Investigation of local density of monomer units and molecular dynamics in solutions of poly-4-vinyl-pyridine by the spin label technique

Abstract

The local density of monomer units of the macromolecule (local density of the host molecule, ϱ host) in poly-4-vinyl-pyridine solutions in ethanol was determined by the spin label technique. In dilute solutions, ϱ host is considerably greater than the mean density of monomer units in the volume of the polymer coil; when the polymer concentration rises from 0.5 to 65 wt%, its increase does not exceed 30%. This indicates that the differences between polymer coil microstructure (mutual positions of monomer units close to a chosen unit) in dilute and concentrated solutions is small. The local density of monomer units of neighbouring macromolecules (guest macromolecules, ϱ guest) is strongly dependent on the polymer concentration in solution. In dilute solutions, ϱ host ⪢ ϱ guest; for polymer concentrations above 2–3 wt%, overlapping and interpenetration of macromolecular coils take place, local density of monomer units of neighbouring macromolecules rises and monotonously increases as polymer concentration grows. The concentration dependence of the local rotational and translational mobility of monomer units is determined by the local density of monomer units of the neighbouring macromolecules.