Acta Chimica Sinica ›› 2004, Vol. 62 ›› Issue (24): 2369-2373.     Next Articles

α-氰基丙烯酸乙酯阴离子聚合的密度泛函理论研究

周亚红1,2, 卑凤利1, 杨绪杰1, 陆路德1, 汪信1   

  1. 1. 南京理工大学化工学院, 南京, 210094;
    2. 江苏警官学院, 南京, 210012
  • 收稿日期:2004-06-09 修回日期:2004-08-18 出版日期:2004-12-28 发布日期:2014-02-17
  • 通讯作者: 汪信,E-mail:njwmq@vip.163.com E-mail:njwmq@vip.163.com
  • 基金资助:
    国家自然科学基金(No.50372028)和国家教育部博士点基金(No.20030288019)资助项目.

Density Functional Theory Study on the Anionic Polymerization of Ethyl α-Cyanoacrylate

ZHOU Ya-Hong1,2, BEI Feng-Li1, YANG Xu-Jie1, LU Lu-De1, WANG Xin1   

  1. 1. Department of Chemistry, Nanjing University of Science & Technology, Nanjing 210094;
    2. Jiangsu Police Officer College, Nanjing 210012
  • Received:2004-06-09 Revised:2004-08-18 Online:2004-12-28 Published:2014-02-17

Density functional theory (DFT) at the B3LYP level with 6-31G* basis set was employed to optimize the reactant and the transition state on the potential surface of the ethyl α-cyanoacrylate with water for the first time. The charge, energies, IR spectra and thermodynamic properties were obtained. The activation energy of 13.83 kJ/mol in the gas phase and the order of 1010 s-1 of initiating rate constant were obtained for the reaction. The results both in thermodynamics and kinetics illustrate anionic polymerization mechanism. The impacts of solvent effect on the geometries of reactant and transition state as well as the reaction mechanism were systematically studied for the α-cyanoacrylate with water by self-consistent reaction field (SCRF) technique with different dielectric constants of 2.02, 2.38, 7.58 and 12.3. It was found that the solvent effect would depress the activation energy and finally make the initiation reaction without energy barrier in polar solvents.

Key words: DFT, ethylα-cyanoacrylate, hydroxy, solvent effect