ATRP poly(acrylate) star formation: A comparative study between MALDI and ESI mass spectrometry

Hart-Smith, G., Lammens, M., Du Prez, F. E., Guilhaus, M., & Barner-Kowollik, C. (2009) ATRP poly(acrylate) star formation: A comparative study between MALDI and ESI mass spectrometry. Polymer, 50(9).

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Optimised matrix-assisted laser desorption/ionisation (MALDI) and electrospray ionisation (ESI) mass spectrometry (MS) methodologies were systematically compared in terms of their relative abilities to identify distinct chemical species present in samples associated with a polymer mechanistic study. In order to perform the investigation, formation processes involved in atom transfer radical polymerisation (ATRP) mediated methyl acrylate (MA) star polymerisations were studied. In addition to the 4-armed ATRP initiator employed in the polymerisations, initiator side-products were found to generate oligomeric chains. At a relatively high monomer to polymer conversion, terminal Br loss was observed in these oligomers; this Br loss was hypothesised to occur via degradative transfer reactions involving the radicals (CH3)2ĊOH, ĊH3 and ĊH2COCH3, which were derived from the acetone used as a solvent in the polymerisations, as well as hydrogen radicals donated by the ligand N,N′,N′,N″,N″-pentamethyldiethylenetriamine (PMDETA). In performing these studies, ESI was found to identify a greater number of distinct chemical species in the samples under investigation when compared to the employed MALDI technique, suggesting that the utilisation of ESI must be strongly considered in polymer mechanistic investigations if the maximum number of end-group functionalities within a given polymer sample are to be identified. © 2009 Elsevier Ltd. All rights reserved.

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ID Code: 99215
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :20
Export Date: 5 September 2016
Correspondence Address: Du Prez, F.E.; Ghent University, Department of Organic Chemistry, Polymer Chemistry Research Group (PCR), Krijgslaan 281, S4-bis, B-9000 Ghent, Belgium; email:
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Keywords: Atom transfer radical polymerisation (ATRP), Mass spectrometry, Star polymers, ATRP initiators, Chemical species, Comparative studies, Electrospray, End-group functionalities, Formation process, Hydrogen radicals, Ionisation, Maldi and esi mass spectrometries, Matrix-assisted lasers, Mechanistic studies, Methyl acrylates, Polies (acrylate), Polymer samples, Star formations, Transfer reactions, Acetone, Acrylic monomers, Atom transfer radical polymerization, Atoms, Electrospray ionization, Free radical polymerization, Free radical reactions, High performance liquid chromatography, Hydrogen, Mass spectrometers, Oligomers, Polymerization, Polymers, Spectrum analysis, Functional polymers, degradation, oligomer, polyacrylate, polymer, solvent, spectrophotometry
DOI: 10.1016/j.polymer.2009.03.009
ISSN: 00323861
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 22 Sep 2016 04:50
Last Modified: 10 Oct 2016 00:06

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