TWI299759B

TWI299759B -

Info

Publication number: TWI299759B
Application number: TW95132929A
Authority: TW
Inventors: Yee Wen Yen; Ming De Huang
Original assignee: Univ Nat Taiwan Science Tech
Priority date: 2006-09-06
Filing date: 2006-09-06
Publication date: 2008-08-11
Also published as: TW200813244A

Description

1299759 九、發明說明：【發明所屬技術領域】本發明係有關於一種奈米碳管（Carbon Nanotubes, CNTs)的製造方法’尤其是關於一種藉由高分子聚合物於 - 原位(in situ)快速進行熱裂解反應製造奈米碳管的方法。【先前技術】奈米碳管自90年代被發現以來，由於其具有奈米等級 • 的尺寸與很大的表面基，且具有由六方碳原子點陣構成之特殊圓柱管結構，以及具有獨特的電、磁、光學特性和應用潛力，因此特別受到矚目。奈米碳管材料應用的潛力深廣，已知的領域包含氣體儲存、吸附元件、光電元件、電子元件、生化醫學、燃料電池、人造鑽石、觸媒載體等。另外，奈米礙管的高長徑比(aspect ratio)和小頂端曲率半徑 (tip radii of curvature)很適合場發射(electron field emission) 的光特性。在場發射平面顯示器(field emission display，FED) φ 中，可取代金屬微端(metal microtip)，其亮度高且效果好；而在記錄媒體之應用上，可作為Tb級容量(Tera byte = 1，000 Mb)之讀取頭。此外，奈米碳管為製造其他奈米結構材料的基材，例如以奈米礙管為模板(template)製備奈米線 (nanowire)和奈米棒(nanorod)。現今製備奈米碳管的方法，主要包含電弧放電法 (Arc-discharge)、化學氣相沉積法（Chemical Vapor Deposition，CVD)、脈衝雷射蒸鍍膜法（Pulsed Laser 5 12997591299759 IX. Description of the Invention: [Technical Field] The present invention relates to a method for producing carbon nanotubes (CNTs), in particular, a polymer based on-in situ A method for rapidly producing a carbon nanotube by a thermal cracking reaction. [Prior Art] Since the discovery of the carbon nanotubes in the 1990s, due to its size and large surface area, it has a special cylindrical tube structure composed of hexagonal carbon atom lattices, and has a unique Electrical, magnetic, optical properties and application potential are particularly attractive. Nanocarbon tube materials have a wide range of potential applications, including gas storage, adsorption components, optoelectronic components, electronic components, biochemical medicine, fuel cells, synthetic diamonds, and catalyst carriers. In addition, the high aspect ratio and tip radii of curvature of the nanotubes are well suited to the light characteristics of the electron field emission. In the field emission display (FED) φ, it can replace the metal microtip, which has high brightness and good effect. In the application of recording media, it can be used as Tb level capacity (Tera byte = 1). , 000 Mb) read head. In addition, the carbon nanotubes are substrates for making other nanostructure materials, for example, nanowires and nanorods are prepared by using a nanotube as a template. The current method for preparing carbon nanotubes mainly includes Arc-discharge, Chemical Vapor Deposition (CVD), and pulsed laser evaporation (Pulsed Laser 5 1299759).

Deposition)、電漿輔助化學氣相沉積法(Plasma Enhanced CVD)、微波電漿化學氣相沉積法(Microwave Plasma CVD) 及雷射剝削法(laser ablation)等方法，其中以電弧放電法及化學氣相沉積法較常被使用。但因這些方法所需的溫度較高（約在至少l〇〇〇°C以上），所需的成本亦較高，且其前置步驟與製程的步驟均較繁雜且危險性高。Deposition), Plasma Enhanced CVD, Microwave Plasma CVD, and laser ablation, among which arc discharge and chemical gas Phase deposition is more commonly used. However, because the temperature required by these methods is relatively high (about at least l〇〇〇°C or more), the cost required is also high, and the steps of the pre-step and the process are complicated and dangerous.

