Synthesis and microstructural study of stereoblock elastomeric polypropylenes from metallocene catalyst (2‐PhInd)2ZrCl2 activated with cocatalyst mixtures

Abstract Various elastomeric polypropylenes (PPs) are synthesized through homogeneous propylene polymerization with metallocene catalyst (2‐PhInd)2ZrCl2 in the presence of different cocatalyst mixtures: triethylaluminum (TEA)/methylaluminoxane (MAO) or triisobutylaluminum (TIBA)/MAO in the range of AlAlR3/AlMAO = 0.0–0.9. The cocatalyst formulation impacts the resultant polymer microstructure and the thermal and dynamic mechanical properties of the produced PPs. 13C NMR analysis of the polymers reveals essentially atactic PP, with mmmm = 7.9%, when AlAlR3/AlMAO = 0.0. The mmmm pentad content is maximized when AlAlR3/AlMAO = 0.8; for TIBA, mmmm = 23.5%; and for TEA, mmmm = 17.6%. Differential scanning calorimetry analysis and dynamic mechanical thermal analysis corroborate these findings. Specifically, Tm, ΔHm, and Tg are essentially maximized under these conditions, and the minimum damping is observed for AlAlR3/AlMAO = 0.6–0.8. 1H NMR analysis of the mixtures of catalyst and cocatalysts (without monomer) shows very minor differences for [Zr]:AlAlR3 in the range of 1:1–1:5. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013