Premium
Significant Polar Comonomer Enchainment in Zirconium‐Catalyzed, Masking Reagent‐Free, Ethylene Copolymerizations
Author(s) -
Chen Jiazhen,
Motta Alessandro,
Wang Binghao,
Gao Yanshan,
Marks Tobin J.
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201902042
Subject(s) - comonomer , copolymer , monomer , olefin fiber , polymer chemistry , ethylene , reagent , catalysis , zirconium , chemistry , post metallocene catalyst , polymerization , materials science , organic chemistry , metallocene , polymer
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.