Synthesis of Functional Polyolefins Using Cationic Bisphosphine Monoxide–Palladium Complexes

The copolymerization of ethylene with polar vinyl monomers,
such
as vinyl acetate, acrylonitrile, vinyl ethers, and allyl monomers,
was accomplished using cationic palladium complexes ligated by a bisphosphine
monoxide (BPMO). The copolymers formed by these catalysts have highly
linear microstructures and a random distribution of polar functional
groups throughout the polymer chain. Our data demonstrate that cationic
palladium complexes can exhibit good activity for polymerizations
of polar monomers, in contrast to cationic α-diimine palladium
complexes (Brookhart-type) that are not applicable to industrially
relevant polar monomers beyond acrylates. Additionally, the studies
reported here point out that phosphine-sulfonate ligated palladium
complexes are no longer the singular family of catalysts that can
promote the reaction of ethylene with many polar vinyl monomers to
form linear functional polyolefins.