The effect of polymer chain length on the thermodynamics of acrylate/cyanobiphenyl mixtures

Abstract

The effect of polymer molecular mass on the phase behaviour and solubility limits of polymer/liquid crystal mixtures is studied for blends of poly(methyl methacrylate) (PMMA) and the small‐molecule liquid crystal, 4′‐octyl‐4‐biphenylcarbonitrile (8CB). The phase diagrams from optical microscopy show a limit to the effect of increasing polymer molecular mass. The Flory–Huggins theory (FH) for polymer solutions is used to extract the interaction parameter, χ, from the phase diagrams. The initial FH fits are performed with the assumption that χ is independent of polymer molecular mass, but result in poor correlation to the microscopy data. When χ is allowed to scale with M _w, however, the FH fits are consistent with the limiting molecular mass behaviour. This result represents, to our knowledge, the first time that this scaling behaviour has been observed in polymer/liquid crystal blends. The solubility limit, β, of 8CB in PMMA for each polymer molecular mass is also determined and, when compared with the results of previous studies, support the concept that β is independent of both polymer composition and molecular masses when the polymer molecular mass exceeds ca. 5×10⁵ g mol⁻¹.