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

✍ Scribed by 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

• Publisher: John Wiley and Sons
• Year: 1997
• Tongue: English
• Weight: 867 KB
• Volume: 198
• Category: Article
• ISSN: 1022-1352
• DOI: 10.1002/macp.1997.021980518

✦ Synopsis

Abstract

Pulsed‐laser polymerization (PLP) in conjunction with molar mass distribution (MMD) measurement is the method of choice for determining the propagation rate coefficient k~p~ 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 k~p~ 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 k~p~ 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

The 95% joint confidence interval for these Arrhenius parameters is also given. In so doing, we describe the most appropriate statistical methods for fitting k~p~(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 k~p~, factors which may apply even when this technique is functioning well. At the same time we discuss how such systematic errors in k~p~ can be minimized.