THE EFFECTS OF FLUORINE SUBSTITUTION ON THE PROPERTIES AND REACTION RATES OF GLYCIDYL ETHERS.

Two series of fluorine-containing monoglycidyl ethers have been synthesized, and the kinetics of the reaction of these compounds with dibutylamine has been studied by the use of a gas chromatographic method of reaction rate analysis. In tertiary amyl alcohol solution at initial concentrations of 0.200M, all reactions were second order, and the rate constants at 60C were in the range from 5.12 to 0.001114 litersmole-sec. The effects of fluorine quantity and molecular position on these rate constants are used to support a cyclic-transition-state mechanism for the glycidyl ether-amine reaction. Also, the physical properties of the compounds, including surface tensions, viscosities, densities, and refractive indices, are given Arrhenius parameters for the reactions, including activation energies, frequency factors, and entropies of activation, have also been determined. A series of related fluorine-containing diglycidyl ethers has been synthesized and obtained as high-purity compounds. The physical characteristics of these ethers are given. It is shown that fluorinated diols can be used as reactants with the diglycidyl ethers to produce fluorinated polyols, and some overall concentration-vs-time plots for these reactions are shown. Author