Role of Titanium in Ti/SiO2-Supported Metallocene-based Olefin Polymerization Catalysts. Part 2: Particle Fragmentation

Silvia Zanoni; Nikolaos Nikolopoulos; Alexandre Welle; Virginie Cirriez; Bert M. Weckhuysen

doi:10.1002/cctc.202300222

Role of Titanium in Ti/SiO₂-Supported Metallocene-based Olefin Polymerization Catalysts. Part 2: Particle Fragmentation

Silvia Zanoni, Nikolaos Nikolopoulos, Alexandre Welle, Virginie Cirriez, Bert M. Weckhuysen^*

^*Corresponding author for this work

Sub Organic Chemistry and Catalysis

Research output: Contribution to journal › Article › Academic › peer-review

Abstract

A commercial SiO₂ modified by the addition of a TiO₂ layer on its surface and pore walls offers a support for metallocene-based ethylene polymerization catalysts with a 35 % improved catalytic activity. The effect of such support modification on the catalyst particle fragmentation during polymerization reactions were assessed. This was performed by exposing the internal cross-section of several SiO₂ and Ti/SiO₂-based metallocene catalyst particles, polymerized at a wide range of reaction conditions, with a Focused-Ion Beam Scanning Electron Microscope (FIB-SEM), followed by a semi-quantitative analysis of polymer, catalyst and macropores of each 2D image obtained. The titanation of the SiO₂ lead to a support framework that fractures earlier and more efficiently. This was evidenced by the presence of several empty (polymer-free) cracks along the support dense-shell, found more extensively in the Ti-modified polymerized catalyst particle, which also resulted in a more sustained polymerized particles macroporosity during the course of the reaction.

Original language	English
Article number	e202300222
Pages (from-to)	1-12
Number of pages	12
Journal	ChemCatChem
Volume	15
Issue number	10
DOIs	https://doi.org/10.1002/cctc.202300222
Publication status	Published - 19 May 2023

Bibliographical note

Funding Information:
Coen Mulder and Helen de Waard (Utrecht University, UU) are acknowledged for performing the ICP‐OES experiments and Koen Bossers (UU) for the fruitful discussion. The authors acknowledge project funding from TotalEnergies.

Publisher Copyright:
© 2023 The Authors. ChemCatChem published by Wiley-VCH GmbH.

Funding

Coen Mulder and Helen de Waard (Utrecht University, UU) are acknowledged for performing the ICP‐OES experiments and Koen Bossers (UU) for the fruitful discussion. The authors acknowledge project funding from TotalEnergies.

Keywords

fragmentation
metallocene
polymerization
support
titania

Access to Document

10.1002/cctc.202300222Licence: CC BY-NC-ND

ChemCatChem - 2023 - Zanoni - Role of Titanium in Ti SiO2‐Supported Metallocene‐based Olefin Polymerization Catalysts PartFinal published version, 17.5 MBLicence: CC BY-NC-ND

Cite this

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abstract = "A commercial SiO2 modified by the addition of a TiO2 layer on its surface and pore walls offers a support for metallocene-based ethylene polymerization catalysts with a 35 \% improved catalytic activity. The effect of such support modification on the catalyst particle fragmentation during polymerization reactions were assessed. This was performed by exposing the internal cross-section of several SiO2 and Ti/SiO2-based metallocene catalyst particles, polymerized at a wide range of reaction conditions, with a Focused-Ion Beam Scanning Electron Microscope (FIB-SEM), followed by a semi-quantitative analysis of polymer, catalyst and macropores of each 2D image obtained. The titanation of the SiO2 lead to a support framework that fractures earlier and more efficiently. This was evidenced by the presence of several empty (polymer-free) cracks along the support dense-shell, found more extensively in the Ti-modified polymerized catalyst particle, which also resulted in a more sustained polymerized particles macroporosity during the course of the reaction.",

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N1 - Funding Information: Coen Mulder and Helen de Waard (Utrecht University, UU) are acknowledged for performing the ICP‐OES experiments and Koen Bossers (UU) for the fruitful discussion. The authors acknowledge project funding from TotalEnergies. Publisher Copyright: © 2023 The Authors. ChemCatChem published by Wiley-VCH GmbH.

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N2 - A commercial SiO2 modified by the addition of a TiO2 layer on its surface and pore walls offers a support for metallocene-based ethylene polymerization catalysts with a 35 % improved catalytic activity. The effect of such support modification on the catalyst particle fragmentation during polymerization reactions were assessed. This was performed by exposing the internal cross-section of several SiO2 and Ti/SiO2-based metallocene catalyst particles, polymerized at a wide range of reaction conditions, with a Focused-Ion Beam Scanning Electron Microscope (FIB-SEM), followed by a semi-quantitative analysis of polymer, catalyst and macropores of each 2D image obtained. The titanation of the SiO2 lead to a support framework that fractures earlier and more efficiently. This was evidenced by the presence of several empty (polymer-free) cracks along the support dense-shell, found more extensively in the Ti-modified polymerized catalyst particle, which also resulted in a more sustained polymerized particles macroporosity during the course of the reaction.

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