Gennady Zaikov

To identify the specific features of the kinetics of oxidation of polymer mixtures, determine the key structural elements, and create a model that can describe the mechanism of thermal oxidation of polymer mixtures, it is necessary to determine the relation between the initial structure of a polymer mixture, structural rearrangements associated with oxidation and the kinetics of the process. The aim of this book is to elucidate the complicated problem concerning the connection between the structure and mechanism of oxidation of heterogeneous and heterophase polymer systems. The material presented in this book concerns the specific features of the kinetics of oxidation and those of the structure of polymer systems. The book deals with an analysis of the key factors that can affect principally the mechanism of thermal oxidation of polymer mixtures, determines the role of the phase morphology, structure of components, and the interface layer (or boundary) in the kinetics of oxidation of heterophase system by an example of mixtures of polyolefines. Along with the kinetics of oxidation of heterophase systems, problems of investigation of their structural parameters in the oxidized state are considered. With this aim, the material presented in the book concerns not only the mechanism of oxidation of polymer mixtures but also homopolymers of diverse morphology and model systems.

The basic problem of polymer physics is obtaining ‘structure-properties’ correlations for their future application for practical purposes. However, these cannot be obtained without the development of a quantitative model of the polymer structure. This problem has been actively investigated during the last 45 years, which resulted in obtaining a great amount of experimental (mostly indirect) proofs of existence of the local order in the polymer amorphous state. Now, the time has come for creating a structural model of polymer basing based on the local order ideas. The cluster model, as presented in this monograph, of the polymer amorphous state structure represents the realization of such attempts. The development of this cluster model is based on well-known experimental observation: the behavior of glassy polymers in the area of stimulated high-elasticity plateau is described in the framework of rubber elasticity concepts. This gives an opportunity to present the local order (cluster) zone as a multifunctional entanglement of the physical network consisting of several collinear closely packed segments of different macromolecules (the amorphous analogue of crystallite with extended chains) and surrounded by a packless matrix. An independent method for assessing local order zone fraction in the structure has been elaborated. Segment length in the cluster equals the length of the chain statistical segment that gives a correlation between molecular and structural parameters of the polymer. Application of the cluster model allowed description and obtaining of analytical ‘structure-properties’ correlations for many processes proceeding in polymers: elasticity, yielding, degradation, transport, some thermodynamic processes, structural relaxation, plasticization, structural stabilization at thermo-oxidative degradation, etc. The relation between the cluster model and some modern physical concepts, for instance fractal analysis, fluctuation free volume kinetic

This volume in the book series New Concepts in Polymer Science deals with the damaging effects, which microorganisms such as bacteria, fungi, etc. can have on a range of materials in machinery. The book aims to provide theoretical notions about the mechanisms of material damaging by microorganisms under operation conditions as well as to give recommendations for protection of technical articles and machinery. This monograph consists of the following topics: finding of kinetic regularities, analytical models and quantitative indices for stages material biodamaging; study of influence of properties of materials, features of microorganisms, temperature, humidity and other factors on interaction between a material and a biodestructor; and, compilation of guidelines to determine and forecast biological resistance (bioresistance) of materials, development of means and methods for their protection as well as estimates of their efficiency. This monograph will be of value and interest to researchers and engineers working in fields in which materials are subject to active microbiological aging and destruction.

This book examines the current state of the art, new challenges, opportunities, and applications in the area of polymer nanocomposites. Special attention has been paid to the processing-morphology-structure-property relationship of the system. Various unresolved issues and new challenges in the field of polymer nanocompostes are discussed. The influence of preparation techniques (processing) on the generation of morphologies and the dependence of these morphologies on the properties of the system are treated in detail. This book also illustrates different techniques used for the characterization of polymer nanocomposites. The handpicked selection of topics and expert contributors across the globe make this survey an outstanding resource reference for anyone involved in the field of polymer nanocompostes for advanced technologies.

Most developed Si-N containing oligomers and polymers are silazaneorganic oligomers and polymers - one of the applicable siliconorganic poly-functional compounds with inorganic-organic main chains. They are using for production of various important technical compositions and materials with specific properties: polymer varnishes and coatings, water-repellents, polymer ceramics and silicon-nitride fibers, etc. They also successfully used in nanotechnology and as modifiers of the other organic and elementorganic oligomers, polymers and materials on their basis. In this book are described practically important and technologically justified four methods for obtaining polyfunctional siliconorganic polymers with organic - inorganic main chains.

