Exploration of the morphological transition phenomenon of polyaniline from microspheres to nanotubes in acid-free aqueous 1 -propanol solution in a single polymerization process

摘要

Polyaniline micro- or nanostructures have been widely investigated due to their unique physical and chemical properties. Although several studies have reported the synthesis of polyaniline microspheres and nanotubes, their mechanisms of formation remain controversial. This study reports our observation of the morphological transition of polyaniline from microspheres to nanotubes in a single polymerization process and also tries to propose their mechanisms of formation. The polymerization of aniline monomer in acid-free aqueous 1 -propanol solutions (1 and 2 mol L~(-1)) produces polyaniline microspheres and nanotubes at different reaction stages through a morphology transition process with treatment using ultrasound. In the initial reaction stage, Fourier transform infrared spectra indicate that the aniline monomers form phenazine-like units, producing polyaniline microspheres with an outside diameter of 1-2 μm. The hydrogen bonds between 1-propanol and polyaniline serve as the driving force for the polyaniline chains to build microspheres. As the reaction continues, observation indicates the microspheres decompose and reform one-dimensional nanotubes. In this stage, a structure consisting of a head of phenazine-like units and a tail of acid-doping para-linked aniline units develops. The protonation of the para-linked aniline units provides the driving force for the formation of nanotubes through a self-curling process. We report here the unique morphology transition of polyaniline from microspheres to nanotubes in a single polymerization process. The results indicate that the structural change of polyaniline leads to this morphological change. The mechanisms of formation of the microspheres and nanotubes in a polymerization process are also well explained.