Aggregation Behavior and Intermolecular Interaction of Cationic Trisiloxane Surfactants: Effects of Unsaturation

Imidazolium/pyridinium-based trisiloxane surfactants containing a phenyl or vinyl group in the hydrophobic siloxane chain, bis(vinyldimethylsiloxy)methylsilylpropyl-pyridinium chloride (Vi-Si₃pyrCl), bis(vinyldimethylsiloxy)methylsilylpropyl-imidazolium chloride (Vi-Si₃minCl), and bis(phenyldimethylsiloxy)methylsilylpropylimidazolium chloride (Ph-Si₃minCl), were synthesized and confirmed by nuclear magnetic resonance (NMR) (¹H, ¹³C, and ²⁹Si NMR), mass spectrometry, and Fourier transform infrared spectrometry. The effect of the phenyl/vinyl group on their micellization behavior was studied by surface tension, electric conductivity, dynamic light scattering, 2D nuclear Overhauser effect spectroscopy (NOESY) NMR, and transmission electron microscopy. Owing to the hydrophobicity of the siloxane groups and cationic head groups, the critical micelle concentration (cmc) values follow the order Ph-Si₃minCl < Vi-Si₃pyrCl < Vi-Si₃minCl < Si₃pyrCl. Ph-Si₃minCl has a larger γ_cmc value, resulting from the introduction of the phenyldimethylsiloxy unit (π-π stacking interaction). The β values of Vi-Si₃minCl and Ph-Si₃minCl increase with the increase in temperature, which is attributed to the intermolecular interaction which hinders the association of Cl^- with the imidazolium ring and confirmed by 2D NOESY NMR. In aqueous solutions, the investigated cationic trisiloxane surfactants can self-assemble into spherical aggregates.