Self-Assembled Structures of Giant Surfactants Exhibit a Remarkable Sensitivity on Chemical Compositions and Topologies for Tailoring Sub-10 nm Nanostructures

• DOI: 10.1021/acs.macromol.6b02446
• Publication Date: 2016-12-20T18:56:49Z
• Authors: Kan Yue; Chang Liu; Mingjun Huang; Jiahao Huang; Zhe Zhou; Kan Wu; Hao Liu; Zhiwei Lin; An-Chang Shi; Wen-Bin Zhang; Stephen Z. D. Cheng
• Keywords: Silsesquioxane

We report a remarkable sensitivity of self-assembled structures giant surfactants on their chemical compositions and molecular topology, which facilitate the engineering various nanophase-separated with sub-10 nm feature sizes. Two classes composed functionalized polyhedral oligomeric silsesquioxane (POSS) heads tethered one or two polystyrene (PS) tails were efficiently prepared from common precursors vinyl-substituted POSS–PS conjugates via one-step "thiol–ene" postpolymerization functionalization. With identical weights PS tails, resulting exhibited distinct highly ordered phases, as evidenced by small-angle X-ray scattering transmission electron microscopy observations. Moreover, comparison between topological isomers revealed that are also sensitive to topology. Introduction half-length not only shifted boundaries different phases but altered packing configurations functional POSS cages, leading further reduced sizes nanodomains. Interestingly, lower order–disorder transition temperature was observed in fluorinated F13POSS PS17 compared its isomer PS35 tail, indicating effect existed phase behaviors. These results provide insights rationally design precisely tailor controlling both primary topology POSS-based surfactants.