Effect of a cocatalyst modifier in the synthesis of ultrahigh molecular weight polyethylene having reduced number of entanglements

Abstract The use of a hindered phenol to trap free trimethylaluminum (TMA) in methylaluminoxane (MAO) solutions has been reported to improve the performance of single‐site, homogeneous catalysts for olefin polymerization. In the present study, with the help of rheological analyses, we have investigated and compared the molecular weight, molecular weight distribution and entanglement density of ultrahigh molecular weight polyethylene synthesized with a single‐site catalyst activated by MAO and phenol‐modified MAO. While the number average molecular weight ( M n ) of the obtained polymers remains the same for both activations, a higher yield and a higher entanglement density are found in the initial stages of polymerization on using phenol‐modified MAO as the cocatalyst. These results suggest that on using the phenol‐modified MAO as activator, a higher number of active sites are obtained. Surprisingly in the presence of untreated MAO, a tail in the higher molecular mass region is produced. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013