Aluminoxane co-catalysts for the activation of a bis phenoxyimine titanium (IV) catalyst in the synthesis of disentangled ultra-high molecular weight polyethylene

Abstract

New activation systems for the bis[N-(3-tert-butylsalicylidene)pentafluoroanilinato] Ti (IV) dichloride catalyst (FI) for the synthesis of ultra-high molecular weight polyethylene (UHMWPE) with reduced entanglement density are explored. Together with the well-studied FI catalyst-methylaluminoxane (MAO) catalytic system, different aluminoxanes, namely polymethylaluminoxane-improved performance (PMAO), modified methylaluminoxane type 12 (MMAO12) and type 3A (MMAO3A) have been used. The catalyst activity increases with the addition of a co-catalyst modifier (2,6-di-tert-butyl-4-methylphenol, BHT). For an example when using MMAO3A as co-catalyst in combination with BHT the catalyst activity increases by tenfold. The synthesized UHMWPEs have been characterized via rheology, differential scanning calorimetry and uniaxial solid-state deformation to evaluate the influence that the different co-catalysts have on the catalyst activation and the entangled state of the polymer. Entanglement density increases when PMAO is used as a co-catalyst influencing the rheological response of the polymer melt and melting kinetics of nascent powder. Mechanical properties increase when MMAO12 is used in place of MMAO3A as co-catalyst. However, the earlier reported mechanical properties of UHMWPE synthesized using the FI/MAO are found to be better than those obtained using the co-catalysts investigated in this study.