Homogeneous Tandem Catalysis of Bis(2-decylthioethyl)amine−Chromium Trimerization Catalyst in Combination with Metallocene Catalysts

Homogeneous tandem catalysis involving a highly selective, aluminoxane-activated bis(2-decylthioethyl)amine·CrCl 3 complex for the synthesis of 1-hexene in tandem with a number of metallocene catalysts is discussed. Analysis by means of DSC, CRYSTAF, HT-GPC, 13 C NMR, and FTIR suggests that copolymers of 1-hexene and ethylene are produced with significant selectivity toward 1-hexene as comonomer. The selectivity of 1-hexene incorporation by the metallocene catalysts follows the trend in the order [Me 2 Si(2-Me-Ind) 2 ]ZrCl 2 > [Me 2 Si(2,3,4,5-Me-Cp)( t -Bu-N)]TiCl 2 > Cp 2 ZrCl 2 . The highly selective nature of the ethylene trimerization catalyst employed in this study means that the industrial application of tandem catalysis is becoming increasingly viable since it approaches conventional 1-hexene LLDPE in terms of polymer microstructure control.