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PHYSICS RESEARCH AND TECHNOLOGY
RESEARCH PROGRESS IN CHEMICAL PHYSICS AND BIOCHEMICAL PHYSICS
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PURE AND APPLIED SCIENCE
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Additional E-books in this series can be found on Nova’s website under the E-book tab.
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Additional books in this series can be found on Nova’s website under the Series tab.
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PHYSICS RESEARCH AND TECHNOLOGY
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PHYSICS RESEARCH AND TECHNOLOGY
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RESEARCH PROGRESS IN CHEMICAL PHYSICS AND BIOCHEMICAL PHYSICS
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PURE AND APPLIED SCIENCE
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GENNADY E. ZAIKOV ALEXANDR A. BERLIN KRZYSZTOF MAJEWSKI AND
EDITORS
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ANDREY A. PIMERZIN
New York
All rights reserved. No part of this book may be reproduced, stored in a retrieval system or transmitted in any form or by any means: electronic, electrostatic, magnetic, tape, mechanical photocopying, recording or otherwise without the written permission of the Publisher.
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For permission to use material from this book please contact us: Telephone 631-231-7269; Fax 631-231-8175 Web Site: http://www.novapublishers.com
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Copyright © 2014 by Nova Science Publishers, Inc.
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NOTICE TO THE READER The Publisher has taken reasonable care in the preparation of this book, but makes no expressed or implied warranty of any kind and assumes no responsibility for any errors or omissions. No liability is assumed for incidental or consequential damages in connection with or arising out of information contained in this book. The Publisher shall not be liable for any special, consequential, or exemplary damages resulting, in whole or in part, from the readers’ use of, or reliance upon, this material. Any parts of this book based on government reports are so indicated and copyright is claimed for those parts to the extent applicable to compilations of such works. Independent verification should be sought for any data, advice or recommendations contained in this book. In addition, no responsibility is assumed by the publisher for any injury and/or damage to persons or property arising from any methods, products, instructions, ideas or otherwise contained in this publication.
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This publication is designed to provide accurate and authoritative information with regard to the subject matter covered herein. It is sold with the clear understanding that the Publisher is not engaged in rendering legal or any other professional services. If legal or any other expert assistance is required, the services of a competent person should be sought. FROM A DECLARATION OF PARTICIPANTS JOINTLY ADOPTED BY A COMMITTEE OF THE AMERICAN BAR ASSOCIATION AND A COMMITTEE OF PUBLISHERS.
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Additional color graphics may be available in the e-book version of this book.
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Library of Congress Cataloging-in-Publication Data
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ISBN: 978-1-63117-066-9
Published by Nova Science Publishers, Inc. † New York
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c. Preface
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CONTENTS
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Ozonation of Hydrocarbons S. Rakovsky, M. Anachkov, V. Georgiev, A. Berlin, M. Belitski and G. E. Zaikov
Chapter 2
Synthesis and Investigation Properties of Epoxy Containing Compounds and Composite Materials on their Basis E. Markarashvili, T. Tatrishvili, N. Koiava, A. Berlin, G. E. Zaikov, J. Aneli and O. Mukbaniani
Biodetoxication of Aromatic Hydrocarbons in Aqueous Media M. D. Goldfein, A. S. Tregub and O. V. Turkovskaya
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Chapter 5
Hydrosilylation Reactions of Polymethylhydrosiloxane with Acrylates and Methacrylates and Solid Polymer Electrolyte Membranes on their Basis T. Tatrishvili, G. Titvinidze, N. Pirckheliani, J. Aneli, G. E. Zaikov and O. Mukbaniani
