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Remarkably Active Non-Metallocene Ethylene Polymerization Catalysts

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journal contribution
posted on 28.04.1999, 00:00 by Douglas W. Stephan, Frédéric Guérin, Rupert E. v. H. Spence, Linda Koch, Xiaoliang Gao, Steve J. Brown, John W. Swabey, Qinyan Wang, Wei Xu, Peter Zoricak, Daryll G. Harrison
The bis(tri-tert-butylphosphinimide) complexes (t-Bu3PN)2TiCl2 (1) and (t-Bu3PN)2TiMe2 (2) were prepared and characterized crystallographically. Stoichiometric reactions of 2 with PhNMe2H[B(C6F5)4] in the presence of PMe3 afforded [(t-Bu3PN)2TiMe(PMe3)][B(C6F5)4] (3), while reaction of 2 with B(C6F5)3 affords (t-Bu3PN)2TiMe(μ-Me)B(C6F5)3 (4). Under laboratory conditions these compounds are effective ethylene polymerization catalysts. Under commercially relevant solution polymerization conditions, these catalysts are exceptionally active. Complex 2, when activated with Ph3C[B(C6F5)4], produces high molecular weight polyethylene with a narrow polydispersity at a rate approximately 4 times faster than the constrained geometry catalyst ((C5Me4SiMe2N-t-Bu)TiX2). As such, these catalysts represent the first non-cyclopentadienyl, single-site catalysts competitive with derivatives of metallocenes under commercially relevant polymerization conditions.