Strategies For The Synthesis Of Block Copolymers With Biodegradable Polyester Segments

The controlled synthesis of block copolymers offers great potential for the valorization of biodegradable polyesters, many of which can be bioderived. Combining polyester blocks with other oxygenated polymers through ring-opening polymerization (ROP) and copolymerization (ROCOP) reactions allows for the synthesis of new materials with tunable properties. In this review article, we describe recent advances in the synthesis of diblock and multiblock polyesters, as well as polyether and polycarbonate block copolymers bearing biodegradable polyester block segments. Due to the great diversity of oxygenated monomers available from petrochemical and biomass sources, a great number of polymerization strategies have been developed involving metal- and organo-catalysts with different degrees of control. This review aims to provide an overview of the strategies available for the synthesis of different block copolymers: from the more widespread sequential addition methods to the more rare systems displaying high degrees of kinetic control in a mixture of monomers or those with controlled switchable behavior.