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Kinetic Model of a Methacrylate-Based Monolith Polymerization

I. Mihelič, M. Krajnc, T. Koloini, A. Podgornik

Ind. Eng. Chem. Res. 2001, 40, 3495-3501

Monolithic stationary phases are becoming more and more important in the field of liquid chromatography, because they enable extremely fast separations. Methacrylate-based monoliths are produced via a free-radical bulk polymerization of glycidyl methacrylate and ethylene dimethacrylate using a benzoyl peroxide as an initiator. Preparation of large monoliths represents a big problem because of the heat release during the polymerization, which consequently leads to the distortion of the structure. A closer investigation of the polymerization, using differential scanning calorimetry, was performed in order to determine global kinetic parameters. A multiple heating rate method, based on the work of Ozawa, Flynn, and Wall, was applied for estimation of the values of the apparent activation energy, preexponential factor, and reaction order. Global polymerization kinetics is of first order with A = 1.681 × 109 s-1 and Ea,app = 81.5 kJ/mol, where the heat of polymerization is approximately 190 J/g. In addition, the influence of air and nitrogen atmosphere on polymerization is presented.

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