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

G. Evan Roberts, Christopher Barner-Kowollik, Thomas P. Davis, Johan P.A. Heuts

Research output: Contribution to journalArticleResearchpeer-review

23 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)1054-1062
Number of pages9
JournalMacromolecules
Volume36
Issue number4
DOIs
Publication statusPublished - 25 Feb 2003
Externally publishedYes

Cite this

Roberts, G. Evan ; Barner-Kowollik, Christopher ; Davis, Thomas P. ; Heuts, Johan P.A. / Cobalt(II)-mediated catalytic chain transfer polymerization of styrene : Estimating individual rate coefficients via kinetic modeling. In: Macromolecules. 2003 ; Vol. 36, No. 4. pp. 1054-1062.
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Cobalt(II)-mediated catalytic chain transfer polymerization of styrene : Estimating individual rate coefficients via kinetic modeling. / Roberts, G. Evan; Barner-Kowollik, Christopher; Davis, Thomas P.; Heuts, Johan P.A.

In: Macromolecules, Vol. 36, No. 4, 25.02.2003, p. 1054-1062.

Research output: Contribution to journalArticleResearchpeer-review

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