New chiral [N,N,N]‐ligand containing titanium/zirconium precatalysts for 1‐hexene polymerization

The ring‐opening reaction of (S)‐N‐tosyl‐2‐phenylaziridine by benzylamine in ethanol at 80 °C resulted in the formation of the (S,S)‐bis(N‐tosyl‐2‐amino‐2‐phenylethyl)benzylamine ligand in a 60% yield. The corresponding titanium complex, 1‐TiCl₂, was prepared by the reaction of the dilithiated parent ligand with TiCl₄. This precatalyst, in combination with methylaluminoxane, was capable of polymerizing 1‐hexene with good activities, resulting in the formation of good yields of low‐dispersity, high‐molecular‐weight polymers at low temperatures but higher yields of lower molecular weight polymers at higher temperatures. ¹H and ¹³C NMR spectra of the polymers suggested high isotacticity and predominant chain termination via β‐hydride elimination. The enantiomerically pure catalysts, (R,R)‐1‐TiCl₂ and (S,S)‐1‐TiCl₂, showed nearly identical polymerization results at various polymerization temperatures. However, when the catalyst was prepared from a racemic ligand, the obtained polymers had lower molecular weights with a bimodal distribution. This observation suggested diastereomeric aggregation of the racemic catalyst, which was well supported by the NMR studies, and a modified Arrhenius plot (the natural logarithm of the number‐average molecular weight vs the reciprocal of the temperature) also showed sigmoidal behavior, indicating the existence of two or more active species. Analogous zirconium precatalysts showed similar results in the polymerization of 1‐hexene. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4006–4014, 2006