新型具三苯胺衍生物之熱固性環氧樹脂合成與電致變色特性之研究

Abstract

本研究所使用的三種二胺單體4,4'-diamino-4'-methoxytriphenylamine， N,N'-bis(4-aminophenyl)-N,N'-di(4-methoxylphenyl)-1,4-phenylenediamine和 N,N'-bis(4-aminophenyl)-N,N'-di(4-methoxylphenyl)-4,4'-biphenyldiamine在本實驗室之前發表的文獻中已合成過。本論文分為四個章節，第一章為總體序論。第二章包含了以4,4'-diamino-4'-methoxytriphenylamine， N,N'-bis(4-aminophenyl)-N,N'-di(4-methoxylphenyl)-1,4-phenylenediamine和 N,N'-bis(4-aminophenyl)-N,N'-di(4-methoxylphenyl)-4,4'-biphenyldiamine為主體與diglycidyl ether bisphenol A經由熱硬化合成出一系列新型的熱固性電致變色環氧樹脂。第三章包含了以4,4'-diamino-4'-methoxytriphenylamine和N,N'-bis(4-aminophenyl)-N,N'-di(4-methoxylphenyl)-1,4-phenylenediamine為主體與脂肪族環氧樹脂triglycidyl isocyanurate 經由熱硬化合成出一系列新型的熱固型色淡電致變色環氧樹脂。第四章為結論。這四個系列新型三苯胺取代衍生之熱固型環氧樹脂之合成與基本特性、電化學及電致變色性質已被研究與比較。所有的熱固型環氧樹脂皆有好的玻璃轉移溫度、出色的熱穩定性及機械性質。在利用電化學與光譜電化學的方法下，大部分的熱固型環氧樹脂也展現很好且可逆的電致變色特性。相較於三苯胺對應的聚醯胺，導入三苯胺衍生物進入環氧樹脂可有效的增加氧化的階段及呈現多段電致變色的性質。此外，由於脂肪族的環氧樹脂含有較剛硬的結構，故相較於芳香族的環氧樹脂表現出較高的玻璃轉移溫度。直至目前為止，以三苯胺結構之二胺當作交聯劑，合成出具三苯胺之電致變色熱固性環氧樹脂，尚未被製備並且系統化探討，故本研究開創了一個環氧樹脂的新的應用領域。

The three diamines which were used in this research, 4,4'-diamino-4'-methoxytriphenylamine, N,N'-bis(4-aminophenyl)-N,N'-di(4-methoxylphenyl)-1,4-phenylenediamine, and N,N'-bis(4-aminophenyl)-N,N'-di(4-methoxylphenyl)-4,4'-biphenyldiamine, were published by our group before. This study has been separated into four chapters. Chapter 1 is general introduction. Chapter 2 includes a series of novel electrochromic thermoset epoxy resins based on 4,4'-diamino-4'-methoxytriphenylamine, N,N'-bis(4-aminophenyl)-N,N'-di(4-methoxylphenyl)-1,4-phenylenediamine and N,N'-bis(4-aminophenyl)-N,N'-di(4-methoxylphenyl)-4,4'-biphenyldiamine, and diglycidyl ether bisphenol A via curing reaction. The chapter 3 include a series of novel electrochromic aliphatic-typed thermoset epoxy resins and derived from 4,4'-diamino-4'-methoxytriphenylamine and N,N'-bis(4-aminophenyl)-N,N'-di(4-methoxylphenyl)-1,4-phenylenediamine, and triglycidyl isocyanurate by curing reaction. Chapter 4 is conclusions. The synthesis, thermal properties, electrochemical and electrochromic properties of four series of novel aromatic triphenylamine (TPA)-substituted derived thermoset epoxy resins were investigated and compared. All thermoset epoxy resins had good high Ts values, good thermal stability, and mechanical properties. Most of the obtained epoxy resins also revealed excellent reversibility of electrochromic characteristics by the electrochemical and spectroelectrochemical methods. Comparing with corresponding polyamides, introduction of triarylamine derivatives into epoxy resins could effectively increase the oxidation stages and reveal multielectrochrmic behaviors. Besides, comparing with aromatic-typed epoxy resins, due to its rigid structure and highly crosslinking density, the aliphatic-typed thermoset epoxy resins showed much higher Ts values than aromatic-typed. To the best of our knowledge, the TPA-based electrochromic thermoset epoxy materials derived from diamines with triarylamine structures as curing agent have not been prepared and investigated systemically. This study opens a new world of application in epoxy resins.