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Highly Tunable Nanostructures in a Doubly pH‐Responsive Pentablock Terpolymer in Solution and in Thin Films
Author(s) -
Jung Florian A.,
Schart Maximilian,
Bührend Lukas,
Meidinger Elisabeth,
Kang JiaJhen,
Niebuur BartJan,
Ariaee Sina,
Molodenskiy Dmitry S.,
Posselt Dorthe,
Amenitsch Heinz,
Tsitsilianis Constantinos,
Papadakis Christine M.
Publication year - 2021
Publication title -
advanced functional materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 6.069
H-Index - 322
eISSN - 1616-3028
pISSN - 1616-301X
DOI - 10.1002/adfm.202102905
Subject(s) - materials science , copolymer , nanostructure , cationic polymerization , methacrylate , aqueous solution , methyl methacrylate , polyelectrolyte , polymer chemistry , thin film , chemical engineering , nanotechnology , polymer , composite material , organic chemistry , chemistry , engineering
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.