应用化学 ›› 1989, Vol. 0 ›› Issue (6): 89-91.

• 研究简报 • 上一篇    

ZrCl4/AlEt2Cl和ZrCl4/AlEt2Cl-n-C4H9ONa催化剂体系锆的ESR动态表征

林青松, 王瑀, 何仁   

  1. 大连理工大学化学系
  • 收稿日期:1989-01-26 修回日期:1989-07-15 出版日期:1989-12-10 发布日期:1989-12-10

DYNAMIC ESR CHARACTERIZATION OF CATALYSTS ZrCl4/AlEt2Cl and ZrCl4/AlEt2Cl-n-C4 H9ONa

Lin Qingsong, Wang Yu, He Ren   

  1. Department of Chemistry, Dalian University of Technology
  • Received:1989-01-26 Revised:1989-07-15 Published:1989-12-10 Online:1989-12-10

摘要: 迄今为止关于锆的ESR研究报导甚少。CaMaTOB等[1]发表了掺杂在YPO4中的Zr3+的ESR谱参数; Abraham等[2]报导了俘获干磷酸单晶中Zr3+的ESR研究;Kartel等[3]用ESR手段表征了ZrPO4的微孔结构;Robert等[4]以LiAlH(OCMe3)3为还原剂由CP2ZrCl(CH2PPh2)制得Cp2ZrH(CH2PPh2),然后热解所得产物,观测到Zr3+络合物的ESR信号;Atkinson等[5,6]研究了有机金属锆系列化合物,获得有机自由基信号和Zr3+的ESR信号。本文研究ZrCl4的Ziegler-Natta体系催化乙烯齐聚中锆的价态及自旋浓度的变化。

关键词: ESR, 锆, 乙烯齐聚反应, 催化

Abstract: ESR spectra of zirconium in ZrCl4/AlEt2Cl and ZrCl4/AlEt2Cl-n-C4H9ONa catalystsystems were recorded at various reaction times, the g=1.978, △Hpp=22.4×10-4T. The spin concentration s were determined for two systems. It is shown that Zr4+is first reduced to Zr3+, which is further reduced to lower state. The reduction rate of Zr4+and Zr3+ in ZrCl4/AlEt2Cl-n-C4H9ONa system is lower than that in ZrCl4/AlEt2Cl system.This fact indicates that n-C4H9ONa plays an importent rolc in restraining reduction of Zr4+ and Zr3+.

Key words: ESR, Zirconium, Oligomerization of ethylene Catalysis