Polymerization is widely involved in the fabrication of high-performance materials. With its advantages, microreactors are typically applied to reaction processes which are limited by transport properties of conventional batch reactors. As demonstrated in this review, numerous polymerization processes are suitable to be conducted in microreactors with showing excellent polymerization performance (e.g., precisely controllable molecular weights and structures of polymer products). However, distinctive differences between polymerization processes and small-molecular reaction systems can be easily expected since fluid physical properties vary significantly during the polymerization. Herein, we firstly clearly describe the engineering principles such as mass transport phenomena and energy dissipation related to polymerization processes in microreactors, and then give a great deal of application examples (classified as homogeneous polymerization, heterogeneous polymerization, and photopolymerization) through which readers indeed can further understand these relevant principles. Finally, the remaining challenges associated with the application of microreactor technology for polymerization processes and remarking conclusions are presented.
Keywords: Flow chemistry; Mass transfer; Microreactors; Photochemistry; Polymerization; Polymers.