含胺基五苯荑衍生物之合成及其與苯胺電化學共聚合之性質研究

本論文主要是在合成與探討新型聚苯胺材料之研究，利用五苯荑衍生物AP、APAN和APA作為單體分子，以電化學氧化聚合的方式與苯胺單體於ITO工作電極表面進行共聚，以期能將五苯荑分子引入聚苯胺高分子鏈中。我們利用吸收光譜儀及電化學對AP、APAN和APA單體進行分子中心之共軛長度分析，發現由於受到分子扭轉效應的影響，APAN並未因中心共軛長度最長而在光譜上有最大的紅位移現象。透過改變電化學實驗參數及聚合反應條件，探討AP、APAN和APA與苯胺共聚合的反應機制，我們發現AP由於立障太大的緣故，無法參與共聚。然而APAN和APA可與苯胺進行共聚，且因為相較於苯胺有較低的氧化電位而有加速聚合反應的現象產生。此外，透過臨場光譜電化學法觀察定電位下之共聚合高分子成長的情形，我們發現含有APAN和APA進行共聚時，可在較低的起始電位進行聚合，且由於共聚物高分子的平面性下降，於吸收光譜有藍位移的現象。此外，我們利用掃描式電子顯微鏡(SEM)觀察含五苯荑架構之聚苯胺高分子的粒子形狀，相較於傳統聚苯胺會有部分纖維狀的粒子生成，poly(ANI-co-APAN)所呈現的是較大米粒狀的粒子生成。因此得知五苯荑的三維立體結構會對於聚合初期所產生的寡聚物之堆疊效應產生影響。我們推測poly(ANI-co-APAN)的生成會以APAN作為核心進行鏈的成長，進而對共聚物的奈米結構產生變化，由於APAN與苯胺共聚不用經過誘導期的階段，因此可呼應電化學所觀察到加速聚合反應的現象。

關鍵字

聚苯胺；五苯荑；電化學共聚合

並列摘要

In this thesis, we report the design and synthesis of a series of pentiptycene derivatives, AP, APAN, and APA, to prepare the novel polyaniline materials. A novel pentiptycene-containing polyaniline was synthesized via electro-co-polymerization of APAN or APA with aniline by using cyclic voltammetry on ITO electrode surfaces. Among three pentiptycene derivatives compounds, the UV-vis spectroscopy and cyclic voltammetry reveal that APAN having the longest conjugation length was not observed significantly red-shifted due to twisted effect. By changing electrochemical experimental parameters and polymerization conditions, we realized APAN or APA could polymerize with ANI, but AP could not. Because the APAN and APA have a lower redox potential than ANI, they can accelerate the polymerization rate. Furthermore, the copolymer formation was obtained through spectroelectrochemical studies. By recording UV-visible spectra during constant potential electropolymerization, We observed that the existence of APAN or APA in polyaniline could decline the planarity of polymer chains. The UV-visible spectra show the phenomenon of blue -shift at long wavelength region for polymer containing APAN or APA. Additionally, SEM images show oxidation of ANI produces some nanotubes, while the oxidation of copolymer, poly(ANI-co-APAN), just produce granule particles under the same experimental conditions. Therefore, we know that the rigid 3-D structure of pentiptycene change the aggregation effect in the early stages of polymerization. We predicted that APAN can serve as the nucleation center for the poly(ANI-co-APAN) chain growth.