Ansa-zirconocene complexes are widely employed as precatalysts for olefin polymerization. Their synthesis generally leads to mixtures of their rac and meso isomers, whose separation is often problematic. In this contribution, we report on the synthesis of a novel silyl-bridged bis(indenyl)-based metallocene, and on the separation of its rac and meso isomers by simple recrystallization from toluene. The two complexes, activated by methylaluminoxane (MAO), have been used as precatalysts in ethylene/1-hexene copolymerization. Regardless of the reaction conditions, the meso complex outperformed its rac congener. A similar trend was observed by performing the process in the presence of the silica-supported versions of the complexes. This is remarkable, since meso metallocenes generally display lower activities than their rac analogues. Furthermore, the meso isomer generates polymer products that are more in line with the targets for the preparation of a bimodal PE grade made of a lower-MW high-density (HDPE) fraction and a higher-MW linear low-density (LLDPE) fraction.

Meso- and Rac-[bis(3-phenyl-6-tert-butylinden-1-yl)dimethylsilyl]zirconium Dichloride: Precatalysts for the Production of Differentiated Polyethylene Products with Enhanced Properties

Santoro, Orlando;
2022-01-01

Abstract

Ansa-zirconocene complexes are widely employed as precatalysts for olefin polymerization. Their synthesis generally leads to mixtures of their rac and meso isomers, whose separation is often problematic. In this contribution, we report on the synthesis of a novel silyl-bridged bis(indenyl)-based metallocene, and on the separation of its rac and meso isomers by simple recrystallization from toluene. The two complexes, activated by methylaluminoxane (MAO), have been used as precatalysts in ethylene/1-hexene copolymerization. Regardless of the reaction conditions, the meso complex outperformed its rac congener. A similar trend was observed by performing the process in the presence of the silica-supported versions of the complexes. This is remarkable, since meso metallocenes generally display lower activities than their rac analogues. Furthermore, the meso isomer generates polymer products that are more in line with the targets for the preparation of a bimodal PE grade made of a lower-MW high-density (HDPE) fraction and a higher-MW linear low-density (LLDPE) fraction.
2022
2022
https://www.mdpi.com/2073-4360/14/11/2217
ansa-zirconocene; bimodal polyethylene; dual site; rac/meso isomers; short-chain branches
Giffin, Kaitie A; Cirriez, Virginie; Santoro, Orlando; Welle, Alexandre; Kirillov, Evgueni; Carpentier, Jean-François
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11383/2137743
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