Abstract

The synthesis of poly(N-isopropyl acrylamide) (pNIPA)-based polymers via the surfactant-free precipitation polymerization (SFPP) method produced thermosensitive nanospheres with a range of distinctive physicochemical properties. Nano- and microparticles were generated using various initiators, significantly influencing particle characteristics, including the hydrodynamic diameter (DH), which varied from 87.7 nm to 1618.1 nm. Initiators, such as potassium persulfate and 2,2′-azobis(2-methylpropionamidine) dihydrochloride, conferred anionic and cationic functionalities, respectively, impacting the electrokinetic potential (EP) of the particles. Notably, certain particles with cationic initiators exhibited negative EP values at 18 °C, attributed to residual initiator components that affected the surface charge distribution. The presence of hydrophilic N-(2-hydroxyethyl)acrylamide (HEAA) segments also influenced solubility and phase transition behaviors, with critical dependencies on the HEAA/NIPA (N-isopropyl acrylamide) molar ratios. EP measurements taken at 18 °C and 42 °C revealed substantial differences, primarily governed by the initiator type and polymer composition. Observed variations in particle stability and size were associated with the choice of crosslinking agents and comonomer content, which affected both DH and EP in distinct ways. This study provides insights into key factors influencing colloidal stability and electrostatic interactions within thermosensitive polymer systems, underscoring their potential applications in biomedical and industrial fields.

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