重合溶液中のアニオンや添加有機溶媒によるポリ(N-メチルアニリン)の導電性変化

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概要

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• Poly (N-methylaniline) (PNMA) is prepared by the electro-oxidation of N-methylaniline in aqueous acid solutions. To prepare highly conductive PNMA, N-methylaniline was electropolymerized in several aqueous acidic solutions containing different organic solvents (acetonitrile, N,N-dimethylformamide an dimethylsulfoxide) and anions (ClO4−, Cl−, NO3− and SO42−). After the initial stage of the electropolymerization for the polymerizing solutions without the organic solvents, the anodic current linearly increased for the Cl−, NO3− and SO42− solutions, while it decreased for the ClO4− solution. The decreasing current for the ClO4− solution meant that the polymerization proceeded by oligomer-coupling reactions. The linear increasing current for the Cl−, NO3− and SO42− solutions implied one-dimensional nucleation growth of PNMA on the electrode surface. The polymerization rate estimated from the slope values of the i-t curves was in the order of SO42−>NO3−>Cl−. The conductivity of the obtained PNMAs was of the same order and the highest conductivity of 2.2×10−3 S cm−1 was seen for the SO42− doped PNMA. The order was explained by the Hofmeister series of the anions which are based on lyophilicity. During the polymerization, both the anion release from the monomer-anion and oligomer-anion ion pairs and the anion doping of the polymer occurred most frequently for SO42− with the lowest lyophilicity. The organic solvents were added to the SO42− polymerizing solution and the electropolymerization was performed. The conductivity of the obtained PNMAs was further enhanced. The most conductive PNMA was obtained when dimethylsulfoxide was added (σ=1.0×10−2 S cm−1). The PNMA polymer chains were tangled and stacked with each other by electron-donating association, and the tangling and stacking prevented the anion doping reaction. The addition of the organic solvents suppressed the tangling and stacking and the anion doping reaction was effectively promoted.

• 社団法人電気化学会の論文

著者

• 吉川 裕子

  Faculty of Engineering, Kyushu Sangyo University

• 向井 智美

  Faculty of Engineering, Kyushu Sangyo University

• YANO Jun

  Department of Pediatrics, Kyoto University Graduate School of Medicine

• Kitani Akira

  Faculty Of Engineering Hiroshima University

• Yamasaki Sumio

  Faculty Of Engineering Kyushu Sangyo University

• 矢野 潤

  Department Of Engineering Science Niihama National College Of Technology

• YOSHIKAWA Hiroko

  Faculty of Engineering, Kyushu Sangyo University

• MUKAI Tomomi

  Faculty of Engineering, Kyushu Sangyo University

• KITANI Akira

  Faculty of Engineering, Hiroshima University

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