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Mid-Chain Radical Migration in the Radical Polymerization of n-Butyl Acrylate
dc.contributor.author | Ballard, Nicholas | |
dc.contributor.author | Veloso Fernández, Antonio | |
dc.contributor.author | Asua González, José María | |
dc.date.accessioned | 2018-11-21T09:18:25Z | |
dc.date.available | 2018-11-21T09:18:25Z | |
dc.date.issued | 2018-07 | |
dc.identifier.citation | Polymers 10(7) : (2018) // Article ID 765 | es_ES |
dc.identifier.issn | 2073-4360 | |
dc.identifier.uri | http://hdl.handle.net/10810/29730 | |
dc.description.abstract | The occurrence of intramolecular transfer to polymer in the radical polymerization of acrylic monomers has been extensively documented in the literature. Whilst it has been largely assumed that intramolecular transfer to polymer leads to short chain branches, there has been some speculation over whether the mid-chain radical can migrate. Herein, by the matrix-assisted laser desorption/ionization time of flight (MALDI-TOF) mass spectrometry (MS) of poly(n-butyl acrylate) synthesized by solution polymerization under a range of conditions, it is shown that this mid-chain radical migration does occur in the radical polymerization of acrylates conducted at high temperatures, as is evident from the shape of the molecular weight distribution. Using a mathematical model, an initial approximation of the rate at which migration occurs is made and the distribution of branching lengths formed in this scenario is explored. It is shown that the polymerizations carried out under a low monomer concentration and at high temperatures are particularly prone to radical migration reactions, which may affect the rheological properties of the polymer. | es_ES |
dc.description.sponsorship | Diputacion Foral de Gipuzkoa, University of Basque Country UPV/EHU (UFI 11/56), Basque Government (GV IT-999-16) are gratefully acknowledged for their financial support. N.B. acknowledges the financial support obtained through the Post-Doctoral fellowship Juan de la Cierva-Incorporacion (IJCI-2016-28442) from the Ministry of Economy and Competitiveness of Spain. | es_ES |
dc.language.iso | eng | es_ES |
dc.publisher | MDPI | es_ES |
dc.relation | info:eu-repo/grantAgreement/MINECO/IJCI-2016-28442 | es_ES |
dc.rights | info:eu-repo/semantics/openAccess | es_ES |
dc.rights.uri | http://creativecommons.org/licenses/by/3.0/es/ | * |
dc.subject | acrylates | es_ES |
dc.subject | radical polymerization | es_ES |
dc.subject | mid-chain radical | es_ES |
dc.subject | intramolecular chain transfer | es_ES |
dc.subject | high-temperature | es_ES |
dc.subject | emulsion polymerization | es_ES |
dc.subject | product distributions | es_ES |
dc.subject | poly(butyl acrylate) | es_ES |
dc.subject | raft polymerization | es_ES |
dc.subject | secondary reactions | es_ES |
dc.subject | mass-spectrometry | es_ES |
dc.subject | rate coefficients | es_ES |
dc.subject | nmr-spectroscopy | es_ES |
dc.title | Mid-Chain Radical Migration in the Radical Polymerization of n-Butyl Acrylate | es_ES |
dc.type | info:eu-repo/semantics/article | es_ES |
dc.rights.holder | © 2018 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/). | es_ES |
dc.rights.holder | Atribución 3.0 España | * |
dc.relation.publisherversion | https://www.mdpi.com/2073-4360/10/7/765 | es_ES |
dc.identifier.doi | 10.3390/polym10070765 | |
dc.departamentoes | Química aplicada | es_ES |
dc.departamentoes | Química física | es_ES |
dc.departamentoeu | Kimika aplikatua | es_ES |
dc.departamentoeu | Kimika fisikoa | es_ES |
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