Competition between CO-philicity and Mixing Entropy Leads to CO Solubility Maximum in Polyether Polyols.

In carbon dioxide-blown polymer foams, the solubility of carbon dioxide (CO) in the polymer profoundly shapes the structure and, consequently, the physical properties of the foam. One such foam is polyurethane-commonly used for thermal insulation, acoustic insulation, and cushioning-which increasingly relies on CO to replace environmentally harmful blowing agents. Polyurethane is produced through the reaction of isocyanate and polyol, of which the polyol has the higher capacity for dissolving CO. While previous studies have suggested the importance of the effect of hydroxyl end groups on CO solubility in short polyols (<1000 g/mol), their effect in polyols with higher molecular weight (≥1000 g/mol) and higher functionality (>2 hydroxyls per chain)-as are commonly used in polyurethane foams-has not been reported. Here, we show that the solubility of CO in polyether polyols decreases with molecular weight above 1000 g/mol and decreases with functionality using measurements performed by gravimetry-axisymmetric drop-shape analysis. The nonmonotonic effect of molecular weight on CO solubility results from the competition between effects that reduce CO solubility (lower mixing entropy) and effects that increase CO solubility (lower ratio of hydroxyl end groups to ether backbone groups). To generalize our measurements, we modeled the CO solubility using a perturbed chain-statistical associating fluid theory (PC-SAFT) model, which we validated by showing that a density functional theory model based on the PC-SAFT free energy accurately predicted the interfacial tension.