Relationship between polymer chain conformation and phase boundaries in a supercritical fluid

Abstract

We investigate the solvent density driven changes in polymer conformation and phase behavior that occur in a supercritical fluid, with a particular emphasis on conditions near the lower critical solution temperature (LCST) phase boundary. Using continuous space Monte Carlo simulations, the mean square end-to-end distance (R) and radius of gyration (Rg) are calculated for a single chain with 20 Lennard-Jones segments in a monomeric solvent over a broad range of densities and temperatures. The chains collapse as temperature increases at constant pressure, or as density decreases at constant temperature. A minimum in R and Rg occurs at a temperature slightly above the coil-to-globule transition temperature (C-GTT), where the chain adopts a quasi-ideal conformation, defined by the balance of binary attractive and repulsive interactions. Expanded ensemble simulations of finite-concentration polymer–solvent mixtures reveal that the LCST phase boundary correlates well with the single chain C-GTT. At temperatures well above the LCST, the chain expands again suggesting an upper critical solution temperature (UCST) phase boundary above the LCST.