Citation: LI Weiwei, MU Hongliang, LIU Jingyu, LI Yuesheng. Nickel(Ⅱ) Complexes Containing RCOO-Substituent as Highly Active Single-Component Catalysts for Ethylene (Co)Polymerization[J]. Chinese Journal of Applied Chemistry, ;2018, 35(1): 89-101. doi: 10.11944/j.issn.1000-0518.2018.01.170031 shu

Nickel(Ⅱ) Complexes Containing RCOO-Substituent as Highly Active Single-Component Catalysts for Ethylene (Co)Polymerization

LI Weiwei ^a,b ,
MU Hongliang ^a,, ,
LIU Jingyu ^a ,
LI Yuesheng ^c

a.
State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
b.
University of Chinese Academy of Sciences, Beijing 100049, China
c.
School of Material Science and Engineering, Tianjin University, Tianjin 300072, China

Corresponding author: MU Hongliang, muhongliang@ciac.ac.cn
Received Date: 13 February 2017
Revised Date: 27 March 2017
Accepted Date: 27 March 2016

Fund Project: Supported by the National Natural Science Foundation of China(No.21304087)National Natural Science Foundation of China 21304087

Figures(8)

Mononuclear nickel complexes[(2, 6-R₂-C₆H₃)NC(H)(3-Ph-5-PhCOO-2-O-C₆H₂)-κ²-N, O]Ni(CH₃)(pyridine)](R=iPr; 3, 5-tBu₂C₆H₃)(Ni¹~Ni²) and binuclear nickel complex(Ni³) were synthesized, characterized and applied in ethylene (co)polymerization. As single-component catalysts, all these complexes are capable of converting ethylene to branched polyethylenes(PE) with moderate relative molecular mass. The electron-donating group PhCOO-facilitates the initiation of catalyst Ni¹, leading to better catalytic activity at low temperature compared to nickel methyl pyridine comples(Ni⁰). Introducing bulky 2, 6-(3, 5-(t-Bu)₂C₆H₃)₂C₆H₃N-moiety, the activities of Ni² up to 1.8×10⁶ g of PE mol^-1·Ni^-1·h^-1(at 5×10⁵ Pa ethylene) were among the highest values using phenoxyiminato neutral nickel catalysts. Binuclear catalyst Ni³ showes better tolerance toward PPh₃ donor additive than its mononuclear counterpart. In the presence of comonomers 1, 5-hexadiene, 1, 7-octadiene, 6-bromo-1-hexene, or methyl 10-undecenoate, these catalysts effectively enchain these comonomers into the polymer chain to give functionalized polyethylenes.
- neutral nickel catalysts,
- electronic effects,
- olefin polymerization,
- functionlized polyolefin
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