CRC Handbook of Phase Equilibria and Thermodynamic Data of Copolymer Solutions

550 Pages·2010·2.769 MB·English

by  Wohlfarth, Christian

C R C H A N D B O O K O F
Phase Equilibria and
Thermodynamic Data
of Copolymer Solutions
© 2011 by Taylor and Francis Group, LLC
K12292_FM.indd 1 10/19/10 1:22 PM
© 2011 by Taylor and Francis Group, LLC
K12292_FM.indd 2 10/19/10 1:22 PM
C R C H A N D B O O K O F
Phase Equilibria and
Thermodynamic Data
of Copolymer Solutions
Christian Wohlfarth

Boca Raton London New York
CRC Press is an imprint of the
Taylor & Francis Group, an informa business
© 2011 by Taylor and Francis Group, LLC
K12292_FM.indd 3 10/19/10 1:22 PM
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© 2011 by Taylor and Francis Group, LLC
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CONTENTS

1. INTRODUCTION

1.1. Objectives of the handbook………………………………………….……………1
1.2. Experimental methods involved…………………………………….…………….2
1.3. Guide to the data tables……………………………………………….…………11
1.4. List of symbols………………………………………………………….……….15
1.5. References……………………………………………………………….………18

2. VAPOR-LIQUID EQUILIBRIUM (VLE) DATA
AND GAS SOLUBILITIES OF COPOLYMER SOLUTIONS

2.1. Binary copolymer solutions………………………………………………….……21
2.2. Table of binary systems where data were published only
in graphical form as phase diagrams or related figures………………….…….….57
2.3. Ternary and quaternary copolymer solutions…………………………….…….…61
2.4. Table of ternary or quaternary systems where data were published
only in graphical form as phase diagrams or related figures……………..……….70
2.5. Classical mass-fraction Henry’s constants of solvent vapors
in molten copolymers………………………………………………………..……71
2.6. References……………………………………………….....................................105

3. LIQUID-LIQUID EQUILIBRIUM (LLE) DATA OF
COPOLYMER SOLUTIONS

3.1. Cloud-point and/or coexistence curves of quasibinary
solutions…………………………………………………………………………111
3.2. Table of binary systems where data were published only

in graphical form as phase diagrams or related figures…………………………150
3.3. Cloud-point and/or coexistence curves of quasiternary
and/or quasiquaternary solutions………………………………………………..174
3.4. Table of ternary or quaternary systems where data were published
only in graphical form as phase diagrams or related figures……………………218
3.5. Upper critical (UCST) and/or lower critical (LCST) solution
temperatures…………………………………………………………….………230
3.6. References………………………………………………………………………235

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© 2011 by Taylor and Francis Group, LLC
4. HIGH-PRESSURE FLUID PHASE EQUILIBRIUM (HPPE) DATA
OF COPOLYMER SOLUTIONS

4.1. Cloud-point and/or coexistence curves of quasibinary
solutions………………………………………………………………………259
4.2. Table of binary systems where data were published only
in graphical form as phase diagrams or related figures………………………310
4.3. Cloud-point and/or coexistence curves of quasiternary
and/or quasiquaternary solutions…………………………………….…….…315
4.4. Table of ternary or quaternary systems where data were published
only in graphical form as phase diagrams or related figures…………………351
4.5. References……………………………………………………………………353

5. ENTHALPY CHANGES FOR COPOLYMER SOLUTIONS

5.1. Enthalpies of mixing or intermediary enthalpies of dilution,
copolymer partial enthalpies of mixing (at infinite dilution),
or copolymer (first) integral enthalpies of solution………………………..…359
5.2. Partial molar enthalpies of mixing at infinite dilution and
enthalpies of solution of gases/vapors of solvents in molten
copolymers from inverse gas-liquid chromatography (IGC)…………………362
5.3. Table of systems where additional information on enthalpy
effects in copolymer solutions can be found…………………………………376
5.4. References……………………………………………………………………377

6. PVT DATA OF COPOLYMERS AND SOLUTIONS

6.1. PVT data of copolymers…………………………………………………..…379
6.2. Excess volumes and/or densities of copolymer solutions……………………406
6.3. References……………………………………………………………………417

7. SECOND VIRIAL COEFFICIENTS (A ) OF COPOLYMER SOLUTIONS
2

7.1. Experimental A data…………………………………………………………419
2

7.2. References……………………………………………………………………461

APPENDICES

Appendix 1 List of copolymers in alphabetical order……………………………471
Appendix 2 List of systems and properties in order of the copolymers………….486
Appendix 3 List of solvents in alphabetical order………………………….…….529
Appendix 4 List of solvents in order of their molecular formulas…………….…535

INDEX…………………………………………………………………………………….…541

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© 2011 by Taylor and Francis Group, LLC
PREFACE

Today, there is still a strong and continuing interest in thermodynamic properties of
copolymer solutions. Thus, ten years after the CRC Handbook of Thermodynamic Data of
Copolymer Solutions was published, necessity as well as desire arises for a supplementary book
that includes and provides newly published experimental data from the last decade.

There are about 500 newly published references containing about 150 new vapor-liquid
equilibrium datasets, 50 new tables containing classic Henry’s coefficients, 250 new liquid-liquid
equilibrium datasets, 350 new high-pressure fluid phase equilibrium datasets, 70 new datasets
describing PVT-properties, densities, or excess volumes, and 40 new enthalpic datasets.
Additionally, a certain amount of data to be included in the supplement was anticipated when the
original handbook was made. This last point is especially mentioned for values of second osmotic
virial coefficients for which this new supplementary volume gives a much larger data table. In
comparison to the original handbook, the new supplementary volume contains a larger amount of
data and will be a useful as well as necessary completion of the original handbook.

