Add time:07/19/2019         Source:sciencedirect.com

The electrochemical oxidation of 3-methyldiphenylamine, 3-MeDPA, and 3-methoxydiphenylamine, 3-MeODPA, in lithium perchlorate CH3CN solutions produced either thin, uniform polymeric films on ITO electrodes or high quality, free-standing polymeric films with good electrochemical response. Thin polymer films exhibited multiple colour changes (pale yellow-yellow-green-blue) when the potential was cycled between 0.0 and 1.2 V vs. Ag/AgCl in LiClO4-CH3CN. Degradation occurred during long term cycling tests between 0.0 and 1.2 V, and could be inhibited substantially by the addition of strong acids. The polymer films exhibited electrochromic properties when dipped in aqueous solutions at various pHs. The free-standing film of poly(3-methyldiphenylamine), poly(3-MeDPA), showed a highly porous, granular morphology, whereas a dense, fibrous morphology was observed for poly(3-methoxydiphenylamine), poly(3-MeODPA). These free standing films may be doped and undoped chemically by immersing in acid or alkaline media. The chemical oxidation of 3-MeDPA and 3-MeODPA in acetonitrile, using copper perchlorate as an oxidative coupling reagent, also gave polymers with high molecular masses and their IR spectra are similar to those obtained by electrochemical polymerization. The electrical conductivity measurements on pressed pellets and free standing films of poly(3-MeDPA) and poly(3-MeODPA) gave room temperature conductivities in the range of 10−5 and 10−6 S/cm, respectively.

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