Advances in chemistry research volume 8

ADVANCES IN CHEMISTRY RESEARCH ADVANCES IN CHEMISTRY RESEARCH VOLUME No part of this digital document may be reproduced, stored in a retrieval system or transmitted in any form or by any means The publisher has taken reasonable care in the preparation of this digital document, 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 herein This digital document is sold with the clear understanding that the publisher is not engaged in rendering legal, medical or any other professional services ADVANCES IN CHEMISTRY RESEARCH Additional books in this series can be found on Nova’s website under the Series tab Additional E-books in this series can be found on Nova’s website under the E-books tab ADVANCES IN CHEMISTRY RESEARCH ADVANCES IN CHEMISTRY RESEARCH VOLUME JAMES C TAYLOR EDITOR Nova Science Publishers, Inc New York Copyright ©2011 by Nova Science Publishers, Inc 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 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 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 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 Additional color graphics may be available in the e-book version of this book LIBRARY OF CONGRESS CATALOGING-IN-PUBLICATION DATA ISSN: 1940-0950 ISBN: 978-1-61324-936-9 (eBook) Published by Nova Science Publishers, Inc © New York CONTENTS Preface vii  Chapter Association Nature of Dyes Chromaticity Yu A Mikheev, L N Guseva, Yu A Ershov andG E Zaikov  Chapter Thermal Bhaviour and Enthalpy Relaxation in Aromatic Polycarbonate and Syndiotactic Poly(Methyl-Methacrylate) Maurizio Penco, Stefania Della Sciucca, Gloria Spagnoli and Luca Di Landro  Chapter Chapter About Geometrical and Electronic of the Structure of Molecular Insectitsid DDT (Nobel Award 1948, P Muller) V A Babkin, V U Dmitriev and G E Zaikov  Parameters of the Combustion of Differential Propellant in Mixture of Oxidants: Molecular Oxygen-Ozone V A Babkin, K V Sergeeva, E S Titova and G E Zaikov  Chapter Cobaloximes with Functionalized Ligands Alexei A Gridnev, Dmitry B Gorbunov and Gregory A Nikiforov  Chapter The Tacticity Governed Stereomicrostructure in Poly(Methyl Methacrylate) (PMMA) as a Way to Explain its Physical Properties N Guarrotxena  Chapter The Modeling of Transition Metal Complex Catalysts in the Selective Alkylarens Oxidations with Dioxygen: The Role of Hydrogen – Bonding Interactions L I Matienko, L A Mosolova and G E Zaikov 1  29  47  51  55  67  75  vi Chapter Chapter Chapter 10 Chapter 11 Index Contents New Carbofunctional Oligoisiloxanes for the Substrates of Antibiocorrosive Covers N Lekishvili, Sh Samakashvili, G Lekishvili and Z Pachulia  Performance, Stability and Qualification of Developed Multifunctional Materials Jon Meegan, Mogon Patel, Anthony C Swain, Jenny L Cunningham, Paul R Morrell and Julian J Murphy 115  129  Molybdenum-Initiated Ring Opening Metathesis Polymerization of Noborn-5-ene-2-yl Acetate Solmaz Karabulut 145  The Co-Occurrence of Carrageenan and Agaran Structures in Red Seaweeds Marina Ciancia and Alberto S Cerezo 155  193  PREFACE This book presents original research results on the leading edge of chemistry research Each article has been carefully selected in an attempt to present substantial research results across a broad spectrum Topics discussed include thermal behaviour and enthalpy relaxation in aromatic polycarbonate; cobalozimes with functionalized ligands; parameters of the combustion of differential propellant in mixture of oxidants and the modeling of transition metal complex catalysts Chapter - In the range of waves lengths 200-800 nm are studied absorption electronic spectra of individual molecules of triphenilmethane, xanthene and thiazene dyes In triphenilmethane a number are studied the malachite green, crystal violet, diamond green and methyl violet In xanthene number are studied rodamine B and rodamine G; in thiazene a number - methylene blue Molecular solutions of dyes prepared by heptane extraction from commercial powders, and also by thermal processing of triacetate cellulose and the cellophane films, painted by these dyes It is established, that individual molecules of dyes not absorb light in visible range of a spectrum, i.e have no chromogene groups From here follows, that usually observable chromaticity of dyes is caused by supramolecular structures dimers and larger dyes molecules associates at mutual orientation favorable for molecular interaction From here follows, that existing quantum-chemical