On the Thermodynamic Properties of Solutions of Polar Polymers. Theory

Publisher Website
Google Scholar
Abstract
In this paper we present a simple analysis of the thermodynamic properties of solutions of polar polymers. It is found that: (a) In the dilute solution regime, a cluster analysis identical with that used in the theory of solutions of nonpolar polymers can be developed, but with the thermodynamic parameter z now dependent on the dipole moment,dielectric constant, etc. (b) In the concentrated solution regime, a continuum theory can be developed based on the assumption of uniform mixing of polymer chains and the use of cavity field and reaction field arguments. (c) For dilute solutions of a polar polymer in a nonpolar solvent, or a nonpolarizable polar polymer in a polar solvent, the system is equivalent to an ordinary nonpolar polymer‐poor solvent system. (d) It is generally true that the solvent becomes poorer as the dipole moment and/or polarizability of the segment are increased. Also, the solvent becomes better as its dielectric constant increases. (e) In the case of concentrated solutions of a polar polymer in a nonpolar solvent, the polar contribution to the Flory‐Huggins free‐energy parameter, χ p , decreases with increasing concentration. (f) In the case of concentrated solutions of a nonpolar polymer in a polar solvent, χ p increases with increasing concentration. (g) The dilute solutiontheory and concentrated solutiontheory predict the same functional form for χ p in the limit of zero polymer concentration, but the numerical coefficients differ. (h) The results of extensive digital computer calculations are presented in terms of the predicted concentration dependence of χ p with varying properties of both polymer and solvent. Agreement between theory and experiment is examined in detail in the following paper.

This publication has 13 references indexed in Scilit: