Poly /polyaniline synthesis

Due to the utility of the methods and the significance of the materials, the use of Pd-catalyzed fV-arylation reactions in oligoaniline and polyaniline synthesis has remained an active area of research [344, 345]. For example, in recent work Kulszewicz-Bajer and coworkers have employed Pd-catalyzed amination reactions for the synthesis of AT-aryl poly(w,-p-aniline) derivatives that can be oxidized to high-spin radical cations [346, 347]. The preparation of these materials was accomplished by coupling 1,3-dibromobenzene with A TV -diarylphenylenediamine derivatives (Eq. 65). Palladium-catalyzed A -arylation reactions have also been employed for the preparation of partially annulated poly(w-anilines) [348] and other triarylamine-derived polymers [349, 350]. 

Polyanilines. Initial preparations of polyaniline (PANI) led to insoluble materials that were difficult to characterize. Use of model compounds and polymers (124,125) allowed for definitive stmctural analysis. Poly( phenylene amineimine) (PPAI) was synthesized directiy to demonstrate that PANI is purely para-linked (126). The synthesis was designed so as to allow linkage through the nitrogen atoms only (eq. 9). Comparison of the properties of PPAI and PANI showed PPAI to be an excellent model both stmcturaHy and electronically. 

A possible synthesis of poly(p-phenylene methine) from polybenzyl via redox elimination (A). The two limiting structures of polyaniline (B). 

Alva KS, Marx KA, Kumar J, Tripathy SK (1996) Biochemical synthesis of water soluble polyanilines poly(p-aminobenzoic acid). Macromol Rapid Commun 17(12) 859-863... 

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]. 

An extensive review of the synthesis of rc-conjugated polymers is presented using a tutorial approach to provide an introduction to the field intended for the undergraduate student and the experienced chemist alike. The many synthetic methodologies that have been used for the synthesis of conjugated polymers are outlined for each class of polymers with a focus on research from the 1990s. The effect of structure on electrical properties is detailed. Specific systems reviewed include the polyacetylenes, polyanilines, polypyrroles, polythiophenes, poly(arylene vinylenes), and polyphenylenes. 

AlvaK, Kumar J, Marx KA et al (1997) Enzymatic synthesis and characterization of a novel water soluble polyaniline poly(2, 5 diamino benzene sulfonic acid). Macromolecules 30 4024-4029... 

Aqueous colloidal dispersions created by template synthesis, principally used for processing polyaniline and poly(ethylenedioxythiophene), PEDOT. 

Materials studied are polyaniline, poly(3-octylthio-phene)(POT), and mixtures of poly(3-octylthiophene) (POT) and poly(ethylvinylacelate) (EVA). The synthesis of polyaniline was carried out by oxidation of aniline monomer using (NH4)2S20g in HCl (1 M) -I-HBF4 (1 M) or in the eutectic NH4F, 2.35 HF as... 

---