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研究生： 彭俐嘉
Li-Jia Peng
論文名稱： 新型含Benzo[c]cinnoline結構的 1,3,4-噁二唑共軛高分子之合成及表徵
Synthesis and Characterization of Novel Conjugated Poly(1,3,4-oxadiazole) Containing Benzo[c]cinnoline moiety
指導教授： 陳志堅
Jyh-Chien Chen
口試委員: 蕭勝輝
Sheng-Huei Hsiao
劉貴生
Guey-Sheng Liou
許應舉
Ying-Gev Hsu
王英靖
Ing-Jing Wang
學位類別： 碩士
Master
系所名稱： 工程學院 - 材料科學與工程系
Department of Materials Science and Engineering
論文出版年： 2010
畢業學年度： 98
語文別： 中文
論文頁數： 71
中文關鍵詞： 共軛高分子 、電子傳輸層
外文關鍵詞： Benzo[c]cinnoline, conjugated polymer
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    • 本研究使用benzo[c]cinnoline結構的二酸分別與hydrazine sulfate於polyphosphoric acid(PPA)中進行一步法及isophthalic dihydrazide (IPH)與terephthalic dihydrazide (TPH)進行兩步法合成poly(1,3,4-oxadiazole)。在主鏈中導入缺電子的芳香雜環benzo[c]cinnoline及1,3,4-oxadiazole結構，提升π共軛系統的電子親和力。在單體合成上我們利用2,5-dibromonitrobenzene為起始物，經過四個步驟成功地合成3,8-dicarboxylicacidbenzo[c]cinnoline，這是第一次使用這種作法成功合成此單體，且有較好的產率。並利用此一單體分別與hydrazine sulfate、terephthalic dihydrazide、isophthalic dihydrazide合成出：三種poly(1,3,4-oxadiazole)
    – POXD(1)、POXD(I)及POXD(T)；兩種polyhydrazide – PHA(I)、PHA(T)。POXD的溶解度較差但均有良好的熱穩定性，熱分析儀顯示POXD(1)的Tg(DSC)為351℃，5％熱重損失(Td,5％)POXD(1)為456℃、POXD(I)為459℃、POXD(T)為469℃。在UV-Vis光譜中POXD(1)、POXD(I)、POXD(T)在硫酸溶液中之最大吸收波長分別在328、325及334；PL光譜顯示POXD(1)、POXD(I)、POXD(T)分別可放出497、459和474的藍光。根據循環伏安法所量測POXD(I)及POXD(T)的還原圖譜，包含兩個峰形，而其前軀體polyhydrazide(PHA)系列也有一個峰形，顯示主鏈上之兩個雜環都具有還原能力。POXD(I)及POXD(T)之ELUMO值分別為3.42、3.45(eV)，EHOMO值均為6.20(eV)，展現出良好的電子親和力及電洞阻隔能力。

    The objective of this study is to introduce Benzo[c]cinnoline structure into the main chain of the poly(1,3,4-oxadiazole). The incorporation Benzo[c]cinnoline structure has been proven to enhance the electron affinity of poly(1,3,4-oxadiazole) effectively. The novel conjugated polymers in this study were synthesized by using 3,8-Benzo[c]cinnoline dicarboxylic acid with hydrazine sulfate through One-Step reaction and isophthalic dihydrazide、terephthalic dihydrazide through Two-Step reactions. The formed polyhydrazides PHA(I)、PHA(T) have molecular weights in the range of 6000 to 9000 (measured by GPC in DMAc and calibrated by polystyrene standards) and inherent viscosity 0.2~0.23 (determined in NMP, 0.5 g / dL at 30 ℃). These two polymers exhibit excellent solubility in common organic solvents such as NMP、DMAc and DMF. The formed poly(1,3,4-oxadiazole) s POXD(1)、POXD(I)、POXD(T) shows the glass transition at 230~310 ℃(by DSC ) , and the 5% decomposition temperature above 450 ℃. From Uv-visible spectrometric analysis, the maximum absorptions occur at the wavelength λmax between 325 and 345nm.From photoluminesce spectrum, the formed polymer shows maximum emission at wavelength 497、459、474nm(blue light), in sulfuric acid solution. The energy gap (Eg) calculated by the cycle voltammetry test (reduction onset ) ranges from 2.76 to 2.79eV. POXD(I)and POXD(T) show excellent electron withdrawing ability ,EHOMO~6.2eV and ELUMO~3.4eV.The results proven that our novel Conjugated Poly(1,3,4-oxadiazole) Containing Benzo[c]cinnoline moiety are expected to be applicable for electron-transporting materials.

    摘要 I 目錄 II-III Scheme索引 IV Figure索引 V-VI Table索引 VII 第一章 緒論 1 1.1前言 1 1.2有機發光二極體的發展歷程 1 1.3基礎理論 2 1.3.1共軛高分子導電理論 2 1.3.2 共軛系統內各種參數之間的關係 4 1.3.3 螢光與磷光 5 1.3.4影響螢光的因素 6 1.3.5有機電激發光元件發光原理 7 1.3.6高分子電激發光三系統 8 第二章 文獻回顧 10 2.1前言 10 2.2 1,3,4-oxadiazole(OXD)合成方法 12 2.1.1小分子OXD 12 2.2.2高分子POXD(Poly-1,3,4-Oxadiazole) 14 2.3菲環與似菲環(Phenanthrene like)及Benzo[c]cinnoline之文獻回顧 18 2.4研究動機 22 第三章 實驗 23 3.1 實驗儀器 23 3.2 實驗材料 24 3.3 合成方法 26 3.3.1單體製備流程 26 3.3.1.1銅粉活化 26 3.3.1.2 4,4’-Dibromo-2,2’-dinitrobiphenyl (1) 26 3.3.1.3 3,8-Dibromobenzo[c]cinnoline (2) 26 3.3.1.4 3,8-Dicyanobenzo[c]cinnoline (3) 27 3.3.1.5 3,8-Dicarboxylicacidbenzo[c]cinnoline (4) 27 3.3.2 高分子製備流程 28 3.3.2.1一步法合成POXD：POXD(1) 28 3.3.2.2兩步法前軀體Polyhydrazide：PHA(I) 28 3.3.2.3兩步法前軀體Polyhydrazide：PHA(T) 29 3.3.2.4 兩步法熱關環合成POXD：POXD(I)、POXD(T) 29 第四章 結果與討論 30 4.1 單體製備 31 4.2 高分子的合成 42 4.3 高分子的熱性質 51 4.4 高分子的光學性質 56 4.5 高分子的電化學性質 60 第五章 結論 67

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