TY - JOUR
T1 - Immobilization of [VCl3(N-2,6-Me2C6H3)] Complex on Silica Supports
T2 - Synthesis and Catalytic Testing for Ethylene Polymerization
AU - Fiorentino, Antonio
AU - Panariti, Persi
AU - van Turnhout, Lars
AU - Spronck, Mitch
AU - Klein, Axel
AU - Schmitz, Simon
AU - Rastogi, Sanjay
AU - Blom, Burgert
AU - Romano, Dario
N1 - Funding Information:
The authors greatly acknowledge the help of Prof. Frank Wombacher, Institute of Geology and Mineralogy at the University of Cologne for the ICP-MS measurements and Thomas Fischer, University of Cologne, Department of Chemistry, for the TEM/EDX measurements. The authors wish to thank the Maastricht Science Program and the Aachen-Maastricht Institute for Biobased Materials for the financial contribution. This research has also been made possible with the support of the Dutch province of Limburg.
Publisher Copyright:
Copyright © 2020 American Chemical Society.
PY - 2020/7/15
Y1 - 2020/7/15
N2 - The heterogenization of 2,6-dimethylarylimido-vanadium(V) dichloride via chemical tethering on insoluble silica supports is reported. The effects of the silica particle size, drying conditions, and the reaction time were investigated. The drying conditions of the support were found to be a crucial parameter: drying temperatures over 400 °C were needed to achieve successful catalysis. The supported catalytic systems were characterized by Fourier-transform infrared (FT-IR) spectroscopy, transmission electron microscopy-energy-dispersive X-ray (TEM-EDX), and inductively coupled plasma mass spectroscopy (ICP-MS), while the polymers were characterized by FT-IR, differential scanning calorimetry (DSC), and rheology. Ethylene polymerization tests were performed employing the prepared heterogenized catalysts with methylaluminoxane/diethylaluminum chloride as a cocatalyst. The supported catalyst precursor, when activated with diethylaluminum chloride, promotes the synthesis of polyethylene with seemingly controlled particle size in the absence of reactor fouling, suggesting the successful immobilization of the complex over the inert support. The resulting polymer shows features of ultrahigh-molecular-weight polyethylene (UHMWPE). These findings present a proof-of-concept for a new approach toward the heterogenization of arylimido-vanadium complexes.
AB - The heterogenization of 2,6-dimethylarylimido-vanadium(V) dichloride via chemical tethering on insoluble silica supports is reported. The effects of the silica particle size, drying conditions, and the reaction time were investigated. The drying conditions of the support were found to be a crucial parameter: drying temperatures over 400 °C were needed to achieve successful catalysis. The supported catalytic systems were characterized by Fourier-transform infrared (FT-IR) spectroscopy, transmission electron microscopy-energy-dispersive X-ray (TEM-EDX), and inductively coupled plasma mass spectroscopy (ICP-MS), while the polymers were characterized by FT-IR, differential scanning calorimetry (DSC), and rheology. Ethylene polymerization tests were performed employing the prepared heterogenized catalysts with methylaluminoxane/diethylaluminum chloride as a cocatalyst. The supported catalyst precursor, when activated with diethylaluminum chloride, promotes the synthesis of polyethylene with seemingly controlled particle size in the absence of reactor fouling, suggesting the successful immobilization of the complex over the inert support. The resulting polymer shows features of ultrahigh-molecular-weight polyethylene (UHMWPE). These findings present a proof-of-concept for a new approach toward the heterogenization of arylimido-vanadium complexes.
KW - MOLECULAR-WEIGHT POLYETHYLENE
KW - OLEFIN POLYMERIZATION
KW - COCATALYST
KW - SURFACE
U2 - 10.1021/acs.iecr.0c01908
DO - 10.1021/acs.iecr.0c01908
M3 - Article
SN - 0888-5885
VL - 59
SP - 12710
EP - 12718
JO - Industrial & Engineering Chemistry Research
JF - Industrial & Engineering Chemistry Research
IS - 28
ER -