Electrospray ionization mass spectrometric study of end-groups in peroxydicarbonate-initiated radical polymerization
2008 | journal article. A publication with affiliation to the University of Göttingen.
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Electrospray ionization mass spectrometric study of end-groups in peroxydicarbonate-initiated radical polymerization
Buback, M.; Frauendorf, H.; Janssen, O. & Vana, P. (2008)
Journal of Polymer Science Part A Polymer Chemistry, 46(18) pp. 6071-6081. DOI: https://doi.org/10.1002/pola.22919
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- Authors
- Buback, Michael; Frauendorf, Holm; Janssen, Olaf; Vana, Philipp
- Abstract
- Initiation by diethyl peroxydicarbonate (E-PDC), di-n-tetradecyl peroxydicarbonate (nTD-PDC), di-n-hexadecyl peroxydicarbonate (nHD-PDC), and di-2-ethylhexyl peroxydicarbonate (2EH-PDC) of free-radical polymerizations of methyl methacrylate in benzene solution was studied by end-group analysis via electrospray ionization mass spectrometry (ESI-MS). Unambiguous assignment of ESI-MS peaks allows for identification of the type of radical that starts chain growth. In case of initiation by dialkyl peroxydicarbonates with linear alkyl groups, almost exclusively alkoxy carbonyloxyl species, which are the primary fragments from initiator decomposition, occur as end-groups. With 2EH-PDC, however, both the primary 2-ethylhexoxy carbonyloxyl fragment and a second moiety, which is formed by decarboxylation of the 2-ethylhexoxy carbonyloxyl radical, are clearly observed as end-groups. The decarboxylation process is described by a concerted mechanism which involves a 1,5-hydrogen shift reaction. (C) 2008 Wiley Periodicals, Inc.
- Issue Date
- 2008
- Status
- published
- Publisher
- John Wiley & Sons Inc
- Journal
- Journal of Polymer Science Part A Polymer Chemistry
- ISSN
- 0887-624X
- Sponsor
- Deutsche Forschungsgemeinschaft [Bu 426/10-1]