JP2003048705A - Hollow carbon particle and method for producing the same - Google Patents
Hollow carbon particle and method for producing the sameInfo
- Publication number
- JP2003048705A JP2003048705A JP2001235740A JP2001235740A JP2003048705A JP 2003048705 A JP2003048705 A JP 2003048705A JP 2001235740 A JP2001235740 A JP 2001235740A JP 2001235740 A JP2001235740 A JP 2001235740A JP 2003048705 A JP2003048705 A JP 2003048705A
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- Japan
- Prior art keywords
- polymer
- carbon particles
- carbon
- hollow carbon
- producing hollow
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、中空状カーボン粒
子の製造に関するものである。TECHNICAL FIELD The present invention relates to the production of hollow carbon particles.
【０００２】[0002]
【従来の技術】フラーレンに代表される中空状カーボン
粒子は、直径数ｎｍ〜数百ｎｍからなり、壁は５員環ま
たは７員環を含む数〜数十のグラファイト層からなる。
機械的強度、水素貯蔵特性、電界放出特性等の特異な特
性が注目され、その応用研究が進められている。従来
は、不活性ガス雰囲気中でアーク放電によりカーボンを
蒸発させた後、凝集し、分離精製するといった製法が主
であった。しかし、フラーレンの生成割合が低く、カー
ボンブラック状炭素質やアモルファスカーボン等が副生
することが避けられなかった。また、ベンゼンなどの溶
媒を用いた分離精製などが必要で、量産性の著しい低下
が避けられなかった。さらに、前記製法ではフラーレン
を代表とする中空状カーボン粒子の壁層数、直径制御が
実質的に不可能であった。2. Description of the Related Art Hollow carbon particles represented by fullerenes have a diameter of several nanometers to several hundreds of nanometers, and a wall of several to several tens of graphite layers containing a 5-membered ring or a 7-membered ring.
Peculiar characteristics such as mechanical strength, hydrogen storage characteristics, and field emission characteristics are drawing attention, and their applied research is being promoted. Heretofore, a production method has been mainly used in which carbon is evaporated by arc discharge in an inert gas atmosphere, and then the carbon is aggregated and separated and purified. However, the production rate of fullerenes is low, and carbon black-like carbonaceous substances and amorphous carbon are unavoidable as by-products. Further, it is necessary to separate and purify using a solvent such as benzene, and thus a significant decrease in mass productivity cannot be avoided. Further, in the above-mentioned production method, it was substantially impossible to control the number of wall layers and the diameter of hollow carbon particles represented by fullerene.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、前記公知の
製法及びこれから得られるフラーレンに代表される中空
状カーボン粒子の問題点を解決するものである。すなわ
ち本発明は、フラーレンを代表とする中空状カーボン粒
子の壁層数、直径の制御が可能であり、均一な形状及び
特性を効率良く得ること出来る中空状カーボン粒子の製
造法を提供するものである。また本発明は、副生成物が
ほとんど生成せず、溶媒による分離精製が不要で、量産
が比較的容易な中空状カーボン粒子及びその製造法を提
供するものである。DISCLOSURE OF THE INVENTION The present invention solves the problems of the above-mentioned known production method and hollow carbon particles represented by fullerenes obtained therefrom. That is, the present invention provides a method for producing hollow carbon particles, in which the number of wall layers of hollow carbon particles typified by fullerene and the diameter can be controlled, and uniform shapes and characteristics can be efficiently obtained. is there. Further, the present invention provides a hollow carbon particle which produces almost no by-products, does not require separation and purification with a solvent, and is relatively easy to mass-produce, and a method for producing the same.
