Empirical models for viscosity variation in bulk free radical polymerization

Abstract

The validity of the Lyons-Tobolsky equation for bulk polymerization systems was verified by comparing simulation results to experimental data for different reaction conditions (temperature and initiator concentration). In this model, formerly applied for solution polymerization, the viscosity of the reaction mass was used instead of solvent viscosity. For example, the chemically initiated free radical polymerization of methyl methacrylate was considered to be achieved in a batch bulk process. In the Lyons-Tobolsky equation, the viscosity was calculated using the values of the conversion and molecular weight resulting from the kinetic model simulation. Consequently, a general discussion about the concordance between the simulation and experiment was useful, especially to emphasize the causes that generate modeling errors. It is more convenient to estimate the viscosity independently of conversion and molecular weight and, in this way, without solving the kinetic model. Empirical relations which correlate viscosity with time were elaborated using experimental viscosity data. Two kinds of models were proposed: a) two fifth order polynomials corresponding to the conversion domains before and after the gel effect; b) a model that fits the experimental data well in the whole conversion domain. Generally, these empirical models provide good simulation results and they can be easily handled.