Polymerizable Nonionic Microemulsions: Phase Behavior of H₂O−n-Alkyl Methacrylate−n-Alkyl Poly(ethylene glycol) Ether (C_iE_j)

The phase behavior of ternary water−alkyl methacrylate−alkyl polyglycol ether (C i E j ) systems has been examined. Specifically, using seven different alkyl methacrylates ranging from methyl to hexadecyl methacrylate and C 10 E 6 as surfactant, vertical sections through the phase prism were determined, from which the phase inversion temperature, the upper and lower critical temperature of the three-phase body, and the efficiency of the surfactant and its monomeric solubility in the oil were obtained. Keeping hexyl methacrylate as oil-fixed, 18 different surfactants were applied including short- and long-chain surfactants such as C 4 E 3 and C 14 E 8 . The microemulsion systems examined here show the same general patterns as the well-known nonionic microemulsions with alkanes as oil. Notably, the phase inversion temperature is highly dependent on the alkyl chain length of the oil, a fact that is often left out of consideration when choosing a surfactant in emulsion polymerization. For a given oil the phase inversion temperature can be adjusted by appropriate choice of the number of ethylene glycol units of the surfactant. The efficiency of the surfactant systematically depends on the alkyl chain length of both the surfactant and the oil. Interestingly, there is a striking parallel between efficiency of a surfactant and its monomeric solubility in the oil. Finally, in preparation for applying these systems to the synthesis of nanoscaled latexes in microemulsion polymerization the water-rich part of the phase prism was examined. Both the expected shape of the emulsification failure phase boundary and the near-critical phase boundary with its nonmonotonic decay characteristic of branched network structures are delineated. The results of some preliminary polymerizations are briefly discussed.