Enhanced Activity of ATRP Fe Catalysts with Phosphines Containing Electron Donating Groups

被引：63

作者：

Wang, Yu ^{[1
]}

Kwak, Yungwan ^{[1
]}

Matyjaszewski, Krzysztof ^{[1
]}

机构：

[1] Carnegie Mellon Univ, Dept Chem, Ctr Macromol Engn, Pittsburgh, PA 15213 USA

来源：

MACROMOLECULES | 2012年 / 45卷 / 15期

基金：

美国安德鲁·梅隆基金会; 美国国家科学基金会;

关键词：

TRANSFER RADICAL POLYMERIZATION; METHYL-METHACRYLATE; ARGET ATRP; PHOSPHORUS LIGANDS; REDUCING AGENTS; IRON COMPLEXES; STYRENE; ACTIVATORS; POLYMERS; ACID;

D O I：

10.1021/ma3010795

中图分类号：

O63 [高分子化学（高聚物）];

学科分类号：

070305 ; 080501 ; 081704 ;

摘要：

Fe-based atom transfer radical polymerization (ATRP) of styrene (St) with various triarylphosphines containing electron donating methoxy groups was investigated. (FeBr3)-Br-III in the presence of tris(2,4,6- trimethoxyphenyl)phosphine (TTMPP) provided faster ATRP of St than in the presence of tris(4-methoxyphenyl)phosphine (TMPP) and much faster than with triphenylphosphine (TPP) under identical conditions. ATRP of St was carried out with initial ratio of reagents: [St]:[EBiB]:[(FeBr3)-Br-III]:[TTMPP] = 200:1:1:2, in 50% (v/v) anisole at 100 degrees C (EBiB is ethyl 2-bromoisobutyrate). After 21 h, conversion reached 92%, yielding polystyrene with molecular weight M-n = 24 100 and M-w/M-n = 1.25. With TMPP and TPP under the same conditions, the conversion of monomer was only 19% and 9%, respectively. With 1 equiv of TTMPP vs (FeBr3)-Br-III, control was better, M-w/M-n similar to 1.1, but polymerization was slower. The phosphines could directly reduce Fe to Feu but could also act as ligands complexing transition metal and forming efficient ATRP catalysts.

引用

页码：5911 / 5915

页数：5

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