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Critically evaluated rate coefficients for free‐radical polymerization, 1. Propagation rate coefficient for styrene
Author(s) -
Buback Michael,
Gilbert Robert G.,
Hutchinson Robin A.,
Klumperman Bert,
Kuchta FrankDieter,
Manders Bart G.,
O'Driscoll Kenneth F.,
Russell Gregory T.,
Schweer Johannes
Publication year - 1995
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.1995.021961016
Subject(s) - radical polymerization , polymerization , arrhenius equation , styrene , polymer chemistry , chemistry , bulk polymerization , thermodynamics , materials science , polymer , copolymer , organic chemistry , activation energy , physics
Pulsed‐laser polymerization (PLP) in conjugation with molecular weight distribution (MWD) measurement has emerged as the method of choice for determining the propagation rate coefficient k p in free‐radical polymerizations. Detailed guidelines for using this technique (including essential internal consistency checks) and reporting the results therefrom are given by the authors, members of the IUPAC Working Party on Modeling of kinetics and processes of polymerization. The results for PLP‐MWD k p measurements from many laboratories for bulk free‐radical polymerization of styrene at low conversions and ambient pressure are collated, and are in excellent agreement. They are therefore recommended as constituting a benchmark data set, one that is best fitted by\documentclass{article}\pagestyle{empty}\begin{document}$ k_{\rm p} = 10^{7.630} {\rm L} \cdot {\rm mol}^{-1} \cdot {\rm s}^{-1} \exp \left({\frac{{-32.51{\rm kJ} \cdot {\rm mol}^{-1}}}{{R \cdot T}}} \right) $\end{document} (the confidence ellipsoid for the Arrhenius parameters is also given). These benchmark data are also used to evaluate the merits of several other methods for determining k p ; it is found that appropriately calibrated electron paramagnetic resonance spectroscopy appears to yield reliable values of k p for styrene.