This book examines the current state of the art, new challenges, opportunities, and applications in the area of polymer nanocomposites. Special attention has been paid to the processing-morphology-structure-property relationship of the system. Various unresolved issues and new challenges in the field of polymer nanocompostes are discussed. The influence of preparation techniques (processing) on the generation of morphologies and the dependence of these morphologies on the properties of the system are treated in detail. This book also illustrates different techniques used for the characterization of polymer nanocomposites. The handpicked selection of topics and expert contributors across the globe make this survey an outstanding resource reference for anyone involved in the field of polymer nanocompostes for advanced technologies.

This book is a collection of technical papers focusing on the preparation, characterization and application of polymer nanocomposites. The various chapters in the book are written by prominent researchers from industry, academia, and government/private research laboratories across the globe. Different techniques adopted for the preparation of nanocomposites, their methods of characterization and their applications are discussed. The main objective of this book is to summarize in a fairly comprehensive manner many of the recent technical accomplishments in the area of polymer nanocomposites. The book is intended to serve as a one stop reference resource for important research accomplishments in the area of polymer nanocomposites.

The book is devoted to kinetics and thermodynamics of the processes with participation of some biological compounds and their synthetic analogues. Aspects of their acting as model enzymes, molecular receptors, photo sensitizers, pharmocophores, and biopharmaceutical compounds are under consideration. Quantitative characteristics of transfer of cations, anions and small organic molecules, fermentative catalysis, diffusion of the drug molecular through biological membranes are found. Mechanisms of the processes are discussed. Biological activity of studied compounds is evaluated. Bio-damages of materials as well as adhesions of microorganisms on materials surface are investigated.

New fields of science and technology call for new materials with valuable performance characteristics. Long-term resistance to such temperatures can be found only in polymers with chains made up of thermostable fragments. Particularly interesting in this respect are elementorganic polymers with inorganic and organo-inorganic molecular chains. Elementorganic polymers are not only highly thermostable, but also perform well under low temperatures, sunlight, humidity, weather, etc. Thus, these polymers (especially silicones) are widely and effectively used in the electrical, radio, coal, mechanical rubber, aircraft, metallurgical, textile, and other industries. They are of great utility not only in industry, but also in households and in medicine, where their merits can hardly be overestimated. The need to publish this book arose with the scientific and technical developments of the last decade, the reconstruction and technical renovation of existing factories, as well as fundamental changes in some syntheses of elementorganic monomers and polymers. Moreover, nowadays it is essential to train highly skilled chemical engineers with a comprehensive knowledge of current chemistry, of the production technology of elementorganic monomers and polymers, and of their characteristics and applications.

The book generally shows the interrelation between allyl unit structure of the initial ester and composition and structure of its products. The first part studies the pathways of chemical regrouping in chlorallylaryl and bisarylallyl esters using quantum-chemical calculations. Energy parameters, structural features and electron structure of intermediates and transition states are also discussed. Simple and regioselective methods for compound synthesis inaccessible in other production techniques are developed. For the first time, new four- and eight-term nitrogen-containing heterocyclic compounds were produced by aniline alkenylation technique. In 0.05% aqueous solution these compounds displayed 100% activity in suppression of sulfate-reducing bacterium growth. Two new classes of complex action preparations designed for the oil production rate increase were obtained by heterocyclic amine alkenylation. Production methods for N-alkenyl ammonium salts derived from hexamethylene tetramine are developed and introduced into production, and compounds are used on oil fields. In the second part production methods of new mono-, di-, tri- and tetra-tert-butyl hexamethylene tetramine chlorides are discussed. These compounds fully suppress sulfate-reducing bacterium growth already in 200 – 500 mg/l concentration. A universal technology deriving bactericides and sulfide corrosion inhibitors for metals from methallyl chloride is developed. It also gives a method for organochlorine waste and methallyl chloride production wastewater management, safe for the environment.

