The Kinetics of enhanced spin capturing polymerization: Influence of the nitrone structure

Wong, E. H. H., Stenzel, M. H., Junkers, T., & Barner-Kowollik, C. (2009) The Kinetics of enhanced spin capturing polymerization: Influence of the nitrone structure. Journal of Polymer Science, Part A: Polymer Chemistry, 47(4).

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Several nitrones and one nitroso compound have been evaluated for their ability to control the molecular weight of polystyrene via the recently introduced radical polymerization method of enhanced spin capturing polymerization (ESCP). In this technique, molecular weight control is achieved (at ambient or slightly elevated temperatures) via the reaction of a growing radical chain with a nitrone forming a macronitroxide. These nitroxides subsequently react rapidly and irreversibly with propagating macroradicals forming polymer of a certain chain length, which depends on the nitrone concentration in the system. Via evaluation of the resulting number-average molecular weight, Mn, at low conversions, the addition rate coefficient of the growing radicals onto the different nitrones is determined and activation energies are obtained. For the nitrones N-tert-butyl-α- phenylnitrone (PBN), N-methyl-α-phenylnitrone (PMN), and N-methyl-α-(4-bromo-phenyl) nitrone (pB-PMN), addition rate coefficients, kad,macro, in a similar magnitude to the styrene propagation rate coefficient, kp, are found with spin capturing constants C SC (with CSC = kad,macro/kv) ranging from 1 to 13 depending on the nitrone and on temperature. Activation energies between 23.6 and 27.7 kJ mol-1 were deduced for kad,macro, congruent with a decreasing CSC with increasing temperature. Almost constant Mn over up to high monomer to polymer conversions is found when CSC is close to unity, while increasing molecular weights can be observed when the CSC is large. From temperatures of 100 °C onward, reversible cleavage of the alkoxyamine group can occur, superimposing a reversible activation/deactivation mechanism onto the ESCP system. © 2009 Wiley Periodicals, Inc.

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ID Code: 99229
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :34
Export Date: 5 September 2016
Correspondence Address: Junkers, T.; Institut für Technische Chemie und Polymerchemie, Universität Karlsruhe (TH), Karlsruhe Institute of Technology (KIT), Engesserstr. 18, 76128 Karlsruhe, Germany; email:
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Keywords: Activation energy, Controlled radical polymerization, Degree of polymerization (DP), ESR spin traps, Kinetics (polym.), Nitrone, Polystyrene, Structure-reactivity relations, Amines, Atom transfer radical polymerization, Chemical reactions, Dynamic positioning, Electroslag remelting, Molecular weight, Nitrogen oxides, Percolation (solid state), Polymers, Polystyrenes, Spin dynamics, Styrene, Weight control, Free radical polymerization
DOI: 10.1002/pola.23221
ISSN: 0887624X
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: 07 Oct 2016 04:15

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