The synthesis of complex macromolecules involving multiple functional monomers provides access to a broad array of materials with diverse physical and mechanical properties. In this talk, redox-switchable polymerization catalysts are described that enable the synthesis of copolymers and cross-linked polymer networks whose microstructures are dictated by the oxidation state of the catalyst used and the timing in which redox events are incurred. Prior use of redox-switchable polymerization reactions have been limited to certain classes of monomers, and engineering applications that utilize the technique remain uncommon. In this talk, we will describe how using various iron-based complexes leads to redox-switchable reactivity for a diverse array of functional monomers for ring-opening polymerization reactions. Additionally, a new concept in redox-switchable polymerization reactions called redox-switchable polymerization by chain transfer (ReSPCT) will be described that enables incorporation of an even broader array of monomers. These reactions will be used to synthesize new degradable thermoplastic elastomers and degradable cross-linked polymer networks. Finally, application of redox-switchable polymerization in surface-initiated polymerizations will be described that enables the patterning of different polymers on surfaces and provides promising avenues for integrated catalysis.

New concepts and applications of redox-switchable polymerization reactions

ACS Spring 2022

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