Cationic Polyelectrolytes Containing Perfluorinated Groups: Synthesis and Self-Assembly Properties in Aqueous Solutions

In this work, the synthesis and solution self-assembly of partially fluorinated cationic polyelectrolytes based on post-polymerization-modified poly(2-(dimethylamino) ethyl methacrylate), incorporating hydrophobic fluorinated groups along the polymer chain, is reported. The post-polymerization modification aims to establish amphiphilic characteristics and strong polyelectrolyte properties to the polymer. Therefore, the self-organization characteristics in aqueous media are expected to be affected. The poly(2-(dimethylamino) ethyl methacrylate) (PDMAEMA) homopolymer precursor is synthesized using RAFT polymerization. A quaternization reaction on the amine side groups using heptadecafluoro-10-iododecane results in the poly((2-dimethylamino) ethyl methacrylate-co-quaternized heptadecafluoro-10-iododecane (2-dimethylamino) ethyl methacrylate) (PQFD) amphiphilic statistical copolymers. We intentionally study statistical copolymers in our research of DMAEMA-based polyelectrolytes as there are not many studies about such materials. We have also chosen the incorporation of highly hydrophobic perfluorinated groups to study the changes in the solution properties of the initial hydrophilic homopolymer. The successful synthesis is supported by size-exclusion chromatography (SEC), 1H-NMR, and FTIR experiments. The self-assembly of the copolymers in aqueous solutions along with the dependence of the properties of the resulting aggregates on the pH, temperature, and ionic strength of the solution are studied using light scattering methods (DLS, ELS) and fluorescence spectroscopy (FS). The structural characteristics of the aggregates depend on composition, solution preparation protocol and solution pH, and temperature.