Macromolecular Engineering by Atom Transfer Radical Polymerization

TLDR

This Perspective presents recent advances in macromolecular engineering enabled by ATRP, highlighting its fundamental mechanistic and synthetic features, including low‑concentration Cu catalysts and environmentally friendly media such as water. The authors outline future challenges and perspectives for macromolecular engineering using ATRP. The review explains how monomers, initiators, catalysts, additives, media, and external stimuli influence ATRP reactivity, structure, and polymerization control. Examples of precisely controlled chain uniformity, composition, topology, functionality, complex architectures, hybrids, bioconjugates, and current and forthcoming applications illustrate ATRP’s capabilities.

Abstract

This Perspective presents recent advances in macromolecular engineering enabled by ATRP. They include the fundamental mechanistic and synthetic features of ATRP with emphasis on various catalytic/initiation systems that use parts-per-million concentrations of Cu catalysts and can be run in environmentally friendly media, e.g., water. The roles of the major components of ATRP—monomers, initiators, catalysts, and various additives—are explained, and their reactivity and structure are correlated. The effects of media and external stimuli on polymerization rates and control are presented. Some examples of precisely controlled elements of macromolecular architecture, such as chain uniformity, composition, topology, and functionality, are discussed. Syntheses of polymers with complex architecture, various hybrids, and bioconjugates are illustrated. Examples of current and forthcoming applications of ATRP are covered. Future challenges and perspectives for macromolecular engineering by ATRP are discussed.