Kinetics of propylene polymerization in the initial acceleration stage

Abstract

AbstractThe kinetics of propylene polymerization catalyzed over a superactive and stereospecific catalyst for the initial build‐up period was investigated in slurry‐phase. The catalyst was prepared from Mg(OEt)2/benzoyl chloride/TiCl4 co‐activated with AlEt3 in the absence or presence of external donor. Despite a very fast activation of the prepared catalyst the acceleration stage of polymerization could be identified by the precise estimation of polymerization kinetics for a very short period of time after the commencement of polymerization (ca. 2 min). The initial polymerization rate, (dRp/dt)0 extrapolated to the beginning of the polymerization was second order with respect to monomer concentration. The dependence of initial polymerization rate on the concentration of AlEt3 could be represented by Langmuir adsorption mechanism. The initial rate was maximum at about Al/Ti ratio of 20. The activation energy for the initiation reaction was estimated to be 14.3 kcal/mol for a short‐time polymerization. The addition of a small amount of p‐ethoxy ethyl benzoate (PEEB) as an external donor increased the percentage of isotactic polymer, which was obtained after 120 s of polymerization, to 98% and the initial polymerization rate decreased sharply as [PEEB]/[AlEt3] increased. © 1994 John Wiley & Sons, Inc.