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Mechanism of Dithiobenzoate‐Mediated RAFT Polymerization: A Missing Reaction Step
Author(s) -
Buback Michael,
Vana Philipp
Publication year - 2006
Publication title -
macromolecular rapid communications
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 154
eISSN - 1521-3927
pISSN - 1022-1336
DOI - 10.1002/marc.200600317
Subject(s) - reversible addition−fragmentation chain transfer polymerization , raft , polymerization , radical polymerization , chain transfer , chemistry , polymer chemistry , living free radical polymerization , living polymerization , photochemistry , polymer , organic chemistry
Summary: The debate on the mechanism of dithiobenzoate‐mediated RAFT polymerization may be resolved by including the reaction between a propagating radical and the star‐shaped combination product from irreversible termination into the kinetic scheme. By this step, a highly reactive propagating radical and a not overly stable three‐arm star species are transformed into the resonance‐stabilized RAFT intermediate radical and a very stable polymer molecule. The time evolution of concentrations is discussed for the main‐equilibrium range of CDB‐mediated methyl acrylate polymerization.Illustration of the novel understanding of the RAFT mechanism in dithiobenzoate‐mediated RAFT polymerization.