Effect of molecular weight distribution on the liquid–liquid phase separation behavior of polydispersed polyethylene solutions at high temperatures

The phase behaviors of the hexane + polydispersed polyethylene (PE) systems were measured to clarify the effect of the molecular weight distribution (MWD) of PE on liquid–liquid (LL) phase boundaries. The weight fraction for the PE portion of a maximum LL phase separation pressure in the LL phase boundary decreased as the polydispersity of PE increased. Moreover, depression of the phase separation pressure from the maximum phase separation pressure on the higher PE weight fraction side was more drastic as the polydispersity of the PE increased. The LL phase boundaries were correlated using the Sanchez–Lacombe equation of state (S–L EOS). For the correlations, the polydispersed PEs were regarded as mixtures of 16 types of monodispersed PEs with different molecular weights, and the characteristic parameters of the S–L EOS, P*, ρ* and T*, were assigned the same values for all monodispersed PEs even though the molecular weights differed. However, the interaction parameters of the hexane–PE pairs depended on the molecular weight of the PE and the temperature. The correlated results capably reproduced the effect of the MWD of the PE on the LL phase boundaries for the hexane + polydispersed PE systems.

► The phase behaviors of the hexane + polydispersed PE systems were measured.
► The effect of the polydispersity of PE on the phase behavior was investigated.
► The experimental LL phase boundaries were correlated using the Sanchez–Lacombe EOS.
► PEs were regarded as the mixture of 16 types of monodispersed PEs in the correlation.
► The temperature- and molecular weight-dependent interaction parameters were used.