NIPAm Microgels Synthesised in Water: Tailored Control of Particles’ Size and Thermoresponsive Properties

Microgels, combining the properties of hydrogels and microparticles, are emerging as versatile materials for varied applications such as drug delivery and sensing, although the precise control of particle size remains a challenge. Advances in synthetic methodologies have provided new tools for tailoring of properties, however costs and scalability of the processes remains a limitation. We report here the water-based synthesis of a library of <i>N</i>-isopropylacrylamide-based microgels covalently crosslinked with varying contents of <i>N</i>,<i>N'</i>-methylenebisacrylamide. The results highlight the versatility of water as a synthetic medium, which yields large and monodisperse microgels, with excellent control over size. Dynamic light scattering data demonstrate that by increasing the total monomer concentration from 1 to 3 wt%, the particle size is increased by up to 4.9-fold. Crosslinker content allows fine-tuning of microgel size, with greater relevance for functionalised microgels. Functional co-monomers such as <i>N</i>-(3-aminopropyl)methacrylamide hydrochloride and <i>N</i>-(hydroxymethyl)acrylamide are shown to influence size and thermoresponsive behaviour, with hydrogen-bonding monomers reducing particle size and increasing the volume phase transition temperature by 2 °C. Positively charged monomers show a size reduction upon heating but provide colloidal stability at temperatures up to 60 °C. These findings emphasize the importance of tailoring synthetic conditions and formulations to optimize microgel properties for specific applications.