Simulation of free radical bulk/solution homopolymerization using mono- and bi-functional initiators

Monofunctional and bifunctional peroxides are extensively utilized in the p roduction of polystyrene. However, their decomposition kinetics is still an important area to investigate. A computer package developed previously by Gao and Penlidis (1996), which was based on mono-functionally initiated pol ymerization, is extended in this study to cover homopolymerization of styre ne using bifunctional initiators. A database of a wide variety of bifunctio nal peroxides used in polystyrene production is developed along with a data base for twelve new monofunctional initiators. The package handles several different scenarios of styrene polymerization, whether it is in bulk / solu tion or isothermal / non-isothermal medium. The model is tested with a wide range of conversion and average molecular weight data either from the lite rature or available from industry. Simulation results agree with the data t rends, which makes the simulator a very powerful tool in aid of initiator s election and evaluation. At the end of the paper, results on homopolymeriza tions of acrylates and methacrylates are also discussed.