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Nitroxide‐Mediated Polymerization of Methyl Methacrylate Using an SG1‐Based Alkoxyamine: How the Penultimate Effect Could Lead to Uncontrolled and Unliving Polymerization
Author(s) -
Guillaneuf Yohann,
Gigmes Didier,
Marque Sylvain R. A.,
Tordo Paul,
Bertin Denis
Publication year - 2006
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.200600125
Subject(s) - nitroxide mediated radical polymerization , polymerization , methyl methacrylate , chemistry , dissociation (chemistry) , radical polymerization , polymer chemistry , photochemistry , organic chemistry , polymer
Abstract Summary: The nitroxide‐mediated polymerization (NMP) of MMA initiated with a new crowded SG1‐based alkoxyamine was performed. Contrary to the results expected after a kinetic analysis (Fischer's diagram), the polymerization of MMA at 45 °C with SG1 showed only partial control and livingness during the first 15% of conversion. Simulations using PREDICI highlighted that the kinetic rate constants currently in use had not been correctly estimated and that a strong penultimate effect drastically increased the equilibrium constant K (7 × 10 −7 ), preventing a well‐controlled polymerization. Experimental determination of the k c value (1.4 × 10 4 L · mol −1 · s −1 ) confirmed a strong penultimate effect on the recombination reaction, whereas for the dissociation reaction this effect is lower ( k d = 10 −2 · s −1 ).Nitroxide‐mediated polymerization of MMA at 45 °C initiated with a new crowded SG1‐based alkoxyamine.