Modeling of diffusion-controlled reactions in free radical solution and bulk polymerization: Model validation by DSC experiments

• Published in: Journal of applied polymer science Vol. 116; no. 3; pp. 1842 - 1856
• Main Authors: Achilias, Dimitris S, Verros, George D
• Format: Journal Article
• Language: English
• Published: Hoboken Wiley Subscription Services, Inc., A Wiley Company 05.05.2010; Wiley
• Subjects: Applied sciences; Bulk polymerization; Conversion; Differential scanning calorimetry; Diffusion; diffusion-controlled; Exact sciences and technology; Free radicals; Mathematical models; modeling; Organic polymers; Physicochemistry of polymers; poly(methyl methacrylate); poly(vinyl acetate); Polymerization; Polymethyl methacrylates; Preparation, kinetics, thermodynamics, mechanism and catalysts; radical polymerization; Vinyl acetate; Differential scanning calorimetry; Experimental test; poly(methyl methacrylate); Bulk polymerization; diffusion-controlled; Theoretical study; Methyl methacrylate polymer; Modeling; Solution polymerization; radical polymerization; Kinetic model; Free radical polymerization; poly(vinyl acetate); Vinyl acetate polymer; Reaction mechanism; Measurement method; Vinyl ester polymer
• ISSN: 0021-8995; 1097-4628; 1097-4628
• DOI: 10.1002/app.31675

In this work, a detailed experimental study of diffusion-controlled reactions in free radical polymerization by using differential scanning calorimetry (DSC) was carried out. The systems studied include the methyl methacrylate bulk polymerization as well as the solution and the bulk polymerization of vinyl acetate at a wide range of experimental conditions including initial initiator concentration, reaction temperature, and type and amount of solvent. The conversion data obtained by DSC was successfully simulated by using a mathematical model based on sound principles such as the free volume theory. The estimated parameters, by fitting predictions of this model to conversion data obtained by DSC were found to be in close agreement with the reported parameters in the literature, thus validating both the experimental and theoretical methods used in this work.