This book deals with the fundamental laws of passing of fast liquid-phase chemical as well as heat and mass transfer processes in turbulent flows. The fundamental laws of passing of fast liquid-phase chemical and also heat and mass transfer processes in turbulent flows are considered in the book. Development of a macrokinetics approach is generalized to the analysis of fast chemical reactions mainly based on an example of cationic isobutylene polymerization, which falls into to a new class of liquid-phase processes. The ways of decision of the hydrodynamical, thermal and kinetic movement’s equations of reaction mixture in which the fast exothermic chemical reaction runs are described. The principles and laws of formation of the essentially new mode of quasi-plug-flow mode are considered in turbulent flows ensuring quasi-isothermal conditions in zone reaction. The principles of work and area of industrial use of tubular turbulent devices cylindrical reactor, divergent-covergent reactor, shell-and-tube reactor, and reactor with fractional introduction of reactants are considered.

This book presents investigation results of thermal transformations in thermoresistant polymers: polysulfones, polyester-imides, aliphatic-aromatic polyimides and polyamides, liquid-crystal aromatic co-polyesters, polyphenylquinoxalines at temperatures of materials and articles processing and operation. An important result of investigations is the determination of thermooxidative degradation regularities for aliphatic-aromatic heterochain polymers and description of the degradation mechanism. The applied aspect of this work is the approach to stabilization of thermoresistant polymers and composite materials derived from them using additives and analysis of the mechanism of high-temperature inhibited oxidation. The book presents results which have been obtained through many years of research until recently, mostly obtained by scientists of G. S. Petrov Research Institute of Polymeric Materials (Moscow, Russia) – one of the leading Institutes in this branch - which have not been available in international scientific publications before.

The main focus in this monograph is on models of the kinetics of photo-initiated polymerization of mono- and bi-functional monomers up to the high conversion stage, their derivation, analysis and comparison with the experimental data. This monograph can be useful for scientists, engineers, post-graduate training students and students who are interested in problems both of the polymerization kinetics and general chemical kinetics.

The behavior of substances in solutions may not be adequately characterized by the effect of any single physicochemical parameter of solvents, nor are numerous semi-empirical scales of the solvent effect (their ‘polarity’) suitable for their limited selections only. In recent decades, it has been found that the variation of reaction rate constants in solutions or that spectral parameters of dissolved substances are determined by the total effect of different solvation processes. This monograph presents numerous examples of such an approach and characterizes various empirical and semi-empirical scales of solvent properties. It is shown that additional consideration of some structural parameters of solvents, namely, their cohesive energy and the molar volume, may provide for spreading this approach on homolytical and catalytic reaction. It is also shown that for the solvolysis reaction, one of the excessive reagents may represent either a reagent or a solvent, which requires additional consideration of its structural characteristics in the Hammeth equation. The application of the principle of free energy linearity also allowed adequate generalization of data on the effect of solvents on different physicochemical processes, such as dissolution of gases and solids in various solvents, swelling of polymers and solid fossil fuels, coal extraction, adsorption, absorption, diffusion, and chromatography. Special attention is paid to substance distribution between two immiscible phases. Properties of both an extractive phase and an active extractant dissolved in inert diluter are taken into account. The majority of these processes indicate the efficiency of solvent self-association factor that defines the energy consumption for formation of a void for an alien molecule injection.

The monograph is intended for elucidation of the novel trend in chemical physics regarding the polymer non-crystalline phase. It stresses the physical phenomena affecting the kinetics and mechanism of chemical reactions proceeding in the non-crystalline polymer matrix (NCPM). NCPM is depicted in terms of a supramolecular (carcass-micellar) model. The model is thought to reflect heterophase packing of polymeric chains, which co-operate as a molecular-chain sponge. The NCPM model presented is proved for adequate description of principal structure-physical phenomena to elaborate the scheme of structural-kinetic modeling of chemical reactions in bulky polymers. Structure-physical phenomena elucidated in the monograph are: - peculiarities of polymer plasticization and polymer blending with liquids; - structural and thermodynamic aspects of sorption of low molecular species; - properties of ESR (spin) probes and optical (molecular) probes; - features of water absorbed by polymers; - mechanical and thermal effects generated by the molecular-chain sponge; - supramolecular aspects of NCPM chemical physics. This monograph includes the structural-kinetic modeling of complex polymer chemical reactions. It deals with the problem of mechanism and kinetics of free radical chain reactions using thermal and photochemical model reactions of dibenzoyl peroxide with glassy-like polymers (cellulose triacetate, polycarbonate, polystyrene, polyamide PA-548), viscoelastic polymers (atactic polypropylene, polyamide PA-548, polyethylene, polyisobutylene, melted poly(ethylene oxide), and isotactic polypropylene. In all cases, the supramolecular heterophase mechanism of the processes, which was unknown for homogeneous systems, was proved. Furthermore, heterophase mechanisms of photochemical reaction between naphthalene and cellulose triacetate and photolysis of poly(methyl methacrylate) proceeding as a photochain reaction are indicated.

