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Please use this identifier to cite or link to this item: http://hdl.handle.net/1942/24097

Title: Kinetic Monte Carlo Generation of Complete Electron Spray Ionization Mass Spectra for Acrylate Macromonomer Synthesis
Authors: Van Steenberge, Paul H. M.
Vandenbergh, Joke
Reyniers, Marie-Françoise
Junkers, Tanja
D'hooge, Dagmar R.
Marin, Guy B.
Issue Date: 2017
Citation: MACROMOLECULES, 50(7), p. 2625-2636
Abstract: Absolute electron spray ionization mass spectrometry (ESI-MS) data are reported, for the first time, over the complete chain length range for the synthesis of welldefined macromonomers (MMs) obtained via activation of bromine-capped poly(n-butyl acrylate) (0.1 mass %; solvent: anisole; 140 degrees C) with CuBr2/Me6TREN (Me6TREN: tris(2-(dimethylamino)ethyl)amine) and tin ethylhexanoate. These data are generated based on bivariate kinetic Monte Carlo simulations, tracking the chain lengths and the positions of radicals/characteristic groups along the chains (>100 reactions, 12 radical/dormant species types, and 7 characteristic end/ mid-groups). Based on qualitative tuning to experimental data, migration is found to be 50 times slower than backbiting but 15 times faster than beta C-scission, making it a dominant reaction. Benefiting from the absence of monomer, the chain transfer to polymer rate coefficient is assessed as 6 x 10(2) L mol(-1) s(-1) (140 degrees C). Model analysis shows that consecutive backbiting/migration/beta C-scission leads to a favoring of MMs with even chain lengths and a hydrogen chain end over MMs with the nonreactive chain end originating from the initial dormant polymer. The obtained insights contribute to a better fundamental understanding of hydrogen abstractions in acrylate radical polymerization and open the path for a more detailed polymer product characterization in general.
Notes: [Van Steenberge, Paul H. M.; Reyniers, Marie-Francoise; D'hooge, Dagmar R.; Marin, Guy B.] Univ Ghent, LCT, Technol Pk 914, B-9052 Ghent, Belgium. [Vandenbergh, Joke; Junkers, Thomas] Hasselt Univ, Inst Mat Res IMO, Polymer React Design Grp, Agoralaan Bldg D, B-3590 Diepenbeek, Belgium. [Junkers, Thomas] IMEC Associated Lab IMOMEC, Wetenschapspk 1, B-3590 Diepenbeek, Belgium. [D'hooge, Dagmar R.] Univ Ghent, Ctr Text Sci & Engn, Technol Pk 904, B-9052 Ghent, Belgium.
URI: http://hdl.handle.net/1942/24097
DOI: 10.1021/acs.macromol.7b00333
ISI #: 000399263900003
ISSN: 0024-9297
Category: A1
Type: Journal Contribution
Appears in Collections: Research publications

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