【０００４】[0004]
【課題を解決するための手段】本発明は、次の各発明に
関する。
（１） 熱分解消失性ポリマーを用いて形成された中空
と、炭素前駆体ポリマーを用いて形成されたカーボンの
殻を有してなる中空状カーボン粒子。
（２） 熱分解消失性ポリマーと炭素前駆体ポリマーと
を組合せて作製することを特徴とする中空状カーボン粒
子の製造法。The present invention relates to each of the following inventions. (1) Hollow carbon particles having a hollow formed by using a heat decomposition disappearing polymer and a carbon shell formed by using a carbon precursor polymer. (2) A method for producing hollow carbon particles, which is characterized in that it is produced by combining a thermally decomposable polymer and a carbon precursor polymer.
【０００５】（３） 熱分解消失性ポリマーと炭素前駆
体ポリマーとからマイクロカプセルを製作し、焼成して
作製することを特徴とする前記（２）記載の中空状カー
ボン粒子の製造法。
（４） 熱分解消失性ポリマーとして残炭率が１０重量
％以下、炭素前駆体ポリマーとして残炭率が１５重量％
以上のポリマーを用いることを特徴とする前記（２）又
は（３）記載の中空状カーボン粒子の製造法。(3) The method for producing hollow carbon particles according to the above (2), characterized in that microcapsules are produced from the heat decomposition disappearing polymer and the carbon precursor polymer and then produced by firing. (4) The residual carbon rate is 10% by weight or less as the thermal decomposition disappearing polymer, and the residual carbon rate is 15% by weight as the carbon precursor polymer.
The method for producing hollow carbon particles according to the above (2) or (3), wherein the above polymer is used.
【０００６】（５） 前記マイクロカプセルを界面化学
的手法で調製することを特徴とする前記（３）記載の中
空状カーボン粒子の製造法。
（６） 前記マイクロカプセルの調整法がシード重合で
あることを特徴とする前記（３）記載の中空状カーボン
粒子の製造法。(5) The method for producing hollow carbon particles according to (3), wherein the microcapsules are prepared by a surface chemical method. (6) The method for producing hollow carbon particles according to (3) above, wherein the method for preparing the microcapsules is seed polymerization.
【０００７】（７） 前記炭素前駆体ポリマーが、ラジ
カル重合性基を有するモノマーから形成されたポリマー
である前記（３）記載の中空状カーボン粒子の製造法。
（８） 前記炭素前駆体ポリマーが、アクリロニトリル
の単量体から形成されるユニットをポリマー中に３５モ
ル％以上含むことを特徴とする前記（７）記載の中空状
カーボン粒子の製造法。(7) The method for producing hollow carbon particles according to (3), wherein the carbon precursor polymer is a polymer formed from a monomer having a radically polymerizable group. (8) The method for producing hollow carbon particles according to (7) above, wherein the carbon precursor polymer contains 35 mol% or more of a unit formed from an acrylonitrile monomer in the polymer.
【０００８】（９） 前記熱分解消失性ポリマーが、ラ
ジカル重合性基を有するモノマーから形成されたポリマ
ーである前記（３）記載の中空状カーボンファイバーの
製造法。
（１０） 熱分解消失性ポリマー及び炭素前駆体ポリマ
ーが、ラジカル重合性基を有するモノマーから形成され
たポリマーであり、かつ、その重合開始剤として、炭
素、水素、酸素、窒素、りん、硫黄、フッ素、塩素、臭
素及びよう素の中から選ばれた元素のみで構成される化
合物を用いることを特徴とする前記（３）記載の中空状
カーボン粒子の製造法。(9) The method for producing a hollow carbon fiber according to the above (3), wherein the thermally decomposable polymer is a polymer formed from a monomer having a radical polymerizable group. (10) The thermally decomposable polymer and carbon precursor polymer are polymers formed from a monomer having a radically polymerizable group, and the polymerization initiator thereof is carbon, hydrogen, oxygen, nitrogen, phosphorus, sulfur, The method for producing hollow carbon particles according to (3) above, wherein a compound composed of only an element selected from fluorine, chlorine, bromine and iodine is used.
