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Reactivity Study of Elementary Steps in the Polymerization Mechanism of Acrylfuranic Compounds by Frontier Molecular Orbital Theory
Author(s) -
Lange J.,
Lozano A. E.,
GarcíaYoldi I.
Publication year - 2011
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.201100058
Subject(s) - reactivity (psychology) , crystallography , intermolecular force , polymerization , molecular orbital , chemistry , physics , nuclear magnetic resonance , molecule , polymer , organic chemistry , medicine , alternative medicine , pathology
A reactivity study of the most important elementary steps (propagation, intermolecular degradative transfer, and re‐initiation) in free‐radical polymerization of acrylfuranic systems, furfuryl acrylate (FA), and furfuryl methacrylate (FM), using the frontier molecular orbital theory is described. A qualitative explanation of reactivity trends of these steps for both systems is given based on absolute values of the SOMO/HOMO gap. The small difference between values of k p for FA and FM compared to that found for MA and MMA ( ${{k_{{\rm p}}^{{\rm (FA)}} } \mathord{\left/ {\vphantom {{k_{{\rm p}}^{{\rm (FA)}} } {k_{{\rm p}}^{{\rm (FM)}} }}} \right. \kern-\nulldelimiterspace} {k_{{\rm p}}^{{\rm (FM)}} }}< {{k_{{\rm p}}^{{\rm (MA)}} } \mathord{\left/ {\vphantom {{k_{{\rm p}}^{{\rm (MA)}} } {k_{{\rm p}}^{{\rm (MMA)}} }}} \right. \kern-\nulldelimiterspace} {k_{{\rm p}}^{{\rm (MMA)}} }}$ ) is justified semi‐quantitatively by applying a formulation for the change of energy in the transition state using second‐order perturbation theory.