Iztok Hace, J. Golob, M. Krajnc
2003
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0
Influential Citations
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Journal
Chemical and Biochemical Engineering Quarterly
Abstract
A mathematical model describing free radical polymerization of diallyl terephthalate in a bulk, which exhibits strong diffusion limitations from the beginning of the reaction, was developed. The diffusion limitations are viewed as an integral part of the chain propagation and termination processes. The influence of temperature and initiator loading on the reaction process was investigated. Initiator decomposition rate constants were obtained from special experiments, by using the dead end theory. The ratios of degradative and the effective chain transfer rate coefficients to propagation rate coefficients were in range between 0.01 to 0.06 for k Deg /k p and between 0.001 to 0.008 for k Eff /k D . Ratios were evaluated from GPC molar mass measurements. The kinetic parameters were estimated by fitting the experimentally obtained conversion measured by FTIR for various initiators in temperature range from 50 °C to 150 °C by using peroxide initiators CHPC and DCPO. Activation energies estimated from kinetic modeling were 36.9 kJ mol -1 for propagation and 144.7 kJ mol -1 for termination, respectively.