Chinese Journal of Organic Chemistry >
Preparation of Polyolefin Elastomers by Neutral Nickel Catalysts: Synergistic Effect of Steric Hindrance and Secondary Interaction
Received date: 2024-05-07
Revised date: 2024-06-12
Online published: 2024-07-02
Supported by
National Natural Science Foundation of China(22122110); National Natural Science Foundation of China(U23B6011); Jilin Provincial Science and Technology Department Program(20230101347JC)
Salicylaldiminato neutral nickel catalysts is a family of classic ethylene polymerization catalysts. Through elabrate modulation of the structures, various polyethylene materials with different characteristics can be prepared, such as highly branched polyethylene oil and ultra-high molecular weight polyethylene with low branching. However, these catalysts face certain challenges in the preparation of elastomeric materials. In this study, two arylamines containing both sterically hindered groups and adjacent heteroatom groups were designed and synthesized for the synthesis of salicylaldiminato ligands and the corresponding neutral nickel catalysts ({N-[2,4-bis(dibenzosuberyl)-6-phenoxy]phenyl-3-tert-butylsalicylideneiminato}-nickel(II)-(phenyl)(triphenylphosphine) (Ni2) and {N-[2,4-bis(dibenzosuberyl)-6-benzenesulfonyl]phenyl-3-tert-butylsalicyli- deneiminato}-nickel(II)-(phenyl)(triphenylphosphine) (Ni3)). The effects of temperature and ethylene pressure on catalytic performance were systematically investigated, revealing the variation patterns of catalyst thermal stability, catalytic activity, polymer molecular weight and branching density. The combination of the secondary coordination effect of the heteroatom groups and the steric effect of the arylamine allowed catalyst Ni3 containing SO2Ph group to achieve a balance between branching density (61 brs/1000C) and polymer molecular weight (Mn=15.29×104), providing strong support for the preparation of polyethylene elastomer with excellent mechanical properties. The synergistic effect of steric hindrance and secondary interaction provides new ideas for the development of novel salicylaldiminato neutral nickel catalysts and the design and optimization of related catalysts.
Qiankun Li , Hongliang Mu , Zhongbao Jian . Preparation of Polyolefin Elastomers by Neutral Nickel Catalysts: Synergistic Effect of Steric Hindrance and Secondary Interaction[J]. Chinese Journal of Organic Chemistry, 2024 , 44(11) : 3399 -3408 . DOI: 10.6023/cjoc202403034
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