Accessing the chain length dependence of the termination rate coefficient for disparate length radicals via reversible addition fragmentation chain transfer chemistry: A theoretical study

Lovestead, T. M., Theis, A., Davis, T. P., Stenzel, M. H., & Barner-Kowollik, C. (2006) Accessing the chain length dependence of the termination rate coefficient for disparate length radicals via reversible addition fragmentation chain transfer chemistry: A theoretical study. Macromolecules, 39(15).

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Abstract

On the basis of the recently introduced reversible addition fragmentation chain transfer chain length dependent termination (RAFT-CLD-T) method, a novel approach is presented to access the termination rate coefficient for disparate length radicals, Kts.l. In-depth simulation is employed to validate this approach, which utilizes reversible addition fragmentation chain transfer (RAFT) chemistry to generate two nearly monodisperse chain length distributions with disparate average lengths, s and l. These disparate length radicals are generated by prepolymerizing a polyRAFT species to a chain length significantly greater than unity and subsequently progressing the polymerization of the polyRAFT species in the presence of a suitable RAFT agent of initial chain length 1. The present study demonstrates that the chain length dependence of the termination rate coefficient for disparate length radicals can be obtained accurately regardless of the extent of the prepolymerization period of the polyRAFT species, the input kinetic parameters, and whether the geometric or the harmonic mean approximation is assumed for the relationship between k t and the individual radical chain lengths s and l. Thus, for the first time a facile and accurate method for quantification of kt s,l; is validated theoretically allowing for a complete characterization of free radical termination processes for disparate length radicals. © 2006 American Chemical Society.

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ID Code: 99128
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :15
Export Date: 5 September 2016
CODEN: MAMOB
Correspondence Address: Barner-Kowollik, C.; Centre for Advanced Macromolecular Design, School of Chemical Sciences and Engineering, University of New South Wales, Sydney, NSW 2052, Australia; email: camd@unsw.edu.au
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Keywords: Characterization, Computer simulation, Free radical polymerization, Chain length dependence, Disparate length radicals, In-depth simulation, Reversible addition fragmentation, Reaction kinetics
DOI: 10.1021/ma060646x
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: 30 Sep 2016 02:18

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