1302575 九、發明說明： 【發明所屬之技術領域】 — 本發明係有關極細微的碳纖維與活性碳纖維之製造方法，尤指以聚稀 ^ 烴(Polyolefin)與含碳的聚合物(polymer)為鞘部及聚烯烴為芯部，利用芯 鞘型（Sheath & Core)溶融抽絲方法直接抽絲成含碳前驅物(precursor) 的蕊鞘型纖維，在有溫度的環境下使芯鞘型纖維穩定化(stabilization), 最後在沁氣體中，於600乞-15001下，將穩定化芯鞘型纖維經高溫碳化處 • 理成纖維細度為20〜800nm之極微細碳纖維。前述所得極微細碳纖維可在 C〇2、水蒸氣與空氣或其混合氣體中於60叱—150代下使其活性化成為極微 細活性碳纖維。前述所得極微細碳纖維也可再於Ar氣體中於1500\>3000 C下间bnL石墨化處理得到極微細石墨碳纖維。 【先前技術】 碳纖維以其具有優越的機械特性、尤其以比強度、比彈性模數較高的 特徵，正被廣用於航太用途、休閒器材、一般產業用途等方面❶然而其性 • 能隨著用途之不同而仍嫌不足，對需具有高強度、微細且質輕、導熱性及 導電性良好、可廣泛運用於強化複合材料補強材、儲氫材料、鋰離子電池 電極、超两電容器或過濾用途等高性能的微細碳纖維或活性碳纖維之開發 的需求亦正日益增加著。 因此，以断機能性為目的而以微粒子等的職混合不_化合物至 碳纖維内部的技術（日本特公昭61_58號公報、特開平卜奶號公 報特開平4-272236號公報）或使各種樹脂與聚丙稀腈系聚合物混合的 技術（日本制平5_19讓號錢、台料.告峨Μ·)，再於真 1302575 空中使固態或氣態的原子或分子離子化並藉由電場加速使注入碳纖維之表 層和對表層構造進行改質的技術（日本特開平3_18〇514號公報）等均有 k出專利申請著。 • 然而，對上述含有微粒子的碳纖維而言，微粒子以雜質異物散佈於單 纖内部的全體__著，在製絲及燒成步驛中常造成斷料，使成形性 降低成為使拉伸強度等機械特性降低的原因。另外，至於使壓縮強度提 升的一種手段，已知降低正構成碳纖維之石墨結晶的尺度並提升石墨結晶 鲁的剪斷強度或橫向強度是有效的，但若混合已含有金屬元素的微粒子時 ，則由於觸媒石墨化作用反而使結晶成長而亦有不利於壓縮強度的情形。 因此，以不採用微粒子而改質碳纖維之微細構造的目的，將各種樹脂 混入聚丙烯腈系聚合物等方法雖被嘗試著，但欲得均勻的構造之碳纖維係 困難的且常導致強度之降低。又，將雜質元素離子植入碳纖維並改質表質 層之構造的技術，雖被認為有提升碳纖維之基本特性的功效，但需要在真 空下的處理且未能製得微細碳纖維，並未達工業規模製造的地步。 _ 又有以氣相生成法製造奈米級碳纖維的技術在台灣專利公告編號 73021被提及，此種氣相生成法是於高溫時使含碳類氣體於金屬觸媒上熱分 解而形成奈米碳纖維，利用此方法製得的奈米碳纖維，可利用極便宜的含 碳類氣體原料來生產奈米級架構的極細碳纖維，且可以一種單一步驟的製 程製得。此種氣相成長法又可稱為化學氣相沈積法(CVD)，但其製造時間 長，產量少，尚需改良製法。 曰本群馬大學大谷朝男（Asao Oya)教授發表於日本機能材料2〇〇〇年4 1302575 月號(vol· 20, No· 4，Page 20-26)之極細碳纖維的開發技術，其利用可碳化 及熱易分解的聚合物以溶劑混摻成微粒，結合熔融抽絲及碳化的方法以製 ' 備極細碳纖維，其方法是以溶劑將可碳化聚合物溶解在溶劑中後再於可包 • 覆於表面的另一聚合物溶液中形成微米大小顆粒，原料需先經過溶劑處理 加工，製作過程複雜且易有環境污染問題產生。至於極細碳纖維之製備方 面，前述大谷朝男教授在2000年發表的聚合物以溶劑混摻熔融抽絲法，係 利用混摻可碳化及熱易分解的聚合物，形成微粒再以熔融抽絲及碳化的方 φ 法來製備微細碳纖維’藉由溶劑製出小於數微米大小的酴媒聚合物，使包 覆於聚乙烯聚合物内，除去溶劑形成酚醛—聚乙烯聚合物微珠。利用小於數 微米大小的微珠、聚乙烯以3 : 7之重量比例，以i5(Tt熔融混合後經熔融 方式抽絲’此纖維使於酸性的環境下穩定化，用氨水中和、去離子水洗及1302575 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for producing extremely fine carbon fibers and activated carbon fibers, and more particularly to a sheath of a polyolefin and a carbon-containing polymer. The part and the polyolefin are core parts, and are directly drawn into a core-sheath type fiber containing a carbon precursor by a sheath-type (Sheath & Core) melt-spinning method, and the core-sheath type fiber is used in a temperature environment. Stabilization, finally, in a helium gas, the stabilized core-sheath fiber is subjected to high-temperature carbonization at a temperature of 600 乞 to 15 001 to form a very fine carbon fiber having a fiber fineness of 20 to 800 nm. The ultrafine carbon fibers obtained as described above can be activated into ultrafine activated carbon fibers in 60 叱 to 150 passages in C 〇 2, steam and air or a mixed gas thereof. The ultrafine carbon fibers obtained as described above may be further graphitized by bnL at 1500/>3000 C in Ar gas to obtain ultrafine graphite carbon fibers. [Prior Art] Carbon fiber is widely used in aerospace applications, leisure equipment, general industrial applications, etc. due to its superior mechanical properties, especially in terms of specific strength and specific modulus of elasticity. It is still insufficient due to different uses. It needs high strength, fineness, light weight, good thermal conductivity and good electrical conductivity. It can be widely used in reinforced composite reinforcement materials, hydrogen storage materials, lithium ion battery electrodes, super two capacitors. There is also an increasing demand for the development of high-performance fine carbon