Environmental Polymer Degradation: Using the Distonic Radical Ion Approach to Study the Gas-Phase Reactions of Model Polyester Radicals

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.