導電性星狀高分子與星狀嵌段式共聚物之合成與性質分析

Synthesis and characterization of electro-active materials prepared from starburst homopolymer and block copolymer

王邑文(Yih-Wen Wang)

指導教授 ： 王立義

國立臺灣大學/工學院/高分子科學與工程學研究所/碩士(2005年)

https://doi.org/10.6342/NTU.2005.01556

摘要

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。

關鍵字

導電高分子 ； 星狀高分子 ； 原子轉移自由基聚合 ； 聚丙烯酸正丁酯 ； 聚苯乙烯磺酸 ； PSS/PEDOT

並列摘要

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.

並列關鍵字

star polymer ； PEDOT/PSS ； polystyrene ； conducting polymer ； poly(n-butyl acrylate) ； ATRP

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