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 C10H8(O)C[N(naphthyl)CH3]; Mt Ni, Pd}, were synthesized. In the presence of B(C6F5)3, both complexes exhibited high activity toward the homo-polymerization of norbornene (NB) (as high as 2.7 × 105 gpolymer/molNi·h for Ni(bchkni)2/B(C6F5)3 and 2.3 × 105 gpolymer/molPd·h for Pd(bchkni)2/B(C6F5)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 × 105g/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(C6F5)3 and 8.8–14.6% for Pd(bchkni)2/B(C6F5)3 catalytic system by varying comonomer feed ratios from 10 to 70 mol %. The reactivity ratios of two monomers were determined to be r1-octene = 0.052, rNB = 8.45 for Ni(bchkni)/B(C6F5)3 system, and r1-octene = 0.025, rNB = 7.17 for Pd(bchkni)/B(C6F5)3 system by the Kelen-TUdOs method. The achieved NB/1-octene copolymers were confirmed to be noncrystalline and exhibited good thermal stability (Td > 400°C, Tg = 244.1–272.2°C) and showed good solubility in common organic solvents. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

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