Significant Polar Comonomer Enchainment in Zirconium-Catalyzed, Masking Reagent-Free, Ethylene Copolymerizations

Jiazhen Chen, Alessandro Motta, Binghao Wang, Yanshan Gao, Tobin J Marks

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7 Citations (Scopus)


In principal, the direct copolymerization of ethylene with polar comonomers should be the most efficient means to introduce functional groups into conventional polyolefins but remains a formidable challenge. Despite the tremendous advances in group 4-centered catalysis for olefin polymerization, successful examples of ethylene + polar monomer copolymerization are rare, especially without Lewis acidic masking reagents. Here we report that certain group 4 catalysts are very effective for ethylene + CH 2 =CH(CH 2 ) n NR 2 copolymerizations with activities up to 3400 Kg copolymer mol −1 -Zr h -1 atm -1 , and with comonomer enchainment up to 5.5 mol % in the absence of masking reagents. Group 4 catalyst-amino-olefin structure–activity-selectivity relationships reflect the preference of olefin activation over free amine coordination, which is supported by mechanistic experiments and DFT analysis. These results illuminate poorly understood facets of d 0 metal-catalyzed polar olefin monomer copolymerization processes.

Original languageEnglish
JournalAngewandte Chemie - International Edition
Publication statusPublished - Jan 1 2019



  • copolymerization
  • DFT study
  • olefin polymerization
  • polar monomer
  • zirconium

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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