The possibility of using EPR spectroscopy to monitor the current concentration of polyaniline and control the kinetics of aniline polymerization is shown. Kinetic measurements were carried out for various temperatures, initial concentrations of reagents. Autocatalysis was detected in all cases. It was shown that the order of polyaniline-catalyzed oxidation of aniline changes from the first to the second as a result of a decrease in the monomer concentration. A new approach to deriving an equation for the rate of oxidative polymerization of aniline and its derivatives is proposed taking into account the physical adsorption and chemisorption of the monomer, and the reaction mechanism is considered.

Aspects of application of nitrogen-containing polyconjugated systems in electronics are considered. It is shown that the use of polyaniline and polypyrrole in the manufacture of structural elements of current sources and supercapacitors has significant prospects for increasing the efficiency of these devices. The fundamental possibility of using polyaniline in the creation of electrochromic displays and photovoltaic cells is shown.

Kinetics of the oxidative polymerization of aniline in toluene induced by manganese (IV) oxide deposited on the surface of silica gel was studied using ESR spectroscopy. The initial rate of an interfacial process decreases rapidly, and then polymerization proceeds as pseudo-first order reaction for the surface concentration of manganese (IV) oxide with an activation energy of 23 kJ x mol(-1). A low activation energy indicates that the overall rate is controlled by aniline diffusion into the reaction zone. The specific surfaces and the distribution of pore volume by radii of the silica gel samples before and after the deposition of manganese (IV) oxide on its surface, as well as after oxidative polymerization of aniline were determined. Oxidative polymerization of aniline causes a shift in the pore volume distribution along the radii to the region of larger pore radii, which indicates the predominant filling of pores of small diameter with polyaniline.

The study of pyrrole oxidative polymerization in toluene localized on the surface of silica gel modified with manganese oxide (IV) was carried out. The kinetics of pyrrole oxidative polymerization on the surface was established, a kinetic model was proposed, and its parameters were calculated. It was shown that the activation energy is close to free energy of the viscous toluene flow that indicates diffusion control of the process. The changes of the specific surface area of silica gel and the pore volume distribution along the radii during the modification with manganese dioxide and the subsequent polymerization of pyrrole were determined.

Current ideas about the electronic and crystal structures of nitrogen-containing conductive polymers are considered. A comparative critical analysis of literature data on electronic, vibrational, and NMR spectra for different nuclei, and X-ray diffraction data for various forms of polyaniline, polyphenylenediamine, and polypyrrole is presented. Particular attention is paid to the relationship between the electronic and crystal structure of nitrogen-containing polyconjugated systems and their electrical conductivity.

Kinetics of the oxidative polymerization of pyrrole in an aqueous solution of poly(vinyl alcohol) under the action of ammonium peroxydisulfate has been studied. The obtained kinetic data has been quantitatively described with regard to the formation of a new phase, the values of activation energy for the non-catalytic and catalytic stages of the oxidative pyrrole polymerization have been determined. Various mechanisms of oxidative polymerization of pyrrole have been critically evaluated, and the calculated kinetic parameters have been compared with their values available in the literature for oxidative pyrrole polymerization in the absence of stabilizers.

Synthesis of amphiphilic oligomers of acrylic acid via radical polymerization in the presence of thiols as molecular mass regulators is described. The effect of the length of the introduced hydrophobic terminal group on the critical micellization concentration of the acrylic acid oligomers has been elucidated. It has been shown that the incorporation of an antituberculous drug (prothionamide) in the micelles of acrylic acid oligomers is enhanced with the increase in the length of the hydrophobic moiety. The preparation of hydroxyapatite-filled calcium-polycarboxylate bone cements containing prothionamide (promising for the sealing of postoperative cavities) is described.

A procedure was suggested for preparing nanoparticles consisting of magnetite and poly(o-phenylenediamine) by combining the hydrolysis of a mixture of iron(II) and (III) sulfates with oxidative polymerization of o-phenylenediamine. These nanoparticles efficiently bind phenylalanine, thyrosine, tryptophan, and doxorubicin in aqueous solution.

