Chemically Triggered C-ON Bond Homolysis in Alkoxyamines. Part 2: DFT Investigation and Application of the pH Effect on NMP

被引：32

作者：

Bagryanskaya, Elena ^{[2
]}

Bremond, Paul ^{[1
]}

Edeleva, Mariya ^{[2
]}

Marque, Sylvain R. A. ^{[1
]}

Parkhomenko, Dmitriy ^{[2
]}

Roubaud, Valerie ^{[1
]}

Siri, Didier ^{[1
]}

机构：

[1] Aix Marseille Univ, F-13397 Marseille 20, France

[2] Int Tomog Ctr, Novosibirsk 630090, Russia

来源：

MACROMOLECULAR RAPID COMMUNICATIONS | 2012年 / 33卷 / 02期

关键词：

CuON bond homolysis; kinetics; nitroxide-mediated polymerization; pH effect polymerization; NITROXIDE-MEDIATED POLYMERIZATION; LIVING RADICAL POLYMERIZATIONS; MULTIPARAMETER ANALYSIS; SG1-BASED ALKOXYAMINES; BLOCK-COPOLYMERS; PYRIDINES; POLAR;

D O I：

10.1002/marc.201100590

中图分类号：

O63 [高分子化学（高聚物）];

学科分类号：

070305 ; 080501 ; 081704 ;

摘要：

In recent work, a 15-fold increase in the CON bond homolysis rate constant kd of 4-pyridylethyl-SG1-based alkoxyamine was observed upon protonation of the pyridyl moiety in organic solvent. In this report, the pH dependence of kd (pKa = 4.7) is investigated in D2O/CD3OD (v/v 1:1). A 64-fold increase in kd is observed at acidic pH. Calculations show that the increase in kd upon protonation is due to both an increase in the stabilization of the protonated 4-pyridylethyl radical and an increase of the destabilization of the starting materials through an increase in the polarity of the alkyl fragment. This new alkoxyamine is applied to NMP of styrene and sodium styrene sulfonate.

引用

页码：152 / 157

页数：6

共 29 条

[1] Long-range polar and steric effects in propionate-SG1-type alkoxyamines (SG1-CHMeCOOX): a multiparameter analysis [J].