導電性星狀嵌段式高分子前驅物之合成與分析

Synthesis and characterization of electro-active starburst block copolymer precursors.

黃培澤(Pei-Ze Huang)

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(2004年)

https://doi.org/10.6342/NTU.2004.01489

摘要

在本研究中，我們分別以四、六及十二臂鏈烷基鹵化物為起始劑，利用原子轉移自由基聚合法來聚合丙烯酸正丁酯，形成具有不同臂鏈之星狀聚丙烯酸正丁酯高分子，並以此為基礎合成出星狀嵌段式高分子前驅物；其包含利用ethanolamine與星狀聚丙烯酸正丁酯末端Br基團經由取代反應將末端改質為羥基，最後利用酯化反應將噻吩單體以共價鍵結的形式衍生在星狀體的末端，該噻吩末端基可進一步進行氧化聚合反應，形成電活性星狀嵌段式高分子。我們利用1H-NMR及13C-NMR證明不同臂鏈起始劑之化學結構與組成；高分子分析方面則分別利用1H-NMR證實結構及計算平均聚合度，並由GPC測量星狀體之分子量及分子量分佈。
另外，我們更進一步將四臂鏈高分子前驅物以氧化聚合法聚合，將己基噻吩單元連接至星狀體各臂鏈之末端形成共聚物，並且分別以1H-NMR及FT-IR證實此四臂鏈導電性嵌段式高分子之結構，亦由GPC得到分子量及分子量分佈。其UV-vis吸收光譜圖則明顯顯示聚己基噻吩鏈段組成之外殼所產生之紅位移現象。

關鍵字

聚丙烯酸正丁酯 ； 吩噻高分子前驅物 ； 星狀高分子 ； 氧化聚合 ； 酯化反應

並列摘要

In this study, a novel route for preparing electro-active starburst macromolecular precursors based on core-first method has been developed. First, poly(n-butyl acrylate) stars were synthesized by ATRP (atom transfer radical polymerization) method using four, six or twelve functional alkyl halides as core molecules. Theω-bromo ends of these star polymers were subsequently modified to generate the same number of hydroxyl groups. Finally, the hydroxyl ends of the star polymers were then esterified with 3-thiophene acetic acid to form thiophene-capped starburst poly(n-butyl acrylate). The corresponding structures were identified by 1H-NMR and 13C-NMR. The studies of molecular weight characteristics of these thus-prepared star polymers were performed on 1H-NMR and GPC instruments.
The preparation of electroactive starburst poly(n-butyl acrylate-b-3-hexyl thiophene) copolymers was carried out by growing poly(3-hexyl thiophene) chains from the terminated thiophene unit of four-armed stars via oxidative polymerization method. Chemical structure and molecular weight characteristics of these copolymers were studied by IR、NMR, and GPC techniques. The apparent red shift of the absorption peaks of the star copolymers compared with the thiophene-capped PBA stars in the UV-vis spectra reveals the formation of the conjugated chains on the end of each arm.

並列關鍵字

poly(n-butyl acrylate) ； star polymer ； esterification ； thiophene ； oxidative polymerization ； polymer precursor

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