A Ziegler-type spherical cap model reveals early stage ethylene polymerization growth versus catalyst fragmentation relationships
Bossers, Koen W.; Mandemaker, Laurens D.B.; Nikolopoulos, Nikolaos; Liu, Yuanshuai; Rohnke, Marcus; de Peinder, Peter; Terlingen, Bas J.P.; Walther, Felix; Dorresteijn, Joren M.; Hartman, Thomas; Weckhuysen, Bert M.
(2022) Nature Communications, volume 13, issue 1
(Article)
Abstract
Polyolefin catalysts are characterized by their hierarchically complex nature, which complicates studies on the interplay between the catalyst and formed polymer phases. Here, the missing link in the morphology gap between planar model systems and industrially relevant spherical catalyst particles is introduced through the use of a spherical cap Ziegler-type
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catalyst model system for the polymerization of ethylene. More specifically, a moisture-stable LaOCl framework with enhanced imaging contrast has been designed to support the TiCl4 pre-active site, which could mimic the behaviour of the highly hygroscopic and industrially used MgCl2 framework. As a function of polymerization time, the fragmentation behaviour of the LaOCl framework changed from a mixture of the shrinking core (i.e., peeling off small polyethylene fragments at the surface) and continuous bisection (i.e., internal cleavage of the framework) into dominantly a continuous bisection model, which is linked to the evolution of the estimated polyethylene volume and the fraction of crystalline polyethylene formed. The combination of the spherical cap model system and the used advanced micro-spectroscopy toolbox, opens the route for high-throughput screening of catalyst functions with industrially relevant morphologies on the nano-scale.
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Keywords: General Chemistry, General Biochemistry,Genetics and Molecular Biology, General, General Physics and Astronomy
ISSN: 2041-1723
Publisher: Nature Publishing Group
Note: Funding Information: We would like to thank Jan Willem de Rijk (Utrecht University, UU) for his help to build the low-pressure polymerization set-up, Peter Thüne (Fontys/Differ) for sharing his knowledge on polyolefin model systems and Gert de Cremer (DSM Materials Science Center), Sven Kreisig (DSM Materials Science Center), John Severn (DSM Materials Science Center), Lanti Yang (SABIC), Nicolaas Friederichs (SABIC), Maarten Jongkind (Utrecht University, UU) and Silvia Zanoni (Utrecht University, UU) for helpful discussions. This work was funded by the Netherlands Organization for Scientific Research (NWO) in the frame of a NWO-TA grant (no. 731.015.203) with SABIC, DSM Resolve, Fontys University of Applied Sciences and the University of Maastricht. M.R. thanks the DFG for funding of the Hybrid-SIMS under grant number INST 162/544-1 FUGG. Funding Information: We would like to thank Jan Willem de Rijk (Utrecht University, UU) for his help to build the low-pressure polymerization set-up, Peter Thüne (Fontys/Differ) for sharing his knowledge on polyolefin model systems and Gert de Cremer (DSM Materials Science Center), Sven Kreisig (DSM Materials Science Center), John Severn (DSM Materials Science Center), Lanti Yang (SABIC), Nicolaas Friederichs (SABIC), Maarten Jongkind (Utrecht University, UU) and Silvia Zanoni (Utrecht University, UU) for helpful discussions. This work was funded by the Netherlands Organization for Scientific Research (NWO) in the frame of a NWO-TA grant (no. 731.015.203) with SABIC, DSM Resolve, Fontys University of Applied Sciences and the University of Maastricht. M.R. thanks the DFG for funding of the Hybrid-SIMS under grant number INST 162/544-1 FUGG. Publisher Copyright: © 2022, The Author(s).
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