【０００９】[0009]
【発明の実施の形態】本発明は、焼成の際に熱分解消失
するポリマーを用いて形成された中空と、焼成によって
カーボンとなる炭素前駆体ポリマーを用いて形成された
外殻を有してなる中空状カーボン粒子であり、これは熱
分解消失性ポリマーと炭素前駆体ポリマーとを組合せて
作製される。BEST MODE FOR CARRYING OUT THE INVENTION The present invention has a hollow formed using a polymer that thermally decomposes and disappears during firing, and an outer shell formed using a carbon precursor polymer that becomes carbon by firing. The hollow carbon particles are formed by combining a heat decomposition disappearing polymer and a carbon precursor polymer.
【００１０】その具体的な手段としては、熱分解消失性
ポリマーと炭素前駆体ポリマーからなるマイクロカプセ
ルを調製し、焼成して作成する製造法が、好ましい方法
としてあげられる。この方法によれば、各工程における
反応制御が容易となる。また、本発明は、前述した公知
の製法に比べ、フラーレンを代表とする中空状カーボン
粒子の形状制御が容易となり、且つ高収率での製造が可
能となる。As a concrete means therefor, a preferable method is a production method in which microcapsules composed of a heat decomposition disappearing polymer and a carbon precursor polymer are prepared and fired. According to this method, the reaction control in each step becomes easy. Further, according to the present invention, the shape of hollow carbon particles typified by fullerene can be controlled more easily and the production can be performed at a high yield, as compared with the above-described known production method.
【００１１】本発明におけるマイクロカプセルの調製で
は、熱分解消失性樹脂として残炭率が１０重量％以下、
炭素前駆体ポリマーとして残炭率が１５重量％以上のポ
リマーを用いることを特徴とする。熱分解消失性樹脂と
して残炭率が１０重量％以下の樹脂を用いることで、中
空状カーボン粒子の細孔径が比較的容易に制御されると
共に、壁を形成するグラファイト層の構造制御が容易と
なる。熱分解性消失樹脂として残炭率が１５重量％より
高い樹脂を用いた場合、細孔径の制御が困難となり、壁
を形成するグラファイト層の構造制御が困難となり、結
果的に任意形状への制御が著しく困難となる。In the preparation of the microcapsules according to the present invention, the residual carbon content of the thermally decomposable resin is 10% by weight or less,
It is characterized in that a polymer having a residual carbon rate of 15% by weight or more is used as the carbon precursor polymer. By using a resin having a residual carbon content of 10% by weight or less as the pyrolysis disappearing resin, the pore size of the hollow carbon particles can be controlled relatively easily, and the structure of the graphite layer forming the wall can be controlled easily. Become. When a resin having a residual carbon content of more than 15% by weight is used as the thermally decomposable resin, it becomes difficult to control the pore size, and it becomes difficult to control the structure of the graphite layer forming the wall, and as a result, control to an arbitrary shape is achieved. Becomes extremely difficult.
【００１２】本発明におけるマイクロカプセルの原料と
しては、前記条件を満たすものであれば特に制限はな
い。具体的に列挙すると、熱分解消失性樹脂としては、
ポリエチレン、ポリプロピレン等のオレフィン系樹脂、
ポリブタジエン等のジエン系樹脂、ポリアクリル酸メチ
ル、ポリアクリル酸エチル等のアクリル樹脂、ポリメタ
クリル酸メチル、ポリメタクリル酸エチル等のメタクリ
ル樹脂、ポリ酢酸ビニル樹脂、ポリビニルアルコール樹
脂、ポリエチレングリコール、ポリプロピレングリコー
ル等のポリエーテル系樹脂等が挙げられる。なかでも、
ポリアクリル酸メチル、ポリアクリル酸エチル等のアク
リル樹脂、ポリメタクリル酸メチル、ポリメタクリル酸
エチル等のメタクリル樹脂などが好ましいものとして挙
げられる。The raw material of the microcapsule in the present invention is not particularly limited as long as it satisfies the above conditions. Specifically enumerated, as the heat decomposition disappearing resin,
Olefin resins such as polyethylene and polypropylene,
Diene resins such as polybutadiene, acrylic resins such as polymethyl acrylate and polyethyl acrylate, methacrylic resins such as polymethyl methacrylate and polyethyl methacrylate, polyvinyl acetate resins, polyvinyl alcohol resins, polyethylene glycol, polypropylene glycol, etc. Examples of the polyether resin include Above all,
Preferred examples include acrylic resins such as polymethyl acrylate and polyethyl acrylate, and methacrylic resins such as polymethyl methacrylate and polyethyl methacrylate.
