Environmental Polymer Degradation: Using the Distonic Radical Ion Approach to Study the Gas-Phase Reactions of Model Polyester Radicals
AuthorTaggert, BI; O'Hair, RAJ; Wille, U
Source TitleThe Journal of Physical Chemistry A: Isolated Molecules, Clusters, Radicals, and Ions; Environmental Chemistry, Geochemistry, and Astrochemistry; Theory
PublisherAMER CHEMICAL SOC
AffiliationSchool of Chemistry
Document TypeJournal Article
CitationsTaggert, B. I., O'Hair, R. A. J. & Wille, U. (2017). Environmental Polymer Degradation: Using the Distonic Radical Ion Approach to Study the Gas-Phase Reactions of Model Polyester Radicals. JOURNAL OF PHYSICAL CHEMISTRY A, 121 (28), pp.5290-5300. https://doi.org/10.1021/acs.jpca.7b04217.
Access StatusOpen Access
A novel precursor to the distonic O- and C-centered radical cations Oxo+O• and Oxo+C• was designed and synthesized, which represents model systems for radicals produced during polyester degradation. The precursor is equipped with a nitrate functional group, which serves as a masked site for these alkoxyl and carbon radicals that are unleashed through collision-induced dissociation (CID). Oxo+O• and Oxo+C• feature a cyclic carboxonium ion as permanent charge tag to enable monitoring their ion-molecule reactions on the millisecond to second time scale in the ion trap of the mass spectrometer. The reactions of Oxo+O• and Oxo+C• with cyclohexene, cyclohexadiene, ethyl acetate, 1,1-dimethoxyethane, and 1,2-dimethoxyethane, which exhibit structural features present in both intact and defective polyesters, were explored through product and kinetic studies to identify "hot spots" for radical-induced damage in polyesters. All reactions with Oxo+O• were extremely fast and proceeded predominantly through HAT. Oxo+C• was about two orders of magnitude less reactive and did not noticeably damage aliphatic ester moieties through hydrogen abstraction on the time scale of our experiments. Radical addition to alkene π systems was identified as an important pathway for C-radicals, which needs to be included in polymer degradation mechanisms.
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