Cosolvent-Driven Interfacial Polymerization for Superior Separation Performance of Polyurea-Based Pervaporation Membrane.

A thin-film composite (TFC) polyurea membrane was fabricated for the dehydration of an aqueous tetrahydrofuran (THF) solution through interfacial polymerization, wherein polyethyleneimine (a water-soluble amine monomer) and m-xylene diisocyanate (an oil-soluble diisocyanate monomer) were reacted on the surface of a modified polyacrylonitrile (mPAN) substrate. Cosolvents were used to tailor the membrane properties and increase the membrane permeation flux. Four types of alcohols that differed in the number of carbon (methanol, ethanol, isopropanol, and tert-butanol) were added as cosolvents, serving as swelling agents, to the aqueous-phase monomer solution, and their effect on the membrane properties and pervaporation separation was discussed. Attenuated total reflection Fourier transform infrared spectroscopy confirmed the formation of a polyurea layer on mPAN. Field emission scanning electron microscopy and surface water contact angle analysis indicated no change in the membrane morphology and hydrophilicity, respectively, despite the addition of cosolvents for interfacial polymerization. The TFC membrane produced when ethanol was the cosolvent exhibited the highest separation performance (permeation flux = 1006 ± 103 g·m-2·h-1; water concentration in permeate = 98.8 ± 0.3 wt.%) for an aqueous feed solution containing 90 wt.% THF at 25 °C. During the membrane formation, ethanol caused the polyurea layer to loosen and to acquire a certain degree of cross-linking. The optimal fabrication conditions were as follows: 10 wt.% ethanol as cosolvent; membrane curing temperature = 50 °C; membrane curing time = 30 min.