Focal Point Association of Core-Crystalline Micelles with an Amphiphilic Corona Block

We report the preparation of star-like supermicelles by the secondary association of triblock comicelles or scarf-like micelles driven by a change in solvency. These building blocks were synthesized by seeded growth in which crystallites of a triblock terpolymer, either PFS₂₇-<i>b</i>-PTDMA₈₁-<i>b</i>-POEGMA₄₅ (to form triblock comicelles) or PFS₆₆-<i>b</i>-PTDMA₈₁-<i>b</i>-POEGMA₄₅ (to form scarf-like micelles), served as seeds for crystallization-driven self-assembly (CDSA). PFS-<i>b</i>-PTDMA unimers were added in the seeded growth step. The corona-forming block PTDMA-POEGMA is amphiphilic and sensitive to polarity changes of the solvents. We sought solvents in which the upper critical solution temperature (UCST, <i>T</i>_UCST) of POEGMA was slightly above room temperature (RT). Examples included 1-decanol and 1-decanol/decane mixtures. Seeded growth proceeded normally in solvents above the UCST of POEGMA. When the solution temperature was lowered below <i>T</i>_UCST, or when the triblock comicelles or scarf-like micelles were transferred to a solvent (e.g., 1-decanol) below its <i>T</i>_UCST, the center blocks associated to form star-like supermicelles. The addition of small amounts of THF to the medium to increase the solvency for POEGMA led to dissociation of the supermicelles. Transfer of the triblock comicelles to 1-pentanol at RT, below the UCST of PTDMA, also led to controlled secondary association to form supermicelles with a different morphology. Seeded growth with PFS₂₅-<i>b</i>-PDMAEMA₁₈₄ unimers led to supermicelles in which the poly(dimethylaminoethyl methacrylate) corona chains could serve as carriers for gold nanoparticles (AuNPs). These AuNP@supermicelle complexes could serve as recoverable catalysts, for example to catalyze the condensation polymerization of bis(dimethylsilyl)benzene and pentanediol. They were highly active catalysts and showed excellent mechanical robustness for recovery and reuse.