|138. Schmitt, B.; Müller, A.H.E.: Anionic Polymerization of (Meth)acrylates in the Presence of Tetraalkylammonium Halide - Trialkyl Aluminum Complexes in Toluene, 3. Kinetic Investigations on Primary Acrylates, Macromolecules 34, 2115 (2001)|
The polymerization of n-butyl acrylate initiated by ester enolates in the presence of tetraalkylammonium halide-trialkylaluminum complexes, R4N[AlnR'3nX] (n = 1, 2), in toluene has a controlled character at -78 °C only for selected combinations of the complex. Quantitative monomer conversions are usually reached with Me4N[AlnBui3nCl] leading to polymers with narrow molecular weight distributions (Mw/Mn < 1.2). Kinetic investigations show a complex mechanism of the polymerization, implying an equilibrium between at least two active species. Besides, various acrylate homopolymers and block copolymers (PMMA-b-polyacrylate) can be synthesized with this new initiating system.