In this review, we summarize and discuss our experimental data published in a number of papers on the transfer reactions of polymer chains in the polymerization of ethylene, propylene, and hexene-1, and the copolymerization of ethylene with α-olefins over multisite supported titanium–magnesium catalysts (TMC). Three groups of transfer reactions are discussed in the review: (1) transfer reactions with AlEt₃ cocatalyst, (2) transfer reactions with hydrogen, and (3) transfer reactions with participation of α-olefins in the case of ethylene copolymerization with α-olefins. We have found polymerization conditions where it is possible to observe heterogeneity of active sites of TMC for all three groups of the indicated reactions. It is shown that (1) the transfer reaction with AlEt₃ proceeds with higher reactivity on the active sites that produce polymers with low molecular weight; (2) the transfer reaction with hydrogen, in the case of α-olefin polymerization and copolymerization of ethylene with α-olefins, proceeds with higher reactivity on the active sites which produce polymers with high molecular weight; (3) the transfer reaction with α-olefins proceed with higher reactivity on the active sites that produce high molecular weight polymers.

Data were obtained on the copolymerization of ethylene with α-olefins over supported titanium–magnesium catalysts (TMC) prepared on the same magnesium dichloride support but differing in the composition and oxidation state of titanium. The copolymerization kinetics of ethylene with 1-hexene over TMC of different compositions were studied. Data on the composition of the produced ethylene–1-hexene copolymers, their molecular weight distribution, thermophysical characteristics, and branching distribution were presented. The constants of ethylene–1-hexene copolymerization over catalysts with different compositions were calculated. The TMC containing only Ti(II) compounds as the active component exhibited increased copolymerizing ability compared to the conventional TiCl₄/MgCl₂ catalyst containing Ti(III) compounds as the active component. In addition, TMC with Ti(II) as an active component produces copolymers with a more uniform branching distribution. It was shown that the TMC containing isolated Ti(II) ions could be used to produce X-ray amorphous ethylene-propylene elastomers with a high yield.

A comparative study of propylene polymerization in liquid monomer is performed under laboratory conditions using the IK-8-21 Ti-Mg catalyst designed at the Boreskov Institute of Catalysis and imported industrial catalysts (conditionally labeled TMC-1, -2, and -3). The activity and stereospecificity of the catalysts are estimated along with properties of the resulting polypropylene (granular composition and physicomechanical characteristics). It is shown that the IK-8-21 catalyst is not inferior to imported counterparts in terms of catalytic properties in the synthesis of polypropylene. The polypropylene powder formed on IK-8-21 is homogeneous and has good morphology. The physicomechanical characteristics of polypropylene synthesized on the domestic IK-8-21 catalyst are similar to those for polypropylene prepared with the imported TMK-1 catalyst.

Ethylene polymerization with bis(imino)pyridlyiron precatalysts generally produces linear polyethylene (PE) even with the presence of α-olefins because α-olefins are not incorporated into polymeric products. Interestingly, α-olefins, such as hexene-1 or butene-1, have been found to act as effective chain transfer agents in the ethylene polymerization promoted by nonsymmetrical bis(imino)pyridyliron complexes with modified methylalumoxane (MMAO), resulting in higher catalytic activities with higher amounts of polymers with lower molecular weights, and, more importantly, narrower molecular weight distributions of the resultant polyethylenes (PE). This phenomenon confirms the assistance of α-olefins in the chain-termination reaction of iron-initiated polymerization and regeneration of the active species for further polymerization. Besides higher activities of the catalytic system, the formation of linear PE with trans-vinylene terminal groups and lower molecular weights are explained. The observation will provide a new pathway for enhancing catalytic activity and improving the quality of polyethylenes obtained by regulation of molecular weights and molecular weight distribution.

Ethylene polymerization and ethylene/1-hexene copolymerization over the titanium–magnesium catalytic system in the presence of chlorocyclohexane (CHC) and hexachloro-p-xylene (HCPX) has been studied. Modification of TMC with chlorocyclohexane and hexachloro-p-xylene increased catalyst activity severalfold for both ethylene polymerization and ethylene/1-hexene copolymerization. The key kinetic regularities of ethylene homopolymerization and ethylene/1-hexene copolymerization in the presence of CHC and HCPX were determined, and the copolymerization constants were measured. Molecular characteristics and the copolymer composition were determined for the synthesized samples of ethylene homopolymers and ethylene/hexene copolymers. Modification of the titanium–magnesium catalyst with chlorinated organic compounds reduced 1-hexene content in the copolymer; polymerization was sensitive to 1-hexene as a regulator of polymer molecular weight. The potential mode of action of chlorinated organic modifiers on catalytic properties of titanium–magnesium catalyst is discussed.