Key intermediates in metallocene-and post-metallocene-catalyzed polymerization |
| |
Authors: | E P Talsi K P Bryliakov N V Semikolenova V A Zakharov M Bochmann |
| |
Institution: | (1) Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, 630090, Russia;(2) University of East Anglia, Norwich, NR4 7TJ, UK |
| |
Abstract: | The structures of intermediates formed upon the activation by methylaluminoxane (MAO) of a wide range of metallocene and post-metallocene catalysts of olefin polymerization were studied by 13C, 1H, and 19F NMR. For all metallocenes considered (L2ZrCl2 and L2TiCl2), under conditions similar to real polymerization conditions (Al/Zr > 200), two types of intermediates were identified in the reaction solution, namely, heterodinuclear ion pairs L2 M(μ-Me)2AlMe2]+Me-MAO]? (III) and zwitterionic intermediates L2 MMe+←Me-Al?≡MAO (IV (M = Zr, Ti). The relative concentration of III increases with an increase in the Al/Zr ratio. In the post-metallocene/MAO catalytic systems, the reaction solution can be dominated either by heterodinuclear pairs of type III (bis(imino)pyridyl iron complexes) or by zwitterionic intermediates of type IV (half-titanocenes, complexes with restricted geometry). Both species III and species IV catalyze olefin polymerization. Both the species initiating polymerization, L 2 ′ TiMe(S)]+Me-MAO]?, and the species responsible for chain growth, L L 2 ′ TiP]+Me-MAO]? (P is the polymer chain, and S is a solvent molecule), were characterized in the bis(phenoxyimine) titanium complex/MAO system. |
| |
Keywords: | |
本文献已被 SpringerLink 等数据库收录! |
|