Liquid–liquid equilibria of copolymer mixtures based on an equation of state

Liquid–liquid equilibria of copolymer mixtures were studied by an equation of state (EoS) for chain-like fluids. The equation consists of a reference term for hetero-nuclear hard-sphere chain fluids developed by Hu et al. where the next-to-nearest-neighbor correlations have been taken into account; and a perturbation term from Alder et al.’s square-well attractive potential. The segment parameters, including number of segments, segment diameter and interaction energy between segments, are obtained by fitting pVT data of pure homopolymer. For the case of different species in the same copolymer, the interaction parameters for unlike segment pairs are obtained by fitting pVT data of pure copolymer. For the interaction between segment of homopolymer and different species in copolymer, the parameters are treated as adjustable by fitting liquid–liquid equilibria data. In the latter case, the difference between different species in a copolymer is simply neglected as an approximation. Therefore, in general, only one pair of adjustable interaction parameter is determined from LLE data. To model miscibility maps of copolymer mixtures having two or three kinds of species, the interaction parameters are obtained from the boundary between miscible and immiscible regions. The EoS used in this work can correlate phase behavior including coexistence curves, miscibility windows and miscibility maps.