ATRP and ROMP: Modular chemical tools for advanced macromolecular engineering

Well-defined graft copolymers were synthesized through the combination of two highly controlled polymerizations, ATRP (Atom Transfer Radical Polymerization) and ROMP (Ring-Opening Metathesis Polymerization). Synthesis of α-cyclobutenyl polystyrene-b-poly(tert-butyl acrylate) macromonomers was first performed by ATRP from an original initiator. ROMP of these macromonomers using Grubb’s generation II catalyst ((IMesH2)(Cy3P)RuCl2(CHPh)) has allowed to synthesize well-defined graft copolymers with a polybutadiene backbone and polystyrene-b-poly(tert-butylacrylate) grafts. α-Cyclobutenyl polystyrene-b-poly(acrylic acid) macromonomers were prepared by acidolysis. An amphiphilic water-soluble α-cyclobutenyl polystyrene-b-poly(acrylic acid) macromonomer has been successfully employed as stabilizer in emulsion polymerization of styrene.