Precision Polymerization beyond Conventional Classifications of Active Species and Polymerization Mechanisms toward Advanced Polymer Networks

Abstract

Precision polymerization has enabled the synthesis of polymers with well-defined primary structures; however, the precise control and analysis of polymer network structures remain challenging because of their inherent heterogeneity and insolubility. This review summarizes our recent studies on precision polymerization systems beyond conventional classifications based on active species and polymerization mechanisms, and their application to advanced polymer networks. Particular emphasis is placed on mechanistic transformation through RAFT terminals, interconvertible radical/cationic living polymerization, precise synthesis of branched poly(vinyl alcohol)s, selectively degradable polymer networks, and controlled/living click polymerization. In particular, degradable branching points and active-species transformation have enabled the design of analyzable and structurally controlled network polymers. These studies demonstrate that integrating precise polymer synthesis with controllable and analyzable network architectures provides a promising strategy for the development of advanced functional and sustainable polymer materials.