fibers or activated carbon fibers such as filtration applications. For this reason, it is a technique of mixing the non-compounds to the inside of the carbon fiber for the purpose of the function of the detachment of the particles (Japanese Patent Publication No. Sho 61-58, Japanese Patent Publication No. Hei-4-272236) or various resins and The technology of mixing polyacrylonitrile-based polymers (Japanese made 5_19, the money, the material, the warning), and then ionized the solid or gaseous atoms or molecules in the air and accelerated the electric field to inject carbon fiber. The surface layer and the technique for modifying the surface structure (Japanese Patent Laid-Open No. Hei 3_18〇514) have been patented. However, in the above-mentioned carbon fiber containing fine particles, the fine particles are dispersed in the entire interior of the single fiber by the foreign matter, and the yarn is often broken during the spinning and baking steps, and the moldability is lowered to the tensile strength. The reason for the decrease in mechanical properties. Further, as a means for increasing the compressive strength, it is known that it is effective to reduce the scale of the graphite crystal which is constituting the carbon fiber and to increase the shear strength or the transverse strength of the graphite crystal, but if the fine particles containing the metal element are mixed, Since the graphitization of the catalyst causes the crystal to grow, there is also a case where the compressive strength is disadvantageous. Therefore, the method of mixing various resins into a polyacrylonitrile-based polymer for the purpose of modifying the fine structure of carbon fibers without using fine particles has been attempted, but it is difficult to obtain a carbon fiber having a uniform structure and often causes a decrease in strength. . Moreover, the technique of implanting the impurity element ions into the carbon fiber and modifying the structure of the surface layer is considered to have the effect of improving the basic characteristics of the carbon fiber, but it requires treatment under vacuum and fails to produce fine carbon fibers, which does not reach The point of industrial scale manufacturing. _ Another technique for producing nano-carbon fibers by gas phase generation is mentioned in Taiwan Patent Publication No. 73021. This gas phase formation method is to thermally decompose carbon-containing gases on metal catalysts at high temperatures to form nai. Rice carbon fiber, nano carbon fiber produced by this method, can produce very fine carbon fiber of nano-scale structure by using very cheap carbon-containing gas raw material, and can be obtained by a single-step process. Such a vapor phase growth method is also called chemical vapor deposition (CVD), but it has a long manufacturing time and a small yield, and an improved method is required. Prof. Asao Oya from Sakamoto Gunma University published in the development of ultra-fine carbon fiber of Japanese Functional Materials 2 2 4 4123575 (vol. 20, No. 4, Page 20-26). The carbonized and thermally decomposable polymer is mixed with a solvent into fine particles, combined with melt spinning and carbonization to prepare a very fine carbon fiber by dissolving the carbonizable polymer in a solvent in a solvent. The micron-sized particles are formed in another polymer solution covering the surface, and the