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Please use this identifier to cite or link to this item: http://hdl.handle.net/1942/21554

Title: Kilohertz Pulsed-Laser-Polymerization: Simultaneous Determination of Backbiting, Secondary, and Tertiary Radical Propagation Rate Coefficients for tert-Butyl Acrylate
Authors: Wenn, Benjamin
Junkers, Thomas
Issue Date: 2016
Publisher: WILEY-V C H VERLAG GMBH
Citation: MACROMOLECULAR RAPID COMMUNICATIONS, 37 (9), p. 781-787
Abstract: For the first time, a 1000 Hz pulse laser has been applied to determine detailed kinetic rate coefficients from pulsed laser polymerization-size exclusion chromatography experiments. For the monomer tert-butyl acrylate, apparent propagation rate coefficients k(p)(app) have been determined in the temperature range of 0-80 degrees C. k(p)(app) in the range of few hundreds to close to 50 000 L.mol(-1).s(-1) are determined for low and high pulse frequencies, respectively. The apparent propagation coefficients show a distinct pulse-frequency dependency, which follows an S-shape curve. From these curves, rate coefficients for secondary radial propagation (k(p)(SPR)), backbiting (k(bb)), midchain radical propagation (k(p)(tert)), and the (residual) effective propagation rate (k(p)(app)) can be deduced via a herein proposed simple Predici fitting procedure. For k(p)(SPR), the activation energy is determined to be (17.9 +/- 0.6) kJ.mol(-1) in excellent agreement with literature data. For k(bb,) an activation energy of (25.9 +/- 2.2) kJ.mol(-1) is deduced.
Notes: [Wenn, Benjamin; Junkers, Thomas] Univ Hasselt, Inst Mat Res IMO, Polymer React Design Grp, Martelarenlaan 42, B-3500 Hasselt, Belgium. [Junkers, Thomas] IMEC Associated Lab IMOMEC, Wetenschapspk 1, B-3590 Diepenbeek, Belgium.
URI: http://hdl.handle.net/1942/21554
DOI: 10.1002/marc.201600011
ISI #: 000375683300007
ISSN: 1022-1336
Category: A1
Type: Journal Contribution
Validation: ecoom, 2017
Appears in Collections: Research publications

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