Chinese Journal of Applied Chemistry ›› 2017, Vol. 34 ›› Issue (11): 1259-1264.DOI: 10.11944/j.issn.1000-0518.2017.11.170236

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Pyridyl/Quinolyl-imine Ni(Ⅱ) Complexes:Synthesis and Application for Preparation of Liquid Polybutadiene

ZHUANG Ruiab,DONG Boc,ZHAO Wenpengab,HU Yanminga,ZHANG Xuequana*()   

  1. aCAS Key Laboratory of Synthetic Rubber,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun 130022,China
    bUniversity of Chinese Academy of Sciences,Beijing 100039,China
    cCollege of Materials Science and Engineering,Jilin University,Changchun 130022,China
  • Received:2017-07-05 Accepted:2017-09-16 Published:2017-11-08 Online:2017-11-08
  • Contact: ZHANG Xuequan
  • Supported by:
    Supported by the National Basic Research Program of China(No.2015CB654700, No.2015CB674702)

Abstract:

The introduction of side arm soft donors(S or P) is an efficient method to improve catalytic performance of the complexes. A series of NNP-tridentate nickel(Ⅱ) complexes bearing pyridyl/quinolyl-imine ligands(2a~2d) was synthesized and characterized by Fourier transform infrared spectroscopy(FTIR) and elemental analysis. X-ray diffraction analysis(XRD) reveals that complexes 2a and 2d adopt square-pyramidal and trigonal bipyramid geometries, respectively. Activated by ethylaluminum sesquichloride(EASC), all complexes are highly active for butadiene polymerization to afford liquid polybutadienes having number-average relative molecular masses of 4200~7700 and medium cis-1,4 mole fraction(74.5%~79.9%). The ligand has little influence on the catalytic behaviors. The catalytic activity increases with the increment of polymerization temperature, and the catalytic system still exhibits high activity even at 90 ℃, indicating high thermal stability of the generated active species.

Key words: imine structure, NNP-tridentate ligand, nickel complex, liquid polybutadiene