raw materials need to be subjected to solvent treatment, and the manufacturing process is complicated and environmental pollution problems are easily generated. As for the preparation of very fine carbon fibers, the above-mentioned polymer published by Professor Otani Ou in 2000 is a solvent-mixed melt-spinning method which utilizes a polymer which can be carbonized and thermally decomposed to form fine particles and then melt-spun and The carbonized square φ method is used to prepare fine carbon fibers. A solvent polymer of less than a few micrometers is prepared by a solvent to be coated in a polyethylene polymer, and the solvent is removed to form a phenol-polyethylene polymer microbead. Using microbeads smaller than a few micrometers, polyethylene in a weight ratio of 3:7, i5 (Tt melt-mixed and melt-spun after spinning) This fiber stabilizes in an acidic environment, neutralized with ammonia, deionized Washed and
丨 I 乾燥等，如此而得的穩定化纖維具有數十微米之纖維直徑，最後於6〇〇乞氮 氣下碳化10分鐘，此種碳纖維經碳化後將聚乙烯分解而留下一束紛路樹脂 何生的極細碳纖維，纖維直徑約為2〇〇—25〇奈米。此法須用溶劑將聚合物 •痛後再使包覆於另—聚合物溶液巾，而後除去溶_成微米大小顆粒， 原料需先經過溶劑處理加工，生產過程複雜且易有環境污染問題。 日本a開特許公報特開2〇〇1—73226揭示酚醛系極細碳纖維製法，其以 祕樹脂與聚乙稀於混練溫度12〇t - 16(TC下混合-段時間後形成塑膠粒 而後以120 02001熔融紡絲成纖維為最佳製法，並於酸性環境9忙下 _ 24 λ!、時後’用氨水中和、去離子水洗及乾燥等，如此而得的穩定化纖 維具有數十微米之纖維直徑，最後於氮氣下6〇〇<t碳化ι〇分鐘，留下一束 1302575 酚醛樹脂衍生的極細碳纖維。此方式須於酚醛樹脂與聚乙烯混練時需有一 段混練時間，例如酚醛樹脂與聚乙烯約100g時其混練時間約5〇分鐘。 【發明内容】 - 為解決上述習知技術之缺點（產量少、生產步驟複雜且使用溶劑、生 產時間較長、生產成本較高），經精心研究及檢討，發現以聚烯烴與含碳的 聚合物為鞘部及聚烯烴為芯部，利用芯鞘型熔融抽絲方法直接抽絲成含碳 刖驅物的芯鞘型纖維（參閱第1圖），在有溫度的環境下使芯鞘型纖維穩定 Φ 化’最後在N2中於6〇〇°C- 1500 °C下，將穩定化芯鞘型纖維經高溫碳化處 理成纖維直徑為20〜800 nm之極微細碳纖維。前述所得極微細碳纖維可 在C〇2、水蒸氣與空氣或其混合氣體中於60〇t— i5〇〇t：下使其活性化成為 極微細活性碳纖維。前述所得極微細碳纖維也可再於氣體中於15〇〇乞一 3000X：下高溫石墨化處理得到極微細石墨碳纖維，因此發展出利用芯鞘熔 融抽絲方法之更有效率的極微細碳纖維製造技術。 第1圖的芯勒型纖維係以二種及/或以上的聚合物分別由具有芯鞘形喷 φ 絲口的芯及鞘經予、熔融擠壓出形成芯鞘型纖維，其斷面圖視用於芯/勒的聚 合物量，可為90重量％〜1〇重量％至1〇重量％〜9〇重量％之範圍，斷面圖 形狀可為同心圓、偏心圓、三片葉狀等形狀。 前述含碳的聚合物包含聚酴駿（Phenol-Formaldehyde ; PF)、熱塑性 聚丙烯腈系聚合物（Thermoplastic Polyacrylonitrile ; TPAN)、熱塑性 聚乙烯醇(Thermoplastic Polyvinyl alcohol ;TPVA)、聚氣乙稀（p〇lyVinyi chloride ; PVC)、中間相瀝青（mesophase pitch ; MP)等聚合物。 1302575 w述聚烯烴’通常可採聚苯乙埽⑽、聚乙蝉（pE)、聚丙烯（pp)、 聚甲基戍烯或含埽烴之共聚合物等聚烯烴類。 ^可供抽絲成祕纖維者，係採用數目平均分子量5⑽〜漏之祕 -齡’通巾可Μ式紡絲或乾式觸轉未硬化的祕纖維 ，但不易以熔 融抽絲製付未硬化的祕纖維，因熔融抽絲時容易斷絲。未硬化的祕纖 維而後在例如於鹽酸、磷酸、硫酸等酸性觸媒與例如甲酸、聚甲搭、三口夸 口山（trioxane)四口7口山（tetra〇xane)等駿類之混合水溶液中硬化處理， φ或使於上述混合水溶液中未硬化的酚醛纖維之外層部分預硬化，接著以諸 如氨水、六亞甲基四胺、尿素、氫氧化卸等驗性水溶液使中和纖維而得硬 化酚醛纖維。通常，上述酸性觸媒、鹼性水溶液、醛類，係各自採用鹽酸、 氨水、甲醛。又，硬化酚醛纖維其本身為不熔性，而且含碳率高，可適用 作碳纖維用的前驅物纖維。 可用於本發明方法之含碳的聚合物中的聚驗酿樹脂(PF)其數目平均分 子量2000〜10000，需與容易熔融抽絲的聚烯烴同時利用芯鞘型熔融抽絲方 法直接抽絲成未穩定化的齡齡聚稀烴芯鞘型纖維。 由於單獨以石油系或碳系瀝青、等向性或異向性瀝青進行抽絲時，通 常受空氣阻力的影響，欲製得纖維直徑在5//m以下的含碳前驅物纖維是較 難的。其原因在於瀝青的黏度對溫度相依性較大所致，由喷絲孔吐出的遊 青因急速的細化，即使充分控制抽絲時的冷風溫度，亦大大的影響抽絲原 料之瀝青的黏度變異，極容易引起斷紗。因此瀝青系原料係較難如高八子 般可予拉伸，常需抽絲成5〜15 ara的低纖度，因此喷絲孔吐出量較小喷 1302575 絲孔背壓亦較一般的局分子為低。因此若有兩黏度的雜質時，常容易引起 喷絲孔阻塞現象。因此為防範此現象，需去除粗原料的石油系或碳系重油 : 中之咼黏度雜質。雖然供作抽絲原料的瀝青在去除雜質固形份後，但仍在 蒸餾、中間相瀝青化等的加熱處理或氧化處理等經時變化引起抽絲原料瀝 青之高黏度，仍引起喷絲孔阻塞現象而使斷紗。因此，以中間相瀝青為抽 絲原料或可解決上述問題點。 適用於本發明方法之含碳的聚合物中的中間相瀝青，可由煤焦油在鎳 φ 鉬系觸媒之存在下，吹入氫氣使在4〇(TC反應120分鐘。對所得的氫化煤焦 油以濾網過濾，去除固形物後在35(rt蒸餾，可得氫化瀝青。其次在 520 C、17mmHg熱處理7分鐘，而得中間相瀝青。適用於碳纖維用前驅物纖 維的中間相瀝青，可採用軟化點為235〜267t，甲苯不溶物含量為731重 量％以上，異向性量85〜90· 1%的中間相瀝青。 纟製備微細碳纖維時’長久以來其製程方面或有以微粒子等的形態混 ；合不同種化合物至魏維内部的技術、或有使各種樹脂與聚丙稀腈系聚 • 合物混合的技術，或有植入雜質元素離子於碳纖維並改質表質層之構造的 技術’或有氣相生成法製造奈米級碳纖維的技術，或單獨以石油系或碳系 !遞青、等向性或異向性遞青進行抽絲時，較難製得纖維直徑在以下的 ：含碳雜誠維，或赠贿備__旨鮮⑽魏絲錄微米顆粒 ’或以祕樹脂與聚乙烯混練長時間後以熔融滅或乾式抽絲及碳化的方 法以製備極細碳纖維，但有產量少、生產步驟複雜且使用溶劑、生產時間 較長、生產成本較高等的製程缺點，並不適用。 