利用氧化偶合法合成電活性聚醯胺與多層奈米碳管複合材料及其電性質之研究與電化學感測器之應用

Synthesis and electrical properties of electroactive polyamide/multiwalled carbon nanotube mixture via oxidative coupling polymerization for electrochemical sensing

林統機(Tung-Chi 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/cycu201300682

摘要

本研究主要利用氧化偶合法合成電活性聚醯胺與多層奈米碳管複合材料及其電性質與電化學感測器之應用為研究之方向。聚醯胺高分子本身有優越之機械性質、耐磨性、吸水性與流動性佳等特性，但電性較差與低溫耐擊性強度不足，因此限制其應用。
所以，本研究所合成之新型電活性聚醯胺與多層奈米碳管複合材料，使電活性高分子上的醌環和多層奈米碳管更有效率得進行交互作用，促進物質間電子轉換提升導電度並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。首先從N-phenyl-p-phenylenediamine和癸二酰氯反應中得到高產率的苯胺寡聚體。接著用MASS、NMR和FTIR的資料來證明苯胺寡聚體的明確結構。並在多磷酸與五氧化二磷介質裡，多層奈米碳管利用4-aminobenzoic acid經由Firedel-Crafts acylation reaction之方式改質奈米碳管，使碳管表面具有-NH2之活化官能基，並利用氧化偶合法將苯胺寡聚體與對胺基苯甲酸進行反應形成共價鍵結。再利用奈米碳管之高導電特性，合成電活性聚醯胺/多層奈米碳管複合材料，使材料具有較高之導電度。接著再透過FTIR、TEM、CV及UV等儀器，驗證醌環存在於和多層奈米碳管鍵結的電活性聚醯胺上。並藉由循環伏安法鑑定，以證明電活性聚醯胺/多層奈米碳管複合材料的電化學性質和充放電能力。
研究中多層奈米碳管重量百分濃度增加至10 wt%時，其多層奈米碳管與電活性聚醯胺複合材料的導電度將由10-7提升到10-2 S/cm，增加了5個級數，較文獻中電活性聚醯胺要來得高。
另外，以多層奈米碳管與電活性聚醯胺複合材料修飾碳糊電極(carbon paste electrode, CPE)作為抗壞血酸(vitamin C, AA)之傳感器並探討其電催化氧化反應效能。實驗中利用苯胺寡聚體結構之可逆氧化還原能力，在電催化的反應中，由於抗壞血酸氧化過程還原苯胺寡聚體，故可使用循環伏特安培儀加以偵測，於氧化電位時偵測到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，其氧化電流跟抗壞血酸濃度間可得一線性趨勢。在電流應答測試中，其線性迴歸值(R2值) 為0.9931，階梯數(n值) 為15，偵測極限為3.1 μM (S/N = 3)，由此結果得知多層奈米碳管與電活性聚醯胺複合材料修飾電極可用於偵測抗壞血酸等化學物質。

關鍵字

電活性聚醯胺 ； 維生素C ； 感測器

並列摘要

In this thesis, we presented the study of synthesis and electrical properties of electroactive polyamide/multiwalled carbon nanotube mixture (EPA/MWCNT) via oxidative coupling polymerization and applied it to the electrochemical sensing of ascorbic acid (AA). First, The oligoaniline was synthesized in high yield from the reaction of N-phenyl-p-phenylenediamine and sebacoyl chloride. Liquid chromatograph mass, 1H-nuclear magnetic resonance and Fourier transform infrared spectra (FTIR) data were used to characterize the precise structure of the oligoaniline. Subsequently, EPA was synthesized from the reaction of oligoaniline and p-phenylenediamine through an oxidative coupling polymerization. MWCNTs were grafted with 4-aminobenzoic acid in a medium of polyphosphoric acid/phosphorous pentoxide to obtain MWCNTs functionalized with 4-aminobenzoyl groups (AF-MWCNTs). The amino functional groups on the AF-MWCNTs reacted with an oligoaniline by oxidative coupling polymerization to obtain the EPA/MWCNT composites. FTIR spectra and UV-visible spectra revealed that the quinoid rings present on the EPA graft interacted with the MWCNTs. Cyclic voltammetry studies indicated improved electrochemical properties of the EPA/MWCNT composites demonstrating the occurrence of efficient electron/charge transfer between the MWCNT and the EPA graft. A linear relationship between the concentration of AA added and the change of peak current obtained was observed. In addition, the calibration curve of the amperometric response of the EPA/MWCNT sensors to the concentration of AA was also linear. The limit of quantitation measured was 3.1 μM and the limit of detection for the EPA- carbon paste electrode was estimated 0.0173μA/μM at signal/noise (S/N) of 3.

並列關鍵字

electroactive polyamide ； sensor ； ascorbic acid

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