Free-radical bulk polymerization of styrene: ESR and near-infrared spectroscopic study of the entire conversion range

Yamazoe, H., Zetterlund, P.B., Yamada, B., Hill, D.J.T. and Pomery, P.J. (2001) Free-radical bulk polymerization of styrene: ESR and near-infrared spectroscopic study of the entire conversion range. Macromolecular Chemistry And Physics, 202 6: 824-829. doi:10.1002/1521-3935(20010301)202:6


Author Yamazoe, H.
Zetterlund, P.B.
Yamada, B.
Hill, D.J.T.
Pomery, P.J.
Title Free-radical bulk polymerization of styrene: ESR and near-infrared spectroscopic study of the entire conversion range
Journal name Macromolecular Chemistry And Physics   Check publisher's open access policy
ISSN 1521-3935
1022-1352
Publication date 2001-04-18
Sub-type Article (original research)
DOI 10.1002/1521-3935(20010301)202:6
Volume 202
Issue 6
Start page 824
End page 829
Total pages 6
Place of publication Weinheim, Germany
Publisher Wiley-VCH
Collection year 2001
Language eng
Subject C1
250502 Physical Chemistry of Macromolecules
780103 Chemical sciences
Abstract The free radical polymerization of styrene in bulk was monitored by ESR and FT near-infrared spectroscopy at 70°C for a series of concentrations of the initiator, dimethyl 2,2′-azobis(isobutyrate). In order to obtain detailed kinetic information over the intire conversion range, and the gel effect range in particular, conversion and free radical concentration data points were accumulated with exceptionally short time intervals. The polystyrene radical concentration ([St•]) went through a sharp maximum at the gel effect, a feature that has hitherto escaped observation due to the rapid concentration changes in the gel effect range relative to the data point time intervals of previous studies. Temperature measurements throughout the polymerization were employed to calculate that a temperature increase was not the cause of the [St•] maximum, which thus appeares to be a genuine feature of the gel effect of this system under isothermal conditions. The propagation rate constant (kp) as a function of monomer conversion exhibited a marked dependence on initiator concentration at high monomer conversion; the sharp decrease in kp with increasing conversion was shifted to higher conversions with increasing initiator concentration.
Keyword Polymer Science
Propagation Rate Coefficient
Methyl-methacrylate
Rate Constants
Homogeneous Polymerization
Isothermal Reactions
Kinetic-parameters
Termination
Dependence
Copolymerization
Resonance
Q-Index Code C1

Document type: Journal Article
Sub-type: Article (original research)
Collection: School of Chemistry and Molecular Biosciences
 
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Created: Tue, 14 Aug 2007, 15:28:23 EST