New Ligands for the Living Isotactic Anionic Polymerization of Methyl Methacrylate in Toluene at 0 °C. 1. Ligation of Butyllithium by Lithium Silanolates

sBuLi and tBuLi have been combined with a new family of ligands, i.e. lithium silanolates, and used as initiators for the ligated anionic polymerization (LAP) of methyl methacrylate (MMA) in toluene at 0 °C. Compared to other known μ-ligands, the accordingly formed Bu(Me 2 )SiOLi are more efficient stabilizers for the active centers. Under appropriate reaction conditions, a fast polymerization proceeds quantitatively without self-termination at 0 °C and leads to high molecular weight polymer of narrow molecular weight distribution ( M̄ w / M̄ n < 1.2) and high isotacticity (90% isotactic triads).