【００１３】一方、炭素前駆体ポリマーとしては、ポリ
アクリロニトリル系樹脂、フェノール樹脂、フラン樹
脂、ジビニルベンゼン樹脂、不飽和ポリエステル樹脂、
ポリイミド樹脂、ジアリルフタレート樹脂、ビニルエス
テル樹脂、ポリウレタン樹脂、メラミン樹脂、ユリア樹
脂等が挙げられる。シード重合でマイクロカプセルを合
成する場合には、ラジカル重合性を持つモノマーから合
成することが好ましいので、アクリロニトリルを単量体
に用いたポリアクリロニトリル系樹脂が好ましく、アク
リロニトリルの単量体ユニットをポリマー中に３５モル
％以上含むポリアクリロニトリル系樹脂が好ましい。On the other hand, as the carbon precursor polymer, polyacrylonitrile resin, phenol resin, furan resin, divinylbenzene resin, unsaturated polyester resin,
Examples thereof include polyimide resin, diallyl phthalate resin, vinyl ester resin, polyurethane resin, melamine resin, urea resin and the like. When synthesizing microcapsules by seed polymerization, it is preferable to synthesize them from radically polymerizable monomers, so polyacrylonitrile-based resins using acrylonitrile as a monomer are preferable, and acrylonitrile monomer units are used in the polymer. A polyacrylonitrile-based resin containing 35 mol% or more is preferable.
【００１４】本発明におけるマイクロカプセルの製造法
には特に制限がないが、作業性を考慮すると、直径０．
００１μｍ〜１００μｍの熱分解性消失性樹脂粒子をシ
ードとしたシード重合、コアセルべーション法、界面縮
合法、スプレー乾燥法、ハイブリダイザーを用いた湿式
混合法などが好ましい。直径０．００１μｍ〜１μｍの
熱分解性消失性樹脂粒子を用いる場合はシード重合が好
ましい。The method for producing the microcapsules according to the present invention is not particularly limited, but in view of workability, the diameter of 0.
Preferred are seed polymerization using 001 μm to 100 μm of thermally decomposable disappearing resin particles as a seed, a coacervation method, an interfacial condensation method, a spray drying method, and a wet mixing method using a hybridizer. When heat-decomposable vanishing resin particles having a diameter of 0.001 μm to 1 μm are used, seed polymerization is preferred.
【００１５】直径０．００１μｍ〜１００μｍの熱分解
性消失性樹脂粒子の製造法には特に制限がなく、熱分解
性消失性樹脂を粉砕必要により篩い分けする方法、逆相
乳化重合、乳化重合、ソープフリー乳化重合、非水分散
重合、シード重合、懸濁重合などの重合により直接粒子
を得る方法があげられるが、作業性を考慮すると、逆相
乳化重合、乳化重合、ソープフリー乳化重合、非水分散
重合、シード重合、懸濁重合などの重合により直接粒子
を得る方法が好ましく、直径０．００１μｍ〜１μｍ熱
分解性消失性樹脂粒子を得る場合には、乳化重合、ソー
プフリー乳化重合が好ましい。The method for producing the heat-decomposable fugitive resin particles having a diameter of 0.001 μm to 100 μm is not particularly limited, and the heat-decomposable fugitive resin particles are pulverized and sieved if necessary, reverse phase emulsion polymerization, emulsion polymerization, Examples of the method include directly obtaining particles by polymerization such as soap-free emulsion polymerization, non-aqueous dispersion polymerization, seed polymerization, and suspension polymerization.However, considering workability, reverse-phase emulsion polymerization, emulsion polymerization, soap-free emulsion polymerization, A method of directly obtaining particles by polymerization such as water dispersion polymerization, seed polymerization, and suspension polymerization is preferable. When obtaining thermally decomposable disappearing resin particles having a diameter of 0.001 μm to 1 μm, emulsion polymerization and soap-free emulsion polymerization are preferable. .