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Chapter 4
Biodegradable Binary and Ternary Blends of Cellulose and Ethyl Cellulose with Synthetic and Natural Polymers S. Z. Rogovina, K. V. Aleksanyan, S. M. Lomakin and E. V. Prut
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Chapter 3
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Chapter 1
Modern Immunochemical and Biosensor Technologies for Analysis of Environmental Ecotoxicants M. D. Goldfein and V. V. Zyryanov
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Chapter 6
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Chapter 7
Chapter 8
Poly (3-Hydroxybutyrate) with Ethylene-Propylene Copolymer Blends: Structure and Calorimetry Properties A. A. Ol'khov, L. S. Shibryaeva, Yu. V. Tertyshnaya, A. L. Iordanskii, M. A. Goldshtrakh and G. E. Zaikov Adaptogens Decrease the Generation of Reactive Oxygen Species by Mitochondria V. Zhigacheva and E. B. Burlakova
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Contents
Chapter 13
Chapter 14
Chapter 15
Reaction of Ozone with Some Oxygen-Containing Organic Compounds S. Rakovsky, M. Anachkov and G. E. Zaikov
Enhanced Oil Recovery Using Binary Mixture (BM) Reaction Products as an Alternative to Increasing Reservoir Water Content E. N. Aleksandrov, P. E. Aleksandrov, N. M. Kuznetsov, V. Yu. Lidzhi-Goryaev and A. L. Petrov Assessment of the Potential of Enhanced Oil Recovery from Reservoirs with High Water Content Using the Heat of Nitrate Oxidation Reactions and In Situ Hydrocarbon Oxidation E. N. Aleksandrov, P. E. Aleksandrov, N. M. Kuznetsov, A. L. Petrov and V. Yu. Lidzhi-Goryaev Blends of Poly (3-Hydroxybutyrate) with an Ethylene-Propylene Copolymer A. A. Ol'khov, A. L. Iordanskii, K. Majewski and G. E. Zaikov
Chapter 18
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Degradation of Films Based on Mixtures of Vinyl Alcohol with Vinyl Acetate Copolymers and Polyhydroxybutyrate under UV-Radiation A. A. Ol’khov, A. L. Iordansky, G. E. Zaikov, O. V. Stoyanov, L. A. Zenitova and S. Yu. Sofina
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Chapter 17
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Kinetics of Photoinitiated Copolymerization of Bifunctional (Meth)Acrylates till High Conversion: Numerical Verification of Kinetic Model of the Process G. I. Khovanets', Yu. G. Medvedevskikh, I. Yu. Yevchuk and G. E. Zaikov
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Chapter 16
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Chapter 12
Structures (Monomer and Dimer) of Sodium and Potassium 2-(N-Methylamide)-2-(3',5'-Di-tert.butyl-4-hydroxybenzyl)Malonates and Biological Properties G. E. Zaikov, A. A. Volodkin, V. N. Erokhin, E. B. Burlakova and S. M. Lomakin
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Chapter 11
Formation of Ozonides and their Stability in the Process of Unsaturated Polymers in Latex P. T. Poluektov, L. A. Vlasova, S. S. Nikulin and V. M. Misin
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Chapter 10
Quantum-Chemical Calculation of Some Molecules Aromatic Olefines by the Method MNDO V. A. Babkin, D. S. Zakharov and G. E. Zaikov
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Chapter 9
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Nanofibrous Polyhydroxybutyrate-Based Biomaterials A. A. Ol’khov, O. V. Staroverova, Yu. N. Filatov, G. M. Kuzmicheva, A. L. Iordansky, G. E. Zaikov, O. V. Stoyanov and L. A. Zenitova
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Chapter 21
Chapter 22
Chapter 23
Challenges and Development Perspectives on Nanopatterned Implants Loaded with Drugs A. L. Iordanskii, S. Z. Rogovina, I. Afanasov and A. A. Berlin
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Chapter 27
Chapter 28
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The Regularity of Cracks Formation on Vulcanized Elastomers under Ozone Action: Polyisoprene V. Podmasteryev, S. Razumovsky and G. E. Zaikov
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The Evaluation of Efficiency of Deposition of Dispersed Particles in Inertial Dust Separator R. R. Usmanova, Krzysztof Majewski and G. E. Zaikov
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Comparative Evaluation of Viability of Cells of Probiotic Strains by Luminescence Microscopy and Flow Cytometry L. P. Blinkova, Yu. D. Pakhomov, O. V. Dmitrieva, R. V. Zhelankin and E. A. Akhmatov
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Chapter 25
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The Structural Analysis of Nanocomposites Polymer/Organoclay Flame-Resistance I. V. Dolbin, G. V. Kozlov and G. E. Zaikov
