Recent Advances in Sequence-Controlled Ring-Opening Copolymerizations of Monomer Mixtures.

Abstract

Transforming renewable resources into functional and degradable polymers is driven by the ever-increasing demand to replace unsustainable polyolefins. However, the utility of many degradable homopolymers remains limited due to their inferior properties compared to commodity polyolefins. Therefore, the synthesis of sequence-defined copolymers from one-pot monomer mixtures is not only conceptually appealing in chemistry, but also economically attractive by maximizing materials usage and improving polymers' performances. Among many polymerization strategies, ring-opening (co)polymerization of cyclic monomers enables efficient access to degradable polymers with high control on molecular weights and molecular weight distributions. Herein, we highlight recent advances in achieving one-pot, sequence-controlled polymerizations of cyclic monomer mixtures using a single catalytic system that combines multiple catalytic cycles. The scopes of cyclic monomers, catalysts, and polymerization mechanisms are presented for this type of sequence-controlled ring-opening copolymerization.