Free radical polymerizations associated with the trommsdorff effect under semibatch reactor conditions. I: Modeling

Several important polymerizations [e.g., poly(methyl methacrylate) (PMMA), polystyrene] exhibit gel and glass effects during polymerization. These are associated with the decrease of the diffusivities of the macroradicals and monomer molecules with increasing viscosities of the reaction mass. A new model has been developed to account for the gel and glass effects, both under batch and semibatch reactor operations. The free volume theory of Vrentas and Duda has been used to account for the changes in the diffusion coefficients. The model parameters are tuned using experimental data on the isothermal bulk and solution polymerizations of MMA in batch reactors. Conversion histories and molecular weights have been obtained for cases where solvent, initiator or monomer are added to (or removed from) the reaction mass after some reaction has taken place. In addition, studies involving step changes in temperature hav been carried out. It is found that the conversion vs. time behavior after such step changes depend upon a complex interplay of three factors: Polymer concentration, molecular weight, and the temperature at the point these changes are effected.