Ethylene and Propylene Polymerization Using In Situ Supported Me2Si(Ind)2ZrCl2 Catalyst: Experimental and Theoretical Study

Abstract

AbstractSummary: Me2Si(Ind)2ZrCl2 was in situ immobilized onto SMAO and used for ethylene and propylene polymerization in the presence of TEA or TIBA as cocatalyst. The catalytic system Me2Si(Ind)2ZrCl2/SMAO exhibited different behavior depending on the amount and nature of the alkylaluminum employed and on the monomer type. The catalyst activity was nearly 0.4 kg polymer · g cat−1 · h−1 with both cocatalysts for propylene polymerization. Similar activities were observed for ethylene polymerization in the presence of TIBA. When ethylene was polymerized using TEA at an Al/Zr molar ratio of 250, the activity was 10 times higher. Polyethylenes made by in situ supported or homogeneous catalyst systems had practically the same melting point (Tm). On the other hand, poly(propylenes) made using in situ supported catalyst systems had a slightly lower Tm than poly(propylenes) made using homogeneous catalyst systems. The nature and amount of the alkylaluminum also influenced the molar mass. The poly(propylene) molar mass was higher when TIBA was the cocatalyst. The opposite behavior was observed for the polyethylenes. Concerning the alkylaluminum concentration, the molar mass of the polymers decreased as the amount of TEA increased. In the presence of TIBA, the polyethylene's molar mass was almost the same, independent of the alkylaluminum concentration, and the poly(propylene) molar mass increased with increasing amounts of cocatalyst. The deconvolution of the GPC curves showed 2 peaks for the homogeneous system and 3 peaks for the heterogeneous in situ supported system. The only exception was observed when TEA was used at an Al/Zr molar ratio of 500, where the best fit was obtained with 2 peaks. Based on the GPC deconvolution results and on the theoretical modeling, a proposal for the active site structure was made.Molar mass distribution deconvolution of polyethylene prepared with the system Me2Si(Ind)2ZrCl2/SMAO/TIBA with 500 mol/mol of alkylaluminum as cocatalyst.magnified imageMolar mass distribution deconvolution of polyethylene prepared with the system Me2Si(Ind)2ZrCl2/SMAO/TIBA with 500 mol/mol of alkylaluminum as cocatalyst.