The possibility of polyelectrolytes to interact with oppositely charged counterions (host-guest interplay) can be exploited for an electrochemically-induced film formation when using redox-active counterions. The charge of these guest molecules can be altered electrochemically changing concomitantly the solubility of the polyelectrolyte-counterion complexes at the electrode. Under certain circumstances film formation on the electrode can be observed. Previous work has shown that polyelectrolyte microgels show an insufficient deposition behavior compared to other polyelectrolyte systems. Hence, we address various architectures of cationic polymers made of quaternized poly(dimethylaminoethyl methacrylate) to mimic the architectural features present in the crosslinked porous and swollen microgel network. Thereby linear polymers are chosen to imitate the bridges between the crosslinks while the polymer stars resemble the situation around these crosslinking points. Electrodeposition of the different systems is studied with hydrodynamic voltammetry exploiting a rotating ring disk electrode (RRDE) allowing for quantification of the deposition efficiency <i>DE</i>. Results demonstrate linear polymers of moderate molar mass to be most efficient in the deposition due to pronounced intermolecular physical crosslinking (by help of the hexacyanoferrates). Branching and higher molar mass favor more intramolecular physical crosslinking. The combination of both aspects, branching and high molar masses, aggravates deposition for the polyelectrolyte microgel.

Polyelectrolyte microgels oppose electrodeposition

255th National Meeting (2018)

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