有機可溶電活性聚亞甲胺與電活性聚亞醯胺及其奈米碳管複合材料之合成與性質研究

Preparation and Properties of Organo-Soluble Electroactive Polyazomethine and Electroactive Polyimide as well as Their Carbon Nanotube Composites

黃朝晟(Tsao-Cheng Huang)

指導教授 ： 葉瑞銘 ； 吳吉輝

中原大學/理學院/化學研究所/博士(2011年)

https://doi.org/10.6840/cycu201100412

摘要

本研究以氧化偶合法合成電活性聚亞甲胺與電活性聚亞醯胺高分子及其奈米碳管複合材料為研究之方向。聚亞甲胺高分子有優越之光學性質與熱穩定特性，但傳統之聚亞甲胺高分子因溶解度差而限制其應用。為增加溶解度，文獻多合成具側鏈之聚亞甲胺高分子為主，此方法可提升聚亞甲胺之溶解度，但同時卻大大降低聚亞甲胺高分子之熱性質與導電特性。
本研究所合成之新型電活性聚亞甲胺具有良好之溶解度可溶於NMP, DMAc, DMF等溶劑，並使導電度由10-8 S/cm提升至10-4 S/cm。由TGA量測可得其熱裂解點約為530 oC，證明其熱穩定性優越，實驗同時發現經由電位控制可使電活性聚亞甲胺具有電致變色之特性。
電活性聚亞醯胺高分子則著重於防蝕特性之研究，由文獻得知聚苯胺具有防腐蝕之特性，其主因在於聚苯胺塗佈於金屬材料上，可形成鈍性氧化層並以SEM與ESCA鑑定證實。主鏈苯胺寡聚體之氧化還原特性亦可使電活性聚亞醯胺高分子具有電致變色之應用。
此外為使電活性高分子具有較高之導電特性，本文使用Friedel-Crafts acylation reaction之方式改質奈米碳管，使碳管表面帶有胺基官能基，並利用氧化偶合反應合成電活性聚亞甲胺與聚亞醯胺/奈米碳管複合材料，經由傅利葉轉換紅外線光譜儀、紫外光可見光光譜儀、循環伏特安培儀等儀器研究其電荷轉移之機制與導電性質。

關鍵字

電活性高分子 ； 聚亞甲胺 ； 聚亞醯胺 ； 防腐蝕 ； 電致變色

並列摘要

Electroactive polymer (polyazomethines, polyimide) and electroactive polymer/carbon nanotube composite were synthesized through simple oxidative coupling polymerization in this thesis. Conjugated polyazomethines are interesting class of conjugated polymers containing nitrogen atoms in a polymer backbone. However, their insolubility in organic solvents usually limited their processing. To promote the solubility of polyazomethines, flexible alkyl or alkoxy side groups was synthesized on aromatic rings. All polymers synthesized from this approach were found to be soluble in common organic solvents, but conductivity of as-prepared polymers was found much lower (σ~10-8 S/cm) than those of reported polyazomethines (σ~10-4 S/cm) and sacrificing their thermal stability. This novel electroactive polyazomethines (EPA) with aniline pentamer in the main chain was found to exhibit good solubility in organic solvents, good film formation ability, high thermal stability at operational temperature of ~ 530 oC and acceptable electrical conductivity of 2.1 × 10-4 S/cm.
The aniline pentamer-based Electroactive polyimide (AP-based EPI) coating was found to exhibit enhanced corrosion protection effect on cold-rolled steel (CRS) electrodes as compared to that of corresponding non-electroactive (NEPI) coating based on a series of electrochemical measurements in 5 wt % NaCl electrolyte. Significant enhancement of corrosion protection of AP-based EPI coating on CRS electrodes as compared to NEPI counterpart might probably be attributed to the redox catalytic property of as-prepared AP-based EPI coatings, inducing the formation of passive layer of metal oxide, which was identified by Scanning electron microscopy (SEM) observation and Electron spectroscopy for chemical analysis (ESCA) studies. The electrochromic performance of AP-based EPI was investigated by electrochromic photographs and UV-visible absorption spectra.
Polymer/carbon nanotubes (CNTs) composites have been tremendous interest since CNTs first observation by Iijima. Owing to its unique properties CNTs is considered to be the ideal candidates for applications as fillers in composite materials to enhance mechanical and electrical properties. However, electroactive polymer/CNTs composites have seldom been mentioned. In this study, electroactive polymer/CNTs composites were synthesized through oxidative coupling polymerization. The conductivity of electroactive polymer/CNTs are higher than the value obtained from as-prepared electroactive polymer after doped with HCl. Fourier-transform infrared (FTIR) and UV-Vis spectra reveal that the aniline oligomer segment on the electroactive polymer could interact with CNTs. The results of cyclic voltammetry (CV) studies indicate enhanced electrochemical and charge transfer behavior of electroactive polymer /CNTs composite.

並列關鍵字

polyazomethines ； polyimide ； corrosion ； electrochromic ； electroactive polymer

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