THERMODYNAMIC DATA of COPOLYMER SOLUTIONS

C R C H A N D B O O K O F THERMODYNAMIC ATA of COPOLYMER OLUTIONS C R C H A N D B O O K O F THERMODYNAMIC ATA of COPOLYMER OLUTIONS Christian Wohlfarth CRC Press Boca Raton London New York Washington, D.C. Library of Congress Cataloging-in-Publication Data Catalog record is available from the Library of Congress This book contains information obtained from authentic and highly regarded sources. Reprinted material is quoted with permission, and sources are indicated. A wide variety of references are listed. Reasonable efforts have been made to publish reliable data and information, but the author and the publisher cannot assume responsibility for the validity of all materials or for the consequences of their use. 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Visit the CRC Press Web site at www.crcpress.com © 2001 by CRC Press LLC No claim to original U.S. Government works International Standard Book Number 0-8493-1074-1 Printed in the United States of America 1 2 3 4 5 6 7 8 9 0 Printed on acid-free paper Foreword Practical applications of thermodynamics as well as theoretical calculations of thermodynamic properties generally require data of real systems. In most cases these data rest on laboratory measurements of various physical properties. The study of phase behavior and thermodynamic properties of polymers and mixtures containing polymers has been subject of interest during the last 50 years. Investigations on such properties for copolymer systems were emphasized during the last decade when copolymers gained an increasing commercial interest because of their unique physical properties. Much effort has been devoted over the years to compiling thermodynamic data for types of systems from literature and preparing compilations and databases for both scientific and industrial use. However, scarcely anything is found when one looks for compilations or databases that provide thermodynamic properties of polymer, or even more specially, copolymer solutions. Experimental information is spread over many articles and journals. There are only a small number of data books that cover this field. The author of this handbook wrote one of them on vapor-liquid equilibria of binary polymer solutions in 1994. He is known for his experience and his own experimental investigations on polymer and copolymer solutions for more than 20 years. With his new Handbook of Thermodynamic Data of Copolymer Solutions for the first time a compilation of thermodynamic data for copolymer solutions from the original literature is available. Taking into account vapor-liquid equilibrium (VLE) data, liquid-liquid equilibrium (LLE) data, high-pressure phase equilibrium (HPPE) data of copolymer solutions in supercritical fluids, volumetric property (PVT) data of copolymer melts, enthalpy data, and second osmotic virial coefficients of copolymer solutions, the book covers all the necessary areas for researchers and engineers who work in this field. When dealing with copolymer systems, one encounters the special problem of copolymer characterization since a copolymer is far from well-defined only by its chemical formula. Copolymers vary by a number of characterization variables. Molar mass, chemical composition, and distribution functions, tacticity, sequence distribution, branching, and end groups determine their thermodynamic behavior in solution. It is far from clear how these parameters influence the thermodynamic properties in detail. Unfortunately, there usually is not much information in the original papers; the available ones are added to each system in this book. In comparison to low-molecular systems, the amount of data for copolymer solutions is still rather small. About 300 literature sources were perused for the purpose of this handbook, including some dissertations and diploma papers. Several hundred vapor-pressure isotherms, Henry’s constants, LLE and HPPE data sets, a number of PVT data and some second osmotic virial coefficients are reported. I am sure that readers interested in the field of thermodynamic properties of polymer solutions will benefit from this handbook and will identify the work that has to be done in the future. Henry V. Kehiaian Chairman IUPAC-CODATA Task Group on Standard Physico-Chemical Data Formats PREFACE Knowledge of thermodynamic data of copolymer solutions is a necessity for industrial and laboratory processes. Such data serve as essential tools for understanding the physical behavior of copolymer solutions, for studying intermolecular interactions, and for gaining insights into the molecular nature of mixtures. They also provide the necessary basis for any developments of theoretical thermodynamic models. Scientists and engineers in academic and industrial research need such data and will benefit from a careful collection of existing data. The CRC Handbook of Thermodynamic Data of Copolymer Solutions provides a reliable collection of such data for copolymer solutions from the original literature. The Handbook is divided into seven chapters: (1) Introduction, (2) Vapor-Liquid Equilibrium (VLE) Data of Binary Copolymer Solutions, (3) Liquid-Liquid Equilibrium (LLE) Data of Quasibinary or Quasiternary Copolymer Solutions, (4) High-Pressure Phase Equilibrium (HPPE) Data of Quasibinary or Quasiternary Copolymer Solutions in Supercritical Fluids, (5) Enthalpy Changes for Binary Copolymer Solutions, (6) PVT Data of Molten Copolymers, and (7) Second Virial Coefficients (A2) of Copolymer Solutions. Finally, four appendices quickly route the user to the desired data sets. Original data have been gathered from approximately 300 literature sources, including also a number of dissertations and diploma papers. The Handbook provides about 250 vapor-pressure isotherms, 75 tables of Henry’s constants, 50 LLE data sets, 175 HPPE data sets, and 70 PVT data tables for more than 165 copolymers and 165 solvents. Data are included only if numerical values were published or authors provided their numerical results by personal communication (and I wish to thank all those who did so). No digitized data have been included in this data collection, but some tables include systems data published in graphical form. The Handbook is the first complete overview about this subject in the world’s literature. The closing day for the data collection was October 1, 2000. The Handbook results from parts of a more general database, Thermodynamic Properties of Polymer Systems, which is continuously updated by the author. Thus, the user who is in need for new additional data sets is kindly invited to ask for new information beyond this book via e-mail at wohlfarth@chemie.uni-halle.de. Additionally, the author will be grateful to users who call his attention to mistakes and make suggestions for improvements. The Handbook also highlights the work still to be done − obvious, when one compares the relatively small number of copolymer solutions for which data exist with the number of copolymers in use today. Additionally, only a small minority of possible solutions of the copolymers covered by this book were properly investigated (in relation to the combinatorial number of copolymer/solvent pairs, although it is appreciated that not all make thermodynamic sense or are of practical use). The CRC Handbook of Thermodynamic Data of Copolymer Solutions will be useful to researchers, specialists, and engineers working in the fields of polymer science, physical chemistry, chemical engineering, material science, and those developing computerized predictive packages. The Handbook should also be of use as a data source to Ph.D. students and faculty in Chemistry, Physics, Chemical Engineering, and Materials Science Departments at universities. Merseburg, January 2001 Christian Wohlfarth ... - tailieumienphi.vn