Novel Ni and Pd(benzocyclohexan‐ketonaphthylimino) 2 complexes for copolymerization of norbornene with octene

Two novel late transition metals complexes with bidentate OˆN chelate ligand, Mt(benzocyclohexan‐ketonaphthylimino) 2 {Mt(bchkni) 2 : bchkni C 10 H 8 (O)C[N(naphthyl)CH 3 ]; Mt Ni, Pd}, were synthesized. In the presence of B(C 6 F 5 ) 3 , both complexes exhibited high activity toward the homo‐polymerization of norbornene (NB) (as high as 2.7 × 10 5 g polymer /mol Ni ·h for Ni(bchkni) 2 /B(C 6 F 5 ) 3 and 2.3 × 10 5 g polymer /mol Pd ·h for Pd(bchkni) 2 /B(C 6 F 5 ) 3 , respectively). Additionally, both catalytic systems showed high activity toward the copolymerization of NB with 1‐octene under various polymerization conditions and produced the addition‐type copolymer with relatively high molecular weights (0.1–1.4 × 10 5 g/mol) as well as narrow molecular weight distribution. The 1‐octene content in the copolymers can be controlled up to 8.9–14.0% for Ni(bchkni) 2 /B(C 6 F 5 ) 3 and 8.8–14.6% for Pd(bchkni) 2 /B(C 6 F 5 ) 3 catalytic system by varying comonomer feed ratios from 10 to 70 mol %. The reactivity ratios of two monomers were determined to be r 1‐octene = 0.052, r NB = 8.45 for Ni(bchkni)/B(C 6 F 5 ) 3 system, and r 1‐octene = 0.025, r NB = 7.17 for Pd(bchkni)/B(C 6 F 5 ) 3 system by the Kelen‐TÜdÕs method. The achieved NB/1‐octene copolymers were confirmed to be noncrystalline and exhibited good thermal stability ( T d > 400°C, T g = 244.1–272.2°C) and showed good solubility in common organic solvents. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013