1302575 為此，本發明乃採各種製程的優點，使能以由聚烯氫聚合物與含碳之 聚合物為鞘部及聚烯氫聚合物為鞘部，直接用芯鞘型抽絲模式連續抽出含 : 碳前驅物的芯鞘纖維，不用再經溶劑製備或混練長時間的問題。在有溫度 - 環境下使芯鞘纖維穩定化，最後在N2氣體下，於6001-15001下，將穩定 化芯鞘纖維經高溫碳化處理將聚烯烴分解而留下含碳前驅物樹脂衍生的直 徑為20〜800nm之極微細碳纖維。 對可供作含碳前驅物之聚合物，有熱塑性聚酚醛、熱塑性聚丙烯腈系 φ 聚合物、熱塑性聚乙烯醇、聚氯乙烯、中間相瀝青等視必要予以組合作為 鞘材，使此等含碳的聚合物利用芯鞘熔融抽絲方法直接抽成含碳前驅物的 芯鞘纖維，於鞘材部份為由含碳聚合物與聚烯烴聚合物利用直接熔融混摻 模式，形成原纖維-基質（fibirl-matrix)形態（參閱第2圖），含碳的聚合 物為原纖維部分（第2圖中的21)，聚烯烴為基質部分(參閱第2圖中的22)。 而芯材則由聚烯烴聚合物組成（參閱第2圖中的23)，因其具有容易熔融抽絲 而且不容易斷絲之優點，使具支撐蕊鞘型纖維的強度，避免芯鞘型纖維提 g 早斷裂。對此芯鞘纖維在有溫度的環境中使芯鞘纖維穩定化，最後在N2惰性 氣體下，於600-15001下，將穩定化芯鞘纖維經高溫碳化後將聚烯烴分解 而留下含碳的聚合物衍生的極微細碳纖維，若再經C〇2、水蒸氣與空氣或其 混合氣體環境於600 - 15001下，則可形成極微細活性碳纖維。 前述芯鞘型熔融抽絲時的鞘材部分對芯材部分之使用量設在2〇重量％ 〜80重量％至80重量％〜20重量％範圍内為宜，鞘材部分的含碳聚合物與聚 烯烴聚合物之使用重量比例設在：1:5至3:2之範圍内為宜。 11 1302575 藉由本發明方法，對由含碳前驅物的聚合物與聚烯烴聚合物組成的鞘 材部份及由聚烯烴聚合物組成的芯材部分，直接利用熔融芯鞘型抽絲方 式，可製得鞘材部分含有極細碳前驅物的芯鞘型纖維，為製造極細碳纖維 的基本材料。 【實施内容】 實施例1 使用聚酚路樹脂（Dynea公司製品，固體片狀酚醛樹脂，數目平均分子量 3000)、聚乙烯樹脂（卡達石化公司（qatar PETROCHEMICAL COMPANY LIMITED)，Lotrene，固體粒狀低密度聚乙烯)及聚丙烯樹脂（福聚股份有限 公司製品，福聚烯Pro-fax PT231，固體粒狀聚丙烯均聚物）利用芯鞘型熔 ； . •卜 融抽絲方法，以芯鞘型喷絲嘴之熔融抽絲溫度設定為205t：、抽絲速度設定 為400m/min，原料混合重量比例設定為鞘材部分成分(5〇重量:聚酚駿 20重:g% +聚乙稀30重量％與怒材部分成分(5〇重量％):聚丙烯5〇重董%之 1 - . 條件下直接進行芯鞘熔融抽絲，而後將芯鞘型纖維浸以18%甲醛水溶液與 • 1挪鹽酸水溶液中於95°c下使其形成穩定化（交聯）芯鞠型纖維，用氨水中 和、水洗及乾燥等，最後再行高溫碳化處理，在N2氣體下，於8〇〇^進行碳 化處理1小時後形成極微細碳纖維，纖維直徑為100—600咖。所得的極微 細碳纖維之電子顯微鏡照片，纖維直徑為100一600nm (參閱第3囷）。再於 lOOOt下熱處理時導入水蒸汽，可製得具有極細微多孔的極微細活性碳纖 維。 12 1302575 實施例2 使用中間相瀝青（三菱瓦斯股份有限公司（胞蝴油— :C〇.)製品AR，固體粒狀）及聚丙烯加咖m31，固體粒狀）利用芯勒 型㈣麟方法，⑽觀喷絲嘴之紐㈣溫度蚊為3赃、抽絲速度 設定為5_/min，原料混合重量比例設定為贿部分成分⑽重㈣：中 !間相遞青25重船聚丙烯35重《與芯材部分成細重觸：聚丙稀 40重量％之條件下進行芯鞘型熔融抽絲，芯勒型纖維再以㈣啊條件下 #進行拉伸穩定化處理’最後再行高溫碳化_，在㈣體下，於⑽忙碳 |化形成極微細碳纖維，纖徑為2〇-_咖。所得的極微細碳纖維之的電 」子顯微鏡照)ί，纖維直縣13()nm (翔第4圖）。此極微細碳纖維可再於 .ί &續巾於25GG<t Τ高溫石墨域理得雜微細石墨碳纖維。 -! 依本發明方法’由於製程步驟簡化，可價格低廉的大量生產極微細碳 ；纖維與極微細活性碳纖維’具有高、質輕、導熱性良好及高的導電性， 丨纖維細度可達2〇 - _簡，可廣泛運用於強化複合材料補強材、儲氣材料、 __子電池電極及超高電容器等製品，另爾魏良好，極具有產業上的 可利用性。 、 ! 【圖式簡單說明】 | 第1圖為本發明方法製得的極微細碳纖維之芯鞘型纖維的斷面示意圖。 I 帛2縣本發财法製得的極微細碳齡之職顏料的勒部份及 蕊部份之斷面示意圖。 13 1302575 第3圖為以本發明方法之一實施例製得的極微細碳纖維之電子顯微鏡 照片圖。 第4圖為以本發明方法之另一實施例製得的極微細碳纖維之電子顯微 鏡照片圖。 【主要元件符號說明】 21鞘材中的原纖維部分 22鞘材中的基質部分 23芯材丨I drying, etc., the stabilized fiber thus obtained has a fiber diameter of several tens of micrometers, and finally carbonized under nitrogen for 6 minutes under carbon dioxide, and the carbon fiber is carbonized to decompose the polyethylene to leave a bundle of resin Hesheng's extremely fine carbon fiber has a fiber diameter of about 2〇〇25〇N. This method requires solvent to polymerize the polymer to the other polymer solution towel, and then remove the solution into micron-sized particles. The raw material needs to be processed by solvent treatment, and the production process is complicated and easy to have environmental pollution problems. Japanese Patent Publication No. 2〇〇732-2626 discloses a method for preparing a phenolic fine carbon fiber by using a resin and a polyethylene at a mixing temperature of 12 〇t - 16 (mixed under TC - forming a plastic pellet after a period of time and then 120 02001 melt spinning into fiber is the best method, and in the acidic environment 9 busy _ 24 λ!, then 'aqueous ammonia, deionized water and dry, etc., so that the stabilized fiber has tens of microns The fiber diameter is finally 6 〇〇<t carbonized in nitrogen for a minute, leaving a bundle of 1,002,575 phenolic resin-derived ultrafine carbon fibers. This method requires a mixing time for the phenolic resin and polyethylene, such as phenolic resin. When the polyethylene is about 100g, the