A Missing Reaction Step in Dithiobenzoate‐Mediated RAFT Polymerization
- 1 February 2007
- journal article
- research article
- Published by Wiley in Macromolecular Symposia
- Vol. 248 (1) , 158-167
Abstract
The debate on the mechanism of dithiobenzoate‐mediated RAFT polymerization may be overcome by taking the so‐called “missing step” reaction between a highly reactive propagating radical and the three‐arm star‐shaped product of the combination reaction of an intermediate RAFT radical and a propagating radical into account. The “missing step” reaction transforms a propagating radical and a not overly stable three‐arm star species into a resonance‐stabilized RAFT intermediate radical and a stable polymer molecule. The enormous driving force behind the “missing step” reaction is estimated via DFT calculations of reaction enthalpies and reaction free enthalpies.Keywords
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