应用化学 ›› 1988, Vol. 0 ›› Issue (1): 15-20.

• 研究论文 • 上一篇    下一篇

铁体系催化丁二烯聚合的研究 Ⅵ.催化剂中含氮配位体的作用机理

王凤江, 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:1986-12-01 修回日期:1987-04-02 出版日期:1988-02-10 发布日期:1988-02-10

STUDIES ON THE POLYMERIZATION OF BUTADIENE IN THE PRESENSE OF IRON CATALYST Ⅵ.EFFECTS OF NITROGENCONTAINING LIGANDS ON THE POLYMERIZATION AND THE MICROSTRUCTURE OF POLYMER

Wang Fengjiang, Liu Guozhi, Qian Baogong   

  1. Changchun Institute of Applied Chemistry, Academia Sinica
  • Received:1986-12-01 Revised:1987-04-02 Published:1988-02-10 Online:1988-02-10

摘要: 本文比较了三个系列的含氮配位体对FeCl3-(i-C4H9)3Al体系催化丁二烯聚合及对聚合物微观结构的影响:ⅰ)吡啶、喹啉、2,2'-联吡啶、邻啡啰啉、2,2',2"-三联吡啶、2,2',2",2"'-四联吡啶;ⅱ)吡啶、2-氰基吡啶、2,6-二氰基吡啶;ⅲ)三乙胺、N,N,N',N'-四甲基乙二胺、二乙撑三胺.考察了配位体用量及烷基铝用量对聚合反应及聚合物特性粘数的影响,同时观察到聚合物的1,2-结构随配位体的配位齿数的增加而增加,这是由于配位体占据活性中心上的空轨道,使丁二烯在活性中心上单配位几率增加所致.用这一机理亦解释了各配位体之间聚合活性的差别.

关键词: 配位聚合, 丁二烯, 含氮配位体, 三氯化铁, 机理

Abstract: In order to investigate their effects on the polymerization of butadiene and the microstructure of polymers, three series of nitrogen-containing compounds were added into the catalyst system of FeCl3-(i-C4H9)3Al i.e.1), pyridine, quinoline, 2,2'-bipyridine, 2,2',2"-terpyri-dine, 2,2',2",2'"-tetrapyridine;2), pyridine, 2-cyanopyridine, 2,6-dicyanopyridine; 3),triethylamine, N,N,N',N"-tetramethylethylenediamine, diethylenetriamine. The effects of concentration of ligands as well as alkylaluminum on both catalytic activity and the [η] of polymers were investigated. It was observed that the larger the number of nitrogen atomsin the ligand, the more the 1,2-structural content of polybutadieneo It is considered that the ligand coordinated to active center would occupy the empty orbitals, increasing the opportunity of trans-configuration of butadiene on the active center as well as the content of 1,2-units in polymer. The mechanism is also used to explain the difference in catalytic activities caused by various ligands.

Key words: Coordination polymerization, Butadiene, Nitrogen containing ligand, Ferric chloride, Mechanism