Cu(0)- RDRP of styrene: balancing initiator efficiency and dispersity

Cu(0)-RDRP is a powerful technique to synthesise a wide range of polymeric materials and architectures with controlled molecular weight, low dispersities and high end group fidelity. The vast majority of reports using this technique focus on the polymerisation of acrylates or methacrylates, with very limited examples on styrene, which is surprising as this is one of the most important vinyl monomers. Herein we present the first Cu(0)-wire mediated polymerisation of styrene with enhanced initiator efficiency and dispersity. The structure of the ligand, the type of the initiator, the nature of the solvent and the catalyst concentration have been systematically varied to afford polystyrene at relatively high molecular weights (approximate to 50000 g mol(-1)) with excellent agreement between theoretical and experimental number average molecular weight values and good control over the molecular weight distributions (D approximate to 1.15).