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Kinetic Modeling of Nitroxide‐Mediated Polymerization: Conditions for Living and Controlled Polymerization
Author(s) -
Gigmes Didier,
Bertin Denis,
Lefay Catherine,
Guillaneuf Yohann
Publication year - 2009
Publication title -
macromolecular theory and simulations
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.37
H-Index - 56
eISSN - 1521-3919
pISSN - 1022-1344
DOI - 10.1002/mats.200900019
Subject(s) - nitroxide mediated radical polymerization , polymerization , disproportionation , kinetic energy , chemistry , dissociation (chemistry) , dispersity , radical polymerization , polymer chemistry , living free radical polymerization , organic chemistry , physics , polymer , catalysis , classical mechanics
Simulations of conversion versus time, molecular weight ( $\overline M _{\rm n}$ ), polydispersity index (PDI), and living fractions versus conversion plots are performed using the PREDICI software, to study the influence of several kinetic parameters on the living and controlled character of nitroxide‐mediated polymerization (NMP). In particular, the crucial role of the main equilibrium represented by both k d and k c (the rate coefficients respectively of dissociation and recombination) is highlighted. On the other hand, the importance of the initiation step, the targeted $\overline M _{\rm n}$ value, and the initial excess of free nitroxide are also demonstrated. It is further proved that side reactions, such as disproportionation and transfer to solvent, have a strong impact on the polymerization characteristics.