Kinetics of Free Radical Polymerization of Styrene to Complete Conversion

Abstract

<p> Polymerization of bulk styrene initiated thermally as well as with di-tertiary-butyl peroxide was studied in isothermal batch reactors. Thermal polymerization was carried out at 100, 140, 170 and 200°C while polymerization with di-tertiary butyl peroxide was at 100 and 140°C. A kinetic model was derived therefrom accounting for initiation reactions from a first order decomposition of catalyst and a second order reaction between two monomer molecules to form two monoradicals, propagation, chain transfer to monomer and termination by combination only. Gel effect was allowed by the variation of rate constants with conversion. Both the thermal initiation rate constant and the first order decomposition rate constant of di-tertiary butyl peroxide were found to agree with literature values with the present values slightly higher. The initial rate constants for propagation, chain transfer to monomer, and termination were extrapolated to the range, 100-200°C using literature data. This kinetic model was used in the simulation of polymer reactor systems studying the effect of recycle and operating conditions on the molecular weight distribution and rate of production of polymer products.</p> <p> The main body of this thesis reports the polymerization study and the development of the kinetic model. The details of the kinetic equations and methods of solution, experimental techniques involved, and the simulation of polymer reactor systems are reported in the Appendices.</p>