為解決前述習知技術中所存在的問題中華民國專利公告第562778號中，揭示一種中空奈米碳管之製造方法，其係將聚碳矽烷、觸媒及溶劑混合後，對該混合物進行加熱以使聚碳矽烷進行熱裂解反應，而使碳原子於觸媒表面析出，進而形成中空奈米碳管。惟該方法所需之反應溫度仍高達70G〜1_°C，且由簡使闕格昂#的奈米級金屬粒子(小於100 nm)做為觸媒，致使該方法於操作做上仍有其困難性，且其製造成本仍高。為此中華民國發明第1255792號專利中，另揭示了一In order to solve the problems in the prior art, the Chinese Patent Publication No. 562778 discloses a method for producing a hollow carbon nanotube by heating a mixture of a mixture of a polycarbane, a catalyst and a solvent. The polycarbodecane is subjected to a thermal cracking reaction to precipitate carbon atoms on the surface of the catalyst to form a hollow carbon nanotube. However, the reaction temperature required for this method is still as high as 70G~1_°C, and the nano-sized metal particles (less than 100 nm) of the 阙格昂# are used as catalysts, which makes the method still difficult to operate. And its manufacturing cost is still high. To this end, the Republic of China invented the patent No. 1,255,792, another disclosure

種奈米碳管的製造方法，其係將聚乙二醇、觸媒及溶劑混合後’對魏合物騎㈣段之加熱溫度處理(細〜4〇叱與6〇〇-mrc)，以使聚乙二醇進行熱裂解反應，進而形成奈米碳官。雖然該方法可降低進行熱裂解反應所需之溫 ^ ’但該^輯-種枝都具有需要較長之熱裂解反應時間(反應時間長達3-1〇小時)的問題。【發明内容】為了克服習知技術所遭遇之困難與問題，本發明之目 6 1299759 碳管的製造方法，藉以縮短碳米碳之一種奈米碳管的製造方法，其步The method for producing a carbon nanotube is prepared by mixing polyethylene glycol, a catalyst and a solvent, and then treating the heating temperature of the Wei compound riding (four) section (fine ~ 4 〇叱 and 6 〇〇 - mrc) to The polyethylene glycol is subjected to a thermal cracking reaction to form a nanocarbon official. Although this method can reduce the temperature required for the thermal cracking reaction, the plant has a problem that requires a longer thermal cracking reaction time (up to 3-1 hours). SUMMARY OF THE INVENTION In order to overcome the difficulties and problems encountered by the prior art, the method for manufacturing a carbon tube of the present invention is to reduce the production method of a carbon nanotube of carbon carbon.

(A)將—㈣高分子聚合物與-金屬觸媒混合，並藉由一溶劑使兩者混合均#形成-混合物；(A) mixing - (iv) a high molecular polymer with a metal catalyst, and mixing the two by a solvent to form a mixture;

