Second-Order Transition Temperatures and Related Properties of Polystyrene. I. Influence of Molecular Weight

Dilatometric and viscometric data on fractionated polystyrenes containing diethylbenzene end groups are presented over wide temperature ranges. The second-order transition temperature, viscosity-temperature coefficient, and specific volume all change rapidly with increasing molecular weight toward asymptotic limits which are practically reached at M≅30,000. Empirical expressions are presented relating these properties to molecular weight and temperature. In each case the dependence on molecular weight is expressed as a simple function of M̄n−1. These observations are interpreted and correlated on the basis of the hypothesis that the local configurational order in a liquid polymer is disturbed by the introduction of end groups to a degree that is proportional to their number. The second-order transition does not represent an isoviscous state. The internal local configurational structure appears to be equivalent, and independent of temperature, in all polystyrenes below their second-order transition temperatures.