kneading time is about 5 minutes. [Explanation] - To solve the above disadvantages of the prior art (small yield, complicated production steps, use of solvent, long production time, high production cost), Carefully researched and reviewed, it was found that polyolefin and carbon-containing polymers are used as the core of the sheath and polyolefin, and the core-sheath type fiber is directly drawn into a carbon-containing ruthenium-driven fiber by a core-sheath type melt-spinning method (see 1)), the core-sheath fiber is stabilized and Φ in a temperature environment. Finally, the stabilized core-sheath fiber is subjected to high-temperature carbonization to a fiber diameter at 6 ° C to 1500 ° C in N2. Very fine carbon fibers of 20 to 800 nm. The extremely fine carbon fibers obtained above can be activated into ultrafine activated carbon fibers under C〇2, steam and air or a mixed gas thereof at 60 〇t-i5〇〇t:. The ultrafine carbon fiber obtained as described above can be further graphitized at a high temperature of 15 〇〇乞 to 3000×: to obtain ultrafine graphite carbon fiber, thereby developing a more efficient ultrafine carbon fiber manufacturing technology using the core sheath melt spinning method. The core-type fiber of Fig. 1 is obtained by melt-extruding a core and a sheath having a core-sheath-shaped φ wire opening to form a core-sheath type fiber, respectively, of two or more polymers. The amount of the polymer used for the core/Leh may range from 90% by weight to 1% by weight to 1% by weight to 9% by weight, and the cross-sectional shape may be concentric, eccentric, or trilobal. The same shape. The aforementioned carbon-containing polymer comprises polyfluorene (Phenol-Formaldehyde; PF), Thermoplastic Polyacrylonitrile (TPAN), Thermoplastic Polyvinyl Alcohol (TPVA), Polyethylene Ethylene (PVC), Mesophase Pitch (mesophase pitch; MP) and other polymers. 1302575 w polyolefins can usually be obtained by copolymerization of polystyrene (10), polyethyl hydrazine (pE), polypropylene (pp), polymethyl decene or hydrazine-containing hydrocarbons. Polyolefins such as materials. ^ can be used to draw silk into secret fiber, the use of the number average molecular weight of 5 (10) ~ the secret of the secret - age 'towels can be twisted or dry twisted unhardened secret fiber, but not easy to melt and wire to pay unhardened The secret fiber is easy to break due to melt drawing. The unhardened secret fiber is then hardened in an aqueous solution of, for example, hydrochloric acid, phosphoric acid, sulfuric acid, and the like, and a mixed aqueous solution such as formic acid, polymethylated, trioxane, tetracyclic xane, or the like. Treating, φ or pre-hardening the outer layer portion of the uncured phenolic fiber in the above mixed aqueous solution, and then neutralizing the fiber with an aqueous solution such as ammonia water, hexamethylenetetramine, urea, or hydroxide to obtain a hardened phenolic resin fiber. Usually, each of the above acidic catalyst, alkaline aqueous solution, and aldehyde is hydrochloric acid, ammonia water, or formaldehyde. Further, the hardened phenolic fiber itself is infusible and has a high carbon content, and can be suitably used as a precursor fiber for carbon fibers. The poly-harvest resin (PF) which can be used in the carbon-containing polymer of the method of the invention has a number average molecular weight of 2000 to 10000, and