的即在於提供一種奈米管的製備時間。根據本發明所指出驟包含：〇將《亥此口物置入一反應容器中並自該反應容器的下部通入一载流氣體； (C) 對該反應容ϋ下部與上部分別以不同溫度進行加熱以進行熱裂解反應；以及 (D) 降至室溫回收奈米碳管，其中’献應容器下部的加熱溫度為尊工麵。c，該反應容器上部的加熱溫度為祕觸。C，且下部的加熱溫度鬲於上部的加熱溫度。 -根，本發明所指出之奈米碳管的製造方法，可有效縮短以固^分子為反應物經由熱裂解方法製備奈米碳管的時間，將科技術中所需的3_丨ο小時，有效地縮短至2小時以内。糾，本發明係利用固態高分子經熱裂解反應製備奈米碳管，故可以免去習知技術使用氣態碳氫化合物(例如，甲烷、乙烷等)進行熱裂解時所造成的危險性。本發明將藉由下述的詳細說明及實施例做進一步的說明，這些實施例並不限制本發明前面所揭示之内容。熟習本务明之技藝者，可做些許之改良與修飾，但仍不脫離本 7 1299759 發明之範_。【實施方式】 - 為清楚地解說本發明之方法，在此伴隨著第一圖做詳 . 盡之說明。第一圖為用以執行本發明方法之裝置的一具體實施例之示意圖。在此具體實施例中可用以執行本發明方法之裝置係為一流體化床反應器1 〇，其包含一反應腔體 12,其内部下方處中設有一氣體分散器14。氣體分散器14 春係為一多孔性材質所製備(例如，多孔性二氧化石夕薄板），其係用以使輸入反應腔體12中的載流氣體得以均勻分散進入反應腔體12中。反應腔體12的下部設有一氣體輸入口 32，上部則設有一排出口 34。當欲以本發明方法製備奈米碳管時，首先係將一固態高分子聚合物與一金屬觸媒混合後，並藉由一溶劑使其混合均勻以形成一混合物。接著，將此混合物中的溶劑完全去除。鲁别述之咼分子聚合物，只要是任何習知主要以碳、氫、氧所組成之固態的高分子聚合物，皆可被應用於本發明中。前述之固態高分子聚合物係指於常溫常壓下以固態呈 • 現之高分子聚合物。在此可舉出的例子，包含聚乙烯 (Polyethylene，PE)、聚丙烯(p〇iypr〇pyiene，pp)與聚乙二醇 (polyethylene glycol，PEG)等，但並不僅限於此。熟習本發明技術領域之技藝者藉由閱讀本發明之說明亦可了解到，前述之固態高分子聚合物除碳、氳、氧外，亦可進一步包 8 1299759 含一無機原子來組成，例如，聚碳矽烷(polycarbosilane， PCS)，但並不僅限於此。前述之聚碳矽烷聚合物之重複單體係如下式（1)所示者：It is to provide a preparation time of a nanotube. According to the present invention, the method comprises: 置 placing the mouthpiece into a reaction vessel and introducing a carrier gas from the lower portion of the reaction vessel; (C) different temperatures of the lower portion and the upper portion of the reaction vessel respectively Heating is carried out to carry out the thermal cracking reaction; and (D) the carbon nanotubes are recovered to room temperature, wherein the heating temperature in the lower part of the conserving container is a respected surface. c, the heating temperature of the upper portion of the reaction vessel is a secret touch. C, and the heating temperature of the lower portion is higher than the heating temperature of the upper portion. - Root, the method for manufacturing a carbon nanotube indicated by the present invention can effectively shorten the time for preparing a carbon nanotube by a thermal cracking method using a solid molecule as a reactant, and the time required for the technique is 3 丨 ο hours , effectively shortened to less than 2 hours. Correctly, the present invention utilizes a solid polymer to prepare a carbon nanotube by thermal cracking reaction, thereby eliminating the danger caused by the conventional technique of using gaseous hydrocarbons (e.g., methane, ethane, etc.) for thermal cracking. The invention will be further illustrated by the following detailed description and examples, which are not intended to limit the invention. Those skilled in the art will be able to make some improvements and modifications, but still do not deviate from the invention of this 7 1299759 invention. [Embodiment] - In order to clearly explain the method of the present invention, the description will be made with reference to the first figure. The first figure is a schematic representation of a specific embodiment of an apparatus for performing the method of the present invention. The apparatus which can be used in this embodiment to carry out the process of the present invention is a fluidized bed reactor 1 which comprises a reaction chamber 12 having a gas disperser 14 disposed therein. The gas disperser 14 is made of a porous material (for example, a porous silica sheet), which is used to uniformly disperse the carrier gas input into the reaction chamber 12 into the reaction chamber 12. . A gas inlet port 32 is provided in the lower portion of the reaction chamber 12, and a row of outlet ports 34 is provided in the upper portion. When a carbon nanotube is to be produced by the method of the present invention, a solid polymer is first mixed with a metal catalyst and mixed by a solvent to form a mixture. Next, the solvent in this mixture was completely removed. The molecular polymer of 别述 , can be used in the present invention as long as it is any solid polymer which is mainly composed of carbon, hydrogen and oxygen. The above-mentioned solid polymer refers to a polymer which is solid in the normal temperature and normal pressure. Examples which may be mentioned herein include, but are not limited to, polyethylene (PE), polypropylene (p〇iypr〇pyiene, pp), and polyethylene glycol (PEG). It is also understood by those skilled in the art that the solid polymer of the present invention can be further composed of an inorganic atom in addition to carbon, helium or oxygen, for example, by reading the description of the present invention, for example, Polycarbosilane (PCS), but not limited to this. The above repeating single system of the polycarbodecane polymer is as shown in the following formula (1):

Rj Η (i) R2 Η 其中，:^與尺2可分別為氫、1_4個碳的烷基或苯基。Rj Η (i) R2 Η wherein: ^ and the ruler 2 are respectively hydrogen, an alkyl group of 1 to 4 carbons or a phenyl group.

