Heterogeneity of active sites of Ziegler‐Natta catalysts: The effect of catalyst composition on the MWD of polyethylene

Abstract

AbstractExperimental data on the molecular weight distribution (MWD) of polyethylene (PE) produced over a broad number of Ziegler‐Natta catalysts differing in composition and preparation procedure are presented. These catalysts include nonsupported TiCl3 catalyst, four types of supported titanium‐magnesium catalysts (TMC) differing in the content of titanium and the presence of various modifiers in the composition of the support, and a supported catalyst containing VCl4 as an active component instead of TiCl4. The studied catalysts produce PE with different molecular weights within a broad range of polydispersity (Mw/Mn = 2.8–16) under the same polymerization conditions. The heterogeneity of active sites of these catalysts was studied by deconvolution of experimental MWD curves into Flory components assuming a correlation between the number of Flory components and the number of active site types. Five Flory components were found for PE produced over nonsupported TiCl3 catalysts (Mw/Mn = 6.8), and three–four Flory components were found for PE produced over TMC of different composition. A minimal number of Flory components (three) was found for PE samples (Mw/Mn values from 2.8 to 3.3) produced over TMC with a very low titanium content (0.07 wt %) and TMC modified with dibutylphtalate. It was shown that five Flory components are sufficient to fit the experimental MWD curve for bimodal PE (Mw/Mn = 16) produced over VMC. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010