needs to be directly drawn into a core-sheath type melt-spinning method simultaneously with the polyolefin which is easily melt-spun. Unstabilized age-old polyolefin core-sheath fibers. When spinning with petroleum or carbon-based pitch, isotropic or anisotropic pitch alone, it is usually difficult to obtain a carbon-containing precursor fiber having a fiber diameter of 5/m or less due to air resistance. of. The reason is that the viscosity of the asphalt is highly dependent on the temperature. The rapid release of the tourant from the spinning hole, even if the cold air temperature during the spinning is fully controlled, greatly affects the viscosity of the asphalt of the drawn material. Variation, it is very easy to cause yarn breakage. Therefore, the asphalt raw material is difficult to stretch as high as eight, often need to be drawn into a low fineness of 5~15 ara, so the spun hole discharge is small, 1302575, the back pressure of the wire hole is also more than the general molecular low. Therefore, if there are two viscosity impurities, it is often easy to cause the nozzle hole to block. Therefore, in order to prevent this phenomenon, it is necessary to remove the petroleum-based or carbon-based heavy oil of the crude raw material: the viscosity impurity in the middle. Although the bitumen used as the raw material for the spinning removes the solid content of the impurities, the heat treatment of the distillation, the mesophase pitching, etc., or the oxidation treatment causes a high viscosity of the spinning raw material pitch, which still causes the nozzle hole to be blocked. The phenomenon causes the yarn to break. Therefore, the use of mesophase pitch as the raw material for the spinning can solve the above problems. The mesophase pitch in the carbon-containing polymer suitable for use in the process of the present invention may be blown into the hydrogen by coal tar in the presence of a nickel φ molybdenum-based catalyst at 4 Torr (TC reaction for 120 minutes. The resulting hydrogenated coal tar) Filtration with a strainer, removal of solids, and distillation at 35 (rt, hydrogenated bitumen is obtained. Secondly, heat treatment is carried out at 520 C, 17 mmHg for 7 minutes to obtain mesophase pitch. Mesophase pitch suitable for carbon fiber precursor fibers can be used. The softening point is 235 to 267t, the toluene insoluble content is 731% by weight or more, and the anisotropic amount is 85 to 90·1% of the mesophase pitch. When preparing fine carbon fibers, the process has long been in the form of fine particles. Mixing; techniques for combining different compounds into Weiwei, or techniques for mixing various resins with polyacrylonitrile-based polymers, or techniques for implanting impurity element ions into carbon fibers and modifying the surface layer 'When there is a technique for producing nano-carbon fibers by gas phase generation, or when spinning with petroleum or carbon; cyan, isotropic or anisotropic, it is difficult to obtain a fiber diameter below :including杂诚维, or bribery __ 旨 fresh (10) Wei Si recorded micron granules ' or a resin mixed with polyethylene for a long time after melting or dry spinning and carbonization to prepare very fine carbon fiber, but with less yield The disadvantages of the process, the complicated production steps, the use of solvents, the long production time, and the high production cost are not applicable. 