合成分子量均一之聚芴導電高分子及利用偶合反應合成導電/絕緣之團聯共聚高分子

Abstract

本研究是利用Suzuki-Miyaura 偶合反應合成出一系列具均一分子量分布(monodisperse)的聚芴高分子 (poly(9,9-di-n-octyl-2,7-fluorene), PFO) ，並利用帶有醛基的金屬鈀錯合物為觸媒合成出尾端帶有醛基的聚芴高分子，再以陰離子聚合法合成兩組不同分子量大小且分子量分布(polydispersity index, PDI) 均在1.2以內的聚2乙烯吡啶 (poly(2-vinylpyridine) ，再將兩種高分子進行尾端偶合反應，得到兩組導電─絕緣團聯共聚高分子。 將四組聚芴高分子及兩組共聚高分子進行基本的性質測試。包含以膠體滲透層析儀 (Gel Permeation Chromatography, GPC) 測量其分子量與分子量分布情形、以質譜儀 (MALDI-TOF) 鑑定尾端官能基結構、以及用紫外光─可見光光譜儀 (UV-Vis Spectrophotometer) 和螢光光譜儀 (Photoluminescence) 量測其光學性質，還有利用熱重分析儀 (Thermogravimetric Analyzer, TGA) 及微差掃描卡計 (differential scanning calorimeter, DSC) 進行熱性質量測，了解團聯共聚高分子與原組成高分子的性質差異之處。也藉由小角度X光散射 (small angle X-ray scattering, SAXS)、廣角度X光散射 (wide angle X-ray scattering, WAXS) 及穿透式電子顯微鏡 (Transmission Electron Microscope, TEM) 來偵測聚芴高分子及共聚高分子的微結構排列情形、使用偏光顯微鏡 (polarized optical microscopy, POM) 來觀測相轉換的情形。總結以上的數據資訊，獲得不同分子量之聚芴高分子、以聚芴和聚2乙烯吡啶所組成的團聯共聚高分子之基本特性與其在微結構方面的認識。

In the thesis, a series of low polydispersity poly(9,9-di-n-octyl-2,7-fluorene) (PFO) was synthesized by Suzuki-Miyaura coupling reaction, and was tried to use arylpalladium(II) halide complexes with formyl group as catalysts to convert aldehyde-terminated PFO. In addition, a monodispersed homopolymer living anion of poly(2-vinyl pyridine) (P2VP) was synthesized via anionic polymerization using sec-butyllithium as an initiator. Block copolymers of PFO-b-P2VP were synthesized by a nucleophilic addition reaction between P2VP living anion and aldehyde-terminated PFO. Two PFO-b-P2VP block copolymers with different PFO/P2VP molar ratio were successfully synthesized with high yield. The synthesized PFO and PFO-b-P2VP were characterized by using various techniques including Gel Permeation Chromatography (GPC), MALTI-TOF, UV-Vis, Photoluminescence (PL), Thermogravimetric Analyzer (TGA), Differential Scanning Calorimeter (DSC). Furthermore, we used the small angle X-ray scattering (SAXS), wide angle X-ray scattering (WAXS) and Transmission Electron Microscope (TEM) techniques to study the crystalline structures of homo PFO and PFO in the PFO-b-P2VP nanostructures, and used Polarized Optical Microscopy (POM) to observe phase transition phenomenon. It was found that the different properties and microstructures of PFO and their block copolymers.