Issue 11, 2020

Physicochemical surface-structure studies of highly active zirconocene polymerisation catalysts on solid polymethylaluminoxane activating supports

Abstract

Physicochemical surface-structure studies of highly active slurry-phase ethylene polymerisation catalysts has been performed. Zirconocene complexes immobilised on solid polymethylaluminoxane (sMAO) (sMAO–Cp2ZrX2), have been investigated using SEM-EDX, diffuse reflectance FT-IR (DRIFT) and high field (21.1 T) solid state NMR (ssNMR) spectroscopy. The data suggest a common surface-bound cationic methylzirconocene is the catalytically active species. 91Zr solid sate NMR spectra of sMAO–Cp2ZrCl2 and sMAO–Cp2ZrMe2 are consistent with a common surface-bound Zr environment. However, variation of the σ-donor (X) groups on the metallocene precatalyst leads to significant differences in polymerisation activity. We report evidence for X group transfer from the precatalyst complex onto the surface of the aluminoxane support, which in the case of X = C6F5, results in a 38% increase in activity.

Graphical abstract: Physicochemical surface-structure studies of highly active zirconocene polymerisation catalysts on solid polymethylaluminoxane activating supports

Supplementary files

Article information

Article type
Research Article
Submitted
14 Jul 2020
Accepted
07 Sep 2020
First published
07 Sep 2020
This article is Open Access
Creative Commons BY-NC license

Mater. Chem. Front., 2020,4, 3226-3233

Physicochemical surface-structure studies of highly active zirconocene polymerisation catalysts on solid polymethylaluminoxane activating supports

A. F. R. Kilpatrick, N. H. Rees, Z. R. Turner, J. Buffet and D. O’Hare, Mater. Chem. Front., 2020, 4, 3226 DOI: 10.1039/D0QM00482K

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