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Multicenter nature of titanium-based Ziegler–Natta catalysts: Comparison of ethylene and propylene polymerization reactions



This article discusses the similarities and differences between active centers in propylene and ethylene polymerization reactions over the same Ti-based catalysts. These correlations were examined by comparing the polymerization kinetics of both monomers over two different Ti-based catalyst systems, δ-TiCl3-AlEt3 and TiCl4/DBP/MgCl2-AlEt3/PhSi(OEt)3, by comparing the molecular weight distributions of respective polymers, in consecutive ethylene/propylene and propylene/ethylene homopolymerization reactions, and by examining the IR spectra of “impact-resistant” polypropylene (a mixture of isotactic polypropylene and an ethylene/propylene copolymer). The results of these experiments indicated that Ti-based catalysts contain two families of active centers. The centers of the first family, which are relatively unstable kinetically, are capable of polymerizing and copolymerizing all olefins. This family includes from four to six populations of centers that differ in their stereospecificity, average molecular weights of polymer molecules they produce, and in the values of reactivity ratios in olefin copolymerization reactions. The centers of the second family (two populations of centers) efficiently polymerize only ethylene. They do not homopolymerize α-olefins and, if used in ethylene/α-olefin copolymerization reactions, incorporate α-olefin molecules very poorly. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1745–1758, 2003