Citation:
HAN Chao, LIU Heng, YANG Feng, HU Yanming, ZHANG Xuequan. Pyrazolylimine Ni (Ⅱ) Complexes:Synthesis,Characterization,and Catalytic Behaviors for 1,3-Butadiene Polymerization[J]. Chinese Journal of Applied Chemistry,
;2015, 32(8): 909-915.
doi:
10.11944/j.issn.1000-0518.2015.08.140425
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A series of NN-bidentate nickel (Ⅱ) complexes bearing pyrazolylimine ligands (4a~4e) was synthesized and characterized by FTIR and elemental analysis.Determined by X-ray single crystal diffraction,complex 4b adopted distorted trigonal bipyramidal geometry around the central metal.Activated by ethylaluminum sesquichloride (EASC),all complexes exhibited high cis-1,4 selectivity towards 1,3-butadiene polymerization to afford liquid polybutadienes (PB) with relative molecular mass of 4500~9000 and 91% cis-1,4 content.The catalytic activity of the complex decreased as the hindrance of the substituent on the ligand increased.The effects of Al/Ni molar ratio and polymerization temperature on the polymerization were further investigated in details.The catalytic activity increased with the increase of polymerization temperature from20℃ to 60℃,and the polymer yield only slightly decreased even at a high temperature of 80℃,indicating high thermal stability of the active species generated by the present catalytic system.
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