Coordination-insertion copolymerization of fundamental polar monomers

The copolymerization of polar vinyl monomers with nonpolar olefins and the copolymerization of olefins and imines with carbon monoxide in transition-metal catalyzed coordination-insertion copolymerization of fundamental polar monomers, were studied. Brookhart and coworkers found that a series of cationic Pd α-diimine complexes catalyzed the copolymerization of ethylene and MA. The low ester incorporation ratio and the results of experiments suggested that copolymerization proceeded through the coordination-insertion mechanism rather than radical or anionic polymerization, which produce MA-rich copolymer. Pugh and coworkers reported that neutral catalysts generated in situ from Pd(dba)₂ or Pd(OAc)₂ and phosphonium-sulfonate, [2c]H, produced highly linear ethylene/alkyl acrylate copolymers with in-chain acrylate incorporation. Although applications of copolymers consisting of polar vinyl monomers with CO have not yet been explored, further studies on their physical and chemical properties will lead to the development of functional polymers that exhibit truly novel properties.