Comproportionation versus Disproportionation in the Initiation Step of Cu(0)-Mediated Living Radical Polymerization

被引：51

作者：

Harrisson, Simon ^{[1
]}

Couvreur, Patrick ^{[1
]}

Nicolas, Julien ^{[1
]}

机构：

[1] Univ Paris Sud, Inst Galien Paris Sud, UMR 8612, CNRS,Fac Pharm, F-92296 Chatenay Malabry, France

来源：

MACROMOLECULES | 2012年 / 45卷 / 18期

基金：

欧洲研究理事会;

关键词：

SET-LRP; METHYL ACRYLATE; MULTIBLOCK COPOLYMERS; METHACRYLATE; KINETICS; LIGAND; ACTIVATION; RELEVANT; CATALYST; SOLVENT;

D O I：

10.1021/ma301034t

中图分类号：

O63 [高分子化学（高聚物）];

学科分类号：

070305 ; 080501 ; 081704 ;

摘要：

We present a study of the initiation step in copper(0)-mediated atom transfer radical polymerization (also known as SET-LRP or SARA ATRP), in which a nitroxide free radical, N-tert-butyl-N[1-diethylphosphono-(2,2-dimethylpropyl)] nitroxide (SG1), is used to trap radicals derived from ethyl 2-bromoisobutyrate (EBiB), copper metal and pentamethyl diethylene triamine (PMDETA) ligand. A kinetic model was developed relating the rate of conversion of EBiB to the rate constants of activation by copper metal (k(20) and comproportionation of Cu-0 and Cu-II (k(comp)). This allowed the determination of these parameters in several solvents, including dimethyl sulfoxide (DMSO), imethylformamide (DMF), ethanol (EtOH), and acetonitrile (MeCN), in which significant levels of comproportionation were observed, leading to autoacceleration of the reaction. A similar treatment of copper-mediated polymerization kinetics predicts 1/2 order dependence on initiator concentration and copper surface area, in accordance with previously published experimental data.

引用

页码：7388 / 7396

页数：9

共 47 条

[1] Atom Transfer Radical Polymerization: A Robust and Versatile Route for Polymer Synthesis [J].