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(Me2)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 (Mw/Mn < 1.2) and high isotacticity (90% isotactic triads).