中华医学超声杂志

应用化学 ›› 1987, Vol. 0 ›› Issue (4): 1-5.

• 研究论文 •    下一篇

铁体系催化丁二烯聚合的研究——Ⅴ.ESR、NMR和IR研究聚合机理

王凤江, 詹瑞云, 刘国智, 钱保功   

  1. 中国科学院长春应用化学研究所
  • 收稿日期:1986-08-20 出版日期:1987-08-10 发布日期:1987-08-10
  • 基金资助:
    中国科学院科学基金

STUDIES ON THE POLYMERIZATION OF BUTADIENE IN THE PRESENCE OF IRON CATALYST Ⅴ.ESR,NMR AND IR APPROACH TO THE MECHANISM OF POLYMERIZATION

Wang Fengjiang, Zhan Ruiyun, Liu Guozhi, Qian Baogong   

  1. Changchun Institute of Applied Chemistry, Academia Sinica
  • Received:1986-08-20 Published:1987-08-10 Online:1987-08-10

PDF

430

被引次数

56

摘要： 本文用ESR、1H-NMR及IR研究了Fe(phen)Cl3-(i-C4H9)3Al体系催化丁二烯聚合的机理。ESR谱表明,聚合活性中心上的铁为Fe(Ⅱ)。同时观察到自由基的信号,为其还原历程提供了证据。体系中不存在丁二烯时有很宽的ESR信号(ΔHpp=900G)、加入丁二烯时可以观察到一窄信号(ΔHpp=50G),二者有明显区别。提出了Fe(phen)Cl3-(i-C4H9)3Al体系催化丁二烯聚合的反应机理,两个体系的1H-NMR和IR谱图的比较证实了这个机理。

Abstract: ESR, 1H-NMR and IR were combined so as to give information concerning the mechanism of butadiene polymerization in the presence of catalyst system Fe(phen)Cl3-(i-C4H9)3Al. It was shown by the ESR spectra that the iron in active species is reduced into Fe(Ⅱ) by triisobatyl aluminium during the polymerization and the signal of free radical could be observed,so a reduction mechanism is proposed. Two systems, Fe(phen)Cl3-(i-C4H9)3Al and Fe(phen)Cl3-(i-C-4H9)3Al-butadiene, have diffferent spectra in ESR. The former gives a very wide signal(△Hpp=900G), but the latter shows a more sharp one (△Hpp=50G).The overall polymerization mechanism has been proposed, which is supported by 1H-NMR and IR spectra measurements of the system.

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