Cyano-functionalized polyethylenes from ethylene/acrylamide copolymerization

Shu-Yang Yu, Xiao-Yan Wang, Xiu-Li Sun, Yanshan Gao (), Yanan Zhao (), Xiao-Shan Ning, Gang Ji, Yuan Lu, Jie Yang, Zhi-Pan Liu and Yong Tang ()
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Shu-Yang Yu: Chinese Academy of Sciences
Xiao-Yan Wang: Chinese Academy of Sciences
Xiu-Li Sun: Chinese Academy of Sciences
Yanshan Gao: Chinese Academy of Sciences
Yanan Zhao: Chinese Academy of Sciences
Xiao-Shan Ning: Chinese Academy of Sciences
Gang Ji: Chinese Academy of Sciences
Yuan Lu: Chinese Academy of Sciences
Jie Yang: Chinese Academy of Sciences
Zhi-Pan Liu: Chinese Academy of Sciences
Yong Tang: Chinese Academy of Sciences

Nature Communications, 2025, vol. 16, issue 1, 1-10

Abstract: Abstract Synthesizing functionalized polyethylenes via ethylene coordination copolymerization with fundamental low-cost vinyl polar monomers provides a very attractive approach. However, it is also very challenging as the functional group (FG) to be introduced onto the polyolefin chain is directly derived from the corresponding vinyl polar monomers (CH2 = CH-FG), which often cause catalyst poisoning due to the FG coordination to active metal center and β-X elimination during catalysis, etc. It is especially true for the synthesis of cyano-functionalized polyethylenes (PEs) via ethylene/acrylonitrile copolymerization, which can only rely on Pd catalysis with low activity. Here we present an approach utilizing binuclear Ni catalysis for ethylene/acrylamide copolymerization and the synthesis of cyano-functionalized PEs (>99%) with great activity up to 4.1 × 106 g/(mol cat·h). Extensive polymer characterizations (NMR, GPC, model experiments, etc) confirm significant chain transfer and the conversion of amide to nitrile during catalysis. Mechanistic investigations, including comprehensive control experiments, deuterium labeling and computational studies, support an isomerization-mediated chain transfer polymerization (ICTP) mechanistic pathway, which include tandem acrylamide enchainment, amido group conversion into CN group, and active catalyst regeneration by Et2AlCl. Catalyst poisoning could be largely circumvented by this catalyst system.

Date: 2025
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DOI: 10.1038/s41467-025-57489-z

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