Amide-Functionalized Polyolefins and Facile Post-Transformations

Direct copolymerization of olefins with polar monomers to produce functionalized polyolefins has attracted much attention; however, highly efficient incorporation of amide functions into polyolefins is a long-standing challenge because the amide function is pronounced to retard chain growth. In this contribution, Vince Lactam’s derivatives ( VL H, VL Me, and VL Boc ) that contain high ring strain and an amide moiety are utilized in ethylene copolymerization mediated by palladium catalysts. Amide-functionalized polyethylenes, poly(E-VL Boc )s, are accessible with key characteristics of high amide incorporations (up to 30.1 mol %), high copolymer molecular weights, and high catalytic activities. The incorporation of the amide comonomer converts crystalline poly(E-VL Boc )s ( T m = 115–125 °C) to noncrystalline and transparent poly(E-VL Boc )s ( T g = 98–196 °C, optical transmittance ( T ) = 87.6%–90.4%). Both characteristics of cyclic amide functions and high amide incorporations in poly(E-VL Boc ) enable facile post-transformations under mild conditions to produce hydrogen bond-containing (-C(O)NH-) poly(E-VL H ), difunctionalized (-COOH and -NHR) poly(E-VL NHBoc ), and water-soluble ammonium-functionalized poly(E-VL NH 3 + ). The ammonium functionality endows polyolefin with antibacterial properties.