【００１６】マイクロカプセルを製造する際に用いられ
る重合開始剤に特に制限はないが、最終的に製造した中
空状カーボン粒子の純度が高いことが望ましい場合に
は、炭素化工程で炭素以外の元素が残らない化合物、す
なわち、炭素、水素、酸素、窒素、りん、硫黄、フッ
素、塩素、臭素、よう素の中から選ばれた元素のみで構
成される化合物が好ましい。これらの化合物としては、
アゾビスイソブチロ二トリル、アゾビス（２−アミノプ
ロパン）二塩酸塩、アゾビス−４−シアノペンタン酸、
アゾビスジメチルバレロニトリル等のジアゾ化合物、過
酸化ベンゾイル等の有機過酸化物、過硫酸アンモニウム
等の過酸化物塩が挙げられる。The polymerization initiator used in the production of the microcapsules is not particularly limited, but when it is desired that the finally produced hollow carbon particles have high purity, an element other than carbon is used in the carbonization step. Is preferable, that is, a compound composed only of an element selected from carbon, hydrogen, oxygen, nitrogen, phosphorus, sulfur, fluorine, chlorine, bromine and iodine. These compounds include
Azobisisobutyronitrile, azobis (2-aminopropane) dihydrochloride, azobis-4-cyanopentanoic acid,
Examples thereof include diazo compounds such as azobisdimethylvaleronitrile, organic peroxides such as benzoyl peroxide, and peroxide salts such as ammonium persulfate.
【００１７】本発明における炭素化は５００℃〜３２０
０℃の温度範囲で行うことが好ましく、６００℃〜３０
００℃の温度で行うことがより好ましい。炭素化温度が
５００℃未満の場合、グラファイト層の形成が十分では
なく、機械的強度、水素貯蔵特性、電界放出特性等の諸
特性が低下する。また、炭素化を３２００℃より高い温
度で行った場合、グラファイト層を形成する炭素原子の
一部またはほとんどが昇華し、グラファイト層に欠陥が
生じる傾向がある。The carbonization in the present invention is 500 ° C to 320 ° C.
It is preferably carried out in a temperature range of 0 ° C, and 600 ° C to 30 ° C.
More preferably, it is carried out at a temperature of 00 ° C. When the carbonization temperature is lower than 500 ° C., the graphite layer is not sufficiently formed, and various characteristics such as mechanical strength, hydrogen storage characteristics and field emission characteristics are deteriorated. Further, when carbonization is performed at a temperature higher than 3200 ° C., some or most of the carbon atoms forming the graphite layer are sublimated, and defects tend to occur in the graphite layer.
【００１８】[0018]
【実施例】以下、本発明を実施例により説明する。
実施例１
（１） 熱分解消失性樹脂の合成
１０００ｍｌフラスコにメタクリル酸メチル３５ｍｌ、
イオン交換水３５０ｍｌ、過硫酸アンモニウム２９ｍｇ
を入れ、窒素をバブリングしながら超音波を３０分間照
射した。フラスコに攪拌羽根を装着し、３００ｒｐｍの
攪拌速度、７０℃で５時間、引続き８０℃で３０分間反
応して、熱分解消失性 ポリマー乳化液を得た。EXAMPLES The present invention will be described below with reference to examples. Example 1 (1) Synthesis of Pyrolytic Dissipative Resin 35 ml of methyl methacrylate was added to a 1000 ml flask.
