Synthetic Routes to Stimuli‐Responsive Micelles, Vesicles, and Surfaces via Controlled/Living Radical Polymerization∗

Controlled/living polymerization (CLRP) techniques have recently been developed that offer unprecedented opportunities for synthesis of materials with precisely tailored nano‐ and micro‐scale features. This account focuses on significant developments in the field of stimuli‐responsive block copolymers with immediate and future utility in advanced formulation and surface science. Specifically, stable free radial polymerization (SFRP), atom transfer polymerization (ATRP), and reversible addition fragmentation chain transfer (RAFT) polymerization techniques for preparation of responsive micelles and vesicles, stabilized nanoparticles, thin films, polymer brushes, and other ordered structures are described. Conformational changes in response to external stimuli are manifested in changes in physiochemical properties including surface wetting, adsorption, adhesion, lubricity, and permeability.