1302575 For this reason, the present invention adopts various processes to enable the use of polyalkylene hydrogen polymers and carbonaceous materials. The polymer is a sheath portion and a polyene hydrogen polymer is a sheath portion, and the core sheath fiber containing the carbon precursor is continuously extracted by the core sheath type spinning mode, and the solvent is not prepared or mixed for a long time. The core sheath fiber is stabilized under temperature-environment, and finally the stabilized core sheath fiber is decomposed by high-temperature carbonization under N2 gas at 6001-15001 to leave a carbon-containing precursor resin-derived diameter of 20 Very fine carbon fiber of ~800nm. For the polymer which can be used as carbon-containing precursor, there are thermoplastic polyphenol aldehyde, thermoplastic polyacrylonitrile φ polymer, thermoplastic polyvinyl alcohol, polyvinyl chloride, mesophase pitch, etc. To be combined as a sheath material, the carbonaceous polymer is directly extracted into a core sheath fiber of a carbonaceous precursor by a core sheath melt spinning method, and the carbonaceous polymer and the polyolefin polymer are partially in the sheath material. The fibril-matrix morphology is formed by direct melt mixing mode (see Figure 2), the carbon-containing polymer is the fibril portion (21 in Figure 2), and the polyolefin is the matrix portion (see 22) in the second figure. The core material is composed of a polyolefin polymer (see 23 in Fig. 2), because it has the advantage of being easy to melt and is not easy to break, so that the core-sheath fiber is supported. The strength of the core-sheath fiber is prevented from prematurely breaking. The core-sheath fiber stabilizes the core-sheath fiber in a temperature environment, and finally stabilizes the core-sheath fiber under the N2 inert gas at 600-15001. After high-temperature carbonization, the polyolefin is decomposed to leave a carbon-containing polymer-derived ultra-fine carbon fiber, and if it is further mixed with C〇2, water vapor and air or a mixed gas atmosphere thereof at 600 - 15001, extremely fine activity can be formed. carbon fiber. Preferably, the sheath portion of the core-sheath type melt-drawing is used in an amount of from 2% by weight to 80% by weight to 80% by weight to 20% by weight to the core portion, and the carbonaceous polymer of the sheath portion is preferred. The weight ratio to the polyolefin polymer used is preferably in the range of 1:5 to 3:2. 11 1302575 The method of the present invention directly utilizes a molten core-sheath type spinning method for a sheath portion composed of a polymer containing a carbonaceous precursor and a polyolefin polymer and a core portion composed of a polyolefin polymer. A core-sheath type fiber in which a sheath portion contains an extremely fine carbon precursor is obtained, which is a basic material for producing extremely fine carbon fibers. [Implementation] Example 1 Polyphenol road resin (Dynea company product, solid sheet phenolic resin, number average molecular weight 3000), polyethylene resin (qatar PETROCHEMICAL COMPANY LIMITED, Lotrene, solid granular low) Density polyethylene) and polypropylene resin (products of Fuju Co., Ltd., Pro-fax PT231, solid granular polypropylene homopolymer) using core-sheath type melting; • Bu-twisting method, core sheath The melt spinning temperature