Thermodynamic and Conformational Properties of Polystyrene. II. Intrinsic Viscosity Studies on Dilute Solutions of Linear Polystyrenes

Abstract

The results of an extensive study of the intrinsic viscosity [η] of a series of linear, homogeneous (anionically prepared) polystyrenes (1.9<10−4M<440) over a wide temperature interval (10°<T<110°C) in decalin and toluene are described. The data are discussed in relation to the interaction parameter z=B0(〈s2〉0/M)−3/2(1−Θ/T)M1/2 in which the constants B0, Θ, and 〈s2〉0/M have been determined from thermodynamic studies reported in Part I of this series. It is found that [η]/[η]0 is not a single-valued function of z except for M>∼106. Above this molecular weight the dependence of [η]/[η]0 on z is satisfactorily predicted by recent calculations of Fixman; [η]/[η]0 is not linear in z contrary to other recent suggestions. The failure of the data on lower molecular weight polymers to be a single-valued function of z is discussed in terms of partial draining effects.