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