Chemical synthesis of polyaniline in the presence of poly(amidosulfonic acids) with different rigidity of the polymer chain

Abstract

Conducting polyaniline (PANI) was chemically synthesized in the presence of water-soluble aromatic polyamides containing sulfonic groups: poly-(p,p’-(2,2′-disulfonic acid)-diphenylene-tere-phthalamide) (t-PASA, rigid backbone), poly-(p,p’-(2,2′-disulfonic acid)-diphenylene-iso-phthalamide) (i-PASA, semi-rigid backbone) and their copolymer (co-PASA) with the monomers ratio 1:1, as well as in the presence of flexible-backbone polyacids: poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPSA) and poly(styrene sulfonic acid) (PSSA). In these conditions the matrix polymerization of aniline results in the formation of water-soluble interpolymer complexes of PANI with the above cited polyacids. The character of spectral changes in the UV, visible and near IR (UV–Vis–NIR) range during the synthesis and the polymerization rates depend strictly on the structure of polyacid matrix. Higher flexibility of the polyacid backbone (PAMPSA, PSSA) contributes to higher relative absorption of localized polarons (750 nm), while in the spectrum of interpolymer complexes with rigid-chain polyacid (t-PASA) the absorption of delocalized polarons (1300–1500 nm) prevails. The complexes with semi-flexible i-PASA and co-PASA exhibit intermediate behavior. The results are interpreted in terms of differences in the inter-chain interactions in the interpolymer complexes of different structure. Fourier transform infrared (FTIR) spectroscopy data support the assumption of the incorporation of the polyacids in the PANI through an interaction between sulfonic groups of the polyacids and nitrogen atoms of PANI. Spectroelectrochemical and electrochemical (cyclic voltammetry) studies of the films cast from the obtained solutions showed that the formation of quinoid units at high oxidation level is retarded in the interpolymer complexes of PANI with rigid- and semi-rigid-chain polyacids. Atomic force microscopy (AFM) and direct current (DC)-conductivity data are also presented.