微波輔助合成含二萘嵌苯共聚物及其特性研究

Microwave-assisted synthesis and properties of copolymers containing perylene units

謝春宏(Chun-Hong Sie)

指導教授 ： 廖建勛

元智大學/工程學院/化學工程與材料科學學系/碩士(2007年)

https://doi.org/10.6838/YZU.2007.00298

摘要

本研究利用單模聚焦微波反應器，聚縮合不同核心改質之二萘嵌苯(perylene)衍生物和不同長度親水性烷氧基寡聚體，合成聚醯亞胺嵌狀共聚物。以UV-vis吸收和PL放射圖譜，針對含不同改質二萘嵌苯嵌段與不同長度烷氧鏈的聚醯亞胺共聚物，分別探討其溶液和固態薄膜的光性質，及聚集效應的溫度依存性。微波輔助合成使聚醯亞胺反應時間，由傳導加熱的24小時以上，縮短為1小時。二萘嵌苯衍生物於聚縮合前後的UV-vis吸收和PL放射圖譜並無明顯變化，可知烷氧鏈的長度與種類對聚合物的光吸收與放射影響很小。二萘嵌苯上之取代基對光吸收和發射影響較明顯，取代基為推電子基(異丁酚氧基)的共聚物，造成光吸收紅移50nm，光放射紅移90nm；若二萘嵌苯核心為拉電子基(氯)取代，則光吸收稍微藍移10nm，而光放射紅移16nm。觀察溫度對UV-vis吸收的變化，發現π-π堆疊在高溫時被破壞，降低溫度則發現分子堆疊具有可逆性。含無取代二萘嵌苯的聚醯亞胺共聚物，因二萘嵌苯分子團較平坦，具有較佳的堆疊性，使PL呈現凝集的特徵波峰。聚醯亞胺嵌狀共聚物熱性質經TGA和DSC分析判斷，熱裂解溫度(5%裂解)和玻璃轉移溫度分別在235-400℃和100-168℃，顯示共聚物的熱穩定性佳。

關鍵字

微波輔助合成 ； 二萘嵌苯 ； 雙親性嵌段共聚體 ； 凝集態

並列摘要

Single-mode focused microwave reactor was applied for the synthesis of perylene diimide (PDI) derivatives and the followed imidization with various hydrophilic block segements to obtain the amphilic multi-block copolymers. The effect of substitutents of PDI and length of hydrophilic segments on the temperature dependent of chain conformation and aggregate of block polyimides were investigated by electronic absorption and emission spectra in solution and solid state. The reaction time of imidization decreases from 24 h of convection heating to 1h of microwave-assisted synthesis. There is no difference between the electronic spectra of PDI monomer and copolymers, so we know the length of hydrophilic segments have no significant effect on electronic spectra. The electron absorption of S0-S1 transition shifts 10nm toward shorter wavelength and emission shifts 16nm toward longer wavelength for the copolyimide containing electron withdrawing Cl-substituted PDI. On the other hand, the electron donating tertbutyl phenoxy group on PDI results in the red shift of absorption of S0-S1 transition with 50 nm and the red shift of maximum emission with 90 nm. The extent of π-π stacking PDI units decreases with increasing temperature. It also exhibits reversible temperature dependence. The block copolyimide without substiutent of PDI possesses ordered π-π stacking structure and emits light with characteristic emission of aggregated form. The substittents on PDI destroy the π-π stacking order and emit featureless. The thermal behavior of amphilic block copolymers was evaluated with TGA and DSC. The temperatures of 5% weight loss in nitrogen is between 235-400℃, and the glass-transition temperatures is between 100-168℃. It shows the thermal stability of amphilic multi-block copolymers is excellent.

並列關鍵字

Microwave-assisted synthesis ； perylene ； amphilic block copolymer ； aggregate

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