Effects of Chain Transfer Agent and Temperature on Branching and β-Scission in Radical Polymerization of 2-Ethylhexyl Acrylate

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dc.contributor.authorLena JB
dc.contributor.authorDeschamps M
dc.contributor.authorSciortino NF
dc.contributor.authorMasters SL
dc.contributor.authorSquire MA
dc.contributor.authorRussell GT
dc.date.accessioned2018-08-06T23:59:27Z
dc.date.available2018-08-06T23:59:27Z
dc.date.issued2018en
dc.date.updated2018-05-18T06:40:57Z
dc.description.abstract© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Poly(2-ethylhexyl acrylate) is synthesized by conventional radical bulk polymerization both with and without 1-dodecane thiol as chain transfer agent (CTA) at temperatures from 4 to 140 °C. Electrospray-ionization mass spectrometry is used to analyze the polymer. This reveals the occurrence of significant β-scission at high temperature and confirms the presence of CTA-capped polymers at all temperatures, as well as combination products from 4 to 65 °C. Subsequent 13 C melt-state NMR analysis allows quantification of branching and β-scission. Both are reduced when CTA is present, consistent with a "patching" effect. As expected, the amounts of β-scission and branching increase with synthesis temperature, although β-scission dominates at the highest temperature. The backbiting rate coefficient of 2-ethylhexyl acrylate is determined from NMR results, taking β-scission into account for the first time. Remarkable agreement with literature k bb values is obtained, especially for activation energy. This strongly suggests family-type behavior for acrylate k bb .en
dc.identifier.doihttps://doi.org/10.1002/macp.201700579
dc.identifier.issn1022-1352
dc.identifier.issn1521-3935
dc.identifier.urihttp://hdl.handle.net/10092/15728
dc.language.isoen
dc.subjectPoly(2-ethylhexyl acrylate)en
dc.subjectelectrospray ionization (ESI)-mass spectrometryen
dc.subjectNMRen
dc.subjectβ-scissionen
dc.subjectbranchingen
dc.subject.anzsrcField of Research::03 - Chemical Sciences::0303 - Macromolecular and Materials Chemistryen
dc.titleEffects of Chain Transfer Agent and Temperature on Branching and β-Scission in Radical Polymerization of 2-Ethylhexyl Acrylateen
dc.typeJournal Articleen
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