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化学学报
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化学学报 ›› 1993, Vol. 51 ›› Issue (5): 438-443. 上一篇    下一篇

研究论文

固态二乙炔拓扑聚合反应动力学的量子化学研究

颜顺启;张启元;严继民   

  1. 中国科学院化学研究所
  • 发布日期:1993-05-15

Quantum-chemical investigation on the reaction kinetics of topochemical polymerization of solid-state diacetylenes

YAN SHUNQI;ZHANG QIYUAN;YAN JIMIN   

  • Published:1993-05-15

PDF

378

被引次数

5

利用协同反应模型和EHCO-ASED量子化学方法, 对固态二乙炔的拓扑聚合反应:MDA(Molecular diacetylenes)→PBT(Polybutatrienes)→PDA(Polydiacetylenes)的势能曲线进行了计算, 并对其轨道对称性以及能隙随反应坐标的变化进行了分析; 很好地解决了文献中用Woodward-Hoffmann轨道对称守恒原理对此反应进行分析时所遇到的问题, 指出了此反应是热允许的原因。

关键词: 反应机理, 反应动力学, 聚合, 势能, 乙炔 P, 拓扑, 分子轨道对称守恒

The potential curve of the 1,4-polymn. of diacetylene to prepare polybutatrienes and further polydiacetylenes was studied based on the topochem. model and the quantum-chem. method of EHCO-ASED. The transformation of the frontier orbital symmetry along the reaction coordinates was analyzed. The problem about the Woodward-Hoffmann's orbital symmetry conservation of such reactions in the literatures was solved., and then the reasons why these reactions might be thermally allowed were presented.

Key words: REACTION MECHANISM, REACTION KINETICS, POLYMERIZATION, POTENTIAL ENERGY, ACETYLENE P, TOPOLOGY, CONSERVATION OF SYMMETRY OF MOLECULAR ORBITAL

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