Combinations (Є) among controlled/living polymerizations and utilizations of efficient chemical reactions for the synthesis of novel polymeric materials

Abstract

Building on the 1^st-generation method of living anionic polymerization in the 1950s, various 2^nd-gen controlled/living polymerization (CLP) techniques were developed in the 1980s–1990s. The CLP techniques now include ionic, radical, ring-opening (metathesis), and condensation polymerizations, allowing us to precisely control molecular weight, polydispersity, and complex architectures. However, the polymerizable monomers restrict the use of single-initiation systems, thereby limiting the synthesis of innovative macromolecules. Polymer chemists are thus interested in investigating ways to design or overcome the obstacles presented by two-initiation or more methods. Our review mainly focuses on the investigations of such combination approaches, represented by the symbol “Є”, in diverse and robust polymerizations. We also depict numerous combinations of revolutionary polymerizations and effective reactions to prepare novel polymeric materials and discuss their relevant, unique properties and applications. Notably, we further address the synthesis of novel macromolecules, including block copolymers (BCPs), bottlebrush polymers (BBPs), hyperbranched polymers (hbPs), and (miktoarm) star copolymers ((μ-)SCPs). This review aims to showcase the effectiveness of synthetic method combinations and highlight the diverse applications of these innovative materials.