Highly Tunable Nanostructures in a Doubly pH-Responsive Pentablock Terpolymer in Solution and in Thin Films

Florian A. Jung, Maximilian Schart, Lukas Bührend, Elisabeth Meidinger, Jia Jhen Kang, Bart Jan Niebuur, Sina Ariaee, Dmitry S. Molodenskiy, Dorthe Posselt, Heinz Amenitsch, Constantinos Tsitsilianis, Christine M. Papadakis*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review


Multiblock copolymers with charged blocks are complex systems that show great potential for enhancing the structural control of block copolymers. A pentablock terpolymer PMMA-b-PDMAEMA-b-P2VP-b-PDMAEMA-b-PMMA is investigated. It contains two types of midblocks, which are weak cationic polyelectrolytes, namely poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and poly(2-vinylpyridine) (P2VP). Furthermore, these are end-capped with short hydrophobic poly(methyl methacrylate) (PMMA) blocks in dilute aqueous solution and thin films. The self-assembly behavior depends on the degrees of ionization α of the P2VP and PDMAEMA blocks, which are altered in a wide range by varying the pH value. High degrees of ionization of both blocks prevent structure formation, whereas microphase-separated nanostructures form for a partially charged and uncharged state. While in solutions, the nanostructure formation is governed by the dependence of the P2VP block solubility of the and the flexibility of the PDMAEMA blocks on α, in thin films, the dependence of the segregation strength on α is key. Furthermore, the solution state plays a crucial role in the film formation during spin-coating. Overall, both the mixing behavior of the 3 types of blocks and the block sequence, governing the bridging behavior, result in strong variations of the nanostructures and their repeat distances.

Original languageEnglish
Article number2102905
JournalAdvanced Functional Materials
Issue number32
Publication statusPublished - 9 Aug 2021


  • block polymers
  • dynamic light scattering
  • grazing-incidence small-angle X-ray scattering
  • pH-responsive polymers
  • self-assembly
  • small-angle X-ray scattering
  • thin films

ASJC Scopus subject areas

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics


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