Novel titanium (IV) complexes with 1,2-diolate ligands: Synthesis, structure and catalytic activities in ultra-high molecular weight polyethylene production

A series of titanium (IV) complexes 3a-f stabilized by 1,2-diolate ligands 2 a-e have been synthesized. Structures of complexes 3d and 3e have been determined by X-ray diffraction. Titanium atoms in these complexes have a distorted square-pyramidal environment. All resulting complexes are highly active in ethylene polymerization in the presence of {3Et2AlCl + MgBu2} or {1.5Et3Al2Cl3 + MgBu2} binary co-catalysts. In the latter case, higher molecular weights of UHMWPE samples (up to 7.7 106) are achieved. Obtained polymers are suitable for the modern processing methods – the solvent-free solid state formation of super high-strength (over 2.0 – 2.8 GPa) and high-modulus (up to 145 GPa) oriented film tapes. © 201

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

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. © 2019 Elsevier B.V

Novel titanium(IV) diolate complexes with additional O-donor as precatalyst for the synthesis of ultrahigh molecular weight polyethylene with reduced entanglement density: Influence of polymerization conditions and its implications on mechanical properties

New alkoxo-titanium(IV) complexes with diolate ligand containing additional donor oxygen atom have been synthesized from readily available and scalable precursors. The structure of complex 4 was established by X-ray diffraction. Titanium atom adopts a distorted tetrahedral geometry formed by six oxygen atoms of ligands. The resulting complexes 3–4 are moderately or highly active in ethylene polymerization in the presence of {EtnAlCl3–n + Bu2Mg} binary cocatalysts. The influence of the nature of the solvent, the organoaluminum cocatalyst and the polymerization temperature on the activity of catalytic systems, and the properties of the resulting polymers were studied. The obtained polymers are linear polyethylene of ultrahigh molecular weight (up to 5.8·106 g mol−1) with a broad molecular weight distribution. The polymers are suitable for the modern methods of polymer processing—the solventless solid-state formation of super high-strength (breaking strength up to 2.8 GPa) and high-modulus (elastic modulus up to 140 GPa) oriented films and film tapes. The possibility of scaling up the synthesis of ultrahigh molecular weight polyethylene (UHMWPE) without a significant drop in the productivity of the catalytic system and polymer properties is shown. UHMWPE samples have been investigated by small-angle X-ray scattering (SAXS) methods to study the structural changes induced by solid-state drawing of nascent reactor powders. © 2021 John Wiley & Sons, Ltd