本篇論文當中，我們使用三個步驟分別製備四、六、十二臂鏈之水溶性的星狀導電高分子(PSS/PEDOT和PBA-b-PSS/PEDOT)。首先，以四、六、十二臂鏈烷基鹵化物為起始中心，利用原子自由基轉移聚合方法( atom transfer radical polymerization, ATRP)來合成聚苯乙烯(PS)及聚丙烯酸正丁酯-聚苯乙烯共聚物(PBA-b-PS)。接下來，利用磺酸化試劑(acetyl sulfate)將聚苯乙烯鏈段改質為水溶性聚苯乙烯磺酸。最後，以聚苯乙烯磺酸為模板，藉由in-situ 聚合法將導電高分子PEDOT分別纏繞至星狀聚苯乙烯磺酸(PSS)以及星狀嵌段式聚(丙烯酸正丁酯-苯乙烯磺酸)共聚物(PBA-b-PSS)，形成兩組不同系統之星狀導電高分子。利用紅外光光譜儀(FT-IR)、核磁共振光譜儀 (1H NMR)及凝膠滲透層析儀(GPC, gel permeation chromatography)來鑑定其分子結構及分子量，同時也觀察到星狀高分子其每一臂鏈的分子量分佈相當平均且利用時間的控制得到不同分子量之星狀高分子。另外由可見光光譜(UV-vis) 當中我們發現在800nm至1000nm波長之間有很強的吸收峰，可以有較好的電子跳躍能力。

A three-step synthetic route for preparing an aqueous dispersion of starburst polystyrene sulfonic acid/ polyethylenedioxythiophene (PSS/PEDOT) and poly( n-butyl acrylate-b-styrene sulfonate)/ polyethylenedioxythiophene (PBA-b-PSS/PEDOT) electro-active composites based on core-first method has been developed. First, PS and PBA-b-PS starburst polymers were synthesized by atom transfer radical polymerization (ATRP) method using four, six, and tweleve -functional alkyl halides as core molecules. Second, polymers of PS and PBA-b-PS were converted into water-soluble star PSS and PBA-b-PSS through the sulfonation of PS segments by acetyl sulfate. Finally, 3, 4-ethylenedioxythiophene monomer was in-situ polymerized using ammonium persulfate as an oxidant in the presence of starburst PS and PBA-b-PSS. The UV-visible absorption spectra showed very strong polaron peak between 800nm and 1000nm, indicating the high doping level of PEDOT by PSS during the polymerization process. Chemical structure and molecular weight characteristics of these copolymers were studied by NMR, IR and GPC techniques. The GPC and 1H NMR showed that each polymeric arm of the star exhibited a well-defined chain length and a well-control charge fraction.

中文摘要……………………………………………………………….i
英文摘要……………………………………………………………….ii
目錄…………………………………………………………………….iii
圖目錄………………………………………………………………….vi
表目錄……………………………………………………………….xii
第一章 緒論……………………………………………………………1
1-1 前言……………………………………………………………1
1-2 研究目的………………………………………………………3
第二章 文獻回顧………………………………………………………6
2-1 控制/活性自由基聚合反應……………………………………6
2-1-1 簡介………………………………………………………6
2-1-2 原子轉移自由基聚合之反應機制與控制因…………11
2-1-3 原子轉移自由基聚合之相關用………………………18
2-2 星狀高分子…………………………………………………22
2-2-1 簡介……………………………………………………22
2-2-2 臂鏈起始之星狀高分子……………………………23
2-2-3 核心起始之星狀高分子…………………24
2-2-4 星狀高分子之相關應用………………………………26
2-3導電高分子……………………………………………………28
2-3-1 簡介……………………………………………………28
2-3-2 導電理論與摻雜原理…………………………………32
2-3-3 常見的導電高分子……………………………………34
2-3-4 導電高分子之相關應用………………………………35

第三章 實驗………………………………………………………39
3-1實驗藥品……………………………………………………39
3-2 分析儀器……………………………………………………42
3-3 四、六、十二臂鏈之星狀PSS/PEDOT導電高分子合成……45
3-3-1 星狀核心ATRP起始劑之合成…………………………45
3-3-2 星狀聚苯乙烯之合成……………………………………49
3-3-3 星狀聚苯乙烯磺酸之合成………………………………53
3-3-4 星狀PSS/PEDOT導電高分子之合成…………………56
3-4 四、六、十二臂鏈之導電性星狀嵌段式PBA-b-PSS/ PEDOT
高分子之合成………………………………………………59
3-4-1星狀聚丙烯酸正丁酯巨起始劑之合成…………59
3-4-2 星狀嵌段式聚(丙烯酸正丁酯－苯乙烯)共聚物之合成..63
3-4-3星狀嵌段式聚(丙烯酸正丁酯－苯乙烯磺酸)共聚物之合
成………67
3-4-4導電性星狀嵌段式PBA-b-PSS/PEDOT之合成.....70
第四章 結果與討論…………………………………………………73
4-1 導電性星狀PSS/PEDOT高分子錯合物…………………73
4-1-1 四、六、十二臂鏈星狀核心ATRP起始劑之合成與鑑定
………………………………………………………73
4-1-2 四、六、十二臂鏈星狀聚苯乙烯之合成與鑑定………77
4-1-3 四、六、十二臂鏈星狀聚苯乙烯磺酸之合成與鑑定…90
4-1-4 四、六、十二臂鏈導電性星狀PSS/PEDOT之合成與鑑
定………………………………………………………104
4-2導電性星狀嵌段式PBA-b-PSS/PEDOT高分子錯合物......112
4-2-1 四、六、十二臂鏈星狀核心起始劑之合成與鑑定.....112
4-2-2 四、六、十二臂鏈星狀聚丙烯酸正丁酯巨起始劑之合成
與鑑定................................112
4-2-3 四、六、十二臂鏈星狀嵌段式聚(丙烯酸正丁酯-苯乙烯)
共聚物之合成與鑑定………………………………118
4-2-4 四、六、十二臂鏈星狀嵌段式聚(丙烯酸正丁酯-苯乙烯
磺酸)共聚物之合成與鑑定……………………………130
4-2-5四、六、十二臂鏈導電性星狀嵌段式PBA-b-PSS/PEDOT
之合成與鑑定…………………………………………135
4-3 導電度之量測………………………………………………142
4-3-1 量測方法………………………………………………142
4-3-2 量測結果………………………………………………143
第五章 結論………………………………………………………144
參考文獻…………………………………………………………146

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