Novel alkoxo-titanium(IV) complexes with fluorinated 2-hydroxymethylphenol derivatives as catalysts for the formation of ultra-high molecular weight polyethylene nascent reactor powders

[Display omitted] •A novel Ti(IV) complexes with fluorinated 2-hydroxymethylphenoles were synthesized.•Complexes activated by alkylaluminum chlorides and MgBu2 catalyzed UHMWPE formation.•The most active pre-catalysts contain bis-(trifluoromethyl)-carbinol fragment.•The UHMWPE powders were solid-state processed into high strength and high modulus oriented films. A series of titanium (IV) complexes 3a–g stabilized by fluorinated derivatives of 2-hydroxymethylphenol have been synthesized; their composition and structure have been confirmed by NMR, IR-spectroscopy and elemental analysis. The structures of compounds 3c, 3f and 3g have been unambiguously established by X-ray diffraction study. The complexes in the presence of a binary cocatalysts {alkyl aluminum chloride + MgBu2} catalyze ethylene polymerization to afford Ultra High Molecular Weight Polyethylene (UHMWPE). The effects of substituents in the ligands on the catalytic activity and properties of the obtained polymer – molecular weight, DSC melting behavior, and morphology of nascent reactor powders have been investigated. UHMWPE samples were processed by a solid-state uniaxial deformation into high-strength (up to 2.65 GPa) and high-modulus (over 140 GPa) oriented film tapes, which indirectly indicates a low degree of entanglements between the macromolecular chains.