Progress in reactor engineering of controlled radical polymerization: a comprehensive review

Controlled radical polymerization (CRP) represents an important advancement in polymer chemistry. It allows synthesis of polymers with well-controlled chain microstructures. Reactor engineering is essential in bringing lab-scale chemistry to industrial realization. This paper reviews the research progress in reactor engineering of CRP, namely, atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer radical polymerization (RAFT), and nitroxide-mediated or stable free radical polymerization (NMP or SFRP). Research activities in semi-batch reactors, tubular reactors, and continuous stirred-tank reactors (CSTR) of both homogeneous (bulk and solution) and heterogeneous (emulsion, mini-emulsion, heterogeneous catalyst, etc.) CRP systems are summarized. Typical examples are selected and discussed in detail. Perspectives on the current status and future development are also provided.