Controlled/living heterogeneous radical polymerization in supercritical carbon dioxide

Supercritical carbon dioxide (scCO 2 ) is an inexpensive and environmentally friendly medium for radical polymerizations. ScCO 2 is suited for heterogeneous controlled/living radical polymerizations (CLRPs), since the monomer, initiator, and control reagents (nitroxide, etc.) are soluble, but the polymer formed is insoluble beyond a critical degree of polymerization ( J crit ). The precipitated polymer can continue growing in (only) the particle phase giving living polymer of controlled well‐defined microstructure. The addition of a colloidal stabilizer gives a dispersion polymerization with well‐defined colloidal particles being formed. In recent years, nitroxide‐mediated polymerization (NMP), atom transfer radical polymerization (ATRP), and reversible addition fragmentation chain transfer (RAFT) polymerization have all been conducted as heterogeneous polymerizations in scCO 2 . This Highlight reviews this recent body of work, and describes the unique characteristics of scCO 2 that allows composite particle formation of unique morphology to be achieved.