Ethylene polymerization using zirconocenes supported on pentafluorophenyl-modified solid polymethylaluminoxane

Three permethylindenyl zirconocenes have been supported on a hexane-insoluble form of polymethylaluminoxane modified with 40 wt % pentafluorophenol (sMAO(PFP)). The solid precatalysts were characterized by solid-state nuclear magnetic resonance spectroscopy, and their ethylene polymerization activit...

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Main Authors: Lamb, JV, Buffet, J-C, Turner, ZR, O'Hare, D
Format: Journal article
Language:English
Published: American Chemical Society 2020
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author Lamb, JV
Buffet, J-C
Turner, ZR
O'Hare, D
author_facet Lamb, JV
Buffet, J-C
Turner, ZR
O'Hare, D
author_sort Lamb, JV
collection OXFORD
description Three permethylindenyl zirconocenes have been supported on a hexane-insoluble form of polymethylaluminoxane modified with 40 wt % pentafluorophenol (sMAO(PFP)). The solid precatalysts were characterized by solid-state nuclear magnetic resonance spectroscopy, and their ethylene polymerization activity was studied. When supported on sMAO(PFP), Me2SB(Cp,I*)ZrX2 ({(η5-C9Me6)Me2Si(η5-C5H4)}ZrX2; X = Cl, CH2Ph, and Me) showed ethylene polymerization activities up to 25% higher than when supported on unmodified sMAO with the same [Al]0/[Zr]0 catalyst loading: activities of 6454 and 5144 kgPE molZr–1 h–1 bar–1 at 80 °C for Me2SB(Cp,I*)ZrCl2 supported on sMAO(PFP) and sMAO, respectively. The systems produced relatively low-molecular weight polyethylenes (Mw < 170 kg mol–1 at 80 °C) with minimal defects and branching. The polymers showed good flowability, although they displayed more aggregated morphologies than polyethylenes produced from unmodified sMAO. On increasing the solvent volume fivefold, the activity and polymer molecular weights approximately doubled.
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spelling oxford-uuid:97612122-f608-4094-af91-69a07d49f01f2022-03-26T23:59:03ZEthylene polymerization using zirconocenes supported on pentafluorophenyl-modified solid polymethylaluminoxaneJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:97612122-f608-4094-af91-69a07d49f01fEnglishSymplectic ElementsAmerican Chemical Society 2020Lamb, JVBuffet, J-CTurner, ZRO'Hare, DThree permethylindenyl zirconocenes have been supported on a hexane-insoluble form of polymethylaluminoxane modified with 40 wt % pentafluorophenol (sMAO(PFP)). The solid precatalysts were characterized by solid-state nuclear magnetic resonance spectroscopy, and their ethylene polymerization activity was studied. When supported on sMAO(PFP), Me2SB(Cp,I*)ZrX2 ({(η5-C9Me6)Me2Si(η5-C5H4)}ZrX2; X = Cl, CH2Ph, and Me) showed ethylene polymerization activities up to 25% higher than when supported on unmodified sMAO with the same [Al]0/[Zr]0 catalyst loading: activities of 6454 and 5144 kgPE molZr–1 h–1 bar–1 at 80 °C for Me2SB(Cp,I*)ZrCl2 supported on sMAO(PFP) and sMAO, respectively. The systems produced relatively low-molecular weight polyethylenes (Mw < 170 kg mol–1 at 80 °C) with minimal defects and branching. The polymers showed good flowability, although they displayed more aggregated morphologies than polyethylenes produced from unmodified sMAO. On increasing the solvent volume fivefold, the activity and polymer molecular weights approximately doubled.
spellingShingle Lamb, JV
Buffet, J-C
Turner, ZR
O'Hare, D
Ethylene polymerization using zirconocenes supported on pentafluorophenyl-modified solid polymethylaluminoxane
title Ethylene polymerization using zirconocenes supported on pentafluorophenyl-modified solid polymethylaluminoxane
title_full Ethylene polymerization using zirconocenes supported on pentafluorophenyl-modified solid polymethylaluminoxane
title_fullStr Ethylene polymerization using zirconocenes supported on pentafluorophenyl-modified solid polymethylaluminoxane
title_full_unstemmed Ethylene polymerization using zirconocenes supported on pentafluorophenyl-modified solid polymethylaluminoxane
title_short Ethylene polymerization using zirconocenes supported on pentafluorophenyl-modified solid polymethylaluminoxane
title_sort ethylene polymerization using zirconocenes supported on pentafluorophenyl modified solid polymethylaluminoxane
work_keys_str_mv AT lambjv ethylenepolymerizationusingzirconocenessupportedonpentafluorophenylmodifiedsolidpolymethylaluminoxane
AT buffetjc ethylenepolymerizationusingzirconocenessupportedonpentafluorophenylmodifiedsolidpolymethylaluminoxane
AT turnerzr ethylenepolymerizationusingzirconocenessupportedonpentafluorophenylmodifiedsolidpolymethylaluminoxane
AT ohared ethylenepolymerizationusingzirconocenessupportedonpentafluorophenylmodifiedsolidpolymethylaluminoxane