Asymmetric Microgels with Tunable Morphologies by Assembly‐Guided Polymerization of Liquid Crystalline Monomers

Abstract Understanding and controlling the morphology of microgels is crucial for optimizing their properties and functions in diverse areas of application. The fabrication of microgels that exhibit both structural and chemical anisotropy using a template‐free approach faces significant challenges. Existing approaches toward such microgels are typically limited to templating methods with low throughput. Here, an alternative bottom‐up approach is developed for producing non‐spherical N‐vinylcaprolactam (VCL) based microgels through semi‐batch precipitation polymerization, incorporating a functional comonomer with a liquid crystalline (LC) moiety. 4‐methoxybenzoic acid 4‐(6‐acryloyloxy‐hexyloxy)phenyl ester (LCM) is used as the LC comonomer. The resulting morphology of those microgels is tuned to multilobe‐, dumbbell‐, and raspberry‐like shapes. The different morphologies are obtained by varying the addition time of LCM, temperature, solvent ratio, and monomer ratio. The microgel morphologies are characterized by (cryogenic) transmission and scanning electron microscopy. The thermoresponsiveness is investigated by dynamic light scattering (DLS), while the incorporation of LCM into the microgel structure is determined via ¹H‐NMR and Raman spectroscopy. The experimental data indicate that adjusting reaction conditions enables the fabrication of microgels with various morphologies. Finally, their capability to solubilize hydrophobic substances is demonstrated by successfully facilitating the uptake of the hydrophobic dye Nile Red (NR).