Synthesis of nanostructured conducting polyaniline in the presence of 5-sulfosalicylic acid

Abstract

Oxidative polymerizations of aniline with ammonium peroxydisulfate in aqueous solution of 5-sulfosalicylic acid (SSA), were performed at the constant molar ratio [oxidant]/[monomer] = 1.25, by using various initial molar ratios of SSA to aniline. It was shown that the ratio [SSA]/[aniline] has a crucial influence on the molecular structure, morphology, and conductivity of synthesized polyaniline5-sulfosalicylate (PANI-SSA), as well as on the yield and temperature profile i.e. the mechanism of polymerization process. The yield of PANI-SSA was 80 - 86% for [SSA]/[aniline] ratios in the range 0.25-1.0. Granular PANI-SSA was obtained by the oxidative polymerization of in situ formed anilinium 5-sulfosalicylate ([SSA]/[aniline] = 1.0). The initial induction period was followed by the rapid exothermic polymerization of aniline during the oxidation of anilinium 5-sulfosalicylate with peroxydisulfate. Nanostructured PANI-SSA was synthesized by the oxidation of the mixture of dianilinium 5-sulfosalicylate and aniline ([SSA]/[aniline] = 0.25), which proceeds in two exothermic phases well separated with an athermal period. The presence of nanocylinders (nanorods, possibly nanotubes), with the average diameter of 95-250 nm and the length of 0.5-1.0 μm has been revealed by scanning electron microscopy. It was concluded that PANI nanocylinders are formed when reaction solution has the initial pH > 3.5. Electroconductivity of synthesized polyanilines was in the range 0.01-0.17 S cm-1, and it increases with increasing molar ratio of SSA to aniline. Molecular structure of synthesized polyanilines was investigated by FTIR spectroscopy. Besides the characteristic bands of standard PANI in emeraldine form (benzenoid, quinonoid, and semiquinonoid units), the band attributable to substituted phenazine structural units was observed at -1415 cm-1 in the FTIR spectrum of nanostructured PANI-SSA sample.

Elektroprovodni nanostrukturirani polianilin sintetisan je oksidacijom, anilina u vodenom rastvoru 5-sulfosalicilne kiseline, koristeći amonijum peroksidisulfat kao oksidaciono sredstvo. Utvrđeno je da početni molski odnos 5-sulfosalicilne kiseline i anilina ima odlučujući uticaj na temperaturni profil i prinos reakcije polimerizacije, kao i na molekulsku strukturu, morfologiju i elektroprovodljivost dobijenog polianilina. Prisustvo nanoštapića prosečnog prečnika 95-250 nm i dužine 0,5-1,0 μm utvrđeno je skenirajućom elektronskom mikroskopijom. Gelpropusnom hromatografijom određene su vrednosti molame mase usrednjene po masi i indeksa polidisperznosti. Elektroprovodljivost sintetisanih uzoraka polianilina je 0,01-0,17 S cm-1. FTIR spektroskopijom ispitana je molekulska struktura sintetisanih polianilina.