Copper-Mediated Controlled/"Living" Radical Polymerization in Polar Solvents: Insights into Some Relevant Mechanistic Aspects

被引：66

作者：

Guliashvili, Tamaz ^{[1
]}

Mendonca, Patricia V. ^{[2
]}

Serra, Armenio C. ^{[3
]}

Popov, Anatoliy V. ^{[4
]}

Coelho, Jorge F. J. ^{[2
]}

机构：

[1] GE Power & Water, Water & Proc Technol, Trevose, PA 19053 USA

[2] Univ Coimbra, Dept Chem Engn, P-3030290 Coimbra, Portugal

[3] Univ Coimbra, Dept Chem, P-3004535 Coimbra, Portugal

[4] Univ Penn, Dept Radiol, Philadelphia, PA 19104 USA

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2012年 / 18卷 / 15期

关键词：

copper; heterogeneous catalysis; polymerization; radical reactions; transition metals; CYCLIZATION ATRC REACTIONS; SET-LRP; ELECTRON-TRANSFER; METHYL ACRYLATE; ULTRAFAST SYNTHESIS; REDUCING AGENTS; ACTIVATION STEP; ADDITION ATRA; COMPLEXES; CATALYST;

D O I：

10.1002/chem.201102183

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The field of transition-metal-mediated controlled/living radical polymerization (CLRP) has become the subject of intense discussion regarding the mechanism of this widely-used and versatile process. Most mechanistic analyses (atom transfer radical polymerization (ATRP) vs. single-electron transfer living radical polymerization (SET-LRP)) have been based on model experiments, which cannot correctly mimic the true reaction conditions. We present, for the first time, a determination of the [CuIBr]/[L] (L=nitrogen-based chelating ligand) ratio and the extent of CuIBr/L disproportionation during CLRP of methyl acrylate (MA) in dimethylsulfoxide (DMSO) with Cu0 wire as a transition-metal catalyst source. The results suggest that Cu0 acts as a supplemental activator and reducing agent of CuIIBr2/L to CuIBr/L. More importantly, the CuIBr/L species seem to be responsible for the activation of SET-LRP.

引用

页码：4607 / 4612

页数：6

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