New prospects for “living” anionic polymerization of (meth) acrylic esters

The living low temperature polymerization in polar solvents of most methacrylates, even functional ones, can now be performed by direct and experimentally convenient anionic methods, thanks to the use of α-methylstyrene and of complex-purified monomers. A diversified family of block copolymers has thus been generated, that are used as compatibilizing agents in the designing of interesting heterophase materials: i.e. blends of polymers and inorganic fillers, and liquid-solid dispersions. The living polymerization of acrylates (or of methacrylates under more drastic conditions) raises additional requirements: they have been met to a large extent by the use of specific ligands of the growing ion-pair. Resulting structures such as f.i. block copolymers and end-functionalized oligomers of a low dispersity, should have a great interest in the molecular engineering of (meth)acrylate-based products. Finally, these new initiators lend themselves to structural and mechanistic studies which should shed some light on the critical features of these living propagation processes.