The new supplementary volume is again divided into the seven chapters as used before:
(1) Introduction, (2) Vapor-Liquid Equilibrium (VLE) Data and Gas Solubilities of Copolymer
Solutions, (3) Liquid-Liquid Equilibrium (LLE) Data of Copolymer Solutions, (4) High-Pressure
Fluid Phase Equilibrium (HPPE) Data of Copolymer Solutions, (5) Enthalpy Changes for
Copolymer Solutions, (6) PVT Data of Copolymers and Solutions, and (7) Second Virial
Coefficients (A ) of Copolymer Solutions. Finally, appendices quickly route the user to the desired
2
datasets.

Additionally, tables of systems are provided where results were published only in
graphical form in the original literature to lead the reader to further sources. 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.

The closing day for the data compilation was December 31, 2009. However, the user who
is in need of new additional datasets is kindly invited to ask for new information beyond this book
via e-mail at [email protected]. Additionally, the author will be grateful to

all users who call his attention to mistakes and make suggestions for improvements.

The new CRC Handbook of Phase Equilibria and Thermodynamic Data of Copolymer
Solutions will again be useful to researchers, specialists, and engineers working in the fields of
polymer science, physical chemistry, chemical engineering, material science, biological science
and technology, and those developing computerized predictive packages. The book should also be
of use as a data source to Ph.D. students and faculty in chemistry, physics, chemical engineering,
biotechnology, and materials science departments at universities.

Christian Wohlfarth
Halle, March 2010

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© 2011 by Taylor and Francis Group, LLC
© 2011 by Taylor and Francis Group, LLC
About the Author

Christian Wohlfarth is associate professor for physical chemistry at Martin Luther
University Halle-Wittenberg, Germany. He earned his degree in chemistry in 1974 and wrote his
Ph.D. thesis in 1977 on investigations of the second dielectric virial coefficient and the
intermolecular pair potential, both at Carl Schorlemmer Technical University Merseburg. In 1985,
he wrote his habilitation thesis, Phase Equilibria in Systems with Polymers and Copolymers, at the
Technical University Merseburg.

Since then, Dr. Wohlfarth’s main research has been related to polymer systems. Currently,
his research topics are molecular thermodynamics, continuous thermodynamics, phase equilibria in
polymer mixtures and solutions, polymers in supercritical fluids, PVT behavior and equations of
state, and sorption properties of polymers, about which he has published approximately 100
original papers. He has written the following books: Vapor-Liquid Equilibria of Binary Polymer
Solutions, CRC Handbook of Thermodynamic Data of Copolymer Solutions, CRC Handbook of
Thermodynamic Data of Aqueous Polymer Solutions, CRC Handbook of Thermodynamic Data of
Polymer Solutions at Elevated Pressures, CRC Handbook of Enthalpy Data of Polymer-Solvent
Systems, and CRC Handbook of Liquid-Liquid Equilibrium Data of Polymer Solutions.

He is working on the evaluation, correlation, and calculation of thermophysical properties
of pure compounds and binary mixtures resulting in eleven volumes of the Landolt-Börnstein New
Series. He is a contributor to the CRC Handbook of Chemistry and Physics.

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© 2011 by Taylor and Francis Group, LLC
1. INTRODUCTION

1.1. Objectives of the handbook

Knowledge of thermodynamic data of polymer solutions is a necessity for industrial and
laboratory processes. Furthermore, such data serve as essential tools for understanding the physical
behavior of polymer 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. However, the database
for polymer solutions is still modest in comparison with the enormous amount of data for low-
molecular mixtures, and the specialized database for polymer solutions is even smaller. On the
other hand, there is still a strong and continuing interest in thermodynamic properties of copolymer
solutions, and during the last ten years after the former CRC Handbook of Thermodynamic Data of
Copolymer Solutions was published, a large amount of new experimental data has been published,
that is now provided with this new CRC Handbook of Phase Equilibria and Thermodynamic Data
of Copolymer Solutions.

Basic information on polymers can still be found in the Polymer Handbook (1999BRA),
and there is also a chapter on properties of polymers and polymer solutions in the CRC Handbook
of Chemistry and Physics (2009LID1). Older data for copolymer solutions can be found in
1992WEN and 1993DAN, but also in the data books written by the author of this Handbook
(1994WOH, 2001WOH, 2004WOH, 2005WOH, 2006WOH, 2008WOH). The Handbook does not
present theories and models for polymer solution thermodynamics. Other publications (1971YAM,
1990FUJ, 1990KAM, 1999KLE, 1999PRA, and 2001KON) can serve as starting points for
investigating those issues.

The data within this book are divided into six chapters:

 Vapor-Liquid Equilibrium (VLE) Data and Gas Solubilities of Copolymer
Solutions
 Liquid-Liquid Equilibrium (LLE) Data of Copolymer Solutions
 High-Pressure Fluid Phase Equilibrium (HPPE) Data of Copolymer Solutions
 Enthalpy Changes for Copolymer Solutions
 PVT Data of Copolymers and Solutions
 Second Virial Coefficients (A ) of Copolymer Solutions
2

Data from investigations applying to more than one chapter are divided and appear in the
relevant chapters. Data are included only if numerical values were published or authors provided
their results by personal communication (and I wish to thank all those who did so). No digitized
data have been included in this data collection. However, every data chapter is completed by a
table that includes systems and references for data published only in graphical form as phase
diagrams or related figures.
© 2011 by Taylor and Francis Group, LLC