期刊
ACS MACRO LETTERS
卷 8, 期 10, 页码 1316-1322出版社
AMER CHEMICAL SOC
DOI: 10.1021/acsmacrolett.9b00598
关键词
-
资金
- CSIRO Research Office
Electrochemical activation of thiocarbonylthio reversible addition fragmentation chain transfer (RAFT) agents (S=C(Z)S-R) is explored as a potential method for initiating RAFT polymerization under mild conditions without producing initiator-derived byproducts. Herein we apply cyclic voltammetry to establish a predominant reduction mechanism, where electrochemical reduction is coupled to an irreversible first-order chemical reaction. Structure-dependent trends in cyclic voltammograms (CVs), and comparison to absorption spectra, clarify the role of R- and Z-groups in determining reduction processes. The major reduction peak moves to more cathodic potentials in the series dithiobenzoates > trithiocarbonates > heteroaromatic dithiocarbamates > xanthates similar to N-alkyl-N-aryldithiocarbamates, due to the Z-group influence on thiocarbonyl bond reactivity. More active (electron-withdrawing, radical stabilizing) R-groups shift the reduction peak anodically, in part due to their influence on the rate of the coupled chemical reaction. Analysis of CVs across a range of scan rates revealed that kinetic control over the reduction mechanism is influenced by both the charge transfer rate and chemical reaction rate.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据