Synthesis of polystyrene microspheres by dispersion polymerization in supercritical carbon dioxide using a poly(dimethylsiloxane)-based macroazoinitiator

The synthesis of polystyrene microspheres was achieved by the dispersion polymerization of styrene in supercritical carbon dioxide using azobisisobutylonitrile (AIBN) and a poly(dimethylsiloxane) (PDMS)-based macroazoinitiator, VPS-1001. VPS-1001 contained seven to nine molecules of the azo groups and the PDMS blocks with a molecular weight of 10,000 per molecule. The polymerization in the presence of both VPS-1001 and AIBN produced polystyrene microspheres with a diameter below 4 μm in over 85% yields, whereas the polymerization with VPS-1001 in the absence of AIBN provided a nonspecific polystyrene in only 20% yield. The particle size decreased as a result of increasing the concentration of VPS-1001. It was confirmed that the polystyrene particles were stabilized by the PDMS-block-polystyrene formed through the polymerization initiated by VPS-1001 because the polymerization using a PDMS homopolymer provided nonspecific polystyrene as a precipitate during the polymerization.