具吡咯基取代之三苯胺基團之高性能高分子 的合成與電化學及光致發光性質之研究

Synthesis, Electrochemistry and Photoluminescence of High-Performance Polymers Bearing Pyrrole-substituted Triphenylamino Groups

蔣加聖(Chia-Sheng Chiang)

指導教授 ： 蕭勝輝

大同大學/工程學院/化學工程學系所/碩士(2007年)

摘要

本論文包含兩個研究主題，第一部分是在探討含有4-(N-pyrrolyl)triphenylamine結構的新穎芳香族聚(胺-醯胺)之合成與性質。一種新型由吡咯衍生及含有三苯胺結構的二羧酸4,4'-dicarboxy-4"-(N-pyrrolyl)triphenylamine, 是由4-fluorobenzonitrile 和4-(N-pyrrolyl)aniline的鈉塩進行-芳香親核取代反應，然後在鹼性條件下水解二氰中間產物而得到。一系列固有黏度介於0.52-0.88 dL/g 的聚(胺-醯胺)是由此二羧酸單體與各種芳香族二胺以直接磷酸化聚縮合反應製備而得。這些聚(胺-醯胺)都可溶於多數的有機溶劑並可經溶液重鑄成強韌的薄膜。這些聚(胺-醯胺)具有高的玻璃轉化溫度 (Tg＝275–326℃) 及在氮氣下10 % 的熱重量損失溫度在450 ℃以上，顯示出不錯的熱穩定性。這些聚合物溶在NMP的稀薄溶液的光激發光譜顯示出在波長446-455 nm的藍光區有中等到強的放光現象，其量子效率最高可達38 %。
本論文第二部分係探討以含有吡咯基取代的三苯胺結構的新穎poly(amine-hydrazide)s及poly(amine-1,3,4-oxadiazole)s之合成與性質。兩種新穎之poly(amine-hydrazide)s的聚合物，是由4,4'-dicarboxy-4"-(N-pyrrolyl)triphenylamine 與 terephthalic dihydrazide (TPH) 和 isophthalic dihydrazide (IPH) 經由Yamazaki磷酸化反應所合成出來。這些poly(amine-hydrazide)s 可溶於多數的有機溶劑，例如N-methyl-2-pyrrolidone (NMP) 和 N,N-dimethylacetamide (DMAc) 並可經它們的溶液鑄成強韌的薄膜。由IPH 衍生的 poly(amine-hydrazide)在NMP溶液中的光激發光譜顯示出在波長478 nm的藍光區有強的放光現象，其量子效率可達33 %。經由示差掃描量熱分析 (DSC) 結果顯示，這兩種分別由TPH 與IPH衍生的hydrazide聚合物的玻璃轉化溫度分別為252℃以及235℃，並且會在300-400℃的溫度範圍內脫水轉化成相對應的poly(amine-1,3,4-oxadiazole)s。這兩個poly(amine-1,3,4-oxadiazole)s的玻璃轉化溫度 Tg在266–268℃附近，在氮氣下10 % 的熱重量損失溫度可在543 ℃以上，和在氮氣下800℃時的焦炭殘餘量可高達70%。與不含吡咯側鏈基的相類似聚合物比較時，本論文所合成的poly(amine-amide)s及poly(amine-hydrazide)s具有相對較差的電化學穩定性。

關鍵字

吡咯 ； 三苯胺 ； 聚醯胺 ； 光致發光

並列摘要

This thesis consists of two parts. The first part describes the synthesis and properties of novel aromatic poly(amine-amide)s containing 4-(N-pyrrolyl)triphenylamine moieties. A new pyrrole-derived triphenylamine-containing dicarboxylic acid monomer, 4,4'-dicarboxy-4"-(N-pyrrolyl)triphenylamine, was synthesized via the aromatic nucleophilic fluoro-displacement reaction of 4-fluorobenzonitrile with 4-(N-pyrrolyl)aniline using sodium hydride as the base, followed by alkaline hydrolysis of the dinitrile intermediate. One series of poly(amine-amide)s with inherent viscosities of 0.52-0.88 dL/g were prepared by the direct phosphorylation polycondensation from the synthesized diacid monomer with various aromatic diamines. The resultant poly(amine-amide)s were readily soluble in a variety of organic solvents and could afford strong and tough films via solution casting. These aromatic poly(amine-amide)s have useful levels of thermal stability associated with high glass transtion temperatures (Tg＝275-326 ℃) and 10 % weight loss temperatures in excess of 450 ℃ in nitrogen. In dilute NMP solution, these polymers exhibited a medium to strong photoluminescence in the blue region at 446~455 nm with quantum yield up to 38 %.
The second part of this thesis investigates the synthesis and properties of novel poly(amine-hydrazide)s and poly(amine-1,3,4-oxadiazole)s containing pyrrolyl-substituted triphenylamine units. Two novel poly(amine-hydrazide)s were synthesized from 4,4'-dicarboxy-4"-(N-pyrrolyl)triphenylamine with terephthalic dihydrazide (TPH) and isophthalic dihydrazide (IPH) via the Yamazaki phosphorylation reation. The obtained poly(amine-hydrazide)s were easily soluble in polar organic solvents such as N-methyl-2-pyrrolidone (NMP) and N,N-dimethylacetamide (DMAc) and could be solution-cast into free-standing or strong films. The poly(amine-hydrazide) derived from IPH exhibited strong blue photoluminescence at 478 nm in NMP with 33 % quantum yield. Differential scanning calorimetry (DSC) indicated that these two hydrazide polymers had Tg values of 252℃ (from TPH) and 235℃ (from IPH), respectively, and could be thermally cyclodehydrated into the corresponding oxadiazole polymers in the range of 300-400℃. The resulting poly(amine-1,3,4-oxadiazole)s exhibited Tg around 266-268℃, 10 % weight-loss temperature in excess of 543℃, and char yield at 800℃ in nitrogen higher than 70 %. In comparison with the parent triphenylamine-based analogs without the pyrrole pendent group, the newly synthesized poly(amine-amide)s and poly(amine-hydrazide)s containing the 4-(N-pyrrolyl)triphenylamine unit revealed a relatively decreased electrochemical stability.

並列關鍵字

Polyamide ； Photoluminescence ； Pyrrole ； Triphenylamine

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