A Density Functional Theory Study of Secondary Reactions in n‐Butyl Acrylate Free Radical Polymerization. Issue 2 (24th January 2013)

• Record Type: Journal Article
• Authors: Cuccato, Danilo; Mavroudakis, Evangelos; Dossi, Marco; Moscatelli, Davide
• Is Part Of: Macromolecular theory and simulations. Volume 22:Issue 2(2013)
• Page Start: 127
• Page End: 135
• Publication Date: 2013-01-24
• Subjects: Macromolecules -- Periodicals; Polymers -- Periodicals; Polymerization -- Periodicals; Macromolécules -- Périodiques; 547.705
• DOI: 10.1002/mats.201200079
• Languages: English
• ISSNs: 1022-1344

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>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 <italic>j</italic>:<italic>j</italic> + 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. <boxed-text content-type="graphic" position="anchor" orientation="portrait"><graphic position="anchor" mimetype="image" xlink:href="ark:/27927/pgg1ttrzn80" orientation="portrait" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /></boxed-text></p> </abstract>