A comprehensive understanding of co-solvent effects on interfacial polymerization: Interaction with trimesoyl chloride

Co-solvent assisted interfacial polymerization (CAIP) has been widely used to increase the water permeability of thin-film composite (TFC) reverse osmosis (RO) membranes. However, its outcomes are often poorly understood or unpredictable. To bridge the gap between conventional wisdom and the real effects of the co-solvent, we report—for the first time, to the best of our knowledge—empirical evidence in terms of the actual interfacial tension between two immiscible solutions used in CAIP. According to our results, dimethyl sulfoxide (DMSO), which is frequently used as a co-solvent, influences IP by interacting with trimesoyl chloride (TMC). The dipole-dipole interaction between DMSO and TMC was estimated to increase the TMC concentration at the interface and, thereby, the reaction rate. Due to the fast reaction, the diffusion barrier forms quickly, reducing the thickness and roughness of the active layer. The cross-linking degree was also determined to decrease due to the incomplete reaction that occurs when one of three acyl chloride groups interacts with S^δ+−O^δ− electrostatic dipoles of DMSO at the interface, as evidenced by the variation in unreacted acyl chloride groups in the active layer and by the nitrogen/oxygen ratio. Such morphological changes were consistent with the trend in the performances of the RO membranes prepared with different amounts of DMSO, and were used to interpret the possible transport phenomena.