CHAPTER 1

Polymer Properties

1.1. APPROACH AND OBJECTIVE

The continuous development of the modern process industries has made it increasingly
important to have information about the properties of materials, including many new
chemical substances whose physical properties have never been measured experimen-
tally. This is especially true of polymeric substances. The design of manufacturing and
processing equipment requires considerable knowledge of the processed materials and
related compounds. Also for the application and final use of these materials this knowl-
edge is essential.
In some handbooks, for instance the Polymer Handbook (Brandrup et al., 1966, 1975,
1989, 1999), Physical Constants of Linear Homopolymers (Lewis, 1968), International
Plastics Handbook for the Technologist, Engineer and User (Saechtling, 1988), Polymer
Data Handbook (Mark, 1999) and similar compilations, one finds part of the data
required, but in many cases the property needed cannot be obtained from such sources.
The major aim of the present book is twofold:
1. To correlate the properties of known polymers with their chemical structure, in other words: to
establish structureproperties relationships.
2. To provide methods for the estimation and/or prediction of the more important properties of
polymers, in the solid, liquid and dissolved states, in cases where experimental values are not to
be found.
Thus, this book is concerned with predictions. These are usually based on correlations of
known information, with interpolation or extrapolation, as required. Reid and Sherwood
(1958) distinguished correlations of three different types:
Purely empirical; on extrapolation these correlations are often unreliable, or even
dangerous to use.
Purely theoretical; these are seldom adequately developed or directly usable.
Partly empirical but based on theoretical models or concepts; these semi-empirical
correlations are the most useful and reliable for practical purposes.
Among scientists there is often a tendency to look down upon semi-empirical approaches
for the estimation of properties. This is completely unjustified. There are almost no purely
theoretical expressions for the properties in which practice is interested.
One of the great triumphs of theoretical physics is the kinetic theory of gases. On the
basis of an interactionpotential function, e.g. the LennardJones force function, it is

Properties of Polymers # 2009 Elsevier B.V.

DOI: 10.1016/B978-0-08-054819-7.00001-7 All rights reserved.

3
4 Properties of Polymers

possible to develop theoretical expressions for all the important properties of gases, such
as the pvT relationships, viscosity, molecular diffusivity, thermal conductivity and
thermal-diffusion coefficient. The predicted variations of these properties with tempera-
ture are in excellent agreement with experimental data. But it should be realized that this
extremely successful theoretical development has a purely empirical basis, viz. the force
function. Except for the simplest cases, there is no sufficiently developed theory for a
quantitative description of the forces between molecules. Whereas the theory of gases is
relatively advanced, that of solids is less well understood, and the theory of liquids is still
less developed.
In the relatively new field of macromolecular matter the semi-empirical approach is mostly
necessary, and sometimes even the only possible way.
Fundamental theory is generally too remote from the phenomena, which have to be
described. What is needed in practice is a formulation that is designed to deal directly with the
phenomena and makes use of the language of observation. This is a pragmatic approach that is
designed specifically for use; it is a completely non-speculative procedure.
In the low-molecular field Reid et al. (1977) have performed this task in a most
admirable way, as far as gases and liquids are concerned. For molecular crystals and
glasses Bondi (1968) gave a similar contribution, which partly covers the polymeric field,
too.
In the macromolecular field the amount of literature is extremely large. Nevertheless
the researcher is often confronted with the problem that neither directly measured proper-
ties, nor reliable methods to calculate them, can be found. This is the justification of the
present book. The value of estimation and correlation methods largely depends, however,
on their simplicity. Complicated methods have to be rejected. This has been one of our
guiding principles.
The simplest and yet very successful method is based on the concept of additive group
contributions.
The underlying idea in this concept is the following: There are thousands of chemical
compounds of interest in science and practice; however, the number of structural and
functional groups, which constitute all these compounds, is very much smaller. The
assumption that a physical property of a compound, e.g. a polymer, is in some way
determined by a sum of contributions made by the structural and functional groups in
the molecule or in the repeating unit of the polymer, forms the basis of a method for
estimating and correlating the properties of a very large number of compounds or poly-
mers, in terms of a much smaller number of parameters which characterize the contribu-
tions of individual groups. These group contributions are often called increments.
Such a group contribution- or increment-method is necessarily an approximation, since
the contribution of a given group in one surroundings is not necessarily the same as that in
another environment.
The fundamental assumption of the group-contribution technique is additivity. This
assumption, however, is valid only when the influence of any one group in a molecule or
in a structural unit of a polymer is not affected by the nature of the other groups. If there is
mutual interaction, it is sometimes possible to find general rules for corrections to be made
in such a case of interaction (e.g. conjugation of double bonds or aromatic rings). Every
correction or distinction in the contribution of a group, however, means an increase in the
number of parameters. As more and more distinctions are made, finely the ultimate group
will be recovered, namely the molecule or the structural unit of the polymer itself. Then
the advantage of the group-contribution method is completely lost.
So the number of distinct groups must remain reasonably small, but not so small as to
neglect significant effects of molecular structure on physical properties. For practical
 Polymer Properties 5

