Synthesis of Polyethylenes with Controlled Branching with α‑Diimine Nickel Catalysts and Revisiting Formation of Long-Chain Branching

The synthesis of polyethylenes with precise branching, especially long-chain branching (LCB), using ethylene monomer as a single feedstock is of a significant academic and industrial interest. On the basis of the ortho-aryl effect, a series of α-diimine nickel complexes with monoaryl-substituted anilines has been designed and prepared for the synthesis of the polyethylenes with controlled branching. The introduction of the ortho-aryl on aniline moieties enhanced the branching control ability of the α-diimine nickel catalysts. A different mechanistic model was proposed to interpret the presence of methyl and LCB but absence of other short branches in the obtained polyethylenes. LCB was formed by ethylene insertion into the primary Ni-alkyl species originating from nickel migration to methyl terminal of the growing chain because of restricted ethylene insertion into secondary Ni-alkyl species with an α-ethyl or a bulkier alkyl group.