Poly-aniline with emeraldine base

Fig. 4.6 Schematic diagrams of (a) cyclodextrins, (b) poly-aniline with emeraldine base, and (c) inclusion complex formation of cyclodextrins and a conducting polymer chain insulated molecular wire. (From ref. [32])...

The common form of polyaniline is a 1 1 combination of alternating reduced (A) and oxidized (C) units it is termed emeraldine (or emeraldine base). The emeraldine base is essentially non-conductive, but its conductivity increases by 9-10 orders of magnitude by treating with aqueous protonic acids. The conductive form of poly aniline can therefore be roughly depicted as a 1 1 combination of alternating A and D units. 

We have re-analyzed the available data in comparison with the results of band structure calculation to provide the basis for an understanding of the electronic structure of the four principal forms of poly aniline the fuUy reduced leucoemeraldine, (1 A)n the partially oxidized emeraldine base, [(1 A)(2A)]n the oxidized and fully protonat emeraldine salt, [IS] (A )n and the fully oxidized bipolaron lattice, (-B-NH+=Q=NH+-)n. 

Both, aniline and anilium hydrochloride were polymerized in direct and in inverse miniemulsion, respectively [140]. The polymerization of anilium hydrochloride, which was initiated by hydrogen peroxide, yielded a highly crystaUine emeraldine polyaniline. In direct miniemulsions, additional stabilizers (e.g., poly(vinyl pyrroU-done) or PVA) were employed to preserve colloidal stability. The polymerization of aniline in direct miniemulsion has also been reported [141] in this case, following polymerization the polymer was first treated with stannous chloride and then doped with p-toluenesulfonic acid. A dramatic increase in conductivity after treatment with stannous chloride was considered due to pernigraniline moiety in the emeraldine base structure having been reduced. Such oxidative polymerization of aniline may be used to add an additional conductive shell to preformed latexes. For example, Li et al. polymerized aniline in the presence of dodecylbenzesulfonic acid on the surface of polyurethane and polyurethane/poly(methyl methacrylate) nanoparticles prepared in miniemulsion [142]. 

We have prepared a series of nylon / poly aniline blends using the solvent hexafluoroisdpropanol (HFIP), which is an excellent solvent for polyaniline emeraldine base (PANI-EB), polyaniline doped with various sulfonic acids (PANI-ES) and for hi molecular weight nylon 6 and nylon 12. It was observed that conductivity and morphology of the blends varied with the compatibility of the sulfonic acid anion with the nylon. Methanesulfonic acid, butane sulfonic acid dodecylbenzene sulfonic acid and camphor sulfonic acid were used as PANI dopants and the PANI-ES / nylon blends were characterized by electrical conductivity (room and low temperature) and transmission electron microscopy. The results of these various measurements and the conclusions which can be drawn regarding morphology and conductivity of Ihe blends, will be reported. 

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