utility always a compromise must be attained; it is this compromise that determines the
potential accuracy of the method.
It is obvious that reliable experimental data are always to be preferred to values
obtained by an estimation method. In this respect all the methods proposed in this book
have a restricted value.
The first edition of the present book appeared in 1972, i.e. almost 40 years ago. The
approach then proposed found a growing number of applications.
That the approach is useful has been demonstrated in a variety of ways in the literature,
including a Russian translation of the book and a book by Askadskii and Matvyeyev (1983,
in Russian), which is also devoted to the group contribution method and its applica-
tion in polymer science and engineering. In 2002 the 3rd edition of Biceranos book
Prediction of Polymer Properties appeared; it is based on a different way of group
contributions; nevertheless in the preface of this edition he mentions: Much of the
information provided by Van Krevelens classic textbook, Properties of Polymers was
extremely valuable in our work.

BIBLIOGRAPHY
Askadskii AA and Matvyeyev Yu I, Khimicheskoye Stroyeniye i Fizicheskiye Svoistva Polimerov (Chemical Struc-
ture and Physical Properties of Polymers). Nauka, Moskva, 1983.
Bicerano J, Prediction of Polymer Properties. Marcel Dekker, New York, 3rd Ed, 2002.
Bondi A, Physical Properties of Molecular Crystals, Liquids and Glasses. Wiley, New York, 1968.
Brandrup J, Immergut EH and Grulke EA (Eds) Polymer Handbook. Wiley-Interscience, New York, 1st Ed, 1966;
2nd Ed, 1975; 3rd Ed, 1989; 4th Ed, 1999.
Lewis OG, Physical Constants of Linear Homopolymers. Springer, Berlin, New York, 1968.
Mark JE, Polymer Data Handbook. Oxford University Press, 1999.
Reid RC and Sherwood Th K, The Properties of Gases and Liquids. McGraw-Hill, New York, 1st Ed 1958; 2nd Ed,
1966.
Reid RC, Prausnitz JM and Sherwood Th K, The Properties of Gases and Liquids. McGraw-Hill, New York, 3rd Ed,
1977.
Saechtling H, International Plastics Handbook for the Technologist, Engineer and User. Oxford University Press,
New York, 1988.

Encyclopaedic works
Encyclopaedia of Polymer Science and Engineering, Editors: Mark HF, Bikales NM, Overberger CG, Menges G and
Kroschwitz JI, Wiley, New York, 2nd Ed, 19841990.
Encyclopaedia of Materials Science and Engineering, 198687. Editor in chief: Bever MB, Pergamon Press, Oxford.
Comprehensive Polymer Science, The Synthesis, Characteristics, Reactions and Applications of Polymers,
8 Volumes. Editors: Allen SG and Bevington JC, Pergamon Press, Oxford, 1989.