Reversible Deactivation Radical Polymerization in Heterogeneous Systems: Enhancing Access to High Molecular Weight Polymers

High molecular weight (HMW) polymers (Mn > 500 kg mol–1) are indispensable in advanced applications owing to their superior physical properties and performance characteristics. While homogeneous reversible deactivation radical polymerization (RDRP) systems struggle with viscosity-driven limitations at high conversions, heterogeneous RDRP techniques (emulsion, miniemulsion, dispersion) offer compelling environmental, kinetic, and processing advantages. This Perspective examines the synthesis of HMW polymers in these heterogeneous systems, highlighting their unique mechanistic features, rapid kinetics, and scalability. We also outline the challenges and opportunities in system engineering, polymer chain engineering, polymerization techniques, and circularity. By bridging fundamental insights with industrial scalability, heterogeneous RDRP systems stand at the forefront of macromolecular innovation for next-generation materials that harmonize performance with sustainability.