The effect of remote substituents in free radical addition reactions: new evidence for the penultimate unit effect

被引：26

作者：

Coote, ML

Davis, TP

Radom, L ^{[1
]}

机构：

[1] Australian Natl Univ, Res Sch Chem, Canberra, ACT 0200, Australia

[2] Univ New S Wales, Sch Chem Engn & Ind Chem, Sydney, NSW 2052, Australia

来源：

JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM | 1999年 / 461卷

基金：

澳大利亚研究理事会;

关键词：

gamma substituent effect; penultimate unit effect; free radical; addition; polymerization;

D O I：

10.1016/S0166-1280(98)00427-8

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：

Ab initio molecular orbital calculations of the barrier for the addition of gamma-substituted propyl radicals to various alkenes indicate that substituents at the gamma position of a radical can significantly affect the barrier. This finding supports recent experimental evidence for an enthalpic penultimate unit effect in free-radical copolymerization. For the reactions studied in the present work, this penultimate unit effect is consistent with a significant polar contribution. (C) 1999 Elsevier Science B.V. All rights reserved.

引用

页码：91 / 96

页数：6

共 23 条

[1] copolymerization propagation kinetics of styrene and methyl methacrylate - Revisited. 1. Pulsed laser polymerization study [J].