Reversible Chain Transfer between Organoyttrium Cations and Aluminum : Synthesis of Aluminum-Terminated Polyethylene with Extremely Narrow Molecular-Weight Distribution

Titelangaben

Kretschmer, Winfried ; Meetsma, Auke ; Hessen, Bart ; Schmalz, Thomas ; Qayyum, Sadaf ; Kempe, Rhett:
Reversible Chain Transfer between Organoyttrium Cations and Aluminum : Synthesis of Aluminum-Terminated Polyethylene with Extremely Narrow Molecular-Weight Distribution.
In: Chemistry : a European Journal. Bd. 12 (2006) Heft 35 . - S. 8969-8978.
ISSN 1521-3765
DOI: https://doi.org/10.1002/chem.200600660

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Abstract

Aminopyridinato-ligand-stabilized organoyttrium cations are accessible in very good yield through alkane elimination from trialkyl yttrium complexes with sterically demanding aminopyridines, followed by abstraction of one of the two alkyl functions using ammonium borates. At 80 °C and in the presence of small amounts of aluminum alkyl compounds, very high ethylene polymerization activities are observed if very bulky aminopyridinato ligands are used. During these polymerizations a reversible polyethylene chain transfer is observed between the organoyttrium cations and aluminum alkyls. The chain-transfer catalyst system described here is able to produce relatively long-chain (up to 4000 g mol−1) Al-terminated polyethylene with a molecular-weight distribution <1.1. In the synthesis of higher molecular PE a slight increase in polydispersity with increasing chain length (15 600 g mol−1, ∼1.4) is observed owing to reduced reversibility caused by higher viscosity and precipitation of polymer chains (temperature of 80–100 °C).