可應用於本發明中之金屬觸媒，較佳為金屬化合物，例如三氧化二鐵(FeW3)、四氧化三鐵(Fe3〇4)、氧化鎂 (MgO)、硫酸鐵(FeXSO4)3)、氫氧化鐵(Fe0(0H))、硝酸鐵 (Fe(N03)3)、硝酸鎳（Ni(N〇3)2 · 6H20)、硫酸鎳 (NiS04 · 6H20)、硝酸鈷(Co(N〇3)2 · 6h2〇)…等，但並不僅限於此。為獲彳于較佳的奈米碳管品質，上述金屬觸媒的使用量’較佳為高分子聚合物使用量的15-4〇%(w/w)，更佳為 20-33%(w/w)，亦即金屬觸媒··高分子聚合物(重量比)較佳為 1 ·· 2·5 〜1 : 6.7，更佳為 1 ·· 3 〜1 ·· 5。前述之溶劑，本發明中並沒有特別的限制，只要是可於200C下藉由加熱而揮發者，皆可被應用於本發明中。例如，水、有機溶劑(如，甲醇、乙醇、丙醇）等，但二僅限於此。 —北不 ^外’上述㈣去除的方式在此並沒有制的限制， ^要疋任何g知可將混合溶液中溶劑去除的方法皆可被應 9 1299759 用本發明中。例如，藉由加熱使溶劑蒸發。為使以本發明方法製備奈米碳管時有更佳之效率，前述混有高分子聚合物與金屬觸媒之混合物於去除溶劑後，可將其進一步研磨成粉末，以使該混合物得以均勻受熱，以利於熱裂解反應之進行。The metal catalyst which can be used in the present invention is preferably a metal compound such as ferric oxide (FeW3), ferroferric oxide (Fe3〇4), magnesium oxide (MgO), iron sulfate (FeXSO4) 3), Iron hydroxide (Fe0(0H)), iron nitrate (Fe(N03)3), nickel nitrate (Ni(N〇3)2 · 6H20), nickel sulfate (NiS04 · 6H20), cobalt nitrate (Co(N〇3) ) 2 · 6h2〇)...etc, but not limited to this. In order to obtain better carbon nanotube quality, the amount of the above metal catalyst used is preferably 15-45% (w/w), more preferably 20-33%, of the amount of the polymer used. w/w), that is, the metal catalyst·polymer (weight ratio) is preferably 1 ·· 2·5 〜1 : 6.7, more preferably 1 ·· 3 〜1 ·· 5 . The solvent described above is not particularly limited in the present invention, and any one which can be volatilized by heating at 200 C can be used in the present invention. For example, water, an organic solvent (e.g., methanol, ethanol, propanol), etc., but only two. - North is not external The above (4) removal method is not limited here, and any method for removing the solvent in the mixed solution can be used in the present invention. For example, the solvent is evaporated by heating. In order to achieve better efficiency in the preparation of the carbon nanotubes by the method of the present invention, the mixture of the high molecular polymer and the metal catalyst may be further ground into a powder after the solvent is removed, so that the mixture is uniformly heated. In order to facilitate the thermal cracking reaction.

接著，將前述混有高分子聚合物與金屬觸媒之混合物 24裝填至第一圖中流體化床反應器10的反應腔體12内，並使其位於氣體分散器14上。藉由一氣體供應器22，自，置於反應腔體12下部之氣體輸入口 32持續輸入一載流氣體。載流氣體輸入反應腔體12内的流速可藉由一流量計 26來控制。於熱裂解反應與形成奈米碳管的過程中，反應腔體12中的壓力係維持於常壓下。 μNext, the aforementioned mixture of the high molecular polymer and the metal catalyst 24 is loaded into the reaction chamber 12 of the fluidized bed reactor 10 in the first figure, and is placed on the gas disperser 14. The gas input port 32, which is placed in the lower portion of the reaction chamber 12, is continuously supplied with a carrier gas by a gas supply unit 22. The flow rate of the carrier gas into the reaction chamber 12 can be controlled by a flow meter 26. During the thermal cracking reaction and formation of the carbon nanotubes, the pressure in the reaction chamber 12 is maintained at normal pressure. μ

