Improving microisotacticity of Ziegler–Natta catalyzed polypropylene by using triethylaluminum/triisobutylaluminum mixtures as cocatalyst

Propylene was polymerized with TiCl4/Di/MgCl2 catalyst and cocatalysts containing triethylaluminum (TEA) and triisobutylaluminum (TiBA) in the presence of Ph2Si(OMe)2 (external donor) and hydrogen. Chain structure of the formed polypropylene (PP) was characterized by temperature-rise elution fractionation (TREF) combined with DSC and 13C NMR analysis of the main fractions. Increasing the amount of TiBA in cocatalyst leads to decrease of isotactic index of PP, meanwhile the microisotacticity of the main TREF fractions of PP was enhanced. PP produced with the catalyst activated by a 50/50 TEA/TiBA mixture has the same content of highly isotactic chains as PP produced with the TEA activated catalyst, but main TREF fractions of the former has higher microisotacticity than the later. Fast alkyl exchanges in TEA/TiBA mixtures are found by 1H NMR analysis of the mixtures. By analyzing alkanes released from hydrolyzed catalysts that have been treated with the cocatalyst, alkylation power of TEA/TiBA mixture was found to decrease with increasing its TiBA content. The effects of TEA/TiBA mixture in propylene polymerization is explained by the weaker alkylation power and lower Lewis acidity of the mixed alkylaluminums than pure TEA. Decrease in the alkylation power leads to reduction of active centers with the highest stereospecificity, meanwhile decrease in Lewis acidity intensified the role of De in enhancing stereospecificity of different active centers. When the amount of TiBA in TEA/TiBA mixture falls in a suitable range, the later effect becomes dominant, and evident improvement in microisotacticity of PP can be achieved.