Tetrahydrofuran in TiCl4/THF/MgCl2: a Non-Innocent Ligand for Supported Ziegler-Natta Polymerization Catalysts

Etienne Grau (1, 2, 3) , Anne Lesage (4) , Sébastien Norsic (2) , Christophe Copéret (1) , Vincent Monteil (2) , Philippe Sautet (3)

1 Laboratory of Inorganic Chemistry
2 C2P2 - Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265
3 LC - Laboratoire de Chimie - UMR5182
4 ISA - Centre de RMN à très hauts champs

While Ziegler-Natta (ZN) polymerization is one of the most important catalytic industrial processes, the atomic-scale nature of the catalytically active surface species remains unknown. Coupling high-resolution solid-state NMR spectroscopy with periodic density functional theory (DFT) calculations, we demonstrate that the major surface species in the ZN precatalyst corresponds to an alkoxy Ti(TV) surface species, which probably results from the ring-opening of tetrahydrofuran (THF) on a cationic Ti(IV) species.

Mots clés: ethylene polymerization; Ziegler-Natta catalysis; surface chemistry; SS-NMR spectroscopy; DFT calculations; HETEROGENEOUS CATALYSIS; PROPENE POLYMERIZATION; OLEFIN POLYMERIZATION; 1ST PRINCIPLES; DISCOVERY; MGCL2

Domaines: Chimie théorique et/ou physique; Polymères; Matériaux; Chimie

Etienne Grau, Anne Lesage, Sébastien Norsic, Christophe Copéret, Vincent Monteil, et al.. Tetrahydrofuran in TiCl4/THF/MgCl2: a Non-Innocent Ligand for Supported Ziegler-Natta Polymerization Catalysts. ACS Catalysis, 2013, 3 (1), pp.52-56. ⟨10.1021/cs300764h⟩. ⟨hal-00799544⟩