Synthesis, Characterization and Structure - Property Relationships of Post - sulfonated Poly(arylene ether sulfone) Membranes for Water Desalination

Abstract

Clean water is critical to the safety, security and survivability of humankind. Nearly 41% of the Earth's population lives in water-stressed areas, and water scarcity will be exacerbated by an increasing population. Over 96% of the total water is saline and only 0.8% is accessible fresh water. Thus, saltwater desalination has emerged as the key to tackle the problem of water scarcity. Our current work deals with the membrane process of reverse osmosis. Sulfonated polysulfones are a potential alternative to state-of-the-art thin film polyamides. Synthesized by step growth polymerization, polysulfone membranes have smooth surfaces and they are more chemically resistant relative to polyamides. Previously studied sulfonated polysulfone membranes were synthesized by direct copolymerization of pre-disulfonated comonomer and the sulfonate ions were placed on adjacent rings of bisphenol moiety. This study focuses on placing the sulfonate ions differently along the polysulfone backbone on isolated rings of hydroquinone moiety, and on adjacent rings of biphenol moiety- and its effect on the transport and hydrated mechanical properties of the membranes. Selective post sulfonation of poly(arylene ether sulfone) in mild conditions was also found to be an effective way to strategically place the sulfonate ions along the backbone of the polymer chain without the need to synthesize a new monomer. Hydroquinone based, amine terminated oligomers were synthesized with block molecular weights of 5000 and 10,000 g/mol. They were post-sulfonated and crosslinked at their termini with epoxy reagents. Such crosslinked and linear membranes had sulfonate ions on isolated rings of hydroquinone moiety. Synthesis and kinetics of controlled post-sulfonation of poly(arylene ether sulfones) that contained biphenol units were also reported. The sulfonation reaction proceeded only on the biphenol rings. The linear membranes had sulfonate ions on adjacent rings of biphenol moieties. The tensile measurements were performed on the membranes under fully hydrated conditions. All membranes remained glassy at values of water uptake. It was found that elastic moduli and yield strengths in the hydroquinone- based linear and crosslinked membranes increased with decrease in water uptakes in the membranes. The effect of plasticization of water superseded the effect of block length and degree of sulfonation in the membranes. The highest elastic modulus of 1420 MPa at lowest water uptake of 18% was observed in cross linked membrane with 50% repeat units being sulfonated (50% repeat units contain hydroquinone)and target molecular weight of 5000 g/mol. However, the hydroquinone membranes broke at low strains of < 20%. The hydrated mechanical properties could be improved by replacing the hydroquinone with biphenol moieties. The biphenol based post-sulfonated membrane showed high elastic modulus that was comparable to the hydroquinone-based counterparts at similar values of water uptake. The biphenol based membrane broke at higher strains of >80%. The post-sulfonated membranes- hydroquinone-based linear and crosslinked membranes and biphenol-based linear membranes had better transport properties than the previously studied sulfonated polysulfones that were synthesized by disulfonated comonomers.The post sulfonated hydroquinone-based membranes did not show a compromise in the rejection of monovalent ions in the presence of divalent ions in mixed feed water. The superior properties of the post-sulfonated membranes can potentially be attributed to the kinked backbone that potentially increased the free volume in the membranes and the sulfonate ions were spaced apart to potentially reduce their chelation with calcium (divalent) ions in mixed feed water. Interestingly, the biphenol based post-sulfonated membranes also did not have any compromise in the rejection of monovalent ions in the presence of divalent ions. This was potentially because the sulfonate ions were spaced far apart on the non-planar biphenol rings.