Highly Active Immobilized Catalyst for Ethylene Polymerization: Neutral Single Site Y(III) Complex Bearing Bulky Silylallyl Ligand.

Autor: Chiari V; CPE Lyon, CNRS, UMR 5128, Catalysis, Polymerization, Processes and Materials (CP2M), Université Claude Bernard Lyon 1, 43 Bd du 11 Novembre 1918, 69616, Villeurbanne, France.; INEOS Olefins & Polymers Europe, Rue de Ransbeek 310, 1120, Bruxelles, Belgium., Rouge P; CPE Lyon, CNRS, UMR 5128, Catalysis, Polymerization, Processes and Materials (CP2M), Université Claude Bernard Lyon 1, 43 Bd du 11 Novembre 1918, 69616, Villeurbanne, France., Taam M; CPE Lyon, CNRS, UMR 5128, Catalysis, Polymerization, Processes and Materials (CP2M), Université Claude Bernard Lyon 1, 43 Bd du 11 Novembre 1918, 69616, Villeurbanne, France., Dugas PY; CPE Lyon, CNRS, UMR 5128, Catalysis, Polymerization, Processes and Materials (CP2M), Université Claude Bernard Lyon 1, 43 Bd du 11 Novembre 1918, 69616, Villeurbanne, France., Pannier G; INEOS Olefins & Polymers Europe, Rue de Ransbeek 310, 1120, Bruxelles, Belgium., Boyron O; CPE Lyon, CNRS, UMR 5128, Catalysis, Polymerization, Processes and Materials (CP2M), Université Claude Bernard Lyon 1, 43 Bd du 11 Novembre 1918, 69616, Villeurbanne, France., Szeto KC; CPE Lyon, CNRS, UMR 5128, Catalysis, Polymerization, Processes and Materials (CP2M), Université Claude Bernard Lyon 1, 43 Bd du 11 Novembre 1918, 69616, Villeurbanne, France., de Mallmann A; CPE Lyon, CNRS, UMR 5128, Catalysis, Polymerization, Processes and Materials (CP2M), Université Claude Bernard Lyon 1, 43 Bd du 11 Novembre 1918, 69616, Villeurbanne, France., Boisson C; CPE Lyon, CNRS, UMR 5128, Catalysis, Polymerization, Processes and Materials (CP2M), Université Claude Bernard Lyon 1, 43 Bd du 11 Novembre 1918, 69616, Villeurbanne, France., Taoufik M; CPE Lyon, CNRS, UMR 5128, Catalysis, Polymerization, Processes and Materials (CP2M), Université Claude Bernard Lyon 1, 43 Bd du 11 Novembre 1918, 69616, Villeurbanne, France.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2024 Oct 17; Vol. 30 (58), pp. e202402427. Date of Electronic Publication: 2024 Oct 02.
DOI: 10.1002/chem.202402427
Abstrakt: Exploring the surface organometallic chemistry on silica of highly electrophilic yttrium complexes is a relatively uncommon endeavor, particularly when focusing on tris-alkyl complexes characterized by Y-C σ-alkyl bonds. A drawback with this class of complexes once grafted on silica, is the frequent occurrence of alkyl transfer by ring opening of siloxane groups, resulting in a mixture of species. Herein, we employed a more stable homoleptic yttrium allyl complex bearing bulky η 3 -1,3-bis(trimethylsilyl)allyl ligand to limit this transfer reaction. This strategy has been validated by comparing the reactivity between [Y{ η 3 -1,3-C 3 H 3 (SiMe 3 ) 2 } 3 ] and [Y(o-CH 2 PhNMe 2 ) 3 ] with SiO 2-700 , where the undesired alkyl transfer reaction occurred for [Y(o-CH 2 PhNMe 2 ) 3 ] leading to a bipodal [(≡SiO) 2 Y(o-CH 2 PhNMe 2 )] as major surface species, 2, while [Y{ η 3 -1,3-C 3 H 3 (SiMe 3 ) 2 } 3 ] resulted selectively in a monopodal species, [(≡SiO)Y{η 3 -1,3-C 3 H 3 (SiMe 3 ) 2 } 2 ], 1. The materials obtained were characterized by DRIFT, solid state NMR, mass balance analysis and EXAFS. Catalyst 1 showed high activity compared to 2 in ethylene polymerization. The catalytic performance of this neutral catalyst 1 was extended to pre-industrial scale in the presence of hydrogen and 1-hexene. An unprecedented activity, up to 7400 g PE  g cat -1  h -1 was obtained even with very low concentration of scavenger AliBu 3 (TIBA/Y=1.2). The obtained HDPE exhibited desired spherical particle morphology with broad molar mass distribution.
(© 2024 Wiley-VCH GmbH.)
Databáze: MEDLINE
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