Dual/heterofunctional initiators for the combination of mechanistically distinct polymerization techniques

This review highlights 20 years of research concerning the synthesis of block copolymer structures with dual and, more general, heterofunctional initiators, allowing the combination of mechanistically distinct polymerization reactions without the need for intermediate transformation and protection steps. This strategy, which has known an exponential growth since the year 2000, has offered new opportunities in the design and application of functional polymeric materials for a broad spectrum of emerging technologies. Block copolymer structures with both linear (AB, ABA, (AB)n, multiblocks, etc) and branched macromolecular architectures (star block, graft, miktoarm star, dendrimer-like,…), obtained by the combination of uncontrolled and/or controlled polymerization reactions starting from a single molecule, are discussed. Not only small organic molecules but also polymers containing two initiation functions, further referred to as macro dual initiators, which can initiate different polymerizations independently and selectively, are described.