Angular correlation in linear copolymers from the compositional dependence of their dipole moments. VI. Time dependent correlations in poly(4-chlorostyrene, 4-methylstyrene) copolymers

The compositional dependence of the shape of the map in the complex plane of the dielectric constant of undiluted poly(4-chlorostyrene, 4-methylstyrene) copolymers, P(4CS,4MS), has been investigated at temperatures above the glass transition. The copolymer method, which was developed for the study of equilibrium dipole–dipole angular correlations, has been adapted to include time dependence for this investigation. Results are given in terms of differences of the shapes of contributions of 000, 010, 011, and 111 sequences, where 0 and 1 represent 4MS and 4CS units, respectively. The short range (next neighbor) of the compositional dependence of the relaxation characteristics relative to the longer range already established for the equilibrium angular correlations suggests that the latter represent averages over rotational states of backbone bonds that are undergoing fast and nearly independent transitions from one state to another.