Dispersion polymerization of 2-hydroxyethyl methacrylate (HEMA) using siloxane-based surfactant in supercritical carbon dioxide and in compressed liquid dimethyl ether

The free radical dispersion polymerization of 2-hydroxyethyl methacrylate (HEMA) has been carried out in supercritical carbon dioxide (scCO₂) and compressed liquid DME using several surfactants. The polymerization are performed in the presence of fluorine-based poly(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl acrylate) poly(HDFDA)], poly(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl methacrylate) poly(HDFDMA)], or poly(HDFDMA-co-MMA) and siloxane-based PDMS-g-pyrrolidonecarboxylic acid (Monasil PCA™) or PDMS modified surfactants, SS-5050K™ and KF6017™ as polymerization surfactants. When scCO₂ was used as a polymerization medium, the PHEMA were heavily agglomerated. However, the spherical and relatively uniform poly(2-hydroxyethyl methacrylate) (PHEMA) particles could be produced even at 20 bar, with a narrow particle size distribution in compressed liquid DME. It was observed that fluorine-based surfactants were not a good surfactant as siloxane-based surfactants for the dispersion polymerization of HEMA. The average particle size of PHEMA was shown to be dependent on the type of the surfactant, the amount of the surfactant and initiator added to the system. The effect of two continuous phases, which are scCO₂ and compressed liquid DME, as a polymerization medium, the surfactant types and the concentration, initiator concentration, and monomer concentration on the morphology and size of the polymer particles was also investigated.