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

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.

The influences of electronic effect and isomerization of salalen titanium(iv) complexes on ethylene polymerization in the presence of methylaluminoxane.

Herein, two salalen titanium(iv) complexes were synthesized and characterized. These complexes coexisted as two isomers in certain conditions and underwent isomerization, as evidenced by 1H NMR spectroscopy. Furthermore, the molar ratio of the two isomers ranged from 100 : 15 at 30 °C to 100 : 34 at 120 °C, driven by thermal energy, based on variable temperature 1H NMR characterization. Both complexes were employed as catalysts for ethylene polymerization in the presence of methylaluminoxane (MAO). The influence of the electronic effects of different substituent groups at the ortho position of the phenolate on ethylene polymerization behaviors, molecular weight and molecular weight distributions of the resulting polyethylene was investigated. The fluorinated salalen titanium(iv) complex revealed relatively high catalytic activity and thermal stability owing to the electron-withdrawing inductive effect. Moreover, disentangled linear polyethylene with ultrahigh molecular weight (M w up to 3000 kDa) and narrow molecular weight distribution (M w/M n ∼ 2) was obtained in the polymerization temperature range of 30 °C to 50 °C.