Synthesis of well-defined polymer architectures by successive catalytic olefin polymerization and living/controlled polymerization reactions

Polyolefins account for more than half of worldwide production of thermoplastics. The majority is used as commodity polymers but they may also provide the starting backbones for original architectures. Most polyolefins are obtained by catalytic polymerization and this powerful technique may be used to produce polyolefins incorporating interesting functional groups that can serve as initiating sites for other successively applied polymerization techniques. This review describes the state of the art in strategies employing catalytic olefin polymerization followed by a living or controlled polymerization. The latter methodologies are classified according to the living/controlled polymerization technique used including anionic polymerization, nitroxide-mediated radical polymerization (NMRP), atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer (RAFT).