Polymerization, anionic electrochemical

Shimizu et al. used simple rhodium-aqua ions (Rh3+) immobilized onto polymer-modified electrodes to perform the electrochemical reduction of NAD+ [114]. Rh3+ was loaded onto polymeric anion doped-polypyrrole membranes coated on the surface. Electrochemical reduction of NAD+ with immobilized Rh3+ was performed at —0.85 V, where Rh3+ was reduced to Rh+. NADH was produced without detectable formation of NAD-dimers. 

Some applications of polypyrrole, such as drug delivery devices, require specific ion transport. Control of the ion transport process requires determination of the identity of the mobile ion, which is complicate by the fact that there are several ions present in the system. Moreover, Shimidzu and co-woiicers [138,139] demonstrated that ion transport in polypyrrole can be modified by the use of polymeric anions as dopants. Miller and Zhou [140] proved that the electrochemical switching of polypyrrole could achieve controlled release of small anions (such as CIO4), while the incorporation of an immobile polyanion (such as polystyrene sulfonate) resulted in cation transport. The polyanions become trapped within the polypyrrole matrix due to their large size and, perhaps more important, their entanglement with the polypyrrole chains. This increases the stability and mechanical strength of polypyrrole and improves electrical conductivity and electroactivity [141,142]. Therefore it has been of significant interest in the polymerization of pyrrole in polyanion electrolyte solutions [143,144]. 

The electrochemical polymerization often proceeds with an electrochemical stoichiometry of 2 electrons/polymerized unit. A charge in excess of 2 is consumed in the doping or partial oxidation of the polymeric film which is formed on the carrier electrode. In the oxidative polymerization anions of the electrolyte are incorporated into the polymer matrix. 

Many perfluoroaUphatic ethers and tertiary amines have been prepared by electrochemical fluorination (1 6), direct fluorination using elemental fluorine (7—9), or, in a few cases, by fluorination using cobalt trifluoride (10). Examples of lower molecular weight materials are shown in Table 1. In addition to these, there are three commercial classes of perfluoropolyethers prepared by anionic polymerization of hexafluoropropene oxide [428-59-1] (11,12), photooxidation of hexafluoropropene [116-15-4] or tetrafluoroethene [116-14-3] (13,14), or by anionic ring-opening polymeriza tion of tetrafluorooxetane [765-63-9] followed by direct fluorination (15). 

Reactive radical ions, cations and anions are frequent intermediates in organic electrode reactions and they can serve as polymerization initiators, e.g. for vinylic polymerization. The idea of electrochemically induced polymerization of monomers has been occasionally pursued and the principle has in fact been demonstrated for a number of polymers But it appears that apart from special cases with anionic initiation the heterogeneous initiation is unfavorable and thus not competitive for the production of bulk polymers A further adverse effect is the coating of electrodes... 

E. Bakker and E. Pretsch, Lipophilicity of tetraphenylborate derivatives as anionic sites in neutral carrier-based solvent polymeric membranes and lifetime of corresponding ion-selective electrochemical and optical sensors. Anal. Chim. Acta 309, 7-17 (1995). 

Polymeric mixed-valent Rh(I)-Rh(II) complexes of the type [Rh2(Me-C02)(N-N)2(anion)] (N-N = bipy, phen anion = BF4, PF6) have been also structurally characterized,49 but no electrochemical intervention has been occurred in their preparation. 

There are a few reports of poly(naphthalene) thin films. Yoshino and co-workers. used electrochemical polymerization to obtain poly(2,6-naphthalene) film from a solution of naphthalene and nitrobenzene with a composite electrolyte of copper(II) chloride and lithium hexafluoroarsenate. Zotti and co-workers prepared poly( 1,4-naphthalene) film by anionic coupling of naphthalene on. platinum or glassy carbon electrodes with tetrabutylammonium tetrafluoroborate as an electrolyte in anhydrous acetonitrile and 1,2-dichloroethane. Recently, Hara and Toshima prepared a purple-colored poly( 1,4-naphthalene) film by electrochemical polymerization of naphthalene using a mixed electrolyte of aluminum chloride and cuprous chloride. Although the film was contaminated with the electrolyte, the polymer had very high thermal stability (decomposition temperature of 546°C). The only catalyst-free poly(naphthalene) which utilized a unique chemistry, Bergman s cycloaromatization, was obtained by Tour and co-workers recently (vide infra). 

Quinaxoline-containing monomer 14 was electrochemically polymerized to yield a polythiophene that changed from a yellow to orange color upon the addition of fluoride or pyrophosphate anions (Aldakov and Anzenbacher 2004). Analyte binding could be detected spectroscopically and electrochemically. 

---