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Polyolefins [such as high density polyethylene (HDPE), linear low density polyethylene (LLDPE), and polypropylene (PP)] are important synthetic polymers generally produced by transition metal catalyzed olefin polymerization. Design of more effective molecular catalysts for precise polymerization is very important for the synthesis of new polymers as well as development of more efficient processes1)~10). Vanadium complex catalysts offer unique characteristics (high reactivity toward olefins) as reported by the classical Ziegler-type vanadium catalyst systems [VOCl3 and Et2AlCl , EtAlCl2, BuLi etc . ]7),11)~14). ( Imido)vanadium(V) complexes containing monodentate anionic donor ligands (L) of the type, V(NAr)Cl2(L) [L =aryloxo (1a,b)15)~18), ketimide (2)19),20), imidazolin2-iminato (3)21) etc., Scheme 1], are known to exhibit remarkable catalytic activities for the ethylene polymerization15)~21) and the copolymerization with norbornene (NBE)16)~18),21). Moreover, we recently reported that the (arylimido)vanadium(V) complexes containing anionic N-heterocyclic carbenes with a weakly coordinating borate [B(C6F5)3] moiety (WCA-NHC)22),23) of the type, V(NAr)Cl2(WCA-NHC) [4, NHC=1,3bis(2,6-dimethylphenyl)imidazolin-2-ylidene, Scheme 1], exhibited remarkably high catalytic activity for ethylene polymerization in the presence of AlBu3, which has been considered as an ineffective Al cocatalyst in the metal catalyzed polymerization1)~21). The activity of 4 in the presence of AlBu3 for ethylene polymerization was apparently higher than that of 4 in the presence of methylaluminoxane (MAO), Et2AlCl cocatalyst24); 4 also efficiently copolymerized ethylene with NBE in the presence of AlBu3 (Scheme 1)25). 282 Journal of the Japan Petroleum Institute, 61, (5), 282-287 (2018)

journal of the japan petroleum institute

Solution XAS Analysis of Various (Imido)vanadium(V) Dichloride Complexes Containing Monodentate Anionic Ancillary Donor Ligands: Effect of Aluminium Cocatalyst in Ethylene/Norbornene (Co)polymerization