A Ziegler-type spherical cap model reveals early stage ethylene polymerization growth versus catalyst fragmentation relationships

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 i...

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Published in:Nature communications Vol. 13; no. 1; pp. 4954 - 11
Main Authors: 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.
Format: Journal Article
Language:English
Published: London Nature Publishing Group UK 24.08.2022
Nature Publishing Group
Nature Portfolio
Subjects:
140/146
147/135
147/3
639/638/440/950
639/638/77/885
639/638/77/887
Catalysts
Fragmentation
High-throughput screening
Humanities and Social Sciences
Magnesium chloride
Moisture effects
Morphology
multidisciplinary
Polyethylene
Polyethylenes
Polymerization
Polymers
Polyolefins
Science
Science (multidisciplinary)
Spectroscopy
Spherical caps
ISSN:2041-1723, 2041-1723
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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 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 TiCl 4 pre-active site, which could mimic the behaviour of the highly hygroscopic and industrially used MgCl 2 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. Ziegler-type polyolefin catalysts have proven to be hard to characterize. Here the authors present a model system consisting of patterned LaOCl spherical caps, simulating bulk particles while facilitating the use of micro(-spectro)scopic characterization techniques specifically aimed at surfaces.
AbstractList Ziegler-type polyolefin catalysts have proven to be hard to characterize. Here the authors present a model system consisting of patterned LaOCl spherical caps, simulating bulk particles while facilitating the use of micro(-spectro)scopic characterization techniques specifically aimed at surfaces.
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 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. Ziegler-type polyolefin catalysts have proven to be hard to characterize. Here the authors present a model system consisting of patterned LaOCl spherical caps, simulating bulk particles while facilitating the use of micro(-spectro)scopic characterization techniques specifically aimed at surfaces.
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 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 TiCl 4 pre-active site, which could mimic the behaviour of the highly hygroscopic and industrially used MgCl 2 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. Ziegler-type polyolefin catalysts have proven to be hard to characterize. Here the authors present a model system consisting of patterned LaOCl spherical caps, simulating bulk particles while facilitating the use of micro(-spectro)scopic characterization techniques specifically aimed at surfaces.
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 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.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 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.
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 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 TiCl 4 pre-active site, which could mimic the behaviour of the highly hygroscopic and industrially used MgCl 2 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.
ArticleNumber 4954
Author de Peinder, Peter
Bossers, Koen W.
Nikolopoulos, Nikolaos
Mandemaker, Laurens D. B.
Hartman, Thomas
Weckhuysen, Bert M.
Rohnke, Marcus
Dorresteijn, Joren M.
Liu, Yuanshuai
Terlingen, Bas J. P.
Walther, Felix
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Snippet Polyolefin catalysts are characterized by their hierarchically complex nature, which complicates studies on the interplay between the catalyst and formed...
Ziegler-type polyolefin catalysts have proven to be hard to characterize. Here the authors present a model system consisting of patterned LaOCl spherical caps,...
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SubjectTerms 140/146
147/135
147/3
639/638/440/950
639/638/77/885
639/638/77/887
Catalysts
Fragmentation
High-throughput screening
Humanities and Social Sciences
Magnesium chloride
Moisture effects
Morphology
multidisciplinary
Polyethylene
Polyethylenes
Polymerization
Polymers
Polyolefins
Science
Science (multidisciplinary)
Spectroscopy
Spherical caps
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Title A Ziegler-type spherical cap model reveals early stage ethylene polymerization growth versus catalyst fragmentation relationships
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