交聯性聚丙烯酸正丁酯-聚噻吩星狀共聚物之合成與性質分析

Abstract

為了改善導電高分子之加工及機械性質，本研究中，我們發展出內核為星狀聚丙烯酸正丁酯，外殼為導電性高分子鏈段的星狀高分子共聚物。首先，我們合成出十二臂鏈之星狀起始劑{2,2',2',2',2',2'-(2,2',2'-(4,4',4'-(ethane-1,1,1-triyl)tr is(benzene-4,1-diyl))tris(oxy)tris(oxomethylene)tris(2-methylpropane-3,2,1-triyl))hexakis(oxy)hexakis(oxomethylene)hexakis(2-methylpropane-3,2,1-triyl)dodecakis(2-bromo-2-methylpropanoate)}再利用原子轉移自由基聚合反應(atom transfer radical polymerization, ATRP)製備出星狀高分子。此星狀體以擁有良好加工性質的聚丙烯酸正丁酯[poly (n-butyl acrylate)] (PBA)為核心，並利用末端改質反應與含醛基寡噻吩衍生物M1、M2連結，使星狀體末端帶有導電高分子單體形成交聯型導電性高分子前驅物。我們透過紫外-可見光光譜儀(UV-Vis)、紅外光線光譜儀(FT-IR)、動態光散射儀(DLS)、核磁共振光譜儀(1H-NMR)、凝膠滲透層析儀(GPC)來鑑定分子結構與分子量。此前驅物高分子具有高溶解度、加工性好以及良好基材附著性。之後，我們將此前驅物製備成薄膜，並利用固態氧化交聯法使導電高分子單體鏈段交聯聚合形成交聯型導電性高分子共聚物導電薄膜。此薄膜利用紫外-可見光光譜儀(UV-Vis)、四點碳針(four point probe meter)、螢光發射光譜(PL)量測其光電性質。

In order to improve the processability and mechanical properties of conducting polymers, a new type of starburst copolymer containing poly(n-butyl acrylate) as core and conjugated thiophene derivatives segments as shell was synthesized. Firstly, 12-armed starburst poly(n-butyl acrylate) (12-PBA) was prepared by the atom transfer radical polymerization method using { 2,2',2',2',2',2'-(2,2',2'-(4,4',4'-(ethane-1,1 ,1-triyl)tris(benzene-4,1-diyl))tris(oxy)tris(oxomethylene)tris(2-methylpropane-3,2,1-triyl))hexakis(oxy)hexakis(oxomethylene)hexakis(2-methylpropane-3,2,1-triyl)dodecakis(2-bromo-2-methylpropanoate), 12-armed ATRP initator } as initator. Then, the end groups of 12-PBA were modified to generate thiophene derivatives-caped starburst 12-PBA-M1 and 12-PBA-M2. The chemical structure and molecular weight characterization of these copolymers were studied by UV-Vis, 1H-NMR, FT-IR, DLS and GPC techniques. Finally, electrically conductive thin films were fabricated via the solid-state oxidative cross-linking method using FeCl3 as oxidant and their optoelectronic properties were investigated by UV-Vis, PL and four-point probe. The thus-produced conductive film exhibited excellent flexibility, good adhesion to glass substrate and low conductivity percolation threshold.