Branched Poly(arylene ether ketone sulfone)s with Ultradensely Sulfonated Branched Centers for Proton Exchange Membranes: Effect of the Positions of the Sulfonic Acid Groups.

Branched sulfonated polymers present considerable potential for application as proton exchange membranes, yet investigation of branched polymers containing sulfonated branched centers remains to be advanced. Herein, we report a series of polymers with ultradensely sulfonated branched centers, namely, B-x-SPAEKS, where x represents the degree of branching. In comparison with the analogous polymers bearing sulfonated branched arms, B-x-SPAEKS showed a reduced water affinity, resulting in less swelling and lower proton conductivity. The water uptake, swelling ratio (in-plane), and proton conductivity of B-10-SPAEKS at 80 °C were 52.2%, 57.7%, and 23.6% lower than their counterparts, respectively. However, further analysis revealed that B-x-SPAEKS featured significantly better proton conduction under the same water content due to the formation of larger hydrophilic clusters (∼10 nm) that promoted efficient proton transportation. B-12.5-SPAEKS exhibited a proton conductivity of 138.8 mS cm-1 and a swelling ratio (in-plane) of only 11.6% at 80 °C, both of which were superior to Nafion 117. In addition, a decent single-cell performance of B-12.5-SPAEKS was also achieved. Consequently, the decoration of sulfonic acid groups on the branched centers represents a very promising strategy, enabling outstanding proton conductivity and dimensional stability simultaneously even with low water content.

Semi-crystalline sulfonated poly(ether ketone) proton exchange membranes: The trade-off of facile synthesis and performance.

Improving the performance of proton exchange membranes (PEMs) through the synthesis of sulfonated polymers with elaborate molecular structures has received extensive approval. However, the tedious synthetic process and consequently high costs restrain their possible substitution for Nafion, a classic PEM material. Herein, a series of semi-crystalline sulfonated poly(ether ketone)s with fluorene-based units were prepared via direct copolymerization of commercially available monomers and followed post-sulfonation, namely SPEK-FD-x, where × represents the molar ratio of the fluorene-containing monomer to the employed bisphenol monomers. The entire synthetic pathway was facile without involving hardly accessible materials. Subsequently, various properties of SPEK-FD-x membranes were investigated and further compared with Nafion 117. Due to the formation of the well-defined hydrophilic-hydrophobic microphase separation morphology and the reinforcement of the PEK crystalline regions, the SPEK-FD-x membranes exhibited outstanding proton conductivity, resistance for methanol permeation, as well as dimensional, thermal, oxidative, and mechanical stability. Among them, the overall behavior of the SPEK-FD-25 membrane was comparable to or even greater than that of Nafion 117, most importantly, it also performed decently in both H2/air fuel cells and direct methanol fuel cells. Therefore, with the straightforward synthesis and superior performance, the SPEK-FD-x membranes may serve as a promising alternative to Nafion.

Facile Fabrication of Multi-Hydrogen Bond Self-Assembly Poly(MAAc-co-MAAm) Hydrogel Modified PVDF Ultrafiltration Membrane to Enhance Anti-Fouling Property.

In this work, a facile preparation method was proposed to reduce natural organics fouling of hydrophobic membrane via UV grafting polymerization with methacrylic acid (MAAc) and methyl acrylamide (MAAm) as hydrophilic monomers, followed by multihydrogen bond self-assembly. The resulting poly(vinylidene fluoride)-membranes were characterized with respect to monomer ratio, chemical structure and morphology, surface potential, and water contact angle, as well as water flux and organic foulants ultrafiltration property. The results indicated that the optimal membrane modified with a poly(MAAc-co-MAAm) polymer gel layer derived from a 1:1 monomer ratio exhibited superior hydrophilicity and excellent gel layer stability, even after ultrasonic treatment or soaking in acid or alkaline aqueous solution. The initial water contact angle of modified membranes was only 36.6° ± 2.9, and dropped to 0° within 13 s. Moreover, flux recovery rates (FRR) of modified membranes tested by bovine serum albumin (BSA), humic acid (HA), and sodium alginate (SA) solution, respectively, were all above 90% after one-cycle filtration (2 h), significantly higher than that of the pure membrane (70-76%). The total fouling rates (Rt) of the pure membrane for three foulants were as high as 47.8-56.2%, while the Rt values for modified membranes were less than 30.8%. Where Rt of BSA dynamic filtration was merely 10.7%. The membrane designed through grafting a thin-layer hydrophilic hydrogel possessed a robust antifouling property and stability, which offers new insights for applications in pure water treatment or protein purification.