Kinetics and modeling of diethylene glycol bisallyl carbonate bulk polymerization

• Published in: Journal of applied polymer science Vol. 96; no. 2; pp. 345 - 357
• Main Authors: Hace, Iztok, Golob, Janvit, Krajnc, Matjaž
• Format: Journal Article
• Language: English
• Published: Hoboken Wiley Subscription Services, Inc., A Wiley Company 15-04-2005; Wiley
• Subjects: Applied sciences; diffusion; Exact sciences and technology; modeling; monomers; Organic polymers; Physicochemistry of polymers; Polymerization; Preparation, kinetics, thermodynamics, mechanism and catalysts; diffusion; Bulk polymerization; monomers; Molecular weight determination; Priming activity; Bifunctional compound; Experimental study; Modeling; Kinetic model; Radical catalyst; Free radical polymerization; Allyl resin; Crosslinked polymer; Kinetics; Rate constant; Polycarbonate; Comparative study; Organic peroxide
• ISSN: 0021-8995; 1097-4628; 1097-4682
• DOI: 10.1002/app.21418

The free‐radical polymerization kinetics of diethylene glycol bisallyl carbonate in bulk were investigated with Fourier transform infrared and Fourier transform Raman techniques in a wide temperature range of 50–140°C with four different peroxide initiators. In addition, the ratios of the degradative kinetic rate constant to the propagation rate constant under different reaction conditions were obtained from molecular weight measurements under various reaction conditions. The ratio of the chemically controlled termination and propagation rate constants of the polymerization system were obtained with the initial rates of polymerization and the number‐average molecular weight data, which were between 8.22 × 10−5 and 1.47 × 10−3 L mol−1 s−1. The initiator efficiencies were evaluated with special experiments at low initiator concentrations with the theory of dead‐end polymerization. The computed conversions from the developed kinetic model were in good agreement with the conversion and molecular weight measured data. The values of the diffusion‐controlled propagation and termination rate constants, with clear and physical meaning, were the only two parameters obtained from the developed kinetic model fitting the measured conversion points. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 345–357, 2005