Synthesis of methyl acrylate graft copolymers by the combination of a polynorbornene containing pendant vinylbenzene groups by using coordination and reverse atom transfer polymerization

Copolymerization of norbornene and 1,4‐divinylbenzene was successfully performed using a β‐ketoamine chelate nickel complex–methylaluminoxane, yielding random copolymer of norbornene and 1,4‐divinylbenzene containing a few pendant styrene groups. With the initiation of copper dichloride and 2,2′‐azobisisobutyronitrile, the pendant styrene groups were quantitatively polymerized with methyl acrylates, which allowed the successful synthesis of polynorbornene‐based graft copolymers by reverse atom transfer radical polymerization mechanism. The analyses of the product by 1H NMR and gel permeation chromatography gave the verification of ‘true’ copolymer. The thermal property of the graft copolymer was controlled by varying the monomer feed ratio.