之後，使用第-加熱器16與第二加熱器18分別對反應腔體12的下部與上部，以不同溫度加熱。其中，第一加熱器16所施加之溫度較佳為70(M00(TC，第二熱器18所施加之溫度較佳為，且第—加熱器16施时加之溫度需高於第二加熱器18所施加之溫度。前述之第一加敎哭 16與第二加熱11 18可藉由—溫控器20來馳其加熱溫度。於树明中以兩種不同加熱溫度進行熱裂解的目的係在南分子聚合物進行熱裂解反應需要較高之溫度，而當局分子聚合物經熱裂解於金屬觸媒表面析出碳原子，進而成長出奈米碳管時的還原反應，則不需要如此高的溫度此外、、二熱衣解後的碳原子因會被载流氣體懸浮於反應腔體12内的上部。因此，本發明即藉由先以第-加熱器 1299759 16提供之較高溫度’使聚合物進行熱鶴，之後再以第二加熱器18提供-相龍低的溫度，以㈣浮於載流氣體中的碳原子得以進行還原反應，進而於金屬觸媒表面析出並成長出奈来碳管。最後’藉由本發明方法所製備出的奈米碳管，即可藉由載流氣體自排出口 34輸出。前述本發明中之载流氣體，為避免於加熱過程中產生不必要的反應’其較佳係為鈍性氣體，在此可舉出的例子包含氮氣(n2)、氦氣(He)、氖氣(Ne)、氬氣(Ar)等惰性氣體，但並不僅限於此。但為使碳原子於金屬觸絲面析出並成長出奈米碳管時有較佳之還原反應，較佳為似氣體中進 -步包含H)-2〇%(v/v)的氫氣。料，載流氣體的流量較佳係在700-1300毫升/分。由於本發明方法使用載流氣體懸浮反應物，因此可使付反應物受熱較為快速且均勻，因此以根據本發明方法所進行之奈米碳管的製備僅需2小時以内即可完成，且可製得直徑為數十奈米，長度為1微米以上之奈米破管。做為本發明方法的另一具體實施例，於將混有高分子艰合物與金屬觸媒之混合物24裝填至第一圖中流體化床反應器10的反應腔體12内前，於反應腔體12内氣體分散器14上可進一步填充另一金屬觸媒顆粒3〇 (例如，鎳顆粒）’藉以加速熱裂解的反應速率（第二圖）。本發明方法係使用固恶向分子聚合物做為礙源，相較於習知技術中所使用的有機氣體(如，甲烷、乙烷），固態 11 1299759 高分子聚合物較亦於韻，傳輸運送上也較為簡便。另一 ^面’在室溫下，固態高分子聚合物的化學性質十分穩定，幾乎無毒性，相較於有機氣體，其具有較佳的安全性。、再者，本發明方法中使用具有高質傳與高熱傳特性的 "IL體化床來製備奈米碳管，因此這使得奈米碳管之大量且連續操作的生產變成可能，故而以本發明方法進行太^石山管之製備將有利於製成的放大。 "^ 雖然本發明已以較佳實施例揭露如上，然其並非用以限定本發明，任何熟習此技藝者，在不脫離本發明之精神和範圍内，當可作些許之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。實施例一取聚碳矽烷與相對於聚碳矽烷使用量33% (w/w)的三氣化二鐵混合。藉由酒精溶液使其混合均勻，之後以8(M〇〇 • 七加熱去除酒精。將所得之團塊研磨成粒徑約為5-6μιη的粉末。將此粉末填充至第一圖的反應腔體内，以上層溫度為850C、下層溫度為950°C，以及載流氣體(混有1(^20% - (v/v)氫氣的氬氣)流量為244毫升/分之條件下進行奈米碳管的製備。於進行反應1.5小時後，所製得之奈米碳管以電子顯微鏡觀察所得的影像示於第三圖中。參閱第三圖，由第三圖中可得奈米碳管的直徑約為 l〇_90nm，而長度則可達數微米以上。 12 1299759 實施例二同實施例一之方法與條件，但改以 :载流氣體流量改為_升，分。於進行心圖2得之奈米碳㈣電子顯微鏡祕所得的影像示於第四參閱第四圖，由第四圖中可得奈米碳管的直徑約為2〇 nm ’而長度則可達1微米以上。Thereafter, the lower portion and the upper portion of the reaction chamber 12 are heated by the first heater 16 and the second heater 18 at different temperatures. The temperature applied by the first heater 16 is preferably 70 (M00 (TC, the temperature applied by the second heater 18 is preferably, and the temperature of the first heater 16 is higher than the second heater). 18 applied temperature. The first twisting 16 and the second heating 11 18 can be heated by the thermostat 20. The purpose of thermal cracking in two different heating temperatures in Shuming is In the thermal cracking reaction of the southern molecular polymer, a higher temperature is required, and the reduction reaction of the molecular polymer of the host by thermal cracking on the surface of the metal catalyst to grow the carbon nanotubes does not need to be so high. In addition, the carbon atoms after the second hot coating are suspended by the carrier gas in the upper portion of the reaction chamber 12. Therefore, the present invention is achieved by first providing the higher temperature of the first heater 1299759 16 The polymer carries the hot crane, and then the second heater 18 provides a low temperature of the phase dragon, and (4) the carbon atoms floating in the carrier gas are subjected to a reduction reaction, and then precipitated on the surface of the metal catalyst and grows up. Carbon tube. Finally 'by the present invention The carbon nanotubes prepared by the method can be output from the discharge port 34 by the carrier gas. The carrier gas in the present invention is used to avoid unnecessary reaction during the heating process. Examples of the gas include an inert gas such as nitrogen (n2), helium (He), neon (Ne), or argon (Ar), but are not limited thereto, but in order to make carbon atoms in the metal When the contact surface of the wire is precipitated