A new model for radical desorption in emulsion polymerization

A new first principles model for radical desorption in emulsion polymerization was developed. It was demonstrated that the previous models were erroneous. The new model predicts unexpected dependences of the radical desorption rate coefficient upon the number of polymer particles, particle size, and initiator type and concentration. This may be the reason previous kinetic analysis based on extensive experimental designs were not conclusive in terms of the elucidation of the mechanisms of radical exit. A practical consequence is that the desorption rate coefficients determined under some given experimental conditions cannot be directly used to predict the behavior of emulsion polymerization systems under different conditions.