In Situ Synchrotron SAXS Study of Polymerizable Microemulsions

Abstract

We present for the first time a real-time small-angle X-ray scattering (SAXS) study of the structural transition of fluid microemulsion to solid polymerized material in a silicone polymerizable microemulsion system. A reactive methacrylate-terminated siloxane macromonomer (MTSM, Mn ∼ 1000 g/mol) was synthesized and used for microemulsion formulations comprising MTSM (oil phase), water, and a mixture of nonionic surfactant (Teric G9A8) with isopropanol. In situ synchrotron SAXS was used to investigate time-dependent nanostructure evolution during the polymerization reaction, which was directly initiated by X-ray radiation. The SAXS data were analyzed using both the Teubner-Strey model and the core-shell model. The results obtained by the Teubner-Strey model showed that the domain size (d) decreased while the correlation length (I¾) increased upon polymerization. The analysis in terms of the core-shell model displayed that adding water to the precursor microemulsion caused the water droplets to start swelling, which resulted in the discontinuity of water in oil microemulsion. There exhibited large differences in morphologies of polymerized materials from the microemulsion formulations with different water and surfactant contents. The core and shell sizes of water droplets decreased during the course of polymerization when there was 15 wt % or more water in the microemulsion formulation; the polymerized material thus exhibited increasingly discrete granular morphology. When there was 10 wt % or less water content in the precursor microemulsion, the rearrangement of water domains could be minimized during the course of polymerization and transparent polymerized material was obtained.