New Titanium(IV)-Alkoxide Complexes Bearing Bidentate OO Ligand with the Camphyl Linker as Catalysts for High-Temperature Ethylene Polymerization and Ethylene/1-Octene Copolymerization.

In order to increase the thermal stability of olefin polymerization precatalysts, new titanium(IV) complexes with diolate ligands differing in the degree of steric hindrances were synthesized from readily available precursor (±)camphor. The structures of the complexes were established by X-ray diffraction. Complexes in the presence of an activator {EtAlCl + BuMg} catalyzed the synthesis of UHMWPE with an M up to 10 million and a productivity of up to 3300 kg/mol·atm·h. The obtained polymers are obviously characterized by a low density of macromolecular entanglement, which makes it possible to use the solid-phase method for their processing. The mechanical characteristics of the oriented UHMWPE films had a breaking strength up to 2.7 GPa and an elastic modulus of up to 151 GPa. The precatalysts were also active in ethylene/1-octene copolymerization. The comonomer content was in the range of 1.4-4.6 mol%. The use of a rigid linker and an increase in the steric load of the diolate complexes ensured the thermal stability of the catalytic system in the range of 50-70 °C.