Synthesis of Branched Polyethylene and Ethylene-MA Copolymers Using Unsymmetrical Iminopyridyl Nickel and Palladium Complexes,Organometallics

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Synthesis of Branched Polyethylene and Ethylene-MA Copolymers Using Unsymmetrical Iminopyridyl Nickel and Palladium Complexes
Organometallics ( IF 2.5 ) Pub Date : 2021-08-26 , DOI: 10.1021/acs.organomet.1c00388
You Ge ₁ , Shuaikang Li ₁ , Hui Wang ₂ , Shengyu Dai _{1,

2}

Affiliation

It is usually challenging to obtain high-molecular-weight polyethylene in the iminopyridyl Ni(II) and Pd(II) system due to the only one side axial steric structure of the iminopyridine ligand. In this study, the effectiveness of the dibenzosuberyl substituent in retarding the chain transfer in the iminopyridyl Ni(II) and Pd(II) catalysts has been demonstrated. The complexes Ni5 and Pd5 with phenyl and dibenzosuberyl substituents are noted to generate polyethylene and ethylene-MA copolymers with significantly higher molecular weight as compared to the complexes Ni1–4 and Pd1–4 with various diarylmethyl moieties. The synergistic effect of phenyl and dibenzosuberyl groups can further enhance the function of the catalyst to suppress the chain transfer. Further, polyethylene, ethylene oligomers, and ethylene-MA co-oligomers obtained in this study are observed to be highly branched. In addition, the iminopyridyl palladium catalysts can effectively promote the copolymerization of ethylene and MA to obtain the polar functionalized ethylene-MA co-oligomers with high incorporation ratios (up to 15.2 mol %).

中文翻译：

使用不对称亚氨基吡啶基镍和钯配合物合成支化聚乙烯和乙烯-MA 共聚物

由于亚氨基吡啶配体只有一侧的轴向空间结构，因此在亚氨基吡啶基 Ni(II) 和 Pd(II) 体系中获得高分子量聚乙烯通常具有挑战性。在这项研究中，已经证明了二苯并辛基取代基在阻止亚氨基吡啶基 Ni(II) 和 Pd(II) 催化剂中的链转移方面的有效性。络合物NI5和PD5用苯基和二苯并环庚取代基注意到以生成聚乙烯和乙烯- MA共聚物显著较高分子量相比，复合物NI1 - 4和PD1 - 4具有各种二芳甲基部分。苯基和二苯并辛基的协同作用可以进一步增强催化剂抑制链转移的功能。此外，观察到本研究中获得的聚乙烯、乙烯低聚物和乙烯-MA 共聚低聚物是高度支化的。此外，亚氨基吡啶基钯催化剂可有效促进乙烯与MA的共聚，获得高掺入率（高达15.2 mol%）的极性官能化乙烯-MA共聚低聚物。

更新日期：2021-09-13

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