and the carbon nanotubes are grown, there is a preferred reduction reaction, and it is preferred that the gas contains H) -2% (v/v) of hydrogen in the step-by-step process. Preferably, the method of the present invention uses a carrier gas to suspend the reactants, so that the reactants are heated more quickly and uniformly, so that the preparation of the carbon nanotubes by the method according to the invention is only It can be completed in less than 2 hours, and a nano tube having a diameter of several tens of nanometers and a length of 1 micrometer or more can be obtained. As another specific embodiment of the method of the present invention, it is difficult to mix the polymer. The mixture of the material and the metal catalyst 24 is loaded into the reaction of the fluidized bed reactor 10 in the first figure. Before the body 12, the gas disperser 14 in the reaction chamber 12 can be further filled with another metal catalyst particle 3 (for example, nickel particles) to accelerate the reaction rate of thermal cracking (second diagram). The use of solid and malignant molecular polymers as a source of interference, compared to the organic gases used in the prior art (eg, methane, ethane), the solid 11 1299759 polymer is also more rhyme, transport transport also It is relatively simple. Another surface 'at room temperature, the solid polymer is very stable in chemical properties, almost non-toxic, and has better safety than organic gases. Furthermore, in the method of the present invention The use of a "IL body bed having high mass transfer and high heat transfer characteristics to prepare a carbon nanotube, thus making it possible to produce a large number of continuously operated carbon nanotubes, and thus the method of the present invention is carried out. The preparation will facilitate the enlargement of the fabrication. The present invention has been described above by way of a preferred embodiment, and is not intended to limit the invention, and may be modified and modified without departing from the spirit and scope of the invention. Therefore, the scope of the invention is defined by the scope of the appended claims. Example 1 Polycarbane was mixed with tri-evaporized diiron in an amount of 33% (w/w) relative to polycarbane. The mixture was uniformly mixed by an alcohol solution, and then the alcohol was removed by heating at 8 (M〇〇·7). The obtained agglomerate was ground into a powder having a particle diameter of about 5-6 μm. This powder was filled into the reaction chamber of the first figure. In the body, the upper layer temperature is 850C, the lower layer temperature is 950 ° C, and the carrier gas (argon mixed with 1 (^20% - (v/v) hydrogen) flow rate is 244 ml / min. Preparation of carbon nanotubes. After 1.5 hours of reaction, the obtained carbon nanotubes were observed by electron microscopy in the third image. Referring to the third figure, the carbon nanocrystals available in the third figure The diameter of the tube is about l〇_90nm, and the length can be several micron or more. 12 1299759 Embodiment 2 is the same as the method and condition of the first embodiment, but is changed to: the flow rate of the carrier gas is changed to _liter, minute. The image obtained by the nanometer carbon (4) electron microscope is shown in the fourth figure. The carbon nanotubes in the fourth figure have a diameter of about 2 〇 nm and the length is up to 1 μm. the above.

