High-internal-phase emulsion-templated macroporous polymers (polyHIPEs) have attracted much interest, but their surface functionalization remains a primary concern. Thus, competitive surface functionalization via physical self-assembly of macrosurfactants was reviewed. Dendritic and diblock-copolymer macrosurfactants were tested, and the former appeared to be more topologically competitive in terms of solubility, viscosity, and versatility. In particular, hyperbranched polyethyleneimine (PEI) was transformed into dendritic PEI macrosurfactants through click-like N-alkylation with epoxy compounds. Free-standing PEI macrosurfactants were used as molecular nanocapsules for charge-selective guest encapsulation and robustly dictated the surface of a macroporous polymer through the HIPE technique, in which the macroporous polymer could act as a well-recoverable adsorbent. Metal nanoparticle-loaded PEI macrosurfactants could similarly lead to polyHIPE, whose surface was dictated by its catalytic component. Unlike conventional Pickering stabilizer, PEI macrosurfactant-based metal nanocomposite resulted in open-cellular polyHIPE, rendering the catalytic sites well accessible. The active amino groups on the polyHIPE could also be transformed into functional groups of aminopolycarboxylic acids, which could efficiently eliminate trace and heavy metal species in water.
Highly Permeable Macroporous Polymers Synthesized from Pickering Medium and High Internal Phase Emulsion Templates