Titanium Complex Containing a Saligenin Ligand - New Universal Post-Metallocene Polymerization Catalyst: Copolymerization of Ethylene with Higher α-Olefins

Copolymerization reactions of ethylene with three α-olefins, 1-hexene, 1-octene and 1-decene, were carried out with a new post-metallocene catalyst based on Ti complex with a bidentate saligenin-type ligand I and two co catalysts, MAO and a combination of AlEt2Cl and MgBu2. Ability of the I - AlEt2Cl - MgBu2 system to copolymerize α-olefins with ethylene is far superior to that of the I - MAO system. Reactivity of α-olefins in copolymerization reactions with ethylene decreases in the sequence: 1-hexene>1-octene>1-decene. Both catalyst systems, I - MAO and I - AlEt2Cl - MgBu2, contain several populations of active centers that greatly differs both in the average molecular weights and in composition of the copolymer molecules they produce. Active centers in both catalytic systems show significant tendency to alternate monomer units in copolymer chains

First example of cationic titanium (III) complexes with crown ether as catalysts for ethylene polymerization

Complex cations with a vacant coordination site are considered as the most plausible catalytically active centers of metallocene and post-metallocene polymerization catalysts. For the first time we demonstrated that cationic titanium (III) complexes stabilized with crown ether can be used as pre-catalysts for ethylene polymerization. In the presence of alkyl aluminum chlorides and MgBu2 as cocatalysts, these complexes catalyze ethylene polymerization to produce Ultra High Molecular Weight Polyethylene (UHMWPE) with productivity up to 4650 kgPE/mol Ti h⋅atm and molecular weight up to 1.8·106 Da. UHMWPE powders were processed by the solid-phase method with subsequent orientation drawing into high-strength (1.4–2.1 GPa) and high-modulus (91–118 GPa) films. © 2022 Elsevier Lt

Effect of Activator and Outgoing Ligand Nature on the Catalytic Behavior of Bis(phenoxy-imine) Ti(IV) Complexes in the Polymerization of Ethylene and Its Copolymerization with Higher Olefins

A series of bis(phenoxy-imine) (FI) titanium(IV) and zirconium(IV) complexes have been synthesized. The effect of the nature of the activator (MAO, combinations EtnAlCl3-n + Bu2Mg and iBu3Al + [Ph3C]+[B(C6F5)4]−) on the catalytic activity and properties of the resulting polymers was studied. It was found that Ti-Fi complexes, despite the nature of the outgoing ligands (Cl or iPrO) in the presence of Al/Mg activators, effectively catalyze the polymerization of ethylene (with the formation of UHMWPE); copolymerization of ethylene with 1-octene (with the formation of ultra-high molecular weight copolymers); and the ternary copolymerization of ethylene, propylene and 5-vinyl-2-norbornene (with the formation of polyolefin elastomers). It has been shown that Zr-FI complexes are not activated by these Al/Mg compositions. The resulting UHMWPE can be processed by a solventless method into high-strength and high-modulus oriented films; however, their mechanical characteristics do not exceed those obtained using MAO