Abstract
The combination of ethylene (E), 1,3-butadiene (BD), and carbon dioxide (CO2), three extensively utilized feedstocks, into a polymer via the copolymerization pathway is of great interest in both academia and industry. However, copolymerization for even two of them (E/BD, E/CO2, BD/CO2) is highly challenging; thus, copolymerization for three of them (E/BD/CO2) together is more elusive and remains unexplored. In this contribution, by employing a two-step strategy of palladium-catalyzed coupling and subsequent insertion polymerization, the E/BD/CO2 copolymerization via an allyl acrylate-type intermediate was achieved for the first time. The palladium-catalyzed [Pd(acac)2/PCy3] C–C coupling reaction of BD and CO2 followed by ring cleavage and esterification first generated the desired trifunctional monomer methyl-2-ethylidene-5-hydroxyhept-6-enoate acrylate (II). Subsequent palladium-catalyzed [(P^O)PdMedmso] coordination–insertion copolymerization of E and II afforded ester-functionalized polyethylenes inclu...
Published Version
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