Mechanistic studies on olefin polymerization catalysts

Mechanistic studies on olefin polymerization catalysts

Along with the SPR studies, we cultivate fundamental investigations on the mechanisms of catalytic olefin polymerizations, aiming to identify the origin of the observed stereo-, regio- and chemo-selectivities for heterogeneous as well as molecular systems, and the dominant chain transfer pathways presiding over their polymer molecular weight capability. We typically do that by combining molecular kinetic observations with in-depth NMR polymer microstructure analyses. A recent example is the elucidation of the subtle effects governing tandem molecular catalysis under reversible trans-alkylation (“chain shuttling”) regime.

Purely computational tools can be exploited to model the elementary reaction steps of the polymerization process when the structure of the active species can be assumed to be known. At LSP we have carried out a solid benchmark of DFT protocols for modelling various reactions of interest in olefin polymerization, from simple olefin insertion to metal-carbon bond homolysis. Thanks to the so- optimized approach, accuracy needed not only for mechanistic understanding but also for reliable kinetic modelling has been achieved. This has been proven, for instance, by the successful modelling of comonomer affinities in ethene/α-olefin copolymerization.

More often, experimental and computational tools are combined in highly integrated studies. This is almost invariably the case for heterogeneous catalyst systems (e.g. of Ziegler-Natta type). Recent successful examples in molecular catalysis concern the correlations between structure and properties of octahedral bis(phenolate-ether) ‘post-metallocenes’,  as  well  as  the  identification of unprecedented pathways of chain transfer to solvent and to monomer.

Furthermore, LSP has a long-standing tradition in investigating the complex cross reactivity of precatalysts and cocatalysts (activators). Recently, especially interesting results have been obtained on the structure and reactivity of methylaluminoxane (MAO) and some modifications thereof, by successfully integrating DFT modelling and advanced NMR spectroscopy (in collaboration with the research group of Prof. Alceo Macchioni at the University of Perugia).


LSP is a global competence center for fundamental and applied studies on olefin polymerization chemistry and catalysis.


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LSP specializes in fundamental and applied studies of catalytic olefin polymerizations, aiming to better understand and improve…


LSP is one of the very few academic groups operating a comprehensive HTE workflow for organometallic catalysis.

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