Polybenzimidazole Confined in Semi-Interpenetrating Networks of Crosslinked Poly (Arylene Ether Ketone) for High Temperature Proton Exchange Membrane.

As a traditional high-temperature proton exchange membrane (HT-PEM), phosphoric acid (PA)-doped polybenzimidazole (PBI) is often subject to severe mechanical strength deterioration owing to the "plasticizing effect" of a large amount of PA. In order to address this issue, we fabricated the HT-PEMs with a crosslinked network of poly (arylene ether ketone) to confine polybenzimidazole in semi-interpenetration network using self-synthesized amino-terminated PBI (PBI-4NH2) as a crosslinker. Compared with the pristine linear poly [2,2'-(p-oxdiphenylene)-5,5'-benzimidazole] (OPBI) membrane, the designed HT-PEMs (semi-IPN/xPBI), in the semi-IPN means that the membranes with a semi-interpenetration structure and x represent the combined weight percentage of PBI-4NH2 and OPBI. In addition, they also demonstrate an enhanced anti-oxidative stability and superior mechanical properties without the sacrifice of conductivity. The semi-IPN/70PBI exhibits a higher proton conductivity than OPBI at temperatures ranging from 80 to 180 °C. The HT-PEMFC with semi-IPN/70PBI exhibits excellent H2/O2 single cell performance with a power density of 660 mW cm-2 at 160 °C with flow rates of 250 and 500 mL min-1 for dry H2 and O2 at a backpressure of 0.03 MPa, which is 18% higher than that of OPBI (561 mW cm-2) under the same test conditions. The results indicate that the introduction of PBI containing crosslinked networks is a promising approach to improve the comprehensive performance of HT-PEMs.

High performance poly(urethane-co-amide) from CO2-based dicarbamate: an alternative to long chain polyamide.

Due to its high strength, toughness, corrosion resistance and wear resistance, long chain polyamide (LCPA) has attracted broad interest. Nevertheless, its wide application in industrial fields is still being restricted because the starting material acquisition step involving diacid and diamine remains a major obstacle. Herein, we circumvent this obstacle by developing a novel polymer with similar properties by a green and efficient copolymerization process of carbon dioxide (CO2)-based dicarbamate with diamide diol under vacuum conditions, named poly(urethane-co-amide) (PUA). The semi-crystalline PUAs with high number-weight-average molecular weights (M n, up to 41.3 kDa) were readily obtained, and these new polymers show high thermal stability (above 300 °C). Thanks to its unique chain structure, the amide, urethane and urea groups can endow the polymer with a high density cross-linking network via hydrogen bonds and high crystallinity that can result in high strength, up to 54.0 MPa. The dynamic thermomechanical analysis (DMA) results suggest that the phase separation exists within the new polymers, endowing the PUAs with a toughness higher than that of long chain polyamides. Consequently, this work not only develops a useful new polymer like commercial polyamides with high performance as a long chain polyamide candidate, but also provides a new way of utilizating CO2.