theories of chromaticity of the studied dyes classes are incorrect and demand revision Chapter - The structural relaxation of polymers depends on the kinetic character of the glass-transition phenomenon: amorphous polymers below their Tg are not at equilibrium and their structures continuously relax in attempt to reach the equilibrium state Several phenomenological and molecular approaches have been proposed to describe the structural relaxation but a universal model is still lacking The enthalpy relaxation of glasses is usually described with models developed on the basis of Tool-Narayanaswamy-Moynihan (TNM) theory [1,2]: it is assumed that the instantaneous relaxation time(s) (τ) for enthalpy relaxation depends on both the temperature (T) and the structure of the glass, identified by its fictive temperature (Tf) This approach is able to describe the enthalpy relaxation in low-molecularweight glass-forming system fairly well [3,4], but discrepancies have been observed in several polymeric systems [5,6] One of these discrepancies concerns the overestimation of enthalpy lost on aging the samples for long periods of time Hodge [7], Gomez Ribellez [8] and Cowie [9] ascribed this features in polymers to the effect of topological constraints, such as chain entanglements, which are completely ignored in the TNM-based models viii James C Taylor In this work, the enthalpy relaxation of aromatic polycarbonates and of syndiotactic poly(methyl methacrylate)s (PMMA) are investigated performing DSC experiments with the intention of characterize the effect of the composition and of the molar mass in aromatic polycarbonates and the relaxation dynamic as a function of the molecular mass and to highlight the effect of PMMA entanglement mass (Me) in syndiotactic poly(methyl methacrylate)s (PMMA) Chapter - Quantum-chemical calculation of molecular of insectitsid DDT was done by method AB INITIO in base 6-311G** Optimized by all parameters geometric and electronic structures of these compound was received The universal factor of acidity was calculated (pKa=26.5) Molecular of insectitsid DDT pertain to class of very weak Н-acids (рКа>14) Chapter - Calculation of the mixture of oxidants of differential propellant (molecular oxygen – ozone) was made by classical quantum-chemical semitheoretical method CNDO/2 in parametrization of Santri-Poppl-Segal Optimized geometric and electronic structure of the combination of these oxidants was received Parameters of the combustion of this mixture were evaluated Parameters of the combustion of mixture of oxidants (O2+O3) practically not differ from parameter of the combustion of the molecular oxygen Chapter - Cobaloximes, alkylcobaloximes and borofluoride adducts on the basis of asymmetric functionalized ligandes have been synthesized These cobaloxime systems form geometric isomers The presence of chiral center in axial ligand gives rise to the appearance of diastereotopics effect Chapter - Three industrial samples of Poly(methyl methacrylate) (PMMA), prepared under different conditions, have been extensively analyzed by means of 1H-NMR spectroscopy Starting from the mm, rr and mrandrm triad contents, as given by the spectra, the type of tacticity statistics distribution has been deduced Sample X appears to be completely Bernoullian, while samples Y and Z deviate somewhat from this behaviour exhibiting a tiny trend towards Markovian statistics The fraction of mmrm and rrrm pentads and that of pure heterotactic and atactic triad moieties has been calculated by assuming either a Markovian statistics for samples Y and Z or a Bernoullian statistics for all the samples On the other hand, the fraction of the same pentads has been determined by deconvoluting the overall triad signals of the spectra into the corresponding pentad signals An appreciably good agreement with the values obtained assuming Bernoullian statistics for all the samples appears evident As a result, the evolution of every pentad content from sample X to Sample Z could be stated Thus the samples prove to be appropriate models to study the relationship between any physical property and the stereomicrostructure of PMMA as was done previously for Poly(vinyl chloride) (PVC) and Polypropylene (PP) Chapter - The different methods of improvement of catalytic activity of transition metal complexes in the oxidations of alkylarens with molecular oxygen are stated briefly The offered at first by authors and developed in their works the method of control of catalyst activity of