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Chapter 24
The Study of Influence of Dihydroquercetin and Cyclodextrin Inclusion Complex with the New Dihydroquercetin Derivative on Ozone Oxidation of Fibrinogen V. S. Rogovsky, T. M. Arzamasova, M. A. Rosenfeld, M. L. Konstantinova, V. B. Leonova, S. D. Razumovsky, G. E. Zaikov, A. I. Matyoushin, N. L. Shimanovsky, A. M. Koroteev, S. E. Mosyurov, M. P. Koroteev, T. S. Kuhareva and E. Е. Nifantiev
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Chapter 20
Influence of Aminoalkoxy- and Glycidoxyalkoxysilanes on Adhesion Characteristics of Ethylene Copolymers N. E. Temnikova, S. N. Rusanova, S. Yu. Sofina, O. V. Stoyanov, R. M. Garipov, A. E. Chalykh, V. K. Gerasimov and G. E. Zaikov
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Chapter 19
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Contents
The Interrelation Structure and Thermodynamic Properties in the Five-Membered O- and N-Heterocyclic Compounds Sergey P. Verevkin, Vladimir N. Emel’yanenko, Andrey A. Pimerzin and Elena Е. Vishnevskaya Thermodynamic Properties and Structure of Heteroatom Derivatives of Indene Sergey P. Verevkin, Vladimir N. Emel’yanenko, Andrey A. Pimerzin and Elena Е. Vishnevskaya Development of Thermoplastic Vulcanizates Based on Isotactic Polypropylene and Ethylene-Propylene-Diene Elastomer E. V. Prut and T. I. Medintseva
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405
431
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Contents
Conclusion
Technology Transfer for Development New Products G. E. Zaikov and L. L. Madyuskina
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Index
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PREFACE
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The editors and contributors of this volume will be quite pleased if the readers can understand and accept the contents and ideas of this monograph. In this book, we decided to include information about the synthesis and investigation properties of epoxy containing compounds and composite materials on their basis, such as: hydrosilylation reactions of polymethylhydrosiloxane with acrylates and methacrylates and solid polymer electrolyte membranes on their basis; biodegradable binary and ternary blends of cellulose and ethyl cellulose with synthetic and natural polymers; biodetoxication of aromatic hydrocarbons in aqueous media; modern immunochemical and biosensor technologies for the analysis of environmental ecotoxicants; the morphology of poly(3hydroxybutyrate) with an ethylene-propylene copolymer blend; the development of thermoplastic vulcanizates based on isotactic polypropylene and ethylene-propylene-diene elastomer, as well as the mechanical and chemical properties of modern basalt fibers and epoxy basaltoplastics. We collected the reviews and original papers about technology transfer for the development of new products, chemical and biochemical physics. Special attention is given to adaptogens that decrease the generation of reactive oxygen species by mitochondria. Quantum-chemical calculation of the aromatic olefines of some molecules is performed using the MNDO method, and the formation of ozonides and their stability in the process of unsaturated polymers in latex, as well as structures ( monomer and dimer) of sodium and potassium 2-(N-_methylamide)-2-(3',5'-di-tert.butyl-4-hydroxybenzyl)-malonates and biological properties are also discussed. The interrelation structure and thermodynamic properties in the five-membered O- and N-heterocyclic compounds, including the thermodynamic properties and structure of heteroatom derivatives of indene, are explored further. Many interesting results in the field of the reaction of ozone with some oxygen containing organic compounds are discussed, including: enhanced oil recovery using binary mixture reaction products as an alternative to increasing reservoir water content; assessment of the potential of enhanced oil recovery from reservoirs with high water content using the heat of nitrate oxidation reactions and in situ hydrocarbon oxidation; structural features of poly(3-hydroxybutyrate) with an ethylene-propylene copolymer blends; and the kinetics of photoinitiated copolymerization of bifunctional (meth)acrylates till high conversion. The numerical verification of kinetic model of the process and the degradation of films based on
Gennady E. Zaikov, Alexandr A. Berlin, Krzysztof Majewski et al.
