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Scandium‐Catalyzed Self‐Assisted Polar Co‐monomer Enchainment in Ethylene Polymerization
Author(s) -
Chen Jiazhen,
Gao Yanshan,
Wang Binghao,
Lohr Tracy L.,
Marks Tobin J.
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201708797
Subject(s) - chemistry , monomer , ethylene , polymer chemistry , catalysis , polyolefin , copolymer , lewis acids and bases , scandium , polymerization , olefin fiber , cationic polymerization , reagent , polymer , organic chemistry , layer (electronics)
Direct 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 d 0 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; H 2 C=CH(CH 2 ) n NR 2 ] copolymerizations in the absence of a Lewis‐acidic masking reagent. Both activity (up to 4.2×10 2 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.