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Patchy Wormlike Micelles with Tailored Functionality by Crystallization-Driven Self-Assembly: A Versatile Platform for Mesostructured Hybrid Materials
Judith Schöbel, Matthias Karg, Dominic Rosenbach, Gert Krauss, Andreas Greiner, Holger Schmalz:
Macromolecules, 49, 7, 2761-2771 (2016)
doi: 10.1021/acs.macromol.6b00330

One-dimensional patchy nanostructures are interesting materials due to their excellent interfacial activity and their potential use as carrier for functional nanoparticles. Up to now only wormlike crystalline-core micelles (wCCMs) with a nonfunctional patchy PS/PMMA corona were accessible using crystallization-driven self-assembly (CDSA) of polystyrene-block-polyethylene-block-poly(methyl methacrylate) (SEM) triblock terpolymers. Here, we present a facile approach toward functional, patchy wCCMs, bearing tertiary amino groups in one of the surface patches. The corona forming PMMA block of a SEM triblock terpolymer was functionalized by amidation with different N,N-dialkylethylenediamines in a polymer analogous fashion. The CDSA of the functionalized triblock terpolymers in THF was found to strongly depend on the polarity/solubility of the amidated PMMA block. The lower the polarity of the amidated PMMA block (increased solubility), the higher is the accessible degree of functionalization upon which defined, well-dispersed wCCMs are formed. Interestingly, also the structure of the patchy corona can be tuned by the composition/chemistry of the functional patch, giving rise to spherical patches for R = methyl, ethyl and rectangular patches for R = isopropyl. Patchy wCCMs were successfully used as template for the selective incorporation of Au nanoparticles within the amidated corona patches, showing their potential as versatile platform for the construction of functional, mesostructured hybrid materials.