The butyllithium initiated bulk anionic polymerization of α‐methylstyrene

Butyllithium (BuLi) initiates α‐methylstyrene polymerization in bulk at room temperature. Both initiation and propagation reactions are very slow and propagation/depropagation occurs along with other side reactions, e.g., transfer. At slightly elevated temperatures (40–50°C) irreversible termination takes place. Molecular weights change inversely but not linearly with changes in [BuLi] and distributions are broad (M̄w/M̄n = 1.55 to 2.2) as would be expected from equilibria considerations. These results are generally different than those reported with sodium initiated reactions.