Preliminary Study on Kinetic Modeling of Electrochemically Mediated Atom Transfer Radical Polymerization

A detailed kinetic model about electrochemically mediated atom transfer radical polymerization (eATRP) was constructed by the method of moments. Based on the model, the difference between eATRP and normal ATRP was elucidated, and the effects of overpotential, catalyst loading and initiator concentration on polymerization behavior were predicted. The results show that overpotential and catalyst concentration both have a positive effect on the polymerization rate, while the former has no influence on the polydispersity index (PDI) and the later reduces the PDI. When the catalyst concentration (ratio of the catalyst and monomer concentration) decreases to 3× 10^-5, PDI is as high as 1.2 and cannot get steady within the reaction time. Besides, the initiator concentration mainly affects the induction period of the reaction. When the ratio of the initiator concentration to the monomer concentration declines to 0.5:300, the induction period is extended from 200 s to about 400 s rapidly.