This study aimed to determine the solubility and temperature dependence of methanol and ethanol vapor caused by the difference in the substituents of polyhedral oligomeric silsesquioxane (POSS)‐containing polymethacrylate membranes and the spacer length between the backbone and POSS backbone. Vapor sorption of methanol and ethanol was measured at 25°C, 35°C, and 45°C for three kinds of POSS‐containing polymer membranes, namely, poly(methacryl isobutyl POSS), poly(methacrylate isobutyl POSS), and poly(methacryl phenyl POSS). The primary structures of the three POSS‐containing polymer chains were columnar. The solubility of alcohol vapor on the POSS‐containing polymer membranes followed the mechanism of solid adsorption and not the general dissolution diffusion. The sorption amount at all three temperatures was related to the surface area of the cylindrical primary structure and the solid adsorption property of the alcohol molecule of the POSS substituent. The sorption amount increased because of the large surface area and adsorption property of alcohol molecules. Although a typical glassy polymer shows exothermic mixing and a rubbery polymer displays endothermic mixing, the sample with the POSS substituent of isobutyl group exhibited an unusual behavior of endothermic mixing despite being a glassy polymer.
In this study, the sorption amount of alcohols (ethanol, 1-propanol, and 2-propanol) vapors on poly(lactic acid) (PLA) membrane was measured resulting in high increase in sorption. Sorption amount increases as the molecular volume of vapor decreases in the low-pressure region. The sorption amount of branched 2-propanol is lower than that of linear 1-propanol. In the high-pressure region, the PLA film tends to swell or plasticize as the cluster size increases, thereby increasing sorption. In addition, the alcohol vapor sorbed in the PLA film causes vapor-induced crystallization, which is in contrast to solvent- and thermally-induced crystallization, and forms an unknown crystal structure.
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