Modeling termination kinetics of non-stationary free-radical polymerizations

Buback, M., Barner-Kowollik, C., Egorov, M., & Kaminsky, V. (2001) Modeling termination kinetics of non-stationary free-radical polymerizations. Macromolecular Theory and Simulations, 10(4).

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Pulsed-laser induced polymerization is modeled via an approach presented in a previous paper. An equation for the time dependence of free-radical concentration is derived. It is shown that the termination rate coefficient may vary significantly as a function of time after applying the laser pulse despite of the fact that the change in monomer concentration during one experiment is negligible. For the limiting case of t ≫ c-1 (kpM)-1, where c is a dimensionless chain-transfer constant, kp the propagation rate coefficient and M the monomer concentration, an analytical expression for kt is derived. It is also shown that time-resolved single pulsed-laser polymerization (SP-PLP) experiments can yield the parameters that allow the modeling of kt in quasi-stationary polymerization. The influence of inhibitors is also considered. The conditions are analyzed under which M (t) curves recorded at different extents of laser-induced photo-initiator decomposition intersect. It is shown that such type of behavior is associated with chain-length dependence of kt.

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15 citations in Web of Science®
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ID Code: 99047
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :17
Export Date: 5 September 2016
Correspondence Address: Kaminsky, V.; Karpov Inst. of Physical Chemistry, ul. Vorontsovo pole 10, Moscow 103064, Russian Federation; email:
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Keywords: free radical, monomer, article, chemical reaction kinetics, laser, mathematical model, polymerization
DOI: 10.1002/1521-3919(20010401)10:4<209::AID-MATS209>3.0.CO;2-Z
ISSN: 10221344
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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