SOME LIGHT ON THE CONCEPT OF UNREACTIVITY ARISING FROM ACTIVE CENTERASSOCIATION IN ANIONIC POLYMERIZATIONS

A long held assumption in hydrocarbon based anionic polymerizations involving organolithiums is that the aggregated species are unreactive and thus serve only as reservoirs from which the active singlet species momentarily emerge to participate in the initiation or propagation events. This work demonstrates that contrary to the notion of aggregate dormancy such species can participate in monomer addition. The approach involved freeze-dried vitrified polystyryllithium which was found to be reactive toward butadiene and methanol vapors. The sub-glass transition state of the polystyryllithium eliminates the establishment of the aggregate : singlet equilibrium as a result of the inability of chains to undergo diffusion. Furthermore, it is shown that the lower bound gradient for the dependence of propagation rate on active center concentration, within experimental error, is about 1/5 for the majority of those diene systems where the active center concentration covers at least two decades. A computer evaluation of the propagation rate : active center data was done with the aim of testing and determining the equilibrium constants of these aggregated systems.