Achieving strictly linear polyethylenes by the NNN‐Fe precatalysts finely tuned with different sizes of ortho‐cycloalkyl substituents
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N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry
of Siberian Branch of Russian Academy of Sciences

The paper of NIOCh's researchers (with the international collaboration) is published on the site of the journal  Applied Organometallic Chemistry   (IF=3,14)  


Achieving strictly linear polyethylenes by the NNN‐Fe precatalysts finely tuned with different sizes of ortho‐cycloalkyl substituents

Hongyi Suo, Zilong Li, Irina V. Oleynik, Zheng Wang, Ivan I. Oleynik, Yanping Ma, Qingbin Liu, Wen‐Hua Sun



Applied Organometallic Chemistry 
Online Version of Record before inclusion in an issue e5937


 https://doi.org/10.1002/aoc.5937

 

Abstract

Six examples of newly synthesized α,α’‐bis (aryl)‐2,3:5,6‐bis (pentame thylene)pyridyliron complexes [2,3:5,6‐{C4H8C(NAr)}2C5HN]FeCl2 (Ar = 2‐(c‐C5H9)‐6‐MeC6H3 Fe1 , 2‐(c‐C6H11)‐6‐MeC6H3 Fe2 , 2‐(c‐C8H15)‐6‐MeC6H3 Fe3 , 2‐(c‐C5H9)‐4,6‐Me2C6H2 Fe4 , 2‐(c‐C6H11)‐4,6‐Me2C6H2 Fe5 , 2‐(c‐C8H15)‐4,6‐Me2C6H2 Fe6 refers as cyclic), on activation with methylalumoxane (MAO) or modified MAO (MMAO), exhibit high activities towards ethylene polymerization, producing strictly linear polyethylenes with terminal vinyl groups. The catalytic performances are systematically investigated along with various polymerization parameters as well as the microstructures of resultant polyethylenes. The steric hindrances of ortho‐cycloalkyl substituents of Nimino‐aryl groups significantly affect the activities of the corresponding iron precatalysts as well as the microstructures of resultant polyethylenes: higher steric hindrance the ortho‐cycloalkyl substituents, higher activity the iron precatalyst, lower molecular weight the resultant polyethylenes. Experimental observations are additionally supported by the computational study. The resultant polyethylenes exhibited excellent hydrophobicity.

Funding Information

  • Bureau of International Cooperation of Chinese Academy of Sciences. Grant Numbers: 121111KYSB20190005, No. 121111KYSB20190005
  • Russian Foundation for Basic Research. Grant Numbers: 18‐53‐80031, No. 18‐53‐80031
  • Russian State funded budget project. Grant Numbers: 0302‐2019‐0007, No. 0302‐2019‐0007
  • National Natural Science Foundation of China. Grant Number: No. 21871275 and 51861145303

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