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Acta Chimica Sinica ›› 2011, Vol. 69 ›› Issue (18): 2085-2091. Previous Articles     Next Articles

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β-二酮亚胺钛化合物催化乙烯和环戊二烯共聚合反应机理的密度泛函理论研究

王永霞1,2，段雪梅*,1，王钦1，李悦生2，刘靖尧1   

  1. (1吉林大学理论化学研究所 理论化学计算国家重点实验室 长春 130023)
    (2中国科学院长春应用化学研究所 长春 130022)
  • 投稿日期:2011-01-03 修回日期:2011-03-26 发布日期:2011-05-23
  • 通讯作者: 刘靖尧 E-mail:ljy121@jlu.edu.cn
  • 基金资助:

    国家自然科学基金;国家自然科学基金;国家自然科学基金

DFT Study on the Copolymerization Mechanism of Ethylene with Cyclopentadiene by the Titanium Complexes Bearing Two β-Enaminoketonato Ligands

Wang Yongxia1,2 Duan Xuemei*,1, Wang Qin1 Li Yuesheng2 Liu Jingyao1   

  1. (1 Institute of Theoretical Chemistry, State Key Laboratory of Theoretical and Computational Chemistry, Jilin University, Changchun 130023)
    (2 Changchun Institute of Applied Chemistry, Changchun 130022)
  • Received:2011-01-03 Revised:2011-03-26 Published:2011-05-23
  • Contact: Jing-Yao LIU E-mail:ljy121@jlu.edu.cn

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We employed DFT calculations for copolymerization mechanism of ethylene (E) with cyclopentadiene (CPD) catalyzed by [PhNC(CH3)CHC(CF3)O]2TiCl2. Our calculations show that the CPD can incorporate into polymer chain via both 1,2 and 2,1-insertion, and it is predicted that 1,2-insertion might be a preferred pathway due to the lower barrier. And in the copolymerization process, reaction barriers of ethylene insertion into both Metal-E and Metal-CPD bonds are lower than the barriers of CPD insertion, consequently, there might be more E sequences in the growing polymer chain. The CPD insertion into Metal-E bond can occur a certain extent due to the relative low insertion barrier, while for the process of CPD insertion into Metal-CPD chain, its insertion barrier is too high to make this reaction occur. The present conclusion is in line with the experimental fact that no consecutive sequence of CPD has been observed in the polymer product.

Key words: density functional theory, transition metal catalyst, copolymerization, ethylene, cyclopentadiene

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