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A Density Functional Theory Study of Secondary Reactions in n ‐Butyl Acrylate Free Radical Polymerization
Author(s) -
Cuccato Danilo,
Mavroudakis Evangelos,
Dossi Marco,
Moscatelli Davide
Publication year - 2013
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.201200079
Subject(s) - branching (polymer chemistry) , radical , chemistry , acrylate , polymer chemistry , radical polymerization , polymerization , monomer , kinetics , butyl acrylate , polymer , photochemistry , organic chemistry , physics , quantum mechanics
In this work, secondary reactions involved in the free radical polymerization of butyl acrylate are investigated using quantum chemistry. First, various backbiting reactions are studied by adopting a simplified molecular model suitable for treating long polymer chains. The predicted reaction kinetics suggest the possibility of a radical migration along the poly(butyl acrylate) (PBA) chain as a consequence of subsequent j : j + 4 hydrogen abstractions, which are characterized by a low activation energy. Moreover, branching propagation and β‐scission reactions originating from mid‐chain radicals are investigated using a complete PBA model composed of five monomer units. The reaction kinetics involving short‐branch radicals are also examined, and a novel backbiting step leading to the formation of short branches is proposed.