Compressible models of equilibrium polymerization.

Flory-Huggins-type models of equilibrium polymerization are extended to describe compressible systems and, hence, the pressure dependence of thermodynamic properties. The theory is developed for three different mechanisms of equilibrium polymerization (the free association, monomer-activated polymerization, and chemically initiated polymerization models). In contrast to previous approaches for describing the pressure dependence, the theory delineates the thermodynamic consequences of the size disparities between solvent molecules, unpolymerized monomers, and the monomers within polymers. Basic thermodynamic properties (the extent of polymerization, density, heat capacities CP and CV, etc.) are calculated analytically as functions of pressure, temperature, and composition of the associating species. Illustrative calculations refer to systems that polymerize upon cooling and demonstrate general agreement with numerous experimental trends. Comparisons with results from other theories are also discussed. [ABSTRACT FROM AUTHOR]