Deionized water 350 ml, ammonium persulfate 29 mg
Then, ultrasonic waves were applied for 30 minutes while bubbling nitrogen. The flask was equipped with a stirring blade and reacted at 300 rpm with a stirring speed of 70 ° C. for 5 hours and then at 80 ° C. for 30 minutes to obtain a thermal decomposition disappearing polymer emulsion.
【００１９】（２） 熱分解消失性ポリマーと炭素前駆
体ポリマーとからマイクロカプセルの製造
（１）で作成した熱分解消失性 ポリマー乳化液９０
ｍｌ、アクリロニトリル４ｍｌ、イオン交換水２７０ｍ
ｌ、過硫酸アンモニウム５ｍｇを１０００ｍｌフラスコ
に入れ、３０分間窒素をバブリングした。フラスコに攪
拌羽根を装着し３００ｒｐｍの攪拌速度、７０℃で５時
間、引続き８０℃で３０分間反応させ、マイクロカプセ
ル乳化液を得た。乳化液から凍結乾燥に水を除去するこ
とで、マイクロカプセルを得た。(2) Production of Microcapsules from Pyrolysis Decomposable Polymer and Carbon Precursor Polymer Pyrolysis Decomposable Polymer Emulsion 90 prepared in (1)
ml, acrylonitrile 4 ml, deionized water 270 m
1, 5 mg of ammonium persulfate were placed in a 1000 ml flask, and nitrogen was bubbled for 30 minutes. The flask was equipped with a stirring blade and reacted at 300 rpm with a stirring speed of 70 ° C for 5 hours and then at 80 ° C for 30 minutes to obtain a microcapsule emulsion. Microcapsules were obtained by removing water from the emulsion by freeze-drying.
【００２０】（３） マイクロカプセルの炭素化
（２）で作製したマイクロカプセルを３０ｍｌ／分の空
気気流中で不融化処理を行った。次いで窒素気流下、焼
成炉にて昇温１０℃／時間で１０００℃まで焼成を行
い、次いでタンマン炉にて昇温３０℃／時間で３０００
℃まで黒鉛化処理を行った。得られたカーボン粒子は細
孔径３〜３０ｎｍ、直径５〜５０ｎｍ、壁を構成するグ
ラファイト層が３〜数十層からなる中空状カーボン粒子
であった。(3) Carbonization of microcapsules The microcapsules prepared in (2) were subjected to infusibilization treatment in an air flow of 30 ml / min. Then, under a nitrogen stream, firing is performed in a firing furnace at a temperature rise of 10 ° C./hour to 1000 ° C., and then in a Tammann furnace at a temperature rise of 30 ° C./hour to 3000.
Graphitization was performed up to ℃. The obtained carbon particles were hollow carbon particles having a pore size of 3 to 30 nm, a diameter of 5 to 50 nm, and a graphite layer constituting the wall of 3 to several tens layers.
【００２１】[0021]
【発明の効果】本発明を用いてフラーレンに代表される
中空状カーボン粒子を調整することで、粒子径、細孔径
及び壁を形成するグラファイト層の厚さ、結晶性などを
任意に制御することが可能である。また、副生成物がほ
とんど生成しないため溶媒などによる分離精製が不要
で、目的とする形状の中空状カーボン粒子を高収率で得
ることができる。EFFECT OF THE INVENTION By adjusting hollow carbon particles represented by fullerene according to the present invention, it is possible to arbitrarily control the particle diameter, the pore diameter, the thickness of the graphite layer forming the wall, the crystallinity and the like. Is possible. Further, since by-products are hardly produced, separation and purification with a solvent or the like is unnecessary, and hollow carbon particles having a target shape can be obtained in high yield.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 田口 矩之 東京都港区芝浦四丁目９番25号 日立化成 工業株式会社工業材料事業本部内 (72)発明者 平井 修 茨城県日立市東町四丁目13番１号 日立化 成工業株式会社総合研究所内 Ｆターム(参考） 4G046 CA00 CA04 CB02 CC01 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Noriyuki Taguchi Hitachi Chemical, 4-9-25 Shibaura, Minato-ku, Tokyo Kogyo Co., Ltd., Industrial Materials Division (72) Inventor Osamu Hirai Hitachi, Ichiba, Ibaraki Prefecture Seisei Co., Ltd. Research Institute F-term (reference) 4G046 CA00 CA04 CB02 CC01
Claims (10)
中空と、炭素前駆体ポリマーを用いて形成されたカーボ
ンの殻を有してなる中空状カーボン粒子。1. Hollow carbon particles having a hollow formed using a heat decomposition disappearing polymer and a carbon shell formed using a carbon precursor polymer.
ーとを組合せて作製することを特徴とする中空状カーボ
ン粒子の製造法。2. A method for producing hollow carbon particles, which is characterized in that it is produced by combining a heat decomposition disappearing polymer and a carbon precursor polymer.
ーとからマイクロカプセルを製作し、マイクロカプセル
を焼成して作製することを特徴とする請求項２記載の中
空状カーボン粒子の製造法。3. The method for producing hollow carbon particles according to claim 2, wherein microcapsules are produced from the thermal decomposition disappearing polymer and the carbon precursor polymer, and the microcapsules are fired.
重量％以下、炭素前駆体ポリマーとして残炭率が１５重
量％以上のポリマーを用いることを特徴とする請求項２
又は３記載の中空状カーボン粒子の製造法。4. A residual coal rate of 10 as a thermal decomposition disappearing polymer.
3. A polymer having a carbon content of 15% by weight or less and a residual carbon rate of 15% by weight or more is used as the carbon precursor polymer.
Alternatively, the method for producing hollow carbon particles as described in 3 above.
調製することを特徴とする請求項３記載の中空状カーボ
ン粒子の製造法。5. The method for producing hollow carbon particles according to claim 3, wherein the microcapsules are prepared by a surface chemical method.
合であることを特徴とする請求項３記載の中空状カーボ
ン粒子の製造法。6. The method for producing hollow carbon particles according to claim 3, wherein the method for preparing the microcapsules is seed polymerization.
性基を有するモノマーから形成されたポリマーである請
求項３記載の中空状カーボン粒子の製造法。7. The method for producing hollow carbon particles according to claim 3, wherein the carbon precursor polymer is a polymer formed from a monomer having a radical polymerizable group.
リルの単量体から形成されるユニットをポリマー中に３
５モル％以上含むことを特徴とする請求項７記載の中空
状カーボン粒子の製造法。8. The carbon precursor polymer comprises a unit formed from an acrylonitrile monomer in the polymer.
The method for producing hollow carbon particles according to claim 7, wherein the content is 5 mol% or more.
合性基を有するモノマーから形成されたポリマーである
請求項３記載の中空状カーボン粒子の製造法。9. The method for producing hollow carbon particles according to claim 3, wherein the thermally decomposable polymer is a polymer formed from a monomer having a radically polymerizable group.
リマーが、ラジカル重合性基を有するモノマーから形成
されたポリマーであり、かつ、その重合開始剤として、
炭素、水素、酸素、窒素、りん、硫黄、フッ素、塩素、
臭素及びよう素の中から選ばれた元素のみで構成される
化合物を用いることを特徴とする請求項３記載の中空状
カーボン粒子の製造法。10. The heat decomposition disappearing polymer and the carbon precursor polymer are polymers formed from a monomer having a radical polymerizable group, and as a polymerization initiator thereof,
Carbon, hydrogen, oxygen, nitrogen, phosphorus, sulfur, fluorine, chlorine,
The method for producing hollow carbon particles according to claim 3, wherein a compound composed of only an element selected from bromine and iodine is used.
