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Pure Appl. Chem., 2007, Vol. 79, No. 8, pp. 1463-1469


Critically evaluated rate coefficients for free-radical polymerization Part 6: Propagation rate coefficient of methacrylic acid in aqueous solution (IUPAC Technical Report)

Sabine Beuermann1, Michael Buback1, Pascal Hesse1, Frank-Dieter Kuchta2, Igor Lacík3 and Alex M. van Herk2

1 Institute of Physical Chemistry, Georg-August-Universität Göttingen, Tammannstrasse 6, D-37077, Göttingen, Germany
2 Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands
3 Polymer Institute of the Slovak Academy of Sciences, Dúbravská cesta 9, 842 36 Bratislava, Slovak Republic

Abstract: Critically evaluated propagation rate coefficients, kp, for free-radical polymerization of methacrylic acid, MAA, in aqueous solution are presented. The underlying kp values are from two independent sources, which both used the IUPAC-recommended technique of pulsed-laser-initiated polymerization (PLP) in conjunction with molar mass distribution (MMD) analysis of the resulting polymer by size-exclusion chromatography (SEC). Different methods of measuring the MMD of the poly(MAA) samples have, however, been used: (i) direct analysis via aqueous-phase SEC and (ii) standard SEC with tetrahydrofuran as the eluent carried out on poly(methyl methacrylate) samples obtained by methylation of the poly(MAA) samples from PLP. Benchmark kp values for aqueous solutions containing 15 mass % MAA are presented for temperatures between 18 and 89 °C. The Arrhenius pre-exponential and activation energy of kp at 15 mass % MAA are 1.54 × 106 L mol-1 s-1 and 15.0 kJ mol-1, respectively. Also reported are critically evaluated kp values for 25 °C over the entire MAA concentration range from dilute aqueous solution to bulk polymerization.