posted on 2016-05-27, 14:53authored byJun-Kang Guo, Yin-Ning Zhou, Zheng-Hong Luo
An iron- and methyl
methacrylate (MMA)-based electrochemically
mediated atom transfer radical polymerization (eATRP) system was developed
for the first time. Kinetic behaviors, including the effect of applied
potential and catalyst loading, were systematically investigated.
Results indicated that with more negative electrode potential, the
polymerization rate increased until the mass transport limitation
was reached. However, reduction of the catalyst loading had adverse
effects on polymerization behaviors, such as decreased polymerization
rate and increased molecular weight distributions (Mw/Mn). In addition, a kinetic
model based on the method of moments was also constructed to explain
the mismatch in Mn and Mn,theo. Simulation results showed that slow initiation
significantly influenced on the kinetic behaviors in this system.
Iron(II) bromide-catalyzed normal ATRP, iron(III) bromide-catalyzed
eATRP, and copper(II) bromide-catalyzed eATRP were conducted to compare
and elucidate their respective polymerization reaction kinetic characteristics
qualitatively. This work expanded the scope of eATRP from a copper-based
system to an iron-based system in terms of polymerization kinetics,
with the hope of promoting the widespread application of this method.