2012-02-152024-05-16https://scholars.lib.ntu.edu.tw/handle/123456789/666717摘要：早期科學家認為碳自由態的二維晶體結構，一直被認為在熱力學上一直處於不穩定狀態，無法在一般環境中獨立存在，自從2004年以後，幾個研究團隊陸續成功地將石墨烯分離，並分析此2D晶體結構材料獨特的物性與化性，除單層Graphene 外，雙層或多層石墨烯材料也相繼被探討與分析。奈米石墨烯(Nanoscale Graphene Platelet; NGP)係指石墨層厚度介於0.34~100 nm 的新型奈米碳材料，具有相當優異的物性、化性和機械性質，包括楊氏係數、斷裂強度、熱傳導、高Charge Mobility和比表面積等。目前能夠大量且低成本量產Graphene的製程技術尚未完全開發完成，且產物特性的穩定性控制不易，也將限制其材料的應用開發，預計以Graphene 材料為主的元件系統至少還需五到十年的時間。 本研究之目的在製備石墨烯混成材料。第一部份利用多官能基之樹枝狀聚亞醯胺高分子插層改質氧化石墨並探討其脫層化機制，由二酸酐類之ODPA與三胺類之Jeffamine&reg; T-403合成出帶有外圍胺基及amidoacid鍵結之hyperbranched poly(amic acid)s高分子，改變其比例而獲得不同官能基度與分子量之醯胺酸系列HBPAA11、HBPAA21和HBPAA23，再以熱醯胺化(imidization)方式轉化成醯亞胺形式之相對應hyperbranched polyimides，即HBPI11、HBPI21和HBPI23，控制此雙性超分枝狀高分子的分子量、親疏水性及官能基數目，調控其酸鹼值特性製備成uni-micelle並探究其分子自組裝行為，用以探討雙性超分枝狀高分子插層氧化石墨的作用機制。其次，透過氧化石墨上的活性官能基與過量之T-403進行表面改質，形成共價鍵結化，以此改質氧化石墨上之官能基進行A2+B3之合成超分枝狀高分子，使其in situ成長於氧化石墨表面及層間，透過其逐步撐開層間距並達完全脫層化，因其具有共價鍵結故可在還原為石墨烯時有效分離純化之。 由於有機/無機混成之最終究性質表徵會受到兩者比例之影響；第二部分則試圖導入導電性聚苯胺高分子，合成聚苯胺/氧化石墨混成材料，可透過上述第一部分之含酸基表面改質氧化石墨粉體HBPAA/GO或單純GO，分散於酸性溶液中形成安定分散液，經由進一步氧化聚合反應及還原化而形成聚苯胺/氧化石墨及聚苯胺/石墨烯混成材料，並進行聚苯胺/氧化石墨、聚苯胺/石墨烯混成材料的特性分析，包括XRD、TEM、XPS、Raman酸鹼特性及導電特性等。 <br> Abstract: In this project, a solution process will be used, involving direct molecular exfoliation of graphite oxide (GO) stacked layers, to obtain individual graphene oxide platelets (GOPs) through amphiphilic hyperbranched polymers (HPs). The HPs will be synthesized based on poly(amic acid) and polyimide with terminal amino functionalities. Subsequently, these globular HPs are to be inserted into the interlayer spaces of GO to prepare a series of GO/HP nanohybrids exhibiting intercalated and exfoliated morphologies. The intercalation processes are expected feature various degrees of enlargements occurred to the interlayer spacings, depending on the content of the bulky embedded HPs as investigated by transmission electron microscopy and powder X-ray diffraction analysis. Incorporating the bulky three-dimensional globular structure into the layered GO significantly would influence the solution exfoliation, allowing us to examine the intercalating behavior of GO intergallery. This solution-phase methodology, through direct HP molecular exfoliation, provides the way toward obtaining individual nanosheets, opening up opportunities for platelet-like nanographene oxide materials in many technological applications. In addition, using macromolecular polyaniline (PANI) as a layered space enlarger, individual GOSs at room temperature through in situ polymerization of aniline upon the two-dimensional GOS platform will be attempted. The chemically modified GOS platelets formed unique 2D layered GOS/PANI hybrids, with the PANI nanorods embedded between the GO inter-layers and extended over the GO surface will be investigated by X-ray diffraction and transmission electron microscopy. The dispersion/exfoliation methodology in this project is a facile means of preparing individual GOS platelets with high throughput, potentially expanding the applicability of nanographene oxide materials. Further reduction of these above mentioned platelet-like nanographene oxide materials will also be pursued.石墨烯雙性高分子(amphiphilic)插層機制聚苯胺(polyaniline)超分枝高分子Graphene oxideHyperbranched polymerBasal spacingIntercalationExfoliationNanohybridpolyaniline