Direct copolymerization of ethylene with protic comonomers enabled by multinuclear Ni catalysts

Nature Communications

Xing-Min Zhang¹  Qi Shen¹  Yanan Zhao²  Jiajie Sun²  Yi Luo³  Xiao-Shan Ning⁴  Xiu-Li Sun⁴  Jun-Bo Zhao⁴  Yong Tang⁴  Jun-Fang Li⁴  Xiao-Yan Wang⁴  Bo Zhang⁴  Gang Ji⁴  Yin-Long Guo⁴  Zhou Chen⁴  Wen-Jie Tao⁴  Yanshan Gao⁴  Hao-Yang Wang⁴  Chong-Jie Xu⁵ 

[1] School of Chemistry and Chemical Engineering, Soochow University, Suzhou, China;State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian, China;State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian, China;Petrochina Petrochemical Research Institute, Beijing, China;State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, China;State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, China;School of Chemistry and Chemical Engineering, Soochow University, Suzhou, China;

DOI  :  10.1038/s41467-021-26470-x

来源: Springer

【 摘 要 】

Ethylene/polar monomer coordination copolymerization offers an attractive way of making functionalized polyolefins. However, ethylene copolymerization with industrially relevant short chain length alkenoic acid remain a big challenge. Here we report the efficient direct copolymerization of ethylene with vinyl acetic acid by tetranuclear nickel complexes. The protic monomer can be extended to acrylic acid, allylacetic acid, ω-alkenoic acid, allyl alcohol, and homoallyl alcohol. Based on X-ray analysis of precatalysts, control experiments, solvent-assisted electrospray ionization-mass spectrometry detection of key catalytic intermediates, and density functional theory studies, we propose a possible mechanistic scenario that involves a distinctive vinyl acetic acid enchainment enabled by Ni···Ni synergistic effects. Inspired by the mechanistic insights, binuclear nickel catalysts are designed and proved much more efficient for the copolymerization of ethylene with vinyl acetic acid or acrylic acid, achieving the highest turnover frequencies so far for both ethylene and polar monomers simultaneously.

【 授权许可】

CC BY