scholarly journals The charge percolation mechanism and simulation of Ziegler-Natta polymerizations, Part VII: Effects of the distribution of chromium active centers on silica on the polymerization of ethylene

2008 ◽  
Vol 73 (1) ◽  
pp. 97-111 ◽  
Author(s):  
Dragoslav Stoiljkovic ◽  
Branka Pilic ◽  
Misa Bulajic ◽  
Nebojsa Djurasovic ◽  
Nikolaj Ostrovskii

The charge percolation mechanism (CPM) of olefin polymerization in the presence of transition metal compounds has been applied to explain the polymerization of ethylene by silica supported chromium oxide. In the previous work of this series, the fundamental issues and mechanism of this polymeri?zation were presented. In this work the compatibility of the CPM with the em?pirical findings is confirmed. The CPM has been applied to explain: the appea?rance of an induction period; the deactivation of active centers and the forma?tion of oligomers; the effects of chromium concentration on the silica surface, the silica surface discontinuity and the pore size of silica on polymerization and the formation of the structure of polyethylene. A mathematical model has been derived to explain the effects of the CrOx/SiO2 ratio on the productivity of Phil?lips catalysts in the polymerization of ethylene. The empirical findings have also been confirmed by computer simulations.

Author(s):  
R. Morris Bullock ◽  
Geoffrey M. Chambers

This perspective examines frustrated Lewis pairs (FLPs) in the context of heterolytic cleavage of H 2 by transition metal complexes, with an emphasis on molecular complexes bearing an intramolecular Lewis base. FLPs have traditionally been associated with main group compounds, yet many reactions of transition metal complexes support a broader classification of FLPs that includes certain types of transition metal complexes with reactivity resembling main group-based FLPs. This article surveys transition metal complexes that heterolytically cleave H 2 , which vary in the degree that the Lewis pairs within these systems interact. Many of the examples include complexes bearing a pendant amine functioning as the base with the metal functioning as the hydride acceptor. Consideration of transition metal compounds in the context of FLPs can inspire new innovations and improvements in transition metal catalysis. This article is part of the themed issue ‘Frustrated Lewis pair chemistry’.


1980 ◽  
Vol 34 (1) ◽  
pp. 45-50 ◽  
Author(s):  
A.Nørlund Christensen ◽  
S.E. Rasmussen ◽  
G. Thirup

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