Facile Synthesis of Well-Defined Telechelic Alkyne-Terminated Polystyrene in Polar Media Using ATRP With Mixed Fe/Cu Transition Metal Catalyst

The synthesis of polystyrene (PS) by atom transfer radical polymerization using the Fe(0)/CuBr2 catalytic system in dimethylformamide is reported. The effects of temperature, ligand, initiator structure, and monomer to solvent ratio on the polymerization kinetics are evaluated. PS with high molecular weight, low polydispersity, and telechelic structure are achieved and successfully used for further reinitiation or the copper(I)-catalyzed Huisgen 1,3-dipolar cycloaddition click reaction between alkyne- and azide-terminated PS. For the first time, suitable styrene polymerization rates are achieved using this cost-effective and environmentally attractive catalytic system. This method can be very useful in macromolecular engineering to afford PS-based materials with well-controlled structure.