Control of Active Centers Reactivity in the High Temperature Bulk Anionic Polymerization of Hydrocarbon Monomers

The control of the reactivity in the anionic polymerization of styrene at elevated temperature (100 °C) and in the bulk has been achieved by the use of dialkylmagnesium additives to polystyryllithium. The rate of polymerization was found to decrease with increasing dialkylmagnesium/ polystyryllithium ratio ® in the range 0 to 20. In addition, chain initiation by the magnesium derivatives allows keeping low metal/chain ratios (<2). The results are interpreted by the formation of “ate” complexes in dynamic equilibrium.