A versatile approach for the preparation of micrometer-sized, monodisperse, "mushroom-like" Janus polymer particles in aqueous dispersed systems is proposed. The synthetic methodology of the Janus particles consists of the following two steps. The first step is the preparation of spherical poly(methyl methacrylate) (PMMA)/poly(styrene-2-(2-bromoisobutyryloxy)ethyl methacrylate) (P(S-BIEM)) Janus particles based on the internal phase separation induced by solvent evaporation from the solvent droplets dissolving the polymers. The second step is surface-initiated atom transfer radical polymerization (ATRP) of 2-(dimethylamino)ethyl methacrylate (DM) using the Janus particles with ATRP initiator groups at one side of the surface as macroinitiator. As a consequence, mushroom-like PMMA/P(S-BIEM)-graft-poly(DM) Janus particles were prepared, which had pH-responsive property.

"Mushroom-like" Janus poly(methyl methacrylate) (PMMA)/poly(styrene-2-(2-bromoisobutyryloxy)ethyl methacrylate)-graft-poly(2-(dimethylamino)ethyl methacrylate) (PDM) particles synthesized in our previous report were applied as particulate surfactants. The PDM moiety at the one side of the Janus particles reversibly exhibited the volume phase transition in response to pH and temperature in an aqueous medium; that is, the surface property of the Janus particles comprising both PDM and PMMA reversibly changed between amphiphilic and hydrophobic based on the nature of PDM. Consequently, 1-octanol-in-water emulsion droplets stabilized by the amphiphilic Janus particles coalesced in the alkaline region and at 60 degrees C around neutral pH because of desorption of the hydrophobized Janus particles from the interface to the oil phase.

Summary: The effect of polymer end group on the morphology of polystyrene (PS)/poly(methyl methacrylate) (PMMA) composite particles was investigated on the basis of experimental observations and theoretical predictions. Both polymers with potassium persulfate (KPS)‐derived hydrophilic end group(s) and 2,2′‐azobis(isobutyronitrile) (AIBN)‐derived hydrophobic end group(s) were synthesized by emulsifier‐free emulsion polymerizations and solution polymerizations, respectively. Composite particles with the same end groups were prepared by release of toluene from PS/PMMA/toluene (1/1/24, w/w/w) droplets dispersed in an aqueous solution of sodium dodecyl sulfate (SDS). At a low SDS concentration, when the polymers with KPS‐derived end group(s) were employed, acornlike particles were formed. On the other hand, when the polymers with AIBN‐derived end group(s) were used, particles having a dimple were obtained. The interfacial tensions between toluene solutions of the polymers and SDS aqueous medium were lower for KPS‐derived end group(s) than for AIBN‐derived end group(s), and the difference was much larger for PS phase than PMMA phase. The predicted morphologies obtained from calculation of the minimum total interfacial free energy using the interfacial tensions agreed well with the experimentally observed morphologies in both cases. Moreover, the morphology of PS/PMMA composite particles with different end groups was also examined.