Abstract:
The kinetics of living anionic polymerizations of styrene has been studied with lithium as gegenion
in solution in binary mixtures of 1,2-dimethoxyethane and benzene at 0, 25 and 35°C. The contri
bution of intermolecular triple ions is suggested from kinetic and conductivity data. The dissociation
constant of the ion pairs increases as the temperature is lowered, while that of the triple ions decreases.
Both the ion-pair and triple-ion dissociation constants increase as the dielectric constant is increased.
The rate constants for the ion pairs, free ions and triple ions were determined. The triple ions are
suggested to be of a solvent-separated intermolecular type and to be much more reactive than the free
ions. No effect of electric field on the kinetics was observed in this system.
