The past decades have witnessed an
increasing interest in developing
advanced polymerization techniques subjected to external fields. Various
physical modulations, such as temperature, light, electricity, magnetic
field, ultrasound, and microwave irradiation, are noninvasive means,
having superb but distinct abilities to regulate polymerizations in
terms of process intensification and spatial and temporal controls.
Gas as an emerging regulator plays a distinctive role in controlling
polymerization and resembles a physical regulator in some cases. This
review provides a systematic overview of seven types of external-field-regulated
polymerizations, ranging from
chain-growth to step-growth polymerization. A detailed account of
the relevant mechanism and kinetics is provided to better understand
the role of each external field in polymerization. In addition, given
the crucial role of modeling and simulation in mechanisms and kinetics
investigation, an overview of model construction and typical numerical
methods used in this field as well as highlights of the interaction
between experiment and simulation toward kinetics in the existing
systems are given. At the end, limitations and future perspectives
for this field are critically discussed. This state-of-the-art research
progress not only provides the fundamental principles underlying external-field-regulated
polymerizations but also stimulates new development of advanced polymerization
methods.