AbstractThe behavior of PVC plastisols during gelation and fusion was studied by the ATR‐FTIR technique (Attenuated Total Reflectance‐Fourier Transform Infrared Spectroscopy). DBP, DOP, and DIDP, three common phthalate plasticizers for PVC, were used in plastisols formulations. Three heating rates—5, 10 and 15°C/min—and formulations with different plasticizer concentrations were studied. The IR spectra of a plastisol coincides with the IR spectra of the plasticizer except for the bands at 1435 and 613 cm−1from the PVC (CH2wagging and C—Cl stretching, respectively). When the plastisol is heated, a progressive decrease of the plasticizer bands areas can be observed, while bands from PVC increase their intensity, probably because of the adsorption of the plasticizer by the resin. On cooling, the area of all bands follows the same path as when heating, but the paths separate at a certain temperature, showing the irreversible nature of this process. The analysis of the band at 1280 cm−1(C(O)—O from plasticizer) during heating and cooling, shows that the temperature of separation areas (Ts) takes place at temperatures coherent with plasticizer compatibility. Studies at different heating rates and different plasticizer content are in good agreement with results using other techniques, available i