Study of the reaction between resorcinol and formaldehyde

The reactions between resorcinol and formaldehyde were led in aluminium pans of a d.s.c. Perkin Elmer calorimeter. The products were separated by means of high performance liquid chromatography and identified by ¹H and ¹³C n.m.r. Depending on the catalyst concentration and molar ratio the mixtures reacted at two different temperature ranges, 317–332K and 332–366K. The heat of the reaction in the first temperature range was between 16.8 and 45.0 kJ mol^?1 for molar ratios 1:1 and 1:3 respectively. By ¹H and ¹³C n.m.r. spectroscopy five addition products were determined. The reaction heat in the second temperature range was 73.5 kJ mol^?1 and was attributed to condensation reactions. The activation energies were 95.0 and 120.0 kJ mol^?1 for addition and condensation reactions respectively. For addition, order two and for condensation, order one of reaction was established. On the basis of these foundings tentative reaction schemes were prepared.