Cationic [TiCl6]+2 and anionic [TiCl6-xLx]-(2-x) titanium complexes with crown ether as pre-catalyst for ethylene polymerization

A series of ionic complexes of composition [M. Crown]+ [TiCl5]-, where M -Li, Na, K; Crown - dibenzo-18-Crown-6, benzo-15-crown-5, dibenzo-24-crown-8 has been synthesized by the interaction of alkali metal chlorides, ti-tanium tetrachloride and crown ethers in anhydrous toluene. Carrying out these syntheses in acetonitrile results in crystallization of complexes solvated with acetonitrile. The structure of three complexes was determined by X-ray diffraction. In the presence of an activator - {Et2AlCl + Bu2Mg}, the complexes catalyze the polymerization of ethylene with a productivity of up to 4500 kg PE/mol Ti h atm. The resulting ultra-high molecular weight polyethylene (Mv in the range 1.4 - 2.8*106 Da) can be processed by a solventless method into high-strength (up to 2.1 GPa) and high-modulus (up to 118 GPa) oriented films.