SET-LRP of methyl acrylate to complete conversion with zero termination

被引：124

作者：

Nguyen, Nga H. ^{[1
]}

Levere, Martin E. ^{[1
]}

Percec, Virgil ^{[1
]}

机构：

[1] Univ Penn, Dept Chem, Roy & Diana Vagelos Labs, Philadelphia, PA 19104 USA

来源：

JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY | 2012年 / 50卷 / 05期

基金：

美国国家科学基金会;

关键词：

chain-end analysis; kinetics (polym; MALDI; single electron transfer-living radical polymerization (SET-LRP); termination; LIVING RADICAL POLYMERIZATION; CHAIN-END FUNCTIONALITY; DENDRITIC MACROMOLECULES; MULTIBLOCK COPOLYMERS; CONVENTIONAL MONOMERS; DIVERGENT SYNTHESIS; ITERATIVE STRATEGY; MOLECULAR-WEIGHT; DMSO; COMBINATION;

D O I：

10.1002/pola.25838

中图分类号：

O63 [高分子化学（高聚物）];

学科分类号：

070305 ; 080501 ; 081704 ;

摘要：

The single electron transfer-living radical polymerization of methyl acrylate (MA) initiated by bis(2-bromopropionyl)ethane (BPE) in dimethyl sulfoxide was carried out to 100% monomer conversion and complete absence of bimolecular termination under the following reaction conditions: [MA]/[BPE]/[Me6-TREN]/[CuBr2] = 60/1/0.21/0.01 and [MA]/[BPE]/[TREN]/[CuBr2] = 60/1/0.25/0.05. These polymerizations were mediated by 0.5 cm of hydrazine-activated Cu(0) wire of 20 gauge (0.812 cm in diameter), corresponding to a surface area of 0.14 cm2 of Cu(0) per 3 mL reaction volume (2/1 v/v monomer/solvent). A higher extent of bimolecular termination (513%) was observed at complete conversion when longer lengths of Cu(0) wire were used. In the absence of CuBr2 the activated Cu(0) wire/Me6-TREN catalyst in dimethyl sulfoxide also allowed the synthesis of perfectly bifunctional and monofunctional PMAs at complete conversion. This was also demonstrated by the quantitative reinitiation experiments from the chain(s) end(s) of these macroinitiators. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

引用

页码：860 / 873

页数：14

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