Cross-linked polybenzimidazole membranes were obtained by heating at 160 C, using 4,4 0diglycidyl(3,3 0 ,5,5 0 -tetramethylbiphenyl) epoxy resin (TMBP) as the cross-linker. The cross-linking reaction temperature was determined by DSC and the successful completion of the cross-linking reaction was shown by FTIR and solubility tests. The cross-linked membranes showed high proton conductivity and strong mechanical properties, as well as low swelling after immersion in 85% phosphoric acid at 90 C. For instance, the membrane with a cross-linker content weight percent of 20% (PBI-TMBP 20%) with a PA doping level of 4.1 exhibited a proton conductivity of 0.010 S cm À1 and a low swelling volume of 50%. Moreover, the cross-linked membranes showed excellent oxidative stability. The PBI-TMBP 20% cross-linked membrane tested in Fenton's reagent (3% H 2 O 2 solution, 4 ppm Fe 2+ , 70 C) kept its shape for more than 480 h and did not break. In particular, the proton conductivity of the PA-PBI-TMBP 20% membrane after Fenton's test (30% H 2 O 2 , 20 ppm Fe 2+ , 85 C) remained at a high level of 0.009 S cm À1 . This investigation proved that cross-linking is a very effective approach for improving the performance of proton exchange membranes.

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As size-amplified analogues of canonical macromolecules, polymeric chains built up by “giant” monomers represent an experimental realization of the “beads-on-a-string” model at larger length scales, which could provide insights into fundamental principles of polymer science. In this work, we modularly constructed discrete giant polymeric chains using nanosized building blocks (polyhedral oligomeric silsesquioxane, POSS) as basic repeat units through an efficient and robust iterative exponential growth approach, with precise control on molecular parameters, including size, composition, regioconfiguration, and surface functionalities. Their chemical structures were fully characterized by nuclear magnetic resonance spectroscopy, size-exclusion chromatography, and matrix-assisted laser desorption ionization time-of-flight mass spectrometry. With elaborately designed amphiphilic block POSS chains and their analogues made of conventional monomers, the size effects were delicately studied and highlighted. Interesting assembly behaviors emerge as a result of distinct interactions and molecular dynamics. This category of molecules shares general self-assembly characteristics as the conventional counterparts in terms of phase transition and evolution. Meanwhile, it turns out that the monomer size has profound impacts on phase stability, as a trade-off between entropic and enthalpic contributions. It may open up a door for modular and programmable design of interesting materials with complex structures and diverse functions.

Novel self-crosslinked alkaline anion exchange membranes with high alkaline stability, excellent dimensional stability and extraordinary methanol resistance were synthesized successfully without using any catalyst or a separate crosslinker.

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