of the spinning nozzle is set to 205t: the spinning speed is set to 400m/min, and the raw material mixing weight ratio is set to the sheath component (5〇 weight: polyphenol spring 20 weight: g% + polyethylene) 30% by weight and part of the anger material (5〇% by weight): polypropylene 5〇重董%1 - . Under direct conditions, the core sheath melts the wire, and then the core-sheath fiber is immersed in 18% formaldehyde solution and 1 ° hydrochloric acid aqueous solution at 95 ° c to form a stabilized (crosslinked) core fiber, with ammonia, water, washing and drying, and finally high temperature carbonization, under N2 gas, at 8 〇〇 ^Formation after 1 hour of carbonization Fine carbon fiber with a fiber diameter of 100-600 ga. The electron micrograph of the extremely fine carbon fiber obtained has a fiber diameter of 100-600 nm (see Section 3). Water vapor is introduced into the heat treatment at 1000 rpm to obtain a very fine Porous very fine activated carbon fiber. 12 1302575 Example 2 Use of mesophase pitch (Mitsubishi Gas Co., Ltd. (cell oil -: C〇.) product AR, solid granular) and polypropylene plus coffee m31, solid granular) Using the core type (four) lin method, (10) view the nozzle of the nozzle (4) temperature mosquito is 3 赃, the spinning speed is set to 5 _ / min, the raw material mixing weight ratio is set to bribe part (10) heavy (four): medium! 25 heavy ship polypropylene 35 weight "with the core material part of the fine touch: 40% by weight of polypropylene under the conditions of core-sheath type melt-drawing, core-type fiber and then (4) under conditions # tensile stabilization treatment 'At the end of the high-temperature carbonization _, under the (four) body, in (10) busy carbon | formation of very fine carbon fiber, fiber diameter of 2 〇 - _ coffee. The electric micro-micrograph of the obtained extremely fine carbon fiber is ί, and the fiber straight county 13 () nm (Xiang 4). The ultrafine carbon fiber can be further processed in a 25GG<t Τ high temperature graphite to obtain a fine graphite carbon fiber. -! According to the method of the present invention, due to the simplification of the process steps, the ultrafine carbon can be produced in large quantities at low cost; the fiber and the extremely fine activated carbon fiber have high, light weight, good thermal conductivity and high electrical conductivity, and the fineness of the ray fiber can be reached. 2〇- _ Jane, can be widely used to strengthen composite materials, gas storage materials, __ sub-cell electrodes and ultra-high capacitors and other products, the other is good, very industrially available. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] Fig. 1 is a schematic cross-sectional view showing a core-sheath type fiber of extremely fine carbon fibers obtained by the method of the present invention. I 帛2 County is a schematic diagram of the cross-section and the core part of the extremely fine carbon-aged pigment produced by the local financial method. 13 1302575 Figure 3 is an electron micrograph of an extremely fine carbon fiber produced by an embodiment of the method of the present invention. Fig. 4 is an electron micrograph photograph of an extremely fine carbon fiber obtained by another embodiment of the method of the present invention. [Main component symbol description] 21 fibril portion in sheath material 22 matrix portion in sheath material 23 core material