3 years ago

Scandium-Catalyzed Self-Assisted Polar Comonomer Enchainment in Ethylene Polymerization

Binghao Wang, Yanshan Gao, Tobin Jay Marks, Tracy L Lohr, Jiazhen Chen
Direct coordinative copolymerization of ethylene with functionalized comonomers is a long-sought approach to introducing polyolefin functionality. However, functional group Lewis basicity typically depresses catalytic activity and comonomer incorporations. Finding alternatives to intensively studied group 4 d0 and late transition metal catalysts is crucial to addressing this long-standing challenge. Here, we show that mono- and binuclear organoscandium complexes with a borate cocatalyst are active for ethylene + amino-olefin (AO; H2C=CH(CH2)nNR2) copolymerizations in the absence of a Lewis acidic masking reagent. Both activity (up to 4.2 × 102 kg/mol·h·atm) and AO incorporation (up to 12% at 0.2 M [AO]) are appreciable. Linker length (n)-dependent AO incorporation and mechanistic probes support an unusual functional group-assisted enchainment mechanism. Furthermore, the binuclear catalysts exhibit enhanced AO tolerance and enhanced long chain AO incorporation.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201708797

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