實施例三同實施例二之方法與條件，但上層溫度改為75(rc，下層溫度改為85Gt：，且載流氣體流量改為4⑻毫升/分。於進行反應1小時後’所製得之奈米碳管以高解析穿^式電子顯微鏡(HRTEM)觀察所得的影像示於第五圖中。"The third embodiment is the same as the method and condition of the second embodiment, but the upper layer temperature is changed to 75 (rc, the lower layer temperature is changed to 85 Gt:, and the carrier gas flow rate is changed to 4 (8) ml/min. After the reaction is performed for 1 hour' The image of the carbon nanotubes observed by a high-resolution electron microscope (HRTEM) is shown in the fifth figure. "

參閱第五圖’由第五圖中可清楚的看到一層一層的石墨層’進-步經由傅立葉轉換(F〇urier transf〇rm)計算，可仔知其層與層之間距為G.34 nm，此結果符合石墨之平面層間距，因此可證實本發财法所製備出來的產物確為太: 碳管。不 13 1299759 【圖式簡單說明】第一圖為用以執行本發明方法之裝置的一具體實施例之不意圖，第二圖為用以執行本發明方法之裝置的另一具體實施例之示意圖；第三圖為經以本發明方法所製備出之奈米碳管的一實施例，經以電子顯微鏡觀察所得之影像圖； (a) 穿透式電子顯微鏡影像；Referring to the fifth figure 'the graphite layer layered one layer can be clearly seen from the fifth figure', the calculation is carried out by Fourier transform (F〇urier transf〇rm), and the distance between the layers is G.34. Nm, this result is consistent with the plane spacing of graphite, so it can be confirmed that the product prepared by this method is indeed too: carbon tube. BRIEF DESCRIPTION OF THE DRAWINGS The first figure is a schematic representation of one embodiment of a device for performing the method of the present invention, and the second figure is a schematic view of another embodiment of a device for performing the method of the present invention. The third figure is an image of the carbon nanotube prepared by the method of the present invention, which is observed by an electron microscope; (a) a transmission electron microscope image;

(b) 掃描式電子顯微鏡影像；第四圖為經以本發明方法所製備出之奈米碳管的又一實施例，經以電子顯微鏡觀察所得之影像圖；以及 (a) 穿透式電子顯微鏡影像； (b) 掃描式電子顯微鏡影像；第五圖為經以本發明方法所製備出之奈米碳管的再一實施例，經以高解析穿透式電子顯微鏡觀察所得之影像圖。【主要元件符號說明】 10流體化床反應器 12反應腔體 14氣體分散器 16第一加熱器 18第二加熱器 20溫控器 14 1299759 22氣體供應器 24混合物 26流量計 30金屬觸媒顆粒 32氣體輸入口 34排出口(b) scanning electron microscope image; the fourth figure is another image of the carbon nanotube prepared by the method of the present invention, which is observed by an electron microscope; and (a) a penetrating electron Microscope image; (b) Scanning electron microscope image; Figure 5 is a further image of the carbon nanotube prepared by the method of the present invention, which was observed by a high-resolution transmission electron microscope. [Main component symbol description] 10 fluidized bed reactor 12 reaction chamber 14 gas disperser 16 first heater 18 second heater 20 thermostat 14 1299759 22 gas supply 24 mixture 26 flow meter 30 metal catalyst particles 32 gas input port 34 outlet

