Coordination‐Insertion Copolymerization of Norbornene and p ‐Substituted Styrenes Using Anilinonaphthoquinone‐Ligated Nickel Complexes

Coordination‐insertion copolymerization of norbornene (N) and p‐ substituted styrene (XS) (X = MeO, Me F, Cl, and Br) is carried out using anilinonaphthoquinone‐ligated nickel complexes [Ni(C 10 H 5 O 2 NAr)(Ph)(PPh 3 ): 1a , Ar = C 6 H 3 ‐2,6‐ i Pr; 1b , Ar = C 6 H 2 ‐2,4,6‐Me; 1c, Ar = C 6 H 5 ] with modified methylaluminoxane (MMAO) as a cocatalyst. The ligand of the nickel complex affects the catalytic activity. The effect of the p ‐substituent on the activity is remarkable and the activity decreases in the following order, Br > Cl > F > Me > MeO. The molecular weight of the produced polymer also decreases with the same order. The activity increases with raising the temperature from 0 to 70 °C accompanied by the decrease in the molecular weight of the produced polymers. The incorporation of XS determined by 1 H and 13 C NMR decreases in the following order, MeO ≥ Me > F > Cl > Br. The glass transition temperatures of the N/XS copolymers determined by differential scanning calorimetry show a broad range from 120 to 365 °C according to the XS content.