Closed Loop of Polyurethanes: Effect of Isocyanate Index on the Properties of Repolyols and Rebiopolyols Obtained by Glycolysis

This paper presents the effect of the isocyanate index of polyurethane foams on the properties of repolyols and rebiopolyols obtained through glycolysis and on the foaming process of the new polyurethane systems. An FTIR spectral analysis confirmed that as the isocyanate index decreased, the intensity of the bands’ characteristic of urethane and urea bonds also decreased, indicating a lower proportion of carbonyl groups and hard segments in the polymer structure. Simultaneously, an increase in the hydroxyl number of the repolyols and the rebiopolyols was observed, along with a decrease in their viscosity and average molar masses. Both effects are consequences of a lower degree of cross-linking in the parent foams. An analysis of the foaming process using a Foamat apparatus revealed that the viscosity and the molar mass of the repolyols and the rebiopolyols significantly affected the system’s reactivity, maximum reaction temperature, and the time required to reach it. Differences in foaming dynamics resulted in different cellular structures of the foams, their apparent density, and mechanical properties. The foams obtained from the repolyols derived from foams with a lower isocyanate index exhibited a lower degree of cross-linking and a lower strength, while the foams with the rebiopolyols tended to shrink. The intensity of the shrinkage was limited by a higher degree of cell openness. These results confirm the crucial role of the properties of repolyol and rebiopolyol in shaping the reactivity, morphology, and properties of final polyurethane foams, providing a basis for designing new, sustainable polyurethane systems.