Construction methodologies and sequence-oriented properties of sequence-controlled oligomers/polymers generated via radical polymerization

Abstract

The chain-growth polymerization mechanism is essentially unsuitable for sequence control due to the statistical propagation feature. However, the development of reversible-deactivation radical polymerization (RDRP) has opened the door to sequence control for carbon–carbon bond-based synthetic polymers carrying various pendant groups on their repeating units. Our group has developed some methodologies and concepts for the synthesis of sequence-controlled oligomers/polymers via radical polymerization. It is crucial to introduce some additional components into the initiator and/or the monomer for RDRP, and in most cases, these components are designed to be removed or transformable afterward. This review focuses on the methodologies we have recently developed for sequence regulation via radical polymerization processes and the sequence-oriented properties of the resultant sequence-controlled polymers. The chain-growth polymerization mechanism is essentially unsuitable for sequence control due to its statistical propagation feature. However, the development of reversible-deactivation radical polymerization has opened the door to the sequence control. Our group has developed some methodologies and concepts for the synthesis of sequence-controlled oligomers/polymers via radical polymerization: it is crucial to introduce some additional components into the initiator and/or the monomer for reversible-deactivation radical polymerization and in most cases these components are designed to be removed or transformable afterward.