Enzyme-catalysis breathes new life into polyester condensation polymerizations

Traditional chemical catalysts for polyester synthesis have enabled the generation of important commercial products. Undesirable characteristics of chemically catalyzed condensation polymerizations include the need to conduct reactions at high temperatures (150–280 °C) with metal catalysts that are toxic and lack selectivity. The latter is limiting when aspiring towards synthesis of increasingly complex and well-defined polyesters. This review describes an exciting technology that makes use of immobilized enzyme-catalysts for condensation polyester synthesis. Unlike chemical catalysts, enzymes function under mild conditions (≤100 °C), which enables structure retention when polymerizing unstable monomers, circumvents the introduction of metals, and also provides selectivity that avoids protection–deprotection steps and presents unique options for structural control. Examples are provided that describe the progress made in enzyme-catalyzed polymerizations, as well as current limitations and future prospects for developing more efficient enzyme-catalysts for industrial processes.