Termination rate coefficient of dimethyl itaconate: Comparison of modeling and experimental results

Vana, P., Yee, L. H., Barner-Kowollik, C., Heuts, J. P. A., & Davis, T. P. (2002) Termination rate coefficient of dimethyl itaconate: Comparison of modeling and experimental results. Macromolecules, 35(5).

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The termination kinetics of dimethyl itaconate (DMI) in bulk free radical polymerization at 40°C have been studied by both experimental and theoretical approaches. The chain length distributions obtained from pulsed laser polymerization experiments have been analyzed in combination with rate measurements to extract chain length dependent termination rate coefficients. The full chain length distributions were modeled using a comprehensive kinetic scheme with both experimentally determined and adjustable kinetic parameters. The chain length average termination rate coefficient, kt, was found to be close to 5.5 × 105 L mol-1 s-1. Termination occurs almost exclusively via disproportionation. Such low kt values are typical for sterically hindered monomers. The chain length dependence associated with the termination rate coefficient is almost negligible. The reasons for the very weak chain length dependence may be due to the solvent quality of the monomer toward its own polymer or due to the rigid structure of the formed polymer chains, therefore preventing the formation of a statistical coil.

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ID Code: 99066
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :17
Export Date: 5 September 2016
Correspondence Address: Davis, T.P.; Ctr. for Adv. Macromolecular Design, Sch. of Chem. Eng. Industrial Chem., The University of New South Wales, Sydney, NSW 2052, Australia
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Keywords: Alkyl methacrylates, Bimolecular termination, Dimethyl itaconate, Iterative optimization, Methyl methacrylate, Statistical coil, Termination rate coefficient, Computer simulation, Free radical polymerization, Molecular structure, Pulsed laser applications, Reaction kinetics, Size exclusion chromatography, Temperature, Monomers
DOI: 10.1021/ma011535v
ISSN: 00249297
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: 22 Sep 2016 04:50

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