新型具三芳香胺材料之熱固性環氧樹脂合成與電致變色性質之探討

Abstract

本論文分為四章。首先，第一章為總體緒論，介紹了環氧樹脂、電致變色（EC）的發展和價間電子轉移（IVCT）。其次，在第二章中，合成了四種對氨基取代的TPA衍生物（TPPA-2N、TPPA-4N、TPB-2N和TPB-4N）。利用循環伏安法（CV）、微分脈衝伏安法（DPV）和能斯特分析，研究這些TPA衍生物的電致變色特性。這些TPA衍生物的多段電致變色和低驅動電壓特性成為電致變色應用的優勢。此外，這些氨基取代的TPA在長時間之連續測量中顯示出高穩定性。進一步將這些電活性TPA材料製作成電致變色元件（ECDs），並研究它們的電化學和光譜電化學特性。在第三章中，利用三種對氨基取代的TPA衍生物（TPA-3N、TPPA-4N和TPB-4N）與雙環氧化物BDGE合成了熱固性環氧聚合物（TPA-3N_BDGE、TPPA-4N_BDGE和TPB-4N_BDGE），藉由一系列的差示掃描量熱法（DSC）的測量來決定反應進行的條件，並通過將合成的環氧聚合物浸入濃硫酸中與傅立葉變換紅外光譜（FTIR）來確認是否成功合成環氧聚合物。我們也使用了熱重分析儀（TGA）和熱機械分析儀（TMA）對熱性質進行進一步研究。此外，還測量了循環伏安法、微分脈衝伏安法和能斯特分析等電化學和光譜電化學特性。最後，在第四章中，對實驗結果進行了總結。我們發現，儘管氨基助色團被轉化為二烷基胺基團，對氨基取代的TPA衍生物的多段電致變色行為和優異穩定性依然得以保持，且外圍氮原子的氧化能力未受影響，表明這些材料在未來應用中具有很大潛力。

There are four chapters in this study. Firstly, a general introduction was provided in CHAPTER 1, introducing epoxy resins, the development of electrochromism (EC), and intervalence charge transfer (IVCT). Secondly, in CHAPTER 2, four derivatives of para-amino-substituted TPA (TPPA-2N, TPPA-4N, TPB-2N, and TPB-4N) were synthesized. With cyclic voltammetry (CV), differential pulse voltammetry (DPV), and Nernstian analysis, the EC properties of these TPA derivatives were recorded. The multi-electrochromic and low-driving-voltage attributes became the advantages for electrochromic applications. Moreover, these amino-substituted TPA revealed high stability in continuous measurement. The electroactive TPA chromophores were further fabricated as electrochromic devices (ECDs). The properties of electrochemistry and spectroelectrochemistry were also investigated. Then, in CHAPTER 3, three para-amino-substituted TPA derivatives (TPA-3N, TPPA-4N, and TPB-4N) were used to synthesize thermoset epoxy polymers (TPA-3N_BDGE, TPPA-4N_BDGE, and TPB-4N_BDGE) with diepoxy BDGE according to a series of differential scanning calorimetry (DSC) measurements. Whether the epoxy polymers were successfully synthesized was checked by dipping them into concentrated sulfuric acid and Fourier-transform infrared spectroscopy (FTIR). The thermal properties were investigated by thermogravimetric analyzer (TGA) and thermal mechanical analyzer (TMA). Furthermore, electrochemistry and spectroelectrochemistry, such as CV, DPV, and Nernstian analysis, were also measured. Finally, in CHAPTER 4, the results were summarized. We found that the properties, such as the multi-electrochromic behavior and outstanding stability of the para-amino-substituted TPA derivatives, could be retained, although the amino auxochromes were transformed into dialkylamine groups without losing the original ability of the peripheral nitrogens to undergo further oxidation. Indicating promising thermoset epoxy materials for future applications.