|478. Betthausen, E.; Hanske, C.; Müller, M.; Fery, A.; Schacher, F.H.; Müller, A.H.E.; Pochan, D.J.: Self-Assembly of Amphiphilic Triblock Terpolymers Mediated by by Multifunctional Organic Acids: Vesicles, Toroids, and (Undulated) Ribbons, Macromolecules 47, 1672–1683 (2014) -- DOI: 10.1021/ma402555c|
The self-assembly of block copolymers in the presence of additives represents an elegant strategy to adjust micellar morphologies in solution and to design complex structures that are not accessible otherwise. Herein, we use linear ABC triblock terpolymers comprising a polyamine block: polybutadiene-block-poly(tert-butyl methacrylate)-block-poly(2-(dimethylamino)ethyl methacrylate) (PB-b-PtBMA-b-PDMAEMA) terpolymers coassembled with organic di- or triacids in mixtures of THF and water. The interactions between the organic multiacids and the hydrophilic PDMAEMA block can be adjusted via the chain architecture, amount, and functionality of added acid, the solvent quality, and the PDMAEMA block length. Consequently, these parameters allow a certain level of control over the resulting micellar morphology. Characterization by (cryogenic) transmission electron microscopy and atomic force microscopy revealed the formation of spherical, disk-shaped, and toroidal structures, alongside ribbons featuring enlarged end-caps. In the latter case, changing the solvent composition or the amount/type of organic diacid induced the formation of undulated ribbons and, eventually, partition into spherical particles.