An evaluation of the concept of unreactivity arising from head-group aggregation in anionic polymerizations

The long-standing presumption that aggregated organolithium species are unreactive in hydrocarbons has been examined for styryllithium head-groups. A computer based curve-fitting evaluation of the equilibrium constants assumed to govern the perceived dimer: singlet equilibria for polystyryllithium in benzene, cyclohexane, and toluene was done. From the calculated concentrations of singlet head-groups and the experimental propagation rates, the rate constant (k_p) values were obtained. Some values were approximately equal to or larger than those measured for the ion-pair in etherial solvents. These hydrocarbon solution values are improbably large, raising serious doubts about the validity of the mechanism upon which they are based. The data for the styrenic monomers in toluene also failed to lend support to that mechanism. © 1996 John Wiley & Sons, Inc.