Claims

μ) 申請專利範圍： 1一Z— 4 •種奈米奴管的製造方法，其步驟包含： (Α)將-固態⑧分子聚合物與—金屬觸媒混合，並藉由 -溶劑使兩者混合均勻以形成—混合物； (B)將該混合物置人—流體化床反應时，並自該流體化床反應H的下部通人—載流氣體； (C) 對該流體化床反應器下部與上部分仙不同溫度進行加熱以進行熱裂解反應；以及 (D) 降至室溫回收奈米碳管，其中，该流體化床反應器下部的加熱溫度為 700-1000 °C，該流體化床反應器上部的加熱溫度》__9〇(rc，且下部的加熱溫度高於上部的加熱溫度。 2·=申μ專利範圍帛1項所述之製造方法，其中該高分子聚口物係遥自聚乙婦、聚㈣、聚乙二醇與聚碳石夕烧所組成之族群。 .如申請專利範圍第2項所述之製造方法，其中該聚碳石夕烷之重複單體係如下式⑴所示者： Ri Η 十Hv ⑴ R2 Η 其中’ Ri與&可分別為氫、1_4個碳的烷基或苯基。 4·如申請專利範圍第1項所述之製造方法，其中該金屬觸媒係為金屬化合物。 5·如申請專利範圍第4項所述之製造方法，其中該金屬化 1299759 ”選自三氧化二鐵、四氧化三鐵、氧化鎂、硫酸鐵、 =氧化鐵、硝酸鐵、硝酸鎳、硫酸鎳與硝酸鈷所組成之 . ^^群。 • 6. ^請專利範圍第1項所述之製造方法，其中該金屬觸媒的使用量為該高分子聚合物使用量的15_4G%(w/w)。 •如申請專利範圍第1項所述之製造方法，其中該溶劑係為水。 • 8. #申請專利縫第1項所述之製造方法，其中該溶劑係 • 為沸點不超過200°C的有機溶劑。 ~ 9.如申請專利範圍第1項所述之製造方法，其中該有機溶劑係選自曱醇、乙醇與丙醇所組成之族群。 1G.如中請專利範圍第丨項所述之製造方法，其中該步驟(A) 後進一步包含將該混合物中的該溶劑去除的步驟。 11.如申請專利範圍第1〇項所述之製造方法，其中該溶劑係藉由加熱去除。 • I2·如申請專利範圍第10項所述之製造方法，其中於該溶劑去除後進一步再包含一將該混合物研磨成粉末的步驟。 - I3.如申請專利範圍第1項所述之製造方法，其中該步驟(C) 係於常壓下進行。 14·如申請專利範圍第i項所述之製造方法，其中該載流氣體係為鈍性氣體。， 15·如申請專利範圍第i項所述之製造方法，其中該載流氣體係為10-20%(v/v)氫氣與8〇-9〇%(v/v)鈍性氣體的混 17 1299759 合氣體。 16. 如申請專利範圍第14或15項所述之製造方法，其中該鈍性氣體係選自氮氣、氦氣、氖氣與氬氣所組成之族群。 17. 如申請專利範圍第1項所述之製造方法，其中該載流氣體的流量為700-1300毫升/分。 18. 如申請專利範圍第1項所述之製造方法，其中該流體化床反應器内進一步填充有另一金屬觸媒顆粒。 19. 如申請專利範圍第18項所述之製造方法，其中該金屬觸媒顆粒係為鎳顆粒。 18μ) Patent application scope: 1ZZ-4 • A method for manufacturing a nanotube, the steps of which include: (Α) mixing a solid 8-mer polymer with a metal catalyst, and using a solvent to make both Mixing uniformly to form a mixture; (B) placing the mixture in a fluidized bed reaction and passing a man-carrier gas from the lower portion of the fluidized bed reaction H; (C) lowering the fluidized bed reactor Heating at a different temperature from the upper part to perform a thermal cracking reaction; and (D) recovering the carbon nanotubes to a room temperature, wherein the heating temperature of the lower portion of the fluidized bed reactor is 700-1000 ° C, the fluidization The heating temperature of the upper part of the bed reactor is __9 〇 (rc, and the heating temperature of the lower part is higher than the heating temperature of the upper part. 2) = the manufacturing method described in the patent scope of the invention, wherein the polymer polyether is remote The method of manufacturing a polycarbonate, a polyethylene glycol, and a polycarbosulfan. The manufacturing method according to claim 2, wherein the polycarbosulfan repeat system is as follows Persons of formula (1): Ri Η ten Hv (1) R2 Η where ' Ri And < can be a hydrogen, a 1-4 carbon alkyl group or a phenyl group, respectively. 4. The manufacturing method according to claim 1, wherein the metal catalyst is a metal compound. The manufacturing method according to the item 4, wherein the metallization 1299759" is selected from the group consisting of ferric oxide, triiron tetroxide, magnesium oxide, iron sulfate, iron oxide, iron nitrate, nickel nitrate, nickel sulfate and cobalt nitrate. ^^群。 6. The manufacturing method described in the above paragraph 1, wherein the metal catalyst is used in an amount of 15_4 G% (w/w) of the polymer used. The manufacturing method according to the item 1, wherein the solvent is water. 8. The method of manufacturing the product according to the first aspect, wherein the solvent is an organic solvent having a boiling point of not more than 200 ° C. 9. The method of claim 1, wherein the organic solvent is selected from the group consisting of decyl alcohol, ethanol, and propanol. Wherein the step (A) further comprises The method of the present invention, wherein the solvent is removed by heating, wherein the solvent is removed by heating, wherein the solvent is as described in claim 10, wherein the solvent is used in the solvent. Further, after the removal, a step of grinding the mixture into a powder is further included. The method of the invention of claim 1, wherein the step (C) is carried out under normal pressure. The manufacturing method according to the item i, wherein the carrier gas system is a passive gas. The manufacturing method according to claim i, wherein the carrier gas system is 10-20% (v/ v) Hydrogen mixed with 8〇-9〇% (v/v) passive gas 17 1299759 gas. 16. The method of manufacture of claim 14 or 15, wherein the passive gas system is selected from the group consisting of nitrogen, helium, neon and argon. 17. The manufacturing method according to claim 1, wherein the carrier gas has a flow rate of 700 to 1300 ml/min. 18. The method of manufacture of claim 1, wherein the fluidized bed reactor is further filled with another metal catalyst particle. 19. The method of manufacture of claim 18, wherein the metal catalyst particles are nickel particles. 18