TY - JOUR
T1 - Modeling of free radical polymerization up to high conversion
T2 - II. Development of a mathematical model
AU - Tefera, N.
AU - Weickert, G.
AU - Westerterp, K.R.
PY - 1997
Y1 - 1997
N2 - In free radical polymerization diffusion-controlled processes take place simultaneously to the normal chemical reactions. Despite extensive efforts to model such processes a consistent model for the design of a polymerization reactor has not yet been established. In this article a semiempirical model describing the conversion, polymerization degree, and molecular weight distribution (MWD) for the free radical polymerization is developed for the entire course of the reaction. The model includes the change of termination, propagation, transfer, and initiation rate. By simultaneous parameter estimation from the conversion and degrees of polymerization data the model parameters have been determined for isothermal polymerizations of methyl methacrylate (MMA) and styrene (ST). The simulation results for the conversion, degrees of polymerization, and MWD are in good accordance with experimental data for suspension and bulk polymerization of MMA and ST up to very high conversions. The influence of diffusion on the propagation rate in case of polymerization of MMA is negligible compared to the influence of the cage effect on the radical efficiency; in case of ST polymerization both effects must be included in the kinetic model. The model presented is also tested for polymerizations conducted in the presence of solvent and/or chain transfer agents.
AB - In free radical polymerization diffusion-controlled processes take place simultaneously to the normal chemical reactions. Despite extensive efforts to model such processes a consistent model for the design of a polymerization reactor has not yet been established. In this article a semiempirical model describing the conversion, polymerization degree, and molecular weight distribution (MWD) for the free radical polymerization is developed for the entire course of the reaction. The model includes the change of termination, propagation, transfer, and initiation rate. By simultaneous parameter estimation from the conversion and degrees of polymerization data the model parameters have been determined for isothermal polymerizations of methyl methacrylate (MMA) and styrene (ST). The simulation results for the conversion, degrees of polymerization, and MWD are in good accordance with experimental data for suspension and bulk polymerization of MMA and ST up to very high conversions. The influence of diffusion on the propagation rate in case of polymerization of MMA is negligible compared to the influence of the cage effect on the radical efficiency; in case of ST polymerization both effects must be included in the kinetic model. The model presented is also tested for polymerizations conducted in the presence of solvent and/or chain transfer agents.
KW - diffusion-controlled radical polymerization
KW - high-conversion modeling
KW - Mathematical model
U2 - 10.1002/(SICI)1097-4628(19970321)63:12<1663::AID-APP17>3.0.CO;2-0
DO - 10.1002/(SICI)1097-4628(19970321)63:12<1663::AID-APP17>3.0.CO;2-0
M3 - Article
VL - 63
SP - 1663
EP - 1680
JO - Journal of applied polymer science
JF - Journal of applied polymer science
SN - 0021-8995
IS - 12
ER -