Abstract: A new model was developed to describe the diffusion limitation on free radical polyme-rization. In this model the termination rate coefficient (k_t) and propagation rate coefficient (k_p) were expressed as a function of bulk viscosity (η). This model was used to simulate the batch thermal polymerization of styrene (St) and the continuous thermal bulk copolymerization of St (monomer 1) and maleic anhydride (MAH, monomer 2) in a CSTR with on-line monitor of the rheological behavior. The simulated results on polymerization conversion, copolymer composition, molecular weight and its distributions were compared with the experimental data, and the results calculated by two previous gel-effect models i.e. Martin-Hamielec and Tulig-Tirrell models. It was found that the present model produces better prediction than that of the Tulig-Tirrell model and has the same accuracy as that of the Martin-Hamielec model, but is much simpler.

Key words: modeling, diffusion controlled polymerization, bulk viscosity

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