Copper-based ATRP catalysts of very high activity derived from dimethyl cross-bridged cyclam

被引：58
作者：
Tsarevsky, Nicolay V.
Braunecker, Wade A.
Tang, Wei
Brooks, Samuel J.
Matyjaszewski, Krzysztof
Weisman, Gary R.
Wong, Edward H.
机构：
[1] Carnegie Mellon Univ, Dept Chem, Pittsburgh, PA 15213 USA
[2] Univ New Hampshire, Dept Chem, Durham, NH 03824 USA
来源：
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL | 2006年 / 257卷 / 1-2期
基金：
美国国家科学基金会; 美国安德鲁·梅隆基金会;
关键词：
ATRP; bridged cyclam; catalysis; controlled radical polymerization;
D O I：
10.1016/j.molcata.2006.05.031
中图分类号：
O64 [物理化学（理论化学）、化学物理学];
学科分类号：
070304 ; 081704 ;
摘要：
Dimethyl cross-bridged cyclam (DMCBCy) forms a very reducing Cu-I complex that possesses the highest known catalytic activity to date in atom transfer radical polymerization (ATRP) reactions. The value of the ATRP equilibrium constant in a reaction with methyl chloroacetate for (CuCl)-Cl-I/DMCBCy is 30-fold larger than for the very active catalyst (CuCl)-Cl-I/Me6TREN. The activation rate constant for the DMCBCy-based complex was also determined and is about 1.5 times larger than for (CuCl)-Cl-1/Me6TREN. The ATRP of n-butyl acrylate mediated by (CuBr)-Br-I/DMCBCy was fast even at 30 degrees C and yielded well-defined polymers when a sufficient amount (about 10 mol% of the total catalyst) of deactivator ((CuBr2)-Br-II/DMCBCy) was added to the reaction mixture. Side reactions such as electron transfer from the very reducing (CuBr)-Br-I/DMCBCy to the electrophilic acrylate radicals most likely account for the observed limited conversions. (c) 2006 Elsevier B.V. All rights reserved.
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页码：132 / 140
页数：9
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