Selective branch formation in ethylene polymerization to access precise ethylene-propylene copolymers

Yuxing Zhang, Xiaohui Kang () and Zhongbao Jian ()
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Yuxing Zhang: Chinese Academy of Sciences
Xiaohui Kang: Dalian Medical University
Zhongbao Jian: Chinese Academy of Sciences

Nature Communications, 2022, vol. 13, issue 1, 1-9

Abstract: Abstract 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-Me2 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.

Date: 2022
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DOI: 10.1038/s41467-022-28282-z

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