Cobalt(II)-mediated catalytic chain transfer polymerization of styrene: Estimating individual rate coefficients via kinetic modeling

Roberts, G. E., Barner-Kowollik, C., Davis, T. P., & Heuts, J. P. A. (2003) Cobalt(II)-mediated catalytic chain transfer polymerization of styrene: Estimating individual rate coefficients via kinetic modeling. Macromolecules, 36(4).

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Abstract

The individual rate coefficients for hydrogen abstraction (ktr), cobalt-carbon bond formation (kdaec), and cobalt-carbon bond homolysis (kac) have been determined for the cobaloxime-mediated chain transfer polymerization of styrene at 60 °C using kinetic simulations in combination with experimental data. Values of 2.7 × 106 L mol-1 s-1, 4.8 × 104 L mol-1 s-1, and 8.7 × 10-4 s-1 for htr, kdeac, and kac, respectively, were found to adequately describe reactions associated with the catalytic chain transfer process with the overall model reproducing experimental observations such as molecular weight evolution with time and the initiator concentration dependency of the apparent chain transfer constant. The effect of photohomolysis of the Co-C bond, leading to an increased free catalyst concentration in the presence of strong UV radiation or a decreased free catalyst concentration under darkened conditions, was modeled by simply varying the value for kac.

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ID Code: 99073
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :19
Export Date: 5 September 2016
CODEN: MAMOB
Correspondence Address: Heuts, J.P.A.; Ctr. for Adv. Macromolecular Design, Sch. of Chem. Eng./Indust. Chemistry, University of New South Wales, Sydney, NSW 2052, Australia; email: j.heuts@unsw.edu.au
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Keywords: Chain transfer polymerization, Catalysis, Rate constants, Styrene, Ultraviolet radiation, Polymerization
DOI: 10.1021/ma021152c
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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