Chapter 1

INTRODUCTION
A. OBJECTIVES OF THE HANDBOOK OF POLYMER SOLUTION
THERMODYNAMICS
Design and research engineers working with polymers need up-to-date, easy-to-use
methods to obtain specific volumes of pure polymers and phase equilibrium data for
polymer-solvent solutions. Calculations involving phase equilibria behavior are required in
the design and operation of many polymer processes such as polymerization, devolatili-
zation, drying, extrusion, and heat exchange. In addition, there are many product applica-
tions requiring this type of information: e.g., miscibility predictions in polymer alloys, solvent
evaporation from coatings and packaging materials, substrate compatibility with adhesives,
and use of polymers in electronics and prostheses. This Handbook of Polymer Solution
Thermodynamics contains data bases, prediction methods, and correlation methods to aid
the engineer in accurately describing these processes and applications. This Handbook
provides the necessary background information, the most accurate prediction and correlation
techniques, comprehensive data bases, and a software package for DOS based personal
computers to implement the recommended models and access the data bases.
Generally the preferred data source is experimental measurement. Only in rare cases
are prediction methods able to give more accurate estimates than a carefully executed
experiment. Therefore, one of the major objectives of this Handbook is to provide compre-
hensive data bases for the phase equilibria of polymer-solvent systems and pressure-volume-
temperature behavior of pure polymers. Thus, data have been compiled from extensive
literature searches. These data cover a wide range of polymers, solvents, temperatures, and
pressures. The data have been converted into consistent units and tabulated in a common
format. Methods of evaluating and formatting these data banks have been established by
the DIPPR Steering Committee for Project 881 and the Project Investigators.
No matter how broad the scope of the experimental data is, there will always be a
need for data that have not yet been measured or that are too expensive to measure.
Another objective of this Handbook is to provide accurate, predictive techniques. Predictive
techniques not only furnish a source of missing experimental data, they also aid in the
understanding of the physical nature of the systems of interest. The most useful predictive
methods require as input data only the structure of the molecules or other data that are
easily calculated or have been measured. Many of the methods present in this Handbook
are based on the concept of group contributions which use as input only the structure of the
molecules in terms of their functional groups or which use group contributions and readily
available pure component data. In some cases the users of the Handbook will need to
correlate existing data with the hope of extending the correlation to conditions not available
in the original existing data. Several correlative methods of this type are included.
The current state-of-the-art is such that there are no reliable methods of predicting
liquid-liquid equilibria of polymer-solvent systems. Thus, the recommended procedures and
computer programs included in this Handbook treat only vapor-liquid equilibrium. A
discussion of the correlation of LLE data is included in Chapter 2.
Chapter 2 is an in depth discussion of the various theories important to phase
equilibria in general and polymer thermodynamics specifically. First a review of phase
equilibria is provided followed by more specific discussions of the thermodynamic models
that are important to polymer solution thermodynamics. The chapter concludes with an
analysis of the behavior of liquid-liquid systems and how their phase equilibrium can be
correlated.
Chapter 3 contains the recommended predictive and correlative procedures for the
specific volume of pure polymer liquids and the calculation of the vapor liquid equilibria of
polymer solutions. These methods have been tested and evaluated with the data bases
included in this Handbook.
Chapter 4 describes the polymer data bases. This chapter is organized into sections
discussing the experimental methods available for measuring the thermodynamic data of
polymer solutions with an overview of the advantages and disadvantages of each method.
The next section, Data Reduction Methods, describes how the experimental measurements
from these experiments can be used to calculate the activity coefficients that are necessary
for phase equilibria calculations. Finally, a summary of all the systems that are available on
the data diskettes is provided. A user can scan this section or use the computer program
POLYDATA to find if data are available for a particular system.
The Computer Programs section, Chapter 5, describes the two primary computer
programs on the diskettes accompanying this Handbook. POLYPROG is a program which
implements the recommended procedures of Chapter 3. POLYDATA provides an easy
method of accessing the data contained in the many data bases. Chapter 6, contains the
Appendices. The sections included are Glossary of Terms, Standard Polymer Abbreviations,
Nomenclature, Units and Conversion Factors, and References.