新型聚噻吩衍生物之合成與性質研究

Synthesis and characterization of novel poly(thiophene derivative)s

陳台偉(Tai-Wei Chen)

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(2006年)

https://doi.org/10.6342/NTU.2006.00811

摘要

本論文包含兩個研究重點。第一個部分裡，我們利用transetherification合成了兩個3,4-propylenedioxythiophene 的衍生物，分別是benzyl 3,4-dihydro-3-methyl-2H-thieno[3,4-b][1,4] dioxepine -3-carboxylate (ProDOT-PH)和dodecyl 3,4-dihydro-3-methyl-2H-thieno [3,4-b][1,4]dioxepine-3-carboxylate (ProDOT-COOC12H25)。藉著使用氧化聚合反應，可以得到一個不溶於一般溶劑的PProDOT-PH以及一個可以溶於一般溶劑的PProDOT-COOC12H25。其中，我們利用1H-NMR證實PProDOT-COOC12H25結構，並由GPC測量PProDOT-COOC12H25之分子量及分子量分佈，利用UV測其吸收光譜特徵。我們並利用電化學聚合法來聚合兩種ProDOT衍生物，並得到良好的高分子薄膜。我們施加不同的電壓(分別是-0.1V— 0.6V以及-0.1V— 0.7V)來得到其氧化還原態，並得到不同的穿透度對比。
在第二個部分裡，我們並合成了一個星狀導電性共聚合物，這個共聚合物是以帶有12臂鏈poly(n-butyl acrylate) (12PBA) 以及 poly(2-dodecyl-2,3- dihydrothieno[3,4-b][1,4]dioxine)(PEDOT-C12H25)所構成。12PBA先以ATRP的方法合成後，末端基在改質成帶有thiophene的12PBA-TH。相關改質的結構以1H-NMR 和 GPC 分析鑑定。另一種單體則是利用transetherification合成2-dodecyl-2,3-dihydrothieno [3,4-b][1,4] dioxine (EDOT-C12H25)。兩者再以氧化聚合方式合成共聚合物。並利用IR、1H NMR和 GPC來分析。IR及1H NMR證實了有共聚合物的存在，但GPC則顯示尚有線性PEDOT-C12H25未分離乾淨，還需有進一步的純化分離。

關鍵字

聚噻吩衍生物 ； 星狀導電性共聚合物 ； 導電性高分子

並列摘要

This thesis mainly consists of two parts. In the first part, two 3,4-propylenedioxythiophene derivatives, benzyl 3,4-dihydro-3-methyl -2H-thieno[3,4-b][1,4]dioxepine-3-carboxylate (ProDOT-PH) and dodecyl 3,4-dihydro-3-methyl-2H-thieno[3,4-b][1,4]dioxepine-3- carboxylate (ProDOT-COOC12H25) were synthesized by transetherification. PProDOT-PH, which was polymerized by oxidative chemical polymerization, was insoluble in common solvents; however, PProDOT-COOC12H25 was soluble. Chemical structure and molecular weight characteristics of PProDOT-COOC12H25 was studied by IR, 1H NMR, GPC and UV-vis techniques. Both ProDOT-PH and ProDOT-COOC12H25 could form polymer films by electrochemically polymerization method. The oxidized form and reduced form of PProDOT-PH and PProDOT-COOC12H25 with different transmittance contrast were produced under applied certain potentials (-0.1V— 0.6Vand -0.1V— 0.7V).
In the second part, electro-active starburst copolymers of 12-arms poly(n-butyl acrylate)(12PBA) and poly(2-dodecyl-2,3-dihydrothieno [3,4-b][1,4]dioxine)(PEDOT-C12H25) were synthesized. 12PBA was synthesized by the ATRP (atom transfer radical polymerization) method, and the end groups of polymer arms were modified to generate thiophene-capped starburst 12PBA-TH. The corresponding structures were identified by 1H-NMR. The studies of molecular weight characteristics of these star polymers were performed on 1H-NMR and GPC instruments. The monomer of 3,4-ethylenedioxythiophene was prepared by transetherification to give 2-dodecyl-2,3-dihydrothieno [3,4-b][1,4]dioxine (EDOT-C12H25). The preparation of electroactive starburst 12PBA-b-PEDOT-C12H25 copolymers was carried out by growing PEDOT-C12H25 chains from the terminated thiophene unit of 12-armed stars via oxidative polymerization method. Chemical structure and molecular weight characteristics of these copolymers were studied by IR, 1H NMR and GPC techniques. It was confirmed by IR and 1H NMR that the copolymer was successfully synthesized. However, the GPC data implied the existence of plenty of linear PEDOT-C12H25, indicating the need of the development of further purification process.

並列關鍵字

transetherification ； ProDOT ； starburst copolymers

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