The basic problem of polymer physics is obtaining ‘structure-properties’ correlations for their future application for practical purposes. However, these cannot be obtained without the development of a quantitative model of the polymer structure. This problem has been actively investigated during the last 45 years, which resulted in obtaining a great amount of experimental (mostly indirect) proofs of existence of the local order in the polymer amorphous state. Now, the time has come for creating a structural model of polymer basing based on the local order ideas. The cluster model, as presented in this monograph, of the polymer amorphous state structure represents the realization of such attempts. The development of this cluster model is based on well-known experimental observation: the behavior of glassy polymers in the area of stimulated high-elasticity plateau is described in the framework of rubber elasticity concepts. This gives an opportunity to present the local order (cluster) zone as a multifunctional entanglement of the physical network consisting of several collinear closely packed segments of different macromolecules (the amorphous analogue of crystallite with extended chains) and surrounded by a packless matrix. An independent method for assessing local order zone fraction in the structure has been elaborated. Segment length in the cluster equals the length of the chain statistical segment that gives a correlation between molecular and structural parameters of the polymer. Application of the cluster model allowed description and obtaining of analytical ‘structure-properties’ correlations for many processes proceeding in polymers: elasticity, yielding, degradation, transport, some thermodynamic processes, structural relaxation, plasticization, structural stabilization at thermo-oxidative degradation, etc. The relation between the cluster model and some modern physical concepts, for instance fractal analysis, fluctuation free volume kinetic

The demand for organosilicon elastomers used in the production of thermally resistant rubbers and organosilicon polymers for making non-metal composite materials is increasing from year to year. This monograph presents a discussion on the methods used for synthesizing and studying properties of newly designed organosilicon polymers, namely organosiloxane copolymers with cyclolinear structure of macromolecules. This book presents an overview of data on methods of synthesizing primary linear and cyclic organosiloxanes of various structures. This book will be of value and interest to researchers working in the field of chemistry of organosilicons.

This volume in the book series New Concepts in Polymer Science deals with the damaging effects, which microorganisms such as bacteria, fungi, etc. can have on a range of materials in machinery. The book aims to provide theoretical notions about the mechanisms of material damaging by microorganisms under operation conditions as well as to give recommendations for protection of technical articles and machinery. This monograph consists of the following topics: finding of kinetic regularities, analytical models and quantitative indices for stages material biodamaging; study of influence of properties of materials, features of microorganisms, temperature, humidity and other factors on interaction between a material and a biodestructor; and, compilation of guidelines to determine and forecast biological resistance (bioresistance) of materials, development of means and methods for their protection as well as estimates of their efficiency. This monograph will be of value and interest to researchers and engineers working in fields in which materials are subject to active microbiological aging and destruction.

This new volume in the book series New Concepts in Polymer Science focuses on the problem of creating materials with reduced combustibility as well as the use of polymeric materials for protection from fire or overheating. The majority of polymeric materials are combustible, which has led to the development of polymers, and materials based on these, with reduced combustibility. However the combustibility degree or their ability to protect from fire or high temperature can be indicated only in particular cases of combustion. In this volume the results of the development of physicochemical bases for creating organic polymeric materials with reduced combustibility, which are capable of protecting against high temperatures are discussed. A presentation of chlorinated polyolefins as organic polymers with reduced combustibility is also given.

The discovery of molecular and cellular mechanisms of pathology, together with the present data on drug treatment result in enhanced drug design and testing. The known mechanisms of biological activity as displayed by ascorbic acid and other natural reductones are the reason that they are considered to be physiologically compatible antioxidants, many of which are trace elements in food. The pharmacological potential of natural antioxidants may be enhanced by chemical modification. Biotic antioxidants possess an important potential to be a reliable basis of the development of new multipurpose drugs, within the framework of existing technological structures. This book shows approaches for possible use of these natural antioxidants. In particular, such an approach is described for the case of the design of superoxide dismutase models with anti-tumour activity.