25 No. 6
Critically Evaluated Propagation Rate Coefficients in Free-Radical Polymerizations: Part III. Methacry-lates with Cyclic Ester Groups (IUPAC Technical Report)
Pure and Applied Chemistry
Vol. 75, No.
8, pp. 1091-1096 (2003)
Modeling and optimization of free-radical polymerization processes requires the knowledge of accurate individual rate coefficients for the reactions occurring during a polymerization. Pulsed laser-initiated polymerization in conjunction with polymer analysis by size-exclusion chromatography has proven to be a valuable technique to derive propagation rate coefficients kp. The IUPAC Working Party on Modeling of Polymerization Kinetics and Processes has reported critically evaluated rate coefficient data for styrene and alkyl methacrylates. This paper continues the series by reporting propagation rate coefficients, kp, as a function of temperature, for bulk free-radical homopolymerizations of oxiranylmethyl, cyclohexyl, and benzyl methacrylate at ambient pressure and low conversion. For each monomer, the rate coefficients have been independently measured in two laboratories. The data determined from experiments carried out in independent laboratories obey the consistency criteria established for this technique. The rate coefficients for the three monomers are well represented by a single Arrhenius relation.
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