電活性聚醯胺與具三氟甲氧基三苯胺聚亞醯胺之合成與性質研究

Synthesis and properties study of polyimide with trifluoromeoxy-based triphenylamine and electroactive polyamide

林彥任(Yen-Jen Lin)

指導教授 ： 葉瑞銘

中原大學/理學院/化學研究所/碩士(2013年)

https://doi.org/10.6840/CYCU.2013.00090

摘要

本論文的研究重點主要分為兩個部份：(一)、含三氟甲氧基的三苯胺(triphenylamine, TPA)聚亞醯胺高分子的製備及防腐蝕應用探討；(二)、使用電活性聚醯胺修飾碳糊電極(carbon paste electrode, CPE)作為抗壞血酸(vitamin C, AA)傳感器並對其電催化氧化效能進行探討。
第一部先合成具三氟甲氧基的三苯胺二胺單體，利用液態核磁共振光譜、傅利葉轉換紅外線吸收光譜及液相層析質譜進行結構鑑定，並探討合成聚亞醯胺高分子後在防腐蝕上之應用。當導入含氟基團時，可以降低高分子薄膜之表面活化能；而使用三苯胺的結構，使得官能基於分子結構上較直線型二胺分子較為裸露。並由接觸角實驗及電化學防腐蝕測試證明三氟甲氧基的導入，有助於改善三苯胺高分子的防腐蝕效果。
第二部分是利用氧化偶合反應將苯胺五聚體合成於聚亞醯胺主鏈上，因苯胺寡聚體結構具可逆氧化還原能力，在電催化的反應中，選擇抗壞血酸來還原苯胺寡聚體，並利用循環伏特安培儀偵測苯胺寡聚體之氧化電流。隨著緩衝溶液(phosphate buffered saline﹐PBS)溶液中抗壞血酸濃度的增加，電催化氧化電流也隨之提升，且其氧化電流跟抗壞血酸濃度間可得一線性趨勢。而在電流應答測試中，其線性迴歸值(R2值) 為0.996，階梯數 (n值)為15，偵測極限為5.04 μM (S/N = 3)，靈敏度為0.0174 μA/ μM，由此結果得知電活性聚醯胺修飾電極可用於偵測抗壞血酸等化學物質之研究。

關鍵字

感測器 ； 電活性聚醯胺 ； 防腐蝕 ； 三苯胺

並列摘要

This thesis mainly divided into two parts : (1) Synthesis and anti-corrosion effect of trifluoromethoxy-triphenylamine-based polyimide and (2) aniline-pentamer-based electroactive polyamide in electrochemical sensor application were investigated.
In the first part, trifluoromethoxy-triphenylamine-based oligomer was synthesized by SN2 amination and identified by Nuclear magnetic resonance (NMR), Fourier transform infrared (FT-IR) and Liquid chromatography-mass (LC-MS) spectroscopy. And the synthesis of Triphenylamine (TPA) polyimide polymer in the application of anti-corrosion was first discussed. It would reduce surface energy when fluoro-group was introduced. TPA structure, making the functional group based on the molecular structure is more exposed than that with straight structure. The membrane with good hydrophobicity by affected from trifluoromethoxy group subsitituted was presented, as identified by series of electrochemical corrosion measurements.
The second part details electrochemical investigations of carbon paste electrode (CPE) modified with electroactive polyamide (EPA) as ascorbic acid sensor (vitamin C, AA). EPA, with aniline-pentamer-based in the main chain, was synthesized from oligoaniline and p-phenylenediamine by oxidative coupling polymerization. The well-defined molecular structure of the oligoaniline and EPA was confirmed by LC-Mass, NMR and FT-IR spectroscopy. The in-situ chemical oxidation of the reduced form of soluble, EPA in N-methyl-2-pyrrolidone was monitored by UV-Visible absorption spectra. Moreover, the electroactivity of the EPA was evaluated by performing electrochemical cyclic voltammetry studies. A linear relationship between the concentration of AA added and the change of peak current obtained, as shown by the linear calibration curve of the amperometric response of the CPE modified with EPA sensor to the concentration of AA (R2 = 0.996, n = 15). The limit of quantitation measured was 14.89 μM at signal/noise (S/N) of 10 and the limit of detection for the EPA-CPE was estimated 5.04μM at signal/noise (S/N) of 3.

並列關鍵字

sensor ； electroactive polyamide ； corrosion ； triphenylamine

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