Copolymerization of Norbornene and Styrene with Anilinonaphthoquinone-Ligated Nickel Complexes

Poly(norbornene-co-styrene)s were synthesized by the use of anilinonaphthoquinone-ligated nickel complexes [Ni(C₁₀H₅O₂NAr)(Ph)(PPh₃): 1a, Ar = C₆H₃-2,6-ⁱPr; 1b, Ar = C₆H₂-2,4,6-Me; 1c, Ar = C₆H₅] activated with modified methylaluminoxane (MMAO) or B(C₆F₅)₃ in toluene. The effects of the cocatalysts were more significant than those of the nickel complexes, and MMAO gave higher activity than B(C₆F₅)₃. The structural characterizations of the products indicated the formation of statistical norbornene copolymers. An increase of the styrene ratio in feed led to an increase in the incorporated styrene (S) content of the resulting copolymer. The molecular weight of the copolymer decreased with increasing the S ratio in feed at 70 °C. The copolymerization activity, using MMAO as a cocatalyst, decreased with lowering of the temperature from 70 to 0 °C, accompanied by an increase in the molecular weight of the copolymer. The S incorporation up to 59% with M_n of 78,000 was achieved by the 1b-B(C₆F₅)₃ catalytic system. The glass transition temperatures of the norbornene (N)/S copolymers determined by differential scanning calorimetry, decreased from 329 to 128 °C according to the S content.