A perfect couple: PLP/SEC/ESI-MS for the accurate determination of propagation rate coefficients in free radical polymerization

Gruendling, T., Voll, D., Guilhaus, M., & Barner-Kowollik, C. (2010) A perfect couple: PLP/SEC/ESI-MS for the accurate determination of propagation rate coefficients in free radical polymerization. Macromolecular Chemistry and Physics, 211(1).

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Abstract

Pulsed laser polymerization (PLP) in conjunction with online size exclusion chromatography electrospray ionization mass spectrometry (SEC/ESI-MS) has successfully been applied for the determination of accurate propagation rate coefficients, kp, in free radical polymerization. SEC/ESI-MS is used in this context to precisely determine the molecular weight distribution of the polymer produced by the PLP-experiment. The novel approach allows for a highly accurate internal calibration of the size exclusion system to be obtained from first principles, as the molecular weight of the polymer is determined with ppm accuracy by the mass spectrometer and allows corrections for SEC band broadening effects to be made. Molecular weight measurements can furthermore be performed regardless of the monomer class, as long as the macromolecule is amenable to electrospray ionization. The proposed approach successfully eliminates work-steps and problems incurred in the analysis of new and poorly characterized monomers, where universal calibration or multi-detector SEC had to be applied until now and provides an alternative also to PLP/MALDI-MS. Applicability of the method is demonstrated tor the homologous series of methyl-, ethyl- and butyl methacrylate. The experimentally determined kp values were 5-10% higher than the currently available benchmark data. The experimental k p is in agreement with the results of kinetic simulations, assuming a short chain length dependency of kp, in accordance with the empirical model of Smith, Heuts and Russell. (Figure Presented) © 2010 WILEY-VCH Verlag GmbH & Co. KGaA,.

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ID Code: 99240
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :9
Export Date: 5 September 2016
CODEN: MCHPE
Correspondence Address: Barner-Kowollik, C.; Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT), Engesserstr. 18, 76128 Karlsruhe, Germany; email: christopher.barner-kowollik@kit.edu
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Keywords: Accurate propagation rate coefficients (kp), Arrhenius equation, Electrospray ionization mass spectrometry (ESI-MS), Pulsed laser polymerization (PLP), Size exclusion chromatography (SEC), Band-broadening, Benchmark data, Butyl methacrylates, Electrospray ionization mass spectrometry, Empirical model, First-principles, Homologous series, Internal calibration, Kinetic simulation, Molecular weight measurements, Multi-detectors, Propagation rate coefficient, Pulsed laser polymerization, Short chain lengths, Size exclusion, Universal calibration, Atom transfer radical polymerization, Calibration, Chromatographic analysis, Electrospray ionization, Free radicals, Gel permeation chromatography, Ionization, Mass spectrometers, Mass spectrometry, Molecular weight distribution, Monomers, Particle detectors, Pulsed laser applications, Pulsed lasers, Size exclusion chromatography, Free radical polymerization
DOI: 10.1002/macp.200900394
ISSN: 10221352
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: 06 Oct 2016 04:21

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