An examination is made of the kinetic laws governing the oxidative polymerisation of aniline in an aqueous solution of polyvinyl chloride. The change in the order of the reaction with increase in temperature is shown, which is due to the heterogeneous autocatalytic nature of the process.

IR spectroscopy was used in an investigation of the structure of particles obtained by the centrifuging of an aqueous polyaniline dispersion stabilised by polyvinyl alcohol. It was shown that stabiliser chains are fixed by hydrogen bonds.

Kinetics of oxidative polymerization of three isomeric phenylenediamines in aqueous hydrochloric acid solutions initialed by ammonium persulfate has been studied, and kinetic parameters of non-catalytic and catalytic stages of polymerization have been determined. The observed effect of the isomeric substrates structure on the activation energy of the catalytic and non-catalytic stages has been explained.

The kinetics of polymerization of aniline hydrochloride in aqueous poly(ethylene oxide) solution in the presence of ammonium persulfate have been studied. The order of the catalytic step has been found to change from first to second when the molecular weight of poly(ethylene oxide) reaches a certain value. Adsorption equilibrium is rapidly established between the monomer and its oxidation products which give rise to a new phase and exert a catalytic effect.

A mechanism of the oxidative polymerization of aromatic amines, including the step of formation of a complex with charge transfer between quinonediimine fragments of oligomer chains and the monomer, is proposed. Quantitative characteristics of the kinetics of the oxidative polymerization of aromatic amines are theoretically justified and experimentally confirmed. It is demonstrated that the growth of chains during the oxidative polymerization occurs exclusively due to the recombination of the cation-radicals of oligomers of the aromatic amines with monomer cation-radicals.

Technological process for electrochemical modification of the surface of carbon fibers was developed. This process makes it possible to raise by 20% the tensile strength of a carbon-fiber-reinforced composite material based on these fibers as compared with the strength of composite materials with untreated carbon fibers. It is shown that an anodic treatment of a carbon fiber in an aqueous solution of aniline or pyrrole results in that oxidative polymerization occurs on its surface to give polyaniline or polypyrrole, which improves the strength of composite materials based on this carbon fiber.

The kinetics of oxidative polymerisation of 2-methoxyaniline was investigated, and the activation energies of stages of single-electron transfer and complex formation were determined. The parallel occurrence of oxidative degradation of poly-(2-methoxyaniline) under conditions of oxidative polymerisation of 2-methoxyaniline was established.

Kinetics of polymerization of N-ethylaniline hydrochloride initiated in aqueous solution by ammonium persulfate has been studied. The auto-catalytic nature of the reaction has been revealed; the order of the catalytic stage has been determined; the rate constants of single-electron transfer and the complex formation have been calculated. Quinonediimine fragments have been found in the poly-N-ethylaniline; their formation mechanism has been suggested.

Stabilized polypyrrole dispersions were prepared by oxidative polymerization of pyrrole in aqueous solution of polyvinyl alcohol. The influence of the concentration and molecular mass of polyvinyl alcohol in the reaction mixture on the size of the particles formed was examined, and the particle structure was determined. The possibility of preparing hemocompatible films from aqueous polypyrrole dispersions stabilized with polyvinyl alcohol was demonstrated.

Electrochemical oxidative polymerization of o-phenylenediamine on a carbon fiber anode under potentiostatic conditions was studied. Deposition of poly(o-phenylenediamine) on the carbon fiber surface was proved by scanning electron microscopy and IR spectroscopy. The electrodeposition of poly(o-phenylenediamine) on the carbon fiber surface enhances the strength of carbon-fiber-reinforced composite materials with epoxy matrix.

Certain rheological properties of aqueous dispersions of polyaniline in the presence of poly-(N-vinylpyrrolidone) as a stabiliser were investigated. The influence of the molecular weight of poly-(N-vinylpyrrolidone) and also the concentration of aniline and ammonium peroxydisulphate on the size and shape of the polyaniline particles was shown.

Anticorrosion coatings based on a crosslinked copolymer of pyrrole and glycidyl methacrylate and also a copolymer of N-vinylpyrrolidone and allyl glycidyl ether were obtained on the surface of iron and zinc. The inhibition of corrosion by polypyrrole was shown, a mechanism of the process was proposed, and the synthesis of coatings was optimised.