Block copolymers of methyl methacrylate with butyl methacrylate have been synthesized via "living" anionic polymerization technique with a wide variation concerning composition, architecture and molecular weight. DSC and TEM have proven an extended micro phase separation for the resulting products. An unexpected synergism in tensile strength was observed upon investigation of the mechanical properties of the products. Furthermore, a new chelating additive is introduced which enables the well-defined homopolymerization of 2-ethylhexyl acrylate as well as the synthesis of block copolymers with methyl methacrylate. The synthesis of PMMA has been performed in pure toluene at elevated temperature T>-20 °C nearly quantitatively with a relatively narrow molecular weight distribution D<1.25 using the same additive.