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mixtures of vinyl alcohol with vinyl acetate copolymers and polyhydroxybutyrate under UVradiation and polymer-inorganic materials on the basis of tetraethoxysilane are also discussed. We also included information concerning nanofibrous polyhydroxybutyrate-based biomaterials, such as: the influence of aminoalkoxy- and glycidoxyalkoxysilanes on adhesion characteristics of ethylene copolymers; the study of the influence of dihydroquercetin and cyclodextrin inclusion complex with the new dihydroquercetin derivative on ozone oxidation of fibrinogen; challenges and development perspectives on nanopatterned implants loaded with drugs; the use of vegetable oils as platform chemicals for synthesis of thermoplastic biobased polyurethanes; active packaging based on the release of carvacrol and thymol for fresh food; the structural analysis of nanocomposites polymer/organoclay flame-resistance; the regularity of crack formation on vulcanized elastomers under ozone action (polyisoprene); the evaluation of efficiency of deposition of dispersed particles in inertial dust separator; as well as a comparative evaluation of the viability of the cells of probiotic strains by luminescence microscopy and flow cytometry. As we know, the power of innovative solutions is experience, creativity and technology. In this volume the readers can find information about experience and creativity, as well as some information about modern technology. The editors and contributors will be happy to receive some comments from the readers which can be taken into account in our future research.
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Editors: Alexandr A. Berlin Director of N.N. Semenov Institute of Chemical Physics Russian Academy of Sciences 4 Kosygin str., 119991 Moscow, Russia
[email protected] Krzysztof Majewski Military Institute of Chemistry and Radiometry Al. gen. A. Chrusciela “Montera” 105, 00-910 Warsaw, Poland
[email protected]
Andrey A. Pimerzin Deputy of director of Samara State Technical University 244 Molodogvardeyskaya street, Samara 443100, Russia
[email protected]
Gennady E. Zaikov Head of Polymer Division N.M. Emanuel Institute of Biochemical Physics Russian Academy of Sciences 4 Kosygin str., 119334 Moscow, Russia
[email protected]
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In: Research Progress in Chemical Physics ... ISBN: 978-1-63117-066-9 Editors: G. E. Zaikov, A. A. Berlin, K. Majewski et al. © 2014 Nova Science Publishers, Inc.
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Chapter 1
OZONATION OF HYDROCARBONS
S. Rakovsky∗, M. Anachkov, V. Georgiev, A. Berlin‡1, M. Belitski2 and G. E. Zaikov2#
Institute of Catalysis, Bulgarian Academy of Sciences, Sofia, Bulgaria N.N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, Russia 2 N.M. Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, Moscow, Russia
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ABSTRACT
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Investigations on the kinetics and mechanism of ozone reaction with some paraffin including aliphatic and polymeric hydrocarbons have been carried out in liquid and gas phase. In the gas phase, there is evidence for a direct reaction of ozone with alkanes or radical chain reactions initiated by decomposition of ozone to atomic oxygen. The thermochemical and structural-kinetics analysis manifest that the ozonolysis in liquid phase involves radical pair formation (R ⋅⋅⋅⋅ HO3⋅) or an ion pair (R+ ⋅⋅⋅ HO3-). We have confirmed the existence of radical steps in the paraffin ozonolysis by carrying the reaction directly in the ESR resonator. The initial stages of the reaction were studied also by quantum-chemical and experimental methods engaged in ERM (estimation of the reaction mechanism). The results showed that the ozone reacts with paraffin trough a linear transient state formation in which reaction center is located on the CH bond with lowest energy and most likely H-atom abstraction occurs from the hydrocarbon molecule. The kinetic and thermodynamic parameters were also calculated theoretically and comparison with the experimental results has been made. At conditions under which radicals or ionic intermediates can be formed it was found out relation between the rate constants of the reactions and the structure of the paraffin. The reaction ability of hydrocarbons containing primary, secondary or tertiary hydrogen atoms was found as follows 1:60:3692 respectively. The theoretical and kinetic studies reveal that ozone reacts with cycloalkanes via hydrogen atom
∗
[email protected].