Priority Applications (6)
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|---|---|---|---|
| JP2001235740A JP2003048705A (en) | 2001-08-03 | 2001-08-03 | Hollow carbon particle and method for producing the same |
| US09/984,157 US6743500B2 (en) | 2001-08-03 | 2001-10-29 | Hollow carbon fiber and production method |
| EP20010125424 EP1283287A3 (en) | 2001-08-03 | 2001-10-31 | Hollow carbon fiber and production method |
| KR10-2001-0069656A KR100503879B1 (en) | 2001-08-03 | 2001-11-09 | Hollow carbon fiber and production method |
| US10/270,447 US7273652B2 (en) | 2001-08-03 | 2002-10-15 | Hollow carbon fiber and production method |
| US10/270,452 US6641792B2 (en) | 2001-08-03 | 2002-10-15 | Hollow carbon fiber and production method |
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|---|---|---|---|
| JP2001235740A JP2003048705A (en) | 2001-08-03 | 2001-08-03 | Hollow carbon particle and method for producing the same |
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| JP2003048705A true JP2003048705A (en) | 2003-02-21 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012214301A (en) * | 2011-03-31 | 2012-11-08 | Sekisui Plastics Co Ltd | Hollow carbon particle and method for producing the same |
| KR101296373B1 (en) | 2012-06-18 | 2013-08-14 | 한양대학교 산학협력단 | Negative active material for rechargeable lithium battery comprising hollow carbon particles, method of preparing the same and rechargeable lithium battery comprising the same |
| KR101608850B1 (en) | 2014-06-27 | 2016-04-04 | 연세대학교 산학협력단 | Hollow porous carbon particles and their synthetic method |
| JP2017178660A (en) * | 2016-03-30 | 2017-10-05 | 積水化学工業株式会社 | Method for producing carbon particle |
| US10821687B2 (en) | 2014-09-30 | 2020-11-03 | Lg Chem, Ltd. | Method for producing hollow carbon capsules |
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| JPH0598302A (en) * | 1991-10-07 | 1993-04-20 | Nippon Shokubai Co Ltd | Metallic element-carrying fine carbon particle and its production |
| JPH05254814A (en) * | 1992-03-13 | 1993-10-05 | Mitsubishi Kasei Corp | Carbonaceous fine particle and its production |
| JPH1036450A (en) * | 1996-07-16 | 1998-02-10 | Maruzen Petrochem Co Ltd | Starting polyacrylonitrile/pitch material for production of carbonaceous material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0598302A (en) * | 1991-10-07 | 1993-04-20 | Nippon Shokubai Co Ltd | Metallic element-carrying fine carbon particle and its production |
| JPH05254814A (en) * | 1992-03-13 | 1993-10-05 | Mitsubishi Kasei Corp | Carbonaceous fine particle and its production |
| JPH1036450A (en) * | 1996-07-16 | 1998-02-10 | Maruzen Petrochem Co Ltd | Starting polyacrylonitrile/pitch material for production of carbonaceous material |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012214301A (en) * | 2011-03-31 | 2012-11-08 | Sekisui Plastics Co Ltd | Hollow carbon particle and method for producing the same |
| KR101296373B1 (en) | 2012-06-18 | 2013-08-14 | 한양대학교 산학협력단 | Negative active material for rechargeable lithium battery comprising hollow carbon particles, method of preparing the same and rechargeable lithium battery comprising the same |
| KR101608850B1 (en) | 2014-06-27 | 2016-04-04 | 연세대학교 산학협력단 | Hollow porous carbon particles and their synthetic method |
| US10821687B2 (en) | 2014-09-30 | 2020-11-03 | Lg Chem, Ltd. | Method for producing hollow carbon capsules |
| JP2017178660A (en) * | 2016-03-30 | 2017-10-05 | 積水化学工業株式会社 | Method for producing carbon particle |
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