Effect of substituents on radical stability in reversible addition fragmentation chain transfer polymerization: an ab initio study

Date

2005

Authors

Coote, Michelle
Henry, David

Journal Title

Journal ISSN

Volume Title

Publisher

American Chemical Society

Abstract

The substituents effects on radical stability in the reversible addition fragmentation chain transfer (RAFT) polymerization process was investigated using high level ad initio molecular orbital calculations. The RAFT-adduct radicals were stabilized by electron donation from the two sulfur substituents. It was observed that the lone pair donor Z-substituents had smaller effect on radical stability. The results show that the substituent effects on the RAFT agents were qualitatively different and the agents were srongly stabilized by the lone pair donor Z-substituents.

Description

Keywords

Keywords: Dissociation; Electronic properties; Electrons; Enthalpy; Hydrogen bonds; Isomers; Molecular weight; Monomers; Reaction kinetics; Styrene; Substitution reactions; Thermodynamics; Radical stabilization energy (RSE); Reversible addition fragmentation chain

Citation

Source

Macromolecules

Type

Journal article

Book Title

Entity type

Access Statement

License Rights

DOI

10.1021/ma047814a

Restricted until

2037-12-31