Molecular composites obtained by polyaniline synthesis in the presence of p ‐octasulfonated calixarene macrocycle

Polyaniline (PANI) molecular composites were synthesized by chemical oxidative polymerization of the aniline and aniline dimer, N ‐phenyl‐1,4‐phenylendiamine, in the presence of a macrocycle, calix[8]arene p ‐octasulfonic acid (C8S), using ammonium peroxidisulfate as oxidant. The macrocycle has acted both as acid dopant and surfactant to obtain processable PANI‐ES. The PANI/calix[8]arene p ‐octasulfonic acid composite was also obtained by a simple doping of PANI emeraldine base form with calix[8]arene sulfonic acid. The structure of materials was confirmed by Fourier transform infrared, UV–vis and nuclear magnetic resonance spectroscopy. All synthesized composite materials are amorphous and soluble in chloroform, dimethylsulfoxide, NMP, showing excellent solution‐processing properties combined with electrical conductivity. Cyclic voltammetry evidenced a good electroactivity for the composite films. Dielectric properties (dielectric constant and dielectric losses) were determined and are comparable with those of other PANI/ionic acid polymer composites. Preliminary studies have evidenced a high dielectric constant (10 4 at 100 Hz) and electrical conductivity of 6 × 10 −3 S/cm for PANI composites. From sulfur elemental analysis of the PANI/calixarene, it results that the content in macrocycle is ∼30% (weight).