Emeraldine production

Assuming that the polymerisation does occur via a radical intermediate, then coupling is possible at all three positions on the ring (albeit with differing probabilities) and a number of alternative products to the emeraldine-based structure can be... 

FIG. 11.19 Oxidative doping (p-doping) of leuco-emeraldine base and protonic acid doping of emeraldine base, leading to the same final product, emeraldine salt. Reproduced from Fig. 34.3 in Mark (1996). Courtesy Springer Verlag. 

Unsaturated heterocycles and aniline have been polymerized either chemically or electrochemically on electrode surfaces. The systems are attractive as they are often significantly more stable than PA under atmospheric conditions. The importance of quinoid vs. aromatic structure becomes apparent if the chemistry and conductivity of polyaniline fPANIl is examined. The initial emeraldine salt product of PANI is believed to have the following... 

Encapsulation chemistry similar to that described above (exchange of anilinium, followed by oxidation with peroxydisulfate) was foimd to produce polyaniline not only in zeolite Y, but also in montmorillonite clay. 5 Spectral features (UV-VIS, IR and EPR) of the products were indicative of emeraldine salt and base formation, respectively. The change in basal spacing of the montmorillonite upon intercalation provided additional evidence for the inclusion polymerization. 

Leucoemeraldine is the formal hydrogenation product of emeraldine. As shown in reaction 12, each tetramer unit contains one reducible quinonediimine moiety. 

Polyanilines (Scheme 36) are conjugated polymers whose it electrons are delocalized over the whole molecule. They are important conducting polymers that also act as semiconductors, in a similar manner to inorganic semiconductors121 m. They are made by chemical or electrochemical (anodic) oxidation of aniline. The product, a poor textile colorant, dates from the 1860s, and is still known by the name given at that time, emeraldine. In the electrochemical process, it is possible to produce thin films directly on conductive substrates. Polyanilines have been used in photoelectrochemical devices124-126. 

A remarkable recent example of the influence of electropolymerization temperature on the properties of PAn products is observed in the potentiostatic polymerization of aniline in the presence of chiral (+)-HCSA to give optically active PAn/(+)-HCSA films. The CD spectra of the polymers electrodeposited at < 25°C were inverted compared to the spectra of analogous emeraldine salts deposited at > 40°C, indicating an inversion of the preferred helical hand for PAn chains.38 The observations may be rationalized in terms of a temperature-induced interconversion between two initially (kinetically) formed diastereomeric PAn products. 

A wide range of alkyl- and alkoxy-substituted PAn s of the general types 6 and 7 have been synthesized by the chemical or electrochemical oxidation of appropriately substituted aniline monomers.133 Such substitution imparts markedly improved solubility in organic solvents to the emeraldine salt products compared to the parent (unsubstituted) PAn/HA salts. The poly(2-methoxyaniline) (POMA) species, in particular, has been the subject of extensive studies.134 137 This species has the additional attractive feature of being soluble in water after being wet with acetone. 

The related fully sulfonated, self-doped polymer poly(2-methoxyaniline-5-sulfonic acid) (PMAS 9) may be prepared under normal atmospheric pressure by the oxidation of 2-methoxyaniline-5-sulfonic acid (MAS) monomer with aqueous (NH4)2S208 in the presence of ammonia or pyridine (to permit dissolution of the MAS monomer).141 The polymerization pH was therefore >3.5. Subsequent studies showed that the product consisted of two fractions a major fraction with Mw of ca. 10,000 Da whose electrical conductivity and spectroscopic and redox switching properties were consistent with a PAn emeraldine salt, as well as a nonconducting, electroinactive oligomer (Mw ca. 2,000 Da).143 144 Pure samples of each of these materials can be obtained using cross-flow dialysis.145... 

The synthesized produet was a powder by green color that indicates about production of the emeraldine form of polyaniline, exactly emeral-dine salt Vkn-HCl. The produced samples of PAn/nano-Ti02- S composites had more light tinctures their intensities were decreased with the increasing of the TiO content in the initial reaction mixture. 

PANI is one of the earliest known synthetic polymers, which can date back to 1835 as aniline black for any products produced by the oxidation of aniline. The interest toward PANI increased significantly over the past decades due to its low cost, easy preparation, high conductivity, mechanical flexibility, environmentally stability, and unusually doping/dedoping chemistry. Besides, PANI also has three distinct oxidation states with different colors, naming leucoemeraldine, emeraldine, and pernigraniline. 

Introduction Concentrated Emeraldine Base Solutions Containing Secondary Amine Gel Inhibitors Recent Advances in the Production of Base Processed Textile Fibers ... 

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