Abstract
The behavior of the polymerization of α-methylstyrene with the alkyl-magnesium bromide (RMgBr)/hexamethylphosphoramide (HMPA) system was found to be similar to that of the usual anionic equilibrium polymerization. The reactivities of RMgBr as initiators decreased in the order: R=benzyl>allyl>aryl≈s-alkyl>n-alkyl. This result was explained in terms of both the ease of carbanion formation from RMgBr and the activity of the anion formed. In the case of benzylmagnesium bromide/HMPA catalyst, it is suggested that the reactive species in the initiation is a complex formed by the coordination of four HMPA molecules with the magnesium ion.
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