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Kinetic features of iron‐based electrochemically mediated ATRP revealed by Monte Carlo simulation
Author(s) -
Jin Jie,
Guo JunKang,
Zhou YinNing,
Luo ZhengHong
Publication year - 2021
Publication title -
aiche journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.958
H-Index - 167
eISSN - 1547-5905
pISSN - 0001-1541
DOI - 10.1002/aic.17098
Subject(s) - chemistry , kinetic monte carlo , monte carlo method , polymerization , diffusion , kinetic energy , atom transfer radical polymerization , thermodynamics , mass transfer , methyl methacrylate , viscosity , polymer chemistry , materials science , polymer , chromatography , physics , organic chemistry , mathematics , statistics , quantum mechanics
A comprehensive kinetic Monte Carlo (kMC) model of a reaction–diffusion system has been developed to illustrate the heterogeneous reaction of electrochemically mediated atom transfer radical polymerization (eATRP). The equilibrium coefficient for the initiator obtained from the Genetic Algorithm was lower than that for polymeric species, explaining the low initiation efficiency of the iron‐based eATRP of methyl methacrylate (MMA) system. A comparative study demonstrated that the composite k t model, explicitly considering the chain length dependency, presented the most adequate description of the polymerization kinetic behaviors to account for diffusional limitations on termination. In addition, a positive effect of the applied potential on the apparent polymerization rate was observed, and an exponential regression equation correlating the reduction rate coefficient and the applied potential was obtained. Attractively, simulation results indicated the viscosity effect on the mass transfer using the model based on free volume theory enhanced the controllability and livingness of the system.