Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3821
標題: 利用巨環形碳二亞胺改質多壁奈米碳管生成醯基尿素及其在複合材料上之應用
Functionalization of multi-walled carbon nanotubes with macro-cyclic carbodiimide into poly-acylurea for composite applications
作者: 陳冠霖
Chen, Kuan-Lin
關鍵字: carbon nanotube
奈米碳管
carbodiimide
acylurea
blocked isocyanate
碳二亞胺
醯基尿素
封閉型異氰酸鹽
出版社: 化學工程學系所
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摘要: 本研究在多壁奈米碳管(multi-walled carbon nanotubes)上從事化學修飾、分散性測試,以及複合材料的製備。藉由簡單的溶液(solution blending)法,將改質過的碳管與聚羥基高分子(Polyol)基材進行混摻,獲得奈米複合材料。 為了提升奈米碳管於高分子基材中的分散性,必須先在碳管表面進行兩步驟的化學修飾。首先將碳管浸入8N硝酸水溶液中於110℃下迴流3小時,進行羧化處理,使其表面氧化並帶有羧基(-COOH)官能基。接著利用巨環形碳二亞胺(Macrocyclic carbodiimide,MC-CDI),在溫和條件下(60℃),羧化碳管會與MC-CDI反應生成巨環形醯基尿素(CNT-Macrocyclic-acylurea,CNT-MC-ACU),獲得”反應型”奈米碳管。所謂的”反應型”主要係由於碳管上的ACU為一種封閉型異氰酸鹽(blocked isocyanate),在高於180℃下會斷鍵開環而再生具有高反應性的異氰酸鹽(isocyanate)官能基,透過此獨特的性質使其可與帶有羥基之高分子基材反應交聯成氨基甲酸酯(carbamate group),進而改善複材的熱性質、機械性質及導電性質等等。 結果顯示成功的利用二種分子量各為496及1,004的MC-CDI來完成碳管改質,二種改質之CNT並可穩定地分散於THF、DMF、NMP等有機溶劑中長達半年以上。接著利用溶液混摻方式將碳管分別與分子量7,070之聚羥基壓克力共聚物及分子量60,000之典型聚胺酯彈性體基材製備高分子奈米複合材料,進行高溫開環前後,對於複材之物理性質的探討。結果顯示,CNT-MC-ACU經混摻後能均勻分散於高分子基材中,有效提升複材的熱性質與機械性質。添加3wt% CNT-MC-ACU的複材在高溫開環後,熱裂解溫度與玻璃轉移溫度分別提升了51℃及11℃;而拉伸強度與延伸率亦同時增加了2.1MPa(115%)及99%,成功達到碳管與基材分子強化的目的。此獨特性質完整發揮了MC-CDI有機改質碳管上其封閉型異氰酸鹽的優點,將可延伸此策略於難燃性複合材料之領域的應用來發展。
We have carried out a successful chemical functionalization on multi-walled carbon nanotube (MW-CNT) through addition of marcocyclic carbodimides (MC-CDI) onto the carboxylic groups of CNT as a means for its dispersion promotion in organic media. In the meantime, the formed ringed acylurea groups attached to the modified CNT also can serve as latent reactive groups capable of crosslinking polymers in formation of composites with chemically bonding to CNT. In the study, the pristine MW-CNT was first treated with 8 N of nitric acid at 110oC for 3 hours for introducing anchoring carboxylic groups on the CNT walls. Then, MC-CDIs with molecular weights of 496 and 1,004 were mixed with the carboxylic acid bearing MW-CNT at 60 oC in formation of the ringed-acylurea on CNT. The ringed-acylurea functionalized CNT was found to disperse readily in most organic solvents of polar and medium-polar solvents to form homogenous solutions for six months without precipitation. The acylurea functionalized CNTs could also be blended into polymeric solutions. Upon heating at 180 oC or above, isocyanate groups was generated on CNT through ring-opening reactions of the acylurea groups in indicating that the acylurea functionalized CNT can serve as blocked-isocyanate crosslinkers for curing polymeric systems. In order to demonstrate crosslinking potentials, the ringed-acylurea modified CNTs were blended individually with two hydroxyl containing polymer systems, a polyacrylate co-plymer of 7,070 molecular weights and a typical elastomeric polyurethane of about 60,000 molecular weight. The physically blended mixtures were heated to 180 to 200 oC for the curing tests. It was observed that homogenous CNT composites were made both in physically blended and heat-treated CNT composites. Moreover, great enhancements of thermal and mechanical properties were observed at three weight percent addition of the functionalized CNTs. It was observed that the degree of enhancement is more prominent in all those composites which have been fully cured. Although the selection of the polymer systems and curing conditions are still needed for further optimization, our functionalization and demonstration of blocked-isocyanate chemistry on CNT surfaces shown by the ringed-acylurea groups appear to be novel and useful for future CNT composite applications.
URI: http://hdl.handle.net/11455/3821
其他識別: U0005-1808201015565200
文章連結: http://www.airitilibrary.com/Publication/alDetailedMesh1?DocID=U0005-1808201015565200
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