Phase behaviour of rod with flexible side chains/coil/solvent systems: poly(α,l-glutamate) with tri(ethylene glycol) side chains, poly(ethylene glycol), and dimethylformamide

Abstract

Phase behaviour is investigated for ternary solutions composed of rodlike α-helical poly(α,l-glutamate) having triethylene glycol monomethyl ether at the end of the side chains (P3EGLG), randomly-coiled poly(ethylene glycol), and N,N-dimethylformamide (DMF) as solvent. The solution containing lower molecular weight poly(ethylene glycol) (PEG10) separates into an isotropic phase, which is rich in PEG10, and an anisotropic (cholesteric) phase, which is rich in P3EGLG, when the total polymer volume fraction is higher than ca 0.13. The homogeneous anisotropic region, in which a detectable amount of PEG10 exists, is recognized along the P3EGLG-DMF axis in the triangle phase diagram. When the molecular weight of poly(ethylene glycol) is larger, additional phase-separation regions are observed: That is, isotropic-isotropic biphasic region and anisotropic-isotropic-isotropic triphasic region. Theoretical treatments based on the lattice model for nematic solutions are conducted for these rod/coil/solvent ternary systems. Calculated phase diagrams with considering flexible side chains of rodlike solute and isotropic interaction parameters are found to qualitatively reproduce the variation of the experimental phase behaviour with the change of the molecular weight of the coiled component.