We resolved the longtime enigma in emulsion polymerization of styrene with K2S2O8 by showing the fact that hollow polystyrene particles were successfully prepared by heat treatment in the emulsion state.

Submicrometer-sized raspberry-like polystyrene (PS) particles, which were prepared by emulsion polymerization with polyoxyethylene nonylphenyl ether nonionic emulsifier (Emulgen 910, HLB 12.2) and potassium persulfate initiator, contained 8.5 vol % (relative to the particle) of water and 5.5 wt % (relative to PS) of Emulgen 910 in the inside. The water absorption decreased the glass transition temperature of the PS particles dispersed in an aqueous medium. The wt % (relative to PS) of the incorporated Emulgen 910 increased with increasing initial Emulgen 910 concentration in the emulsion polymerization, but the wt % (relative to the total Emulgen 910 used) of the incorporated Emulgen 910 was constant at approximately 50% independent of the initial concentration. The vol % (relative to particle) of water increased to 46% by heat treatment at 90 °C for 24 h, which was based on further water absorption, and resulted in spherical hollow particles, where the amount of the incorporated Emulgen 910 remarkably decreased in a short treatment and then remained almost constant during the heat treatment. After another 24 h treatment, the percentage of nonhollow particles increased gradually, which was based on the escape of the water domain together with Emulgen 910 from the inside of the particles. On the other hand, spherical PS particles prepared by emulsifier-free emulsion polymerization did not contain water in the inside and were not changed to hollow ones by a similar heat treatment. From these results, an innovative easy method to synthesize hydrophobic hollow PS particles is proposed.

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Previously, we have reported the successful preparation of micrometer-sized poly­(methyl methacrylate) particles without submicrometer-sized byproduct particles by microsuspension iodine-transfer polymerization (ms ITP), in which the radical exit depression (RED) effect was expected, with the benzoyl peroxide initiator at 8 wt % relative to the monomer. However, it was difficult to apply it simply under a similar condition for methyl acrylate (MA), which is more hydrophilic than methyl methacrylate (MMA), because the polymerization rate in the water phase (R p w) arising from the oligomer radicals exiting from the monomer droplets is high, resulting in a lot of submicrometer-sized byproduct particles. In this study, the problem was overcome by utilizing a two-step temperature process in the microsuspension polymerization with iodoform (ms I) of MA, which supports the proposed mechanism in the ms ITP of MMA in the previous paper. Although the control of the molecular weight (M n) and the molecular weight distribution (M n/M w) was restricted, the preparation of micrometer-sized particles without byproduct particles was realized and a high conversion was reached within a practical time that meets the demands of the industry by utilizing the ms I. The optimal conditions for MA were 70 °C for 2 h, followed by 80 °C for 4 h with a high content of initiator (8 wt % relative to a monomer).