The effect of AlR3 on propylene polymerization byrac-(EBI)Zr(NMe2)2/AlR3/[CPh3][B(C6F5)4] catalyst

Ansa-zirconocene diamide complex rac-(EBI)Zr(NMe2)2 [rac-1, EBI = ethylene-1,2-bis(1-indenyl)] reacted with AlR3 (R = Me, Et, iBu) or Al(iBu2)H and then with [CPh3][B(C6F5)4] (2) in toluene in order to perform propylene polymerization by cationic alkylzirconium species, which are in situ generated during polymerization. Through the sequential NMR-scale reactions of rac-1 with AlR3 or Al(iBu2)H and then with 2, rac-1 was demonstrated to be transformed to the active alkyzirconium cations via alkylated intermediates of rac-1. The cationic species generated by using AlMe3, AlEt3, and Al(iBu2)H as alkylating reagents tend to become heterodinuclear complex; however, those by using bulky Al(iBu)3 become base-free [rac-(EBI)Zr(iBu)]+ cations. The activity of propylene polymerization by rac-1/AlR3/2 catalyst was deeply influenced by various parameters such as the amount and the type of AlR3, metallocene concentration, [Al]/[2] ratio, and polymerization temperature. Generally the catalytic systems using bulky alkylaluminum like Al(iBu)3 and Al(iBu)2H show higher activity but lower stereoregularity than those using less bulky AlMe3 and AlEt3. The alkylating reagent Al(iBu)3 is not a transfer agent as good as AlMe3 or AlEt3. The polymerization activities show maximum around [Al]/[2] ratio of 1.0 and increase monotonously with polymerization temperature. The overall activation energy of both rac-1/Al(iBu)3/2 and rac-1/Al(iBu)2H catalysts is 6.0 kcal/mol. As the polymerization temperature increases, the stereoregularity of the resulting polymer decreases markedly, which is demonstrated by the decrease of [mmmm] pentad value and by the increase of the amount of polymer soluble in low boiling solvent. The physical properties of polymers produced in this study were investigated by using 13C-NMR, differential scanning calorimetry (DSC), viscometry, and gel permeation chromatography (GPC). © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1523–1539, 1999

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