Polyaniline formation

The mechanism of polyaniline formation is an area of active research and controversy. The wide range of reaction conditions used in polyaniline synthesis and the resulting differences in the structure and characteristics of the polymers has probably contributed to the proposal of many different mechanisms. The majority of the proposed mechanisms begin with the oxidation of aniline to a cation radical (445). Two of these cation radicals couple to form /V-phenyl-p-phenylenediamine (443). The oxidation of the aniline monomers to form dimeric species is the slow step in the polymerization [271,285,286]. The subsequent steps of polymer growth are under discussion. 

Figure 67 Mechanism of polyaniline formation involving the coupling of a dication or cation with neutral monomer. (From Ref. 288.)...

Figure 8.5 Schematic representation of polyaniline formation on graphene surface via oxidative pol5nnerization of aniline by Mn02. Reprinted with permission from Ref 36. Copyright 2010 American Chemical Society.

In order to explain the electrochemical behaviour of polyaniline formation of radical cations near peak I, subsequent oxidation into imine near peak III has been suggested by Glarum et al. [40] and by Stilwell [41]. The mechanism is shown in Scheme 12.2. 

In 1979, the formation of conductive polypyrrole films by the electrochemical oxidation of pyrrole was reported for the first time This work has stimulated intense and fruitful research in the field of organic conducting polymers. Further important conductive polymers are polythiophene, polyaniline and polyparaphenylene. The development and technological aspects of this expanding research area is covered... 

For example, the investigations of the current-generating mechanism for the polyaniline (PANI) electrode have shown that at least within the main range of potential AEn the "capacitor" model of ion electrosorption/ desorption in well conducting emeraldine salt phase is more preferable. Nevertheless, the possibilities of redox processes at the limits and beyond this range of potentials AEn should be taken into account. At the same time, these processes can lead to the fast formation of thin insulation passive layers of new poorly conducting phases (leucoemeraldine salt, leucoemeraldine base, etc.) near the current collector (Figure 7). The formation of such phases even in small amounts rapidly inhibits and discontinues the electrochemical process. 

The emeraldine base form of polyaniline may also react in non-aqueous electrolytes, such as a LiClOl -propylene carbonate solution, with the formation of the conductive emeraldine hydroperchlorate salt ... 

Importantly, deep oxidation of polyaniline leads to a material that becomes insulating and spinless. This phenomenon was demonstrated in case of poly(fV-methylaniline) by monitoring ESR signal and electric conductivity of the sample (Wei et al. 2007). Deep oxidation results in the formation of the so-called polaron pairs that are evidenced by optical spectra. Because the hopping probability of two polarons on a single chain is too small, polaron pairs do not contribute to electric conductivity and ESR signal. 

Similar approach has also been taken by Ferain and Legras [133,137,138] and De Pra et al. [139] to produce nanostructured materials based on the template of the membrane with etched pores. Polycarbonate film was also of use as the base membrane of the template, and micro- and nanopores were formed by precise control of the etching procedure. Their most resent report showed the successful formation of ultrasmall pores and electrodeposited materials of which sizes were as much as 20 nm [139]. Another attractive point of these studies is the deposited materials in the etched pores. Electrochemical polymerization of conjugated polymer materials was demonstrated in these studies, and the nanowires based on polypyrrole or polyaniline were formed with a fairly cylindrical shape reflecting the side wall structure of the etched pores. Figure 10 indicates the shape of the polypyrrole microwires with their dimension changes by the limitation of the thickness of the template. 

Other Substrates Deposition of cadmium was also studied on Bi, Sn and Pb [303], Ni [304], reticulated vitreous carbon [305], Ti [306], and indium tin oxide [307]. UPD of Cd on tellurium results in CdTe formation [270, 308]. Electrodes coated with conducting polymers were also used to deposit cadmium electrochemi-cally. In the case of polyaniline, the metal reduction potential corresponds to the neutral (nonconducting) state of the polymer, therefore cadmium was found to deposit on the substrate-glassy carbon electrode surface, in the open pores of the polymer film [309, 310]. 

The inter-relationship between colloid and polymer chemistries is completed by colloidal polymer particles. The formation of 50-nm-diameter, 100- to 200-nm-long polyaniline fibrils in a poly(acrylic acid)-template-guided polymerization, similar in many ways to those produced from polymerized SUVs (see above), provides a recent example of polymer colloids [449], The use of poly(styenesulfonic acid) as a template yielded globular polyaniline particles which were found to be quite different morphologically from those observed in the regular chemical synthesis of polyaniline [449]. 

---