Atom Transfer Radical Polymerization: From Mechanisms to Applications

Atom transfer radical polymerization (ATRP) is currently one of the most often used synthetic polymerization methods to prepare well‐defined polymers with complex architecture. This review covers some fundamentals of copper‐based ATRP, presents basic structure–reactivity correlation for initiators and catalyst complexes and discusses the radical nature of reactive intermediates. New ATRP initiating processes with ppm amounts of copper catalysts and various reducing agents are described together with recent electrochemically controlled ATRP and polymerization in aqueous homogeneous and dispersed media. Examples of polymers with precisely controlled architecture are presented together with the effect of variable amounts of catalysts on molecular weight distribution and morphology of nanostructured block copolymers. Some current and forthcoming applications of polymers made by ATRP are presented.