Scandium‐Catalyzed Self‐Assisted Polar Co‐monomer Enchainment in Ethylene Polymerization

Abstract

AbstractDirect coordinative copolymerization of ethylene with functionalized co‐monomers is a long‐sought‐after approach to introducing polyolefin functionality. However, functional‐group Lewis basicity typically depresses catalytic activity and co‐monomer incorporation. Finding alternatives to intensively studied group 4 d0 and late‐transition‐metal catalysts is crucial to addressing this long‐standing challenge. Shown herein is 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−1⋅h−1> atm−1>) and AO incorporation (up to 12 % at 0.2 m [AO]) are appreciable. Linker‐length‐dependent (n) 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.