MALDI-TOF/TOF CID study of poly(1,4-dihydroxybenzene terephthalate) fragmentation reactions

MALDI-TOF/TOF collision-induced dissociation (CID) experiments were conducted on model aromatic polyester oligomers. CID fragmentation studies identified initial fracture of the ester bond and subsequent CO loss as a major pathway, consistent with the general fragmentation mechanism used to explain...

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Veröffentlicht in:Polymer (Guilford) 2015-05, Vol.64, p.100-111
Hauptverfasser: Gies, Anthony P., Stow, Sarah M., McLean, John A., Hercules, David M.
Format: Artikel
Sprache:eng
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Zusammenfassung:MALDI-TOF/TOF collision-induced dissociation (CID) experiments were conducted on model aromatic polyester oligomers. CID fragmentation studies identified initial fracture of the ester bond and subsequent CO loss as a major pathway, consistent with the general fragmentation mechanism used to explain the origin of poly(p-phenylenediamine terephthalamide) (PPD-T) fragment ions. Specifically, both charge-remote and charge-site fragmentation were observed. Different parent-ion species were observed, the major ones being carboxyl-hydroxyl, di-carboxyl, di-hydroxyl, and phenyl-carboxyl terminated. One species observed was hydroxyl-diethylamine terminated caused by reaction of carboxyl groups with triethylamine added to the synthesis reaction mixture. Fragment ions reflected the end groups of the parent oligomers. Some MALDI fragment-ion spectra were obtained for species showing exchange between Li and H at the carboxyl end group. Bond energy calculations provide further insight into suggested fragmentation mechanisms. [Display omitted] •First MALDI collision-induced dissociation study of wholly aromatic polyesters.•Effect of polymer end groups and bond energies on collision-induced mass spectra.•Effect of end groups on polymer fragmentation mechanisms.•Fragmentation mechanisms compared to those for aliphatic polyesters and aramids.•Both charge-site and charge-remote fragmentation reactions observed.
ISSN:0032-3861
1873-2291
DOI:10.1016/j.polymer.2015.03.021