有機溶劑可溶聚(1-酮基-2-丁烯酸)吡咯ˋ聚(1-酮基-2-己烷胺)吡咯化合物之合成ˋ結構與物性探討

Studies on synthesis, structure, and properties of organic solvent-soluble Poly〔N-(1-one-2-vinyl-butyric acid)〕pyrrole and Poly〔N-(1-one-6-hexylamine)〕pyrrole

陳効謙(Hsiao-Chien Chen)

指導教授 ： 鄭俊麟 ； 華沐怡

中原大學/工學院/化學工程研究所/碩士(2003年)

https://doi.org/10.6840/cycu200300585

摘要

摘要

本文中已經成功的將馬林酸酐及己內醯胺開環接枝在聚吡咯鏈上合成出氮上取代有機溶劑可溶的聚吡咯，以真實溶液測試來證明溶解度。紅外線光譜儀 (FT-IR) 鑑定其氮-取代聚吡咯化合物之結構。除此之外並以紫外光-可見光光譜 (UV-Vis.)、循環伏安計量 (CV)、熱重量分析儀 (TGA)、X-射線繞射分析 (XRD)、微差掃描熱卡 (DSC) 及螢光掃描器來探討此聚合體之結構與物性。
由真實溶液之紫外光-可見光光譜分析，證實合成出的聚合體在二甲亞碸及二甲基甲醯胺中為真實溶液。在紫外光-可見光光譜中，357 nm 處有pyrrole ring的 π-π* transition ，541 nm 為polaron 的吸收，在去摻雜之後仍有 polaron 的吸收，說明了所合成的聚吡咯衍生物不但具有氯化鐵的摻雜同時還有自身酸摻雜。由循環伏安計量分析中，因為氮上取代造成共平面性差且受到自身摻酸雜的影響而使氧化還原峰均往高電位位移，這和文獻是相符合的。
在熱重量分析中，除了側鏈的裂解，同時也使聚吡咯高分子鏈裂解溫度往低溫移動。X-射線繞射分析及微差掃描熱卡得知導入側鏈後仍為一無定型的聚合物。除此之外，在螢光掃描分析中，當激發波長為 635 nm 時，具有螢光亮度的產生。

關鍵字

吡咯

並列摘要

Abstract

Polypyrrole (PPy) is very difficult to be dissolved in common organic solvents owing to its inherent rigid backbone. In this paper, a novel organic solvent soluble polypyrrole has been synthesized Poly[N-(1-one-2-vinyl-butyric acid)] and Poly[N-(1-one-6-hexylamine)] -pyrrole by branching maleic anhydride and caprolactam. We used true solution test to provide that they can be soluble in organic solvent, ex: dimethyl sulfoxide (DMSO), dimethyl formamide (DMF). The structures are determined by infrared spectrometer (IR). Beside, we study their properties by ultraviolet-visible spectroscopy (UV-Vis), cyclic voltammetry (CV), Thermogravimetric analyzer (TGA), X-ray diffractometer (XRD), Differential scanning calorimeter (DSC), and Fluorescence spectra.
For UV-vis absorption spectra, at 357 nm and at 541 nm are theπ-π* transition of pyrrole ring and the absorption of polaron. After dedoping, the absorption of polaron still appears. This result was confirmed polypyrrole derivatives not only doped by ferric chloride (FeCl3), but also by self-acid-doped. Low co-plane makes the redox peak shift to high potential. According to XRD and DSC result, polypyrrole derivatives belong to amorphous polymers. In Fluorescence spectra analysis, they have fluorescence properties when the excited wavelength is 635 nm.

並列關鍵字

pyrrole

參考文獻

1. T. Ito, H. Shirakawa and S. Ikeda, J. Polym. Sci., Polym. Chem. Ed., 12, 11 (1971).

5. Franz-Hubert Haegel, Julia Schlüpen, Joachim Walter Schultze, Stephan Winkels, and Christian Stromberg, Electrochimica Acta, 46, 3973-3984 (2001).

9. C. Kittel, Introduction to Solid State Physics (1986)

11. A. F. Diaz, K. K. Kanazawa, and G. P. Gradini, J. Chem. Soc., Chem. Commun., 635 (1979).

14. A. A. Pud, Synth. Met. , 66, 1 (1994).