Chemical and electrochemical synthesis of conducting graft copolymer of acrylonitrile with aniline

A new conducting copolymer, polyacrylonitrile‐graft‐polyaniline (PAN‐g‐PANi), has been prepared by chemical and electrochemical methods from a precursor polymer. Poly[acrylonitrile‐co‐(acrylimine phenylenediamine)] (PAN‐co‐PAIPD) was synthesized chemically by reacting PAN with sodium 1,4‐phenylenediamine salt. PAN‐g‐PANi was synthesized chemically using ammonium peroxydisulfate as the oxidant and p‐toluenesulfonic acid in dimethylsulfoxide solution and adding aniline to oxidized PAN‐co‐PAIPD. Electrochemical polymerization was carried out by spin coating PAN‐co‐PAIPD on the surface of a Pt electrode, then the growth of the graft copolymer (PAN‐g‐PANi) in the presence of fresh aniline and acidic solution. The structures of the graft copolymer and PAN‐co‐PAIPD were characterized using UV‐visible, Fourier transform infrared, and 1H and 13C NMR spectroscopies. The thermal properties of PAN‐g‐PANi were studied using thermogravimetric analysis and differential scanning calorimetry. Scanning electron microscopy (SEM) images showed that the morphology of PAN‐g‐PANi copolymer films was homogeneous. Electrical conductivity of the copolymer was studied using the four‐probe method, which gave a conductivity of 4.5 × 10−3 S cm−1 with 51.4% PANi. SEM and electrical conductivity measurements supported the formation of the graft copolymer.