Synthesis of ultrahigh-molecular-weight ethylene/1-octene copolymers with salalen titanium(iv) complexes activated by methyaluminoxane

Abstract

Two salalen titanium(IV) complexes ((H-salalen)TiCl₂ and (F-salalen)TiCl₂) containing hydrogen and fluorine respectively on the phenolate ring close to the imine were synthesized for the copolymerization of ethylene with 1-octene to prepare poly(ethylene-co-1-octene) in the presence of methylaluminoxane (MAO). The (F-salalen)TiCl₂/MAO showed higher catalytic activity and better copolymer characteristics such as a higher molecular weight, narrower molecular weight distribution, and higher 1-octene incorporation than (H-salalen)TiCl₂/MAO, which revealed that the electron-withdrawing conjugated effect introduced by fluorine substituents led to improvements on catalytic performance and thermal stability. The influences of copolymerization conditions including temperature, Al/Ti molar ratios and comonomer feed ratios on the copolymerization behavior of (F-salalen)TiCl₂/MAO and the copolymer microstructure were investigated in detail. Under the activation of MAO, the (F-salalen)TiCl₂ could produce ultrahigh molecular weight poly(ethylene-co-1-octene) with 1-octene incorporation ratios in the range of 0.9–3.1 mol% and exhibit relatively high activity. It could be inferred that long ethylene sequences in the copolymer were segregated by the isolated 1-octene units based on the ¹³C NMR characterization of the copolymer. Moreover, the thermal properties and crystallization of copolymers were determined by DSC and XRD and correlated to the ethylene sequence length distribution. The reactivity ratios calculated by the triad distribution in ¹³C NMR revealed the random comonomer distribution in the copolymer chain.