On demand oligomerization of ethylene is a highly sought-after transformation in petrochemicals industry. It has the advantage of transforming a low-cost feedstock selectively into high potential C6 or C8 oligomers. These are the main co-monomers in making linear low-density polyethylene (LLDPE) and high-density polyethylene (HDPE). Early transition metal organometallic catalysts have shown promise in selective ethylene oligomerization. However, even with highly selective and active organometallic catalysts, unwanted polymer formation is a major drawback in industrial scale operations as they tend to “foul-up” a catalytic reactor.<br/>Solid supported organometallic catalysts are less explored but has the potential to alleviate polymer formation. In this work, we present novel early transition metal organometallic catalysts supported on inorganic oxides such as silica, alumina, titania. By virtue of their molecular design and catalytic site isolation, these solid-supported catalysts exhibit high activity and selectivity towards formation of C6 or C8 oligomers, while considerably reducing polymer formation. By varying the nature and molar ratio of activators in the catalytic cycle, the activities are further enhanced while polymer formation is further suppressed. The superior performance of these catalysts is supported by computational modelling using density functional theory. These solid supported catalysts promise to be excellent choices for industrial scale on-demand transformation of ethylene.

Solid supported early transition metal catalysts for on demand oligomerization of ethylene

ACS Fall 2021

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