Critically evaluated rate coefficients for free-radical polymerization, 2: Propagation rate coefficients for methyl methacrylate

Sabine Beuermann, Michael Buback, Thomas P. Davis, Robert G. Gilbert, Robin A. Hutchinson, Oskar Friedrich Olaj, Gregory T. Russell, Johannes Schweer, Alex M. Van Herk

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Abstract

Pulsed-laser polymerization (PLP) in conjunction with molar mass distribution (MMD) measurement is the method of choice for determining the propagation rate coefficient kp in free-radical polymerizations. The authors, members of the IUPAC Working Party on Modeling of kinetics and processes of polymerization, collate results from using PLP-MMD to determine kp as a function of temperature T for bulk free-radical polymerization of methyl methacrylate at low conversions and ambient pressure. Despite coming from several different laboratories, the values of kp are in excellent agreement and obey consistency checks. These values are therefore recommended as constituting a benchmark data set, one that is best fitted by kp = 106,427 L · mol-1 · s-1 exp(-22, 36 kJ · mol-1/R · T) The 95% joint confidence interval for these Arrhenius parameters is also given. In so doing, we describe the most appropriate statistical methods for fitting kp(T) data and then obtaining a joint confidence interval for the fitted Arrhenius parameters. As well, we outline factors which impose slight limitations on the accuracy of the PLP-MMD technique for determining kp, factors which may apply even when this technique is functioning well. At the same time we discuss how such systematic errors in kp can be minimized. a) Part 1: cf. ref. 1).

Original languageEnglish
Pages (from-to)1545-1560
Number of pages16
JournalMacromolecular Chemistry and Physics
Volume198
Issue number5
DOIs
Publication statusPublished - 1 Jan 1997
Externally publishedYes

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