transition metal complexes with additives of electron-donor mono- or multidentate exo ligands L2 in the oxidations of alkylarens (ethylbenzene, cumene) with molecular oxygen into corresponding hydroperoxides is presented The modeling of catalytic nickel and iron complexes with use of ammonium quaternary salts and macro-cycle polyethers as exo ligands-modifiers is described in detail The role of the Hydrogen–Bonding interactions in mechanisms of homogeneous catalysis is discussed The modeling of catalyst activity of complexes Fe(II,III)(acac)n with R4NBr (or 18-crown-6) (18C6) in the ethylbenzene oxidation in the presence of small amounts additives of water (~10-3 mol/l) is analyzed The role of Preface ix micro steps of the chain initiation (O2 activation), and propagation in the presence of catalyst (Cat + RO2•→) in the mechanism of nickel- and iron-catalyzed oxidation of ethylbenzene is evaluated Chapter - New carbofunctional oligoisiloxanes containing trifluorinepropil and methacrylic groups at silicon atoms have been synthesized and studied On the basis of the data of IR and NMR spectral analysis the process of hydrosilylatrion, composition and structure of synthesized compounds have been investigated By using of diferential-thermal and thermogravimetric analisis method the thermal stability of sintesized oligomers have been studied By the diferential-scanning calomerty method the phase transition temperatures of synthesized oligomers were determined It was established that synthesized oligomers are amorphic one-phase systems The preliminary ivestigation showd that the sybthesized carbofunctional oligomers in combination with polyepoxides and non-volatile bioactive organo-ellement arsenic complex compounds new composite materials of multifunctional application for individual and environmental protection of various materials may be created Chapter - In this article we will review the design, formulation and development of materials exhibiting simplified structure / property relationships, reversible cure mechanisms, increased resistance to physical property changes over time and stress sensitive behaviours These properties are discussed within the context of the external literature The article also provides a brief overview of the processes employed by AWE to qualify materials and further understand their storage, ageing and compatibility properties Chapter 10 - MoCl5-e−-Al-CH2Cl2 catalyst system can efficiently polymerize noborn-5ene-2-yl acetate in moderate yields and in relatively high molecular weights The analyses of the product by FTIR, 1H NMR and 13C NMR spectra give the verification of metathetical polymers The polymer shows narrow molecular weight distribution and good solubility in common organic solvents Chapter 11 - In the last seventeen years it has been shown that red seaweeds classified as “carrageenophytes” also biosynthesize agaran structures, while certain “agarophytes” produce small amounts carrageenan structures No neat separation of these carrageenan/agaran systems was obtained, leading to the idea of “hybrid” molecules, called DL-hybrid galactans Several points concerning these polysaccharide systems have been addressed: Description of the systems of galactans, in which carrageenan and agaran structures were found (DL-galactan systems), as well as the methodology necessary for their detection Isolation of “pure” carrageenans or agarans from these systems using nondegrading conditions and the consequent new hypothesis of the formation of molecular complexes Evidences favoring each hypothesis, namely, the existence of hybrid molecules versus molecular complexes formation Versions of these chapters were also published in Polymers Research Journal, Volume 3, Numbers 1-4, edited by Frank Columbus, published by Nova Science Publishers, Inc They were submitted for appropriate modifications in an effort to encourage wider dissemination of research .. .ADVANCES IN CHEMISTRY RESEARCH ADVANCES IN CHEMISTRY RESEARCH VOLUME No part of this digital document may be reproduced, stored in a retrieval system or transmitted in any form or... E-books tab ADVANCES IN CHEMISTRY RESEARCH ADVANCES IN CHEMISTRY RESEARCH VOLUME JAMES C TAYLOR EDITOR Nova Science Publishers, Inc New York Copyright ©2011 by Nova Science Publishers, Inc All rights... to encourage wider dissemination of research In: Advances in Chemistry Research Volume Editor: James C Taylor ISBN 9 78- 1-61209- 089 -4 ©2011 Nova Science Publishers, Inc Chapter ASSOCIATION NATUREOF