鉛複合体のγ−ブチロラクトン分散体を作製した後２４時間静置したところ、γ−ブチロラクトン分散体は均一な外観を維持しており、非常に良好な分散性を示していた。
(Example 7)
A γ-butyrolactone dispersion of graphite oxide composite was prepared in the same manner as in Example 4 except that the dispersion medium used was γ-butyrolactone, and allowed to stand for 24 hours. Maintained a uniform appearance and exhibited very good dispersibility.
（実施例８）
実施例４で得られた酸化黒鉛複合体の水分散体に、黒鉛相当量で０．６６質量％となるようにさらに水を投入し、卓上型超音波洗浄器（ブランソン社製、ブランソニック、４０５Ｗ）を用いて３０分間超音波を印加することで均一な酸化黒鉛複合体の水分散体を得た。上記酸化黒鉛複合体の水分散体中に還元剤としてＬ−アスコルビン酸（和光純薬工業株式会社製）を黒鉛に対して７．５質量当量投入し、７０℃にて１時間反応させることで還元した。反応後にろ過を行い、ｐＨ試験紙にてろ液が中性となるまで水洗を行った。得られた酸化黒鉛複合体含有ウェットケーキ（原料黒鉛１ｇ相当分）に水１００ｇを加え、撹拌した後、３０分超音波を印加し、酸化黒鉛複合体の水分散体を作製した。得られた水分散体を２４時間静置したところ、相分離は起きず均一な外観を維持し、良好な分散性を示していたが一部凝集物が確認された。実施例８で得られた酸化黒鉛複合体を更に洗浄し得られた酸化黒鉛を分析したところＣ／Ｏ比は５．７であった。
(Example 8)
Water was further added to the aqueous dispersion of the graphite oxide composite obtained in Example 4 so that the graphite equivalent amount was 0.66% by mass, and a desktop ultrasonic cleaner (Branson, Bransonic, 405W) and applying ultrasonic waves for 30 minutes to obtain a uniform aqueous dispersion of graphite oxide composite. By adding 7.5 mass equivalents of L-ascorbic acid (manufactured by Wako Pure Chemical Industries, Ltd.) as a reducing agent to the graphite oxide composite water dispersion and reacting at 70 ° C. for 1 hour. Reduced. Filtration was carried out after the reaction, and washing was carried out with pH test paper until the filtrate became neutral. 100 g of water was added to the obtained graphite oxide composite-containing wet cake (corresponding to 1 g of raw material graphite) and stirred, and then an ultrasonic wave was applied for 30 minutes to prepare an aqueous dispersion of the graphite oxide composite. When the obtained aqueous dispersion was allowed to stand for 24 hours, phase separation did not occur and a uniform appearance was maintained and good dispersibility was shown, but some aggregates were confirmed. When the graphite oxide obtained by further washing the graphite oxide composite obtained in Example 8 was analyzed, the C / O ratio was 5.7.
実施例１〜３及び比較例１、２の結果から、精製工程前に非イオン性界面活性剤を添加することで、良好な精製効率を示した。また実施例４〜８の結果から上記精製法で得られた炭素材料複合体（酸化黒鉛複合体）は各種分散媒に良好な分散性を示した。本発明の炭素材料複合体の製造方法により、高品質な炭素材料複合体を低コストで簡便に得ることができる。また得られた炭素材料複合体（非イオン性界面活性剤及び酸化黒鉛を含んで構成される炭素材料複合体）は分散媒に非常によく分散できる。 From the results of Examples 1 to 3 and Comparative Examples 1 and 2, good purification efficiency was shown by adding a nonionic surfactant before the purification step. Moreover, the carbon material composite body (graphite oxide composite body) obtained by the said refinement | purification method from the result of Examples 4-8 showed favorable dispersibility in various dispersion media. By the method for producing a carbon material composite of the present invention, a high-quality carbon material composite can be easily obtained at low cost. Further, the obtained carbon material composite (a carbon material composite including a nonionic surfactant and graphite oxide) can be very well dispersed in the dispersion medium.
Claims (8)
該製造方法は、黒鉛を酸化する工程、及び、
該酸化工程で得られた酸化黒鉛が分散してなる水系分散液と非イオン性界面活性剤とを混合した後、炭素材料複合体を精製する工程を含むことを特徴とする炭素材料複合体の製造方法。 A method for producing a carbon material composite comprising a nonionic surfactant and graphite oxide,
The production method includes a step of oxidizing graphite, and
A carbon material composite comprising a step of purifying a carbon material composite after mixing an aqueous dispersion obtained by dispersing the graphite oxide obtained in the oxidation step and a nonionic surfactant. Production method.
該酸化黒鉛は、酸素原子数に対する炭素原子数の比（Ｃ／Ｏ）が５．５以下であることを特徴とする炭素材料複合体。 A carbon material composite comprising a nonionic surfactant and graphite oxide,
The graphite oxide is characterized in that the ratio of the number of carbon atoms to the number of oxygen atoms (C / O) is 5.5 or less.
該製造方法は、黒鉛を酸化する工程、及び、
該酸化工程で得られた酸化黒鉛が分散してなる水系分散液と非イオン性界面活性剤とを混合した後、酸化黒鉛を精製する工程を含むことを特徴とする酸化黒鉛の製造方法。 A method for producing graphite oxide, comprising:
The production method includes a step of oxidizing graphite, and
A method for producing graphite oxide, comprising: a step of purifying graphite oxide after mixing an aqueous dispersion obtained by dispersing graphite oxide obtained in the oxidation step and a nonionic surfactant.
The said refinement | purification process is a process of refine | purifying graphite oxide by the at least 1 sort (s) of method selected from the group which consists of filtration, decantation, centrifugation, and liquid separation extraction. A method for producing graphite oxide.
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