Catalytic systems containing TiCl₄ or TiCl₃, THF, organomagnesium (n-Bu₂Mg) and organoaluminum compounds capable of producing ultrahigh molecular weight polyethylene (UHMWPE) were developed. The resulting polymers were characterized by a molecular weight in the range of (1.8–7.8) × 10⁶ Da and desirable morphology, suitable for modern methods of polymer processing—the solvent-free solid-state processing of superhigh-strength (tensile strength up to 2.1 GPa) and high-modulus (elastic modulus up to 125 GPa) oriented films and film tapes. The impacts of a THF additive, the oxidation state of the titanium atom, and the composition and nature of the nontransition organometallic compounds on the formation of catalytic systems for UHMWPE production were evaluated. The results indicate the suitability of individual titanium chloride tetrahydrofuran complex application for the formation of THF-containing catalytic systems. This approach also results in a significant increase in the system catalytic activity and mechanical properties of UHMWPE. The catalysts based on Ti(III) were inferior to systems containing Ti(IV) in productivity but were markedly superior in the mechanical properties of UHMWPE.

A series of ultrahigh molecular weight polyethylenes with viscosity-average molecular weights in the range of 1.6–5.6 × 10⁶ have been prepared by using a novel Ziegler–Natta-type catalytic system—TiCl₄/2,2′-dimethoxy-1,1′-binaphthalene/Et₃Al₂Cl₃/Bu₂Mg at different temperatures (T_poly) in the range between 10 and 70 °C in toluene. The morphology of the nascent reactor powders has been studied by scanning electron microscopy, wide-angle X-ray diffraction, and the DSC melting behavior. Polymers are suitable for the modern processing methods—the solvent-free solid-state formation of super high-strength (tensile strength over 1.8–2.5 GPa) and high-modulus (elastic modulus up to 136 GPa) oriented film tapes. With decrease of T_poly, the drawability of the reactor powders increased significantly.