LAUSR

Polyolefins with branches produced by ethylene alone via chain walking are highly desired in industry. Selective branch formation from uncontrolled chain walking is a long-standing challenge to generate exclusively branched polyolefins, however. Here we report such desirable microstructures in ethylene polymerization by using sterically constrained α-diimine nickel(II)/palladium(II) catalysts at 30 °C–90 °C that fall into industrial conditions. Branched polyethylenes with exclusive branch pattern of methyl branches (99%) and notably selective branch distribution of 1,4-Me 2 unit (86%) can be generated. The ultrahigh degree of branching (>200 Me/1000 C) enables the well-defined product to mimic ethylene-propylene copolymers. More interestingly, branch distribution is predictable and computable by using a simple statistical model of p(1-p) n (p: the probability of branch formation). Mechanistic insights into the branch formation including branch pattern and branch distribution by an in-depth density functional theory (DFT) calculation are elucidated. Selective branch formation from uncontrolled chain walking is a longstanding challenge to generate exclusively branched polyolefins. Here the authors report such desirable microstructures in ethylene polymerization enabled by a nickel catalyst at 30 °C–90 °C that fall into industrial conditions and mimic ethylene-propylene copolymers.