Abstract This work aims to study the cationic miniemulsion polymerization of styrene catalyzed by iron-containing imidazolium-based ionic liquids. The polystyrenes had very high number-average molar mass around 1300 kg mol-1 at 85 °C, molar-mass dispersity close to 2.0 and glass transition temperature higher than 102 °C with average particle diameter that remained practically unchanged during the reaction, indicating that the monomer droplets correspond to the polymerization locus. First-order kinetics up to a limit conversion, along with the increase in molar mass as the temperature decreases, styrene polymerization at low temperatures and catalyst inability to polymerize monomers that react exclusively via free radical and/or anionic polymerization, indicate the cationic nature of polymerization. 1H-NMR and 13C-NMR spectra suggested the formation of polystyrene, allowing for tacticity distribution quantification: 10% isotactic, 20% atactic and 70% syndiotactic configurations. TEM micrographs confirmed the formation of spherical polymer nanoparticles and the presence of catalysts in the polymer matrix.

Abstract A novel nanoencapsulation of n-hexadecane in high molecular weight polystyrene nanoparticles for thermal energy storage was carried out by miniemulsion polymerization using an iron-containing imidazolium-based ionic liquid (IL) as catalyst. The particle size, morphology, molecular weight, and thermal performance of nanoparticles containing the phase change material (PCM) were measured by dynamic light scattering, transmission electron microscopy, gel permeation chromatography, and differential scanning calorimetry, respectively. The nanoparticles were regular spherical, with narrow size distribution and particle size ranged from 138 nm to 158 nm. The enthalpy of melting for the nanoencapsulated PCM increased from 19 J/g to 72 J/g, as the content of n-hexadecane used increased from 20 wt% to 50 wt%. In addition, the nanoparticles showed thermal reversibility after 100 thermal cycles. The high molecular weights of the polymer, up to 1800 kDa, that could be reached with this IL may have contributed positively to this thermal behavior.