Abstract
Nine polyisobutylene (PIB) derivatives with different end groups (chlorine, vinyl, isobutenyl, 2,2-diphenylvinyl, and carboxyl) and molecular weights (1000 to 4500 g/mol), initiated by monofunctional and aromatic bifunctional initiators were studied by atmospheric pressure photoionization mass spectrometry (APPI-MS) in both negative and positive ion modes. Consistent with previous findings, negative ion APPI-MS revealed end-group identities through the formation of PIB adducts with chloride ions formed in situ from a chlorinated solvent (e.g., CCl4) in the presence of a dopant (toluene). In positive ion mode, considerable fragmentation of these PIB derivatives was observed, rendering end-group determinations very difficult. The M n values obtained by APPI(−)-MS were considerably lower than those determined by SEC for PIB derivatives with M n higher than 2000 g/mol. PIBs containing carboxyl termini can undergo collision-induced dissociation, yielding structurally important product ions. The resulting APPI-MS/MS intensities were found to reflect the “arm-length” distribution for PIBs with bifunctional aromatic moieties. In positive ion mode, [M+COCl]+ adducts were observed for PIBs with an aromatic initiator moiety. The origin of the COCl+ species is also discussed.
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Published online September 12, 2009
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Nagy, L., Pálfi, V., Narmandakh, M. et al. Dopant-assisted atmospheric pressure photoionization mass spectrometry of polyisobutylene derivatives initiated by mono- and bifunctional initiators. J Am Soc Mass Spectrom 20, 2342–2351 (2009). https://doi.org/10.1016/j.jasms.2009.08.025
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DOI: https://doi.org/10.1016/j.jasms.2009.08.025