Cyano-functionalized polyethylenes from ethylene/acrylamide copolymerization

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.