期刊
MACROMOLECULAR SYMPOSIA
卷 248, 期 -, 页码 158-167出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/masy.200750217
关键词
kinetics (polym.); living polymerization; quantum chemistry; reaction mechanism; reversible addition fragmentation chain transfer (RAFT)
资金
- Fonds der Chemischen Industrie
- Deutsche Forschungsgemeinschaft
The debate on the mechanism of clithiobenzoate-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.
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