[email protected]. #
[email protected]. ‡
S. Rakovsky, M. Anachkov, V. Georgiev et al.
Keywords: Ozone, ozonolysis, paraffin, kinetics, mechanism
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abstraction. The reactivity of cycloalkanes depends on the direction of the steric energy change during the sp3 → sp2 transition in the active complex. Ozonolysis of cyclohexane yields mainly cyclohexanole and cyclohexanone, in which initial rate of alcohol formation is by about 3 times higher than that of the ketone. There is evidence for peroxide and acids obtaining, including adipic acid as well as water in a number of experiments. To investigate the role of transitions metals such as Co, Ni, Mn, V, on the ozonolysis of paraffin, wide range of experiments have been conducted. The present study has been extended to investigations on ozonation of the C-H bonds in polymer analogs of paraffin - polyethylene, polypropylene, their mixtures and polystyrene, with the aim of elaborating the effect of the polymer structure on this reaction.
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The ozonolysis of hydrocarbons is the rare reactions that going on at low and ambient temperatures and can transform these non-active organics into new valuable oxygencontaining products [1-12] suitable for synthesis and for special usage. This reaction has been studied by a number of authors [13-15]. But the conclusions in most cases differ from one another, perhaps because of differences and complicated contents of formed products. Special interest is pointed out on the action of ozone as an initiator in the oxidation processes [16-18], modifying polymer agent [19-21], oxidizer at the preparation of alcohols, ketones etc. [22-24]. The kinetics and mechanism of this reaction have been intensively discussed [25-46]. The main goal of our present paper is dedicated to the fundamental problems of the kinetic and mechanism of these reactions [47-64].
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I.1. REACTION MECHANISMS
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The first studies on the reaction of ozone with paraffins have been carried out with methane, ethane, propane and butane in gas phase [2-8]. It has been established that the absorption of 1 mol ozone yields 1 mol products. The analysis of the experimental data reveals two mechanisms of ozone action: 1) ozone is decomposed to atomic oxygen, which initiates the oxidation process [2] mechanism - (M.1.1) and 2) ozone interacts directly with the alkane [3-5] mechanism - (M.1.2.):
(M.1.1)
RH + O3 → RO• + •O2H
(M.1.2)
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O 3 → O2 + O RH + O → R• + •OH
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At the analysis of M.1.1 becomes clear that this mechanism can be realized only in gas phase at the temperature range of >>50 - 60oC, because in it the value of the rate constant of thermal decomposition of ozone is 8>7>1>K. Curve K is characterized by a S-shape form whereby three periods are distinguished: 1) the start of the product accumulation; 2) stationary regime in relation to the product; 3) autocatalytic process of product formation (Figure 1.23, A).
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Ozonation of Hydrocarbons
5
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Fig.1.23.A-C. Kinetic curves of products formation during the catalyzed cumene ozonolysis. A-CHP, B-DMPC, C-OZ; 1, 5, 7 and 8 - the number of catalysts according to Table 1.11; K- in the absence of catalyst, WO3 = 1.10-5 M.s-1.
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Upon DMPC formation (Figure 1.23, B) one can also notice some difference in the course of the kinetic curves in the presence (curves 1, 5, 7 and 8) and in the absence (curve K) of the catalyst. It has been found that the rate of DMPC formation is one and the same for all samples studied and it is 4.2.10-6 M.s-1. After 10 min curve K becomes constant and after 15 min it again rises, i.e. its profile is typical for an autocatalytic process. The curves of DMPC formation in the presence of catalyst (1, 5, 7 and 8) are characterized by two sections - an initial one with a bigger slope and a second one with a smaller slope and the transition point is in the interval 5-10 min. Obviously, WDMPC is slowed down in the advanced reaction because
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of the occurrence of secondary reactions associated to the DMPC depletion or are due to the catalyst deactivation. With respect to their activity the samples have the following sequence: 5>1>7>8>K. The kinetics of OZ formation is entirely different from those discussed before (Figure 1.23, C). The initial section of the curves is characterized by the appearance of induction period up to 15 min. These results unambiguously point out that the catalyst direct selectively the process to the oxidation of the isopropyl substituent in the cumene molecule and only after the accumulation of a definite amount of products, which probably block the catalytic surface, the ozone attacs the benzene ring. In this case the order of activity of the samples is just opposite to that of CHP formation, i.e. 5
