Palladium-Catalyzed Homo- and Copolymerization of Polar Monomers: Synthesis of Aliphatic and Aromatic Polymers

Transition-metal-catalyzed coordination-insertion polymerization of olefins is an indispensable tool in polymer synthesis. When polar monomers with polar functional groups are employed, however, the catalysts are often deactivated owing to side reactions such as alpha-coordination and beta-elimination of the functional group. Nevertheless, recent progress in late transition metal catalysis has enabled the synthesis of many types of functional polymers from polar monomers through coordination-insertion polymerization methods. This account describes our achievements in the palladium-catalyzed coordination-insertion (co)polymerization of polar monomers for the syntheses of a variety of functional polymers, ranging from functionalized polyolefins via olefin/polar monomer copolymerization to o-arylene-containing polymers via formal aryne polymerization.